Supramolecular Architecture of Substituted Tetraphenyl-carbo-benzenes from the Energetic Viewpoint.

The use of DFT-calculated energy-vector diagrams (EVDs) featuring the topology of pairwise intermolecular interaction energies is applied to crystals of carbo-benzenes. A homogeneous set of six ideally centrosymmetric tetraphenyl-carbo-benzenes is selected, with various substituents R in para positions: R=4-anisyl, 1-ethyl-2-phenyl-1H-indol-3-yl, 2-chloro-2-(1-ethyl-2-phenyl-1H-indol-3-yl)ethenyl, tetradecyl, and 9,9-dihexyl-9H-fluoren-2-yl, 2-(9,9-dihexyl-9H-fluoren-2-yl)ethynyl. The basic structural motifs (BSMs) of the crystals vary from layers to columns, depending on the size and shape of the substituents R. The BSM cohesion is shown to rely on π-stacking, CH-π and dispersive interactions. Solvate molecules are shown to have a negligible role in the formation of the BSM, whereas they loosen the interaction between neighbouring BSMs.

[1]  C. Duhayon,et al.  3D and 2D supramolecular assemblies and thermotropic behaviour of a carbo-benzenic mesogen. , 2017, Chemical communications.

[2]  C. Duhayon,et al.  Lipidic Carbo-benzenes: Molecular Probes of Magnetic Anisotropy and Stacking Properties of α-Graphyne. , 2017, The Journal of organic chemistry.

[3]  J. Maldonado,et al.  Difluorenyl carbo-Benzenes: Synthesis, Electronic Structure, and Two-Photon Absorption Properties of Hydrocarbon Quadrupolar Chromophores. , 2015, Chemistry.

[4]  R. Chauvin,et al.  "Carbo-aromaticity" and novel carbo-aromatic compounds. , 2015, Chemical Society reviews.

[5]  Mark A Ratner,et al.  Towards graphyne molecular electronics , 2015, Nature Communications.

[6]  R. Zubatyuk,et al.  Investigation of topology of intermolecular interactions in the benzene–acetylene co-crystal by different theoretical methods , 2014, Structural Chemistry.

[7]  R. Chauvin,et al.  Carbo-graphite: Structural, Mechanical, and Electronic Properties , 2013 .

[8]  R. Chauvin,et al.  Enhanced π-frustration in carbo-benzenic chromophores. , 2013, Chemical communications.

[9]  R. Zubatyuk,et al.  Low-melting molecular complexes. Halogen bonds in molecular complexes of bromoform , 2012 .

[10]  R. Chauvin,et al.  From hexaoxy-[6]pericyclynes to carbo-cyclohexadienes, carbo-benzenes, and dihydro-carbo-benzenes: synthesis, structure, and chromophoric and redox properties. , 2012, Chemistry.

[11]  O. Shishkin,et al.  Supramolecular architecture of crystals of fused hydrocarbons based on topology of intermolecular interactions , 2012 .

[12]  R. Zubatyuk,et al.  The C-Cl···π interactions inside supramolecular nanotubes of hexaethynylhexamethoxy[6]pericyclyne. , 2011, Physical chemistry chemical physics : PCCP.

[13]  D. Schollmeyer,et al.  Columnar supramolecular architecture of crystals of 2-(4-Iodophenyl)-1,10-phenanthroline derived from values of intermolecular interaction energy , 2011 .

[14]  A. Gavezzotti.  The lines-of-force landscape of interactions between molecules in crystals; cohesive versus tolerant and 'collateral damage' contact. , 2010, Acta crystallographica. Section B, Structural science.

[15]  S. Desenko,et al.  Layered crystal structure of bicyclic aziridines as revealed by analysis of intermolecular interactions energy , 2010 .

[16]  S. Grimme,et al.  A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. , 2010, The Journal of chemical physics.

[17]  C. Macrae,et al.  Mercury CSD 2.0 – new features for the visualization and investigation of crystal structures , 2008 .

[18]  R. Chauvin,et al.  From macrocyclic oligo-acetylenes to aromatic ring carbo-mers. , 2006, Chemical reviews.

[19]  A. E. Obodovskaya,et al.  Crystallochemical analysis of succinic and maleic anhydrides , 2003 .

[20]  G. Desiraju.  Crystal Design: Structure and Function , 2003 .

[21]  Gautam R. Desiraju,et al.  Chemistry beyond the molecule , 2001, Nature.

[22]  Gautam R. Desiraju,et al.  Supramolecular Synthons in Crystal Engineering—A New Organic Synthesis , 1995 .

[23]  Gautam R. Desiraju.  Supramolekulare Synthone für das Kristall‐Engineering ‐ eine neue organische Synthese , 1995 .

[24]  R. Chauvin,et al.  “Carbomers”. I. A general concept of expanded molecules , 1995 .

[25]  J. Lehn.  Perspectives in Supramolecular Chemistry: From Molecular Recognition Towards Self‐Organisation. , 1995 .

[26]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[27]  A. Becke,et al.  Density-functional exchange-energy approximation with correct asymptotic behavior. , 1988, Physical review. A, General physics.

[28]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[29]  S. F. Boys,et al.  The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors , 1970 .

[30]  P. Hohenberg,et al.  Inhomogeneous Electron Gas , 1964 .

[31]  G. Sheldrick.  A short history of SHELX. , 2008, Acta crystallographica. Section A, Foundations of crystallography.

[32]  R. Parr.  Density-functional theory of atoms and molecules , 1989 .