Cyanide-bridged complexes based on dinuclear Cu(Ⅱ)-M(Ⅱ) [M=Pb and Cu] building blocks: Synthesis, crystal structures and magnetic properties  

作　　者：WANG HaiLong WANG Kang CAO Wei BAI Ming BIANYongZhong JIANG JianZhuang 

机构地区：[1]Marine College, Shandong University at Weihai, Weihai 264209, China [2]Department of Chemistry, University of Science and Technology Beijing, Beijing 100083, China

出　　处：《Science China Chemistry》2012年第6期978-986,共9页中国科学（化学英文版）

基　　金：financially supported by the National Natural Science Foundation of China;Ministry of Education of China;Beijing Municipal Commission of Education;Fundamental Research Funds for the Central Universities

摘　　要：Four cyanide-bridged heterometallic complexes { [CuPb（L1）][FenI（bpb）（CN）2] }2-（C104）2.2H20.2CH3CN （1）, { [CuPb（LI）]2[FeII （CN）6]（HzO）z}＇10H20 （2）, {[Cu2（L2）][Fent（bpb）（CN）2]2}＇2H20＇2CH3OH （3） and {[Cu2（L2）]3[FeIII（CN）6]z（H20）2}-10H20 （4） have been synthesized by treating K[Fem（bpb）（CN）2] [bpb2-=l,2-bis（pyridine-2-carboxamido）benzenate] and K3[Feln（CN）]6 with dinuc[ear compartmental macrocyclic Schiff-base complexes [CuPh（LI）].（C104）2 or [Cu2（L2）]-（CIO4）2, in which H2LJ was derived from 2,6-diformyl-4-methyl-phenol, ethylenediamine, and diethylenetriamine in the molar ratio of 2：1：1 and H2L2 from 2,6-diformyl-4-methyl-phenol and propylenediamine in the molar ratio of 1：1. Single crystal X-ray diffraction analysis reveals that compound 1 displays a cyclic hexanuclear heterotrimetallic molecular structure with alternating [Fem（bpb）（CN）2]- and [CuPb（L＋）]2＋ units. Complex 2 is of a neutral dumb-bell-type pentanuclear molecular configuration consisting of one [Fe（CN）6]4- anion sandwiched in two [CuPu（L1）]2＋ cations, and the pentanuclear moieties are further connected by the hydro- gen bonding to give a 2D supramolecular framework. Heterobimetallic complex 3 is a tetranuclear molecule composed of a centrosymmetric [Cuz（L2）]2＋ segment and two terminal cyanide-containing blocks [Fetn（bpb）（CN）2]-. Octanuclear compound 4 is built from two [Fe（CN）6]3- anions sandwiched in the three [Cu2L2]2＋ cations. Investigation of their magnetic properties reveals the overall antiferromagnetic behavior in the series of complexes except 2.Four cyanide-bridged heterometallic complexes {[CuPb(L 1 )][Fe III (bpb)(CN) 2 ]} 2 ·(ClO 4 ) 2 ·2H 2 O·2CH 3 CN (1), {[CuPb(L 1 )] 2 [Fe II (CN) 6 ](H 2 O) 2 }·10H 2 O (2), {[Cu 2 (L 2 )][Fe III (bpb)(CN) 2 ] 2 }·2H 2 O·2CH 3 OH (3) and {[Cu 2 (L 2 )] 3 [Fe III (CN) 6 ] 2 (H 2 O) 2 }·10H 2 O (4) have been synthesized by treating K[Fe III (bpb)(CN) 2 ] [bpb 2-=1,2-bis(pyridine-2-carboxamido)benzenate] and K 3 [Fe III (CN)] 6 with dinuclear compartmental macrocyclic Schiff-base complexes [CuPb(L 1 )] (ClO 4 ) 2 or [Cu 2 (L 2 )]·(ClO 4 ) 2 , in which H 2 L 1 was derived from 2,6-diformyl-4-methyl-phenol, ethylenediamine, and diethylenetriamine in the molar ratio of 2:1:1 and H 2 L 2 from 2,6-diformyl-4-methyl-phenol and propylenediamine in the molar ratio of 1:1. Single crystal X-ray diffraction analysis reveals that compound 1 displays a cyclic hexanuclear heterotrimetallic molecular structure with alternating [FeⅢ (bpb)(CN) 2 ]- and [CuPb(L 1 )] 2+ units. Complex 2 is of a neutral dumb-bell-type pentanuclear molecular configuration consisting of one [Fe(CN)6] 4- anion sandwiched in two [CuPu(L 1 )] 2+ cations, and the pentanuclear moieties are further connected by the hydrogen bonding to give a 2D supramolecular framework. Heterobimetallic complex 3 is a tetranuclear molecule composed of a centrosymmetric [Cu 2 (L2)] 2+ segment and two terminal cyanide-containing blocks [FeⅢ (bpb)(CN)2 ]- . Octanuclear compound 4 is built from two [Fe(CN)6]3- anions sandwiched in the three [Cu 2 L 2 ] 2+ cations. Investigation of their magnetic properties reveals the overall antiferromagnetic behavior in the series of complexes except 2.

关 键 词：cyanide-bridged complex crystal structures magnetic properties 

分 类 号：O614.821[理学—无机化学] O614.121[理学—化学]