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

Himanshu Arora, Francesc Lloret, Rabindranath Mukherjee

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13 Scopus citations


The synthesis of four discrete tetranuclear complexes {[Ni II(L2)][ClO4]}4·MeCN (1), {[CuII(L1)(O3SCF3)]} 4·H2O (2), {[CuII(L3) (OClO3)]}4·MeCN (3) and {[CuII(L 4)][ClO4]}4·3MeCN·4H 2O (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 NiIIN 3O2 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 ClO 4- 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.

Original languageEnglish
Pages (from-to)9759-9769
Number of pages11
JournalDalton Transactions
Issue number44
StatePublished - 2009
Externally publishedYes


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