%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