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Counter-complementarity control of the weak exchange interaction in a bent {Ni(ii)3} complex with a μ-phenoxide-μ-carboxylate double bridge

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Abstract

We have prepared and structurally characterized a novel {Ni3} bent complex bearing a double μ-phenoxide-μ-carboxylate bridge. Both terminal Ni(II) sites are symmetry related, offering a simplified exchange interaction scheme. DC magnetic data is consistent with a weak antiferromagnetic interaction between the central and terminal Ni(II) ions. As expected for a Ni(II) system, local zero-field splitting is observed, which can be experimentally established. Broken symmetry quantum chemical calculations, as well as ab initio CASSCF-SA-SOC computations that support the magnetic experimental data, were also performed. From the analysis of other reported closely related Ni(II) systems, a counter-complementarity effect exerted by the carboxylate bridge is proposed, which might explain the weaker exchange interactions compared to those observed in double μ-phenoxide bridged Ni(II) compounds.

Graphical abstract: Counter-complementarity control of the weak exchange interaction in a bent {Ni(ii)3} complex with a μ-phenoxide-μ-carboxylate double bridge

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Publication details

The article was received on 11 Jul 2019, accepted on 18 Sep 2019 and first published on 03 Oct 2019


Article type: Paper
DOI: 10.1039/C9NJ03574E
New J. Chem., 2019, Advance Article

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    Counter-complementarity control of the weak exchange interaction in a bent {Ni(II)3} complex with a μ-phenoxide-μ-carboxylate double bridge

    G. Fiorini, L. Carrella, E. Rentschler and P. Alborés, New J. Chem., 2019, Advance Article , DOI: 10.1039/C9NJ03574E

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