摘要
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R_1=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(09)nm^3,Z=4,对4485个可观测反射点R_1=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R_1=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(byp)_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_
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 Kα radiation, λ= 0.071069nm), IR, and UV - vis spectroscopy. They are [(NiCl(bpy)2)22 +] (I3-)2(I2)(1), [(MnCl-(bpy)2)22+](I3-)2(I2) (2) and [(MnCl(bpy)2)22+ (I7- )1/2(I5- )(I3- )1/2(I2)1/2(bPy = 2,2' - bipyridine) (3) with crystallographic data for 1 C40H32Cl2I8N8Ni2, Mr = 1828.26, monoclinic, space group C2/c, a= 1.3709l(3)nm, b = 1.67996(3)nm, c =2.20708(5)nm, β = 91.6114(12)°, V = 5.08106(18)nm3, Z = 4, Dc = 2. 390mg/m3, μ = 5. 745mm-1, F (000) = 3368, R1 = 0. 0674 for 4367 observations; 2 C40H32Cl2I8Mn2N8, Mr=1820.72, monoclinic, space group C2/c, a = 1.38898(3)nm, 6 = 1.70579(4) nm, c = 2.22092(4)nm, β= 92.9168(13)°, V = 5.25523(19)nm3, Z = 4, Dc = 2.301mg/m3, μ = 5.318mm-1, F(000) = 3344, R1 =0.0470 for 4485 observations; and 3 C40H32Cl2I11Mn2N8, Mr = 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)nm3, Z = 2, Dc = 2.553mg/ m3, μ = 6.499mm-1, F(000) = 1990, R1 = 0.0634 for 7156 observations. In the three structures the dinuclear bifurcate (MCl(bpy)2)22+ (M = Ni, Mn) cations build pin - hole like layer structure through the aromatic π -π interaction between the aromatic ligands, bpy. These holes are inserted by I2 molecules or I3 -anions, between the layers locate I2, I3- , I5- , and I7- . They are further linked themselves and together with these intralayer I2 molecules or I3- 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 -reflectance UV - vis spectra (200 -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.
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
2000年第12期1615-1625,共11页
Acta Chimica Sinica
基金
国家自然科学基金(29525101
29831010)
"973"(G1998061300)资助项目
关键词
超分子化学
自组装
多碘离子
双核配合物阳离子
supramolecular chemistry, self-assembly, polyiodide, dinuclear transition metal complex cation, crystal structure.
