具有非正规自旋态的氮氧自由基桥联双镍配合物的合成、表征和磁性研究  

Synthesis Characterization and Magnetism of μ-Nitronyl Nitroxide Binuclear Nickel (Ⅱ) Complexcs with Irregular Spin States

作　　者：孙柏旺[1] 姜宗慧[1] 廖代正[1] 还振威[1] 刘爱俭 王耕霖[1] 

机构地区：[1]南开大学元素有机化学国家重点实验室,南开大学化学系,中国农业科学院畜牧研究所

出　　处：《高等学校化学学报》1995年第11期1672-1676,共5页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金

摘　　要：合成了４种氮氧自由基桥联的五氟丙酸镍双核配合物［Ｎｉ（ｐｆｐｒ）＿２］＿２ＮＩＴＲ·ｎＨ＿２Ｏ．对该配合物进行了元素分析和热重－差热分析，测定了红外光谱、紫外－可见光谱、电子顺磁共振和摩尔电导．讨论了配合物的结构，测量了［Ｎｉ（ｐｆｐｒ）＿２］＿２ＮＩＴＰｈＣｌ·４Ｈ＿２Ｏ和［Ｎｉ（ｐｆｐｒ）＿２］＿２ＮＩＴＰｈＯＭｅ·４Ｈ２Ｏ的变温磁化率（４～３００Ｋ），表明配合物具有非正规自旋态的Ｎｉ（Ⅱ）－Ｃｕ（Ⅱ）－Ｎｉ（Ⅱ）三核体系的磁行为．通过与理论公式拟合，得到交换积分Ｊ值分别为－１５２．８ｃｍ￣（－１）和－１７４．６ｃｍ￣（－１），表明镍－自由基－镍之间有较强的反铁磁相互作用．Four complexes of the general formula[Ni(pfpr)2]2NITR·nH2O, where pfpr=pentafluoropropionate, NITR=2-R-4,4,5,5-tetramethylimidazoline-l-oxyl-3-oxide, and n=2(for R = ph);3(for R = phMe) ;4(for R = phCl,PhOMe),were synthesized,Thesecomplexes were characterized by elemental analyses,TG-DTA IR,electronic spectra,ESR胁and molar conductances. The structures of these complexes were discussed.The variable temperature(4-300 K) magnetic susceptibilities of the complexes[Ni(pfpr)2] 2NITPHCl·4H2O and[Ni(pfpr)2]2 NITPhOMe·4H2O were determined, indicating that the complexes have a magnetic behaviour of trinuclear system Ni(Ⅱ)-Cu(Ⅱ)-Ni(Ⅱ) with irregular spin state. The observed susceptihility data were fitted to those from theoretical magnetic equation,The exchange constants,J,were found to be equal to -152. 8cm(-1) and -174.6 cm(-1),respectively,This indicates a stronger antiferromagnetic spin-exchange interaction between the radical and nickel (Ⅱ) ion.

关 键 词：五氟丙酸镍 氮氧自由基 磁性 镍 配合物 

分 类 号：O614.813[理学—无机化学]