Costes Jean-Pierre, Novitchi Ghenadie, Shova Sergiu, Dahan Françoise, Donnadieu Bruno, Tuchagues Jean-Pierre
Laboratoire de Chimie de Coordination du CNRS, 205 Route de Narbonne, F-31077 Toulouse Cedex, France.
Inorg Chem. 2004 Nov 29;43(24):7792-9. doi: 10.1021/ic048942i.
The monometallic precursors L1Cu and L2Cu (L1H2 standing for 1,3-bis((3-ethoxysalicylidene)amino) propane and L2H2 standing for 1,2-bis((3-methoxysalicylidene)amino) ethane) react with sodium dicyanamide (dca) (NaN3C2), a mixture of gadolinium nitrate, and sodium dicyanamide to yield heterodinuclear L2CuNa(NCNCN) and L1CuGd(NO3)(NCNCN)2 entities. The structural determination shows that two Cu-Na entities are linked by dca with an original mu1,1 coordination mode, evidenced here for the first time, to yield tetranuclear complexes. Two hydrogen bonds operate between the water molecule coordinated to one of the sodium ions and the free nitrogen atoms of two dca ligands, yielding infinite zigzag chains. The structural determination of the Cu-Gd entities indicates that they are held together by two dca ligands, bridging alternately Cu to Gd and Gd to Gd cations, in the more common mu1,5 mode to yield a one-dimensional (1D) network. The dca ligands are not able to transmit interaction between the magnetically active centers in these chains, which are the unique example of structurally characterized Cu-Gd complexes involving dca ligands.
单金属前驱体L1Cu和L2Cu（L1H2代表1,3 - 双（（3 - 乙氧基水杨醛）氨基）丙烷，L2H2代表1,2 - 双（（3 - 甲氧基水杨醛）氨基）乙烷）与双氰胺钠（dca）（NaN3C2）、硝酸钆混合物以及双氰胺钠反应，生成异双核L2CuNa（NCNCN）和L1CuGd（NO3）（NCNCN）2实体。结构测定表明，两个Cu - Na实体通过dca以一种首次在此得到证实的原始μ1,1配位模式相连，形成四核配合物。与其中一个钠离子配位的水分子与两个dca配体的游离氮原子之间存在两个氢键，形成无限之字形链。Cu - Gd实体的结构测定表明，它们通过两个dca配体以更常见的μ1,5模式交替连接Cu与Gd以及Gd与Gd阳离子，形成一维（1D）网络。dca配体无法在这些链中的磁活性中心之间传递相互作用，这些链是涉及dca配体的结构表征Cu - Gd配合物的唯一实例。
