ja404830y_si_007.cif (37.8 kB)
Porphyrins Fused with Strongly Electron-Donating 1,3-Dithiol-2-ylidene Moieties: Redox Control by Metal Cation Complexation and Anion Binding
dataset
posted on 2016-02-19, 02:52 authored by 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. SesslerA 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.