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Biased Bowl-Direction of Monofluorosumanene in the Solid State

  • Yumi Yakiyama*
    Yumi Yakiyama
    Division of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
    Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
    *[email protected]
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    Orcidhttps://orcid.org/0000-0003-4278-2015
  • , 
  • Minghong Li
    Minghong Li
    Division of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
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  • , 
  • Dongyi Zhou
    Dongyi Zhou
    Division of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
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  • , 
  • Tsuyoshi Abe
    Tsuyoshi Abe
    Division of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
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  • , 
  • Chisato Sato
    Chisato Sato
    Graduate School of Engineering, Tohoku University, 6-6 Aramakiazaaoba, Aoba-ku, Sendai 980-8579, Japan
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  • Kohei Sambe
    Kohei Sambe
    Graduate School of Engineering, Tohoku University, 6-6 Aramakiazaaoba, Aoba-ku, Sendai 980-8579, Japan
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  • , 
  • Tomoyuki Akutagawa
    Tomoyuki Akutagawa
    Graduate School of Engineering, Tohoku University, 6-6 Aramakiazaaoba, Aoba-ku, Sendai 980-8579, Japan
    Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan
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    Orcidhttps://orcid.org/0000-0003-3040-1078
  • , 
  • Teppei Matsumura
    Teppei Matsumura
    Division of Chemical Engineering, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan
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  • , 
  • Nobuyuki Matubayasi
    Nobuyuki Matubayasi
    Division of Chemical Engineering, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan
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    Orcidhttps://orcid.org/0000-0001-7176-441X
  • , and 
  • Hidehiro Sakurai
    Hidehiro Sakurai
    Division of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
    Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
    More by Hidehiro Sakurai
    Orcidhttps://orcid.org/0000-0001-5783-4151
Cite this: J. Am. Chem. Soc. 2024, 146, 8, 5224–5231
Publication Date (Web):February 19, 2024
https://doi.org/10.1021/jacs.3c11311

Copyright © 2024 The Authors. Published by American Chemical Society. This publication is licensed under

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Abstract

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A new curved π-conjugated molecule 1-fluorosumanene (1) was designed and synthesized that possesses one fluorine atom on the benzylic carbon of sumanene. This compound can exhibit bowl inversion in solution, leading to the formation of two diastereomers, 1endo and 1exo, with different dipole moments. Experimental and theoretical investigation revealed an energetical relationship among 1exo, 1endo, and solvent to realize the various endo:exo ratios in the single crystals of 1 depending on the crystallization solvent. Significantly, the molecular dynamics (MD) simulations revealed that 1exo positively worked for the elongation of the stacking structure and the final endo:exo ratio was affected by the relative stability difference between 1endo and 1exo derived by solvation. Such an arrangeable endo:exo ratio of 1 realized the preparation of unique materials showing a different dielectric response from the same molecule 1 just by changing the crystallization solvent.

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Introduction

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The process of nucleation, the initial step in crystallization, is largely affected by various factors such as temperature, solvent, concentration of the solute, and impurities. (1) These factors significantly affect the molecular arrangements and morphology of the resulting crystals. Understanding these structural aspects is crucial as they are closely linked to the physical properties of crystalline materials. Notably, the contribution of solvents to the nucleation has been investigated recently by combining the experimental approach using 1H NMR and FT-IR spectroscopies and the theoretical one applying density functional theory (DFT) calculations and molecular dynamics (MD) simulations. The outcomes of these studies have unveiled discernible solvent-induced effects on nucleation events in various small aromatic compounds (2−10) and pharmaceutical molecules. (11−14) Despite these advancements, the general rules governing nucleation and subsequent crystallization processes remain elusive. (15−17) Therefore, the control of crystal packings and the physical properties of the crystals remain a challenging issue.
Buckybowls are the partial structures of fullerenes such as C60 and are recognized as distinctive molecular components in the realm of new molecular materials. Bowl-to-bowl inversion is one of the most representative and attractive phenomena in buckybowl chemistry. This unique property of the curved-π system affords a variety of structural and physical properties that respond to external environments. Consequently, these buckybowls hold potential applications as the molecular switches responsive to external stimuli. (18) One representative buckybowl, sumanene (Sum), also shows dynamic phenomenon involved by its bowl inversion in the solution state (Figure 1). (19,20) Sum possesses three benzylic carbons, and their two geminal protons are not geometrically equivalent due to the bowl structure. This characteristic implies that monobenzyl substitution on sumanene potentially gives endo- (concave side) and/or exo- (convex side) substituted derivatives. The resulting endo:exo product ratio is affected by the electronic factor, namely, the stereoelectronic effect, as well as the structural factor, mainly the steric hindrance between the substituent and the bowl. (21) For example, OH group substitution exclusively yields the endo product, while trimethylsilyl substitution gives only the exo product. The above example shows noticeable energy differences between the corresponding diastereomers. Meanwhile, the reaction with comparable exo and endo populations is also reported if the two diastereomers possess similar energy. In such an occasion, it is expected that other environmental factors such as the temperature, concentration, solvent, and the presence of other additives may affect the final endo:exo ratio. Especially in the crystalline state, in which small intermolecular interactions afford different types of stabilization effects from that in the solution state, it is unsurprising to observe a disparate endo:exo ratio.

Figure 1

Figure 1. Bowl inversion of Sum and the conceptual figure of this work.

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Recently, our focus has been on studying fluorine-introduced buckybowls, (22−24) especially fluorosumanenes (25−28) from both structural and application viewpoints. The salient feature of these compounds is that they form isostructural single crystals of pristine sumanene. (29,30) Particularly intriguing is the instance of difluorosumanene (F2-Sum), where two fluorine atoms are on a single benzylic carbon site. This configuration induces the anisotropic dielectric response due to its strong dipole moment caused by F-introduction. (26) This attribute has been harnessed to create solid solutions with pristine sumanene and change the activation energy of dielectric response depending on the Sum:F2-Sum ratio. (27) In this context, we further extended our interest to another fluorosumanene family, monofluorosumanene (1), which possesses one fluorine atom at the peripheral benzylic carbon. In this paper, we found that 1 was a diastereomeric mixture of its endo- (1endo) and exo- (1exo) substituted products in solution and solid states. Because of the curved structure of the sumanene skeleton, 1endo and 1exo exhibited distinct electronic structures, leading to different dipole moments (1.96 D for 1endo and 4.57 D for 1exo at B3LYP/6-311+G(d,p)). Noteworthy is that 1 gave the isostructural single crystal packing of Sum, and its endo:exo ratio significantly changed depending on the crystallization solvent from 1endo:1exo = 60:40 to 18:82. This alternation in the endo:exo ratio directly corresponds to a remarkable difference in the dielectric response of each crystal. In addition, we investigated its mechanism through quantum chemistry calculations and molecular dynamics simulations to find that solvation and intermolecular interactions in the aggregated structure significantly affected the final endo:exo ratio in the crystals.

Results and Discussion

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Monofluorosumanene (1) was synthesized from direct fluorination of previously reported hydroxysumanene (21) by 135 mol % diethylaminosulfur trifluoride (DAST) in CH2Cl2 in 43% yield (Scheme 1). The fundamental properties of 1 were confirmed by UV–vis spectroscopy and cyclic voltammetry (CV) experiments (Figures S1 and S2). The UV–vis spectrum of 1 showed similar absorption patterns of pristine Sum and other fluorosumanenes, showing an absorption at 276 nm with a broad peak at around 300 nm (Figure S1). These values are in between those of F2-Sum and F6-Sum. (25,26) The voltammogram of 1 in MeCN with tetrabutylammonium perchlorate as a supporting electrolyte showed a clear reduction peak (Epred = −1.81 V (vs Fc0/Fc+), Figure S2) which positively shifted compared with that of Sum (Epred = −2.49 V (vs Fc0/Fc+)). (31)

Scheme 1

Scheme 1. Synthesis of 1-Fluorosumanene (1)
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The thermodynamic relationship between 1endo and 1exo was clarified by theoretical calculation and 1H NMR measuremens. The theoretical analysis operated at the B3LYP/6-311+G(d,p) level of theory indicated that 1endo is 0.67 kcal/mol more stable than 1exo and the bowl inversion energy of 1endo was 20.74 kcal/mol while 1exo was 20.06 kcal/mol (Figure 2). These calculation results agreed with the variable temperature 1H NMR measurements in various solvents (Table 1). Regardless of the solvents and the temperature range, the gem-proton signal on the F-attached benzylic carbon of 1endo showed an intensity higher than that of 1exo, appearing at a higher magnetic field (see Supporting Information). This observation strongly indicated that 1endo was the major component of the system. The van’t Hoff plot based on the experimentally obtained endo:exo ratio at each temperature demonstrated no temperature range (193–373 K), in which the equilibrium relationship between 1endo and 1exo could be reversed (Tables 1 and S1, Figure S3). The thermodynamic parameters ΔrH⊖ and ΔrS⊖ displayed a notable compensatory correlation between enthalpy and entropy, suggesting a consistent inversion mechanism across all solvents (Figure S4). (32,33) It was hypothesized that the positive entropy change, resulting from the flipping from a more crowded environment of 1endo due to the presence of solvent-interactive adjacent H atoms to a more F atom-exposed 1exo structure, serves as the primary driving force behind the bowl inversion process. Although the largest ΔrS⊖ value was obtained with acetone, the molecular size (van der Waals volume: CH2Cl2, 56.27 Å3; acetone, 66.60 Å3; DMF, 77.59 Å3) (34) or polarity (ET(30): CH2Cl2, 40.7 kcal/mol; acetone, 42.2 kcal/mol; DMF, 43.2 kcal/mol) (35) did not explain the results, indicating simple consideration of solvent size and polarity does not solve this relationship, and more detailed and careful investigation of the whole bowl flipping process, including transition state through DFT calculation using cluster model of 1 and solvent molecule, is required, (36) which will be our future work.

Figure 2

Figure 2. Structural and energetic difference between 1endo and 1exo. All the calculation data were obtained at the B3LYP/6-311+G(d,p) level of theory.

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Table 1. endo:exo Ratio of 1 in CD2Cl2, Acetone-d6, and DMF-d7 at Various Temperaturesa
  1endo:1exo
temperature (K) CD2Cl2 acetone-d6 DMF-d7
373     59:41
348     61:39
323     63:37
298 68:32 64:36 64:36
273 72:28 70:30 66:34
243 75:25 78:22 69:31
193 80:20 90:10  
Thermodynamic Parameter
ΔrH⊖ (kJ mol–1) 2.7 7.4 2.5
ΔrS⊖ (J mol–1 K–1) 2.5 20 3.3
a

All the samples were prepared in 1.5 mg/mL. Thermodynamic parameters ΔrH⊖ and ΔrS⊖ obtained via van’t Hoff plot are also shown.

The previous experiments confirmed that no conversion of the major species occurred in the diluted solution state. Nevertheless, considering the slight energetic difference between 1endo and 1exo is small (<1 kcal/mol), it is anticipated that the endo-favored condition is easily replaced by the exo-favored condition when perturbed by intermolecular interactions in a dense system, namely in the solid state. In this context, we next investigated how the endo:exo ratio changes in the solid state by crystallization conditions, such as solvent type and temperature. Single crystal preparation was performed by slow evaporation or vapor diffusion methods using three kinds of solvents, CH2Cl2, acetone, and DMF, with a temperature range from 193 to 323 K (Table 2). All the crystals were isostructural with Sum and already reported other fluorosumanenes, (25,26,29,30) trigonal R3c space group. In all the trials, the temperature effect was not significant, even though the entropic effect seemed to contribute to result in a slightly higher 1endo ratio at more than 298 K. Meanwhile, the endo:exo ratio of 1 in each crystal significantly differed depending on the type of crystallization solvent. Figure 3 shows the typical X-ray analysis results of the single crystals prepared from CH2Cl2 at 193 K. In the structure, we could find no solvent incorporation and observed that only one-third of the sumanene skeleton was independent. Within that, the two-electron densities dangling on the benzylic carbon were not equivalent, indicating the disordering of F atoms in a whole crystal. After refinement of the data, it was found that the occupancy factor of the two F atoms at the endo and the exo sides were 0.154(3) and 0.179(3), respectively; namely, the approximate 1endo:1exo ratio in the present crystal was 46:54 (Figure 3a). The bowl depth, defined by the vertical distance between the bottom hexagonal ring and the peripheral aromatic carbon, was 1.14 Å. This value was in between those of Sum (1.11 Å) (29) and F2-Sum (1.16 Å) (Figure 3b). (26)
Table 2. 1endo:1exo Ratio in a Single Crystal of 1 Prepared in CH2Cl2, Acetone, and DMF at Various Temperatures
  1endo:1exo
temperature (K) CH2Cl2 acetone DMF
323   34:66 22:78
298 45:55 25:75 18:82
243 60:40 27:73 29:71
193 46:54 36:64  

Figure 3

Figure 3. Representative crystal structure of 1. The sample crystal was obtained by the slow evaporation method using CH2Cl2 at 193 K.

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In the crystal structure, 1endo and 1exo formed 1D columnar structure mainly stabilized by intracolumnar CH···π interactions between the benzylic C–H and π-plane of the sumanene skeleton and weak π–π interactions to give the bowl to bowl distance to be 3.890 Å (Figure 3b). All of the 1D-columns were connected through CH···π interactions (C–C: 3.895 Å) between benzylic carbon and neighboring aromatic carbons, probably with a slight contribution of CF···π and F···F interactions (2.393 Å) to stabilize the total packing structure with the distance of the central column axes to be 9.625 Å (Figure 3b,c). Notably, the endo:exo ratio difference did not affect the structural parameters much, supporting that the structural difference between 1endo and 1exo was well relaxed in the packing structures (Table S2). It is reasonable to assume that the slight structural and electronic difference between 1endo and 1exo was magnified in the crystal growing process via intermolecular interactions with solvents to achieve the formation of single crystals with such a variety of endo:exo ratios.
Such a biased endo:exo ratio in the crystal of 1, coupled with the significant difference in dipole moments between 1exo and 1endo, prompted us to apply 1 as a modifiable source of dielectric material. We tried to evaluate the dielectric response on the pelletized crystalline (PC) samples made from two kinds of crushed single crystals: recrystallized from DMF (PCDMF) or CH2Cl2 (PCCH2Cl2) (1endo:1exo = 27:73 for PCDMF, 47:53 for PCCH2Cl2). Both samples underwent measurements at several frequencies with the temperature range from 300 to 420 K (Figure 4) under N2 atmosphere. There was a significant difference in the dielectric properties depending on the endo:exo ratio. In the case of PCDMF, both real (ε1) and imaginary (ε2) parts of the dielectric constant were enhanced above ∼360 K at 1 MHz, with a Debye-type dielectric relaxation (Figure 4a,b). This phenomenon was quite similar to that of already reported F2-Sum, (26) indicating that the in-plane directional thermal vibration of polarized 1exo worked as the main contributor to the dielectric response. The ln(τ)–Tp1–1 plots of PCDMF indicated a linear correlation (Figure S5), where Tp1 is the dielectric ε1-peak and the τ-value is the relaxation time of the inverse of the measured f-values of τ = 1/(2πf). The activation energy for the thermally activated motion of PCDMF was evaluated to be Ea = 70 kJ/mol, comparable to previously reported F2-Sum and other reported π-planar organic dielectrics (Figure S5). (37,38) On the contrary, PCCH2Cl2 showed significantly high dielectric constants as a simple organic molecule even after carefully drying up the possibly containing solvents. After the first heating, the dielectric constant decreased significantly (Figure 4c–f). Based on the experimental results, considerable structural relaxation was expected to occur at high temperatures, leading to a more stabilized structure in which the thermally activated motion of 1exo is strongly prohibited.

