【作者】 李莉；

【导师】 徐如人； 李激扬；

【作者基本信息】 吉林大学 ， 无机化学， 2010， 博士

【摘要】 本论文基于Zn-P-M-T（M:过渡金属元素,T:有机胺）合成体系,利用水热/溶剂热合成方法,合成了一系列具有新颖结构的金属亚磷酸和金属磷酸盐开放骨架化合物,并对其结构、性质及合成因素作了详细研究。主要内容包括:在水热体系中合成了一例具有独特发光性质和表面光电压性质的新颖层状磷酸亚磷酸锌化合物[C₆H₁₂（NH₃）₂][Zn₄（HPO₃）₂（PO₄）₂（H₂O）₂]（ZnHPO-CJ47）。ZnHPO-CJ47在紫外灯照射下呈天蓝色,其发射光谱具有多个可分辨的高强度发射峰,这在金属磷酸盐和亚磷酸盐化合物中尚属首次报道。此外,该化合物在外加负电场时还具有p-型半导体的特性。电子自旋共振技术测试表明,这种特殊荧光现象以及光电压产生的原因是由于ZnHPO-CJ47中存在复杂的结构缺陷。同时在该合成体系中,通过掺杂不同过渡金属得到与ZnHPO-CJ47同构的化合物[M_2xZn_2（1-x）（HPO₃）₂（PO₄）₂（H₂O）₂][C₆H₁₂（NH₃）₂] （M=Co,Mn）（ZnCoHPO-CJ47,ZnMnHPO-CJ47）,并对其荧光性质与ZnHPO-CJ47进行了比较。在相似的溶剂热体系中,通过加入不同的过渡金属成功合成了两例新型双金属磷酸盐化合物(Zn_0.67Co_0.33PO₄H)₈[（CH₃）₂NH]₄ （ZnCoPO-CJ48）和(Zn₂Mn₁P₃O₁₂H)₄[H₃O（CH₃）₂NH]₄ （ZnMnPO-CJ49）。系统的研究了过渡金属的掺入对这两例化合物合成的影响。ZnCoPO-CJ48是第一例具有中性骨架的二维层状双金属磷酸锌钴化合物,ZnMnPO-CJ49是一例具有16-元环超大孔道的三维磷酸锌锰化合物。有趣的是,二者的结构都基于相同的具有端羟基的四元环结构基元。以具有24-元环超大微孔亚磷酸锌ZnHPO-CJ1为目标化合物,选择理论预测适合该目标化合物无机骨架生成的三种有机胺,正丙胺、环戊胺和环己胺为模板剂,在水热体系下成功合成了与ZnHPO-CJ1同构的超大微孔亚磷酸锌化合物(C₆H₁₄N)₂[Zn₃（HPO₃）₄] （ZnHPO-CJ2）, (C₅H₁₂N)₂[Zn₃（HPO₃）₄] （ZnHPO-CJ3）和(C₃H₁₀N)₂[Zn₃（HPO₃）₄] （ZnHPO-CJ4）,并详细讨论了不同有机胺对其骨架结构形成的影响。更多还原

