三螺旋N-N桥连的双核Co(Ⅲ)配合物的合成、结构和性质(英文)

A Dicobalt(Ⅲ) Complex Containing Triple Helical N-N Bridges: Synthesis, Structure and Property

以N,N’-二（2-吡啶甲酰）肼为配体（H2L），水热法合成了1个新的双核钻㈣配合物[Co2L3]·8H2O（1），对其进行了紫外、红外、电喷雾质谱、热重、元素分析和单晶结构表征。单晶结构分析表明1属于三方晶系，空间群R3c，a=1．63640（11）nm，α=48．52°，V=2．2556（3）nm3,Z=2，R1=0．062。每个钻（Ⅲ）离子处于八面体[CoN6]中，每个L2-配体通过N-N桥连2个钴（Ⅲ）离子，双核钴的距离为0．3497（2）nm。配合物分子间通过羰基和吡啶环间的氢键形成一维长链，链之间由晶格水连接形成三维超分子结构。热重表明1在90℃失去结晶水，500℃以上分解。变温磁化率显示1为抗磁性（1．8～375K）。

A new dinuclear cobalt（Ⅲ） complex, [Co2L3] ·8H2O （1）, （H2L=N,N＇-bis（2-picolinoyl）hydrazine）, was synthesized by a hydrothermal method and characterized by UV, FT-IR, ESI-MS, TGA, EA and single crystal X- ray crystallography. The complex crystallizes in trigonal system with space group R3c, a=1.636 40（11） nm, α= 48.52°, V=2.255 6 （3） nm3, Z=2, and final R=0.062. Each Co（Ⅲ） has an octahedral [CON6] core. Each L2- ligand binds simultaneously to two Co（Ⅲ） cations in a bis（N,N＇）-bridging coordination mode with a Co…Co distance of 0.349 7（2） nm. The hydrogen bonding interactions between carbonyl group and pyridyl ring link the molecules of 1 into a 1D chain which was further connected by the lattice water to form a 3D supramolecular framework. The TG analysis shows that 1 loses lattice water at 90 ℃ and is stable below 500℃. Magnetic measurement reveals that 1 is a low-spin species in the range of 1.8-375 K. CCDC： 744616.