氰根桥联手性双核、三核Fe(Ⅲ)-Cu(Ⅱ)配合物的合成、结构及磁性研究  

Cyanide-Bridged Chiral bi-and Trinuclear Bimetallic Fe(Ⅲ)-Cu(Ⅱ)Complexes:Synthesis,Crystal Structure and Magnetic Property

作　　者：曹桐 郝晓云 兰文龙 周振 杨璐 张道鹏[1] CAO Tong;HAO Xiao-yun;LAN Wen-long;ZHOU Zhen;YANG Lu;ZHANG Dao-peng(School of Chemistry and Chemical Engineering,Shandong University of Technology,Zibo 255049,China)

机构地区：[1]山东理工大学化学化工学院,山东淄博255049

出　　处：《聊城大学学报（自然科学版）》2020年第6期102-110,共9页Journal of Liaocheng University:Natural Science Edition

基　　金：国家自然科学基金项目(21671121)资助。

摘　　要：采用mer-[PPh4][Fe(mpcq)(CN)3](mpcq=8-(pyridine-3-methyl-6-carboxamido)quinoline anion)与[Cu(R,R-Chxn)](ClO4)2(R,R-Chxn=R,R-1,2-diaminocyclohexane)通过挥发或者H-型双管扩散的方法获得两种手性氰根桥联异金属Fe-Cu配合物{[Cu(R,R-Chxn)[Fe(mpcq)(CN)3]}[Fe(mpcq)(CN)3](1)和{Cu(R,R-Chxn)[Fe(mpcq)(CN)3]2}·2CH3OH·CH3CH2OH·3H2O(2),利用元素分析、红外光谱、PXRD、X射线单晶衍射等方法对其结构进行了表征.单晶结构分析表明,在配合物(1)中,氰根前躯体作为单齿配体利用赤道平面位置的氰根与铜离子发生配位,从而形成氰根桥联阳离子型Fe-Cu双核结构.在配合物(2)中,两个氰根前躯体分别作为单齿配体,利用其轴向氰根与铜配合物单元发生配位,从而形成氰根桥联中性三明治型Fe2Cu三核结构.配合物(1),(2)的变温磁化率和变场磁化强度研究表明,通过氰根桥联的低自旋三价铁离子和二价铜离子之间呈现反铁磁或者铁磁耦合效应.本文研究结果表明,对相同反应底物可以通过采用不同的结晶方法对目标产物结构进行调控,同时也进一步证明了面式吡啶基喹啉酰胺三氰基金属前驱体可以用来组装不同结构的异金属磁性配合物.In this paper,the mer-tricyanoiron(Ⅲ)building block[PPh4][Fe(mpcq)(CN)3](mpcq=8-(pyridine-3-methyl-6-carboxamido)quinoline anion)and chiral copper(Ⅱ)compound[Cu(R,R-Chxn)](ClO4)2(R,R-Chxn=R,R-1,2-diaminocyclohexane)have been employed to assemble cyanide-bridged heterometallic complexes under slow evaporation or diffusion conditions,resulting in two chiral cyanide-bridged Fe(Ⅲ)-Cu(Ⅱ)complexes,{[Cu(R,R-Chxn)[Fe(mpcq)(CN)3]}[Fe(mpcq)(CN)3](1)and{Cu(R,R-Chxn)[Fe(mpcq)(CN)3]2}·2CH3OH·CH3CH2OH·3H2O(2).Both of the two complexes have been characterized by elemental analysis,IR spectroscopy and X-ray structure determination.Single X-ray diffraction analysis shows that complex 1 belong to cyanide-bridged cationic binuclear structure with the anionic cyanide building block as balance anion,while complex(2)can be structurally characterized as neutral sandwich-like trinuclear Fe2Cu entity.The magnetic investigation reveals the weak antiferromagnetic coupling in complex(1)and the weak ferromagnetic interaction in complex(2)between the neighboring Fe(Ⅲ)and Cu(Ⅱ)ions through the bridging cyanide group.The current research results show that the crystallization method play an important role on tuning the structure type of the target complexes,and on the other hand,the mer-tricyanometallates are really good candidate for assembling low-dimensional cyanide-bridged magnetic metal complexes with different structural conformations.

关 键 词：氰根桥联 手性 晶体结构 磁性 

分 类 号：O641.4[理学—物理化学]