Photodriven electron-transfer dynamics in a series of heteroleptic Cu(I)–anthraquinone dyads

Phelan, Brian T.; Xie, Zhu-Lin; Liu, Xiaolin; Li, Xiaosong; Mulfort, Karen L.; Chen, Lin X.

doi:10.1063/5.0188245

Title: Photodriven electron-transfer dynamics in a series of heteroleptic Cu(I)–anthraquinone dyads

Journal Article · 14 April 2024 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/5.0188245 · OSTI ID:2497724

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Argonne National Laboratory (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States); Florida Atlantic Univ., Boca Raton, FL (United States)
Univ. of Washington, Seattle, WA (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)

Solar fuels catalysis is a promising route to efficiently harvesting, storing, and utilizing abundant solar energy. To achieve this promise, however, molecular systems must be designed with sustainable components that can balance numerous photophysical and chemical processes. To that end, here we report on the structural and photophysical characterization of a series of Cu(I)–anthraquinone-based electron donor–acceptor dyads. The dyads utilized a heteroleptic Cu(I) bis-diimine architecture with a copper(I) bis-phenanthroline chromophore donor and anthraquinone electron acceptor. We characterized the structures of the complexes using x-ray crystallography and density functional theory calculations and the photophysical properties via resonance Raman and optical transient absorption spectroscopy. The calculations and resonance Raman spectroscopy revealed that excitation of the Cu(I) metal-to-ligand charge-transfer (MLCT) transition transfers the electron to a delocalized ligand orbital. The optical transient absorption spectroscopy demonstrated that each dyad formed the oxidized copper–reduced anthraquinone charge-separated state. Unlike most Cu(I) bis-phenanthroline complexes where increasingly bulky substituents on the phenanthroline ligands lead to longer MLCT excited-state lifetimes, here, we observe a decrease in the long-lived charge-separated state lifetime with increasing steric bulk. The charge-separated state lifetimes were best explained in the context of electron-transfer theory rather than with the energy gap law, which is typical for MLCT excited states, despite the complete conjugation between the phenanthroline and anthraquinone moieties.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2497724

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 14 Vol. 160; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Photodriven electron-transfer dynamics in a series of heteroleptic Cu(I)–anthraquinone dyads

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