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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.

Citation

Svante Hedström, Subhajyoti Chaudhuri, Nathan T La Porte, Benjamin Rudshteyn, Jose F Martinez, Michael R Wasielewski, Victor S Batista. Thousandfold Enhancement of Photoreduction Lifetime in Re(bpy)(CO)3 via Spin-Dependent Electron Transfer from a Perylenediimide Radical Anion Donor. Journal of the American Chemical Society. 2017 Nov 22;139(46):16466-16469


PMID: 29083146

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