Syntheses, structural, magnetic, and electron paramagnetic resonance studies of monobridged cyanide and azide dinuclear copper(II) complexes: antiferromagnetic superexchange interactions.

The reactions of Cu(ClO4)2 with NaCN and the ditopic ligands m-bis[bis(1-pyrazolyl)methyl]benzene (Lm) or m-bis[bis(3,5-dimethyl-1-pyrazolyl)methyl]benzene (Lm*) yield [Cu2(μ-CN)(μ-Lm)2](ClO4)3 (1) and [Cu2(μ-CN)(μ-Lm*)2](ClO4)3 (3). In both, the cyanide ligand is linearly bridged (μ-1,2) leading to a separation of the two copper(II) ions of ca. 5 Å. The geometry around copper(II) in these complexes is distorted trigonal bipyramidal with the cyanide group in an equatorial position. The reaction of [Cu2(μ-F)(μ-Lm)2](ClO4)3 and (CH3)3SiN3 yields [Cu2(μ-N3)(μ-Lm)2](ClO4)3 (2), where the azide adopts end-on (μ-1,1) coordination with a Cu-N-Cu angle of 138.0° and a distorted square pyramidal geometry about the copper(II) ions. Similar chemistry in the more sterically hindered Lm* system yielded only the coordination polymer [Cu2(μ-Lm*)(μ-N3)2(N3)2]. Attempts to prepare a dinuclear complex with a bridging iodide yield the copper(I) complex [Cu5(μ-I4)(μ-Lm*)2]I3. The complexes 1 and 3 show strong antiferromagnetic coupling, -J = 135 and 161 cm(-1), respectively. Electron paramagnetic resonance (EPR) studies coupled with density functional theory (DFT) calculations show that the exchange interaction is transmitted through the dz(2) and the bridging ligand s and px orbitals. High field EPR studies confirmed the dz(2) ground state of the copper(II) ions. Single-crystal high-field EPR has been able to definitively show that the signs of D and E are positive. The zero-field splitting is dominated by the anisotropic exchange interactions. Complex 2 has -J = 223 cm(-1) and DFT calculations indicate a predominantly d(x(2)-y(2)) ground state.