水热/溶剂热原位合成法制备有机膦酸铜化合物

在水热(溶剂热)条件下,以对苯二甲基二膦酸二乙酯(dixdp)为有机配体,分别以2,2'-联吡啶(bpy)及1,10-菲啰啉(phen)为辅助配体,合成了2个具有零维结构的有机膦酸铜化合物Cu2(H2O)2(H2L)(bpy)2(H3L)2]·2H2O(1)及Cu2(H2O)2(H2L)2(phen)2]·6H2O(2);其中dixdp在水热/溶剂热条件下发生原位水解反应生成对苯二甲基二膦酸(H4L)。化合物1属于单斜晶系,P 21/n空间群,该化合物的每个中心离子Cu采用CuO3N2]四方锥体几何配位,两个相邻金属中心Cu通过H3L-配体相连接形成0D双核铜单元。化合物2属于三斜晶系,P-1空间群,该化合物每个金属中心Cu也采用CuO3N2]四方锥体几何配位,但不同的是化合物2中的两个相邻Cu原子通过H2L2-配体相连接形成双金属环单元。

Copper Phosphonates Based on Hydro/Solvothermal In Situ Ligand Synthesis

Two new copper phosphonates, namely, Cu2(H2O)2(H2L)(bpy)2(H3L)2]?2H2O (1) and Cu2(H2O)2(H2L)2(phen)2]?6H2O (2) (H4L = p-xylylenediphosphonic acid, bpy = 2,2'-bipyridine and phen = 1,10-phenanthroline), have been synthesized under hydro/solvothermal conditions using diethyl p-xylylenediphosphonate (dixdp) and corresponding copper salts as building blocks, in which p-xylylenediphosphonic acid (H4L) was generated via in situ hydrolysis. Compound 1 crystallizes in the monoclinic P 21/n space group, each Cu(II) atom exhibits CuO3N2] square pyramidal coordination geometry, two adjacent copper atoms are connected by H3L- ligands to from 0D binuclear Cu(II) units. Compound 2 crystallizes in the triclinic P 21/n space group, each Cu(II) atom aso exhibits CuO3N2] square pyramidal coordination geometry, but the differences is that the adjacent copper atoms are connected by H2L2- ligands.