具有左手性螺旋链的两个三维钐配合物的合成、结构表征及性质研究

Synthesis, Structures and Properties of the 3D Compounds Containing L-Chiral Helical Chains

通过溶剂热合成法,合成了两种具有左手性双螺旋链的钐配合物,Sm(HCO2)(SO4)(H2O)(1)和KSm(H2O)(SO4)2(2)。在没有添加任何手性配体的情况下合成了含有左手性螺旋链的钐配合物1;在添加手性配体的情况下,合成了含有左手性双重螺旋链的钐配合物2。但是在化合物2中,手性配体没有进入到无机骨架中去而是起诱导手性化合物形成的作用。化合物1结晶于四方晶系P41空间群,而化合物2结晶于三方晶系P31空间群。单晶X-射线衍射分析表明:化合物1中含有两种L型[Sm-O]n螺旋链,相邻的两种螺旋链通过共用Sm(Ⅲ)进一步形成交叉的左手性双螺旋链;化合物2中存在着由[Sm-O-S1-O]n以及[Sm-O-S2-O]n形成的左手性的螺旋链,并且2个相邻的手性螺旋链通过共用Sm(Ⅲ)形成了1个二重螺旋链,2个二重螺旋链相互缠绕并通过钾离子相连在一起形成了手性双螺旋链。此外,我们还对化合物1和2的荧光性质以及二阶倍频效应进行了研究。

Two compounds with L-Chiral helical chains have been solvothermal synthesized： Sm（HCOE）（SO4）（H2O） （1） and KSm（H2O）（SO4）2 （2）. Complex I is synthesized without any chiral auxiliary, while complex 2 is the opposite. However, in 2, chiral auxiliaries do not exsit in the inorganic framework but work as the inducer in the formation of the complex. Single-crystal X-ray diffraction （XRD） demonstrates that complex 1 crystallizes in space group P41 and complex 2 crystallizes in space group P31. Complex 1 is constructed of two types of L-[Sm-O]n chains, every two different kinds of adjacent helical chains are connected by sharing Sm（ Ⅲ ） ions to form Intertwined left-handed double helices. Compound 2 is constructed of two L-chiral helical chains： [Sm-O-Sl-O]n and [Sm-O-S2-O]n, the two adjacent helical chains are connected by sharing Sm （Ⅲ） ions to form double helices chains, every two adjacent double helices chains are connected through K＋ linkages to form Intertwined left- handed double helices. The second-harmonic-generation efficiencies and fluorescence of 1 and 2 were studied. CCDC： 977312, 1; 977313, 2.