Nature of halogen-centered intermolecular interactions in crystal growth and design: Fluorine-centered interactions in dimers in crystalline hexafluoropropylene as a prototype.

摘要: The wide occurrence of halogen-centered noncovalent interactions in crystal growth and design prompted this study, which includes a mini review recent advances the field. Particular emphasis is placed on providing compelling theoretical evidence formation these between sites positive electrostatic potential, as well negative localized surfaces bound fluorine atoms prototypical system, hexafluoropropylene (C3 F6 ), upon its interaction with another same molecule to form )2 dimers. existence σ- π-hole shown for stable Even so, weakly locally responsible holding molecular fragments together cannot should not be overlooked since they are partly determining overall geometry crystal. results combined quantum theory molecules, surface reduced density gradient analyses showed that latter do indeed play role stability crystalline C3 itself A symmetry adapted perturbation energy decomposition analysis leads conclusion great majority dimers examined consequence dispersion (and electrostatics), nonnegligible contribution from polarization, competes an exchange repulsion component determine equilibrium geometries. In few structures dimer, found serve six-center five-bond donor/acceptor, carbon other systems (Malischewski Seppelt, Angew. Chem. Int. Ed. 2017, 56, 368). © 2019 Wiley Periodicals, Inc.