铜(II)-锰(II)四核配合物的合成、晶体结构和磁性  

Synthesis, Crystal Structure and Magnetic Properties of a New Heterotetranuclear Copper(II)-manganese(II) Complex

作　　者：何奕[1] 寇会忠[1] 熊明[2] 王如骥[1] 

机构地区：[1]清华大学化学系,北京100084 [2]中国地质大学地质实验室,北京100083

出　　处：《Chinese Journal of Structural Chemistry》2004年第5期574-579,共6页结构化学（英文）

基　　金：国家自然科学基金(20201008; 50272034)

摘　　要：报道了一个草酰胺桥连的四核Cu(Ⅱ)Mn(Ⅱ)配合物[Mn(CuL)3][Mn(H20)6][N(CN)2]2(C104)2·4H2O(L为l，4，8，ll一四氮杂环十四烷-2，3-二酮)(C34H74C12Cu3Mn2N18O24，Mr=1490．51)的合成、晶体结构和磁性。配合物属于单斜晶系，空间群为C2／c，晶胞参数如下：α=22．295(5)，b=12．852(3)，c=20．109(4)°/A，β=90．47(3)^。，V=5762(2)°/A^3，Dc=1．718g／m^3，Z=4，F(000)=3068，μ=1．701mm^-1，R=0．0915，wR=0．1810(based on F^2)。3个中性Cu(Ⅱ)大环配合物通过6个氧原子与Mn(Ⅱ)配位，Mn-O键长范围为2．190(6)～2．208(5)°/A。[Mn(CuL)3]2+通过高氯酸根离子连接起来形成一个二维层。高氯酸根的氧原子与Cu^Ⅱ键长范围为2．902～2．996°/A，为弱相互作用。[Mn(H20)6]^2+，N(CN)2^-和H2O位于层间，并通过氢键连成三维网络结构。磁性研究表明Cu^Ⅱ-Mn^Ⅱ离子间通过草酰胺传递反铁磁相互作用，用基于各向同性的Hamiltonian算符＾/H=2JMnCu＾/SMn(＾/SCul+＾/SCu2+＾/SCu3)进行磁性拟合得到磁耦合常数JCuMn=-17cm^-1。A new complex [Mn(CuL)3][Mn(H2O)6][N(CN)2]2(ClO4)24H2O (L = 1,4,8,11-tetraazacyclotetradecane-2, 3-dione) has been synthesized and structurally characterized by X-ray diffraction. The complex crystallizes in monoclinic, space group C2/c with a = 22.295(5), b = 12.852(3), c = 20.109(4) , = 90.47(3) and Z = 4. Three neutral copper(II) complexes of tetraazamacrocyclic oxamide coordinate to the manganese(II) ion with six carbonyl oxygen atoms with the MnO bond distances ranging from 2.190(6) to 2.208(5) ? Perchlorate anions are posited within the layers formed by the regular arrangement of [Mn(CuL)3]2+ moieties. The oxygen atoms of perchlorate ions semi-coordinate to copper(II) (CuO: 2.902 to 2.996 ) and link the [Mn(CuL)3]2+ units, generating a two-dimensional structure. [Mn(H2O)6]2+, dca- (dicyanamide anion) and water are distri- buted between the layers to form many H-bonds which connect the layers into a three-dimensional network. Magnetic studies show the presence of antiferromagnetic interaction between the Cu(II) and Mn(II) ions. Best fit to the experimental data by using the Hamiltonian  = 2JMnCuMn(Cu1 + Cu2 + Cu3) gives the coupling constant JMnCu of 17 cm-1.

关 键 词：晶体结构 铜(Ⅱ) 锰(Ⅱ) 四核配合物 磁性 草酰胺 大环配体 

分 类 号：O641.4[理学—物理化学]