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