Di- and tetranuclear heterometallic CuⅡ-LnⅢ complexes (Ln = Gd and Dy): Synthesis, structure and magnetic properties  

作　　者：ZHANG ZeMin GUO FuSheng GUO PengHu LIU JunLiang NI ZhaoPing TONG MingLiang 

机构地区：[1]Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education,State Key Laboratory of Optoelectronic Materials and Technologies,School of Chemistry and Chemical Engineering,Sun Yat-Sen University,Guangzhou 510275,China

出　　处：《Science China Chemistry》2012年第6期934-941,共8页中国科学(化学英文版)

基　　金：supported by the National Natural Science Foundation of China (91122032, 90922009, 21121061);the National Basic Research Program of China (2012CB821704)

摘　　要：Four 3d-4f heterometallic complexes, [CuⅡ-LnⅢ(bpt)2(NO3)3(MeOH)] (Ln = Gd, 1; Dy, 2; bptH = 3,5-bis(pyrid-2-yl)-l,2,4- triazole), [CuⅡ-LnⅢ(μ-OH)2(bpt)4C14 (H2O)2]·6H2O (Ln = Gd, 3; Dy, 4), have been synthesized under solvothermal condi- tions. X-ray structural analyses reveal that 1 and 2 are isostructural while 3 and 4 are isostructural. In each complex, the copper and gadolinium or dysprosium ions are linked by two triazolate bridges and form a CuⅡ-LnⅢ dinuclear unit. The intramolecu- lar Cu-Ln distances are 4.542, 4.525, 4.545 and 4.538 ] for 1, 2, 3 and 4, respectively. Two dinuclear CuLn units are bridged by two OH- groups into the zig-zag tetranuclear {cunzLnm2} structures with the Ln(Ⅲ)...Ln(Ⅲ) distances of 3.742 and 3.684 for 3 and 4, respectively. Magnetic studies show that the antiferromagnetic CulI-Lnm interactions occur in 1 (Jcu = -0,21 cm-1) and 2. The antiferromagnetic interaction occurs in complex 3 with JcuGa = -0.82 cm-1 and JcdGd = --0.065 cm-1, while domi- nant ferromagnetic interaction occurs in complex 4.Four 3d-4f heterometallic complexes, [CuⅡ LnⅢ (bpt) 2 (NO 3 ) 3 (MeOH)] (Ln = Gd, 1; Dy, 2; bptH = 3,5-bis(pyrid-2-yl)-1,2,4- triazole), [CuⅡ 2 LnⅢ 2 (μ-OH) 2 (bpt) 4 Cl 4 (H 2 O) 2 ]·6H 2 O (Ln = Gd, 3; Dy, 4), have been synthesized under solvothermal conditions. X-ray structural analyses reveal that 1 and 2 are isostructural while 3 and 4 are isostructural. In each complex, the copper and gadolinium or dysprosium ions are linked by two triazolate bridges and form a CuⅡ -LnⅢ dinuclear unit. The intramolecular Cu-Ln distances are 4.542, 4.525, 4.545 and 4.538 for 1, 2, 3 and 4, respectively. Two dinuclear CuLn units are bridged by two OH- groups into the zig-zag tetranuclear {CuⅡ 2 LnⅢ 2 } structures with the Ln(Ⅲ) Ln(Ⅲ) distances of 3.742 and 3.684 for 3 and 4, respectively. Magnetic studies show that the antiferromagnetic CuⅡ-LnⅢ interactions occur in 1 (J CuGd = 0.21 cm-1 ) and 2. The antiferromagnetic interaction occurs in complex 3 with J CuGd = 0.82 cm-1 and J GdGd = 0.065 cm-1 , while dominant ferromagnetic interaction occurs in complex 4.

关 键 词：heterometallic complexes copper LANTHANIDES triazolate X-ray crystallography magnetic properties 

分 类 号：O614.33[理学—无机化学]