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Issue 12, 2019
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Versatile coordination architectures of products generated by the in situ reaction of a doubly bis(2-pyridyl)pyrazolate bridged dinuclear copper(II) complex with tetracyanoethylene

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Abstract

The reaction of a doubly bis(2-pyridyl)pyrazolate (bpypz) bridged dinuclear copper(II) complex, [Cu2(bpypz)2]2+, with neutral tetracyanoethylene (TCNE) results in the formation of [Cu4(bpypz)4(TCVA)2]·2TCVA (1) in tetrahydrofuran (THF), syn-[Cu2(bpypz)2(DCNM)2] (2) in MeOH, and anti-[Cu2(bpypz)2(DCNE)2] (3) in EtOH, where TCVA = 1,2,2-tricyanoethenolate, DCNM = 2,2-dicyano-1-methoxyethenolate, and DCNE = 2,2-dicyano-1-ethoxyethenolate. The ligands TCVA, DCME, and DCNE in 1–3 were formed in situ during the reaction in different solvents, and the ligands were confirmed through infrared spectroscopy, single-crystal X-ray diffraction, and elemental analyses. The single-crystal X-ray structures of 1–3 show that each copper(II) centre is five-coordinate in an approximately square pyramidal geometry. 1 is a discrete dimer-of-dimers type tetranuclear complex with the copper(II) centres bridged by two trans2-N,O-TCVA. 2 and 3 are discrete dinuclear complexes. In 2, two apically monodentate N-coordinated DCNM molecules are oriented in a cis manner to one another, consequently adopting a syn-orthogonal configuration. A weak interaction exists between each copper(II) centres and the O atoms of the apically coordinated DCNM molecules of the neighbouring copper(II) dinuclear units, resulting in a pseudo one-dimensional ladder-like coordination polymer arrangement. In 3, two apically monodentate N-coordinated DCNE molecules are oriented in a mutually trans manner across the basal plane of [Cu2(bpypz)2]2+, thereby adopting an anti-orthogonal configuration. Continuous wave X-band electron paramagnetic resonance spectral measurements on finely ground polycrystalline samples of 1–3 confirm a thermally depopulated S = 1 triplet state arising from antiferromagnetically coupled two S = 1/2 spins with orthorhombic g values. Variable-temperature dc magnetic susceptibility measurements of 1–3 indicate significant antiferromagnetic coupling (quantified by the isotropic spin Hamiltonian, H = −2JS1·S2, for the two copper(II) centres: J = −217.7, −210.3, and −188.5 cm−1 for 1, 2 and 3, respectively) for the doubly bpypz bridged copper(II) centres.

Graphical abstract: Versatile coordination architectures of products generated by the in situ reaction of a doubly bis(2-pyridyl)pyrazolate bridged dinuclear copper(ii) complex with tetracyanoethylene

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Publication details

The article was received on 08 Jan 2019, accepted on 13 Feb 2019 and first published on 13 Feb 2019


Article type: Paper
DOI: 10.1039/C9CE00036D
Citation: CrystEngComm, 2019,21, 1886-1894

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    Versatile coordination architectures of products generated by the in situ reaction of a doubly bis(2-pyridyl)pyrazolate bridged dinuclear copper(II) complex with tetracyanoethylene

    R. Ishikawa, S. Ueno, Y. Hamatake, Y. Horii, Y. Miyazaki, M. Nakano, T. Noda, M. Uematsu and S. Kawata, CrystEngComm, 2019, 21, 1886
    DOI: 10.1039/C9CE00036D

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