【作者】 宋维玲；

【导师】 温永红；

【作者基本信息】 青岛科技大学 ， 无机化学， 2010， 硕士

【摘要】 羧酸是构筑配合物的常用配体,羧基配位模式多样化,配位能力强,易与金属离子配位,形成具有多维度网络结构的配合物。这类配合物在吸附分离、催化、磁性材料和光材料等领域显示出潜在的应用前景,此外还可以作为低密度多孔材料,用于储存甲烷和氢气等燃料气体,所以越来越受到化学研究者的青睐。双羧酸类化合物具有多个配位氧原子,易与金属离子形成结构稳定且具有新型功能的配合物。这对配位化学及材料科学等学科的发展都具有重要的意义。本文合成了七种双官能团化合物:1,3-亚丙基双(氧-3-苯甲酸)(L1)、1,4-亚丁基双(氧-3-苯甲酸)(L2)、1,3-亚丙基双(氧-4-苯甲酸)(L3)、1,4-亚丁基双(氧-4-苯甲酸)(L4)、双(3-氟-4-氰基苯氧基)丙烷(L5)、双(3-氟-4-氰基苯氧基)乙烷(L6)以及双(3-氟-4-氰基苯氧基)丁烷(L7)。在水热条件下,使用L3的前体1,3-亚丙基双(氧-4-苯甲酸乙酯)与La2(NO3)3·6H2O反应,合成了配合物[La2(L)2(HL)2]{L为1,3-亚丙基双(氧-4-苯甲酸根)};使用L1合成了四种甲酸根与过渡金属的配位聚合物{[M(HCOO)3][(CH3)2NH2]}n [M = Co、Ni、Zn、Mn],并用元素分析、红外光谱、热重分析及X-射线衍射分析等方法对其结构进行了表征。在反应过程中,L1分解生成甲酸。四种配合物结构相似,均为三斜晶系,空间群R-3c。在配合物的晶体结构中,甲酸根为双齿配位,与中心的金属离子形成八面体结构。这四种配合物结构中存在~6 ?×6 ?×6 ?大小的孔洞,因此这些配合物有望用于气体储存材料。更多还原

【Abstract】 Carboxylic acids are the most usefully ligands to build the complex. Carboxyl groups have variety of coordination modes and strong ability of coordination with the metal ions, so they can form the multi-dimensional network structures. These complexes can be used potentially in many fields, such as adsorption separation, catalysis, magnetic materials and optical materials etc. In addition, they can be used to store the gas fuel like methane and hydrogen as the low density porous material, so close attention has been paid to these complexes by more and more chemical researchers. Dicarboxylic compounds have many oxygen atoms, which can coordinate with metal ions, and can form the structural stability and novel functional complex materials. It is important to the development of coordination chemistry, material science and other sciences.Seven bifunctional compounds, such as 1,3-propyl-bis(oxy-3-benzoic acid) (L1), 1,4-butyl-bis(oxy-3-benzoic acid) (L2), 1,3-propyl-bis(oxy-4-benzoic acid) (L3), 1,4-butyl -bis(oxy-3-benzoic acid) (L4), bis(3-fluoro-4-cyano-phenoxy)propane (L5), bis(3-fluoro-4-cyano-phenoxy)ethane (L6), bis(3-fluoro-4-cyano-phenoxy)butane (L7) have been synthesized. The complex [La2(L)2(HL)2] have been synthesized by the reaction of diethyl 1,3-propylidenebis(4-oxybenzoate) and La2(NO3)3·6H2O. Four coordination polymers {[M(HCOO)3] [(CH3)2NH2]}n [M = Co、Ni、Zn、Mn] have been synthesized by the reaction of L1 and transition metal salts in high purity and higher yield under mild hydrothermal conditions. L1 was decomposed into formate in this reaction condition.These compounds have been characterized by EA, IR, TGA and X-ray diffraction analysis. They have similar composition with the difference in the center metal atoms, and all complexes crystallize in the trigonal systems and space groups R-3c. In the crystal structures of all the four compounds, the formats as the bidentate ligand coordinate with the metal atoms to form the octahedral structure. Approximately 6 ?×6 ?×6 ? void exist in {[M(HCOO)3] [(CH3)2NH2]}n, so they can be used as gas-storage materials.更多还原