Self-assembly of polyiodide with dinuclear transition metal complex cation

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 alpha radiation, lambda = 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 C40H32Cl2I8N8Ni2, M-r = 1828.26, monoclinic, space group C2/c, a = 1.37091(3)nm, b = 1.67996(3)nm, c =2.20708(5)nm, beta =91.6114(12)degrees, V=5.08106(18)nm(3), Z= 4, D-e = 2. 390mg/m(3), mu = 5. 745mm(-1), F(000) = 3368, R1 = 0. 0674 for 4367 observations; 2 C40H32Cl2I8Mn2N8, M-r=1820.72, monoclinic, space group C2/c, a=1.38898(3)nm, b =1.70579(4) nm, c=2.22092(4)nm, beta =92.9168(13)degrees, V=5.25523(19)nm(3), Z =4, D-c = 2.301mg/m(3), mu = 5.318mm(-1), F(000) = 3344, R1 = 0.0470 for 4485 observations; and 3 C40H32Cl2I11Mn2N, M-r = 2201.42, triclinic, space group P-l, a=l. 10793 (4) nm, b=1.43488(5)nm, c=1.98724(8)nm, ct 100.6352(16)degrees, beta =96.4348(19)degrees, gamma =110.0297(19)degrees, V=2.86409(18)nm(3), Z=2, D-c=2.553mg/ m(3), mu = 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 pi-pi interaction between the aromatic ligands, bpy. 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 similar to 50cm(-1)) of these compounds. The powder diffuse-reflectance UV-vis spectra (200 similar to 800nm) of compound 1 and 3 are featureless board band, indicating the electron delocalization over the entire polyiodide network, as revealed by X-ray crystallography.