Figure 4

Figure 4. Temperature dependence of (a, c, e) the real part (ε1) and (b, d, f) the imaginary part (ε2) of the dielectric constant of PCDMF (a, b) and PCCH2Cl2 (c–f) in compressed pellets measured at various frequencies. (e) and (f) represent the 2nd sweep results.

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Regarding utilizing the functional molecules, it is a significant benefit that just a change in crystallization solvent gives a substantial property difference. To obtain more profound insight into how each conformer and solvent contribute to the obtained results, we first conducted DFT calculations to investigate how the intermolecular interactions involved in the crystallization process of 1 affect the final 1endo:1exo ratio in the single crystal of 1. Our analysis employed a simple dimer model of 1endo and 1exo to explore the most stable conformer and stacking order. We focused on evaluating the interaction energies between the upper and bottom sides of 1s in the model. Here, interdimer interactions were not considered as intracolumnar interactions were approximately 10 times stronger than intercolumnar ones, especially for sumanene derivatives that pack in the R3c space group. (27) The dimer model preparation was prepared by optimizing 1endo and 1exo at the ωb97XD/6-311+G(d,p) level of theory, with the bowl-to-bowl distance to be 3.9 Å and a rotation angle θ of F-attached benzylic carbons set to 60° or 180° (Figure 5). It should be noted that all the possible stacking orders (upper or lower sides in the dimer) were considered. The simulation performed at the ωb97XD/6-311+G(d,p) level of theory clearly showed that the two dimers (1endo/1endo and 1exo/1endo), in which 1endo was placed at the bottom part of the stacking structure, were less stable (−18.35 to −18.94 kcal/mol) compared to the others (1exo/1exo and 1endo/1exo) with 1exo at the bottom position (−21.03 to −21.34 kcal/mol). These results were reasonable because the F atom of 1endo connected vertically to the bowl, leading to significant steric hindrance when another 1 came from the concave side. In contrast, the C–F bond on 1exo takes a somewhat in-plane direction of the bowl to avoid serious steric repulsion during stacking formation. These results explained that 1exo was more likely to be incorporated into the stacking column, especially when it approached the convex side. Indeed, the increment of 1exo ratio in all the crystals compared with the solution state data suggested that the above discussion is somewhat applicable to explaining the phenomena. However, the significant differences in the final endo:exo ratio in the crystalline state depending on the crystallization solvent indicated the presence of distinct solvent effects during the crystal growth, which assisted or interfered with introducing 1exo into the resulting crystal structure.

Figure 5

Figure 5. Dimer model preparation and the resulting intermolecular energies based on the stacking species and order.

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To illustrate the relationship between the solvent and the endo:exo ratio in the crystallization process, we applied molecular dynamics (MD) simulation considering three kinds of solvent systems: acetone, CH2Cl2, and DMF. All the molecules were modeled with a potential function based on the general Amber force field (GAFF) through DFT calculations at the B3LYP/6-31G(d,p) level for geometry optimization. (39,40) All the MD simulations were carried out with GROMACS 2020.6 in the NPT ensemble at 300 K, 1 bar for 30 ns (see Supporting Information for the simulation details). (41) We first investigated the effect of the solvent on the aggregation of 1endo and 1exo. Three systems (100% population of each conformer or a 50:50 mixture of endo and exo conformers) were considered in the simulation. Note that there is no conversion between the endo and exo forms during the simulations. The concentration of 1 was 0.5 M at each run, and the population of the aggregates was examined. Here, we set the position of the center of mass on each conformer and defined the specific component as an “aggregate” when all the molecules are connected with a distance between centers of mass of 8 Å or less (see Supporting Information). The monomer population is larger in the order of DMF > CH2Cl2 > acetone for each conformer and the 50:50 mixture (Figure 6). Conversely, the aggregation tendency is stronger with acetone > CH2Cl2 > DMF and is particularly suppressed in DMF. It is also seen in Figure 6 that the 1endo isomers are less likely to aggregate, indicating that the aggregation is more preferable for the 1exo form.

Figure 6

Figure 6. Aggregation state of 1 expressed as the % population of the number of molecules forming an aggregate with the degree of aggregation in the abscissae for (a) 100% 1exo, (b) 100% 1endo, and (c) 50:50 mixture of them in acetone, CH2Cl2, and DMF. The summed values over the degrees of aggregation of 4 or more are also shown in (d) to illustrate the dependence on the conformational states and solvents more clearly.

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The relative preference of the 1exo and 1endo isomers in the monomeric and aggregates states are listed in Table 3. In acetone, for example, the monomeric 1endo and 1exo population is 57:43, implying the preference for the endo form when 1 is monomeric. This agrees with the experimental observation in Table 1, while Table 3 shows that more than half of 1 is in the exo form when the degree of aggregation exceeds 2. The tendency in CH2Cl2 was relatively close to the case in acetone, while in DMF, the 1exo population increment was not as steep as observed in acetone and CH2Cl2, and the average number was 3.3 even at the seventh degree of aggregation.
Table 3. Average Number of 1exo in Each Degree of Aggregation in Acetone, CH2Cl2, and DMFa
  degree of aggregation
solvent 1 2 3 4 5 6 7
acetone 0.43 1.0 1.6 2.2 3.8 3.4 3.8
CH2Cl2 0.44 1.0 1.7 2.3 3.0 3.5 3.9
DMF 0.48 1.0 1.6 2.2 2.6 2.9 3.3
a

The concentration of 1 in the system was 0.5 M, and the endo:exo ratio was 50:50.

We next analyzed the stacking manner of 1 in all of the aggregates, focusing on the neighboring pairs. A pair of 1 is counted as neighbors to each other when their center-of-mass distance is less than 8 Å. The MD simulation in acetone and CH2Cl2 revealed that the population of the 1exo/1exo combination became dominant as the degree of aggregation increased, while others with the endo form were on the decrease (Figure 7). This result matched the conclusion obtained from the DFT calculation that 1exo positively contributed to the elongation of the stacks more than 1endo. The same tendency was observed in the case of DMF, although the population of 1exo/1exo is smaller than those in the other two cases, in agreement with the smaller number for 1exo in Table 3.

Figure 7

Figure 7. Population analysis data for neighboring pairs of 1exo/1exo, 1exo/1endo, 1endo/1exo, and 1endo/1endo in various aggregates in (a) acetone, (b) CH2Cl2, and (c) DMF. The averaged data over the degrees of aggregation of 4 or more are shown in (d) to illustrate the dependence on the solvents more clearly. The definition of the neighboring pairs follows Figure 5.

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The above discussion indicated that 1exo was more easily introduced in the aggregates than 1endo, contributing to its elongation, and that aggregation is somehow suppressed in DMF. It should be noted, though, that the endo and exo conformers ratio is 50:50 in their mixture systems in MD. As shown in Table 1, the experimental endo:exo ratio is not 50:50, and this also affects the extent of exo propensity at recrystallization, as discussed next.
The energetic difference in Figure 1 was computed in a vacuum, and the endo:exo ratio is modified due to the solvation effect. This effect is quantified by the solvation free energy Δμ of a monomeric 1, which is shown in Figures 8. (42,43) It is evident that the exo form interacts more favorably with each solvent than does endo and partially cancels the endo preference in Figure 1. The extent of partial cancellation is stronger in the order of DMF > acetone > CH2Cl2, which means that the exo population is larger in this order when the recrystallization process starts. As discussed in Figure 7, on the other hand, the tendency for exo inclusion is more evident in acetone and CH2Cl2. With the combination of the two effects, accordingly, the exo population in the crystal is high with solvent DMF in Table 2 due to enhanced stability of the exo form at the outset of recrystallization, and it is high with acetone due to the higher inclusion efficiencies of 1exo. Indeed, Table 3 and Figures 7 and 8 show for the solvent effects that the exo form is less favorably incorporated into aggregates when it is more strongly solvated. The energetic preference toward exo pairs in aggregates competes against that for the exo monomer at solvation, and the latter effect is more important than the former to determine the exo propensity at recrystallization. Accordingly, a guideline can be proposed that the crystal becomes richer with exo when the exo–solvent interactions are made stronger.

Figure 8

Figure 8. Solvation free energy Δμ of 1endo and 1exo in acetone, CH2Cl2, and DMF. ΔΔμ = Δμ(1endo) – Δμ(1exo) is noted in units of kcal/mol for each solvent.

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Conclusion

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We successfully synthesized monofluorosumanene 1, which is a diastereomeric mixture of 1exo and 1endo due to bowl inversion. Our experimental and theoretical investigations uncovered the energetic relationship among 1exo, 1endo and solvent, enabling us to arrange the endo:exo ratio in the single crystals of 1 by the appropriate choice of the crystallization solvent. Throughout our project, it was found that the solvation made 1exo more stable, though it was not sufficient to reverse the intrinsic stability of 1endo, resulting in a higher population of 1endo in the solution state. However, the sterically favorable structure of 1exo for aggregation facilitated the inversion of the endo:exo ratio in the solid state. Our DFT calculations and MD simulations played a pivotal role in understanding the underlying mechanisms, highlighting the critical impact of the solvation stabilization effect and the inclusion efficiency of 1exo. Such an arrangeable endo:exo ratio of 1 realized the preparation of unique materials that exhibit entirely different dielectric responses. One showed the Debye type dielectric relaxation, while the other displayed a significantly high dielectric constant, all derived from the same molecule 1, solely by changing the crystallization solvent. This significant achievement opens up new applications for the bowl inversion phenomenon in the curved-π molecules and highlights the remarkable potential of fluorosumanenes as energy materials.

Supporting Information

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.3c11311.

  • Synthesis of 1, 1H NMR, 13C NMR, and 19F NMR charts of 1, detailed experimental procedures, single crystal X-ray analysis details, molecular dynamics simulation detail, computational procedures with Cartesian coordinates, and supplemental figures and tables about optical and electrical properties of 1, equilibrium details of 1 in each solvent, structural parameters of single crystal of 1, and Arrhenius plot obtained from PCDMF (PDF)

Accession Codes

CCDC 2288999–2289010 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

Author Information

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  • Corresponding Author
    • Yumi Yakiyama - Division of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan;  Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan;  Orcidhttps://orcid.org/0000-0003-4278-2015;  Email: [email protected]
  • Authors
    • Minghong Li - Division of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
    • Dongyi Zhou - Division of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
    • Tsuyoshi Abe - Division of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
    • Chisato Sato - Graduate School of Engineering, Tohoku University, 6-6 Aramakiazaaoba, Aoba-ku, Sendai 980-8579, Japan
    • Kohei Sambe - Graduate School of Engineering, Tohoku University, 6-6 Aramakiazaaoba, Aoba-ku, Sendai 980-8579, Japan
    • Tomoyuki Akutagawa - Graduate School of Engineering, Tohoku University, 6-6 Aramakiazaaoba, Aoba-ku, Sendai 980-8579, Japan;  Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan;  Orcidhttps://orcid.org/0000-0003-3040-1078
    • Teppei Matsumura - Division of Chemical Engineering, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan
    • Nobuyuki Matubayasi - Division of Chemical Engineering, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan;  Orcidhttps://orcid.org/0000-0001-7176-441X
    • Hidehiro Sakurai - Division of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan;  Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan;  Orcidhttps://orcid.org/0000-0001-5783-4151
  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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This work was supported by Grant-in-Aid for Scientific Research on Innovative Areas “π Space Figuration” (Grant JP26102002), Grant-in-Aid for Transformative Research Areas “Science of 2.5 Dimensional Materials” (Grants JP21H05232 and JP21H05233), “Hyper-Ordered Structures Sciences” (Grants JP21H05563 and JP23H04112), JSPS KAKENHI (Grants JP19H00912 and JP20H00400), and Dynamic Alliance for Open Innovation Bridging Human, Environment and Materials (Grants 20224023 and 20234025). The X-ray diffraction studies of one of the single crystal of 1 by synchrotron radiation were performed at BL02B1 of SPring-8 (Grant 2022A1330). The theoretical calculations were performed at the Research Centre for Computational Science, Okazaki, Japan (Grant 22-IMS-C068). We thank Prof. Gaku Fukuhara for the fruitful discussions about the solvation phenomena of 1. Y.Y. is grateful for support from the program “Initiative for Realizing Diversity in the Research Environment”, Osaka University. M.L. thanks the China Scholarship Council for support (Grants CSC 201708310115 and CSC 201908050056). N.M. is grateful to the Fugaku Supercomputer Project (Grants JPMXP1020230325 and JPMXP1020230327) and the Data-Driven Material Research Project (Grant JPMXP1122714694) from the Ministry of Education, Culture, Sports, Science, and Technology.

