【作者】 赵朗；

【导师】 于吉红； 徐如人；

【作者基本信息】 吉林大学 ， 无机化学， 2008， 博士

【摘要】 近年，用生物功能分子合成开放骨架化合物引起了广泛的关注。氨基酸由于既含有氨基又含有羧基，在生物化学和药理学等方面都有重要的应用。将手性氨基酸引入到开放骨架有可能产生非心或手性的固体材料，将在对映体选择性催化和分离以及非线性光学等方面具有潜在的应用。本论文以手性生物分子氨基酸为模板剂，开展了空旷骨架结构金属磷酸盐、金属亚磷酸盐的合成，结构及性质研究。此外，还对所合成的大孔和超大孔的亚磷酸盐以及一系列同构的金属配位聚合物的合成，结构和性质进行了研究。在水热／溶剂热体系下，以L-组氨酸为结构导向剂，成功地合成出了三个新颖磷（亚）酸锌结构：手性一维链结构的磷酸锌H₃0·（C₆H₉N₃O₂）₂（C₆H₈N₃O₂）Zn₃（PO₄）₂（ZnPO-CJ40），该结构是由ZnO₃N和PO₄四面体交替连接形成Zn₂P₂的四元环，这些四元环通过共边连接形成沿c轴方向的梯状链结构，并且ZnO₂N₂四面体悬挂在这个链上。值得注意的是配位在无机骨架上的所有组氨酸与实验初始加入的原料具有相同的构象。红外光谱和VCD光谱吻合的比较好，并且构象信息可以从VCD光谱中观察到。强的VCD信号表明化合物ZnPO-CJ40具有光学活性；二维层状磷酸锌(C₆H₁₀N₃O₂)Zn₂（HPO₄）（PO₄）·H₂O（ZnPO-CJ36），该化合物的主要特点是由共边的四元环连接形成一系列的双机轴链，这些双机轴链通过顶点氧原子连接形成无限延伸的平行于ab平面的4×8网层。值得注意的是，与无机层的一面配位的组氨酸都具有绝对的R构象，与另一面配位的组氨酸具有绝对的S构象。这意味着无机骨架与客体氨基酸分子之间存在着某种手性识别作；以及二维层状的亚磷酸锌C₆H₉N₃O₂ZnHPO₃·0．5H₂O（ZnHPO-CJ37），该化合物结构是由严格交替的ZnO₂O_cobalN_im四面体和HPO₃四面体形成Zn₂P₂四元环通过双齿配体组氨酸连接形成了的沿[010]方向的无限二维网层结构。在这个化合物中，组氨酸展现了一种非常不寻常的配位方式：双齿的配体配位于两个不同的金属中心。这种配位方式不同于组氨酸在配合物中以单齿或双齿、三齿配位到单一的金属中心上。通过单晶X-射线衍射对它们进行了结构解析，并对它们进行了荧光性质的研究。此外，在混合溶剂热条件下合成出一个新颖的具有反铁磁性质的18元环超大孔道的亚磷酸钴化合物2H₃0·[Co₈（HPO₃）₉（CH₃OH）₃]·2H₂O（CoHPO-CJ2）；两个同构的三维具有12元环孔道结构的亚磷酸钴化合物Na₂[Co（HPO₃）₂]和亚磷酸镍化合物Na₂[Ni（HPO₃）₂]；以及一系列同构的由色氨酸作配体构筑的过渡金属配位聚合物M_0．5C₁₁H₁₂N₂O₂（M=Zn（1），Co（2），Ni（3）），同时对它们的荧光性质进行了研究。更多还原

