咪唑取代的氧代过氮自由基作为分子内和分子间交换相互作用的介质。

Imidazole-substituted oxoverdazyl radical as a mediator of intramolecular and intermolecular exchange interaction.

作者信息

Norel Lucie, Pointillart Fabrice, Train Cyrille, Chamoreau Lise-Marie, Boubekeur Kamal, Journaux Yves, Brieger Aaron, Brook David J R

机构信息

Laboratoire de Chimie Inorganique et Matériaux Moléculaires, UMR 7071, IFR 2769, UPMC Univ. Paris 6, case 42, 4 place Jussieu, F75252 Paris cedex 05, France.

出版信息

Inorg Chem. 2008 Apr 7;47(7):2396-403. doi: 10.1021/ic701400b. Epub 2008 Mar 5.

DOI:10.1021/ic701400b

PMID:18318482

Abstract

The 3-(2'-imidazolyl)-1,5-dimethyl-6-oxoverdazyl radical (imvd()) and the corresponding tetrazane H3imvd were prepared and structurally characterized, the former as two different hydrates. Reaction of imvd() with [M(hfac)2] led to the formation of monometallic complexes [M(hfac)2(imvd())] (M = Ni and Mn). They were characterized by single-crystal X-ray diffraction. In the solid state, all four radical-containing compounds exhibit imidazole-oxoverdazyl pi stacking. Following the structural analysis, imvd() behaves as an antiferromagnetic (AF) coupled chain with J = -100 cm(-1) (H = -J summation operator SiS(i+1)). The magnetic behavior of [M(hfac)2(imvd(*))] complexes is interpreted with a four-coupled spin model with a metal ion radical intramolecular interaction (JMn = -62.5 cm(-1) and JNi = 193 cm(-1); H = -JSMSimvd) and an AF intermolecular interaction (JMn' = -12.6 cm(-1) and JNi' = -4.3 cm(-1)) related to imidazole-oxoverdazyl pi stacking.

摘要

制备了3-(2'-咪唑基)-1,5-二甲基-6-氧代过氮自由基(imvd())及其相应的四氮烷H3imvd，并对其结构进行了表征，前者为两种不同的水合物。imvd()与[M(hfac)2]反应生成单金属配合物[M(hfac)2(imvd())](M = Ni和Mn)。通过单晶X射线衍射对它们进行了表征。在固态下，所有四种含自由基的化合物都表现出咪唑-氧代过氮π堆积。经过结构分析，imvd()表现为反铁磁(AF)耦合链，J = -100 cm(-1)(H = -J∑SiS(i+1))。[M(hfac)2(imvd(*))]配合物的磁行为用一个四耦合自旋模型来解释，该模型具有金属离子自由基分子内相互作用(JMn = -62.5 cm(-1)和JNi = 193 cm(-1);H = -JSMSimvd)和与咪唑-氧代过氮π堆积相关的AF分子间相互作用(JMn' = -12.6 cm(-1)和JNi' = -4.3 cm(-1))。