光致发光配合物[Au_2(PPh_3)_2(μ-4,4′-bpy)](ClO_4)_2 and [Cu_2(PPh_3)_4(CH_3CN)_2(μ-4,4′-bpy)](BF_4)_2的合成和晶体结构  

Syntheses, Crystal Structures and Photoluminescence of [Au_2(PPh_3)_2(μ-4,4′-bpy)](ClO_4)_2 and [Cu_2(PPh_3)_4(CH_3CN)_2(μ-4,4′-bpy)](BF_4)_2 Complexes

作　　者：李丹[1] 齐志宇[1] 冯巧[1] 李蓉珍[1] 冯小龙[2] 蔡继文[2] 

机构地区：[1]汕头大学化学系,汕头515063 [2]中山大学化学化工学院分析测试中心,广州510275

出　　处：《化学学报》2002年第9期1637-1643,共7页Acta Chimica Sinica

基　　金：国家自然科学基金 (No .2 990 10 0 4);广东省自然科学基金 (No.0 0 0 779);汕头大学"2 11工程"学科建设资助项目

摘　　要：合成了两个在空气中稳定的Au(Ⅰ )和Cu(Ⅰ )配合物 ,并运用元素分析、红外光谱、荧光光谱和X射线单晶衍射结构表征 ,[Au2 (PPh3 ) 2 (μ 4 ,4′ bpy) ](ClO4 ) 2 (1) (4 ,4′ bpy为 4,4′ 联吡啶 ) ,单斜晶系 ,空间群P2 1c,晶胞参数a=1.2 2 5 5 (4 )nm ,b=0 .9973(3)nm ,c=1.85 0 6 (6 )nm ,β =10 1.732 (5 )°,V =2 .2 145 (11)nm3 ,Z =4,最终偏离因子R =0 .0 430 ,wR =0 .0 937.[Cu2 (PPh3 ) 4(CH3 CN) 2 (μ 4 ,4′ bpy) ](BF4 ) 2 (2 ) ,单斜晶系 ,空间群P2 1c,晶胞参数a =1.34 6 3(3)nm ,b =1.46 81(3)nm ,c =2 .0 6 0 8(4 )nm ,β =10 0 .387(4 )° ,V =4.0 0 6 6 (13)nm3 ,Z =2 ,最终偏离因子R =0 .0 45 0 ,wR =0 .116 3.两个双核配合物都是利用 4,4′ 联吡啶桥联配体 ,形成直线结构 ,直线的两端以PPh3 或CH3 CN为端基 .Au(Ⅰ )为 2配位 ,Cu(Ⅰ )为 4配位 .两个配合物均具有光致发光特性 ,其中配合物 1发光来自MLCT激发态 ,而配合物 2则是受配位金属影响的配体内部发光 .Two air-stable Au(Ⅰ) and Cu(Ⅰ) complexes are synthesized and characterized by elemental analysis, IR, fluorescence spectroscopy, and X-ray diffraction crystallography. [Au 2(PPh 3) 2(μ-4,4′-bpy)]^(ClO 4) 2(1) (4,4′-bpy=4,4′-bipyridine) is monoclinic,space group P2 1c, unit cell dimensions, a= 1.2255(4) nm, b= 0.9973(3) nm, c= 1.8506(6) nm, β= 101.732(5)°, V= 2.2145(11) nm 3, Z=4, final R indices R= 0.0430, wR= 0.0937. [Cu 2(PPh 3) 4(CH 3CN) 2(μ-4,4′-bpy)](BF 4) 2(2) is mono^clinic, space group P2 1c, unit cell dimensions, a= 1.3463(3) nm, b= 1.4681(3) nm, c= 2.0608(4) nm, β= 100.387(4)°, V= 4.0066(13) nm 3, Z=2, final R indices R= 0.0450, wR= 0.1163. Each of the two dimeric complexes is linked by the bridging ligand 4,4′-bpy to form a chain structure. The chain is ended by PPh 3 or CH 3CN ligands. The Au(Ⅰ) is two-coordinate while Cu(Ⅰ) is four-coordinate. Both complexes are photoluminescent. The emission of complex 1 is from a MLCT excited state, and that of complex 2 originates from metal-perturbed intraligand.

关 键 词：光致发光配合物 [Au2(PPh3)2(μ-4 4'-bpy)](ClO4)2 [Cu2(PPh3)4(CH3CN)2(μ-4 4’-bpy)](BF4)2 合成 晶体结构 金(I) 铜(I) 三苯基膦 4 4'-联吡啶 

分 类 号：O641.4[理学—物理化学]