系列配位聚合物的合成、表征与性质研究

【作者】 徐东华；

【导师】 周云山； 张立娟；

【作者基本信息】 北京化工大学 ， 化学， 2010， 硕士

【摘要】 金属一有机配位聚合物是有机配体和一种或多种中心金属离子通过配位键自组装形成的。金属有机配位聚合物的研究是一个涉及有机、无机、配位化学、材料化学乃至生命科学等诸多学科的交叉领域。作为新一代多孔材料,兼具高比表面积、骨架结构多样、易于功能化等特性,已成为材料科学领域的研究热点之一。同时,对金属有机配位聚合物的结构和性能研究还展现于这类化合物在光学、磁学、催化等领域的应用前景。本论文采用水热合成法和溶液合成法两种方式,得到了9个具有不同结构的新型配合物,并采用X-射线单晶衍射、热重分析和红外光谱、元素分析等手段对其进行表征,解析了其单晶结构并研究了它们在室温条件下的固体荧光性质。主要工作和创新点如下：1.水热条件下合成三个3D的Eu(Ⅲ)离子配合物[Eu2(INO)2(ox)2(H2O)2]n(1) [Eu2(INO)4(suc)(H2O)2]n(2)和[Eu2(C4H4O4)3(H2O)2]·H2O (3) (HINO=N-氧化异烟酸,ox=草酸,Suc=丁二酸)。利用IR,元素分析,TG/DTA和单晶X-衍射进行表征。单晶衍射晶体结构分析表明,由于第二配体乙酸不同的配位模式和丁二酸的空间构型不同,配合物1,2,3展现了不同的3D空间构型。与配合物1相比,2和3具有较大的孔道结构,可填充溶剂水分子,这表明配合物中孔道结构的大小受二元羧酸链长的影响。配合物1,2,3中Eu(Ⅲ)离子具有典型的红光,由于晶体结构的不同,荧光强度也明显不同。配合物2中水分子没参与配位,其荧光较1和3的强,表明2中配体与Eu(Ⅲ)离子之间存在有效的能量传递。2.以bpp作为柔性配体,成功合成并表征了三个结构新颖的配合物[Zn(CH3C6H4SO3)2(bpp)2]n (4), Cu2(SCN)2(NO3)2(bpp)4]n (5)和{Cu5(SO4)5(bpp)8 (H2O)36(C2H5OH)]·(C2H5OH)}n(6).单晶X-衍射表明,配合物4,5都具有交替的左右手螺旋链,螺旋链通过共用Zn(Ⅱ)或Cu(Ⅱ),分别展现了2-D层状结构,2-D互穿层状结构。配合物2具有两个互穿的2D层状网络。配合物3具有3-D互穿结构。由1D螺旋双链和2D平行层通过SO42-阴离子相互连接形成。由于配体-金属或金属-配体的能量转移,配合物4展现蓝色的反射荧光光谱。我们研究了配合物5、6的电化学性质,6的不可逆还原峰值比5的更底,表明在配合物中一电子还原需要更少的活化能。3.以AlMo6(OH)6O183-型多金属氧酸盐阴离子为建筑单元,构筑了3个新颖的基于Anderson结构多阴离子的多金属钼酸盐衍生物：Na[AlMo6H6024](C7H8N02S)2·2H2O (C7H7NO2S=4-吡啶硫代乙酸)(7),Na2(C6H5NO2)2(C2H3O2)2Eu2(AlMo6H6O24)2·33H20 (C6H5N02=烟酸,C2H302= CH3COO-)(8)和(C6H5NO2)2(C2H3O2)2Eu2(AlMo6H6O24)2(H3O)2·28H20(C6H5NO2=异烟酸,C2H3O2=CH3COO-)(9)。化合物7显示了Anderson结构通过Na+离子连接成的二维层状结构,质子化的4-吡啶硫代乙酸通过氢键作用填充到骨架之间。化合物8显示了Anderson多酸与稀土-烟酸配合物形成的3D超分子结构。Anderson多酸与稀土铕离子-烟酸配合物形成的1D链与Anderson结构通过Na+离子连接成形成的1D链垂直交叉连接。化合物9显示了Anderson多酸与稀土铕离子-异烟酸配合物形成的1D链,游离的Anderson多酸通过氢键作用支撑在相邻的链之间。更多还原

