3 years ago

Thousandfold Enhancement of Photoreduction Lifetime in Re(bpy)(CO)3 via Spin-Dependent Electron Transfer from a Perylenediimide Radical Anion Donor

Thousandfold Enhancement of Photoreduction Lifetime in Re(bpy)(CO)3 via Spin-Dependent Electron Transfer from a Perylenediimide Radical Anion Donor
Benjamin Rudshteyn, Nathan T. La Porte, Svante Hedström, Victor S. Batista, Jose F. Martinez, Subhajyoti Chaudhuri, Michael R. Wasielewski
Spin-dependent intramolecular electron transfer is revealed in the ReI(CO)3(py)(bpy-Ph)–perylenediimide radical anion (ReI-bpy–PDI–•) dyad, a prototype model system for artificial photosynthesis. Quantum chemical calculations and ultrafast transient absorption spectroscopy experiments demonstrate that selective photoexcitation of ReI-bpy results in electron transfer from PDI–• to ReI-bpy, forming two distinct charge-shifted states. One is an overall doublet whose return to the ground state is spin-allowed. The other, high-spin quartet state, persists for 67 ns due to spin-forbidden back-electron transfer, constituting a more than thousandfold lifetime improvement compared to the low-spin state. Exploiting this spin dependency holds promise for artificial photosynthetic systems requiring long-lived reduced states to perform multi-electron chemistry.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b09438

DOI: 10.1021/jacs.7b09438

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