References

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    Crystal Growth & Design (2021), 21 (1), 544-551CODEN: CGDEFU; ISSN:1528-7483. (American Chemical Society)
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    Burton, R. C.; Ferrari, E. S.; Davey, R. J.; Finney, J. L.; Bowron, D. T.
    Journal of Physical Chemistry B (2010), 114 (26), 8807-8816CODEN: JPCBFK; ISSN:1520-6106. (American Chemical Society)
    In this contribution, neutron scattering expts. (with isotopic substitution) of concd. and supersatd. methanolic benzoic acid solns. combined with empirical potential structure refinement (EPSR) were used to investigate the time-averaged atomistic details of this system. Through the detn. of radial distribution functions, quant. details emerge of the soln. coordination, its relationship to the nature of the cryst. phase, and the response of the soln. to imposed supersatn.
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  16. 16
    Joseph, A.; Rodrigues Alves, J. S.; Bernardes, C. E. S.; Piedade, M. F. M.; Minas da Piedade, M. E. Tautomer selection through solvate formation: the case of 5-hydroxynicotinic acid. CrystEngComm 2019, 21, 2220– 2233,  DOI: 10.1039/C8CE02108B
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    16
    Tautomer selection through solvate formation: the case of 5-hydroxynicotinic acid
    Joseph, Abhinav; Rodrigues Alves, Joana S.; Bernardes, Carlos E. S.; Piedade, M. Fatima M.; Minas da Piedade, Manuel E.
    CrystEngComm (2019), 21 (13), 2220-2233CODEN: CRECF4; ISSN:1466-8033. (Royal Society of Chemistry)
    The importance of controlling the crystn. of mols. in specific conformations for the prodn. of cryst. org. materials with highly reproducible physicochem. properties has long been recognized. Using 5-hydroxynicotinic acid (5HNA) as a model the following two questions were addressed in this work: (i) is it possible to promote the crystn. of a tautomeric form dominant in a specific solvent through solvate formation (ii) Does that form persist if the memory of solvation is erased through thermal desolvation. Single crystal X-ray diffraction (SCXRD) anal. indicated that the crystn. of 5HNA from water and DMSO do indeed lead to a monohydrate, 5HNA.H2O, and a monosolvate, 5HNA.DMSO, resp., where the tautomeric form preferred in soln. is preserved (zwitterionic in H2O and neutral in DMSO). Subsequent differential scanning calorimetry (DSC), thermogravimetry (TG), powder X-ray diffraction (PXRD), and diffuse reflectance IR Fourier transform (DRIFT) spectroscopy studies indicated that: (i) albeit upon thermal desolvation different solid forms are initially produced, their structures converge over time to that of the 5HNA starting material, hence to a crystal lattice consisting of the same tautomer; (ii) this tautomer corresponds to a zwitterion. The hydrate and solvate forms showed very distinct solvent loss behaviors at 298 K: 5HNA.H2O did not undergo dehydration even when kept under a reduced pressure, while 5HNA.DMSO was only stable for long periods of time if stored in a closed vial. A thermodn. anal. based on DSC and Calvet drop microcalorimetry results allowed to rationalize these observations indicating that: (i) 5HNA.H2O is predicted to spontaneously lose water, even for a relative humidity of 100%, hence its robustness is most certainly of kinetical origin; (ii) 5HNA.DMSO is thermodynamically stable when a satn. DMSO pressure can be established over the sample, but becomes unstable when exposed to an atm. where the solvent is absent. The kinetically easier desolvation of 5HNA.DMSO compared to 5HNA.H2O may be related to the fact that water is isolated in the crystal lattice (isolated site hydrate) while DMSO is placed in channels (channel solvate).
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    Nakamuro, T.; Sakakibara, M.; Nada, H.; Harano, K.; Nakamura, E. Capturing the Moment of Emergence of Crystal Nucleus from Disorder. J. Am. Chem. Soc. 2021, 143, 1763– 1767,  DOI: 10.1021/jacs.0c12100
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    17
    Capturing the Moment of Emergence of Crystal Nucleus from Disorder
    Nakamuro, Takayuki; Sakakibara, Masaya; Nada, Hiroki; Harano, Koji; Nakamura, Eiichi
    Journal of the American Chemical Society (2021), 143 (4), 1763-1767CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    Crystn. is the process of atoms or mols. forming an organized solid via nucleation and growth. Being intrinsically stochastic, the research at an atomistic level was a huge exptl. challenge. In situ detection is reported of a crystal nucleus forming during nucleation/growth of a NaCl nanocrystal, as video recorded in the interior of a vibrating conical C nanotube at 20-40 ms/frame with localization precision of <0.1 nm. NaCl units were seen assembled to form a cluster fluctuating between featureless and semiordered states, which suddenly formed a crystal. Subsequent crystal growth at 298 K and shrinkage at 473 K took place also in a stochastic manner. Productive contributions of the graphitic surface and its mech. vibration were exptl. indicated.
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  18. 18
    Fujii, S.; Ziatdinov, M.; Higashibayashi, S.; Sakurai, H.; Kiguchi, M. Bowl Inversion and Electric Switching of Buckybowls on Gold. J. Am. Chem. Soc. 2016, 138, 12142– 12149,  DOI: 10.1021/jacs.6b04741
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    Bowl Inversion and Electronic Switching of Buckybowls on Gold
    Fujii, Shintaro; Ziatdinov, Maxim; Higashibayashi, Shuhei; Sakurai, Hidehiro; Kiguchi, Manabu
    Journal of the American Chemical Society (2016), 138 (37), 12142-12149CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    Bowl-shaped π-conjugated compds., or buckybowls, are a novel class of sp2-hybridized nanocarbon materials. In contrast to tubular carbon nanotubes and ball-shaped fullerenes, the buckybowls feature structural flexibility. Bowl-to-bowl structural inversion is one of the unique properties of the buckybowls in solns. Bowl inversion on a surface modifies the metal-mol. interactions through bistable switching between bowl-up and bowl-down states on the surface, which makes surface-adsorbed buckybowls a relevant model system for elucidation of the mechano-electronic properties of nanocarbon materials. Here, we report a combination of scanning tunneling microscopy (STM) measurements and ab initio atomistic simulations to identify the adlayer structure of the sumanene buckybowl on Au(111) and reveal its unique bowl inversion behavior. We demonstrate that the bowl inversion can be induced by approaching the STM tip toward the mol. By tuning the local metal-mol. interaction using the STM tip, the sumanene buckybowl exhibits structural bistability with a switching rate that is two orders of magnitude faster than that of the stochastic inversion process.
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  19. 19
    Sakurai, H.; Daiko, T.; Hirao, T. A Synthesis of Sumanene, a Fullerene Fragment. Science 2003, 301, 1878,  DOI: 10.1126/science.1088290
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    19
    Brevia: A synthesis of sumanene, a fullerene fragment
    Sakurai, Hidehiro; Daiko, Taro; Hirao, Toshikazu
    Science (Washington, DC, United States) (2003), 301 (5641), 1878-1882CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
    The prepn. of sumanene (4,7-dihydro-1H-tricyclopenta[def,jkl,pqr]triphenylene) was reported. Corannulene exhibits a rapid bowl-to-bowl inversion at room temp. with an energy barrier of 10.2 kcal/mol at -64°. In contrast, the cyclopentane rings of sumanene are believed to make it more rigid. Ests. of an inversion energy barrier of 17-24 kcal/mol indicate that sumanene should not undergo inversion on the NMR time scale at room temp. The inversion barrier for sumanene was detd. to be 19.6 kcal/mol at 140°. This result suggests that sumanene is indeed rigid.
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  20. 20
    Amaya, T.; Sakane, H.; Muneishi, T.; Hirao, T. Bowl-to-bowl inversion of sumanene derivatives. Chem. Commun. 2008, 765– 767,  DOI: 10.1039/B712839H
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    Bowl-to-bowl inversion of sumanene derivatives
    Amaya, Toru; Sakane, Hiroyuki; Muneishi, Toshiko; Hirao, Toshikazu
    Chemical Communications (Cambridge, United Kingdom) (2008), (6), 765-767CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
    The bowl-to-bowl inversion of the non-planar bowl-shaped compds. derived from sumanene as a fullerene C3v fragment was found to be slow and tuned by a solvent, and the benzylic mono- and di-anions inverted even more slowly.
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  21. 21
    Higashibayashi, S.; Onogi, S.; Srivastava, H. K.; Sastry, G. N.; Wu, Y.-T.; Sakurai, H. Stereoelectronic Effect of Courved Aromatic Structures: Favoring the Unexpxcted endo Confomration of Benzylic-Substituted Sumanene. Angew. Chem., Int. Ed. 2013, 52, 7314– 7316,  DOI: 10.1002/anie.201303134
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    Stereoelectronic Effect of Curved Aromatic Structures: Favoring the Unexpected endo Conformation of Benzylic-Substituted Sumanene
    Higashibayashi, Shuhei; Onogi, Satoru; Srivastava, Hemant Kumar; Sastry, G. Narahari; Wu, Yao-Ting; Sakurai, Hidehiro
    Angewandte Chemie, International Edition (2013), 52 (28), 7314-7316CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    The stereoelectronic effect of a curved arom. structure, an effect which dominates the endo/exo-R conformational stability of benzylic-substituted sumanenes was reported including natural bond orbital anal. to elucidate the stereoelectronic effect.
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  22. 22
    Kuvychko, I. V.; Dubceac, C.; Deng, S. H. M.; Wang, X.; Granovsky, A. A.; Popov, A. A.; Petrukhina, M. A.; Strauss, S. H.; Boltalina, O. V. C20H4(C4F8)3: A Fluorine-Containing Annulated Corannulene that Is a Better Electron Acceptor Than C60. Angew. Chem., Int. Ed. 2013, 52, 7505– 7508,  DOI: 10.1002/anie.201300796
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    22
    C20H4(C4F8)3: A Fluorine-Containing Annulated Corannulene that Is a Better Electron Acceptor Than C60
    Kuvychko, Igor V.; Dubceac, Cristina; Deng, Shihu H. M.; Wang, Xue-Bin; Granovsky, Alexander A.; Popov, Alexey A.; Petrukhina, Marina A.; Strauss, Steven H.; Boltalina, Olga V.
    Angewandte Chemie, International Edition (2013), 52 (29), 7505-7508CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    The authors report the first synthesis, structure, and electronic properties (soln. and gas phase) of a corannulene deriv., which has a higher electron affinity than the well-studied fullerene electron-acceptor C60.
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  23. 23
    Dubceac, C.; Sevryugina, Y.; Kuvychko, I. V.; Boltalina, O. V.; Strauss, S. H.; Petrukhina, M. A. Self-Assembly of Aligned Hybrid One-Dimensional Stacks from Two Complementary π-Bowls. Cryst. Growth Des. 2018, 18, 307– 311,  DOI: 10.1021/acs.cgd.7b01258
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    Self-Assembly of Aligned Hybrid One-Dimensional Stacks from Two Complementary π-Bowls
    Dubceac, Cristina; Sevryugina, Yulia; Kuvychko, Igor V.; Boltalina, Olga V.; Strauss, Steven H.; Petrukhina, Marina A.
    Crystal Growth & Design (2018), 18 (1), 307-311CODEN: CGDEFU; ISSN:1528-7483. (American Chemical Society)
    Designed synthesis of a new cryst. donor-acceptor org. hybrid was accomplished by using 2 bowl-shaped polycyclic arom. hydrocarbons (PAHs) having complementary structures and properties, namely, C20H10 and C5-C20H5(CF3)5. The x-ray structural characterization of the product, [(C20H10)·(C20H5(CF3)5)]·C6H4Cl2, revealed the formation of aligned columnar stacks of alternating C20H10 and C20H5(CF3)5 mols. with centroid-to-centroid distances of 3.658(8) and 3.787(8) Å and a small bowl slip of 0.086(6) Å. The tight bowl packing is accompanied by notable mol. geometry adjustments of the individual PAHs. The bowl depth increased for corannulene (Δ = +0.019 Å) and decreased for sym-pentakis(trifluoromethyl)corannulene (Δ = -0.011 Å), facilitating enhancement of concave-convex interactions along the stacks. The parallel alignment of 1-dimensional columns is supported by multiple intermol. interactions involving C6H4Cl2 used as the crystn. solvent, forming an infinite 2-dimensional network in the solid state.
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    Haupt, A.; Lentz, D. Corranulenes with Electron-Withdrawing Substituents: Synthetic Approaches and Resulting Structural and Electronic Properties. Chem.─Eur. J. 2019, 25, 3440– 3454,  DOI: 10.1002/chem.201803927
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    Corannulenes with Electron-Withdrawing Substituents: Synthetic Approaches and Resulting Structural and Electronic Properties
    Haupt, Axel; Lentz, Dieter
    Chemistry - A European Journal (2019), 25 (14), 3440-3454CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)
    A review. Corannulene is a multifaceted polyarom. compd. It has many interesting properties; for example, it has a bowl-shaped mol. structure that, in addn., undergoes a dynamic inversion process. It has attracted much attention within the last decades. This is not only due to its structural properties but also its electronic properties and its various potential applications to materials chem. Here, synthetic approaches towards corannulene derivs. with electron-withdrawing substituents are summarized. This includes both selective and unselective methods. Further, the electrochem. properties, i.e., the redn. potentials, are analyzed and compared. As a main conclusion, one can state that the electron affinity depends roughly linearly on the no. of substituents. Finally, the structural behavior of the substituted buckybowls in the solid state is highlighted. This also allows a general statement about the influence of the electronic and steric nature of substituents on the mol. structures and the solid-state packing of the corannulene derivs.
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    Schmidt, B. M.; Topolinski, B.; Higashibayashi, S.; Kojima, T.; Kawano, M.; Lentz, D.; Sakurai, H. The Synthesis of Hexafluorosumanene and Its Congeners. Chem.─Eur. J. 2013, 19, 3282– 3286,  DOI: 10.1002/chem.201204622
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    The Synthesis of Hexafluorosumanene and Its Congeners
    Schmidt, Bernd M.; Topolinski, Berit; Higashibayashi, Shuhei; Kojima, Tatsuhiro; Kawano, Masaki; Lentz, Dieter; Sakurai, Hidehiro
    Chemistry - A European Journal (2013), 19 (10), 3282-3286CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)
    We have prepd. the first directly fluorinated bucky bowl compd. and revealed the columnar-packing structure as well as low redn. potentials for all members of the family.
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    Li, M.; Wu, J.; Sambe, K.; Yakiyama, Y.; Akutagawa, T.; Kajitani, T.; Fukushima, T.; Matsuda, K.; Sakurai, H. Dielectric response of 1,1-difluorosumanene caused by an in-plane motion. Mater. Chem. Front. 2022, 6, 1752– 1758,  DOI: 10.1039/D2QM00134A
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    26
    Dielectric response of 1,1-difluorosumanene caused by an in-plane motion
    Li, Minghong; Wu, JianYun; Sambe, Kohei; Yakiyama, Yumi; Akutagawa, Tomoyuki; Kajitani, Takashi; Fukushima, Takanori; Matsuda, Kazunari; Sakurai, Hidehiro
    Materials Chemistry Frontiers (2022), 6 (13), 1752-1758CODEN: MCFAC5; ISSN:2052-1537. (Royal Society of Chemistry)
    We have designed and synthesized a new curved π-conjugated mol., 1,1-difluorosumanene (1), which possesses two fluorine atoms on the same benzylic carbon of unsubstituted sumanene, producing a large dipole moment along the in-plane direction. Thermal analyses, variable-temp. X-ray diffraction, and IR measurements indicated a 120° in-plane motion of 1 in the stacking columns, which did not cause any phase transition in the cryst. state. Indeed, dielec. measurements on powder and single-crystal forms of 1 showed that both the real (ε1) and imaginary (ε2) parts of the dielec. const. were enhanced above ∼360 K at 1 MHz with a Debye-type dielec. relaxation, confirming that 1 underwent a pendulum fluctuation induced by the external elec. field.
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    Li, M.; Chen, X.; Yakiyama, Y.; Wu, J.; Akutagawa, T.; Sakurai, H. Tuning the dielectric response by co-crystallization of sumanene and its fluorinated derivative. Chem. Commun. 2022, 58, 8950– 8953,  DOI: 10.1039/D2CC02766F
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    27
    Tuning the dielectric response by co-crystallisation of sumanene and its fluorinated derivative
    Li, Minghong; Chen, Xi; Yakiyama, Yumi; Wu, JianYun; Akutagawa, Tomoyuki; Sakurai, Hidehiro
    Chemical Communications (Cambridge, United Kingdom) (2022), 58 (64), 8950-8953CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
    A series of co-crystals of 1,1-difluorosumanene (F2-Sum) and sumanene (Sum) were obtained. The co-crystn. successfully tuned their structural and phys. properties, esp. the dielec. response, without any chem. modifications. X-ray analyses and theor. calcns. revealed the redn. of intermol. interaction energy due to the presence of F2-Sum.
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    Yakiyama, Y.; Li, M.; Sakurai, H. Fluorosumanenes as building blocks for organic crystalline dielectrics. Pure Appl. Chem. 2023, 95, 421– 430,  DOI: 10.1515/pac-2023-0211
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    Fluorosumanenes as building blocks for organic crystalline dielectrics
    Yakiyama, Yumi; Li, Minghong; Sakurai, Hidehiro
    Pure and Applied Chemistry (2023), 95 (4), 421-430CODEN: PACHAS; ISSN:0033-4545. (Walter de Gruyter, Inc.)
    Org. cryst. dielec. materials are attractive target in the field of materials chem. In their designing strategy, the mol. motion induced by the external dielec. field is required to maximize the polarization effect in the materials to realize a large dielec. const. Esp., the mol. motion of curved-π aroms. such as C60 and their supramol. complexes are the known to show characteristic smoothness in the solid state. In this context, we focused on the in-plane motion of the one of the representative buckybowl, sumanene (Sum) in its curve-to-curve-contacted columnar structure as the new platform of the motion for the emergence of dielec. response. The newly designed and synthesized fluorinated sumanene, 1,1-difluorosumanene (F2-Sum), which possesses two fluorine atoms on the same benzylic carbon of pristine sumanene showed a large dipole moment along the in-plane direction. Thermal analyses, variable temp. X-ray diffraction and IR measurements indicated the presence of in-plane motion of F2-Sum although no clear phase transition was involved. This thermal property of F2-Sum realized an anisotropic dielec. response with a Debye-type dielec. relaxation in the single cryst. state. Further trials to form the solid soln. of Sum and F2-Sum in various mixing ratio realized the tuning of the dielec. property.
