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

Derek J. Reid; John E.W. Cull; Kimberley D.S. Chisholm; Alexandre Langlois; Po Heng Lin; Jérôme Long; Olivier Lebel; Ilia Korobkov; Ruiyao Wang; James D. Wuest; Muralee Murugesu; Jennifer Scott

doi:10.1039/c1dt00018g

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

Derek J. Reid
, John E.W. Cull
, Kimberley D.S. Chisholm
, Alexandre Langlois
, Po Heng Lin
, Jérôme Long
, Olivier Lebel
, Ilia Korobkov
, Ruiyao Wang
, James D. Wuest
, Muralee Murugesu
, Jennifer Scott^*

^*Corresponding author for this work

Royal Military College of Canada
University of Ottawa
Queen's University Kingston
University of Montreal

Research output: Contribution to journal › Article › peer-review

12 Citations (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	5009-5017
Number of pages	9
Journal	Dalton Transactions
Volume	40
Issue number	18
DOIs	https://doi.org/10.1039/c1dt00018g
Publication status	Published - 14 May 2011
Externally published	Yes

Access to Document

10.1039/c1dt00018g

Cite this

@article{94f09429ac114b87ab22b993dd5c4371,

title = "Synthesis, structure and magnetism of homodinuclear complexes of Co, Ni and Cu supported by a novel bitriazine scaffold",

abstract = "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.",

author = "Reid, \{Derek J.\} and Cull, \{John E.W.\} and Chisholm, \{Kimberley D.S.\} and Alexandre Langlois and Lin, \{Po Heng\} and J{\'e}r{\^o}me Long and Olivier Lebel and Ilia Korobkov and Ruiyao Wang and Wuest, \{James D.\} and Muralee Murugesu and Jennifer Scott",

year = "2011",

month = may,

day = "14",

doi = "10.1039/c1dt00018g",

language = "English",

volume = "40",

pages = "5009--5017",

journal = "Dalton Transactions",

issn = "1477-9226",

number = "18",

}

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 - https://www.scopus.com/pages/publications/79955037028

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 -

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

Abstract

Access to Document

Other files and links

Fingerprint

Cite this