【作者】 潘勤鹤；

【导师】 徐如人； 于吉红；

【作者基本信息】 吉林大学 ， 无机化学， 2008， 博士

【摘要】 锗酸盐开放骨架化合物由于其丰富的结构化学及其表现出的特殊的孔道特征（如超大孔,低骨架密度,手性结构等）研究已经引起人们的关注。本论文在溶剂热体系下,采用双模板剂的方法合成了系列由Ge₇簇构筑具有新型拓扑结构的锗酸盐开放骨架化合物,并对它们的结构特点和合成规律进行了分析和总结。在GeO₂-NiCl₂·6H₂O-醇胺-H₂O-HF-有机胺的合成体系下,原位自发生成的镍胺配合物为模板剂成功导向合成出了一系列具有新型结构的锗酸盐,它们分别是1-D链状锗酸盐[Ni（dien）₂]₂[Ge₇O13（OH）₂F₂]·Cl （JLG-₇）,首例1-D管状锗酸盐[Ni（1,₂-PDA）3]₂（HOCH₂CH₂CH₂NH3）3（H3O）₂[Ge₇O14F（OH）₂]3 （JLG-4）,₂-D手性层状锗酸盐[Ni（1,₂-PDA）3][Ge₇O14F₂（OC₂NH₇）]·0.₅H₂O （JLG-3）和₂-D层状锗酸盐[Ni₂（TEPA）₂（en）]（H₂en）[Ge₇O14F3]₂·0.₇₅H₂O （JLG-6）。有趣的是,这些由金属有机胺配合物和其他导向剂为共模板所形成的锗酸盐结构均含Ge₇簇结构单元。在这些结果中,引人注目的是,JLG-4是一个新颖的1-D管状的锗酸盐,它是第一次在锗酸盐体系中被发现;JLG-3是首例包含手性层的层状锗酸盐,该手性层是由具有相同手性的Ge₇簇手性衍生物相互连接而成的。在这一系列锗酸盐合成的过程中溶剂醇胺起到了很重要的作用,特别是在JLG-3和JLG-4的合成过程中起到了溶剂和模板剂的双重作用。此外,以吡啶为溶剂,成功合成出了又一例具有一维1₂-元环管状结构的锗酸盐(C₅N₂H₁₄)₄(C₅N₂H₁₃)（H₂O）₄[Ge₇O₁₂O₄/2（OH）F₂][Ge₇O1₂O₅/₂（OH）F]₂[GeO₂/₂（OH）₂] （JLG-₅）,它是由氢键构筑的（H₂O）₁₆水簇和有机胺2-甲基哌嗪共模板作用下生成的。在结构中,存在着一个高对称性的结构单元,它是由12个Ge₇簇构筑而成的68126大笼。值得注意的是,每个68126大笼中容纳了一个氢键构筑的（H₂O）16水簇。该工作提供了一个独特的例子来阐述氢键构筑的（H₂O）16水簇在合成开放骨架材料的过程中所起到的模板剂的作用。本文通过对已知的由Ge₇簇构筑的结构中的Ge₇簇的连接方式进行了总结,得到了四种由Ge₇簇构筑而成的结构单元。从这些结构单元出发可以设计出一系列由Ge₇簇构筑而成的₂-D层状,3-D超大孔道锗酸盐假想结构。我们相信更多的特殊的锗酸盐结构能够用无机簇,如Ge₇簇,或者由Ge₇簇构成的不同的笼来构筑而成。本论文的工作表明,具有多种连接方式的Ge₇簇可以通过不同的构筑方式相连接形成不同的拓扑结构。这对设计合成具有超大孔道和低骨架密度的锗酸盐具有十分重要的意义。更多还原

