Supramolecular architecture of substituted tetraphenyl-carbo-benzenes from the energetic viewpoint

Svitlana V. Shishkina (1, 2) , Viktoriya V. Dyakonenko (1) , Oleg V. Shishkin (1, 2) , Valérie Maraval (3) , Rémi Chauvin (3, 4)

1 SSI - Institute for Single Crystals, National Academy of Science (NAS) of Ukraine
2 Department of Inorganic Chemistry, V. N. Karazin Kharkiv National University
3 LCC - Laboratoire de chimie de coordination
4 UT3 - Université Toulouse III - Paul Sabatier

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.

Mots clés: Carbocycles; Density functional calculations; Noncovalent interactions; pi interactions; Solid-state structures

Domaines: Chimie de coordination

Svitlana V. Shishkina, Viktoriya V. Dyakonenko, Oleg V. Shishkin, Valérie Maraval, Rémi Chauvin. Supramolecular architecture of substituted tetraphenyl-carbo-benzenes from the energetic viewpoint. ChemPhysChem, 2017, 18 (18), pp.2499-2508. ⟨10.1002/cphc.201700584⟩. ⟨hal-01939399⟩