A study of solvent selectivity on the crystal morphology of FOX-7 via a modified attachment energy model

Zhao, Qiangli; Liu, Ning; Wang, Bozhou; Wang, Wenliang

doi:10.1039/c6ra07129e

Cited by 34 publications

(23 citation statements)

References 46 publications

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“…The calculations performed provide insights into the stabilizing dimers and intermoleculari nteractions existingi n the crystal systems under study from at hermodynamic point of view.S olvent effects in crystallization may also influence the packing arrangement in co-crystals [59] and is an emerging area of interestinc rystal engineering. Solvent effects and kinetics in the crystallization process couldb ec onsidered separately by using variousm odeling methods such as molecular dynamics, [60] the modified attachment energy model, [61] and lattice Boltzmann methods. [62] Electronic structure perturbations causedb yv arious packing modes were analyzed from the band-structure and density-of-states calculations of selected co-crystals.…”

Section: Introductionmentioning

confidence: 99%

Structure‐Packing‐Property Correlation of Self‐Sorted Versus Interdigitated Assembly in TTF⋅TCNQ‐Based Charge‐Transport Materials

Niyas

Vijay

Hariharan

2018

Chemistry A European J

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Among the various donor-acceptor (D-A) charge-transfer co-crystals investigated in the past few decades, tetrathiafulvalene-tetracyanoquinodimethane (F⋅Q, popularly known as TTF⋅TCNQ)-based co-crystals have fascinated materials chemists owing to their exceptional conducting and magnetic properties that arise from the packing in crystal structures. Here, crystallographic information files of eighteen F⋅Q-based co-crystals are extracted from the Cambridge Structural Database (CSD) and classified into Class 1 (D-on-D and A-on-A segregated stacks; F⋅Q, F1⋅Q-F6⋅Q, and F⋅Q1), Class 2 (-A-D-A-D-A-D- mixed stacks; F6a⋅Q-F11⋅Q and F⋅Q2), and Class 3 [-A-D-A-A-D-A-; Class 3a (F12⋅Q and F13⋅Q) and -D-D-A-A-; Class 3b (F14⋅Q)] systems according to their packing modes. Hirshfeld surface analysis, PIXEL energy calculations, and quantum theory of atoms in molecules (QTAIM) analysis are performed on the selected multicomponent charge-transfer crystals for the first time, in an attempt to explore the driving forces that give rise to different classes of 3 D crystal packing, which in turn mandates the expedient electronic properties exhibited by the investigated co-crystals. PIXEL calculations reveal that the dispersion energy component makes the maximum contribution to the total lattice energy for most of the F⋅Q-based co-crystals under study. Although the Q-on-Q dimer is the energetically most favored dimer in F⋅Q, the substituents on F capable of forming hydrogen-bonding, C⋅⋅⋅S, and other weak intermolecular interactions result in the greater stability of the F-on-F dimer for F1⋅Q-F6⋅Q (except F2⋅Q). The C⋅⋅⋅S, C ⋅⋅⋅S, S⋅⋅⋅N, and π⋅⋅⋅π interaction-driven D-on-A dimer is found to be the most stable dimer of all the Class 2 co-crystals. Band structure and density-of-state calculations of the representative co-crystals in each class indicate different electronic structures according to the packing arrangement. F⋅Q and F6⋅Q with a high interaction of electronic orbitals between D-on-D and A-on-A in segregated stacks are found to be metal-like (bandgap, E =0.003 eV) and metallic (overlapping bands in the Fermi level), respectively, whereas the polymorph of F6⋅Q belonging to Class 2 (F6a⋅Q) displays a semiconductor-type band structure (E =0.053 eV). F12⋅Q of Class 3a exhibits a metal-like band structure (E =0.001 eV). The fine tuning of chromophores with diverse functional substituents capable of triggering weak intermolecular interactions that give rise to the desired packing and charge-transfer properties has the potential to open floodgates of opportunity for research in the chemistry of materials and fabrication of efficient electronic devices.

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Section: Introductionmentioning

confidence: 99%

Structure‐Packing‐Property Correlation of Self‐Sorted Versus Interdigitated Assembly in TTF⋅TCNQ‐Based Charge‐Transport Materials

Niyas

Vijay

Hariharan

2018

Chemistry A European J

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“…3(b), which demonstrates that the stronger the molecular force is, the faster the crystal grows. 10,11 In Fig. 3(b), the blue lines D r a f t represent strong interaction while red lines represent weak interaction, which indicates that FOX-7 grows faster along the blue lines direction than the red lines direction.…”

Section: Fox-7 Crystal Morphology In Vacuummentioning

confidence: 99%

“…Currently, molecular modelling techniques, with low-cost and security, on the prediction of crystal shape have been extensively developed. [9][10][11][12] In particular, the molecular dynamics (MD) simulation which can provide atomic-scale information becomes a powerful one of these techniques. 13 Therefore, the MD simulation method is used to study the dimethyl sulfoxide (DMSO) and temperature effect on the morphology of FOX-7.…”

mentioning

confidence: 99%

Molecular dynamics simulation on the morphology of 1,1-diamino-2,2-dinitroethylene (FOX-7) affected by dimethyl sulfoxide (DMSO) and temperature

Gao

Jin

et al. 2019

Can. J. Chem.

