View : 35 Download: 0

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

Title
Porphyrins fused with strongly electron-donating 1,3-dithiol-2-ylidene moieties: Redox control by metal cation complexation and anion binding
Authors
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 Fukuzumiscopus
Issue Date
2013
Journal Title
Journal of the American Chemical Society
ISSN
0002-7863JCR Link
Citation
vol. 135, no. 29, pp. 10852 - 10862
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
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.
DOI
10.1021/ja404830y
Appears in Collections:
자연과학대학 > 화학·나노과학전공 > Journal papers
Files in This Item:
There are no files associated with this item.
Export
RIS (EndNote)
XLS (Excel)
XML


qrcode

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.

BROWSE