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    Sakurai, H.; Daiko, T.; Sakane, H.; Amaya, T.; Hirao, T. Structural Elucidation os Sumanene and Generation of Its Benzylic Anions. J. Am. Chem. Soc. 2005, 127, 11580– 11581,  DOI: 10.1021/ja0518169
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    29
    Structural Elucidation of Sumanene and Generation of Its Benzylic Anions
    Sakurai, Hidehiro; Daiko, Taro; Sakane, Hiroyuki; Amaya, Toru; Hirao, Toshikazu
    Journal of the American Chemical Society (2005), 127 (33), 11580-11581CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    The structure of sumanene in a solid state was elucidated. The silyl-substituted sumanene was stereoselectively synthesized through generation of the benzylic anions of sumanene.
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    Mebs, S.; Weber, M.; Luger, P. A.; Schmidt, B. M.; Sakurai, H.; Higashibayashi, S.; Onogi, S.; Lentz, D. Experimental electron density of sumanene, a bowl-shaped fullerene fragment; comparison with the related corannulene hydrocarbon. Org. Biomol. Chem. 2012, 10, 2218– 2222,  DOI: 10.1039/c2ob07040e
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    30
    Experimental electron density of sumanene, a bowl-shaped fullerene fragment; comparison with the related corannulene hydrocarbon
    Mebs, Stefan; Weber, Manuela; Luger, Peter; Schmidt, Bernd M.; Sakurai, Hidehiro; Higashibayashi, Shuhei; Onogi, Satoru; Lentz, Dieter
    Organic & Biomolecular Chemistry (2012), 10 (11), 2218-2222CODEN: OBCRAK; ISSN:1477-0520. (Royal Society of Chemistry)
    The exptl. electron d. of sumanene, C21H12, was extd. from a high resoln. X-ray data set measured at 100 K and topol. analyzed. In addn. to bond topol. and at. properties, information about the d. distribution between adjacent mols., which show close C···C approaches of ∼3.4 Å within the columnar π-stacks in the crystal lattice, are discussed. A comparison is made with the electron d. of the related corannulene mol. based also on the anal. of Electron Localizability Indicator (ELI-D) calcns.
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    Zanello, P.; Fedi, S.; de Biani, F. F.; Giorgi, G.; Amaya, T.; Sakane, H.; Hirao, T. The electrochemical inspection of the redox activity of sumanene and its concave CpFe complex. Dalton Trans. 2009, 9192– 9197,  DOI: 10.1039/b910711h
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    The electrochemical inspection of the redox activity of sumanene and its concave CpFe complex
    Zanello, Piero; Fedi, Serena; Fabrizi de Biani, Fabrizia; Giorgi, Gianluca; Amaya, Toru; Sakane, Hiroyuki; Hirao, Toshikazu
    Dalton Transactions (2009), (42), 9192-9197CODEN: DTARAF; ISSN:1477-9226. (Royal Society of Chemistry)
    The redox properties of sumanene C21H12 and its concave Fe(II) complex [(η5-C5H5)Fe(η6-C21H12)]+ were elucidated through an electrochem. study in nonaq. solvents, i.e. DMF and MeCN. The electron transfer activity of sumanene can be depicted as an irreversible oxidn. and a partially chem. reversible 1-electron redn., both processes being located in proximity of the resp. discharges of the solvents. The Fe(II) complex [(η5-C5H5)Fe(η6-C21H12)](PF6) in turn exhibits the Fe(II)/Fe(I) redn., which in both DMF and MeCN solvents displays features of partial chem. reversibility, coupled to decompn. of the corresponding Fe(I) species [(η5-C5H5)Fe(η6-C21H12)] to fragments which, upon reoxidn., regenerate for the most part the original Fe(II)-sumanene species. In fact, among the fragments produced by exhaustive redn., ESI measurements allowed the detection of ferrocene, the oxidn. of which probably triggers the partial regeneration of the original Fe(II) complex. The pertinent PM6 semiempirical study accounts for the limited chem. reversibility of the redox processes exhibited by both sumanene and its Fe(II) complex.
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    Liu, L.; Guo, Q. Isokinetic Relationship, Isoequilibrium Relationship, and Enthalpy-Entropy Compensation. Chem. Rev. 2001, 101, 673– 696,  DOI: 10.1021/cr990416z
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    Isokinetic Relationship, Isoequilibrium Relationship, and Enthalpy-Entropy Compensation
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    A review, with about 200 refs., which discusses the relationship and differences between the 3 title concepts. The relationships are discussed from both a statistical and a theor. approach. Some applications of these concepts are illustrated.
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    Pan, A.; Biswas, T.; Rakshit, A. K.; Moulik, S. P. Enthalpy-Entropy Compensation (EEC) Effect: A Recisit. J. Phys. Chem. B 2015, 119, 15876– 15884,  DOI: 10.1021/acs.jpcb.5b09925
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    Enthalpy-Entropy Compensation (EEC) Effect: A Revisit
    Pan, Animesh; Biswas, Tapas; Rakshit, Animesh K.; Moulik, Satya P.
    Journal of Physical Chemistry B (2015), 119 (52), 15876-15884CODEN: JPCBFK; ISSN:1520-5207. (American Chemical Society)
    A review. A short account of the developments and perspectives of IKR (iso-kinetic relation) and EEC (enthalpy (H) - entropy (S) compensation) has been presented. The IKR and EEC are known to be extra thermodn. or empirical correlations though linear H-S correlation can be thermodynamically deduced. Attempt has also been made to explain the phenomena in terms of statistical thermodn. In this study, we have briefly revisited the fundamentals of both IKR and EEC from kinetic and thermodn. grounds. A detailed revisit of the EEC phenomenon on varied kinetic and equil. processes has been also presented. Possible correlations among the free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) changes of different similar and non-similar chem. processes under varied conditions have been discussed with possible future projections.
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    Zhao, Y. H.; Abraham, M. H.; Zissimos, A. M. Fast Calculation of van der Waals Volume as a Sum of Atomic and Bond Contributions and Its Application to Drug Compounds. J. Org. Chem. 2003, 68, 7368– 7373,  DOI: 10.1021/jo034808o
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    Fast Calculation of van der Waals Volume as a Sum of Atomic and Bond Contributions and Its Application to Drug Compounds
    Zhao, Yuan H.; Abraham, Michael H.; Zissimos, Andreas M.
    Journal of Organic Chemistry (2003), 68 (19), 7368-7373CODEN: JOCEAH; ISSN:0022-3263. (American Chemical Society)
    The van der Waals vol. is a widely used descriptor in modeling physicochem. properties. However, the calcn. of the van der Waals vol. (VvdW) is rather time-consuming, from Bondi group contributions, for a large data set. A new method for calcg. van der Waals vol. has been developed, based on Bondi radii. The method, termed At. and Bond Contributions of van der Waals vol. (VABC), is very simple and fast. The only information needed for calcg. VABC is at. contributions and the no. of atoms, bonds, and rings. Then, the van der Waals vol. (Å3/mol.) can be calcd. from the following formula: VvdW = .sum. all atom contributions - 5.92NB - 14.7RA - 3.8RNR (NB is the no. of bonds, RA is the no. of arom. rings, and RNA is the no. of nonarom. rings). The no. of bonds present (NB) can be simply calcd. by NB = N - 1 + RA + RNA (where N is the total no. of atoms). A simple Excel spread sheet has been made to calc. van der Waals vols. for a wide range of 677 org. compds., including 237 drug compds. The results show that the van der Waals vols. calcd. from VABC are equiv. to the computer-calcd. van der Waals vols. for org. compds.
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    Journal of Physical Chemistry B (2009), 113 (7), 1954-1962CODEN: JPCBFK; ISSN:1520-6106. (American Chemical Society)
    The voltammetric generation of corannulene anions was studied over a large range of exptl. conditions comprising either traditional electrochem. solvents, such as DMF, MeCN, and THF, or unconventional solvents, such as liq. NH3, liq. methylamine, or liq. dimethylamine, and several different supporting electrolytes. Strong ion pairing effects dominate the electrochem. generation of corannulene higher anions, and through the suitable choice of the solvent/electrolyte system, the authors obsd., for the 1st time, the reversible electrochem. generation of up to the triply reduced corannulene. The std. potentials obtained exptl. compared rather well with the theor. values calcd. by ab initio and d. functional methods, in which solvation and ion pairing effect were explicitly taken into account. In particular, the calcns. considered the effect of the electrolyte cation size on ion pairing to rationalize the occurrence of the 3rd redn. within the exptl. potential window.
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    Harada, J.; Yoneyama, N.; Sato, S.; Takahashi, Y.; Inabe, T. Crystals of Charge-Transfer Complexes with Reorienting Polar Molecules: Dielectric Properties and Order-Disorder Phase Transitions. Cryst. Growth Des. 2019, 19, 291– 299,  DOI: 10.1021/acs.cgd.8b01418
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    Crystals of charge-transfer complexes with reorienting polar molecules: Dielectric properties and order-disorder phase transitions
    Harada, Jun; Yoneyama, Naho; Sato, Shota; Takahashi, Yukihiro; Inabe, Tamotsu
    Crystal Growth & Design (2019), 19 (1), 291-299CODEN: CGDEFU; ISSN:1528-7483. (American Chemical Society)
    Crystals of charge-transfer (CT) complexes were synthesized using the polar mol. tetrachlorophthalonitrile (TCPN) as the electron acceptor and nonpolar arom. hydrocarbons, such as perylene, coronene, chrysene, and pyrene, as the electron donors. Variable-temp. X-ray crystal structure analyses revealed that the TCPN mols. in all the CT crystals exhibit orientational disorder at room temp. Some of the CT crystals undergo an order-disorder-type phase transition upon cooling, where the orientation of the TCPN mols. becomes ordered at low temp. The CT crystals show large dielec. consts. at room temp. arising from in-plane reorientation of the polar TCPN mols. The order-disorder phase transition results in a drastic redn. of the dielec. const. of the CT crystals upon cooling. This study demonstrates that the formation of CT crystals from polar mols. represents a promising method for the development of dielec. cryst. materials, whose properties vary significantly in response to phase transitions.
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    Harada, J.; Ohtani, M.; Takahashi, Y.; Inabe, T. Molecular Motion, Dielectric Response, and Phase Transition of Charge-Transfer Crystals: Acquired Dynamic and Dielectric Properties of Polar Molecules in Crystals. J. Am. Chem. Soc. 2015, 137, 4477– 4486,  DOI: 10.1021/jacs.5b00412
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    Molecular Motion, Dielectric Response, and Phase Transition of Charge-Transfer Crystals: Acquired Dynamic and Dielectric Properties of Polar Molecules in Crystals
    Harada, Jun; Ohtani, Masaki; Takahashi, Yukihiro; Inabe, Tamotsu
    Journal of the American Chemical Society (2015), 137 (13), 4477-4486CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    Mols. in crystals often suffer from severe limitations on their dynamic processes, esp. on those involving large structural changes. Cryst. compds., therefore, usually fail to realize their potential as dielec. materials even when they have large dipole moments. To enable polar mols. to undergo dynamic processes and to provide their crystals with dielec. properties, weakly bound charge-transfer (CT) complex crystals were exploited as a mol. architecture where the constituent polar mols. have some freedom of dynamic processes, which contribute to the dielec. properties of the crystals. Several CT crystals of polar tetrabromophthalic anhydride (TBPA) mols. were prepd. using TBPA as an electron acceptor and arom. hydrocarbons, such as coronene and perylene, as electron donors. The crystal structures and dielec. properties of the CT crystals as well as the single-component crystal of TBPA were studied at various temps. Mol. reorientation of TBPA mols. did not occur in the single-component crystal, and the crystal did not show a dielec. response due to orientational polarization. The CT crystal formation provides a simple and versatile method to develop mol. dielecs., revealing that the mol. dynamics of the TBPA mols. and the dielec. property of their crystals were greatly changed in CT crystals. The TBPA mols. underwent rapid in-plane reorientations in their CT crystals, which exhibited marked dielec. responses arising from the mol. motion. An order-disorder phase transition was obsd. for one of the CT crystals, which resulted in an abrupt change in the dielec. const. at the transition temp.
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    Journal of Computational Chemistry (2004), 25 (9), 1157-1174CODEN: JCCHDD; ISSN:0192-8651. (John Wiley & Sons, Inc.)
    We describe here a general Amber force field (GAFF) for org. mols. GAFF is designed to be compatible with existing Amber force fields for proteins and nucleic acids, and has parameters for most org. and pharmaceutical mols. that are composed of H, C, N, O, S, P, and halogens. It uses a simple functional form and a limited no. of atom types, but incorporates both empirical and heuristic models to est. force consts. and partial at. charges. The performance of GAFF in test cases is encouraging. In test I, 74 crystallog. structures were compared to GAFF minimized structures, with a root-mean-square displacement of 0.26 Å, which is comparable to that of the Tripos 5.2 force field (0.25 Å) and better than those of MMFF 94 and CHARMm (0.47 and 0.44 Å, resp.). In test II, gas phase minimizations were performed on 22 nucleic acid base pairs, and the minimized structures and intermol. energies were compared to MP2/6-31G* results. The RMS of displacements and relative energies were 0.25 Å and 1.2 kcal/mol, resp. These data are comparable to results from Parm99/RESP (0.16 Å and 1.18 kcal/mol, resp.), which were parameterized to these base pairs. Test III looked at the relative energies of 71 conformational pairs that were used in development of the Parm99 force field. The RMS error in relative energies (compared to expt.) is about 0.5 kcal/mol. GAFF can be applied to wide range of mols. in an automatic fashion, making it suitable for rational drug design and database searching.
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    A well-behaved electrostatic potential based method using charge restraints for deriving atomic charges: the RESP model
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    The authors present a new approach to generating electrostatic potential (ESP) derived charges for mols. The major strength of electrostatic potential derived charges is that they optimally reproduce the intermol. interaction properties of mols. with a simple two-body additive potential, provided, of course, that a suitably accurate level of quantum mech. calcn. is used to derive the ESP around the mol. Previously, the major weaknesses of these charges have been that they were not easily transferably between common functional groups in related mols., they have often been conformationally dependent, and the large charges that frequently occur can be problematic for simulating intramol. interactions. Introducing restraints in the form of a penalty function into the fitting process considerably reduces the above problems, with only a minor decrease in the quality of the fit to the quantum mech. ESP. Several other refinements in addn. to the restrained electrostatic potential (RESP) fit yield a general and algorithmic charge fitting procedure for generating atom-centered point charges. This approach can thus be recommended for general use in mol. mechanics, mol. dynamics, and free energy calcns. for any org. or bioorg. system.
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    An approx. functional for the chem. potential of a solute in soln. is presented in the energy representation. This functional is constructed by adopting the Percus-Yevick-like approxn. in the unfavorable region of the solute-solvent interaction and the hypernetted-chain-like approxn. in the favorable region. The chem. potential is then expressed in terms of energy distribution functions in the soln. and pure solvent systems of interest, and is given exactly to second order with respect to the solvent d. and to the solute-solvent interaction. In the practical implementation, computer simulations of the soln. and pure solvent systems are performed to provide the energy distribution functions constituting the approx. functional for the chem. potential. It is demonstrated that the chem. potentials of nonpolar, polar, and ionic solutes in water are evaluated accurately and efficiently from the single functional over a wide range of thermodn. conditions.
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    Sakuraba, S.; Matubayasi, N. ERmod: Fast and Versatile Computation Software for Solvation Free Energy with Approximate Theory of Solutions. J. Comput. Chem. 2014, 35, 1592– 1608,  DOI: 10.1002/jcc.23651
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    Ermod: Fast and versatile computation software for solvation free energy with approximate theory of solutions
    Sakuraba, Shun; Matubayasi, Nobuyuki
    Journal of Computational Chemistry (2014), 35 (21), 1592-1608CODEN: JCCHDD; ISSN:0192-8651. (John Wiley & Sons, Inc.)
    ERmod is a software package to efficiently and approx. compute the solvation free energy using the method of energy representation. Mol. simulation is to be conducted at two condensed-phase systems of the soln. of interest and the ref. solvent with test-particle insertion of the solute. The subprogram ermod in ERmod then provides a set of energy distribution functions from the simulation trajectories, and another subprogram slvfe dets. the solvation free energy from the distribution functions through an approx. functional. This article describes the design and implementation of ERmod, and illustrates its performance in solvent water for two org. solutes and two protein solutes. Actually, the free-energy computation with ERmod is not restricted to the solvation in homogeneous medium such as fluid and polymer and can treat the binding into weakly ordered system with nano-inhomogeneity such as micelle and lipid membrane. ERmod is available on web at http://sourceforge.net/projects/ermod. © 2014 Wiley Periodicals, Inc.
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  • Abstract

