Publication: Synthesis, spectroscopic characterization, X-ray crystal structure and magnetic properties of oxalato-bridged copper(II) dinuclear complexes with di-2-pyridylamine
Issued Date
2003-09-08
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00201693
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2-s2.0-0141672909
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Mahidol University
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SCOPUS
Bibliographic Citation
Inorganica Chimica Acta. Vol.353, (2003), 119-128
Suggested Citation
Sujittra Youngme, Gerard A. Van Albada, Narongsak Chaichit, Pimprapun Gunnasoot, Palangpon Kongsaeree, Ilpo Mutikainen, Olivier Roubeau, Jan Reedijk, Urho Turpeinen Synthesis, spectroscopic characterization, X-ray crystal structure and magnetic properties of oxalato-bridged copper(II) dinuclear complexes with di-2-pyridylamine. Inorganica Chimica Acta. Vol.353, (2003), 119-128. doi:10.1016/S0020-1693(03)00207-X Retrieved from: https://repository.li.mahidol.ac.th/handle/20.500.14594/20807
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Title
Synthesis, spectroscopic characterization, X-ray crystal structure and magnetic properties of oxalato-bridged copper(II) dinuclear complexes with di-2-pyridylamine
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Abstract
The syntheses and characterization of a series of dinuclear μ-oxalato copper(II) complexes of the general type [(NN)1or2Cu(C2O4)Cu(NN)1or2]2+, where NN=didentate dpyam (di-2-pyridylamine) ligand, are described. The crystal structures of three representative complexes have been determined. The dinuclear-oxalate bridged compounds [Cu(dpyam)4(C2O4)](ClO4)2(H2O)3(1) and [Cu2(dpyam)4(C2O4)](BF4)2(H2O)3(2) crystallize in the non-centrosymmetric triclinic space group P1 which are isomorphous and isostructural. The compound [Cu2(dpyam)2(C2O4)(NO3)2((CH3)2SO)2] (3) crystallizes in the centrosymmetric monoclinic space group P1 with all Cu-oxalate contacts in the equatorial plane. All three complexes contain six-coordinate copper centres bridged by planar bis-didentate oxalate groups from the equatorial position of one chromophore to the equatorial position of the other one. Both chromophores in 1 and 2 exhibit the compressed octahedral Cu(II) geometry, while 3 displays an elongated octahedral Cu(II) environment. The IR, ligand field and EPR measurements are in agreement with the structures found. The magnetic susceptibility measurements, measured from 5 to 280 K, revealed a very weak ferromagnetic interaction between the Cu(II) atoms for compound 1 and 2, with a singlet-triplet energy gap (J) of 2.42 and 3.38 cm-1, for compounds 1 and 2, respectively. Compound 3 has a strong antiferromagnetic interaction with a J of -305.1 cm-1, in agreement with coplanarity of the magnetic orbitals. © 2003 Elsevier B.V. All rights reserved.