Gigantic Magnetic Field Effect on the Long-Lived Intermolecular Charge-Separated State Created at the Nonionic...

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.