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Paper | Special issue | Vol 95, No. 1, 2017, pp.380-389
Published online, 22nd December, 2016
DOI: 10.3987/COM-16-S(S)29
π-Expanded Cyclic Oligothiophene 12-Mers as Semishape-Persistent Macrocycles

Mika Imamura, Hideyuki Shimizu, Jun Yamakawa, Hiroyuki Otani, Tohru Nishinaga, and Masahiko Iyoda*

*Department of Chemistry, Graduate School of Science and Engineering, Tokyo Metropolitan University, Hachioji, Tokyo 192-0397, Japan

Abstract

π-Expanded macrocyclic oligothiophene 12-mer E,E-12T10A, 18-mer E,E,E-18T15A, and 24-mer E,E,E,E-24T20A composed of thienylene, ethynylene, and vinylene moieties were synthesized in good total yield by the McMurry coupling reaction of dialdehyde 1. E,E-12T10A was converted to cyclo[12](3,4-dibutyl-2,5-thienylene-ethynylene) 12T12A in 20% yield by bromination-dehydrobromination procedure. Furthermore, the synthesis of 12T12A was carried out by using double elimination procedure starting from the sulfone dianion 22- and dialdehyde 1. The crystal structure of E,E-12T10A was determined by X-ray analysis. In the solid state, macrocyclic oligothiophenes formed nanostructured polymorphs such as single crystals, petal-shaped structure, and chained lumps depending on the ring size.