Syntheses,Sructures And Properties Of Coordination Polymers Based On 1,2,4-Trizoles Derivates

In this dissertation,we design and synthesize four 1,2,4-triazole derivates,that are bitopic 1,1 '-(oxybis(1,4-phenylene))bis(1H-1,2,4-triazole)(OPBT),bis(4-(1H-1,2,4-triazol-1-yl)phenyl)amine(BTPA),tritopic tris(4-(1H-1,2,4-triazol-1-yl)phenyl)amine(TTPA)and tetratopic N4,N4,N4,N4'-tetrakis(4-(1H-1,2,4-triazol-1-yl)phenyl)-(1,1'-biphenyl)-4,4'-diamine(TTPBDA).The four ligands incorporating different multicarboxylates and transition metal ions have been adopted to successfully construct eighteen new coordination polymers under hydrothermal conditions.Their syntheses,crystal structures and properties were investigated and discussed in detail.The main content includes the following four parts:1.Solvothermal reactions of bitopic OPBT ligand with phthalic acid(H2PA),glutaric acid(H2GA)and(1,1'-biphenyl)-4,4'-dicarboxylic acid(H2BDA)in the presence of different transition metal ions yielded six new complexes:[Cu5(?3-OH)2(OPBT)2(PA)4]n(1),[Cd2(OPBT)(PA)2]n(2)5 {[Zn(OPBT)(PA)]·H2O}n(3),[Zn(OPBT)(GA)]n(4),[Cd(?2-H2O)(OPBT)(BDA)]n(5)and[Co(OPBT)2(BDA)]n(6).Complexes 1 and 2 show two-dimensional(2D)layers based on pentanuclear Cu(?)and tetranuclear Cd(?)clusters,respectively.Complex 3 displays a one-dimensional(1D)chain based on binuclear Zn(?)clusters.Complex 4 and 5 feature 2D layers with the sql topologies.Complex 6 possesses a 2D 2-fold interpenetrating polyrotaxane structure(2D + 2D ? 2D)with the sql topology.These structures are further formed into three-dimensional(3D)supramolecular frameworks by interlayer C-H…?,?…? stacking or hydrogen bonding interactions,respectively.In addition,thermal stabilities of these complexes,photoluminescent properties of complexes 2-5,UV-Visible spectra and semiconductive properties of complex 6 have been investigated.Subsequently,mesoporous Co3O4 material is obtained by calcination of complex 5 as a precursor.The electrochemical analyses show that mesoporous Co3O4 material exhibits a relatively higher specific capacitance of 285.4 F g-1 at the current density of 0.5 A g-1 and retain 87%at 3 A g-1 after 3000 cycles in 3 M KOH electrolyte.The results demonstrate that mesoporous Co3O4 material with specific morphology can act as a promising electrode candidate in supercapacitors.2.Seven new coordination polymers {[Cu2TTPA(GA)2]·1.5H2O}n(7),{[Co1.5(TTPA)(BTC)(H20)]2·13H2O}n(8),[Co(TTPA)(PA)]n(9),{[Co(TTPA)(BDA)0.5(NO3)]-3H2O}n(10),{[Co2(TTPA)3(OBA)2(H20)3]·2CH3CN·4H2O}n(11),{[Co(TTPA)(AIP)(H20)]·2H20}n(12)and {[Co(TTPA)(MIP)(H20)]·2H20}n(13),have been prepared by the self-assembly of tritopic TTPA ligand with different multicarboxylate ligands and Cu(II)/Co(II)salts.Complexes 7,12 and 13 feature 2D layers with the sql topologies,which can be further packed into 3D supramolecular structures by ?…? stacking or hydrogen bonding interactions.Complex 8 displays a 4-nodal(3,3,4,8)-connected 3D new topological network with the point symbol of(4·6·8)4(44·67··815·102)(62·84).Complex 9 has a 2-fold interpenetrating 3D framework with the dia topology.Complex 10 displays a binodal(3,4)-connected 4-fold interpenetrating 3D architecture with the fsc-3,4-C2/c topology.Complex 11 shows 2D layers with the hcb topologies,which are further packed into a 3D structure by hydrogen bonding interactions.The structural difference of these complexes may be mainly attributed to the different bridging fashions of TTPA and multicarboxylate ligands.Moreover,the thermal stabilities of these complexes,UV-Visible spectra and semiconductive properties of complexes 8-13 have been also studied in detail.The variable-temperature magnetic susceptibility measurements of complex 7 and 8 reveal antiferromagnetic interactions between divalent metal ions.3.A mixed-ligand synthetic strategy to introduce different functional ligands and further coordinate tetrahedral metal Zn(?)ions for construction of chiral or noncentrosymmetric coordination polymers have been adopted.A pair of new enantiomeric Zn(?)complexes {[Zn(TTPA)(TPDC)]2·2DMA-H2O}n(A-14 and A-14)with 5-fold interpenetrating 3D diamondoid frameworks have been synthesized using two achiral tritopic TTPA and(1,1':3',1"-terphenyl)-4,4"-dicarboxylic acid(H2TPDC)through spontaneous resolution.Fortunately,the handedness of bulk crystals can be controlled by using cheap enantiopure propane-1,2-diol as a chiral induction agent,which is confirmed by single crystal X-ray diffraction and circular dichroism spectroscopy.Notably,the enantiomeric Zn(?)complexes display a strong second-harmonic generation response,which can potentially be applied as non-linear optical materials.Moreover,the thermal stabilities,photoluminescent properties of these complexes have been investigated.4.Three different multitopic phenylamine derivatives,that are bitopic BTPA,tritopic TTPA and tetratopic TTPBDA ligands have been prepared by introducing the different number of 1,2,4-triazole rings into the phenylamine backbones.Besides,a linear terephthalic acid(H2TPA)is also employed with Zn(?)/Cd(?)nitrates under solvethemal conditions to construct four new complexes:{[Zn(BTPA)(TPA)]·H2O}n(15),{[Zn(TTPA)(TPA)]·H2O}n(16),[Cd2(TTPA)2(TPA)2(DMF)]·2H2O}n(17)and{[Cd(TTPBDA)(TPA)]0.5·DMF·H2O}n(18).Complex 15 shows a 2D 3-fold interpenetrating layer(2D + 2D ? 2D)with the sql topology,which is further formed into a 3D supramolecular structure by interlayer ?…? stacking and hydrogen bonding interactions.Complex 16 displays a 2D layer with the hcb topology,which can be further assembled into a 3D 4-fold interpenetrating supramolecular framwork with the 3,4,4T25 topology by hydrogen bonding interactions.Complex 17 possesses a 4-fold interpenetrating 3D(3,4,5)-connected architecture with the 3,4,5T86 topology.Complex 18 features a self-penetrating(4,6)-connected 3D new topological network with the point symbol of(414·8X66).These transparent crystals present gradually increasing dimensionality and complexity upon extension of the dentate number of the phenylamine organic building blocks.The results suggest that these diverse coordination networks mainly can be adjusted by the number of the 1,2,4-triazole substituent of aniline backbone and the coordination geometries of the metal ions.Furthermore,thermal stabilities and photoluminescent properties of these complexes have been studied in detail.And the interactions between solvent molecules and complexes frameworks affect the emission spectra of as-made complexes.