Nonadiabatic Charge Transfer within Photoexcited Nickel Porphyrins

Naumova, M.A. and Paveliuc, G. and Biednov, M. and Kubicek, K. and Kalinko, A. and Meng, J. and Liang, M. and Rahaman, A. and Abdellah, M. and Checchia, S. and Alves, Lima F. and Zalden, P. and Gawelda, W. and Bressler, C. and Geng, H. and Lin, W. and Liu, Y. and Zhao, Q. and Pan, Q. and Akter, M. and Kong, Q. and Retegan, M. and Gosztola, D.J. and Pápai, Mátyás Imre and Khakhulin, D. and Daku, M.L. and Zheng, K. and Canton, S.E. (2024) Nonadiabatic Charge Transfer within Photoexcited Nickel Porphyrins. JOURNAL OF PHYSICAL CHEMISTRY LETTERS, 15 (13). pp. 3627-3638. ISSN 1948-7185

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Abstract

Metalloporphyrins with open d-shell ions can drive biochemical energy cycles. However, their utilization in photoconversion is hampered by rapid deactivation. Mapping the relaxation pathways is essential for elaborating strategies that can favorably alter the charge dynamics through chemical design and photoexcitation conditions. Here, we combine transient optical absorption spectroscopy and transient X-ray emission spectroscopy with femtosecond resolution to probe directly the coupled electronic and spin dynamics within a photoexcited nickel porphyrin in solution. Measurements and calculations reveal that a state with charge-transfer character mediates the formation of the thermalized excited state, thereby advancing the description of the photocycle for this important representative molecule. More generally, establishing that intramolecular charge-transfer steps play a role in the photoinduced dynamics of metalloporphyrins with open d-shell sets a conceptual ground for their development as building blocks capable of boosting nonadiabatic photoconversion in functional architectures through “hot” charge transfer down to the attosecond time scale.

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