Porphyrins fused with strongly electron-donating 1,3-dithiol-2-ylidene moieties: Redox control by metal cation complexation and anion binding

Nathan L. Bill, Masatoshi Ishida, Steffen Bähring, Jong Min Lim, Sangsu Lee, Christina M. Davis, Vincent M. Lynch, Kent A. Nielsen, Jan O. Jeppesen, Kei Ohkubo, Shunichi Fukuzumi, Dongho Kim, Jonathan L. Sessler

研究成果: ジャーナルへの寄稿学術誌査読

50 被引用数 (Scopus)

抄録

A new class of redox-active free base and metalloporphyrins fused with the 1,3-dithiol-2-ylidene subunits present in tetrathiafulvalene, termed MTTFP (M = H2, Cu, Ni, Zn), have been prepared and characterized. The strong electron-donating properties of MTTFP were probed by electrochemical measurement and demonstrated that oxidation potentials can be tuned by metalation of the free base form, H2TTFP. X-ray crystal structures of H 2TTFP, ZnTTFP, and CuTTFP revealed that a severe saddle-shape distortion was observed with the dithiole rings bent out of the plane toward one another in the neutral form. In contrast, the structure of the two-electron oxidized species (CuTFFP2+) is planar, corresponding to a change from a nonaromatic to aromatic structure upon oxidation. A relatively large two-photon absorption (TPA) cross-section value of H2TTFP 2+ (1200 GM) was obtained for the free base compound, a value that is much higher than those typically seen for porphyrins (<100 GM). Augmented TPA values for the metal complexes were also seen. The strong electron-donating ability of ZnTTFP was further enhanced by binding of Cl- and Br - as revealed by thermal electron-transfer between ZnTTFP and Li +-encapsulated C60 (Li+@C60) in benzonitrile, which was "switched on" by the addition of either Cl- or Br- (as the tetrabutylammonium salts). The X-ray crystal structure of Cl--bound ZnTTFP was determined and provided support for the strong binding between the Cl- anion and the Zn 2+ cation present in ZnTTFP.

本文言語英語
ページ(範囲)10852-10862
ページ数11
ジャーナルJournal of the American Chemical Society
135
29
DOI
出版ステータス出版済み - 7月 24 2013
外部発表はい

!!!All Science Journal Classification (ASJC) codes

  • 触媒
  • 化学 (全般)
  • 生化学
  • コロイド化学および表面化学

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