Ligand−structure effects on N−heterocyclic carbene rhenium photo− and electrocatalysts of CO2 reduction

Kearney, L., Brandon, M. P., Coleman, A., Chippindale, A. M. ORCID: https://orcid.org/0000-0002-5918-8701, Hartl, F. ORCID: https://orcid.org/0000-0002-7013-5360, Lalrempuia, R., Pižl, M. and Pryce, M. T. (2023) Ligand−structure effects on N−heterocyclic carbene rhenium photo− and electrocatalysts of CO2 reduction. Molecules, 28 (10). 4149. ISSN 1420-3049 doi: 10.3390/molecules28104149

Abstract/Summary

Three novel rhenium N−heterocyclic carbene complexes, [Re]−NHC−1−3 ([Re] = fac−Re(CO)3Br), were synthesized and characterized using a range of spectroscopic techniques. Photophysical, electrochemical and spectroelectrochemical studies were carried out to probe the properties of these organometallic compounds. Re−NHC−1 and Re−NHC−2 bear a phenanthrene backbone on an imidazole (NHC) ring, coordinating to Re by both the carbene C and a pyridyl group attached to one of the imidazole nitrogen atoms. Re−NHC−2 differs from Re−NHC−1 by replacing N−H with an N−benzyl group as the second substituent on imidazole. The replacement of the phenanthrene backbone in Re−NHC−2 with the larger pyrene gives Re−NHC−3. The two−electron electrochemical reductions of Re−NHC−2 and Re−NHC−3 result in the formation of the five−coordinate anions that are capable of electrocatalytic CO2 reduction. These catalysts are formed first at the initial cathodic wave R1, and then, ultimately, via the reduction of Re−Re bound dimer intermediates at the second cathodic wave R2. All three Re−NHC−1−3 complexes are active photocatalysts for the transformation of CO2 to CO, with the most photostable complex, Re−NHC−3, being the most effective for this conversion. Re−NHC−1 and Re−NHC−2 afforded modest CO turnover numbers (TONs), following irradiation at 355 nm, but were inactive at the longer irradiation wavelength of 470 nm. In contrast, Re−NHC−3, when photoexcited at 470 nm, yielded the highest TON in this study, but remained inactive at 355 nm. The luminescence spectrum of Re−NHC−3 is red−shifted compared to those of Re−NHC−1 and Re−NHC−2, and previously reported similar [Re]−NHC complexes. This observation, together with TD−DFT calculations, suggests that the nature of the lowest−energy optical excitation for Re−NHC−3 has π→π*(NHC−pyrene) and dπ(Re)→π*(pyridine) (IL/MLCT) character. The stability and superior photocatalytic performance of Re−NHC−3 are attributed to the extended conjugation of the π−electron system, leading to the beneficial modulation of the strongly electron−donating tendency of the NHC group.

Item Type	Article
URI	https://reading-clone.eprints-hosting.org/id/eprint/111992
Identification Number/DOI	10.3390/molecules28104149
Refereed	Yes
Divisions	Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry Interdisciplinary centres and themes > Chemical Analysis Facility (CAF) > Xray (CAF)
Publisher	MDPI
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