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Dynamic dimer copper coordination redox shuttles

Lookup NU author(s): Dr Iacopo Benesperi, Hannes Michaels, Professor Mike ProbertORCiD, Dr Paul Waddell, Professor Marina FreitagORCiD

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Abstract

© 2021 Elsevier Inc. Conventional redox mediators based on metal coordination complexes undergo electron transfer through the change in oxidation state of the metal center. However, electron transfer kinetics are offset toward preferred oxidation states when preorganized ligands constrain the reorganization of the coordination sphere. In contrast, we report here on dimeric copper(II/I) redox couples, wherein the extent of oxidation/reduction of two metal centers dictates the dynamic formation of dimer and monomer complexes: the dimeric (Cu(I))2 transitions to monomers of Cu(II). The bis(thiazole/pyrrole)-bipyridine tetradentate ligands stabilize both oxidation states of the unique redox systems. The dynamic dimer redox mediators offer a viable two-electron redox mechanism to develop efficient hybrid solar cells through inhibited recombination and rapid charge transport. Density functional theory calculations reveal inner reorganization energies for single-electron transfer as low as 0.27 eV, marking the dimeric complexes superior redox systems over single complexes as liquid and potentially solid-state electrolytes.

Publication metadata

Author(s): Benesperi I, Michaels H, Edvinsson T, Pavone M, Probert MR, Waddell P, Munoz-Garcia AB, Freitag M

Publication type: Article

Publication status: Published

Journal: Chem

Year: 2022

Volume: 8

Issue: 2

Pages: 439-449

Print publication date: 10/02/2022

Online publication date: 16/11/2021

Acceptance date: 18/10/2021

ISSN (print): 2451-9308

ISSN (electronic): 2451-9294

Publisher: Cell Press

URL: https://doi.org/10.1016/j.chempr.2021.10.017

DOI: 10.1016/j.chempr.2021.10.017

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