【作者】 王欣会；

【导师】 韩克飞；

【作者基本信息】 北京化工大学 ， 有机化学， 2009， 硕士

【摘要】 配位聚合物因其独特的结构特点及其在催化、气体吸附、非线性光学材料等方面具有潜在的应用价值而成为研究的热点之一。本论文以氮杂芳环配体为研究对象,合成了2,2’-联吡啶-4,4’-二羧酸、N-（吡啶基）异烟酸酰胺、3,3’-（4-胺基甲酰基吡啶）-2,2’-联吡啶-3-甲酸、N²,N⁷-双-（2-氨基吡啶）-2,7-萘二磺酸胺、对苯二甲醛缩2-氨基噻唑、水杨醛缩2-氨基噻唑、水杨醛缩2-氨基吡啶和三聚氰胺六乙酸等八个氮杂芳环类配体,并在水热条件下,尝试了这些配体与二价金属离子合成配位聚合物的研究。以带有柔性连接臂的1,3-二（4-吡啶）丙烷（bpp）为中性配体,1,6-萘二磺酸根(nds^2-)为抗衡离子,采用溶剂热法,优化相应的合成条件,成功获得了中心离子为Co²⁺的配位聚合物,经过X-ray单晶衍射确定其结构,相应的结构式为[Co（bpp）₂（H₂O）₂]_n·n（1,6-nds）·7nH₂O。结构解析表明该配位聚合物属于单斜晶系,空间群为P2₁/n,晶胞参数为a=12.56800（10）（?）,b=19.7570（2）（?）,c=17.0510（2）（?）,α=90°,β=97.8230（4）°,γ=90°。在该结构中,1,6-萘二磺酸根作为抗衡离子,Co²⁺采用八面体配位模式,配位原子是四个独立的bpp分别提供的四个N原子和两个水分子提供的O原子。晶胞中还存在七个结晶水分子。采用类似方法,还成功获得了中心离子为Cd²⁺的配位聚合物,经过X-ray单晶衍射确定其结构,相应的结构式为[Cd₂（bpp）₃Cl₄]_n·nH₂O。结构解析表明该配位聚合物属于单斜晶系为三斜晶系,空间群为P（?）,晶胞参数为a=9.5040（3）（?）,b=11.7820（3）（?）,c=18.3990（5）（?）,α=92.9730（9）°,β=98.5090（9）°,γ=92.7320（10）°。在该单元结构中,Cd²⁺采用八面体配位模式,配位原子为两个氯离子和四个独立的bpp分别提供的四个N原子,最终形成三维网络结构。更多还原

【Abstract】 Because of its unique structure and potential application in catalysis, gas adsorption,and nonlinear optical materials,coordination polymer is one of highlights in the field of functionalized material.In this thesis, eight aza-aromatic ligands including N-（pyridin-4-yl）isonicotinamide, 2’2-bipyridyl-4’4-dicarboxylic acid,3’-（pyridin-4-ylcarbamoyl）-2,2’-bipyridine-3-carboxylic acid,N²,N⁷-di（pyridin-2-yl）naphthalene-2,7-disulfonamide,p-phthalaldehyde-2-amino thiazole,salicylaldehyde-2-amino thiazole,salicylaldehyde-2-amino pyridine and melamine hexacetic acid have been synthesized,and the corresponding coordination polymers have been explored by hydrothermal method under different conditions.1,3-Di（4-bipyridyl）propane（bpp） with the flexible linker between two pyridine units has different coordination styles and naphthalene sulfonic anions can act as acceptor of hydrogen bonding interaction in coordination polymer.Here bpp used as neutral ligand and 1,6-naphthalene sulfonic anion used as balance ions,one crystal of Co（Ⅱ） cation has been obtained by solvothermal method.The structure has been determined by single crtstal X-ray diffraction.The results indicate molecular formule of the complex is[Co（bpp）₂（H₂O）₂]_n·n（1,6-nds）·7nH₂O and the crystal belongs to monoclinic system,P2₁/n space group with parameters a = 12.56800（10）（?）,b = 19.7570（2）（?）,c =17.0510（2）（?）,α=90°,β=97.8230（4）°,γ=90°.In the crystal,1,6-naphthalene sulfonic anion acts as counter ion,and Co²⁺ coordinate four N atoms from different bpp ligands and two O atoms from water molecules in octahedron configuration.Similary,one crystal of Cd（Ⅱ） ion involving bpp ligand has been obtained as well.X-ray single crystal diffraction showed its molecular formule of the complex is[Cd₂（bpp）₃Cl₄]_n.nH₂O and the crystal belongs to triclintic system,P（?） space group with parameters a = 9.5040（3）（?）,b =11.7820（3）（?）,c = 18.3990（5）（?）,α=92.9730（9）°,β=98.5090（9）°,γ=92.7320（10）°.In the crystal,Cd²⁺ coordinate four N atoms from different bpp ligands and two chloride ions in octahedron configuration.更多还原