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Novel pyrazolate-based copper(II) [2 x 2] grid complexes: Synthesis, structure and properties

Malinkin, Sergey O.; Moroz, Yurii S.; Penkova, Larysa V.; Haukka, Matti; Szebesczyk, Agnieszka; Gumienna-Kontecka, Elzbieta; Pavlenko, Vadim A.; Nordlander, Ebbe LU ; Meyer, Franc and Fritsky, Igor O. (2012) In Inorganica Chimica Acta 392. p.322-330
Abstract
5-Acetyl-substituted pyrazole-3-carboxylic acid (H2L) forms [2 x 2] grid-like tetranuclear Cu(II) complexes with four five-coordinated copper(II) ions bridged by pyrazolate groups. Despite a significant dissociation of [Cu4L4(H2O)(4)]center dot 4H(2)O (1) in aqueous solution(1), it was possible to substitute the coordinated water molecules by pyridine ligands or azide anions. The resulting tetranuclear complexes [Cu4L4Py4]center dot 2H(2)O (2) and Na-4[Cu4L4(N-3)(4)]center dot 7MeOH (3) were isolated and studied by X-ray diffraction analysis. In 2 and 3 the azide anions or pyridine molecules complete the distorted square-pyramidal coordination of each copper(II) center. Magnetic susceptibilities of the obtained compounds have been measured... (More)
5-Acetyl-substituted pyrazole-3-carboxylic acid (H2L) forms [2 x 2] grid-like tetranuclear Cu(II) complexes with four five-coordinated copper(II) ions bridged by pyrazolate groups. Despite a significant dissociation of [Cu4L4(H2O)(4)]center dot 4H(2)O (1) in aqueous solution(1), it was possible to substitute the coordinated water molecules by pyridine ligands or azide anions. The resulting tetranuclear complexes [Cu4L4Py4]center dot 2H(2)O (2) and Na-4[Cu4L4(N-3)(4)]center dot 7MeOH (3) were isolated and studied by X-ray diffraction analysis. In 2 and 3 the azide anions or pyridine molecules complete the distorted square-pyramidal coordination of each copper(II) center. Magnetic susceptibilities of the obtained compounds have been measured by SQUID techniques. Simulation of the data using a Heisenberg spin Hamiltonian approach showed that the bridges between the metals mediate weak intramolecular antiferromagnetic coupling (J in the range -13.3 to -17.1 cm (1)) and lead to a singlet ground state in all cases. (C) 2012 Elsevier B.V. All rights reserved. (Less)
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Contribution to journal
publication status
published
subject
keywords
Pyrazole ligands, Copper(II), Grid complexes, Magnetic properties
in
Inorganica Chimica Acta
volume
392
pages
322 - 330
publisher
Elsevier
external identifiers
  • wos:000308696200047
  • scopus:84865803097
ISSN
0020-1693
DOI
10.1016/j.ica.2012.03.021
language
English
LU publication?
yes
id
9448e558-656b-4e52-9168-eb4339f4cd8a (old id 3190075)
date added to LUP
2012-12-04 08:16:16
date last changed
2017-10-08 04:02:42
@article{9448e558-656b-4e52-9168-eb4339f4cd8a,
  abstract     = {5-Acetyl-substituted pyrazole-3-carboxylic acid (H2L) forms [2 x 2] grid-like tetranuclear Cu(II) complexes with four five-coordinated copper(II) ions bridged by pyrazolate groups. Despite a significant dissociation of [Cu4L4(H2O)(4)]center dot 4H(2)O (1) in aqueous solution(1), it was possible to substitute the coordinated water molecules by pyridine ligands or azide anions. The resulting tetranuclear complexes [Cu4L4Py4]center dot 2H(2)O (2) and Na-4[Cu4L4(N-3)(4)]center dot 7MeOH (3) were isolated and studied by X-ray diffraction analysis. In 2 and 3 the azide anions or pyridine molecules complete the distorted square-pyramidal coordination of each copper(II) center. Magnetic susceptibilities of the obtained compounds have been measured by SQUID techniques. Simulation of the data using a Heisenberg spin Hamiltonian approach showed that the bridges between the metals mediate weak intramolecular antiferromagnetic coupling (J in the range -13.3 to -17.1 cm (1)) and lead to a singlet ground state in all cases. (C) 2012 Elsevier B.V. All rights reserved.},
  author       = {Malinkin, Sergey O. and Moroz, Yurii S. and Penkova, Larysa V. and Haukka, Matti and Szebesczyk, Agnieszka and Gumienna-Kontecka, Elzbieta and Pavlenko, Vadim A. and Nordlander, Ebbe and Meyer, Franc and Fritsky, Igor O.},
  issn         = {0020-1693},
  keyword      = {Pyrazole ligands,Copper(II),Grid complexes,Magnetic properties},
  language     = {eng},
  pages        = {322--330},
  publisher    = {Elsevier},
  series       = {Inorganica Chimica Acta},
  title        = {Novel pyrazolate-based copper(II) [2 x 2] grid complexes: Synthesis, structure and properties},
  url          = {http://dx.doi.org/10.1016/j.ica.2012.03.021},
  volume       = {392},
  year         = {2012},
}