MISC

2002年

Antiferromagnetism induced by successive protonation of terminal phenol groups of a bis(mu-phenoxide)-bridged dicopper(II,II) complex

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS
  • H Saimiya
  • ,
  • Y Sunatsuki
  • ,
  • M Kojima
  • ,
  • S Kashino
  • ,
  • T Kambe
  • ,
  • M Hirotsu
  • ,
  • H Akashi
  • ,
  • K Nakajima
  • ,
  • T Tokii

3737-3742
19
開始ページ
3737
終了ページ
3742
記述言語
英語
掲載種別
DOI
10.1039/b201741e
出版者・発行元
ROYAL SOC CHEMISTRY

The reaction of a tripodal ligand (H2L = N, N-bis(2-hydroxybenzyl)-N', N'-dimethylethylenediamine) with Cu(NO3)(2).3H(2)O and Cu(ClO4)(2).6H(2)O in methanol yielded [Cu-2 (HL)(2)](NO3)(2).H2O (1) and [Cu-2 (HL)(2)](ClO4)(2) (1'), respectively. When H2L was allowed to react with CuSO4.5H(2)O in the presence of triethylamine (1 : 1 : 2) in methanol, the neutral dicopper(II,II) complex [Cu-2 (L)(2)] (2) was obtained. The monopositive species [Cu-2 (L)(HL)] ClO4. CH3OH.H2O (3) crystallized on mixing 1' and 2 (1 : 1) in methanol-dichloromethane. The crystal structures of 1, 2, and 3 were determined by X-ray crystallography. All of the complexes consist of a discrete dinuclear molecule with bis(mu-phenoxide)-bridges. The tripodal ligand functions as a tetradentate ligand and one of the phenolic oxygen atoms serves as a bridging ligand. Protonation/deprotonation takes place at the terminal phenol moiety and as the phenol group is deprotonated the coordination geometry changes from a distorted square pyramid to a distorted trigonal bipyramid. The two copper ions in 1-3 are antiferromagnetically coupled with 2J = -714 (1), -19.9 (2), and -277 cm(-1) (3). The results clearly demonstrate that protonation/deprotonation causes a change in coordination geometry, which in turn drastically affects magnetic exchange interactions.

Web of Science ® 被引用回数 : 27

リンク情報
DOI
https://doi.org/10.1039/b201741e
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000178348500014&DestApp=WOS_CPL