化学学报 ›› 2000, Vol. 58 ›› Issue (12): 1615-1625. 上一篇    下一篇

研究论文

多碘阴离子与双核配合物阳离子的超分子组装

王哲明;袁敏;何筝;廖春生;严纯华   

  1. 北京大学稀土材料化学及应用国家重点实验室.北京;北京大学-香港大 学稀土材料与生物无机联合实验室
  • 发布日期:2000-12-15

Self-assembly of polyiodide with dinuclear transition metal complex cation

Wang Zheming;Yuan Min;He Zheng;Liao Chunsheng;Yan Chunhua   

  1. .
  • Published:2000-12-15

通过多碘阴离子与双核配合物阳离子的超分子组装获得了3个新的化合物并对其进行了X射线结构测定和红外光谱,紫外-可见光谱的表征。它们是[(NiCl(bpy)~2)~2^2^+](I~3^-)~2(I~2)(1),[(MnCl(bpy)~2)~2^2^+](I~3^-)~2(I~2)(2)和[(MnCl(bpy)~2)~2^2^+](I~7^-)~1~/~2(I~5^-)(I~3^-)~1~/~2(I~2)~1~/~2(bpy=2,2'-bipyridine)(3)。晶体学数据:1单斜晶系,空间群C2/c,a=1.37091(3)nm,b=1.67996(3)nm,c=2.20708(5)nm,β=91.6114(12)°,V=5.08106(18)nm^3,Z=4,对4367个可观测反射点R1=0.0674;2单斜晶系,空间群C2/c,a=1.38898(3)nm,b=1.70579(4)nm,c=2.22092(4)nm,β=92.9168(13)°,V=5.25523(19),Z=4,对4485个可观测反射点R1=0.0470;3三斜晶系,空间群P-1,a=1.10793(4)nm,b=1.43488(5)nm,c=1.98724(8)nm,α=100.6352(16)°,β=96.4348(19)°,γ=110.0297(19)°,V=2.86409(18)nm^3,Z=2,对7156个可观测反射点R1=0.0634。这三个化合物中都含有具有分叉形状的双核配合物阳离子[(MCl(bpy)~2)~2]^2^+(M=Mn,Ni),它们通过配体bpy之间的π-π堆垛构成带孔洞的层状结构,在层中由配体bpy围成的孔洞填充了I~2分子或I~3^-阴离子,组装成由I~2分子或I~3^-阴离子穿越的正电性的层。在层和层之间则占据了相互连接的I~2,I~3^-,I~5^-,I~7^-,并与层中的I~2,I~3^-相连,形成复杂的具有无限扩展结构的多碘离子的网络,在网络中,多碘离子构成了直径达纳米的孔道结构。对化合物的红外光谱(4000~50cm^-^1)进行了归属。化合物1和3的紫外-可见漫反射光谱(200~800nm)为无特征的宽吸收带,源于无限扩展结构的多碘离子上的电子离域。

关键词: 双核络合物, 自组装, 晶体结构, X射线衍射分析, 红外分光光度法, 紫外分光光度法, 镍络合物, 吡啶P

Three compounds were obtained by self-assembly of polyiodide with dinuclear transition metal complex cation, and characterized by single crystal X-ray diffraction method (Mo K~α radiation, λ=0. 071069nm), IR, and UV-vis spectroscopy. They are [(NiCl(bpy)~2)~2^2^+] (I~3^-)~2(I~2)(1), [(MnCl(bpy)~2)~2^2^+](I~3^-)~2(I~2)(2) and [(MnCl (bpy)~2)~2^2^+](I~7^-)~1~/~2(I~5^-)(I~3^-)~1~/~2(I~2)~1~/~2 (bpy=2,2'- bipyridine)(3) with crystallographic data for 1 C~4~0H~3~2Cl~2I~8N~8Ni~2, M~r=1828.26, monoclinic, space group C2/c, a=1.37091(3) nm, b=1.67996(3) nm, c=2.20708(5) nm, β=91.6114(12)°, V=5.08106(18) nm^3, Z=4, D~c=2.390mg/m^3, μ=5.745mm^-^1, F(000)=3368, R1=0.0674 for 4367 observations; 2 C~4~0H~3~2Cl~2I~8Mn~2N~8, M~r=1820.72, monoclinic, space group C2/c, a=1.38898(3) nm, b=1.70579 (4) nm, c=2.22092(4) nm, β=92.9168(13)°, V=5.25523(19), Z=4, D~c=2. 301mg/m^3, μ=5.318mm^-^1, F(000)=3344, R1=0.0470 for 4485 observations; and 3 C~4~0H~3~2Cl~2I~1~1Mn~2N~8, M~r=2201.42, triclinic, space group P-1, a=1.10793(4) nm, b=1.43488(5) nm, c=1. 98724(8) nm, α=100.6352(16)°,β=96.4348(19)°, γ=110.0297(19)°, V=2.86409(18) nm^3, Z=2, D~c=2.553mg/m^3, μ=6.499mm^-^1, F(000)=1990, R1=0.0634 for 7156 observations. In the three structures the dinuclear bifurcate (MCl(bpy)~2)~2^2+ (M=Ni, Mn) cations build pin- hole like layer structure through the aromatic π-π interaction between the aromatic ligands, byp. These holes are inserted by I~2 molecules or I~3^- anions, between the layers locate I~2, I~3^-, I~5^- , and I~7^-. they are further linked themselves and together with these intralayer I~2 molecules or I~3^- anions through weak I-I bonds, to form complicated and extended polyiodide network possessing channels with nanometer diameter. These channels are occupied by the cations. The assignment were made for the IR spectra (4000~50cm^-^1) of these compounds. The powder diffuse-relfectance UV-vis spectra (200~800nm) of compound 1 and 3 are featureless board band, indicating the electron del多碘阴离子与双核配合物阳离子的超分子组装

Key words: DINUCLEAR COMPLEX, CRYSTAL STRUCTURE, X-RAY DIFFRACTION ANALYSIS, INFRARED SPECTROPHOTOMETRY, ULTRAVIOLET SPECTROPHOTOMETRY, NICKEL COMPLEX, PYRIDINE P

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