Synthesis, structure and properties of decakis(phenylthio)corannulene

摘要

Decakis(phenylthio)corannulene has been prepared from decachlorocorannulene by direct nucleophilic substitution; electronic structure properties and the X-ray crystal structure were determined and compared to predictions made by ab initio quantum chemical calculations.rnDecasubstitution of corannulene (1) reduces the depth of the bowl through steric effects around the rim, and tunes the electronic properties of the π system according to the nature of the substituents. Exhaustive over-chlorination/dechlorination of corannulene yields decachlorocorannulene (2), through which decamethyl (3), decapentynyl (4), decakis(alkylthio) and decakis(arylthio)-corannulenes. have been prepared. The electron diffraction structure of 2 as well as the crystal structure of 4 clearly display a shallower bowl, but as predicted computationally, about 50% of the bowl depth persists compared to 1 even when the steric repulsion of persubstitution reduces the bowl-inversion barrier from ca. 12 to ca. 1 kcal mol~(-1).