【作者】 刘丽；

【导师】 庞文琴；

【作者基本信息】 吉林大学 ， 无机化学， 2007， 博士

【摘要】 本论文主要研究在水热和溶剂热反应体系下,新型亚磷酸盐（化合物1-12）和稀土硫酸钕（化合物13-15）微孔化合物的合成与结构表征。旨在合成具有新颖结构的化合物,并在合成研究的基础上,探讨特殊结构化合物的合成条件、成因以及有机组分对无机微孔结构的影响作用。在第一章绪论中,主要从合成化学与结构化学方面介绍了无机微孔化合物的研究进展,其中对亚磷酸盐微孔化合物的研究进展进行了详细的总结;在第二章中,以N,N-二甲基甲酰胺/1,4-二氧六环（DMF/DOA）的混合溶液作为溶剂,合成了系列具有新颖结构的亚磷酸锌化合物,并考察了DMF/DOA的体积比对合成产物的影响,以及有机溶剂的改变对合成产物结构的影响;在第三章中,以具有刚性骨架结构的五员环小分子咪唑及其衍生物为有机胺,对亚磷酸锌-咪唑-H₂O体系进行了系统的研究,合成出系列亚磷酸锌-咪唑化合物;在第四章中,对亚磷酸锌微孔化合物的结构及合成条件进行了一般性总结。同时,开展了对FeHPO₃-amine-HF-H₂O合成体系的探索研究,合成出一例具有新颖结构的氟化亚磷酸铁单晶,磁学性质测试表明该化合物存在明显的反铁磁相互作用;在第五章中,介绍了三个硫酸钕化合物的水热合成,晶体结构和磁学性质,丰富了无机微孔化合物的合成与结构化学。更多还原

