Issue 18, 2011
From the journal:

Dalton Transactions

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  

* 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, Ontario, Canada

c Department of Chemistry, Queen's University, Kingston, Ontario, 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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Article information

DOI
https://doi.org/10.1039/C1DT00018G
Article type
Paper
Submitted
05 Jan 2011
Accepted
24 Feb 2011
First published
30 Mar 2011

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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