Magnetostructural Properties of Some Doubly-Bridged Phenoxido Copper(II) Complexes.

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作者:Massoud Salah S, Louka Febee R, Dial Madison T, Salem Nahed N M H, Fischer Roland C, Torvisco Ana, Mautner Franz A, Nakashima Kai, Handa Makoto, Mikuriya Masahiro
Three new tripod tetradentate phenolate-amines (H(2)L(1), H(2)L(4) and H(2)L(9)), together with seven more already related published ligands, were synthesized, and characterized. With these ligands, two new dinuclear doubly-bridged-phenoxido copper(II) complexes (3, 4), and six more complexes (1, 2, 5-8), a new trinuclear complex (9) with an alternative doubly-bridged-phenoxido and -methoxido, as well as the 1D polymer (10) were synthesized, and their molecular structures were characterized by spectroscopic methods and X-ray single crystal crystallography. The Cu(II) centers in these complexes exhibit distorted square-pyramidal arrangement in 1-4, mixed square pyramidal and square planar in 5, 6, and 9, and distorted octahedral (5+1) arrangements in 7 and 8. The temperature dependence magnetic susceptibility study over the temperature range 2-300 K revealed moderate-relatively strong antiferromagnetic coupling (AF) (|J| = 289-145 cm(-1)) in complexes 1-6, weak-moderate AF (|J| = 59 cm(-1)) in the trinuclear complex 9, but weak AF interactions (|J| = 3.6 & 4.6 cm(-1)) were obtained in 7 and 8. No correlation was found between the exchange coupling J and the geometrical structural parameters of the four-membered Cu(2)O(2) rings.

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