A R T I C L E S
Honda et al.
duced by photoinduced electron transfer.25 Thus, a new strategy
to construct stable supramolecular donor-acceptor systems is
required for further development of supramolecular photofunc-
tional devices.
Another characteristic of porphyrin, especially for free-base
porphyrins (H2P), is the protonation of the pyrroric nitrogen
atoms of the porphyrin ring under acidic conditions to produce
diprotonated porphyrin dications (H4P2+). However, the research
on protonated porphyrins has been limited largely to the
spectroscopic measurements under strongly acidic conditions
because of the low basicity of commonly used planar
porphyrins.26-32 We have developed supramolecular assemblies
composed of diprotonated saddle-distorted dodecaphenylpor-
phyrin (H4DPP2+) based on the high basicity of H2DPP derived
from its deformed structure.33-35 H4DPP2+ forms hydrogen
bonding among the N-H protons of porphyrin and counteran-
ions, such as chloride and carboxylate.33-35 The H4DPP2+ has
been revealed to act as an electron acceptor exhibiting a high
reduction potential comparable to those of fullerenes36 and
quinones,37 whereas free-base porphyrins have normally been
used as an electron donor.
A combination of a variety of electron donors with carboxyl
groups acting as hydrogen-bonding sites with H4DPP2+ would
allow systematic studies on structure and photoinduced electron-
transfer dynamics of porphyrin-based electron donor-acceptor
supramolecules. We report herein the construction of stable
supramolecules composed of H4DPP2+ and electron-donor
molecules bearing the carboxylate group in a polar solvent
(Scheme 1) and photoinduced electron-transfer dynamics ex-
amined by laser flash photolysis and analyzed in light of the
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