摘要
采用常规水相方法合成了一个基于同多阴离子[Mo7O24]6-的离子杂化物.通过单晶X射线衍射、元素分析、红外光谱及热失重等手段确定了其分子式为(NH4)2[CuL(H2O)]2MO7O24?3H2O,L=(HOCH2)3CNH(CH2)3NHC-(CH2OH)3(1).单晶X射线衍射分析表明,杂化物1属于单斜晶系,P21空间群,晶胞参数为:a=10.778(2)?,b=21.391(3)?, c=11.596(3)?,α=90°,β=96.82(1)°,γ=90°, V=2654.4(9)?3, Z=2.在杂化物晶体结构中,二价铜离子与带有两个三羟基官能团的柔性配体L以非对称螯合配位方式结合,并作为抗衡离子与多阴离子之间通过强的O-H???O和N-H???O氢键作用构成二维超分子网络结构.分子间强的氢键作用,使杂化物1表现出较高的结构稳定性和热稳定性.变温磁化率测试表明所合成杂化物1具有强反铁磁性质.
The investigations of the organic-inorganic hybrid materials attract widely attentions in recent years due to their applications in many fields,such as medicine,magnetism and catalysis.As one of the important types of inorganic components,polyoxometalates（POMs）bear the features of various compositions,rich structures and tunable charges,and play key roles in the construction of hybrid materials.Since the first[Mo7O24]^6-polyanion was synthesized and its structure was confirmed by single-crystal X-ray analysis,many different kinds of cations,including inorganic and organic ions,were introduced to this system.While the studies of this type of polyanion with coordination compounds are still rarely,especially for transition metal ions and oxygenated ligands.As our ongoing study in the field of POM-containing compounds,we succeeded in obtaining an organic-inorganic hybrid based on[Mo7O24]^6- polyanion in aqueous solution with CuSO4·5H2O,（NH4）6Mo7O（24）·4H2O and a triol ligand as staring materials.The formula of the obtained compound was determined as（NH4）2[CuL（H2O）]2MO7O24？3H2O,L=（HOCH2）3CNH（CH2）3NHC（CH2OH）3（1）through X-ray analysis,elemental analysis,IR spectrum and TG analysis.Single-crystal X-ray analysis reveals that compound 1 belongs to the monoclinic system with the space group of P21.The unit cell parameters is a=10.778（2）A°,b=21.391（3）A°,c=11.596（3）A°,α=90°,β=96.82（1）°,γ=90°,V=2654.4（9）A°3,Z=2,and the final R1 is 0.0155.In the crystal structure of compound 1,Cu^2＋ cation is in a six-coordination environment and combines with ligand L in the unsymmetrical chelate coordination manner,where two triol groups provide one and two O atoms respectively and the other three positions are occupied by two N atoms and one O atom from water molecule. The [CuL（H2O）]^2＋ subunit connects with [Mo7O24]6-polyanion through the strong O-H…O and N-H…O hydrogen bonds to form a supramolecular two-dimensional network.TG curve shows that compound 1 has a
作者
段凤雪
刘晓婷
徐娓
陶艳春
李豹
吴立新
Fengxue Duan;Xiaoting Liu;Wei XH;Yanchun Tao;Bao Li;Lixin Wu(State Key Laboratory of Supramolecular Structure and Materials,Jilin University,Changchun 130012,China;State Key Laboratory of Inorganic Synthesis ＆ Preparative Chemistry,Jilin University,Changchun 130012,China)
出处
《科学通报》
EI
CAS
CSCD
北大核心
2018年第32期3358-3365,共8页
Chinese Science Bulletin
基金
国家自然科学基金(21574057)
吉林省"长白山学者计划"资助
关键词
多金属氧簇
铜配合物
晶体结构
反铁磁
polyoxometalate
copper-containing compound
crystal structure
antiferromagnetism
