%0 Generic %A Bill, Nathan L. %A Ishida, Masatoshi %A Bähring, Steffen %A Lim, Jong Min %A Lee, Sangsu %A Davis, Christina M. %A Lynch, Vincent M. %A Nielsen, Kent A. %A Jeppesen, Jan O. %A Ohkubo, Kei %A Fukuzumi, Shunichi %A Kim, Dongho %A Sessler, Jonathan L. %D 2016 %T Porphyrins Fused with Strongly Electron-Donating 1,3-Dithiol-2-ylidene Moieties: Redox Control by Metal Cation Complexation and Anion Binding %U https://acs.figshare.com/articles/dataset/Porphyrins_Fused_with_Strongly_Electron_Donating_1_3_Dithiol_2_ylidene_Moieties_Redox_Control_by_Metal_Cation_Complexation_and_Anion_Binding/2393506 %R 10.1021/ja404830y.s007 %2 https://ndownloader.figshare.com/files/4033198 %K metal complexes %K Br %K GM %K Cl %K Redox Control %K H 2TTFP ZnTTFP %K MTTFP %K Porphyrins Fused %K dithiole rings %K base compound %K Anion BindingA %K oxidation potentials %K base form %K electrochemical measurement %K tetrabutylammonium salts %K Augmented TPA values %K crystal %K binding %K Li %K Metal Cation Complexation %X 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 H2TTFP, 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 H2TTFP2+ (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 Zn2+ cation present in ZnTTFP. %I ACS Publications