Design,Synthesis And Properties Of Metal-Organic Frameworks Based On (Three)1,2,4-Triazole Ligands

Triazole ligands contain nitrogen atoms with strong coordination ability,which can coordinate with transition metal atoms to form metal-organic frameworks(MOFs).The varied spatial structures of the metal-organic frameworks make them have potential applications in gas adsorption,chiral materials,luminescent sensors,photocatalytic degradation and other aspects,which have attracted the attention of many scholars.In this thesis,nine coordination polymers were synthesized by the combination of ttpa(ttpa=tris(4-(1,2,4-triazol-1-yl)phenyl)amine)and multicarboxylate ligands,and characterized by elementary analysis,X-Ray single-crystal analysis,IR,TG and PXRD.Part One:A Cu-MOF {[Cu?2(ttpa)2][Cu?(bptc)](3H2O·DMF}n(1)was synthesized using hydrothermal method(ttpa=tris(4-(1,2,4-triazol-1-yl)phenyl)amine,H4bptc=3,3',4,4'-biphenyltetracarboxylic acid).1 exhibits the(3,3)-connected 63-hcb topologic cationic networks[Cu'2(ttpa)2]n encapsulated the[Cu2(bptc)2]4-dimeric anions.1 is the first example that the 2D cationic network encapsulated coordinated M2 dimer anions.1 is also the first example that isolated Cu(?)cations only coordinate N-donor ligand,and Cu(?)cations only coordinate carboxylate ligand in one compound.1 is a good luminescence sensor for multi-detection of Cu2+,Fe3+,Cr2O72-,CrO42-and TNP.1 shows the highest Ksv 2.460 × 105 M-1 for detection of Cu2+of MOFs sensors and the lowest detection limit 0.062 M(3.9 ppb).The quenching constant Ksv for TNP is 6.646 × 104 M-1.The detection limit is 0.22 M(50 ppb).This result demonstrates that 1 can be a highly effective luminescent sensor for detection of TNP,and is comparable to those of the best reported MOF probes.1 is also a good photocatalyst for degradation of methylene blue.The catalytic efficiencies are 1>20 nm TiO2>60 nm TiO2.Part Two:Four nanostructural Ni(?)coordination polymers{[Ni(ttpa)(1,4-ndc)(H2O)2]·2H20}n(2),{[Ni(ttpa)(1,3-bda)]·2H2O-DMF}n(3),{[Ni(ttpa)(1,4-bdc)]·H2O}n(4)and {[Ni(ttpa)(aip)(H2O)]3H2O}n(5)were synthesized using hydrothermal and sonochemical methods(ttpa=tris(4-(1,2,4-triazol-l-yl)phenyl)amine,1,4-ndc=1,4-naphthalenedicarboxylate,1,3-bda=1,3-benzenediacetate,1,4-bdc=1,4-benzenedicarboxylate,aip=5-aminoisophthalate).The effects of sonication power,time and frequency on the size and morphology of nano-sized 2-5 have been studied.2-5 are good catalysts for the degradation of MB under visible light irradiation.The effects of the size and morphology of nano-sized 2-5 on the photocatalytic efficiencies were studied.The higher sonication frequency obtains uniform and smaller nano-sized coordination polymers which have higher catalytic efficiency.Part Three:One Zn(?)coordination polymers {[Zn(ttpa)(1,4-ndc)-2.5H2O]}n(6)was synthesized with flexible ttpa and multicarboxylicate using the hydrothermal method.6 shows a special(4,4)-connected and 4-fold three dimensional network.The polymer 6 is a good luminescence sensor for detection of Nitro explosives,particularly for TNP.When TNP's concentration was 27 ppm and 32 ppm,the fluorescence quenching efficiency reached 94.6%and 97.4%.The polymer 6 also exhibits high sensitivity and selectivity as a luminescence sensor for Fe3,Cu2+,Ag+ and pH.Part Four:Three Cu(?)coordination polymers {[Cu2(ttpa)(suc)]·2H2O}n(7){[Cu(ttpa)(1,3-bda)]·3.5H2O}n(8){[Cu(ttpa)(pim)]·H2O}n(9)have been synthesized.7-9 are highly efficient and universal photocatalysts for the degradation of the organic dyes methylene blue(MB),rhodamine B(RhB)under visible light irradiation,very stable and easily separated from the reaction system for reuse.Finally,the photocatalytic mechanism of catalytic degradation of polymer 9 was discussed in detail.