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化学学报
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化学学报 ›› 2002, Vol. 60 ›› Issue (9): 1637-1643. 上一篇    下一篇

研究论文

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

李丹;齐志宇;冯巧;李蓉珍;冯小龙;蔡继文   

  1. 汕头大学化学系,汕头(515063);中山大学化学化工学院分析测试中心,广州 (510275)
  • 发布日期:2002-09-15

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

Li Dan;Qi Zhiyu;Feng Qiao;Li Rongzhen;Feng Xiaolong;Cai Jiwen   

  1. Department of Chemistry, Shantou University,Shantou(515063)
  • Published:2002-09-15

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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，[Au_2(PPh_3)_2(μ-4,4'-bpy)] (ClO_4)_2（1）（4,4'-bpy为4,4'-联吡啶），单斜晶系，空间群P2_1 c，晶胞参 数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，最终偏离因子R = 0.0430，wR = 0.0937。 [Cu_2(PPh_3)_4(CH_3CN)_2(μ-4,4'-bpy)](BF_4)_2（2），单斜晶系，空间群 P2_1 c，晶胞参数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，最终偏离因子R = 0.0450，wR = 0.1163。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PPh_3或CH_3CN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。

关键词: 金络合物, 铜络合物, 三苯基膦, 联吡啶, 晶体结构

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_1 c, 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 monoclinic, space group P2_1 c, 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.

Key words: GOLD COMPLEX, COPPER COMPLEX, TRIPHENYLPHOSPHINE, BIPYRIDINE, CRYSTAL STRUCTURE

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