【作者】 王学雷；

【导师】 李激扬；

【作者基本信息】 吉林大学 ， 无机化学， 2014， 博士

【摘要】 无机开放骨架金属磷酸盐由于具有丰富多样的骨架结构和规则的孔道在气体分离、工业催化、离子交换、电学、光致发光、磁学、生物学等领域有着广泛的应用。近十几年以来，科研工作者发现使用假四面体构型的[HPO3]2-基团取代具有正四面体构型的[PO4]3-基团而开发出的开放骨架金属亚磷酸盐，具有新颖的骨架结构以及独特的性质。一系列具有特殊结构（手性及螺旋、超大孔道等特征）与新颖性质（光致发光、磁性、光电效应等）的开放骨架金属亚磷酸盐被相继报道。本论文采用水热/溶剂热方法，以不同种类的有机胺为模板剂，在亚磷酸体系下，利用不同种金属源，合成出了一系列新型开放骨架亚磷酸盐化合物，取得了以下研究成果：1.在InCl3-H3PO3-HF-T-M (T:有机胺，M：混合溶剂)合成体系中，以1,2-丙二胺为有机模板剂，溶剂热条件下，通过调控F-离子的用量，合成出两例亚磷酸铟化合物[C3H10N2][In2(HPO3)4](InHPO-CJ11)和[C3H12N2][InF(HPO3)2](InHPO-CJ12)。InHPO-CJ11是一例新颖的具有ABCABC紧密密堆积的三维（3D）结构，包含多维交叉8-元环孔道和独特的左/右手螺旋链。InHPO-CJ12是第一例含氟的亚磷酸铟化合物。有趣的是InHPO-CJ11和InHPO-CJ12的合成条件非常相似，只有氢氟酸的用量不同，而且InHPO-CJ11的结构中含有InHPO-CJ12的1D链，讨论了它们结构的相关性。2.利用1,2-丙二胺和六水哌嗪为模板剂，合成出两例大孔的亚磷酸铟化合物In2(HPO3)3(InHPO-CJ13)和[C4H10N2][In4(HPO3)7(H2O)3](InHPO-CJ14)。InHPO-CJ13是一例新颖的12元环孔道中性开放骨架亚磷酸铟化合物，其结构包含In2O10共面二核铟簇InHPO-CJ13结构中不含有任何有机模板剂，这在以前还没有报道过。InHPO-CJ14是一例三维交叉十二元环孔道的亚磷酸铟化合物。3.利用1,6-己二胺为有机模板剂，在水热体系中合成出一例三维亚磷酸锌无机有机杂化材料(C6N2H16)0.5ZnHPO3(ZnHPO-CJ15)。该化合物含有ZnO3N四面体和HPO3假四面体交替连接构建的4.82无机层，层与层间通过1,6-己二胺分子为柱撑相连接形成三维pillar-layer结构。该化合物在3D-2D-3D的拓扑学转化上有着潜在的研究价值。4.利用3-(氨甲基)吡啶为有机模板剂，在水热体系中合成出一例无机有机杂化的磷酸-亚磷酸盐化合物[C6H9N2][Zn2(PO4)(HPO3)](ZnHPO-CJ16)。ZnHPO-CJ16是一例含有磷酸和亚磷酸两种阴离子基团的无机有机杂化材料，有机分子3-(氨甲基)吡啶配位到无机骨架的Zn原子上，其结构含有4-8网层。由于3-(氨甲基)吡啶含有共轭体系，N原子的电荷更易跃迁到骨架上，所以ZnHPO-CJ16具有较强的荧光性质。5.在水热条件下，以单胺类的正庚胺为有机模板剂，合成出了一例亚磷酸锌化合物(C7H18N)2[Zn(HPO3)2](ZnHPO-CJ17)。它是一例由ZnO4正四面体和HPO3假四面体通过顶点交替连接形成的一维链结构。其中正庚胺分子的氨基与无机骨架中的氧原子之间形成氢键。ZnHPO-CJ17是第一例以单胺为模板剂合成出的一维链状亚磷酸锌。6.以1,4-丁二胺为有机模板剂，合成出一例具有三维pillar-layer结构的亚磷酸钴化合物(C4H12N2)[Co3(HPO3)2(OH)2](CoHPO-CJ10)。该化合物含有Co3O11N2三核钴簇和HPO3假四面体连接构建的二维层，层与层间通过1,4-丁二胺分子为柱撑相连接形成三维pillar-layer结构。该化合物是第一例具无限共边连接Co-O-Co链的亚磷酸钴，具有特殊的钴磷比（Co/P为3/2）。该化合物具有反铁磁性质。7.在1,2-丙二醇和水的混合溶剂条件下，以1,2-丙二胺分子为有机模板剂，合成出一例一维亚磷酸镓化合物[C3H12N2][Ga(HPO3)2(OH)](GaHPO-CJ18)。该化合物是GaO6正八面体和HPO3假四面体交替连接形成的。每个GaO6正八面体除了与两个HPO3假四面体连接外还与下一个GaO6正八面体相连构建Ga-O-Ga连接，其中氧原子除了连接两个镓原子之外，还连接一氢原子，形成羟基。GaO6正八面体之间通过顶点交替连接形成的含有无限共顶点连接Ga-O-Ga一维镓链结构。更多还原