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    Figure 1

    Figure 1. Bowl inversion of Sum and the conceptual figure of this work.

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    Scheme 1

    Scheme 1. Synthesis of 1-Fluorosumanene (1)
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    Figure 2

    Figure 2. Structural and energetic difference between 1endo and 1exo. All the calculation data were obtained at the B3LYP/6-311+G(d,p) level of theory.

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    Figure 3

    Figure 3. Representative crystal structure of 1. The sample crystal was obtained by the slow evaporation method using CH2Cl2 at 193 K.

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    Figure 4

    Figure 4. Temperature dependence of (a, c, e) the real part (ε1) and (b, d, f) the imaginary part (ε2) of the dielectric constant of PCDMF (a, b) and PCCH2Cl2 (c–f) in compressed pellets measured at various frequencies. (e) and (f) represent the 2nd sweep results.

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    Figure 5

    Figure 5. Dimer model preparation and the resulting intermolecular energies based on the stacking species and order.

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    Figure 6

    Figure 6. Aggregation state of 1 expressed as the % population of the number of molecules forming an aggregate with the degree of aggregation in the abscissae for (a) 100% 1exo, (b) 100% 1endo, and (c) 50:50 mixture of them in acetone, CH2Cl2, and DMF. The summed values over the degrees of aggregation of 4 or more are also shown in (d) to illustrate the dependence on the conformational states and solvents more clearly.

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    Figure 7

    Figure 7. Population analysis data for neighboring pairs of 1exo/1exo, 1exo/1endo, 1endo/1exo, and 1endo/1endo in various aggregates in (a) acetone, (b) CH2Cl2, and (c) DMF. The averaged data over the degrees of aggregation of 4 or more are shown in (d) to illustrate the dependence on the solvents more clearly. The definition of the neighboring pairs follows Figure 5.

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    Figure 8

    Figure 8. Solvation free energy Δμ of 1endo and 1exo in acetone, CH2Cl2, and DMF. ΔΔμ = Δμ(1endo) – Δμ(1exo) is noted in units of kcal/mol for each solvent.

