簇合物[WS_(4)Ag_(3)(PPh_(3))_(3){S_(2)P(OCH_(2)Ph)_(2)}]的合成、晶体结构及非线性光学性质  

Synthesis, Crystal Structure and Nonlinear Optical Properties of Cluster [WS_(4)Ag_(3)(PPh_(3))_(3){S_(2)P(OCH_(2)Ph)_(2)}]

作　　者：常青[1] 王燕[2] 李小华[3] 宋瑛林[4] 郑和根[2] 忻新泉[2] S.Shanmuga Sundara Raj Hoong-Kun Fun CHANG Qing;WANG Yan;LI Xiao—Hua;SONG Ying—Lin;ZHENG He—Gen;XIN Xin—Quan;Shanmuga Sundara Raj;Hoong-Kun Fun(College of Electronic Engineering,Heilongfiang University,Harbin 1500802;Coordination Chemistry Institute,State Key Laboratory of Coordination Chemistry,Nanjing University,Nanjing 210093;Department of Chemistry,Nanjing Xiaozhuang College,Nanjing 210017;Applied Physics Department,Harbin Institute of Technology,Harbin 150001;X-Ray Crystallography Unit,School of Physics,University Sains Malaysia,l 1800 USM,Penang,Malaysia)

机构地区：[1]黑龙江大学电子工程学院 [2]南京大学配位化学国家重点实验室 [3]南京晓庄学院化学系 [4]哈尔滨工业大学应用物理系 [5]X-Ray Crystallography Unit School of Physics,University SainsMalaysia,11800USM,Penang,Malaysia

出　　处：《无机化学学报》2003年第6期574-578,共5页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金资助项目(No.20171020,No.10104007);国家自然科学基金重大项目(No.90101028)资助。

摘　　要：本文用(NH_(4))_(2)WS_(4),Ag[S_(2)P(OCH_(2)Ph)_(2)]和PPh_(3)为原料合成了簇合物[WS_(4)Ag_(3)(PPh_(3))_(3)S_(2)P(OCH_(2)Ph)_(2)],并得到了晶体。晶体属正交晶系,空间群为P2_(1)2_(1)2_(1),晶胞参数a=1.32370(4)nm,b=1.34427(4)nm,c=3.83246(11)nm。X-射线单晶结构测定结果表明它具有巢状分子结构,配体(PhCH_(2)O)_(2)PS^(-)_(2)(简称dtp)的两个S原子中的一个硫原子仅与一个金属原子配位,另一个硫原子则同时与两个金属原子配位。簇合物的非线性光学性质用脉宽8ns激光在532nm波长进行了研究。该化合物表现为一定的光学吸收和强的自聚焦效应,其三阶非线性吸收系数α_(2)=1.50×10^(-10)m·W^(-1),折射系数n_(2)=2.45×10^(-11)esu。The cluster[WS4Ag_(3)(PPh_(3))_(3){S_(2)P(OCH_(2)Ph)_(2)}]had been synthesized from the reaction of(NH_(4))_(2)WS_(4),Ag[S_(2)P(OCH_(2)Ph)_(2)]and PPh3,and then it was characterized by IR and elemental analyses.The structure of[WS_(4)Ag_(3)(PPh_(3))_(3){S_(2)P(OCH_(2)Ph)_(2)}]was determined by single crystal X-ray diffraction revealing that the cluster consist of a nest-shaped core.The W atom is tetrahedrally coordinated by four S atoms.The dithiophosphate ligand adopts a triply bridging role,employing two sulfur atoms to coordinate to the three Ag atoms:one sulfur atom binds to one Ag atom,the other to the rest two.The nonlinear optical properties were studied with an 8ns pulsed laser at 532nm.Its optical responses to the incident light exhibited considerably optical absorptive and strong self-focusing effect with alpha(2)=1.50 x 10^(-10)m(.)W^(-1),n(2)=2.45 x 10^(-11)esu.

关 键 词：银(I)配合物 晶体结构 簇合物 非线性光学性质 

分 类 号：O614.122[理学—无机化学] O614.613[理学—化学]