Heterodinuclear MIINiII (M = Co, Ni, Cu, Zn) complexes of a macrocyclic compartmental ligand. Anomalous EPR of CuIINiII complex by coordination of 1-methylimidazole

Ko Ji Inoue, Masaaki Ohba, Hisashi Okawa

研究成果: ジャーナルへの寄稿記事

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A phenol-based macrocyclic compartmental ligand, (L2;2)2-, having N(amine)22and N(imine)2O2 metal binding sites sharing two phenolic oxygen atoms, has formed the following heterodinuclear MIINiII complexes: [CoNi (L2;2)(AcO)]PF6·CH3CN (1), [NiNi(L2;2)(AcO)]PF6 (2), [CuNi(L2;2)(AcO)]PF6 (3) and [ZnNi(L2;2)(AcO)]PF6·CH3CN (4). Furthermore, [CuNi(L2:2)(CH3CN)](PF6)2 ·CH3CN (3′) was obtained when 3 was recrystallized from acetonitrile. X-ray crystallographic studies for 1, 2, 3′ and 4 demonstrate that the Ma resides in the N(amine)2O2 site and the NiII in the N(imine)2O2 site. The NiII in the N(imine)2O2 site has a planar geometry and is diamagnetic in all the complexes. The CoII of 1 and the NiII of 2 in the N(amine)2O2have a six-coordinate geometry together with a bidentate acetate group. The CuII in 3′ has a five-coordinate geometry together with one acetonitrile molecule, and the ZnII 4 has a square-pyramidal geometry together with a unidentate acetate group. Complex 3′ in DMF combines 1-methylimidazole (MeIm) at the axial site of the NiII and the Melm adduct in frozen DMF solution at 77.4 K shows EPR signals of g = 2.06 and g⊥ = 2.26 with a multi-line structure superimposed on the g component (A = 15.8 × 10-4 cm-1). The EPR signals are ascribed to the spin-doublet ground state (ST = 1/2) of antiferromagnetically coupled CuII(S = 1/2) - NiII(S = 1), and the multi-line structure is explained by considering hyperfine interaction with Cu nucleus (ACu = 50.0 × 10-4 cm-1) and superhyperfine interaction with N nucleus of Melm (AN = 15.0 × 10-4 cm-1).

元の言語英語
ページ(範囲)99-107
ページ数9
ジャーナルBulletin of the Chemical Society of Japan
75
発行部数1
DOI
出版物ステータス出版済み - 1 1 2002

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

フィンガープリント Heterodinuclear M<sup>II</sup>Ni<sup>II</sup> (M = Co, Ni, Cu, Zn) complexes of a macrocyclic compartmental ligand. Anomalous EPR of Cu<sup>II</sup>Ni<sup>II</sup> complex by coordination of 1-methylimidazole' の研究トピックを掘り下げます。これらはともに一意のフィンガープリントを構成します。

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