Intra- and Intermolecular Charge-Transfer Dynamics of Carbene–Metal–Amide Photosensitizers. Kellogg, M. S., Mencke, A. R., Muniz, C. N., Nattikallungal, T. A., Cardoso-Delgado, F., Baluyot-Reyes, N., Sewell, M., Bird, M. J., Bradforth, S. E., & Thompson, M. E. The Journal of Physical Chemistry C, 128(16):6621-6635, 2024. 
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Paper doi abstract bibtex 3 downloads A series of steady-state and time-resolved spectroscopies were performed on a set of eight carbene–metal–amide (cMa) complexes, where M = Cu and Au, that have been used as photosensitizers for photosensitized electrocatalytic reactions. Using ps-to-ns and ns-to-ms transient absorption spectroscopies (psTA and nsTA, respectively), the excited-state kinetics from light absorption, intersystem crossing (ISC), and eventually intermolecular charge transfer were thoroughly characterized. Using time-correlated single photon counting (TCSPC) and psTA with a thermally activated delayed fluorescence (TADF) model, the variation in intersystem crossing (ISC), (S1 → T1) rates (∼3–120 × 109 s–1), and ΔEST values (73–115 meV) for these compounds were fully characterized, reflecting systematic changes to the carbene, carbazole, and metal. The psTA additionally revealed an early time relaxation (rate ∼0.2–0.8 × 1012 s–1) attributed to solvent relaxation and vibrational cooling. The nsTA experiments for a gold-based cMa complex demonstrated efficient intermolecular charge transfer from the excited cMa to an electron acceptor. Pulse radiolysis and bulk electrolysis experiments allowed us to identify the character of the transient excited states as ligand–ligand charge transfer as well as the spectroscopic signature of oxidized and reduced forms of the cMa photosensitizer.
@article{doi:10.1021/acs.jpcc.4c01994,
author = {Kellogg, Michael S. and Mencke, Austin R. and Muniz, Collin N. and Nattikallungal, Thabassum A. and Cardoso-Delgado, Fabiola and Baluyot-Reyes, Nina and Sewell, Marielle and Bird, Matthew J. and Bradforth, Stephen E. and Thompson, Mark E.},
title = {Intra- and Intermolecular Charge-Transfer Dynamics of Carbene–Metal–Amide Photosensitizers},
journal = {The Journal of Physical Chemistry C},
volume = {128},
number = {16},
pages = {6621-6635},
year = {2024},
doi = {10.1021/acs.jpcc.4c01994},
URL = {https://doi.org/10.1021/acs.jpcc.4c01994},
eprint = {https://doi.org/10.1021/acs.jpcc.4c01994},
abstract={A series of steady-state and time-resolved spectroscopies were performed on a set of eight carbene–metal–amide (cMa) complexes, where M = Cu and Au, that have been used as photosensitizers for photosensitized electrocatalytic reactions. Using ps-to-ns and ns-to-ms transient absorption spectroscopies (psTA and nsTA, respectively), the excited-state kinetics from light absorption, intersystem crossing (ISC), and eventually intermolecular charge transfer were thoroughly characterized. Using time-correlated single photon counting (TCSPC) and psTA with a thermally activated delayed fluorescence (TADF) model, the variation in intersystem crossing (ISC), (S1 → T1) rates (∼3–120 × 109 s–1), and ΔEST values (73–115 meV) for these compounds were fully characterized, reflecting systematic changes to the carbene, carbazole, and metal. The psTA additionally revealed an early time relaxation (rate ∼0.2–0.8 × 1012 s–1) attributed to solvent relaxation and vibrational cooling. The nsTA experiments for a gold-based cMa complex demonstrated efficient intermolecular charge transfer from the excited cMa to an electron acceptor. Pulse radiolysis and bulk electrolysis experiments allowed us to identify the character of the transient excited states as ligand–ligand charge transfer as well as the spectroscopic signature of oxidized and reduced forms of the cMa photosensitizer.},
bibbase_note={<img src="https://pubs.acs.org/cms/10.1021/acs.jpcc.4c01994/asset/images/medium/jp4c01994_0012.gif">}
}
Downloads: 3
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