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Dynamic dimer copper coordination redox shuttles

DOI: 10.1016/j.chempr.2021.10.017 DOI Help

Authors: Iacopo Benesperi (Uppsala University; Newcastle University) , Hannes Michaels (Uppsala University; Newcastle University) , Tomas Edvinsson (Uppsala University) , Michele Pavone (University of Naples Federico II) , Michael R. Probert (Newcastle University) , Paul Waddell (Newcastle University) , Ana Belén Muñoz-García (University of Naples Federico II) , Marina Freitag (Newcastle University; Uppsala University)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Chem , VOL 5

State: Published (Approved)
Published: November 2021
Diamond Proposal Number(s): 22240

Abstract: 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.

Journal Keywords: coordination chemistry; copper complex; redox chemistry; electrolytedye-sensitized solar cell; coordination complexes; redox mediators; solar cells; charge transfer; dye-sensitized solar cells; copper complexes; low recombination; sustainable materials

Diamond Keywords: Photovoltaics; Semiconductors

Subject Areas: Chemistry, Energy, Environment

Instruments: I19-Small Molecule Single Crystal Diffraction

Added On: 21/11/2021 16:31

Discipline Tags:

Molecular Complexes Physical Chemistry Earth Sciences & Environment Climate Change Energy Sustainable Energy Systems Chemistry

Technical Tags:

Diffraction Single Crystal X-ray Diffraction (SXRD)