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The attachment energy (AE) model is adopted to research the influence of dimethyl sulfoxide (DMSO) and temperature on the crystal morphology of 1,1-diamino-2,2-dinitroethylene (FOX-7). FOX-7 crystal habits in DMSO at different temperatures simulated by the AE model have apparently changed compared with the vacuum morphology, indicating that the solvent and temperature can affect FOX-7 morphology. Moreover, the influence of model dimension on the attachment energy has been studied, and a reasonable model size is obtained based on the model dimension study results. Besides, the radial distribution function analysis shows that the solvent molecules adsorb on the FOX-7 surfaces mainly via the solvent–crystal interface interactions of van der Waals forces (vdW) and Coulomb interactions. The analysis of diffusion coefficient of DMSO molecules on the crystal growth surfaces shows that the growth habit is also influenced by the diffusion capacity of DMSO molecules. These simulation results of this study can provide some guidance for the crystallization process of FOX-7.

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“…Figure 3b visualizes the interactions between the catechol molecules calculated and generated by the Crystal Graph in the morphology module, with the blue and red lines representing strong and weak interactions, respectively. Previous studies indicated that crystals grow faster along the direction with strong molecular interactions [44]. Therefore, catechol crystals grow faster along the blue line direction and the surfaces with fast growth rate may disappear, leaving the slowly growing surface appear in the final morphology with six important faces, (1 0 −1), (1 0 1), (0 1 1), (1 1 0), (0 0 2) and (1 1 −1).…”

Section: Prediction Of Catechol Crystal Morphology In Vacuummentioning

confidence: 99%

“…Crystals 2020, 10, x FOR PEER REVIEW 6 of 17 grow faster along the direction with strong molecular interactions [44]. Therefore, catechol crystals grow faster along the blue line direction and the surfaces with fast growth rate may disappear, leaving the slowly growing surface appear in the final morphology with six important faces, (1 0 −1), (1 0 1), (0 1 1), (1 1 0), (0 0 2) and (1 1 −1).…”

Section: Prediction Of Catechol Crystal Morphology In Vacuummentioning

confidence: 99%

Solvent Effects on Catechol Crystal Habits and Aspect Ratios: A Combination of Experiments and Molecular Dynamics Simulation Study

et al. 2020

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This work could help to better understand the solvent effects on crystal habits and aspect ratio changes at the molecular level, which provide some guidance for solvent selection in industrial crystallization processes. With the catechol crystal habits acquired using both experimental and simulation methods in isopropanol, methyl acetate and ethyl acetate, solvent effects on crystal morphology were explored based on the modified attachment energy model. Firstly, morphologically dominant crystal faces were obtained with the predicted crystal habit in vacuum. Then, modified attachment energies were calculated by the molecular dynamics simulation to modify the crystal shapes in a real solvent environment, and the simulation results were in agreement with the experimental ones. Meanwhile, the surface properties such as roughness and the diffusion coefficient were introduced to analyze the solvent adsorption behaviors and the radial distribution function curves were generated to distinguish diverse types of interactions like hydrogen bonds and van der Waals forces. Results show that the catechol crystal habits were affected by the combination of the attachment energy, surface structures and molecular interaction types. Moreover, the changing aspect ratios of catechol crystals are closely related to the existence of hydrogen bonds which contribute to growth inhibition on specific faces.

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A study of solvent selectivity on the crystal morphology of FOX-7 via a modified attachment energy model

Cited by 34 publications

References 46 publications

Structure‐Packing‐Property Correlation of Self‐Sorted Versus Interdigitated Assembly in TTF⋅TCNQ‐Based Charge‐Transport Materials

Structure‐Packing‐Property Correlation of Self‐Sorted Versus Interdigitated Assembly in TTF⋅TCNQ‐Based Charge‐Transport Materials

Molecular dynamics simulation on the morphology of 1,1-diamino-2,2-dinitroethylene (FOX-7) affected by dimethyl sulfoxide (DMSO) and temperature

Solvent Effects on Catechol Crystal Habits and Aspect Ratios: A Combination of Experiments and Molecular Dynamics Simulation Study

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