【作者】 王崇臣；

【导师】 张丽娟；

【作者基本信息】 北京化工大学 ， 应用化学， 2004， 硕士

【摘要】 无机-有机杂化化合物材料的制备是现代化学分子设计的重要对象,为了制备具有特殊性能的材料,通过分子设计对配位中心金属离子(模板,templating)、多齿有机配体和无机酸根离子(构件,building block)进行选择,然后再进行组装。本课题选择结构和性能独特的多金属氧酸根(POMs)和多齿有机配体作为构件,以金属离子作为模板合成出新型多金属氧酸盐无机-有机杂化化合物。本课题采用水热合成法以CoCl2·6H2O、 4,4’-联吡啶(4,4’-bpy)、NH4VO3、WO3以及13 mL H2O为原料(摩尔比1:2:2:2:3610), 在容积为25 mL的内衬聚四氟乙烯的不锈钢反应罐中保持170℃反应3d,得到以六钨酸根(W6O19)2-和刚性有机配体4,4’-bpy为构件、以中心金属离子Co(II)为模板的无机-有机杂化化合物[Co2(bpy)6(W6O19)2],其晶体结构测定的结果表明[Co2(bpy)6(W6O19)2] 具有二维层状结构,属于单斜晶系,空间群为C2/c,晶胞参数是:a = 19.971(4) ?,α= 90°, b = 11.523(2) ?,( = 96.49(3)°, c = 16.138(3) ?, γ = 90°, V = 3690.0 ?3 和Z = 2。该化合物的晶体结构具有新颖性,因为在此之前尚未出现将(W6O19)2-连接到无限扩展网络结构的化合物。 <WP=4>本课题还采用水热合成法以CoCl2·6H2O、1,3-联(4-吡啶基)丙烷(bpp)以及NH4VO3以及13mL H2O为原料(摩尔比1:2:2:3610),在容积为25 mL的内衬聚四氟乙烯的不锈钢反应罐中保持120℃反应3d,得到以四钒酸根(V4O12)4-和柔性有机配体bpp为构件、以中心金属离子Co(II)为模板的无机-有机杂化化合物[Co(bpp)2V2O6] ·2H2O,其晶体结构测定的结果表明[Co(bpp)2V2O6] ·2H2O具有三维网状结构,属于四方晶系,空间群为I4,晶胞参数是:a = 21.5674(7) ?, α?= 90°,b = 21.5696(7)?, ( = 90°,c = 12.8126(4) ?, γ= 90°, V = 5960.4(3) ?3 和Z = 8。在这种化合物中,二维配位聚合物正离子2∞{Co (bpp)2}n2n+层经过互穿形成三维结构,形成的通道被具有八元环(V4O12)4-通过V-O-Co桥键和Co(II)桥联,这种结构也是前所未有的。通过对这两种化合物分别进行UV-Vis-NIR反射光谱测试,发现这两种化合物的能隙值(Eg)分别是2.2eV和2.1eV,都属于半导体材料。同时还对合成这两种化合物影响因素如反应物的配比、反应溶液的pH值、反应温度等进行探讨,确定了反应体系的最佳反应条件。更多还原

【Abstract】 The synthesis and preparation of organic- inorganic hybrid compounds is an important part of molecule designing in modern chemistry. The self-assembly is adopted to achieve purposeful synthesis through selecting the transition metal cations as templating and organic ligands with multi-coordinate atoms, polyoxometalates (POMs) as building blocks. In this paper, two novel Organic- Inorganic Hybrid Compounds Containing POMs were achieved by selecting POMs with unique structure and properties and organic ligands with bipyridyl groups as building blocks and transition mental cation as templating through hydrothermal reaction.A hydrothermal reaction of WO3, CoCl2 and 4,4’-bipyridine yields a novel organic-inorganic hybrid compound, Co2(bpy)6(W6O19)2, at 170°C. X-ray single crystal structure determination reveals a two-dimensional covalent structure which adopts (W6O19)2- as inorganic building blocks, bpy as organic building blocks, and Co(II) as templating species. Its single crystal structure belong to monoclinic crystal system, space group C2/c, with cell parameters a = 19.971(4) ?, b = 11.523(2) ?, c = 16138(3) ?, ( = 96.49(3)°, V = 3690.0 ?3 and Z = 2. The structure of this <WP=6>compound is novel because (W6O19)2- is connected into extended structure which is unparalleled. A hydrothermal reaction of NH4VO3, CoCl2 and 1,3-bis(4-pyridyl)propane(bpp), yields a novel organic-inorganic hybrid compound, [Co(bpp)2V2O6] ·2H2O, at 120°C. X-ray single crystal structure determination reveals a three-dimensional covalent structure which adopts (V4O12)2- as inorganic building blocks, bpp as organic building blocks, and metal Co(II) as templating species. Its single crystal structure belongs to Tetragonal crystal system, space group I4, with cell parameters a = 21.5674(7) ?, α?= 90°,b = 21.5696(7)?, ( = 90°, c = 12.8126(4) ?, γ= 90°, V = 5960.4(3) ?3 and Z = 8. In this compound, the 2-D 2∞{Co (bpp)2}n2n+ cation chains are interpenetrated into channels which are occupied by (V4O12)4- through V-O-Co bonds. From UV-Vis-NIR reflectance spectra, it’s found that these two compounds have optical energy gap of 2.2eV and 2.1eV, respectively, and both belong to semiconductor.The influence of the reaction conditions on the products such as mole ratio of reactants, the pH value of the reaction solution and the reaction temperature were discussed through many practical experiments; the optimum conditions of these reactions are determinated.更多还原