基于7,7,8,8-四氰基对醌二甲烷-氯化锰反应的二价锰配合物的合成,晶体结构和磁性(英文)  

Synthesis,crystal structure and magnetic performance of a manganous coordination compound based on reaction between 7,7,8,8-tetracyanoquinodimethane and manganese(Ⅱ) chloride

作　　者：王百木 展树中[3] 

机构地区：[1]荣城职业学院 [2]荣城职业学院办公室,河南荣城476600 [3]华南理工大学化学与化工学院,广东广州510640

出　　处：《化学研究》2011年第5期11-18,37,共9页Chemical Research

基　　金：supported from the National Science Foundation of China(20971045);the Research Foundation for Returned Chinese Scholars Overseas of Chinese Education Ministry(B7050170)

摘　　要：以氯化锰、双二苯基膦酸甲烷(dppm)及7,7,8,8-四氰基对醌二甲烷(TCNQ)为原料,合成了标题化合物[Mn(dppmdo)_3][(TCNQ)(DCBE)]1;利用X射线衍射、红外光谱、紫外-可见-近红外光谱和循环伏安等技术对合成产物进行了表征.结果表明,化合物1在近红外区发生配体TCNQ之间的电子转移(TCNQ/TCNQ^-).化合物1中的TCNQ比游离态的TCNQ分子更容易被还原.室温下,化合物1的有效磁矩(12.7μB)远高于预期的由一个高自旋Mn^(2+)离子(S=5/2)、一个TCNQ(S=1/2)阴离子及一个DCBE(S=1/2)阴离子组成基团的有效磁矩(4.58μB),表明它们之间存在着很强的磁相互作用.A new charge transfer compound,[Mn（dppmdo）_3][（TCNQ）（DCBE）]1（dppmdo = bis（diphylphospine oxide） methane,DCBE = p-dicyanomethyl-benzoic methyl ester） was synthesized from the reaction of MnCl2·4H2O,bis（diphenylphosphino） methane（dppm）,and 7, 7,8,8-tetracyanoquinodimethane（TCNQ）.As-synthesized product was characterized by means of X-ray crystallography,infrared spectrometry,ultraviolet-visible light-near infrared spectrometry, and cyclic voltammogram.Results indicate that compound 1 experiences low-energy transitions in near-infrared region,which can be attributed to the intraligand transitions involving radical anions（TCNQ/TCNQ-）.Besides,TCNQ in 1 is easier to be reduced than free TCNQ molecule.And the effective magnetic moment of 1 at room temperature is as high as 12.7μ_B,much larger than 4.58μ_B,the expected effective magnetic moment of the radical consisting of one high spin Mn^（2＋） ion（S = 5/2）,one TCNQ-（S = 1/2） anion,and one DCBE- （S = 1/2） anion,which indicates that there exist strong magnetic interactions among Mn~Ⅱcomplex（[Mn（dppmdo）_3]^（2＋））,TCNQ- and DCBE- ions.

关 键 词：电荷转移化合物 二价锰配合物 TCNQ 晶体结构 磁性能 

分 类 号：O614.7[理学—无机化学]