Chiral Metal Organic Frameworks Based On Amino Acids Modified Imides

The research of metal-mrganic frameworks(MOFs) is a topic of materials and chemical sciences, because of the diverse topological structures by self-assembly as well as its potential applications in proton conduction, gas storage, selective adsorption, and magnetism. Chiral metalorganic frameworks is an important branch, it has contributed significantly in chiral separation, asymmetric catalysis, nonlinear optics and ferroelectric materials.Amino acid derivatives have a good molecular recognition and the diverse of the synthesis of metal-organic frameworks. The robust ligand of 1,8-naphthalimides are rich of optical and electrical properties. Besides, the strong π…π stacking interactions has contributed for the selfassembly to form three-dimension structures. This thesis focous on the design and synthesis chiral metal-organic frameworks materials from new amino acid modified naphthalimide derivatives ligand. The fluorescence, thermal stabability and ferroelectric properties of as-synthesized MOFs have also been investigated.In chapter 1, this paper describes the research background of 1,8-naphthalimide derivatives and the progress of ferroelectric metal-organic frameworks.In chapter 2, considering the concept to design and synthesis of the new ligands, we synthesized a new s-nip ligand by use of 1,8-naphthalic anhydride and chiral amino acids Lhistidine. Two one-dimensional ribbon complexes [Zn(s-nip)2]n(1) and {[Co(s-nip)2]·(H2O)0.5}n(2) were obtained by the self-assembly of zinc or cobalt salt with s-nip ligand under solvothermal conditions. In the crystal structures of 1 and 2, hydrogen bonds and π…π stacking interactions organize their architecture to three-dimensional supramolecular structures. The stability and fluorescence properties were also discussed, both of the two crystals are stable, moreover, it exhibit good fluorescence properties. On the other hand, they crystallize C2 point group belonging to the 10 polar point groups, so we discussed the ferroelectricity of two complexes. The hysteresis loops indicate the spontaneous polarization reversal by an electric field. Simultaneously, temperature dependences of the dielectric constant at different frequencies indicate the ferroelectric because of the complexes occurred dielectric anomalies. A two-dimensional metal-organic frameworks [Cu(nia)2·(H2O)5]n(3) was synthesized by the reaction of copper salt and s-nip ligand in hydrothermal condition, π…π stacking interactions organize the architechture to three-dimensional structure, the 3D supramolecular framework has 1D hydrophilic channels viewed along one direction. Interestingly, the s-nip ligand occurred in the in situ dehydrogenation reaction, the flexible chiral s-nip ligand became the rigid achiral nia ligand.In chapter 3, we used 1,8-naphthalic anhydride and chiral amino acids L-alanine to synthesis HLala ligand, one mononuclear crystal [Zn(HLala)2(phen)2]n(4) was synthesized by assembling of 1,10-phenananthroline, HLala and zinc salt under the solvothermal condition. There are two types of π…π stacking interactions, the first type is formed between phenanthroline ring and naphthalimide ring, the second type is formed between two naphthalimide rings. Solid-state fluorescence, liquid-state fluorescence, uv/vis spectroscopic and thermogravimetric analysis were discussed.In summay, this is the first time introduced the chiral histidine and anhydride to form 1,8-naphthalimide chiral ligand, two ferroelectric metal-organic frameworks were obtained by the ligand. This provides a new idea for the synthesis of ferroelectric metal-organic frameworks, it also provides substance basis for the applications of ferroelectric effect transistor, ferroelectric randon access memory and ferroelectric photovoltaic. Furthermore, the new ligand and copper salt in situ dehydrogen reactions under hydrothermal conditions, it′s very interesting to explore the in situ reaction.