American Chemical Society
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Controlling Excited State Localization in Bichromophoric Photosensitizers via the Bridging Group

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journal contribution
posted on 2024-03-04, 22:24 authored by Georgina E. Shillito, Dan Preston, James D. Crowley, Pawel Wagner, Samuel J. Harris, Keith C. Gordon, Stephan Kupfer
A series of photosensitizers comprised of both an inorganic and an organic chromophore are investigated in a joint synthetic, spectroscopic, and theoretical study. This bichromophoric design strategy provides a means by which to significantly increase the excited state lifetime by isolating the excited state away from the metal center following intersystem crossing. A variable bridging group is incorporated between the donor and acceptor units of the organic chromophore, and its influence on the excited state properties is explored. The Franck–Condon (FC) photophysics and subsequent excited state relaxation pathways are investigated with a suite of steady-state and time-resolved spectroscopic techniques in combination with scalar-relativistic quantum chemical calculations. It is demonstrated that the presence of an electronically conducting bridge that facilitates donor–acceptor communication is vital to generate long-lived (32 to 45 μs), charge-separated states with organic character. In contrast, when an insulating 1,2,3-triazole bridge is used, the excited state properties are dominated by the inorganic chromophore, with a notably shorter lifetime of 60 ns. This method of extending the lifetime of a molecular photosensitizer is, therefore, of interest for a range of molecular electronic devices and photophysical applications.