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      A review. The outcome of synthetic procedures for cryst. org. materials strongly depends on the 1st steps along the mol. self-assembly pathway, a process the authors know as crystal nucleation. New exptl. techniques and computational methodologies have spurred significant interest in understanding the detailed mol. mechanisms by which nuclei form and develop into macroscopic crystals. Although classical nucleation theory (CNT) has served well in describing the kinetics of the processes involved, new proposed nucleation mechanisms are addnl. concerned with the evolution of structure and the competing nature of crystn. in polymorphic systems. In this Review, the authors explore the extent to which CNT and nucleation rate measurements can yield mol.-scale information on this process and summarize current knowledge relating to mol. self-assembly in nucleating systems.
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      The crystal polymorphism of tetrolic acid (CH3C≡CCOOH): a molecular dynamics study of precursors in solution, and a crystal structure generation
      Gavezzotti, A.; Filippini, G.; Kroon, J.; van Eijck, B. P.; Klewinghaus, P.
      Chemistry - A European Journal (1997), 3 (6), 893-899CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH)
      The possible configurations of two mols. of tetrolic acid in a solvent box contg. 226 CCl4 mols. were studied by mol. dynamics with the GROMOS package and force field over periods of up to 2000 ps. The cyclic H-bonded dimer was the most persistent configuration but events leading to the cleavage of one H bond and thus the formation of a precursor to the crystal catemer motif occupy up to 10% of the simulation times. The exptl. bond-breaking enthalpy was correctly reproduced. Two different crystal structure generation procedures were employed to reproduce the two obsd. polymorphic crystal structures and to predict other possible polymorphs; in all cases, some unobserved structures had more cohesive packing energies than the obsd. ones. The possible application of mol. dynamics in the study of the preliminary steps in crystal nucleation is discussed.
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      Davey, R. J.; Blagden, N.; Righini, S.; Alison, H.; Quayle, M. J.; Fuller, S. Crystal Polymorphism as a Probe for Molecular Self-Assembly during Nucleation from Solutions: The Case of 2,6-Dihidroxybenzoic Acid. Cryst. Growth Des. 2001, 1, 59– 65,  DOI: 10.1021/cg000009c
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      Crystal Polymorphism as a Probe for Molecular Self-Assembly during Nucleation from Solutions: The Case of 2,6-Dihydroxybenzoic Acid
      Davey, R. J.; Blagden, N.; Righini, S.; Alison, H.; Quayle, M. J.; Fuller, S.
      Crystal Growth & Design (2001), 1 (1), 59-65CODEN: CGDEFU; ISSN:1528-7483. (American Chemical Society)
      The relation between mol. self-assembly processes and nucleation during crystn. from soln. is an important issue, both in terms of fundamental phys. chem. and for the control and application of crystn. processes in crystal engineering and materials chem. This contribution examines the extent to which the occurrence of crystal polymorphism can be used as an indicator of the nature of mol. aggregation processes in supersatd. solns. For the specific case of 2,6-dihydroxybenzoic acid a combination of soly., spectroscopic, crystn., and mol. modeling techniques were used to demonstrate that there is a direct link between the solvent-induced self-assembly of this mol. and the relative occurrence of its two polymorphic forms from toluene and CHCl3 solns.
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      Spitaleri, A.; Hunter, C. A.; McCabe, J. F.; Packer, M. J.; Cockroft, S. L. A 1H NMR study of crystal nucleation in solution. CrystEngComm 2004, 6, 489– 493,  DOI: 10.1039/b407163h
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      A 1H NMR study of crystal nucleation in solution
      Spitaleri, Andrea; Hunter, Christopher A.; McCabe, James F.; Packer, Martin J.; Cockroft, Scott L.
      CrystEngComm (2004), 6 (), 489-493CODEN: CRECF4; ISSN:1466-8033. (Royal Society of Chemistry)
      Soln. NMR data can provide information about the interactions of mols. in the 1st stages of crystn., and 1H NMR complexation-induced changes in chem. shift can be used to det. high resoln. three-dimensional structures of complexes in soln. The concn.-dependent changes in 1H NMR chem. shift of two different compds. (2,6-difluoro-N-(4-methoxy-2,6-dimethylphenyl)benzamide and sulfamerzine) were used to make predictions about how these compds. pack in the cryst. state. The structures of dimer motifs characterized in soln. agree very well with the structures of dimers found in the corresponding x-ray crystal structures. Soln. NMR expts. therefore provide an exptl. tool for probing the organization of mols. in the solid state.
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      Parveen, S.; Davey, R. J.; Dent, G.; Pritchard, R. G. Linking solution chemistry to crystal nucleation: the case of tetrolic acid. Chem.Commun. 2005, 1531– 1533,  DOI: 10.1039/b418603f
      5
      Linking solution chemistry to crystal nucleation: The case of tetrolic acid
      Parveen, S.; Davey, R. J.; Dent, G.; Pritchard, R. G.
      Chemical Communications (Cambridge, United Kingdom) (2005), (12), 1531-1533CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
      The application of FTIR spectroscopy to concd. solns. of tetrolic acid shows, for the 1st time, a direct relation between mol. self assocn. in soln. and H-bonded motifs in the subsequently crystd. solid phases.
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    6. 6
      Davey, R. J.; Dent, G.; Mughal, R. K.; Parveen, S. Concerning the Relationship between Structural and Growth Synthons in Crystal Nucleation: Solution and Crystal Chemistry of Calboxylic Acids As Revealed thorough IR Spectroscopy. Cryst. Growth Des. 2006, 6, 1788– 1796,  DOI: 10.1021/cg060058a
      6
      Concerning the Relationship between Structural and Growth Synthons in Crystal Nucleation: Solution and Crystal Chemistry of Carboxylic Acids As Revealed through IR Spectroscopy
      Davey, R. J.; Dent, G.; Mughal, R. K.; Parveen, S.
      Crystal Growth & Design (2006), 6 (8), 1788-1796CODEN: CGDEFU; ISSN:1528-7483. (American Chemical Society)
      Little is known concerning the precise mol. pathway that links fluid-phase mols. to those in nascent crystal nuclei. The process of mol. self-assembly was studied in concd. solns. using FTIR spectroscopy. Three carboxylic acids, benzoic, tetrolic, and mandelic acids, were chosen from their differing crystal chemistries, as reflected in obsd. H-bonding motifs. Using the solid-state spectra as a means of unambiguous assignment of carboxyl and hydroxyl vibrations assocd. with H bonding, spectroscopic data are reported for solns. as a function of both compn. and solvent. In the cases of HOBz and tetrolic acid, a link between the growth synthon and the structural synthon is apparent. Mandelic acid, however, provides a more complex case in which strong solvation effects are evident, leading to the conclusion that significant mol. rearrangement must occur within the developing crystal nuclei.
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    7. 7
      Chen, J.; Trout, B. L. Computational Study of Solvent Effects on the Molecular Self-Assembly of Tetrolic Acid in Solution and Implications for the Polymorph Formed from Crystallization. J. Phys. Chem. B 2008, 112, 7794– 7802,  DOI: 10.1021/jp7106582
      7
      Computational Study of Solvent Effects on the Molecular Self-Assembly of Tetrolic Acid in Solution and Implications for the Polymorph Formed from Crystallization
      Chen, Jie; Trout, Bernhardt L.
      Journal of Physical Chemistry B (2008), 112 (26), 7794-7802CODEN: JPCBFK; ISSN:1520-6106. (American Chemical Society)
      The soln. behavior of a model compd., tetrolic acid (TTA), is studied via mol. dynamics simulations in four org. solvents. The results suggest that strong interactions between TTA and solvent mols. (ethanol or dioxane) prevent the formation of carboxylic acid dimers in soln. and thus promote the crystn. of TTA in a catemer-based form or a solvate form. Weak interactions, however, between TTA and solvent mols. (carbon tetrachloride or chloroform) facilitate the formation of carboxylic acid dimers in soln. and thus promote the crystn. of a dimer-based crystal. Detailed solvent structure plays an important role in detg. the relative stability of various growth synthons in soln. and also the barriers along the pathway connecting them. This work illustrates the potential of mol. simulations to aid in the rational selection of solvents to obtain desired polymorphs during crystn.
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    8. 8
      Habgood, M. Solution and nanoscale structure selection: implications for the crystal energy landscape of tetrolic acid. Phys. Chem. Chem. Phys. 2012, 14, 9195– 9203,  DOI: 10.1039/c2cp40644f
      8
      Solution and nanoscale structure selection: implications for the crystal energy landscape of tetrolic acid
      Habgood, Matthew
      Physical Chemistry Chemical Physics (2012), 14 (25), 9195-9203CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
      Soln. and growth effects are in many cases crit. in detg. which crystal structure (polymorph) a mol. will adopt. Contemporary crystal structure prediction (CSP) rarely address formation and growth in a systematic way, relying instead on bulk thermodn. stabilities. In this study, it is shown that anal. of simulated solns. of tetrolic acid in combination with calcn. of stabilities for nanoscale clusters cut from bulk structures can distinguish between four computationally predicted crystal structures, including the two known forms and two speculative forms, rationalizing the formation of one structure rather than another on grounds other than bulk lattice energies. It is concluded that modeling of both soln.-based supramol. species and nanocrystal stabilities are necessary to explain the selection of one structure over another during crystal formation, and that they are sufficient for the specific case of tetrolic acid.
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    9. 9
      Sullivan, R. A.; Davey, R. J.; Sadiq, G.; Dent, G.; Back, K. R.; ter Horst, J. H.; Toroz, D.; Hammond, R. B. Revealing the Roles of Desoluvation and Molecular Self-Assembly in Crystal Nucleation from Solution: Benzoic and p-Aminobenzoic Acids. Cryst. Growth Des. 2014, 14, 2689– 2696,  DOI: 10.1021/cg500441g
      9
      Revealing the Roles of Desolvation and Molecular Self-Assembly in Crystal Nucleation from Solution: Benzoic and p-Aminobenzoic Acids
      Sullivan, R. A.; Davey, R. J.; Sadiq, G.; Dent, G.; Back, K. R.; ter Horst, J. H.; Toroz, D.; Hammond, R. B.
      Crystal Growth & Design (2014), 14 (5), 2689-2696CODEN: CGDEFU; ISSN:1528-7483. (American Chemical Society)
      There was much recent interest in the role of soln. chem. and in particular the importance of mol. self-assembly in the nucleation of cryst. phases. Techniques such as FTIR and NMR have highlighted the existence of soln.-phase dimers which in many cases mirror the structural synthons found in the resulting macroscopic crystals. However, there are no reported examples in which this new insight into the soln. phase was linked directly to the kinetics of crystal nucleation. Here for the 1st time, using a combination of soln. FTIR, computational chem., and measured crystal nucleation rate data, such a link is demonstrated for p-aminobenzoic (PABA) and benzoic acids nucleating from polar and nonpolar solvents. Solute dimerization and desolvation are rate-detg. processes in the overall nucleation pathway.
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    10. 10
      Gaines, E.; Maisuria, K.; Di Tommaso, D. The role of solvent in the self-assembly of m-aminobenzoic acid: a density functional theory and molecular dynamics study. CrystEngComm 2016, 18, 2937– 2948,  DOI: 10.1039/C6CE00130K
      10
      The role of solvent in the self-assembly of m-aminobenzoic acid: a density functional theory and molecular dynamics study
      Gaines, Etienne; Maisuria, Krina; Di Tommaso, Devis
      CrystEngComm (2016), 18 (16), 2937-2948CODEN: CRECF4; ISSN:1466-8033. (Royal Society of Chemistry)
      Solvent can have significant effects on the soln. thermodn. and crystn. kinetics of org. compds. from soln. In the present work, the early stages of aggregation of the org. mol. m-aminobenzoic (mABA) in two different solvents, DMSO (DMSO) and water were studied using a combination of quantum chem., mol. dynamics and metadynamics simulations. D. functional theory (B97-D and M06-2X) calcns. with the continuum solvation SMD model were used to probe the potential energy surface of mol. clusters of m-aminobenzoic acid, (mABA)n (n = 2-4), locate their low-lying energy structures, and compute the Gibbs free energies of (mABA)n in soln. Starting from a large no. of randomly generated candidate structures and by imposing the condition of min. free energy in soln. for the isomers of (mABA)n, we proved that the most stable dimer and tetramer in soln. correspond to the classic carboxylic dimer π-π stacking synthon found in the cryst. form-II of mABA. Mol. dynamics simulations of mABA solns. at different concns. reveal a significant solvent-dependent aggregation behavior for mABA: in water, even at low concns., mABA mols. spontaneously form H-bonded π-π stacking mol. clusters, whereas in organosulfur solns. the mols. of mABA are in a more solvated state. Metadynamics simulations and microsolvation d. functional theory calcns. rationalize the low level of mABA aggregation in DMSO in terms of the energetic barrier for the desolvation of mABA mols. and formation of dimers, and the strength of mABA-solvent interactions, which are both larger in DMSO compared with water. This work shows that the solvent and its specific interaction with the org. solute mols. influences both the thermodn. and kinetics of the mol. self-assembly process.
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    11. 11
      Hunter, C. A.; McCabe, J. F.; Spitaleri, A. Solvent effects of rrthe structures of prenucleation aggregates of carbamazepine. CrystEngComm 2012, 14, 7115– 7117,  DOI: 10.1039/c2ce25941a
      11
      Solvent effects of the structures of prenucleation aggregates of carbamazepine
      Hunter, Christopher A.; McCabe, James F.; Spitaleri, Andrea
      CrystEngComm (2012), 14 (21), 7115-7117CODEN: CRECF4; ISSN:1466-8033. (Royal Society of Chemistry)
      Soln. phase NMR structures of carbamazepine dimers have been detd. in CD3OH and in CDCl3. Dimerization is mediated by arom. interactions in CD3OH and by H-bonding in CDCl3. Comparison of the two soln. phase structures with dimer motifs found the X-ray crystal structure reveals remarkable similarities. The results suggest that the soln. dimers represent first steps on the pathway to crystal nucleation and show that the structures of these prenucleation aggregates depend strongly on solvent.
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    12. 12
      Zeglinski, J.; Kuhs, M.; Khamar, D.; Hegarty, A. C.; Devi, R. K.; Rasmuson, Å. C. Crystal Nucleation of Tolbutamide in Solution: Relationship to Solvent, Solute Conformation, and Solution Structure. Chem.─Eur. J. 2018, 24, 4916– 4926,  DOI: 10.1002/chem.201705954
      12
      Crystal Nucleation of Tolbutamide in Solution: Relationship to Solvent, Solute Conformation, and Solution Structure
      Zeglinski, Jacek; Kuhs, Manuel; Khamar, Dikshitkumar; Hegarty, Avril C.; Devi, Renuka K.; Rasmuson, Aake C.
      Chemistry - A European Journal (2018), 24 (19), 4916-4926CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The influence of the solvent in nucleation of tolbutamide, a medium-sized, flexible and polymorphic org. mol., has been explored by measuring nucleation induction times, estg. solvent-solute interaction enthalpies using mol. modeling and calorimetric data, probing interactions and clustering with spectroscopy, and modeling solvent-dependence of mol. conformation in soln. The nucleation driving force required to reach the same induction time is strongly solvent-dependent, increasing in the order: acetonitrile < Et acetate < n-propanol < toluene. The combined DFT and MD modeling results show that in acetonitrile, Et acetate and n-propanol the nucleation difficulty is a function of the strength of solvent-solute interaction, with emphasis on the interaction with specific H-bonding polar sites of importance in the crystal structure. A clear exception from this rule is the most difficult nucleation in toluene despite the weakest solvent-solute interactions. However mol. dynamics modeling predicts that tolbutamide assumes an intramolecularly H-bonded conformation in toluene, substantially different from and more stable than the conformation in the crystal structure, and thus presenting an addnl. barrier to nucleation. This explains why nucleation in toluene is the most difficult and why the relatively higher propensity for aggregation of tolbutamide mols. in toluene soln., as obsd. with FTIR spectroscopy, does not translate into easier nucleation. Thus, our combined exptl. and mol. modeling study suggests that the solvent can influence on the nucleation not only via differences in the desolvation but also through the influence on mol. conformation.
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    13. 13
      Chai, Y.; Wang, L.; Bao, Y.; Teng, R.; Liu, Y.; Xie, C. Investigating the Solvent Effect on Crystal Nucleation of Etoricoxib. Cryst. Growth Des. 2019, 19, 1660– 1667,  DOI: 10.1021/acs.cgd.8b01571
      13
      Investigating the Solvent Effect on Crystal Nucleation of Etoricoxib
      Chai, Yinghui; Wang, Liping; Bao, Ying; Teng, Rugang; Liu, Yumin; Xie, Chuang
      Crystal Growth & Design (2019), 19 (3), 1660-1667CODEN: CGDEFU; ISSN:1528-7483. (American Chemical Society)
      Induction time measurement expts. for etoricoxib (ETR) were carried out in four solvents. The results suggest the crystal nucleation of ETR becomes increasingly more difficult in the order: toluene, acetone, acetonitrile, and ethanol, and this order is well correlated with the interfacial energies detd. by the classical nucleation theory. The solute-solvent interaction was investigated by soln. IR spectroscopy, mol. dynamic simulations, and d. functional theory computed 1:1 solute-solvent binding energies. The strength of binding energy at the sulfonyl on the ETR mol. is not only related to the IR spectral shift of the sulfonyl band but also related to the nucleation rate. The needle-like crystal morphol. along the b-axis of ETR form I in four solvents indicates that the mol. arrangement along the ac plane is extremely limited in cluster growth during nucleation. The sulfonyl, as a hydrogen bond acceptor, participates in the formation of several hydrogen bonds in the two-dimensional structure of the ac plane. Thus, the combination of solvent on the sulfonyl retards the nucleation of ETR. The stronger the solvent interacts with the sulfonyl on the ETR mol., the more energy is required for desolvation, and the slower the ETR nucleation becomes.
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    14. 14
      Simões, R. G.; Melo, P. L. T.; Bernardes, C. E.; Heilmann, M. T.; Emmerling, F.; Minas da Piedade, M. E. Linking Aggregation in Solution, Solvation, and Solubility of Simvastatin: An Experimental and MD Simulation Study. Cryst. Growth Des. 2021, 21, 544– 551,  DOI: 10.1021/acs.cgd.0c01325
      14
      Linking Aggregation in Solution, Solvation, and Solubility of Simvastatin: An Experimental and MD Simulation Study
      Simoes, Ricardo G.; Melo, Pedro L. T.; Bernardes, Carlos E. S.; Heilmann, Maria T.; Emmerling, Franziska; Minas da Piedade, Manuel E.
      Crystal Growth & Design (2021), 21 (1), 544-551CODEN: CGDEFU; ISSN:1528-7483. (American Chemical Society)
