For
realization of low-cost organic photon-energy conversion, the
supramolecular approach has been a focus of attention as a counter
approach to precise synthesis of covalently linked donor (D)–acceptor
(A) molecules. Here we report photogeneration of a long-lived (∼3
μs) intermolecular charge-separated (CS) state of metal porphyrins
(D) and an alkyl viologen (A) at an interface of a vesicle membrane
formed by self-assembly of nonionic surfactant and cholesterol molecules.
The yield of escaped free radicals is negligibly low as in the case
of CS states in covalently linked D–A systems. Furthermore,
the transient concentration of the CS state dramatically increases
by ∼100% upon application of a magnetic field of 250 mT at
room temperature. The simulation of the spin dynamics of the CS state
indicates that fast (∼107 s–1)
spin-selective recombination and slow (105–106 s–1) dissociation–re-encounter dynamics
are the key processes for the long CS-state lifetime and the gigantic
magnetic field effect. It has turned out that such dynamics are sharply
dependent on temperature and alkyl chain length of the viologen. The
present results would lead to the development of future materials
for light energy conversion, drug delivery, and microscopic bioprobes.