Ag(PPh_3)_3(CN)·(DMF)·0.5(H_2O)配合物的合成和发光性质

Synthesis and Iuminescent Property of the Coordination Compound Ag(PPh_3)_3(CN)·(DMF)·0.5(H_2O)

最近研究表明d10金属离子与氰基构成的配合物一般具有良好的发光性能,是一种潜在的光致发光功能材料。选择氰化银和三苯基磷在四氢呋喃溶剂中反应,产物经过N,N′-二甲基甲酰胺萃取后再通过乙醚扩散,成功地合成出了一个氰化银基配合物,分子式为Ag(PPh3)3(CN).(DMF).0.5(H2O)。通过元素分析、红外光谱以及结合配体的结构特点推测出配合物应该是由Ag(PPh3)3(CN)单元、游离的N,N′-二甲基甲酰胺和水溶剂分子组成。在Ag(PPh3)3(CN)单元中银离子处于变形的四面体中心,分别和一个氰基配体的C原子和3个三苯基磷配体的磷原子配位。荧光光谱研究表明配合物经325 nm光的激发后在440 nm处发出较强的蓝紫色荧光。通过分析配合物及其配体的发光行为指出配合物的发光可以归属为受金属离子微扰的配体(三苯基磷)发光。

Great interest is presently being focused on the controllable preparation of molecular functional materials, transition-metal coordination compounds in the use of cyanometallate and cyanide as Building blocks. Within these complexes, the complexes consisted of d^10 metal ions and cyanide groups commonly possess good luminescent properties, with the potential applications in photo-luminescent functional materials. Based on this, the paper AgCN （silver cyanide） and Ph3P （triphenylphosphine） are selected to react in tetrahydrofuran （THF） solution with slight heat and stir for 6 hour. Mter evaporation to dryn, the resulting solid is extracted with N,N＇- dimethylformamide （ DMF）, then the solution is filtered in a small tube which is loaded into a large vial containing diethyl ether. The large vial was sealed and left undisturbed at room temperature, and orange crystals of the title complex Ag（ PPh3 ）3 （CN） · （DMF） ·0. 5（H2O） are obtained in 10 days. The possible structure of the complex is deduced by elemental analyses, FT-IR spectrum and the structural feature of the ligand （Ph3 P）. The complex should consist in a discrete structure with Ag（ PPh3 ）3 （CN） complex and isolated DMF and aqua solvent molecules. Within the Ag（ PPh3 ）3 （CN） moiety, the silver atom in the center of slightly distorted tetrahedral geometry is coordinated by three PPh3 ligands and one cyanide group. The photoluminescence of the present complex can be ascribed to originate from intraligand charge transfer slightly modified by metal ions through the analysis of the photoluminescent behaviors of the present complex and its PPh3 ligands.