      The soly. is generally thought to be higher if the solvent effectively solvates solute mols. that are well-sepd. from each other. The present work suggests, however, that the formation of large solute aggregates does not necessarily imply less effective solvation and lower soly. Measurements of the soly. of simvastatin (one of the most commonly prescribed antihyperlipidemic drugs) in three solvents with different polarities and protic characters, led to the soly. order acetone > Et acetate > ethanol, in the full temp. range covered by the expts. (283-308 K). An anal. of the structures of the different solns. on the basis of mol. dynamics simulation results indicated that this trend seems to be detd. by a balance between the solute tendency toward aggregation and the ability of the solvent to efficiently solvate it, by integrating the cluster structures, regardless of their size, and effectively establishing solvent-solute interactions. The soly. is generally thought to be higher if the solvent effectively solvates solute mols. that are well-sepd. from each other. Using simvastatin as a model (one of the most widely prescribed antihyperlipidemic drugs) and a combination of exptl. soly. measurements with MD simulations, the present work suggests, however, that the formation of large solute aggregates does not necessarily imply less effective solvation and lower soly.
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    15. 15
      Burton, R. C.; Ferrari, E. S.; Davey, R. J.; Finney, J. L.; Bowron, D. T. The Relationship between Solution Structure and Crystal Nucleation: A Neutron Scattering Study of Supersaturated Methanolic Solutions of Benzoic Acid. J. Phys. Chem. B 2010, 114, 8807– 8816,  DOI: 10.1021/jp103099j
      15
      The Relationship between Solution Structure and Crystal Nucleation: A Neutron Scattering Study of Supersaturated Methanolic Solutions of Benzoic Acid
      Burton, R. C.; Ferrari, E. S.; Davey, R. J.; Finney, J. L.; Bowron, D. T.
      Journal of Physical Chemistry B (2010), 114 (26), 8807-8816CODEN: JPCBFK; ISSN:1520-6106. (American Chemical Society)
      In this contribution, neutron scattering expts. (with isotopic substitution) of concd. and supersatd. methanolic benzoic acid solns. combined with empirical potential structure refinement (EPSR) were used to investigate the time-averaged atomistic details of this system. Through the detn. of radial distribution functions, quant. details emerge of the soln. coordination, its relationship to the nature of the cryst. phase, and the response of the soln. to imposed supersatn.
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    16. 16
      Joseph, A.; Rodrigues Alves, J. S.; Bernardes, C. E. S.; Piedade, M. F. M.; Minas da Piedade, M. E. Tautomer selection through solvate formation: the case of 5-hydroxynicotinic acid. CrystEngComm 2019, 21, 2220– 2233,  DOI: 10.1039/C8CE02108B
      16
      Tautomer selection through solvate formation: the case of 5-hydroxynicotinic acid
      Joseph, Abhinav; Rodrigues Alves, Joana S.; Bernardes, Carlos E. S.; Piedade, M. Fatima M.; Minas da Piedade, Manuel E.
      CrystEngComm (2019), 21 (13), 2220-2233CODEN: CRECF4; ISSN:1466-8033. (Royal Society of Chemistry)
      The importance of controlling the crystn. of mols. in specific conformations for the prodn. of cryst. org. materials with highly reproducible physicochem. properties has long been recognized. Using 5-hydroxynicotinic acid (5HNA) as a model the following two questions were addressed in this work: (i) is it possible to promote the crystn. of a tautomeric form dominant in a specific solvent through solvate formation (ii) Does that form persist if the memory of solvation is erased through thermal desolvation. Single crystal X-ray diffraction (SCXRD) anal. indicated that the crystn. of 5HNA from water and DMSO do indeed lead to a monohydrate, 5HNA.H2O, and a monosolvate, 5HNA.DMSO, resp., where the tautomeric form preferred in soln. is preserved (zwitterionic in H2O and neutral in DMSO). Subsequent differential scanning calorimetry (DSC), thermogravimetry (TG), powder X-ray diffraction (PXRD), and diffuse reflectance IR Fourier transform (DRIFT) spectroscopy studies indicated that: (i) albeit upon thermal desolvation different solid forms are initially produced, their structures converge over time to that of the 5HNA starting material, hence to a crystal lattice consisting of the same tautomer; (ii) this tautomer corresponds to a zwitterion. The hydrate and solvate forms showed very distinct solvent loss behaviors at 298 K: 5HNA.H2O did not undergo dehydration even when kept under a reduced pressure, while 5HNA.DMSO was only stable for long periods of time if stored in a closed vial. A thermodn. anal. based on DSC and Calvet drop microcalorimetry results allowed to rationalize these observations indicating that: (i) 5HNA.H2O is predicted to spontaneously lose water, even for a relative humidity of 100%, hence its robustness is most certainly of kinetical origin; (ii) 5HNA.DMSO is thermodynamically stable when a satn. DMSO pressure can be established over the sample, but becomes unstable when exposed to an atm. where the solvent is absent. The kinetically easier desolvation of 5HNA.DMSO compared to 5HNA.H2O may be related to the fact that water is isolated in the crystal lattice (isolated site hydrate) while DMSO is placed in channels (channel solvate).
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    17. 17
      Nakamuro, T.; Sakakibara, M.; Nada, H.; Harano, K.; Nakamura, E. Capturing the Moment of Emergence of Crystal Nucleus from Disorder. J. Am. Chem. Soc. 2021, 143, 1763– 1767,  DOI: 10.1021/jacs.0c12100
      17
      Capturing the Moment of Emergence of Crystal Nucleus from Disorder
      Nakamuro, Takayuki; Sakakibara, Masaya; Nada, Hiroki; Harano, Koji; Nakamura, Eiichi
      Journal of the American Chemical Society (2021), 143 (4), 1763-1767CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      Crystn. is the process of atoms or mols. forming an organized solid via nucleation and growth. Being intrinsically stochastic, the research at an atomistic level was a huge exptl. challenge. In situ detection is reported of a crystal nucleus forming during nucleation/growth of a NaCl nanocrystal, as video recorded in the interior of a vibrating conical C nanotube at 20-40 ms/frame with localization precision of <0.1 nm. NaCl units were seen assembled to form a cluster fluctuating between featureless and semiordered states, which suddenly formed a crystal. Subsequent crystal growth at 298 K and shrinkage at 473 K took place also in a stochastic manner. Productive contributions of the graphitic surface and its mech. vibration were exptl. indicated.
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    18. 18
      Fujii, S.; Ziatdinov, M.; Higashibayashi, S.; Sakurai, H.; Kiguchi, M. Bowl Inversion and Electric Switching of Buckybowls on Gold. J. Am. Chem. Soc. 2016, 138, 12142– 12149,  DOI: 10.1021/jacs.6b04741
      18
      Bowl Inversion and Electronic Switching of Buckybowls on Gold
      Fujii, Shintaro; Ziatdinov, Maxim; Higashibayashi, Shuhei; Sakurai, Hidehiro; Kiguchi, Manabu
      Journal of the American Chemical Society (2016), 138 (37), 12142-12149CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      Bowl-shaped π-conjugated compds., or buckybowls, are a novel class of sp2-hybridized nanocarbon materials. In contrast to tubular carbon nanotubes and ball-shaped fullerenes, the buckybowls feature structural flexibility. Bowl-to-bowl structural inversion is one of the unique properties of the buckybowls in solns. Bowl inversion on a surface modifies the metal-mol. interactions through bistable switching between bowl-up and bowl-down states on the surface, which makes surface-adsorbed buckybowls a relevant model system for elucidation of the mechano-electronic properties of nanocarbon materials. Here, we report a combination of scanning tunneling microscopy (STM) measurements and ab initio atomistic simulations to identify the adlayer structure of the sumanene buckybowl on Au(111) and reveal its unique bowl inversion behavior. We demonstrate that the bowl inversion can be induced by approaching the STM tip toward the mol. By tuning the local metal-mol. interaction using the STM tip, the sumanene buckybowl exhibits structural bistability with a switching rate that is two orders of magnitude faster than that of the stochastic inversion process.
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    19. 19
      Sakurai, H.; Daiko, T.; Hirao, T. A Synthesis of Sumanene, a Fullerene Fragment. Science 2003, 301, 1878,  DOI: 10.1126/science.1088290
      19
      Brevia: A synthesis of sumanene, a fullerene fragment
      Sakurai, Hidehiro; Daiko, Taro; Hirao, Toshikazu
      Science (Washington, DC, United States) (2003), 301 (5641), 1878-1882CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
      The prepn. of sumanene (4,7-dihydro-1H-tricyclopenta[def,jkl,pqr]triphenylene) was reported. Corannulene exhibits a rapid bowl-to-bowl inversion at room temp. with an energy barrier of 10.2 kcal/mol at -64°. In contrast, the cyclopentane rings of sumanene are believed to make it more rigid. Ests. of an inversion energy barrier of 17-24 kcal/mol indicate that sumanene should not undergo inversion on the NMR time scale at room temp. The inversion barrier for sumanene was detd. to be 19.6 kcal/mol at 140°. This result suggests that sumanene is indeed rigid.
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    20. 20
      Amaya, T.; Sakane, H.; Muneishi, T.; Hirao, T. Bowl-to-bowl inversion of sumanene derivatives. Chem. Commun. 2008, 765– 767,  DOI: 10.1039/B712839H
      20
      Bowl-to-bowl inversion of sumanene derivatives
      Amaya, Toru; Sakane, Hiroyuki; Muneishi, Toshiko; Hirao, Toshikazu
      Chemical Communications (Cambridge, United Kingdom) (2008), (6), 765-767CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
      The bowl-to-bowl inversion of the non-planar bowl-shaped compds. derived from sumanene as a fullerene C3v fragment was found to be slow and tuned by a solvent, and the benzylic mono- and di-anions inverted even more slowly.
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    21. 21
      Higashibayashi, S.; Onogi, S.; Srivastava, H. K.; Sastry, G. N.; Wu, Y.-T.; Sakurai, H. Stereoelectronic Effect of Courved Aromatic Structures: Favoring the Unexpxcted endo Confomration of Benzylic-Substituted Sumanene. Angew. Chem., Int. Ed. 2013, 52, 7314– 7316,  DOI: 10.1002/anie.201303134
      21
      Stereoelectronic Effect of Curved Aromatic Structures: Favoring the Unexpected endo Conformation of Benzylic-Substituted Sumanene
      Higashibayashi, Shuhei; Onogi, Satoru; Srivastava, Hemant Kumar; Sastry, G. Narahari; Wu, Yao-Ting; Sakurai, Hidehiro
      Angewandte Chemie, International Edition (2013), 52 (28), 7314-7316CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The stereoelectronic effect of a curved arom. structure, an effect which dominates the endo/exo-R conformational stability of benzylic-substituted sumanenes was reported including natural bond orbital anal. to elucidate the stereoelectronic effect.
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    22. 22
      Kuvychko, I. V.; Dubceac, C.; Deng, S. H. M.; Wang, X.; Granovsky, A. A.; Popov, A. A.; Petrukhina, M. A.; Strauss, S. H.; Boltalina, O. V. C20H4(C4F8)3: A Fluorine-Containing Annulated Corannulene that Is a Better Electron Acceptor Than C60. Angew. Chem., Int. Ed. 2013, 52, 7505– 7508,  DOI: 10.1002/anie.201300796
      22
      C20H4(C4F8)3: A Fluorine-Containing Annulated Corannulene that Is a Better Electron Acceptor Than C60
      Kuvychko, Igor V.; Dubceac, Cristina; Deng, Shihu H. M.; Wang, Xue-Bin; Granovsky, Alexander A.; Popov, Alexey A.; Petrukhina, Marina A.; Strauss, Steven H.; Boltalina, Olga V.
      Angewandte Chemie, International Edition (2013), 52 (29), 7505-7508CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The authors report the first synthesis, structure, and electronic properties (soln. and gas phase) of a corannulene deriv., which has a higher electron affinity than the well-studied fullerene electron-acceptor C60.
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    23. 23
      Dubceac, C.; Sevryugina, Y.; Kuvychko, I. V.; Boltalina, O. V.; Strauss, S. H.; Petrukhina, M. A. Self-Assembly of Aligned Hybrid One-Dimensional Stacks from Two Complementary π-Bowls. Cryst. Growth Des. 2018, 18, 307– 311,  DOI: 10.1021/acs.cgd.7b01258
      23
      Self-Assembly of Aligned Hybrid One-Dimensional Stacks from Two Complementary π-Bowls
      Dubceac, Cristina; Sevryugina, Yulia; Kuvychko, Igor V.; Boltalina, Olga V.; Strauss, Steven H.; Petrukhina, Marina A.
      Crystal Growth & Design (2018), 18 (1), 307-311CODEN: CGDEFU; ISSN:1528-7483. (American Chemical Society)
      Designed synthesis of a new cryst. donor-acceptor org. hybrid was accomplished by using 2 bowl-shaped polycyclic arom. hydrocarbons (PAHs) having complementary structures and properties, namely, C20H10 and C5-C20H5(CF3)5. The x-ray structural characterization of the product, [(C20H10)·(C20H5(CF3)5)]·C6H4Cl2, revealed the formation of aligned columnar stacks of alternating C20H10 and C20H5(CF3)5 mols. with centroid-to-centroid distances of 3.658(8) and 3.787(8) Å and a small bowl slip of 0.086(6) Å. The tight bowl packing is accompanied by notable mol. geometry adjustments of the individual PAHs. The bowl depth increased for corannulene (Δ = +0.019 Å) and decreased for sym-pentakis(trifluoromethyl)corannulene (Δ = -0.011 Å), facilitating enhancement of concave-convex interactions along the stacks. The parallel alignment of 1-dimensional columns is supported by multiple intermol. interactions involving C6H4Cl2 used as the crystn. solvent, forming an infinite 2-dimensional network in the solid state.
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    24. 24
      Haupt, A.; Lentz, D. Corranulenes with Electron-Withdrawing Substituents: Synthetic Approaches and Resulting Structural and Electronic Properties. Chem.─Eur. J. 2019, 25, 3440– 3454,  DOI: 10.1002/chem.201803927
      24
      Corannulenes with Electron-Withdrawing Substituents: Synthetic Approaches and Resulting Structural and Electronic Properties
      Haupt, Axel; Lentz, Dieter
      Chemistry - A European Journal (2019), 25 (14), 3440-3454CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A review. Corannulene is a multifaceted polyarom. compd. It has many interesting properties; for example, it has a bowl-shaped mol. structure that, in addn., undergoes a dynamic inversion process. It has attracted much attention within the last decades. This is not only due to its structural properties but also its electronic properties and its various potential applications to materials chem. Here, synthetic approaches towards corannulene derivs. with electron-withdrawing substituents are summarized. This includes both selective and unselective methods. Further, the electrochem. properties, i.e., the redn. potentials, are analyzed and compared. As a main conclusion, one can state that the electron affinity depends roughly linearly on the no. of substituents. Finally, the structural behavior of the substituted buckybowls in the solid state is highlighted. This also allows a general statement about the influence of the electronic and steric nature of substituents on the mol. structures and the solid-state packing of the corannulene derivs.
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    25. 25
      Schmidt, B. M.; Topolinski, B.; Higashibayashi, S.; Kojima, T.; Kawano, M.; Lentz, D.; Sakurai, H. The Synthesis of Hexafluorosumanene and Its Congeners. Chem.─Eur. J. 2013, 19, 3282– 3286,  DOI: 10.1002/chem.201204622
      25
      The Synthesis of Hexafluorosumanene and Its Congeners
      Schmidt, Bernd M.; Topolinski, Berit; Higashibayashi, Shuhei; Kojima, Tatsuhiro; Kawano, Masaki; Lentz, Dieter; Sakurai, Hidehiro
      Chemistry - A European Journal (2013), 19 (10), 3282-3286CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)
      We have prepd. the first directly fluorinated bucky bowl compd. and revealed the columnar-packing structure as well as low redn. potentials for all members of the family.
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    26. 26
      Li, M.; Wu, J.; Sambe, K.; Yakiyama, Y.; Akutagawa, T.; Kajitani, T.; Fukushima, T.; Matsuda, K.; Sakurai, H. Dielectric response of 1,1-difluorosumanene caused by an in-plane motion. Mater. Chem. Front. 2022, 6, 1752– 1758,  DOI: 10.1039/D2QM00134A
      26
      Dielectric response of 1,1-difluorosumanene caused by an in-plane motion
      Li, Minghong; Wu, JianYun; Sambe, Kohei; Yakiyama, Yumi; Akutagawa, Tomoyuki; Kajitani, Takashi; Fukushima, Takanori; Matsuda, Kazunari; Sakurai, Hidehiro
      Materials Chemistry Frontiers (2022), 6 (13), 1752-1758CODEN: MCFAC5; ISSN:2052-1537. (Royal Society of Chemistry)
      We have designed and synthesized a new curved π-conjugated mol., 1,1-difluorosumanene (1), which possesses two fluorine atoms on the same benzylic carbon of unsubstituted sumanene, producing a large dipole moment along the in-plane direction. Thermal analyses, variable-temp. X-ray diffraction, and IR measurements indicated a 120° in-plane motion of 1 in the stacking columns, which did not cause any phase transition in the cryst. state. Indeed, dielec. measurements on powder and single-crystal forms of 1 showed that both the real (ε1) and imaginary (ε2) parts of the dielec. const. were enhanced above ∼360 K at 1 MHz with a Debye-type dielec. relaxation, confirming that 1 underwent a pendulum fluctuation induced by the external elec. field.
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    27. 27
      Li, M.; Chen, X.; Yakiyama, Y.; Wu, J.; Akutagawa, T.; Sakurai, H. Tuning the dielectric response by co-crystallization of sumanene and its fluorinated derivative. Chem. Commun. 2022, 58, 8950– 8953,  DOI: 10.1039/D2CC02766F
      27
      Tuning the dielectric response by co-crystallisation of sumanene and its fluorinated derivative
      Li, Minghong; Chen, Xi; Yakiyama, Yumi; Wu, JianYun; Akutagawa, Tomoyuki; Sakurai, Hidehiro
      Chemical Communications (Cambridge, United Kingdom) (2022), 58 (64), 8950-8953CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
      A series of co-crystals of 1,1-difluorosumanene (F2-Sum) and sumanene (Sum) were obtained. The co-crystn. successfully tuned their structural and phys. properties, esp. the dielec. response, without any chem. modifications. X-ray analyses and theor. calcns. revealed the redn. of intermol. interaction energy due to the presence of F2-Sum.
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    28. 28
      Yakiyama, Y.; Li, M.; Sakurai, H. Fluorosumanenes as building blocks for organic crystalline dielectrics. Pure Appl. Chem. 2023, 95, 421– 430,  DOI: 10.1515/pac-2023-0211
      28
      Fluorosumanenes as building blocks for organic crystalline dielectrics
      Yakiyama, Yumi; Li, Minghong; Sakurai, Hidehiro
      Pure and Applied Chemistry (2023), 95 (4), 421-430CODEN: PACHAS; ISSN:0033-4545. (Walter de Gruyter, Inc.)
      Org. cryst. dielec. materials are attractive target in the field of materials chem. In their designing strategy, the mol. motion induced by the external dielec. field is required to maximize the polarization effect in the materials to realize a large dielec. const. Esp., the mol. motion of curved-π aroms. such as C60 and their supramol. complexes are the known to show characteristic smoothness in the solid state. In this context, we focused on the in-plane motion of the one of the representative buckybowl, sumanene (Sum) in its curve-to-curve-contacted columnar structure as the new platform of the motion for the emergence of dielec. response. The newly designed and synthesized fluorinated sumanene, 1,1-difluorosumanene (F2-Sum), which possesses two fluorine atoms on the same benzylic carbon of pristine sumanene showed a large dipole moment along the in-plane direction. Thermal analyses, variable temp. X-ray diffraction and IR measurements indicated the presence of in-plane motion of F2-Sum although no clear phase transition was involved. This thermal property of F2-Sum realized an anisotropic dielec. response with a Debye-type dielec. relaxation in the single cryst. state. Further trials to form the solid soln. of Sum and F2-Sum in various mixing ratio realized the tuning of the dielec. property.
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    29. 29
      Sakurai, H.; Daiko, T.; Sakane, H.; Amaya, T.; Hirao, T. Structural Elucidation os Sumanene and Generation of Its Benzylic Anions. J. Am. Chem. Soc. 2005, 127, 11580– 11581,  DOI: 10.1021/ja0518169
      29
      Structural Elucidation of Sumanene and Generation of Its Benzylic Anions
      Sakurai, Hidehiro; Daiko, Taro; Sakane, Hiroyuki; Amaya, Toru; Hirao, Toshikazu
      Journal of the American Chemical Society (2005), 127 (33), 11580-11581CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      The structure of sumanene in a solid state was elucidated. The silyl-substituted sumanene was stereoselectively synthesized through generation of the benzylic anions of sumanene.