【Abstract】 Metal-organic coordination polymers are assembled from organic ligands together with one or more types of metal centers via coordination bonds. Design and properties of the supramolecular metal coordination complexes are involved in many fields including inorganic, organic, coordinate chemistry, material chemistry and life science et al. As a new type of porous materials which may possess high specific surface area, versatile structures and are easy to be functionalized, they have become a widespread focus in the field of material science with respect to their structure and potential applications in optics, magnetis, catalysis. In this paper, nine novel complexes have been hydrothermally and solvently obtained and characterized by single crystal X-ray diffraction, thermal analysis, elemental analysis,IR spectroscopy and fluorescence. The main achievements and creativity are given below:(1). Three novel europium (Ⅲ) complexes, [Eu2(INO)2(ox)2(H2O)2]n (1),{[Eu2(INO)2(suc)2]·2.99H2O}n(2) and{[Eu2(suc)3(H2O)2]·H2O}n (3) (HNNO=nicotinic acid N-oxide, H2ox=oxalic acid, HINO=isonicotinic acid, H2suc=succinic acid) have been synthesized under hydrothermal conditions and characterized by IR, elemental analysis, TG/DTA and single crystal X-ray diffraction analysis. The 3D frameworks 1,2,and 3 are different due to the different coordination modes of the carboxylates and ligand conformations assumed by succninate. The 3D open frameworks 2 and 3 have bigger channels filled with solvent water molecules than frameworks 1 do, showing that the presence of channels whose size is influenced by the length of the used acyclic binary carboxylates. At room temperature, the complexes 1,2 and 3 in solid state exhibit typical red luminescence from Eu3+ions, however, the luminescence intensity of them is obviously different due to the difference of their crystal and molecular structures. Compared with complex 2, both the complexes 1 and 3 exhibit weaker luminescence due to oscillation of coordinated water molecules, indicating that the energy transfer from the ligands to Eu3+ion in 2 is the most effective.(2). Three novel transition metal-organic frameworks based on a flexible ligand 1,3-bis (4-pyridyl)propane (bpp) with helical structures, [Zn(C7H7SO3)2(bpp)2]n (4), [Cu2(SCN)2(NO3)2(bpp)4]n (5), {[Cu5(SO4)5(bpp)8(H2O)5(C2H5OH)]·(H2O)31(C2H5OH)}n (6) have been synthesized successfully and characterized. Single crystal X-ray diffraction analysis reveals that both 4 and 5 exhibit 2-D layer networks composed of alternate right-handed and left-handed helical chains by sharing Zn(Ⅱ) or Cu(Ⅱ) ions, respectively. Interestingly,5 has two interpenetrating 2-D layer networks. While 6 has a 3-D interpenetrating structure constructed by 1-D helical double chains and 2-D parallel layers linked by sulfates which are further linked by SO42- anions. Compound 4 exhibits blue emission in solid state indicating efficient energy transfer of metal-to-ligand or ligand-to-metal, Electrocatalytic properties of compound 5 and 6 were investigated. It is observed that irreversible reduction peak in 6 is more lower than that in 5, less activation energy is needed in the one-electron reduction in 6.(3). Three new organic/inorganic hybrid complexes Na[AlMo6(OH)6O18](C7H8NO2S)2·2H2O (C7H7NO2S= 4-pyridylthio)acetic acid) (7), Na2(C6H5NO2)2(C2H3O2)2Eu2[AlMo6(OH)6O18]2·33H2O (C6H5NO2= nicotinic acid, C2H3O2= acetate) (8) and (C6H5NO2)2(C2H3O2)2Eu2[AlMo6(OH)6O18]2(H3O)2·28H2O (C6H5NO2= isonicotinic acid) (9) based on [AlMo6(OH)6O18]3- polyoxoanions as building blocks have been gained. Compound 7 possesses two-dimensional layer structure constructed from Anderson polyanions bridged by Na+ cations, while the protonated (4-pyridylthio)acetic acid molecules are situated between the layers via hydrogen bonds. Compound 8 displays a three-dimensional supramolecular framework built up of the Anderson type anions and Eu-nicotinic acid coordination complexes, in which two type of 1D chains are formed:the first type refers to that formed by Anderson polyoxoanions and Eu-nicotinic acid coordination complexes, and the second type refers to that formed by Anderson polyoxoanion and Na+ cations. The two types of chain are vertically cross-connected with each other. Compound 9 possesses a novel one-dimensional chain structure formed by the Anderson polyoxoanions and Eu-isonicotinic acid coordination complexes. The free polyanions are situated between the chains via hydrogen bonds.更多还原