氰根桥连手性Fe^(Ⅲ)-Cu^(Ⅱ)-Ln^(Ⅲ)异三金属配合物的合成、结构和磁性研究  

Cyanide-Bridged Chiral Fe^(Ⅲ)-Cu^(Ⅱ)-Ln^(Ⅲ) Heterotrimetallic Complexes:Synthesis,Structures and Magnetic Properties

作　　者：王子璇 王亚旭 刘晓莉[1] 张梦娇 杨春[1] 王庆伦[2] Wang Zixuan;Wang Yaxu;Liu Xiaoli;Zhang Mengjiao;Yang Chun;Wang Qinglun(School of Chemical Engineering and Technology,Hebei University of Technology,Tianjin 300130,China;College of Chemistry,Nankai University,Tianjin 300071,China)

机构地区：[1]河北工业大学化工学院,天津300130 [2]南开大学化学学院,天津300071

出　　处：《南开大学学报（自然科学版）》2021年第3期98-107,共10页Acta Scientiarum Naturalium Universitatis Nankaiensis

基　　金：国家自然科学基金(21771111,21801137,21601092,21371104);河北省自然科学基金(B2016202280)。

摘　　要：用分步合成法得到了5对互为对映体的氰根桥连Fe(Ⅲ)-Cu(Ⅱ)-Ln(Ⅲ)异三金属配合物[{Cu(RR-valcy)Ln(H_(2)O)1.5(CH_(3)OH)1.5}{Fe(CN)_(6)}]·4H_(2)O·CH_(3)OH(Ln=Dy,1;Ho,3;Er,5;Tm,7;Yb,9)和[{Cu(SS-valcy)Ln(H_(2)O)1.5(CH_(3)OH)1.5}{Fe(CN)_(6)}]·4H_(2)O·CH_(3)OH(Ln=Dy,2;Ho,4;Er,6;Tm,8;Yb,10)(H_(2)valcy=N,N’-双(3-甲氧基水杨醛)-缩-1,2-环己二胺).X-射线单晶衍射分析表明,5对同构的对映体属于单斜晶系,P2(1)空间群,每个[Fe(CN)_(6)]^(3-)与一个[Cu(RR/SS-valcy)Ln(H_(2)O)_(1.5)(CH_(3)OH)_(1.5)]单元通过Fe-C≡N-Ln桥相连接.圆二色光谱测试证明每对配合物的光学活性和对映异构体性质.配合物1、3、5、7和9在2-300 K的直流变温磁化率数据符合Curis-Weiss定律,Weiss常数θ依次为-0.274、-3.64、-9.83、-7.29和-15.32 K.Five pairs of heterotrimetallic complexes[{Cu(RR-valcy)Ln(H_(2)O)1.5(CH_(3)OH)1.5}{Fe(CN)_(6)}]·4H_(2)O·CH_(3)OH(Ln=Dy,1;Ho,3;Er,5;Tm,7;Yb,9)and[{Cu(SS-valcy)Ln(H_(2)O)1.5(CH_(3)OH)1.5}{Fe(CN)_(6)}]·4H_(2)O·CH_(3)OH(Ln=Dy,2;Ho,4;Er,6;Tm,8;Yb,10)(H2valcy=N,N’-bis(3-methoxysalicylidene)-1,2-cyclohexanediamine)were prepared by step-wise synthetic approach.Single-crystal X-ray diffraction analysis revealed that five pairs of enantiomers are all isostructural and monoclinic with space group P2(1)and each[Fe(CN)_(6)]^(3-) is connected with one[Cu(RR/SS-valcy)Ln(H_(2)O)1.5(CH_(3)OH)_(1.5)]fragment via the Fe-C≡N-Ln bridge.The circular dichroism(CD)spectrum measurements confirmed the optical activity and enantiomeric nature of each pairs of complexes.In the temperature range of 2-300 K,the direct-current magnetic susceptibilities of complexes 1,3,5,7 and 9 are consistent with the Curie-Weiss law and give the Weiss constantsθ=-0.274,-3.64,-9.83,-7.29 and-15.32 K,respectively.

关 键 词：SCHIFF碱 氰根 异三金属配合物 晶体结构 磁性 

分 类 号：O614[理学—无机化学]