本文以二环已基18-冠-6(DCH 18 C 6)从盐酸体系萃取氯化铀酰的方法合成了标题化合物。其红外光谱表明冠醚上的C—O—C基团和(?)的反对称拉伸振动波数分别红移至1090cm^(-1)和912cm^(-1)。该化合物的单晶样品经X射线衍射分析得到其晶体学参数:三斜晶系,空间群P,a=10.183(3),b=10.606(3),c=12.850(6),α=72.09(3),β=85.97(4),γ=86.14(2)°,Z=1。结构用重原子法解出,结构修正最后收敛到R=0.062,R_w=0.061。U原子坐落在对称中心上,并与四个氯原子两个氧原子配位,其配位多面体为四方双锥。H_3O^+嵌于冠醚环中央,并与其三个氧原子构成氢键。
Two novel Cd(Ⅱ) coordination polymers, [Cd 2(C 10H 2O 8)\5(H 2O) 6] n (1) and [Cd 4(C 6H 4O 2N) 8(H 2O) 4] n (2) (C 10H 2O 8=1,2,4,5-benzenetetracarboxyl and C 6H 4O 2N=nicotinato), were hydrothermally synthesized and characterized by X-ray diffraction of the single-crystal and fluorescence spectra. Complex 1 crystallizes in triclinic system, space group P1 with a=0.559 62(7) nm, b=0.777 58(6) nm, c=0.969 75(10) nm, α=111.981(5)°, β=101.649(6)°, γ=98.240(5)°, and Z=1. Final R=0.024 8(wR=0.078 5). Complex 2 belongs to orthorhombic system, space group Pbca with unit cell dimensions a=1.144 94(19) nm, b=1.209 69(6) nm, c=1.740 73(8) nm and Z=8. Final R=0.018 5(wR=0.034 8). Both the two complexes are coordination polymers with a two-dimensional infinite structure, the repeat unit is [Cd 2(C 10H 2O 8)(H 2O) 6] (1) and [Cd 4(C 6H 4O 2N) 8(H 2O) 4] (2) which are bridged by the ligands of 1,2,4,5-benzenetetracarboxyl(C 10H 2O 8) and nicotinato(NA), respectively. The two polymers show strong fluorescence with λ em=433 nm(λ ex=333 nm, 1) and λ em=423 nm(λ ex=330 nm, 2) in the solid state at room temperature. The emissions observed in the polymers are tentatively assigned to the ligands fluorescence(LLCT).
