Solvophobicity-directed assembly of microporous molecular crystals

Dense packing is a universal tendency of organic molecules in the solid state. Typical porous crystals utilize reticular strong intermolecular bonding networks to overcome this principle. Here, we report a solvophobicity-based methodology for assembling discrete molecules into a porous form and succeed in synthesizing isostructural porous polymorphs of an amphiphilic aromatic molecule Py6Mes. A computational analysis of the crystal structure reveals the major contribution of dispersion interaction as the driving force for assembling Py6Mes into a columnar stacking while the columns are sterically salient and form nanopores between them. The porous packing is facilitated particularly in solvents with weak dispersion interaction due to the solvophobic effect. Conversely, solvents with strong dispersion interaction intercalate between Py6Mes due to the solvophilic effect and provide non-porous inclusion crystals. The solvophobicity-directed polymorphism is further corroborated by the polymorphs of Py6Mes-analogues, m-Py6Mes and Ph6Mes.

Revisiting stacking interactions in tetrathiafulvalene and selected derivatives using tight-binding quantum chemical calculations and local coupled-cluster method

The engineering of supramolecular architectures needs accurate descriptions of the intermolecular interactions in crystal structures. Tetrathiafulvalene (TTF) is an effective building block used in the construction of promising functional materials. The parallel packing of the neutral TTF–TTF system was studied previously using the high-level quantum chemical method, advancing it as a valuable model system. The recently developed tight-binding quantum chemical method GFN2-xTB and local coupled-cluster method DLPNO-CCSD(T) were used to investigate the stacking interactions of TTF and selected derivatives deposited in the Cambridge Structural Database. Using the interaction energy of the TTF–TTF dimer calculated at the CCSD(T)/CBS level as the reference, the accuracies of the two methods are investigated. The energy decomposition analysis within the DLPNO-CCSD(T) framework reveals the importance of dispersion interaction in the TTF-related stacking systems. The dispersion interaction density plot vividly shows the magnitude and distribution of the dispersion interaction, providing a revealing insight into the stacking interactions in crystal structures. The results show that the GFN2-xTB and DLPNO-CCSD(T) methods could achieve accuracy at an affordable computational cost, which would be valuable in understanding the nature of parallel stacking in supramolecular systems.

Possible approach to estimating the dispersion interaction in powder systems

In this paper, we present the results of testing the algorithm for calculating the Hamaker constant proposed by the authors as characteristics of the dispersion interaction according to experimental data obtained by studying the composition of fine powders of basalt and polymineral sand. For this purpose, based on a number of assumptions, the concept of an analogue Hamaker constant is introduced, which is an experimentally determined quantity.This parameter is recommended to be used when choosing the quantitative ratio of powder raw materials as a criterion for assessing the maximum possible van der Waals effect of dispersion interaction. An assumption was made about the presence of a constant characteristic of a thin film wetting the analyzed surface. Moreover, this thin film has a contact angle of the transition region “film-bulk phase”, the value of which is determined by the nature of the surface and the properties of the wetting liquid. The contact angle of the transition region can be an additional quantitative criterion for the selection of materials that are compatible in nature.