Synthesis and characterization of a tetracopper(II) complex having a [Cu 44-O)] framework stabilized by the tetranucleating macrocyclic ligand

Yuji Miyazato, Eiji Asato, Masaaki Ohba, Tohru Wada

研究成果: Contribution to journalArticle査読

4 被引用数 (Scopus)


A tetranucleating macrocyclic ligand bearing four acetate pendants, L 61, was newly yielded by a stepwise synthesis from [Zn 4(L')(AcO) 2(OH) 2](ClO 4) 2·H 2O (1), which was prepared from [2 + 2] Schiff-base condensation of 2,6-diformyl-4-methylphenol and 1,2-bis(2- aminoethoxy)ethane in the presence of Zn(ClO 4)2·6H 2O, sodium acetate, and triethylamine. A 4-oxo tetracopper(II) complex [Cu 4(L)(μ 4-O)]·H 2O (2) was obtained from the reaction of Cu(ClO 4) 2·6H 2O and Na 2H 4L in methanol under basic conditions, and characterized by X-ray crystallography. Two adjacent copper centers were bridged by the phenoxo oxygen of L 61 to form [Cu 2(μ-OPh)] unit, two pairs of which were further linked by an oxo anion with a distorted tetrahedral geometry, finally creating a tetracopper core [{Cu 2-(μ-OPh)} 24-O)]. Cryomagnetic measurements of 2 in the range of 2300K exhibited antiferromagentic behavior. Magnetic analysis of 2 was carried out by the four spin-exchange interactions model based on the bridging mode and the Cu(μ4-O)Cu angles, JA: Cu1/Cu4, J B: Cu2/Cu3, J C: Cu1/Cu2 and Cu3/Cu4, and J D: Cu1/Cu3 and Cu2/Cu4 pairs. The estimated four magnetic exchange interactions (J A, J B, J C, and J D) were 117, 1161, 1108, and 1109 cm1 1, respectively.

ジャーナルBulletin of the Chemical Society of Japan
出版ステータス出版済み - 8 27 2012

All Science Journal Classification (ASJC) codes

  • 化学 (全般)


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