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Updated: May 31, 2026
Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
Tale of a twist: magnetic and optical switching in copper(II) semiquinone complexes
Pratik Verma1, John Weir, Liviu Mirica
1Department of Chemistry, Stanford University, Stanford, California 94305, USA.
Abstract:
An intermediate (C) that is observed in both phenol hydroxylation and catechol oxidation with the side-on peroxide species [Cu(2)O(2)(DBED)(2)](2+) (DBED = N(1),N(2)-di-tert-butylethane-1,2-diamine) is identified as a copper(II) semiquinone species ([1](+)) through independent synthesis and characterization. The reaction of the redox-active 3,5-di-tert-butylquinone ligand with [(DBED)Cu(I)(MeCN)](+) yields a copper(II) semiquinone [1](+) complex with a singlet ground state and an intense purple chromophore (ε(580) ~ 3500 M(-1) cm(-1)). All other copper(II) semiquinone complexes characterized to date are paramagnetic and weakly colored (ε(800) ~ 500 M(-1) cm(-1)). Antiferromagnetic coupling between the Cu(II) center and the semiquinone radical in [1](+) is characterized by paramagnetic (1)H NMR and SQUID magnetometry. Comparative X-ray crystal structures along with density functional theory calculations correlate the geometric structures of copper(II) semiquinone complexes with their magnetic and optical properties. The unique observable properties of [1](+) originate from an increase in the overlap of the Cu 3d and semiquinone π orbitals resulting from a large rhombic distortion in the structure with a twist of 51°, attributable to the large isotropic demands of the tert-butyl substituents of the DBED ligand. Independent characterization of [1](+) allows the spectroscopic yields of intermediate C to be quantified in this intriguing hydroxylation reaction.
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