Solvent-modulated proton-coupled electron transfer in an iridium complex with an ESIPT ligand

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Proton-coupled electron transfer (PCET), an essential process in nature with a well-known example of photosynthesis, has recently been employed in metal complexes to improve the energy conversion efficiency; however, a profound understanding of the mechanism of PCET in metal complexes is still lacking. In this study, we synthesized cyclometalated Ir complexes strategically designed to exploit the excited-state intramolecular proton transfer (ESIPT) of the ancillary ligand and studied their photoinduced PCET in both aprotic and protic solvent environments using femtosecond transient absorption spectroscopy and density functional theory (DFT) and time-dependent DFT calculations. The data reveal solvent-modulated PCET, where charge transfer follows proton transfer in an aprotic solvent and the temporal order of charge transfer and proton transfer is reversed in a protic solvent. In the former case, ESIPT from the enol form to the keto form, which precedes the charge transfer from Ir to the ESIPT ligand, improves the efficiency of metal-to-ligand charge transfer. This finding demonstrates the potential to control the PCET reaction in the desired direction and the efficiency of charge transfer by simply perturbing the external hydrogen-bonding network with the solvent.
Publisher
ROYAL SOC CHEMISTRY
Issue Date
2022-03
Language
English
Article Type
Article
Citation

CHEMICAL SCIENCE, v.13, no.13, pp.3809 - 3818

ISSN
2041-6520
DOI
10.1039/d1sc07250a
URI
http://hdl.handle.net/10203/292758
Appears in Collection
CH-Journal Papers(저널논문)
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