Synthesis, magnetic properties, and electronic spectra of bis(β-diketonato)chromium(III) and nickel(II) complexes with a chelated imino nitroxide radical: X-ray structures of [Cr(acaMe)2(IM2py)]PF6 and [Ni(acac)2(IM2py)]

Yasunori Tsukahara, Takayuki Kamatani, Atsushi Iino, Takayoshi Suzuki, Sumio Kaizaki

Research output: Contribution to journalArticle

32 Citations (Scopus)

Abstract

Two new series of each of four Cr(III) and Ni(II) imino nitroxide complexes with various kinds of β-diketonates, [Cr(β-diketonato)2(IM2py)]PF6, and [Ni(β-diketonato)2(IM2py)] (IM2py = 2-(2′-(pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxy)) have been synthesized, and their structures and magnetic and optical properties have been examined. The X-ray analysis demonstrated that a IM2py ligand coordinated to Cr(III) and Ni(II) acts as a five-membered bidentate chelate. The variable-temperature magnetic susceptibility measurements indicated the antiferromagnetic and ferromagnetic interaction of Cr(III) and Ni(II) with IM2py, respectively, giving a variety of the magnetic coupling constant J values with varying the β-diketonato ligands. The UV-vis shoulders around (19-20) x 103 and (17-18) x 103 cm-1 for the Cr(III) and Ni(II) complexes, respectively, characteristic of the IM2py complexes were assigned to the metal-ligand charge-transfer transitions, Cr(t2g)-SOMO(π*) and Ni(eg)-SOMO(π*) MLCT in terms of the resonance Raman spectra and the variable-temperature absorption spectra. The absorption components centered around (13-14) x 103 cm-1 for the Cr(III) and Ni(II) complexes were due to the formally spin-forbidden d-d transition within the t2g and eg subshells, associated with the intensity enhancement. The spectroscopic behavior with varying the β-diketonato ligands is discussed in connection with the antiferromagnetic or ferromagnetic coupling constant J values on the basis of the exchange mechanism along with the coligand effect.

Original languageEnglish
Pages (from-to)4363-4370
Number of pages8
JournalInorganic Chemistry
Volume41
Issue number17
DOIs
Publication statusPublished - Aug 26 2002
Externally publishedYes

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Chromium
Nickel
electronic spectra
chromium
Magnetic properties
nickel
magnetic properties
Ligands
X rays
ligands
synthesis
x rays
Magnetic couplings
X ray analysis
shoulders
Magnetic susceptibility
imidazoles
chelates
Charge transfer
Raman scattering

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Synthesis, magnetic properties, and electronic spectra of bis(β-diketonato)chromium(III) and nickel(II) complexes with a chelated imino nitroxide radical : X-ray structures of [Cr(acaMe)2(IM2py)]PF6 and [Ni(acac)2(IM2py)]. / Tsukahara, Yasunori; Kamatani, Takayuki; Iino, Atsushi; Suzuki, Takayoshi; Kaizaki, Sumio.

In: Inorganic Chemistry, Vol. 41, No. 17, 26.08.2002, p. 4363-4370.

Research output: Contribution to journalArticle

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abstract = "Two new series of each of four Cr(III) and Ni(II) imino nitroxide complexes with various kinds of β-diketonates, [Cr(β-diketonato)2(IM2py)]PF6, and [Ni(β-diketonato)2(IM2py)] (IM2py = 2-(2′-(pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxy)) have been synthesized, and their structures and magnetic and optical properties have been examined. The X-ray analysis demonstrated that a IM2py ligand coordinated to Cr(III) and Ni(II) acts as a five-membered bidentate chelate. The variable-temperature magnetic susceptibility measurements indicated the antiferromagnetic and ferromagnetic interaction of Cr(III) and Ni(II) with IM2py, respectively, giving a variety of the magnetic coupling constant J values with varying the β-diketonato ligands. The UV-vis shoulders around (19-20) x 103 and (17-18) x 103 cm-1 for the Cr(III) and Ni(II) complexes, respectively, characteristic of the IM2py complexes were assigned to the metal-ligand charge-transfer transitions, Cr(t2g)-SOMO(π*) and Ni(eg)-SOMO(π*) MLCT in terms of the resonance Raman spectra and the variable-temperature absorption spectra. The absorption components centered around (13-14) x 103 cm-1 for the Cr(III) and Ni(II) complexes were due to the formally spin-forbidden d-d transition within the t2g and eg subshells, associated with the intensity enhancement. The spectroscopic behavior with varying the β-diketonato ligands is discussed in connection with the antiferromagnetic or ferromagnetic coupling constant J values on the basis of the exchange mechanism along with the coligand effect.",
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T1 - Synthesis, magnetic properties, and electronic spectra of bis(β-diketonato)chromium(III) and nickel(II) complexes with a chelated imino nitroxide radical

T2 - X-ray structures of [Cr(acaMe)2(IM2py)]PF6 and [Ni(acac)2(IM2py)]

AU - Tsukahara, Yasunori

AU - Kamatani, Takayuki

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AU - Suzuki, Takayoshi

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