Molecular squares of NiII and CuII: ferromagnetic exchange interaction mediated by syn-anti carboxylate-bridging

Arora, Himanshu ; Lloret, Francesc ; Mukherjee, Rabindra Nath (2009) Molecular squares of NiII and CuII: ferromagnetic exchange interaction mediated by syn-anti carboxylate-bridging Dalton Transactions (44). pp. 9759-9769. ISSN 1477-9226

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Official URL: http://pubs.rsc.org/en/Content/ArticleLanding/2009...

Related URL: http://dx.doi.org/10.1039/B905463D

Abstract

The synthesis of four discrete tetranuclear complexes {[NiII(L2)][ClO4]}4·MeCN (1), {[CuII(L1)(O3SCF3)]}4·H2O (2), {[CuII(L3)(OClO3)]}4·MeCN (3) and {[CuII(L4)][ClO4]}4·3MeCN·4H2O (4), supported by a closely similar group of carboxylate-appended (2-pyridyl)alkylamine ligands [L1(-): 3-[N-methyl-{2-(pyridin-2-yl)ethyl}amino]propionate; L2(-): 3-[(2-(pyridin-2-yl)ethyl){2-(pyridin-2-yl)methyl}amino]propionate; L3(-): 3-[N-isopropyl-{2-(pyridin-2-yl)methyl}amino]propionate and L4(2-): 3-[N-{2-(pyridin-2-yl)methyl}amino]-bis(propionate)] is described. Structural characterization reveals that each NiII centre in 1 has square-pyramidal NiIIN3O2 coordination and each CuII centre in 2-4 has distorted square-pyramidal CuIIN2O3 coordination, utilizing three N and one carboxylate O in 1 and two N and carboxylate O (one in 2 and 3; two in 4) of the ligand and the fifth/fourth coordination is provided by an oxygen atom belonging to the carboxylate group of an adjacent molecule. A CF3SO3- or a ClO4- ion provides an O coordination in 2 and 3, respectively. Temperature-dependent magnetic studies reveal the existence of ferromagnetic exchange interaction in each case, due to the presence of equatorial-equatorial syn-anti carboxylate bridge between MII centres.

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