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Issue 18, 2011
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Synthesis, structure and magnetism of homodinuclear complexes of Co, Ni and Cu supported by a novel bitriazine scaffold

Derek J. Reid,a  John E. W. Cull,a  Kimberley D. S. Chisholm,a  Alexandre Langlois,a  Po-Heng Lin,b  Jérôme Long,b  Olivier Lebel,a  Ilia Korobkov,b  Ruiyao Wang,c  James D. Wuest,d  Muralee Murugesub  and  Jennifer Scott*a 
Author affiliations

* Corresponding authors

a Department of Chemistry and Chemical Engineering, Royal Military College of Canada, Kingston, Canada
E-mail: Jennifer.Scott@rmc.ca
Fax: 1-613-542-9489
Tel: 1-613-541-6000 × 3562

b Department of Chemistry, University of Ottawa, Ottawa, Canada

c Department of Chemistry, Queen's University, Kingston, Canada

d Département de Chimie, Université de Montréal, Montréal, Québec, Canada

Abstract

Btzn (1), an amine-functionalized bi(1,3,5-triazine) 4,4′-(NH2)2-6,6′-(NHC6H5)2-2,2′-(1,3,5-C3N3)2, is reported, and its coordination with Co, Ni and Cu is explored. Reactions of metal salts (2 equiv) with Btzn (1 equiv) result in dimeric species [(Btzn)Co2(NCS)4(EtOH)2(DMF)2], (2), [(Btzn)Ni2(η1-ONO2)2(MeOH)4(DMF)2]·2[NO3], (3), [(Btzn)Cu2Cl4(DMF)2], (4), and [(Btzn)Cu2(η2-O2NO)2(OH2)2(DMF)2]·2[NO3], (5). These complexes are the first examples of the coordination of transition metals with bi(1,3,5-triazine) ligands. Their structures display a bridging bis-bidentate coordination mode for Btzn. Variable-temperature magnetic susceptibility of the complexes reveals antiferromagnetic exchange between the spin carriers, with calculated exchange coupling values (J) of −4.7 cm−1 for 3, −18.2 cm−1 for 4, and −5.5 cm−1 for 5. An in-depth evaluation of the metal geometry highlights the inefficient overlap of the magnetic d-orbitals through the bridging ligand, most likely leading to reduced delocalization and coupling.

Graphical abstract: Synthesis, structure and magnetism of homodinuclear complexes of Co, Ni and Cu supported by a novel bitriazine scaffold

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Publication details

The article was received on 05 Jan 2011, accepted on 24 Feb 2011 and first published on 30 Mar 2011


Article type: Paper
DOI: 10.1039/C1DT00018G
Citation: Dalton Trans., 2011,40, 5009-5017
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    Synthesis, structure and magnetism of homodinuclear complexes of Co, Ni and Cu supported by a novel bitriazine scaffold

    D. J. Reid, J. E. W. Cull, K. D. S. Chisholm, A. Langlois, P. Lin, J. Long, O. Lebel, I. Korobkov, R. Wang, J. D. Wuest, M. Murugesu and J. Scott, Dalton Trans., 2011, 40, 5009
    DOI: 10.1039/C1DT00018G

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