【Abstract】 Inorganic microporous materials have popular application 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. In the last decade, the synthesis of new materials that might combine the nanoporosity of zeolites with the magnetic and optical properties, electronic conductivity and ferrodelctricity of transition metal phosphates such as MnPOs, VPOs, FePOs, ZnPOs and CoPOs have been reported in the literatures. Many of these materials exhibit unique structures and may have potential applications in catalysis and magnetic fields.Chiral molecular sieves attract considerable attention, because of their extensive application in enantioselective catalysis, separation and pharmacy. Although chirality and porosity play important roles in the fields of chemistry and biology, it is still challenging to design a crystalline material combining both properties. The control of chirality in the synthesis of open-framework materials is particularly difficult due to the unclear formation mechanism of the inorganic framework assembled around the organic templates. One effective synthetic approach is to use chiral templates to impart their chirality into the open frameworks. The use of chiral metal complex templates has greatly facilitated the formation of chiral framework metal phosphates. The other synthetic approach is to incorporate chiral groups into organic-inorganic hybrid frameworks. Natural chiral amino acids are attractive building blocks for infinite chiral structures, while the hydro/solvothermal synthesis of an open framework with a chiral topology may open the way to thermally stable materials if chiral templating can be effected. In the literature, a few successes have been achieved in the synthesis of inorganic open-framework structure materials by using amino acid molecules as the templates, including histidine, asparagine, and glycine.Open-framework metal phosphates have been extensively studied due to their rich structural chemistry and potential applications. In particular, the replacement of tetrahedral phosphate groups bypyramidal phosphite units has resulted in a new class of metal phosphite compounds with interesting structural architecture. Interestingly, the incorporation of pseudo-pyramidal units [HPO3]^2- into the framework can partially reduce the connection of M-O-P, and thus may generate more open framework structure. Up to now, one zinc phosphite with 24-ring channels and four extra-large pore zinc phosphites with 16-ring channels have been prepared successfully.In this thesis, we reviewed the rules of the reported synthesis of open-framework with amino acid as the building blocks. We have been focused on the synthesis of new metal phosphites and metal phosphates by using different amino acid as the building blocks in different system. And summarized the rules of the synthesis and provide some information for the synthesis of chiral compounds. At the same time, based on the successful experience of large and extra-large compounds, we aim to develop new large pore and extra-large pore metal phosphites through the replacement of tetrahedral phosphate groups by pyramidal phosphite units and further enrich the compositional and structural chemistry of inorganic micropore material. Main results include:1. An open-framework zinc phosphate H₃O·（C₆H₉N₃O₂）₂（C₆H₈N₃O₂）Zn₃（PO₄）₂ （denoted ZnHPO-CJ40, CJ: China Jilin University） templated by L-histidine, with one dimensional chiral chain has been synthesized hydrothermally. Its structure is constructed by the alternating connection of ZnO₃N and PO4 tetrahedra to form edge-shared Zn₂P₂ 4-ring ladder-like chains, and ZnO₂N₂ tetrahedra as pendants are grafted onto this chain propagating along the c axis. It is noteworthy that all the histidine molecules grafted onto the inorganic moiety have the same configuration as the initial added homochiral L-histidine. There is a good agreement between the VCD and IR spectra. The vibrational modes were identified, and conformational information could also be observed in the VCD spectra. The strong VCD signals showed that most crystals of ZnPO-CJ40 were not racemic.2.A 2D zinc phosphate C₆H₁₀N₃O₂·Zn₂（HPO₄）（PO₄）·H₂O（denoted ZnHPO-CJ36, CJ: China Jilin University） templated by histidine has been synthesized in a solvothermal system. The structure is featured by a series of double crankshaft chains composed of the edge-sharing 4-rings, which are linked by O_carboxyl atoms of histidine molecules to form an infinite 4 x 8 net sheet parallel to the ab plane.The inorganic layers are stacked in an AAAA sequence along the [001] direction. The lattice water molecules occupy the void space between the layers. The histidine molecules are attached to Zn（1） atoms via a carboxyl oxygen atom, and extend into the interlayer regions. It is noteworthy that the histidine molecules on one side of the sheet have the R absolute configuration, while those on the other side of the sheet have the S absolute configuration, implying a chiral recognition effect of the host inorganic network and the guest histidine molecules.3. An open-framework zinc phosphite C₆H₉N₃O₂ZnHPO₃·0.5H₂O （denoted ZnHPO-CJ37, CJ: China Jilin University） templated by L-histidine, with two dimensional layer has been synthesized solvothermally. A main structural motif is the four-membered ring which is formed from two tetrahedral Zn²⁺ cations and two HPO₃^2- phosphite anions, resulting in a neutral （ZnHPO₃）₂ 4-ring.The above inorganic 4-rings are further connected by neutral zwitterionic histidine molecules into a hybrid inorganic-organic super 4-ring. Each histidine molecule serves as a simple bidentate bridge between one pair of inorganic 4-rings. These super 4-rings are extended into infinite two dimensional sheets that are stacked in the crystallographic （101） direction. In this compound, neutral zwitterionic histidine exhibits a rather unusual coordination mode: bidentate linker between two tetrahedral metal centers. This coordination mode is in contrast with monodentate or bi- and tridentate chelating ligands coordinating to a single metal center, as commonly observed in many metal histidine complexes.4. An open-framework cobalt phosphite 2H₃O·[Co₈（HPO₃）₉（CH₃OH）₃]·2H₂O （denoted CoHPO-CJ2, CJ stands for China, Jilin University）, with extra-large 18-ring channels has been synthesized hydrothermally. Its structure is featured by 2D cobalt-oxygen 18-net sheets which are pillared by HPO3 pseudo-pyramids to form a 3D open-framework structure with pendent -CH3 groups protruding into the 18-ring channels. The magnetic property is also studied and the result implies an antiferromagnetic interaction between Co²⁺ ions.5. Two transition-metal phosphites, Na₂[M（HPO₃）₂] （denote CoHPO-CJ3, CJ stands for China, Jilin University M = Co, Ni） have been synthesised under mild solvodrothermal conditions and the solid-state structures have been elucidated by single-crystal X-ray diffraction studies. The crystal structures of these compounds are isomorphic and built up from a 3D open framework with 4-, 6- and 12-membered polyhedral rings of vertex-linked MO₆ and HPO3 building units. The inorganic frameworks contains 12-membered ring channel systems in which the sodium ions are located.6. A series of two-dimensional （2D） layered transition metal coordination polymers, M_0.5C₁₁H₁₂N₂O₂ （M= Zn （1）, Co （2）, Ni （3））, were synthesized under hydrothermal conditions with biological amino acid D, L-tryptophan molecules as ligands. All the compounds 1, 2 and 3 are isomorphic in their crystal structures. In its structure, each zinc center is octahedrally coordinated to four tryptophan ligands that are bonded to the Zn atom in a tridentate fashion through one Zn-N（NH2） and two Zn-O（coo-） bonds. Its structure is featured by left-hand and right-hand helical chains, which are built from Zn-O-C-O-Zn and shared the same zinc atoms to form the layer. We study the solid state fluorescence of 1, 2 and 3.更多还原