【Abstract】 Inorganic microporous materials attract considerable attentions because they have potential applications in catalysis, adsorption and separation, as well as in advanced materials. There is always a general interest in exploring new open-framework materials in novel compositional domains.Germanates are of particular interest because they have metal-oxygen bond distances （≈1.76?） significantly greater than those in silicate-based materials （≈1.61?）, and bond angles Ge-O-Ge （≈130o） smaller than Si-O-Si （≈146o）, which lead to germanium can form GeO4, GeO5, and GeO6 coordinations. Therefore, these geometric factors have an important effect to form germanates with various structures. Recently, more attention has been paid to the synthesis of open-framework germanates, because germanium in the periodic table is an element which can be used as a silicon substituent to build various open-framework structures of zeolites and microporous materials. Particularly, some large and complicated second building units （SBUs） can be formed by the linkage of various Ge-centered polyhedra; typically, SBUs in germanates are Ge7, Ge9 and Ge10 clusters. Notable, some germinate structures with extra large pores and low framework densities are built up from those large clusters, such as ASU-12, ASU-16/SU-12, SU-8, SU-44, FDU-4, SU-M, and SU-MB. By using AASBU approach, it is possible to design more new open-framework germanates with large pores and low-framework density by using such large clusters as SBUs.The main body of this thesis focuses on synthesis and characterization of open-framework germanates with Ge7 cluster in solvothermal by using co-template and transferring the organic solvent. In addition, the corresponding structural characteristics and the roles of synthesis related to these compounds are also studied here.1. In this work, we firstly describe the synthesis of [M（en）₃][GF₆] （JLG-1,M=Ni,Co） using THF as a solvent, which is the first result when we attempt to synthesize germanates templated with chiral metal complexes based on in situ synthesis method. Interestingly, the [GeF₆]^2- anions interact with the chiral complex cations [M（en）₃]²⁺ （M=Ni,Co） in such a way that pseudo-channels were formed along the 63 screw axis in a hexagonal, honeycomb arrays are created based on weak H-bonding of F···N atoms. It is believable that the chiral [M（en）₃]²⁺ cations paired with [GeF₆]^2- anions in a D₃ point symmetry is responsible for the fascinating arrangement in JLG-1（Ni） and JLG-1（Co）. This work will be useful for the design of H-bonded pseudo-channel system.2. Using chiral metal complex as a template, a series of germanantes comprised of Ge₇ cluster, 1-D chain-like germanate [Ni（dien）₂]₂[Ge₇O13（OH）2F3]·Cl （JLG-7）, 1-D tubular germanate of [Ni（1,2-PDA）3]₂（HOCH₂CH₂CH₂NH₃）₃（H₃O）₂[Ge₇O14X₃]₃ （JLG-4）, and 2-D layered [Ni（1,2-PDA）3][Ge₇O14F₂（OC₂NH₇）]·0.5H₂O （JLG-3）, and 2-D layered [Ni₂（TEPA）₂（en）]（H₂en）[Ge₇O14F₃]2·0.75H₂O （JLG-6） have been synthesized under the synthesis conditions of GeO₂-NiCl₂·6H₂O-H₂O-T-S-HF （T= organic amines; S= ethanolamine, 2-amino-1-propanol, 3-amino-1-propanol）. All of those germanates are co-templated by chiral metal complexes and other SDAs. Remarkably, JLG-4 is a 1-D germanate, which is the first tubular structure found in germanates. As for JLG-3, the organic amine C2NH6OH is covalently-bonded to one of five-coordinated germanium atoms to produce a chiral derivative of Ge₇ cluster, such chiral Ge₇ clusters are linked each other to generate an unusual chiral sheet with 10-rings. Under this synthesis conditions of germanates, the solvent play an important role. Especially, it plays a dual role of SDA and solvent in the synthesis of JLG-3 and JLG-4.3. Furthermore, by using pyridine as a solvent, a tubular germanate JLG-5 with 12-ring channels has been obtained by hydro（solvo）- thermal synthesis co-templated by 2-methylpiperazine and the （H₂O）16 water cluster. Notably, an unique hydrogen-bonded （H₂O）16 water cluster is present in each 68126 cavity and probably supports the formation of the cavity. In this thesis, we present a remarkable example of the templating role played by （H₂O）n water clusters in the synthesis of open-framework materials. We believe that more extra germanate structures can be formed by using inorganic building units such as the Ge₇ cluster or the different cavities built by the Ge₇ cluster. Therefore, it is very important to understand well the formation of the building units and how to control the packing of such building units.4. It is important to understand the formation of the building units and to be able to control the packing of such building units. We summarized the various connection modes of Ge7 clusters which have been reported. And further researched germanate structures containing Ge7 cluster, four kinds of PBUs linked by Ge7 cluster can be found. From those PBUs, we design a series of 2-D sheets and 3-D open-framework germanate structures. We believe that more exotic germanate structures can be formed by using inorganic building units such as the Ge7 cluster or the different cavities built by the Ge7 cluster.In summary, by using AASBU approach, it is possible to design more new open-framework germanates by using Ge7 clusters as SBUs. So this thesis will be useful for the design of new open-framework germanates with large pores and low-framework density.更多还原