【Abstract】 Inorganic microporous materials have popular applications in catalysis, adsorption, ion-exchange, separation and host-guest assemblies due to their unique pore architectures. And the rational design and synthesis of new microporous compounds, as well as the development of new synthetic ways are becoming the central topic of microporous materials chemistry. Zeolites （aluminosilicates） are the most well-known microporous molecular sieves. During the past decades, a huge number of new zeolite-like inorganic solids like phosphates, arsenates, germanates, phosphite, sulfate, selenite, carbonate and supertetrahedral sulfides have been synthesized and characterized. The successful syntheses of these new compounds with open-framework open a new field for the microporous compounds. As a new class of inorganic microporous materials, metal phosphites exhibit rich structural and compositional diversity. Since Harrison et al. reported the first organically templated zinc phosphite in 2000, considerable interest in the study of organically templated zinc phosphites has been aroused. Up to date, a number of zinc phosphites with 0D cluster, 1D chain, 2D layer and 3D open-framework structures have been reported. Compared to tetrahedral phosphate group [PO4]3-, the pyramidal phosphite group [HPO₃]2- can only make three P-O-Zn bonds, thus, some more significant structures which are different from those formed by phosphate group have been isolated. The goal of this work is to synthesis and preparation of zinc phosphites continuously and systematically by hydrothermal and solvothermal routes. And also to explore the syntheses of rare earth sulfates templated by organic amine hydrothermally.1. Three novel zinc phosphite compounds, 3D [C₆H₁₃N₂][C₆H₁₂N₂] [Zn₃（H₂PO₃）（HPO₃）3] （1）, 2D [C₄H₁₂N₂]_0.5[（CH₃）₂NH₂][Zn₂（HPO₃）₃] （3）, 1D [C₆H₁₄N₂]_0.5[Zn（H₂PO₃）₂] （4）, have been synthesized in DMF/DOA medium by using DABCO, PIP, N,N-dimethylpiperazine as organic templated agent, respectively:Compound 1 exhibits a 3D chiral open-framework structure with 16-ring channels, which is formed by the distorted {Zn₃P₄O₁₂} secondary building unit （SBU）. The organic amine molecules play dual roles as both ligands and countercations. The bonded DABCO molecule extending from Zn（3） atom occupies the 12-ring. While the free state DABCO molecule resides in the 16-ring channel as countercations balancing the overall negative electrostatic charge of the open-framework structure.Compound 3 exhibits a 2D layered structure with 4- and 12-rings, where diprotonated PIP molecules occupy the middle of 12-ring windows, and monoprotonated dimethylamine molecules （coming from the decompose of DMF） lie in the layers, through the H-bond interacting with the inorganic framework.Compound 4 is the first example of zinc phosphite with 1D neutral chain structure. Non-protonated N,N-dimethylpiperazine molecules through H-bonds interact with the neutral inorganic chain, forming 3D super-molecular structure.2. By changing the kinds of solvent and reaction temperature, we obtain two 3D open-framework structural zinc phosphite compounds, [C₆H₁₃N₂][C₆H₁₂N₂][Zn₃（H₂PO₃）（HPO₃）₃] （1） and [C₆H₁₄N₂][Zn₃（HPO₃）₄] （2）, using DABCO as organic templated agents in the same reaction molar ratio. Compound 1 was obtained in DMF/DOA medium, while compound 2 was obtained in THF/H₂O medium. Compound 2 exhibits a 3D open-framework structure with 8-ring channels, which is different from the structure of compound 1. In addition, we study the Influence of DMF/DOA volume ratio to the product 1.3. Using imidazole and its derivative as organic amine, we extend the research to the ZnHPO₃-imidazole-H₂O system. We have successfully synthesized a series of ZnHPO₃-imidazole compounds （compound 5-10）: In compound 5-7, imidazole and its derivative all act as the organic ligands. The structures are all build up by {ZnO₃N} and {HPO₃} basic structural units and Zn/P ratio of 1:1. Compound 5 exhibits a 1D chiral chain, which is the first example of zinc phosphite possessing the hydrogen-bonded helix. Compounds 6 and 7 with the same formula [C₅H₈N₂][Zn（HPO₃）] and different structures have been hydrothermally synthesized using 2-ethylimidazole and 1,2-dimethylimidazole as organic ligands, respectively. Compound 6 exhibits 1D chain structure, while compound 7 shows a 2D layer with 4,82-topolgy. Interestingly, there is H-bond interaction between the organic ligands and inorganic chains in compound 6, forming the 2D super-molecular layers. And there is no H-bond interaction in compound 7, the structure is stabilized by the strongπ-π* interactions between the organic ligands, which is extended from 2D layers to 3D super-molecular structure. Compounds 8 and 9 have been hydrothermally synthesized using imidazole and 2-methylimidazole as organic templated agent, respectively.The two compounds have the similar inorganic framework structures, which both exhibit 2D double layer structures with double 12-rings. Due to the different space-filling effect of the guest molecules, the stacking mode of adjacent layers and the arrangement mode of the organic amines are distinct. Compound 10, Na2Zn3（HPO3）4, has been hydrothermally synthesized using 2-ethylimidazole or 2-methylimidazole as organic templated agent. Na+ lies in the channels through the static gravitation interacting with the inorganic framework. Though guest molecules do not enter the inorganic framework, it is absolutely necessary in the formation of the framework. Owing to the similar structure of 2-ethylimidazole or 2-methylimidazole, we can obtain compound 10 in similar reaction condition.4. By using DETA as the organic ligand and the structure-directing agent, a new 2D layer zinc phosphite Zn（DETA）Zn2（HPO3）3 （11） has been hydrothermally synthesized. Its structure consists of ZnO4、ZnO3N2 and HPO3 basic building units. The ZnO4 tetrahedra and HPO3 pseudo pyramids are connected to form an infinite 2D sheet with 4-, 8- and 12-rings. It is interesting that {Zn2O2（DETA）2} dinuclear units are grafted in the 12-rings.5. In FeHPO3-amine-HF-H₂O system, a novel 3D fluorinated iron phosphite Fe2（HPO3）F2 （12） has been synthesized using imidazole as organic templated agent. Its structure consists of FeO3F3 and HPO3 structure building units. Interestingly, all the oxygen and fluorin atoms in this framework are tri-bridging atoms. Presence of the -Fe-F-Fe- linkage leading to a 2D layer in the framework is a noteworthy feature. 6. Three novel neodymium sulfate compounds, 2D [C₂N₂H₁₀]_1.5[Nd （SO₄）₃（H₂O）]·2H₂O （13）, 3D [Nd（SO₄）_1.5（H₂O）2]?0.5H₂O （14） and 3D Nd₂（SO₄）₃（H₂O）₄ （15）, have been hydrothermally synthesized by using en and DETA as organic templated agent, respectively. The structures of compounds 13 and 14 both consist of {NdO9} and {SO₄} basic structural units. Compound 15 shows 3D framework structure consisting of {NdO₉} , {NdO₈} and {SO₄} basic structural units.更多还原