Ryota Inoue

Efficient Synthesis, Structure, and Complexation Studies of Electron-Donating Thiacalix[n]dithienothiophene†

A series of thiacalix[n]dithiothiophenes (n=4-10) was prepared by a facile method and X-ray analysis was used to determine the molecular structures of square- (4-mer) and pentagonal-shaped macrocycles (5-mer). In the cyclic voltammograms, reversible multielectron redox processes, which are due to electronic delocalization, were observed at low oxidation potentials. The cyclic 4-mer acted as a Janus-head cavitand for two C60 molecules, whereas the 5- and 6-mer formed stable 1:1 complexes with C60 u2009.

Straightforward Synthesis, Electrochemical Properties, and Gel Formation of Thiacalix[n]thiophenes

A facile synthetic approach toward thiacalix[n]thiophene homologues (n=4-6) is presented herein. Pd-catalyzed coupling of 2,5-dibromothiophene derivatives with stannyl sulfide gave various thiacalix[n]thiophenes in good yields. The optical and electrochemical properties of the produced cavitands were investigated. Furthermore, gelation was observed in some solvents.

Selenacalix[4]dithienothiophene: Synthesis, Structure, and Complexation of a Cyclic Tetramer of Selenide-Bridging Dithienothiophene

An efficient cyclization toward a cyclic tetramer of dithienothiophene (DTT) linked by divalent selenium atoms has been developed via palladium-catalyzed coupling reaction of (nBu3 Sn)2 Se. X-ray analysis revealed its highly symmetrical structure had an alternate arrangement of DTT units. There are several Se⋅⋅⋅π interactions forming a supramolecular network leading to large void channel space. The cyclic tetramer possesses moderate electron-donating ability. Furthermore, the cyclic tetramer undergoes complexation with C60 in a 1:2 ratio in the solid state to give a highly symmetrical three-dimensional array of C60 .