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Supramolecular Assemblies of Trinuclear Copper(II)-Pyrazolato Units: A Structural, Magnetic and EPR Study

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Department of Chemistry and Biochemistry, Florida International University, 11200 SW 8th Street, Miami, FL 33199, USA
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Department of Inorganic Chemistry, Faculty of Science, Palacký University, CZ-77146 Olomouc, Czech Republic
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Institut de Chimie de Strasbourg (UMR 7177, CNRS-Unistra), Université de Strasbourg, 4 rue Blaise Pascal, CS 90032, F-67081 Strasbourg, France
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Authors to whom correspondence should be addressed.
Chemistry 2020, 2(3), 626-644; https://doi.org/10.3390/chemistry2030039
Received: 27 May 2020 / Revised: 16 June 2020 / Accepted: 17 June 2020 / Published: 1 July 2020
(This article belongs to the Special Issue Supramolecular Chemistry in the 3rd Millennium)
Two anionic complexes, {[Cu33-OH)(µ-4-Ph-pz)3Cl3]2[Cu(4-Ph-pzH)4](µ-Cl)2}2− (1) and [Cu33-OH)(µ-pz)31,1-N3)2(N3)] (2), crystallize as one-dimensional polymers, held together by weak Cu-(µ-Cl) and Cu-(µ-N3) interactions, respectively. Variable temperature magnetic susceptibility analyses determined the dominant antiferromagnetic intra-Cu3 exchange parameters in the solid state for both complexes, whereas the weak ferromagnetic inter-Cu3 interactions manifested also in the solid state EPR spectra, are absent in the corresponding frozen solution spectra. DFT calculations were employed to support the results of the magnetic susceptibility analyses. View Full-Text
Keywords: copper(II) complexes; pyrazolato ligands; supramolecular assembly; X-ray crystallography; magnetic susceptibility; EPR spectroscopy; isotropic exchange; antisymmetric exchange; dipolar interaction; DFT calculations copper(II) complexes; pyrazolato ligands; supramolecular assembly; X-ray crystallography; magnetic susceptibility; EPR spectroscopy; isotropic exchange; antisymmetric exchange; dipolar interaction; DFT calculations
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Shi, K.; Mathivathanan, L.; Herchel, R.; Boudalis, A.K.; Raptis, R.G. Supramolecular Assemblies of Trinuclear Copper(II)-Pyrazolato Units: A Structural, Magnetic and EPR Study. Chemistry 2020, 2, 626-644.

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