Long-range dynamics in the photoexcited states of rigidly linked composite molecular systems

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Elucidation of the mechanisms for long-range dynamics is indispensable not only in understanding energy and electron transfer occurs in natural systems but also in designing systems that efficiently harvest light and generate long-lived charge-separated species. While much attention has been paid to the role of the superexchange mechanism in long-range interaction, most of studies have been carried out on linearly-linked molecular systems. In this work, we have studied, i) enhanced intersystem crossing process in a series of copper(II) porphyrin - free base porphyrin dimers linked via an aromatic spacer and ii) long-range singlet-singlet energy transfer of zinc(II) porphyrin - free base porphyrin dimers, which are linked linear or non-linear bridges. Spacer dependence of superexchange mediated excited-dynamics was discussed in rigidly linked donor-bridge-acceptor molecular systems, and it was found that molecular orbitals in the bridge part take an important role.