BASAK, Subhra; SEN, Soma; ROSAIR, Georgina M.; DESPLANCHES, Cédric; GARRIBBA, Eugenio; MITRA, Samiran

doi:10.1071/CH08511

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BASAK, Subhra
Jadavpur University

SEN, Soma
Jadavpur University

ROSAIR, Georgina M.
Heriot-Watt University [Edinburgh] [HWU]

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Australian Journal of Chemistry. 2009, vol. 62, n° 4, p. 366-375

CSIRO Publishing

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A novel tetranuclear copper(ii) complex [Cu4L2(μ1,1- N3)2]·CH3CN (1) has been synthesized using a symmetrical quinquedentate N2O3-donor Schiff-base ligand H3L (N,N′-(2-hydroxypropane-1,3-diyl)bis(2- hydroxyacetophenimine)) and characterized by elemental analysis, Fourier-transform (FT)-IR, UV-visible, electron paramagnetic resonance spectroscopy, and cyclic voltammetry. The X-ray single-crystal structure of 1 reveals three kinds of bridges among the four metal centres: one from the exogenous azido ligand and two from the phenoxo and alkoxo moieties of the Schiff base. The same structure highlights the remarkable versatility of copper(ii) to adopt an array of stereochemistries. Four unusual eight-membered metallacycles exist in 1. The μ1,1-azido, μ2-alkoxo, and μ2-phenoxo bridges among the four copper centres have facilitated interesting magnetic interactions that have been elucidated by variable-temperature magnetic susceptibility measurements and backed up by density functional theory calculations. Detailed analyses have shown that the antiferromagnetic effect through the alkoxo-bridged CuII centres combined with the ferromagnetic interaction through the azido-bridged metal centres results in an S = 0 ground state.< Réduire

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DFT

Magnetism

Molecular compounds

Copper

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A novel µ1,1-azido-, µ2-alkoxo-, and µ2-phenoxo-bridged tetranuclear copper(II) complex with a quinquedentate schiff-base ligand : magneto-structural and DFT studies

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