有机-无机复合杂多化合物的合成、结构及表征

摘要

Three organic-inorganic composite heteropoly compounds based on saturated Keggin polyoxoanions[Pr(pydc)(H2O)6]2H[PMo12O<0]·4H2O(l), [Nd(pydc) (H2O)6]2 H[PMo12 O40]·4H2O(2) and [Tb(pydc)(H2O)6]2H[PMol2O40]·4H2O(3) (pydc = 2,6-pyridine dicar-boxylic acid) have been prepared and characterized by elemental analyses, IR spectra, UV spectra, TG analyses, and X-ray single-crystal diffraction analyses. Results shown that compound 1, 2, and 3 crystallizes all in the tetragonal system, I4(l)/a space group and the cell parameters are that l:a = 1. 521 94(11) nm, 6=1. 521 94(11) nm, c = 2. 848 1(4) nm, Z = 4, J,= 0.067 3, wR2= 0. 167 3;2:a = 1. 532 57(14) nm, b= 1. 532 57(14) nm, c = 2.848 5(5) nm, Z = 4, R1 = 0.045 4, wR2= 0.118 l;3:a = 1.527 68(16) nm, b= 1.527 68 (16) nm, c = 2.833 7(6) nm, Z = 4, R1 == 0.061 2, wR2= 0. 162 3. Compounds 1-3 all consist of a Keggin polyoxoanion [PMo12O4o]3-and two rare earth coordination ions [Ln(pydc) (H2O)6]+ , which connected by electrostatic attraction. Moreover, 0. 5X1 nm apertures along c axis were generated by electrostatic attraction and π-π packing arrangement.%利用常规水溶液法制备了三种基于饱和Keggin结构阴离子的有机-无机复合杂多化合物[Pr(pydc)(H2O)6]2H[PMo12O40]·4H2O(1)、[Nd(pydc)(H2O)6]2H[PMo12O40]·4H2O(2)和[Tb(pydc)(H2O)6]2H[PMo12O40]·4H2O(3)(pydc=2,6-吡啶二羧酸),并借助元素分析、IR、UV、热分析和X射线单晶衍射分析对三种化合物进行了表征.结果表明,三种化合物均属四方晶系,14(1)/a空间群.晶胞参数分别为:1∶a=1.521 94(11)nm,b=1.521 94(11) nm,c=2.848 1(4) nm,Z=4,R1=0.067 3,wR2=0.1673;2∶a=1.532 57(14) nm,b=1.532 57(14) nm,c=2.848 5(5) nm,Z=4,R1=0.045 4,wR2=0.118 1;3∶a=1.527 68(16) nm,b=1.527 68(16) nm,c=2.833 7(6) nm,Z=4,R1=0.061 2,wR2=0.162 3.化合物1～3分子均含有一个Keggin阴离子[PMo12O40]3-和两个稀土配离子[Ln(pydc)(H2O)6]+,二者通过静电引力相结合.分子与分子之间通过静电引力及π-π堆积作用在c轴方向形成了大小约为0.5×1 nm的孔道.