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Mixed-Valent Tetracopper Disulfides Supported by a 1,8-Naphthyridine-Based Ligand: Models for Electronic
Matthew S See1,2, Oscar Gonzalez1, Paul Clark1
1Department of Chemistry, University of California Berkeley, Berkeley, California 94720, United States.
Abstract:
Reaction of a dicopper(I) acetonitrile complex (1) with elemental sulfur resulted in a formally 2CuI:2CuII tetracopper mixed-valent μ-disulfide complex (2). Stoichiometric reduction (with cobaltocene) or oxidation (with Ag[NTf2], [NTf2] = bis(trifluoromethane)sulfonimide) result in reversible interconversions between complex 2, a formally 3CuI:CuII species (3), and a 4CuI species (4). Given the isostructural nature of these complexes, the electronic communication between the metal centers of 2, 3, and 4 were spectroscopically investigated with UV-vis and EPR techniques, revealing the relative delocalization of electron holes on all four copper centers of 2 and 3. Variable temperature magnetometry of 2, 3, and 4 also reveal antiferromagnetic, ferromagnetic, and temperature-independent paramagnetic behavior, respectively. The formally spin-paired (d10)4 complex 4 displays unusual magnetic behavior, exhibiting field-induced paramagnetism.
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