View : 130 Download: 0
Porphyrins fused with strongly electron-donating 1,3-dithiol-2-ylidene moieties: Redox control by metal cation complexation and anion binding
- Porphyrins fused with strongly electron-donating 1,3-dithiol-2-ylidene moieties: Redox control by metal cation complexation and anion binding
- Bill N.L.; Ishida M.; Bahring S.; Lim J.M.; Lee S.; Davis C.M.; Lynch V.M.; Nielsen K.A.; Jeppesen J.O.; Ohkubo K.; Fukuzumi S.; Kim D.; Sessler J.L.
- Ewha Authors
- Shunichi Fukuzumi
- SCOPUS Author ID
- Shunichi Fukuzumi
- Issue Date
- Journal Title
- Journal of the American Chemical Society
- Journal of the American Chemical Society vol. 135, no. 29, pp. 10852 - 10862
- SCIE; SCOPUS
- Document Type
- 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. © 2013 American Chemical Society.
- Appears in Collections:
- 자연과학대학 > 화학·나노과학전공 > Journal papers
- Files in This Item:
There are no files associated with this item.
- RIS (EndNote)
- XLS (Excel)
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.