Synthesis, Crystal Structures And Properties Of Coordination Polymers Based On Tetrazolate And Modified Amino Acids

This thesis reviews the recent development of coordination polymers constructed from metal ions and organic linkers. The design and syntheses of coordination polymers, the growth of single crystal and the network and properties of coordination polymers are introduced. Among them, the properties of coordination polymers such as non-linear optics, luminescence, gas storage, magnetic properties, chirality, ion exchange and catalysis are especially discussed.A series of novel compounds constructed from tetrazolate and modified amide acids have synthesized by hydrothermal methods. Their crystal structures and properties are also studied. This thesis mainly consists of three parts:1. One novel tetrazolate ligand : 4-(1H-tetrazol-5-yl)benzoic acid(H₂(4-TZBA) was successfully synthesized. and a series of modified amide acids such as 4-(carboxymethylamino)benzoic acid(CABA), 2-acetylamino-3-(4-amino-phenyl)-propionic acid methyl ester (AAPM), 3E-[5-(2-amino-2- carboxy-ethyl)-2- methoxy -phenyl]- acrylic acid (AMPA) and 3-(4-amino-phenyl)-2- (methoxycarbonylmethyl- amino)- propionic acid methyl ester (AMPM) were also prepared.2. The reactions of Mn(ClO₄)₂ and 4-(1H-tetrazol-5-yl)benzoic acid(H₂(4-TZBA) give rise to [Mn(4-TZBA^2-)(H₂O)₂] 1å’Œ[Mn₂(4-TZBA^2-)₂(μ2-H₂O)(H₂O)] 2 by mediate the ratio of water/pyridine. 1 can be obtained when the water/pyridine is 0.4mL:0.1mL. When the ratio of water/pyridine is decreased to 0.1mL:0.1mL, 2 can be obtained. Through the synthetic conditions are similar, the crystal crystals of 1 and 2 are different. 1 crystallizes in central space group and there are no channels in 1. 2 crystallizes in chiral space group and there exist triangular channels with the dimensions of 12.147×l2.626×12.634(?) in 2. The synthetic method and crystal of [Co(4-TZBA^2-)(H₂O)₂] 3 are similar to 1, and 3 is paramagnetic. The luminescent emissions of 1, 2 and 3 are strong. 2 is non-linear active and exhibits a second-order coefficient about 0.3 time that of KDP. 3. A series of coordination polymers:[Zn(CABA^2-)](H₂O) 4[Cd(R-AAP)(Py)(H₂O)]·ClO₄) 5,[Cd(S-AAP)(H₂O)₂]·ClO₄) 6,[Zn(R,S-AMPA)(H₂O)]7,[Zn₂(R-ACP)(Py)₃]·ClO₄)₂ 8 are obtained using modified amide acids as organic linkers. According to the layers discussed above, it's the key trunks and the H₂N-CH-COO^- chain acting as the bridges. Thus, the experimental result is consistent with the assumption that we conceived. Both the size and the shape of the grids in the layers are mediated by the positions of the coordinating function groups at modified amino acids. 5, 6 and 8 are non-linear active and exhibit second-order coefficient 0.8,0.6 and 1.5 time that of KDP, respectively.