【Abstract】 Open-framework materials of metal phosphates have exhibited many fascinating structural features and potential applications in catalysis, separation, biology, electrical conductivity, magnetism and photochemistry. Particularly, metal phosphites are of interest because the existence of pseudo pyramidal HPO₃2- units in the framework can reduce the M-O-P connectivity and generate novel open frameworks. As a part of the renaissance in the study of open-framework metal phosphates, metal phosphites appear to show structural diversity and versatility similar to that of the phosphates. So far, series compounds of vanadium phosphite, iron phosphite, cobalt phosphite, manganese phosphite, zinc phosphite and chromic phosphite have been successfully synthesized, and their magnetic and luminescent properties have also been studied.This work focuses on the synthesis and characterization of new metal phosphites/phosphates in the hydrothermal or solvothermal system through selecting suitable templating agents. We aim to develop new bimetal phosphites and bimetal phosphates with novel framework architectures, study their potential applications in the photoluminescence, and futher conclude the formational regularities of them that will further assist in the rational design and synthesis of new microporous materials. Main results include:1. A layered zinc phosphate/phosphite [C₆H₁₂（NH₃）₂][Zn₄（HPO₃）₂（PO₄）₂（H₂O）₂] （denoted as ZnHPO-CJ47） with unique luminescent and photoelectronic properties. Unlike the known luminescent open-framework materials with single wide emission band, ZnHPO-CJ47 exhibits strikingly strong blue emissions with multi resolved peaks, which is firstly observed in metal phosphates/phosphites. It shows p-type conduction character under negative electric-field strength. These properties may be caused by the complex lattice defects revealed by EPR studies. Under similar reaction system, two heteroatom incorporated derivatives [M_2xZn_2（1-x）（HPO₃）₂（PO4）₂（H₂O）₂][C₆H₁₂（NH₃）₂] （M=Co/Mn） （ZnCoHPO-CJ47, ZnMnHPO-CJ47） with distinct luminescent property have been successfully synthesized. All of them emit blue light, the unique emission is caused by the complex lattice defects existed in the framework, and the incorporation of Co and Mn atoms into the framework may fill some defects, resulting in the decrease of the emission peaks and the blue shift of emission broad.2. Two new metal phosphates (Zn_0.67Co_0.33PO₄H)₈[（CH₃）₂NH]₄ （ZnCoPO-CJ48） and (Zn₂Mn₁P₃O₁₂H)₄[（CH₃）₂NHH₃O]4 （ZnMnPO-CJ49） have been solventhermally synthesized. ZnCoPO-CJ48 is the first layered heteroatom incorporated zincophosphate with neutral framework, which is constructed by the connection of MO4 tetrahedra （M=Zn, Co） and PO₃OH tetrahedra forming a novel 2-D sheet. And the structure is connected by the H-bonding between inorganic layer and template to formed pseudo 8-ring channels. Three-dimensional zinc-manganese phosphate ZnMnPO-CJ48 with 16-ring channels was obtained under the similar synthetic conditions. Its structure can be conceptually generated from the layered structure analogous of ZnCoPO-CJ48 connected by a 4-ring building unit. In this work, the synthetic conditions of these two compounds were discussed detailed.3. Three new open-framework zincophosphites ZnHPO-CJn （n=2, 3, 4） possessing desired extra-large 24-ring channels of ZnHPO-CJ1 have been successfully prepared through selecting computationally predicted organic amines, such as cyclohexanamine, cyclopentylamine and n-propylamine molecules as the templates or SDAs. Structure comparison of these compounds indicates that the organic amines influence the resulting structure symmetry, cell parameters, and the opening sizes through the size and shape control although they have similar templating abilities. 4. In the hydrothermal system, three new open-framework vanadium phosphate （VPO-1, 2, 3） possessing 24-ring large pore have been successfully synthesized using n-butylamine, propylamine and piperidine as the templates, respectively. These compounds possess isostructural three-dimensional （3D） open-framework structure with multi-directional intersecting 8-ring, 16-ring channels.5. The morphology control of ZnHPO-CJ2 crystal was investigated by microwave irradiation in mixed-solvents system through incorporation additional metal source. The results show that the microwave synthesis technology can greatly decrease the reaction time and obtaine pure, high-quality large single crystals of ZnHPO-CJ2. In mixed-solvents system, beside ZnHPO-CJ2, a zinc phosphite with one-dimensional can also be prepared.6. By using benzylamine as SDA, a new zinc phosphite （C7H10N）8[Zn4（HPO3）8] has been hydrothermally synthesized, and its structure and fluorescence properties have characterized. Its structure consists of ZnO4 and HPO3 basic building units. The ZnO4 tetrahedra and HPO3 pseudo pyramids are connected to form an infinite 1-D chain along c-axis. Protonated benzylamine cations were located on both sides of the 1-D inorganic chain through hydrogen bonds.更多还原