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    30. 30
      Mebs, S.; Weber, M.; Luger, P. A.; Schmidt, B. M.; Sakurai, H.; Higashibayashi, S.; Onogi, S.; Lentz, D. Experimental electron density of sumanene, a bowl-shaped fullerene fragment; comparison with the related corannulene hydrocarbon. Org. Biomol. Chem. 2012, 10, 2218– 2222,  DOI: 10.1039/c2ob07040e
      30
      Experimental electron density of sumanene, a bowl-shaped fullerene fragment; comparison with the related corannulene hydrocarbon
      Mebs, Stefan; Weber, Manuela; Luger, Peter; Schmidt, Bernd M.; Sakurai, Hidehiro; Higashibayashi, Shuhei; Onogi, Satoru; Lentz, Dieter
      Organic & Biomolecular Chemistry (2012), 10 (11), 2218-2222CODEN: OBCRAK; ISSN:1477-0520. (Royal Society of Chemistry)
      The exptl. electron d. of sumanene, C21H12, was extd. from a high resoln. X-ray data set measured at 100 K and topol. analyzed. In addn. to bond topol. and at. properties, information about the d. distribution between adjacent mols., which show close C···C approaches of ∼3.4 Å within the columnar π-stacks in the crystal lattice, are discussed. A comparison is made with the electron d. of the related corannulene mol. based also on the anal. of Electron Localizability Indicator (ELI-D) calcns.
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    31. 31
      Zanello, P.; Fedi, S.; de Biani, F. F.; Giorgi, G.; Amaya, T.; Sakane, H.; Hirao, T. The electrochemical inspection of the redox activity of sumanene and its concave CpFe complex. Dalton Trans. 2009, 9192– 9197,  DOI: 10.1039/b910711h
      31
      The electrochemical inspection of the redox activity of sumanene and its concave CpFe complex
      Zanello, Piero; Fedi, Serena; Fabrizi de Biani, Fabrizia; Giorgi, Gianluca; Amaya, Toru; Sakane, Hiroyuki; Hirao, Toshikazu
      Dalton Transactions (2009), (42), 9192-9197CODEN: DTARAF; ISSN:1477-9226. (Royal Society of Chemistry)
      The redox properties of sumanene C21H12 and its concave Fe(II) complex [(η5-C5H5)Fe(η6-C21H12)]+ were elucidated through an electrochem. study in nonaq. solvents, i.e. DMF and MeCN. The electron transfer activity of sumanene can be depicted as an irreversible oxidn. and a partially chem. reversible 1-electron redn., both processes being located in proximity of the resp. discharges of the solvents. The Fe(II) complex [(η5-C5H5)Fe(η6-C21H12)](PF6) in turn exhibits the Fe(II)/Fe(I) redn., which in both DMF and MeCN solvents displays features of partial chem. reversibility, coupled to decompn. of the corresponding Fe(I) species [(η5-C5H5)Fe(η6-C21H12)] to fragments which, upon reoxidn., regenerate for the most part the original Fe(II)-sumanene species. In fact, among the fragments produced by exhaustive redn., ESI measurements allowed the detection of ferrocene, the oxidn. of which probably triggers the partial regeneration of the original Fe(II) complex. The pertinent PM6 semiempirical study accounts for the limited chem. reversibility of the redox processes exhibited by both sumanene and its Fe(II) complex.
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    32. 32
      Liu, L.; Guo, Q. Isokinetic Relationship, Isoequilibrium Relationship, and Enthalpy-Entropy Compensation. Chem. Rev. 2001, 101, 673– 696,  DOI: 10.1021/cr990416z
      32
      Isokinetic Relationship, Isoequilibrium Relationship, and Enthalpy-Entropy Compensation
      Liu, Lei; Guo, Qing-Xiang
      Chemical Reviews (Washington, D. C.) (2001), 101 (3), 673-695CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review, with about 200 refs., which discusses the relationship and differences between the 3 title concepts. The relationships are discussed from both a statistical and a theor. approach. Some applications of these concepts are illustrated.
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    33. 33
      Pan, A.; Biswas, T.; Rakshit, A. K.; Moulik, S. P. Enthalpy-Entropy Compensation (EEC) Effect: A Recisit. J. Phys. Chem. B 2015, 119, 15876– 15884,  DOI: 10.1021/acs.jpcb.5b09925
      33
      Enthalpy-Entropy Compensation (EEC) Effect: A Revisit
      Pan, Animesh; Biswas, Tapas; Rakshit, Animesh K.; Moulik, Satya P.
      Journal of Physical Chemistry B (2015), 119 (52), 15876-15884CODEN: JPCBFK; ISSN:1520-5207. (American Chemical Society)
      A review. A short account of the developments and perspectives of IKR (iso-kinetic relation) and EEC (enthalpy (H) - entropy (S) compensation) has been presented. The IKR and EEC are known to be extra thermodn. or empirical correlations though linear H-S correlation can be thermodynamically deduced. Attempt has also been made to explain the phenomena in terms of statistical thermodn. In this study, we have briefly revisited the fundamentals of both IKR and EEC from kinetic and thermodn. grounds. A detailed revisit of the EEC phenomenon on varied kinetic and equil. processes has been also presented. Possible correlations among the free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) changes of different similar and non-similar chem. processes under varied conditions have been discussed with possible future projections.
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    34. 34
      Zhao, Y. H.; Abraham, M. H.; Zissimos, A. M. Fast Calculation of van der Waals Volume as a Sum of Atomic and Bond Contributions and Its Application to Drug Compounds. J. Org. Chem. 2003, 68, 7368– 7373,  DOI: 10.1021/jo034808o
      34
      Fast Calculation of van der Waals Volume as a Sum of Atomic and Bond Contributions and Its Application to Drug Compounds
      Zhao, Yuan H.; Abraham, Michael H.; Zissimos, Andreas M.
      Journal of Organic Chemistry (2003), 68 (19), 7368-7373CODEN: JOCEAH; ISSN:0022-3263. (American Chemical Society)
      The van der Waals vol. is a widely used descriptor in modeling physicochem. properties. However, the calcn. of the van der Waals vol. (VvdW) is rather time-consuming, from Bondi group contributions, for a large data set. A new method for calcg. van der Waals vol. has been developed, based on Bondi radii. The method, termed At. and Bond Contributions of van der Waals vol. (VABC), is very simple and fast. The only information needed for calcg. VABC is at. contributions and the no. of atoms, bonds, and rings. Then, the van der Waals vol. (Å3/mol.) can be calcd. from the following formula: VvdW = .sum. all atom contributions - 5.92NB - 14.7RA - 3.8RNR (NB is the no. of bonds, RA is the no. of arom. rings, and RNA is the no. of nonarom. rings). The no. of bonds present (NB) can be simply calcd. by NB = N - 1 + RA + RNA (where N is the total no. of atoms). A simple Excel spread sheet has been made to calc. van der Waals vols. for a wide range of 677 org. compds., including 237 drug compds. The results show that the van der Waals vols. calcd. from VABC are equiv. to the computer-calcd. van der Waals vols. for org. compds.
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    35. 35
      Reichardt, C. Solvents and Solvent Effects in Organic Chemistry; Wiley-VCH: Weinheim, Germany, 2003.
      There is no corresponding record for this reference.
    36. 36
      Bruno, C.; Benassi, R.; Passalacqua, A.; Paolucci, F.; Fontanesi, C.; Marcaccio, M.; Jackson, E. A.; Scott, L. T. Electrochamical and Theoretical Investigation of Corannulene Reduction Processes. J. Phys. Chem. B 2009, 113, 1954– 1962,  DOI: 10.1021/jp8045092
      36
      Electrochemical and Theoretical Investigation of Corannulene Reduction Processes
      Bruno, Carlo; Benassi, Rois; Passalacqua, Alessio; Paolucci, Francesco; Fontanesi, Claudio; Marcaccio, Massimo; Jackson, Edward A.; Scott, Lawrence T.
      Journal of Physical Chemistry B (2009), 113 (7), 1954-1962CODEN: JPCBFK; ISSN:1520-6106. (American Chemical Society)
      The voltammetric generation of corannulene anions was studied over a large range of exptl. conditions comprising either traditional electrochem. solvents, such as DMF, MeCN, and THF, or unconventional solvents, such as liq. NH3, liq. methylamine, or liq. dimethylamine, and several different supporting electrolytes. Strong ion pairing effects dominate the electrochem. generation of corannulene higher anions, and through the suitable choice of the solvent/electrolyte system, the authors obsd., for the 1st time, the reversible electrochem. generation of up to the triply reduced corannulene. The std. potentials obtained exptl. compared rather well with the theor. values calcd. by ab initio and d. functional methods, in which solvation and ion pairing effect were explicitly taken into account. In particular, the calcns. considered the effect of the electrolyte cation size on ion pairing to rationalize the occurrence of the 3rd redn. within the exptl. potential window.
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    37. 37
      Harada, J.; Yoneyama, N.; Sato, S.; Takahashi, Y.; Inabe, T. Crystals of Charge-Transfer Complexes with Reorienting Polar Molecules: Dielectric Properties and Order-Disorder Phase Transitions. Cryst. Growth Des. 2019, 19, 291– 299,  DOI: 10.1021/acs.cgd.8b01418
      37
      Crystals of charge-transfer complexes with reorienting polar molecules: Dielectric properties and order-disorder phase transitions
      Harada, Jun; Yoneyama, Naho; Sato, Shota; Takahashi, Yukihiro; Inabe, Tamotsu
      Crystal Growth & Design (2019), 19 (1), 291-299CODEN: CGDEFU; ISSN:1528-7483. (American Chemical Society)
      Crystals of charge-transfer (CT) complexes were synthesized using the polar mol. tetrachlorophthalonitrile (TCPN) as the electron acceptor and nonpolar arom. hydrocarbons, such as perylene, coronene, chrysene, and pyrene, as the electron donors. Variable-temp. X-ray crystal structure analyses revealed that the TCPN mols. in all the CT crystals exhibit orientational disorder at room temp. Some of the CT crystals undergo an order-disorder-type phase transition upon cooling, where the orientation of the TCPN mols. becomes ordered at low temp. The CT crystals show large dielec. consts. at room temp. arising from in-plane reorientation of the polar TCPN mols. The order-disorder phase transition results in a drastic redn. of the dielec. const. of the CT crystals upon cooling. This study demonstrates that the formation of CT crystals from polar mols. represents a promising method for the development of dielec. cryst. materials, whose properties vary significantly in response to phase transitions.
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    38. 38
      Harada, J.; Ohtani, M.; Takahashi, Y.; Inabe, T. Molecular Motion, Dielectric Response, and Phase Transition of Charge-Transfer Crystals: Acquired Dynamic and Dielectric Properties of Polar Molecules in Crystals. J. Am. Chem. Soc. 2015, 137, 4477– 4486,  DOI: 10.1021/jacs.5b00412
      38
      Molecular Motion, Dielectric Response, and Phase Transition of Charge-Transfer Crystals: Acquired Dynamic and Dielectric Properties of Polar Molecules in Crystals
      Harada, Jun; Ohtani, Masaki; Takahashi, Yukihiro; Inabe, Tamotsu
      Journal of the American Chemical Society (2015), 137 (13), 4477-4486CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      Mols. in crystals often suffer from severe limitations on their dynamic processes, esp. on those involving large structural changes. Cryst. compds., therefore, usually fail to realize their potential as dielec. materials even when they have large dipole moments. To enable polar mols. to undergo dynamic processes and to provide their crystals with dielec. properties, weakly bound charge-transfer (CT) complex crystals were exploited as a mol. architecture where the constituent polar mols. have some freedom of dynamic processes, which contribute to the dielec. properties of the crystals. Several CT crystals of polar tetrabromophthalic anhydride (TBPA) mols. were prepd. using TBPA as an electron acceptor and arom. hydrocarbons, such as coronene and perylene, as electron donors. The crystal structures and dielec. properties of the CT crystals as well as the single-component crystal of TBPA were studied at various temps. Mol. reorientation of TBPA mols. did not occur in the single-component crystal, and the crystal did not show a dielec. response due to orientational polarization. The CT crystal formation provides a simple and versatile method to develop mol. dielecs., revealing that the mol. dynamics of the TBPA mols. and the dielec. property of their crystals were greatly changed in CT crystals. The TBPA mols. underwent rapid in-plane reorientations in their CT crystals, which exhibited marked dielec. responses arising from the mol. motion. An order-disorder phase transition was obsd. for one of the CT crystals, which resulted in an abrupt change in the dielec. const. at the transition temp.
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      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXksVOru78%253D&md5=77c800201dc26cf54d3725801c105943
    39. 39
      Wang, J.; Wolf, R. M.; Caldwell, J. W.; Kollman, P. A.; Case, D. A. Development and testing of a general amber force field. J. Comput. Chem. 2004, 25, 1157– 1174,  DOI: 10.1002/jcc.20035
      39
      Development and testing of a general Amber force field
      Wang, Junmei; Wolf, Romain M.; Caldwell, James W.; Kollman, Peter A.; Case, David A.
      Journal of Computational Chemistry (2004), 25 (9), 1157-1174CODEN: JCCHDD; ISSN:0192-8651. (John Wiley & Sons, Inc.)
      We describe here a general Amber force field (GAFF) for org. mols. GAFF is designed to be compatible with existing Amber force fields for proteins and nucleic acids, and has parameters for most org. and pharmaceutical mols. that are composed of H, C, N, O, S, P, and halogens. It uses a simple functional form and a limited no. of atom types, but incorporates both empirical and heuristic models to est. force consts. and partial at. charges. The performance of GAFF in test cases is encouraging. In test I, 74 crystallog. structures were compared to GAFF minimized structures, with a root-mean-square displacement of 0.26 Å, which is comparable to that of the Tripos 5.2 force field (0.25 Å) and better than those of MMFF 94 and CHARMm (0.47 and 0.44 Å, resp.). In test II, gas phase minimizations were performed on 22 nucleic acid base pairs, and the minimized structures and intermol. energies were compared to MP2/6-31G* results. The RMS of displacements and relative energies were 0.25 Å and 1.2 kcal/mol, resp. These data are comparable to results from Parm99/RESP (0.16 Å and 1.18 kcal/mol, resp.), which were parameterized to these base pairs. Test III looked at the relative energies of 71 conformational pairs that were used in development of the Parm99 force field. The RMS error in relative energies (compared to expt.) is about 0.5 kcal/mol. GAFF can be applied to wide range of mols. in an automatic fashion, making it suitable for rational drug design and database searching.
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    40. 40
      Bayly, C. I.; Cieplak, P.; Cornell, W. D.; Kollman, P. A. A well-behaved electrostatic potential based method using charge restraints for deriving atomic charges: the RESP model. J. Phys. Chem. 1993, 97, 10269– 10280,  DOI: 10.1021/j100142a004
      40
      A well-behaved electrostatic potential based method using charge restraints for deriving atomic charges: the RESP model
      Bayly, Christopher I.; Cieplak, Piotr; Cornell, Wendy; Kollman, Peter A.
      Journal of Physical Chemistry (1993), 97 (40), 10269-80CODEN: JPCHAX; ISSN:0022-3654.
      The authors present a new approach to generating electrostatic potential (ESP) derived charges for mols. The major strength of electrostatic potential derived charges is that they optimally reproduce the intermol. interaction properties of mols. with a simple two-body additive potential, provided, of course, that a suitably accurate level of quantum mech. calcn. is used to derive the ESP around the mol. Previously, the major weaknesses of these charges have been that they were not easily transferably between common functional groups in related mols., they have often been conformationally dependent, and the large charges that frequently occur can be problematic for simulating intramol. interactions. Introducing restraints in the form of a penalty function into the fitting process considerably reduces the above problems, with only a minor decrease in the quality of the fit to the quantum mech. ESP. Several other refinements in addn. to the restrained electrostatic potential (RESP) fit yield a general and algorithmic charge fitting procedure for generating atom-centered point charges. This approach can thus be recommended for general use in mol. mechanics, mol. dynamics, and free energy calcns. for any org. or bioorg. system.
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    41. 41
      Abraham, M. J.; Murtola, T.; Schulz, R.; Ṕall, S.; Smith, J. C.; Hess, B.; Lindahl, E. GROMACS: High performance molecular simulations through multi-level parallelism from laptops to supercomputers. SoftwareX 2015, 1–2, 19– 25,  DOI: 10.1016/j.softx.2015.06.001
      There is no corresponding record for this reference.
    42. 42
      Matubayasi, N.; Nakahara, M. Theory of Solutions in the Energy Representation. II. Functional for the Chemical Potential. J. Chem. Phys. 2002, 117, 3605– 3616,  DOI: 10.1063/1.1495850
      42
      Theory of solutions in the energy representation and functional for the chemical potential
      Matubayasi, Nobuyuki; Nakahara, Masaru
      Journal of Chemical Physics (2002), 117 (8), 3605-3616CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
      An approx. functional for the chem. potential of a solute in soln. is presented in the energy representation. This functional is constructed by adopting the Percus-Yevick-like approxn. in the unfavorable region of the solute-solvent interaction and the hypernetted-chain-like approxn. in the favorable region. The chem. potential is then expressed in terms of energy distribution functions in the soln. and pure solvent systems of interest, and is given exactly to second order with respect to the solvent d. and to the solute-solvent interaction. In the practical implementation, computer simulations of the soln. and pure solvent systems are performed to provide the energy distribution functions constituting the approx. functional for the chem. potential. It is demonstrated that the chem. potentials of nonpolar, polar, and ionic solutes in water are evaluated accurately and efficiently from the single functional over a wide range of thermodn. conditions.
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    43. 43
      Sakuraba, S.; Matubayasi, N. ERmod: Fast and Versatile Computation Software for Solvation Free Energy with Approximate Theory of Solutions. J. Comput. Chem. 2014, 35, 1592– 1608,  DOI: 10.1002/jcc.23651
      43
      Ermod: Fast and versatile computation software for solvation free energy with approximate theory of solutions
      Sakuraba, Shun; Matubayasi, Nobuyuki
      Journal of Computational Chemistry (2014), 35 (21), 1592-1608CODEN: JCCHDD; ISSN:0192-8651. (John Wiley & Sons, Inc.)
      ERmod is a software package to efficiently and approx. compute the solvation free energy using the method of energy representation. Mol. simulation is to be conducted at two condensed-phase systems of the soln. of interest and the ref. solvent with test-particle insertion of the solute. The subprogram ermod in ERmod then provides a set of energy distribution functions from the simulation trajectories, and another subprogram slvfe dets. the solvation free energy from the distribution functions through an approx. functional. This article describes the design and implementation of ERmod, and illustrates its performance in solvent water for two org. solutes and two protein solutes. Actually, the free-energy computation with ERmod is not restricted to the solvation in homogeneous medium such as fluid and polymer and can treat the binding into weakly ordered system with nano-inhomogeneity such as micelle and lipid membrane. ERmod is available on web at http://sourceforge.net/projects/ermod. © 2014 Wiley Periodicals, Inc.
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    • Synthesis of 1, 1H NMR, 13C NMR, and 19F NMR charts of 1, detailed experimental procedures, single crystal X-ray analysis details, molecular dynamics simulation detail, computational procedures with Cartesian coordinates, and supplemental figures and tables about optical and electrical properties of 1, equilibrium details of 1 in each solvent, structural parameters of single crystal of 1, and Arrhenius plot obtained from PCDMF (PDF)

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