title: Synthesis of thieno-bridged porphyrins: changing the antiaromatic contribution by the direction of the thiophene ring.
abstract: Two types of thieno-bridged porphyrins were synthesized by incorporating a thiophene group across their meso and β positions with different directions of the thiophene ring to investigate the aromaticity of these porphyrins with extended π-systems. The 2,3-thieno-bridged porphyrin showed a larger antiaromatic contribution than did the 3,4-thieno-bridged porphyrin. In the former, the antiaromatic contribution is based on a 20-π-electron conjugated circuit. The two thieno-bridged porphyrins were characterized by calculations of nucleus-independent chemical shift and anisotropy of the induced current density as well as by X-ray crystallography, NMR spectroscopy, UV-vis-NIR absorption spectroscopy, electrochemical studies, time-resolved excited-state analysis, and two-photon absorption cross section measurements. Chemical derivatization of the 2,3-thieno-bridged porphyrin was also demonstrated.
authors.affiliation: Department of Chemistry, School of Science, The University of Tokyo, Hongo, Bunkyo-Ku, Tokyo 113-0033, Japan.
authors.forename: Yusuke
authors.initials: Y
authors.lastname: Mitsushige
authors.forename: Shigeru
authors.initials: S
authors.lastname: Yamaguchi
authors.forename: Byung Sun
authors.initials: BS
authors.lastname: Lee
authors.forename: Young Mo
authors.initials: YM
authors.lastname: Sung
authors.forename: Susanne
authors.initials: S
authors.lastname: Kuhri
authors.forename: Christoph A
authors.initials: CA
authors.lastname: Schierl
authors.forename: Dirk M
authors.initials: DM
authors.lastname: Guldi
authors.forename: Dongho
authors.initials: D
authors.lastname: Kim
authors.forename: Yutaka
authors.initials: Y
authors.lastname: Matsuo