Porphyrins Fused with Strongly Electron-Donating 1,3-Dithiol-2-ylidene Moieties: Redox Control by Metal Cation Complexation and Anion Binding

摘要

A new class of redox-active free base and metalloporphyrins fused with the l,3-dithiol-2-ylidene subunits present in tetrathiafulvalene, termed MTTFP (M = H_2, 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, H_2TTFP. 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 (CuTFFP~(2+)) 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 H_2TTFP~(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 Clˉ and Brˉ as revealed by thermal electron-transfer between ZnTTFP and Li+-encapsulated C_(60) (Li+@C_(60)) in benzonitrile, which was "switched on" by the addition of either Clˉ or Brˉ (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.