Novel Crystalline Coordination Polymer Materials: Syntheses, Structures, And Properties

The main objective of this thesis is to design and investigate novel crystalline coordination polymer materials, based on organic ligands and/or polyoxometalates, which have been synthesized by hydrothermal(solvothermal) method. The influences of reaction conditions and the mechanisms of synthesizing process were investigated. The structure-properties relationship of these compounds was studied.1. Five new coordination compounds have been hydrothermal synthesized based on 1,3,5-BTC and long flexible ligands.[Zn(HBTC)(L1)]·4H2O(1)[Zn3(BTC)2(L2)2(H2O)2]·2H2O(2)[Zn(HBTC)(L3)](3)[Cd(HBTC)(L1)(H2O)]·H2O(4)[Cd(H2BTC)2(L3)2]·2H3BTC(5)Compound 1, 3 and 4 represents 2D structure with sql topology while compound 2 represents 2D structure with(5.62)(52.6)(54.82) topology. Compound 1 exhibits a 2Dâ†'3D entangled structure with the coexistence of polycatenation and interdigitation. Compound 2 features a 2Dâ†'2D polycatenated network. Compound 3 displays a 2Dâ†'2D polythreaded structure while compound 4 shows an unusual 2Dâ†'3D interdigitated network. Furthermore, a comparison between 1 and 4(3 and 5) demonstrates that metal ions have great effects on the structure of coordination polymers, and the comparison of 1, 2 and 3 reveals that ligands with different length and flexibility also have significant effects on the structure of coordination polymers. In addition, the fluorescence properties of these compounds have also been studied.2. Three self-entangled compound have been solvothermal synthesized based on tetrakis[4-(carboxyphenyl)oxamethyl]methane acid and Cd salt.[Cd2L(H2O)2]·solvent(6)[Cd6(L)3(H2O)6]·solvent-R(7)[Cd6(L)3(H2O)6]·solvent-L(8)Compound 6 exhibits a 3D self-catenated noncentrosymmetric framework with three types of helical chains. Compound 7 and 8 were racemes. The SHG measurements indicate that 6 is NLO active, with approximately 3.6 times that of KDP. The solid-state fluorescence measurements reveal that 6 may be good candidate for fluorescent materials.3. Two new porous coordination polymers have been solvothermal synthesized based on 1,4-BDC and Cd salts.[(CH3)2NH2]1.66[Cd1.84Na0.66(BDC)3]·DMF·0.5Et OH(9)[(CH3)2NH2]2[Cd2(BDC)2Cl2]·(CH3)2NH(10)Structural analysis reveals that compound 9 represents eight-connected self-interpenetrating porous framework based on hetero pentanuclear metal carboxylate clusters. And compound 10 shows 3D three folded interpenetrating framework based on binuclear Cd clusters. Iodine adsorption studies indicate that 9 is a good candidate material for iodine enrichment and detection. And the ESI of 9 ? I2 shows that it has a relatively high conductivity at room temperature. The thermally stabilities of compound 9 and 10 were also investigated.4. Eleven POM-based coordination polymers have been hydrothermal synthesized based on N-donor ligands and metal salts.[Cu2(L1)3(H2O)2(P2W18O62)]·H2L1·4H2O(11)[Cu3(L2)6(P2W18O62)]·4H2O(12)[Cu3(L3)5(H2O)(P2W18O62)]·4H2O(13)[Cu3(L4)4(H2O)7(P2W18O62)]·26H2O(14)[(PW12O40)2CuI6(trz)6]·H2O(15)[(PW12O40)2(H2O)6(trz)6]·2H2O(16)[CuI12(trz)8Cl][PMo12O40](17)[(PMo12O40)2(H2O)6(trz)6]·2H2O(18)[Co2(L5)5(H2O)2(Si W12O40)](19)[Cu2(L5)3(H2O)2(Si W12O40)]·H2O(20)[Cu(L5)2(H2O)H(PW12O40)]·7H2O(21)Compound 11 exhibits a 3D framework with(4,4,6)-connected(3·42·5·66·72·83)(3·42·52·6)(3·42·62·7) topology. Compound 12 is an unprecedented 3D framework with SQC-888 topology. Compound 13 shows a 2Dâ†'3D interdigitated network. And compound 14 gives an example of landing a magnetic tri-copper cluster on the surface of a POM anion. Compound 15, which shows highly stability with visible-light-driven photocatalytic properties, exists 3D framework based on hex-nuclear Cu(I) clusters. Compound 19 represents a new type of 2D+2Dâ†'3D polypseudorotaxane motif. Compound 20 exhibits a 3D self-catenated framework with the presence of three types of helical chains. The 3D supramolecular structure of 21 shows dynamic behavior accompanied with removal/adsorption of guest water molecules. Remarkably, the flexible framework of 21 can retain its structure even in 8 mol L-1 hydrochloric, dilute Na OH solution(p H = 12) and boiling water.