【Abstract】 Inorganic open-framework materials have been extensively used in manyindustrial processes, such as catalysis, adsorption and separation. Recently, a newclass of open-framework metal phosphites has been developed by employing thepyramidal phosphite units HPO2-3to replace the tetrahedral phosphate groups PO3-4.Such materials have attracted much attention due to their novel frameworkcompositions and structure features including extra-large pores, chiral and helicalstructures. These materials have potential applications in the areas of optics, magneticchemistry, electrochemistry, catalytic chemistry, etc.In this paper, we have hydrothermally/solvothermally synthesized a series ofmetal phosphites by using different organic amines as the templates. Main resultsinclude:1. Two new indium phosphites [C3H10N2][In2(HPO3)4](InHPO-CJ11) and[C3H12N2][InF(HPO3)2](InHPO-CJ12) have been solvothermally synthesized byusing1,2-propanediamine as the template. InHPO-CJ11displays a novel(3,6)-connected three-dimensional (3D) structure containing multi-directionalintersecting8-ring channels and unique left/right-handed helical chains.InHPO-CJ12has a1D chain-like structure constructed by InO6and HPO3units.Notably, the syntheses of these two compounds are similar except for the use ofhydrofluoric acid. 2. In2(HPO3)3(InHPO-CJ13) and [C4H12N2][In4(HPO3)7(H2O)3](InHPO-CJ14) havebeen solvothermally synthesized in the presence of mixed solvents. InHPO-CJ13possesses a3D inorganic framework with12-ring channels without occludedorganic templates, which is built up by the connection of In2O10face-shareddimers and pseudo pyramidal HPO3units. InHPO-CJ14exhibits a pillar-layeredstructure with intersecting12-ring channels along [100],[010] and [110]directions.3. A three-dimensional (3D) inorganic–organic hybrid zinc phosphite(C6N2H16)0.5ZnHPO3(ZnHPO-CJ15) has been hydrothermally synthesized. It hasa pillar-layered structure, in which1,6-hexamethylenediamine molecules act asthe pillars to link the adjacent4.82zinc phosphite layers to construct the openframework of ZnHPO-CJ15. ZnHPO-CJ15exhibits fluorescence property.4.[C6H9N2][Zn2(PO4)(HPO3)](ZnHPO-CJ16) has been hydrothermally synthesizedby using3-(aminomethyl) pyridine as the organic template. Its frameworkcontains two kinds of anion groups, i.e. phosphate and phosphite. ZnHPO-CJ16possesses a two-dimensional (2D) layer structure, which is constructed by ZnO3Ntetrahedra and HPO3pseudo-pyramids.3-(aminomethyl) pyridine acts as theligands to connect the zinc atoms of inorganic framework. ZnHPO-CJ16possesses fluorescence property due to the existence of3-(aminomethyl) pyridine.5.(C7H18N)2[Zn(HPO3)2](ZnHPO-CJ17) has been hydrothermally synthesized inthe presence of n-heptylamine. Its structure is constructed by ZnO4tetrahedra andHPO3pseudo-pyramids. ZnHPO-CJ17is the first example of1D chain structureof zinc phosphite synthesized by using a single amine as the template.6.(C2H6N)[Co1.5(OH)(HPO3)](CoHPO-CJ10) is a3D inorganic-organic hybridcobalt phosphite. It exhibits a pillar-layered structure with an unusual Co/P ratioof3/2. The1,4-butanediamine molecules act as the pillars to link the adjacentcobalt phosphite layers to form open framework. Interestingly, such structurecontains infinite edge-sharing connected Co–O–Co chains, which is rarely occurred in the structures of cobalt phosphates/phosphites. It exhibitsantiferromagnetic interaction.7. A one-dimensional (1D) galium phosphite [C3H12N2][Ga(HPO3)(OH)2](GaHPO-CJ18) was synthesized by using1,2-propylene amine as the organictemplate. Its inorganic chain is constructed by GaO6octahedra and HPO3pseudo-pyramids. Ga-O-Ga connection mode is found in such structure.更多还原