Crystal structures, magnetic and spectroscopic properties of manganese(II), cobalt(II), nickel(II) and zinc(II) dichloro complexes bearing two 2-pyridyl-substituted imino nitroxides

Y. Yamamoto, Takayoshi Suzuki, S. Kaizaki

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Abstract

Four new complexes of formula [MCl2(IM2py)2], where M = Mn(II), Co(II), Ni(II) or Zn(II); IM2py = 4,4,5,5-tetramethyl-2-(2-pyridyl)-imidazolin-1-oxyl, have been prepared, and examined from viewpoints of the crystal structures, magnetic and spectroscopic properties. All the complexes crystallize in an isomorphous space group C2/c with Z = 4, and exist as discrete mononuclear molecules with OC-6-22 [cis(Cl)-trans(py)] geometrical structure in the crystal. In the zinc(II) complex a moderate intramolecular IM2py-IM2py antiferromagnetic interaction (2J′ = -19.1(1) cm-1) is estimated by the magnetic susceptibility measurement. The magnetic interactions between Mn(II) and IM2py are found to be antiferromagnetic, J = -23.8(2) cm-1. Ferromagnetic interactions of the complexes of Ni(II) and Co(II) are inferred from the magnetic susceptibility. These magnetic properties are substantiated by the variable temperature UV-vis-NIR spectra of which the intensities increase for Mn(II) or decrease for Ni(II) and Co(II) with decreasing temperature for the spin-forbidden d-d transition and/or the metal(II) dσ to IM2py SOMO π* CT transition.

Original languageEnglish
Pages (from-to)1566-1572
Number of pages7
JournalJournal of the Chemical Society, Dalton Transactions
Issue number10
Publication statusPublished - 2001
Externally publishedYes

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Bearings (structural)
Manganese
Cobalt
Nickel
Magnetic susceptibility
Zinc
Crystal structure
Magnetic properties
Metals
Temperature
Crystals
Molecules

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "Crystal structures, magnetic and spectroscopic properties of manganese(II), cobalt(II), nickel(II) and zinc(II) dichloro complexes bearing two 2-pyridyl-substituted imino nitroxides",
abstract = "Four new complexes of formula [MCl2(IM2py)2], where M = Mn(II), Co(II), Ni(II) or Zn(II); IM2py = 4,4,5,5-tetramethyl-2-(2-pyridyl)-imidazolin-1-oxyl, have been prepared, and examined from viewpoints of the crystal structures, magnetic and spectroscopic properties. All the complexes crystallize in an isomorphous space group C2/c with Z = 4, and exist as discrete mononuclear molecules with OC-6-22 [cis(Cl)-trans(py)] geometrical structure in the crystal. In the zinc(II) complex a moderate intramolecular IM2py-IM2py antiferromagnetic interaction (2J′ = -19.1(1) cm-1) is estimated by the magnetic susceptibility measurement. The magnetic interactions between Mn(II) and IM2py are found to be antiferromagnetic, J = -23.8(2) cm-1. Ferromagnetic interactions of the complexes of Ni(II) and Co(II) are inferred from the magnetic susceptibility. These magnetic properties are substantiated by the variable temperature UV-vis-NIR spectra of which the intensities increase for Mn(II) or decrease for Ni(II) and Co(II) with decreasing temperature for the spin-forbidden d-d transition and/or the metal(II) dσ to IM2py SOMO π* CT transition.",
author = "Y. Yamamoto and Takayoshi Suzuki and S. Kaizaki",
year = "2001",
language = "English",
pages = "1566--1572",
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T1 - Crystal structures, magnetic and spectroscopic properties of manganese(II), cobalt(II), nickel(II) and zinc(II) dichloro complexes bearing two 2-pyridyl-substituted imino nitroxides

AU - Yamamoto, Y.

AU - Suzuki, Takayoshi

AU - Kaizaki, S.

PY - 2001

Y1 - 2001

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AB - Four new complexes of formula [MCl2(IM2py)2], where M = Mn(II), Co(II), Ni(II) or Zn(II); IM2py = 4,4,5,5-tetramethyl-2-(2-pyridyl)-imidazolin-1-oxyl, have been prepared, and examined from viewpoints of the crystal structures, magnetic and spectroscopic properties. All the complexes crystallize in an isomorphous space group C2/c with Z = 4, and exist as discrete mononuclear molecules with OC-6-22 [cis(Cl)-trans(py)] geometrical structure in the crystal. In the zinc(II) complex a moderate intramolecular IM2py-IM2py antiferromagnetic interaction (2J′ = -19.1(1) cm-1) is estimated by the magnetic susceptibility measurement. The magnetic interactions between Mn(II) and IM2py are found to be antiferromagnetic, J = -23.8(2) cm-1. Ferromagnetic interactions of the complexes of Ni(II) and Co(II) are inferred from the magnetic susceptibility. These magnetic properties are substantiated by the variable temperature UV-vis-NIR spectra of which the intensities increase for Mn(II) or decrease for Ni(II) and Co(II) with decreasing temperature for the spin-forbidden d-d transition and/or the metal(II) dσ to IM2py SOMO π* CT transition.

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