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Issue 11, 2008
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Structural, magnetic, high-frequency and high-field EPR investigation of double-stranded heterometallic [{Ni(en)2}2(µ-NCS)4Cd(NCS)2]n·nCH3CN polymer self-assembled from cadmium oxide, nickel thiocyanate and ethylenediamine

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Abstract

A novel heterometallic 1D coordination polymer [{Ni(en)2}2(µ-NCS)4Cd(NCS)2]n·nCH3CN (en = ethylenediamine) has been prepared using the self-assembly process in a one-pot reaction of cadmium oxide, nickel and ammonium thiocyanates with an acetonitrile solution of ethylenediamine. The complex consists of an uncommon cis-Cd(SCN)4(NCS)24 fragment and a rare combination of cis-Ni(en)22+ and trans-Ni(en)22+ building blocks linked by µ1,3-NCS bridges into a double-stranded zigzag chain structure. Each chain is comprised of [Ni2Cd2(µ-NCS–N,S)4)] macrocycles with chair-like and rectangular-like shapes arrayed alternately. The shortest intrachain Cd⋯Cd separations are 9.535(1) and 10.868(2) Å, while the nearest Ni⋯Ni distances are 5.418(1) and 6.612(2) Å. A network of weak N–H⋯S hydrogen bonds, involving the terminal NCS ligands and NH2-groups of en, links the infinite chains and results in the formation of an extended supramolecular three-dimensional framework. Variable-temperature (1.8–300 K) magnetic susceptibilities show a slight change of the µB value at low temperature, indicative of weak antiferromagnetic interactions (J = 1.55 cm−1) between magnetic canters. High-field, high-frequency (100–400 GHz) EPR spectra were simulated using S = 1 ground state for separate Ni2+ ions with the spin Hamiltonian parameters g = 2.165, D = 0.45 cm−1 and E = 0.03 cm−1. According to DFT calculations, the D and E parameters are −0.35 cm−1 and 0.049 cm−1 for the cis arrangement of Ni2+ and 0.58 cm−1 and 0.012 cm−1 for trans.

Graphical abstract: Structural, magnetic, high-frequency and high-field EPR investigation of double-stranded heterometallic [{Ni(en)2}2(µ-NCS)4Cd(NCS)2]n·nCH3CN polymer self-assembled from cadmium oxide, nickel thiocyanate and ethylenediamine

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Publication details

The article was received on 29 Aug 2007, accepted on 14 Dec 2007 and first published on 22 Jan 2008


Article type: Paper
DOI: 10.1039/B713252B
Citation: Dalton Trans., 2008, 1431-1436
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    Structural, magnetic, high-frequency and high-field EPR investigation of double-stranded heterometallic [{Ni(en)2}2(µ-NCS)4Cd(NCS)2]n·nCH3CN polymer self-assembled from cadmium oxide, nickel thiocyanate and ethylenediamine

    O. V. Nesterova, S. R. Petrusenko, V. N. Kokozay, B. W. Skelton, J. Jezierska, W. Linert and A. Ozarowski, Dalton Trans., 2008, 1431
    DOI: 10.1039/B713252B

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