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具有褶皱和鞍形结构的铁（III）卟啉自由基阳离子中的自旋-自旋相互作用。

Spin-spin interactions in iron(III) porphyrin radical cations with ruffled and saddled structure.

机构信息

Division of Chemistry, Graduate School of Science, Toho University, Funabashi, Japan.

出版信息

J Inorg Biochem. 2011 May;105(5):718-21. doi: 10.1016/j.jinorgbio.2011.01.008. Epub 2011 Jan 21.

DOI:10.1016/j.jinorgbio.2011.01.008
PMID:21453668
Abstract

Oxidation of essentially pure intermediate-spin iron(III) porphyrinates such as ruffled Fe(T(i)PrP)ClO(4) and saddled Fe(OETPP)ClO(4) produces the corresponding six-coordinate iron(III) porphyrin(por) radical cations [Fe(Por·)(ClO(4))(2)], where T(i)PrP and OETPP are dianions of 5,10,15,20-tetraisopropylporphyrin and 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetraphenylporphyrin, respectively. Spin-spin interactions in these complexes are very much different; while ruffled [Fe(T(i)PrP·)(ClO(4))(2)] exhibits no antiferromagnetic coupling, saddled [Fe(OETPP·)(ClO(4))(2)] does exhibit it. The difference in magnetic behaviors has been explained in terms of the deformation mode and electron configuration of these complexes.

摘要

氧化基本纯的中间自旋铁(III)卟啉配合物，如褶皱 Fe(T(i)PrP)ClO(4) 和鞍形 Fe(OETPP)ClO(4)，生成相应的六配位铁(III)卟啉(por)自由基阳离子[Fe(Por·)(ClO(4))(2)]，其中 T(i)PrP 和 OETPP 分别是 5,10,15,20-四异丙基卟啉和 2,3,7,8,12,13,17,18-八乙基-5,10,15,20-四苯基卟啉的二阴离子。这些配合物中的自旋-自旋相互作用非常不同；虽然褶皱[Fe(T(i)PrP·)(ClO(4))(2)]不表现反铁磁耦合，但鞍形[Fe(OETPP·)(ClO(4))(2)]确实表现出反铁磁耦合。这种磁行为的差异可以用这些配合物的变形模式和电子构型来解释。

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