TY - JOUR
T1 - Synthesis, structure and magnetism of homodinuclear complexes of Co, Ni and Cu supported by a novel bitriazine scaffold
AU - Reid, Derek J.
AU - Cull, John E.W.
AU - Chisholm, Kimberley D.S.
AU - Langlois, Alexandre
AU - Lin, Po Heng
AU - Long, Jérôme
AU - Lebel, Olivier
AU - Korobkov, Ilia
AU - Wang, Ruiyao
AU - Wuest, James D.
AU - Murugesu, Muralee
AU - Scott, Jennifer
PY - 2011/5/14
Y1 - 2011/5/14
N2 - Btzn (1), an amine-functionalized bi(1,3,5-triazine) 4,4′-(NH 2)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)Cu 2Cl4(DMF)2], (4), and [(Btzn)Cu 2(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.
AB - Btzn (1), an amine-functionalized bi(1,3,5-triazine) 4,4′-(NH 2)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)Cu 2Cl4(DMF)2], (4), and [(Btzn)Cu 2(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.
UR - http://www.scopus.com/inward/record.url?scp=79955037028&partnerID=8YFLogxK
U2 - 10.1039/c1dt00018g
DO - 10.1039/c1dt00018g
M3 - Article
AN - SCOPUS:79955037028
SN - 1477-9226
VL - 40
SP - 5009
EP - 5017
JO - Dalton Transactions
JF - Dalton Transactions
IS - 18
ER -