Ferromagnetic interaction in an asymmetric end-to-end azido double-bridged copper(II) dinuclear complex: A combined structure, magnetic, polarized neutron diffraction and theoretical study

A new end-to-end azido double-bridged copper(II) complex [Cu2L2(N-3)(2)] (1) was synthesized and characterized (L=1,1,1-trifluoro-7-(dimethylamino)-4-methyl-5-aza-3-hepten- 2-onato). Despite the rather long Cu-Cu distance (5.105(1) angstrom), the magnetic interaction is ferromagnetic with J = +16 cm(-1) (H=-JS(1)S(2)), a value that has been confirmed by DFT and high-level correlated ab initio calculations. The spin distribution was studied by using the results from polarized neutron diffraction. This is the first such study on an end-to-end system. The experimental spin density was found to be localized mainly on the copper(II) ions, with a small degree of delocalization on the ligand (L) and terminal azido nitrogens. There was zero delocalization on the central nitrogen, in agreement with DFT calculations. Such a picture corresponds to an important contribution of the d(x2-y2) orbital and a small population of the d(z2) orbital, in agreement with our calculations. Based on a correlated wavefunction analysis, the ferromagnetic behavior results from a dominant double spin polarization contribution and vanishingly small ionic forms.