[CuII{(LISQ)˙−}2] (H2L: thioether-appended o-aminophenol ligand) monocation triggers change in donor site from N2O2 to N2O(2)S and valence-tautomerism

Abstract

Using a potentially tridentate o-aminophenol-based redox-active ligand H₂L¹ (2-[2-(benzylthio)phenylamino]-4,6-di-tert-butylphenol) in its deprotonated form, [Cu(L¹)₂] has been synthesized and crystallized as [Cu^II(L¹)₂]·CH₂Cl₂ (1·CH₂Cl₂). A cyclic voltammetry experiment (in CH₂Cl₂; V vs. SCE (saturated calomel electrode)) on 1·CH₂Cl₂ exhibits two oxidative (E¹_1/2 = 0.20 V (peak-to-peak separation, ΔE_p = 100 mV) and E²_1/2 = 0.90 V (ΔE_p = 140 mV)) and two reductive (E¹_1/2 = −0.52 V (ΔE_p = 110 mV) and E²_1/2 = −0.92 V (ΔE_p = 120 mV)) responses. Upon oxidation using a stoichiometric amount of [Fe^III(η⁵-C₅H₅)₂](PF₆), 1·CH₂Cl₂ yielded [Cu(L¹)₂](PF₆) (2). Structural analysis (100 K) reveals that 1·CH₂Cl₂ is a four-coordinate bis(iminosemiquinonato)copper(II) complex (CuN₂O₂ coordination), and that the thioethers remain uncoordinated. The twisted geometry of 1 (distorted tetrahedral) results in considerable changes in the electronic structure, compared to well-known square-planar analogues. Crystallographic analysis of 2 both at 100 K and at 293 K reveals that it is effectively a four-coordinate complex with a CuN₂OS coordination; however, a substantial interaction with the other phenolate O is observed. The metal–ligand bond distances and metric parameters associated with the o-aminophenolate rings indicate a valence-tautomeric (VT) equilibrium involving monocationic (iminosemiquinonato)(iminoquinone)copper(II) and bis(iminoquinone)copper(I). Complex 1·CH₂Cl₂ is a three-spin system and a magnetic study (4–300 K) established that it has a S = 1/2 ground-state, owing to the strong antiferromagnetic coupling between the unpaired spin of the copper(II) and the iminosemiquinonate(1−) π-radical anion. Electron paramagnetic resonance (EPR) spectral studies corroborate this result. Complex 2 is diamagnetic and the existence of VT in 2 was probed using variable-temperature (248–328 K) ¹H NMR and EPR (100–298 K) spectral measurements and X-ray photoelectron spectroscopic studies at 298 K. Remarkably, modification of the well-studied 2-anilino-4,6-di-tert-butylphenol by incorporation of a benzylthioether arm leads to the occurrence of VT in 2. The electronic structure of 1·CH₂Cl₂ and 2 has been assigned using density functional theory (DFT) calculations at the B3LYP-D3 level of theory. Time-dependent (TD)-DFT calculations have been performed to elucidate the origin of the observed UV-VIS-NIR absorptions.