| 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 Ocarboxyl 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 HPO32- 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, M0.5C11H12N2O2 (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.
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