Self-assembly of polyiodide with dinuclear transition metal complex cation

Three compounds were obtained by self - assembly of polyiodide with dinucle ar transition metal complex cation, and characterized by single crystal X - ray diffraction method (Mo K alpha radiation, lambda = 0.071069nm), IR, an d 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, monocl inic, 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 C40 H32Cl2I8Mn2N8, 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, sp ace group P-l, a=l. 10793 (4) nm, b=1.43488(5)nm, c=1.98724(8)nm, ct 100.63 52(16)degrees, beta =96.4348(19)degrees, gamma =110.0297(19)degrees, V=2.86 409(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 bifu rcate (MCl(bpy)(2))(2)(2+) (M = Ni, Mn) cations build pin - hole like layer structure through the aromatic pi-pi interaction between the aromatic liga nds, bpy. These holes are inserted by I-2 molecules or I-3(-) anions, betwe en the layers locate I-2, I-3(-), I-5(-), and I-7(-). They are further link ed themselves and together with these intralayer I-2 molecules or I-3(-) an ions through weak I-I bonds, to form complicated and extended polyiodide ne twork possessing channels with nanometer diameter. These channels are occup ied by the cations. The assignment were made for the IR spectra (4000 simil ar 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 b and, indicating the electron delocalization over the entire polyiodide netw ork, as revealed by X- ray crystallography.