Syntheses,Structures And Sensing Properties Of Luminescent Coordination Polymers Based On Triphenylamine Ligands

This thesis consist of three parts:Firstly,we employed two semi-rigid triphenylamine ligands tris（4-（pyridin-4-yl）phenyl）amine（TPPA）and tris（4-（1H-imidazol-1-yl）phenyl）amine（TIPA）,three coordination polymers have been synthesized hydrothermally.Secondly,three coordination polymers have been synthesized hydrothermally based on nitrogen-containing and carboxylic acid-containingbifunctionaltriphenylamineligands4,4’-（（4-（1H-imidazol-1-yl）phenyl）azanediyl）dibenzoic acid（H₂TPI）,4,4’-（（4-（1H-1,2,4-triazol-1-yl）phenyl）azanediyl）dibenzoic acid（H₂TPT）and transition metal ions.Thirdly,three coordination polymers have been synthesized hydrothermally based on H₂TPI,H₂TPT and rare earth metal ions.1.Syntheses,structures,and properties of coordination polymers based on TPPA and TIPAThe solvothermal reactions of TPPA,4,4’-sulfonyldibenzoic acid（H₂sdba）and Co（NO₃）₂·6H₂O yielded a compound,namely,[Co₂（TPPA）（sdba）₂]_n（1）.Solvothermal reactions of TIPA,heptanedioic acid（H₂pim）and Zn（NO₃）₂·6H₂O yielded two compounds,namely,{[[Zn（TIPA）（pim）0.5]·2H2O·NO3]}_n（2）,{[[Zn（TIPA）（pim）]·3H₂O]}_n（3）.Compound 1 features a 2-fold interpenetration 3D framework with cds topology.Compound 2 is a 2-fold interpenetrating 3D framework containing four chiral（10,3）-a subnets.Compound 3 is a 2D+2D→2D entangled network.The electrochemical properties and photocatalytic activity of 1 have been researched,1 was used as an electrode materials for a supercapacitor,the maximum specific capacitance is 75.7 F g^–1 at current density 0.5 A g^–1,the 1’s pyrolysis product Co₃O₄ was also used as an electrode materials for a supercapacitor,capacitances of118.6 F g^–1 was achieved at current density of 0.5 A g^–1,both two materials have excellent recycling stability.Furthermore,compound 1 also displays photocatalytic activity for the decomposition of RhB under UV irradiation.The fluorescence properties of compounds 2 and 3 were studied.In contrast,the compound 2 has better fluorescence properties,so the compound 2 was selected for a series fluorescence experiments.The fluorescence sensing experiments demonstrated that 2 can serve as a dual-functional fluorescence sensor for the detection of nitroaromatic compounds and highly selective detection of ofloxacin（OFX）antibiotics.The possible sensing mechanisms have also been investigated through density functional theory（DFT）calculations and UV-vis absorption spectrums analysis.In addition,the SHG measurements of 1 exhibit a modest SHG efficiency（⁰.8 time that of KDP）.2.Syntheses,structures,and properties of coordination polymers based on H₂TPI,H₂TPT and transition metal ionsThree coordination polymers have been synthesized by employed nitrogen-containing and carboxylic acid-containing bifunctional triphenylamine ligands H₂TPI,H₂TPTandtransitionmetalions,namely,{[Zn₂（TPI）₂]·3H₂O}_n（4）,{[Cd₂（TPI）₂·2H₂O]·4H₂O}_n（5）,{[Zn₂（TPT）₂]·3H₂O}_n（6）.Compound 4 is a 2-fold interpenetrating（3,6）-connected network;Compound 5 is a（3,6）-connected network;Compound 6 and 4 are isostructural.The fluorescence properties of the compounds 4-6 were studied.Compounds 4 and 5 were selected for a series of fluorescence sensing experiments.The results show that both compounds 4 and 5 can be used as a good sensing materials for detection nitro compounds by fluorescence quenching and detection ofloxacin antibiotics by fluorescence enhancement.The possible sensing mechanisms have also been investigated through density functional theory（DFT）calculations and UV-vis absorption spectrums analysis.Compound 6 is mainly for comparison with compound 4,the fluorescence of the compounds are affected by the ligands.3.Syntheses,structures,and properties of coordination polymers based on H₂TPI,H₂TPT and lanthanide metal ionsThree coordination polymers have been synthesized by employed H₂TPI,H₂TPT and lanthanide metal ions,namely,{[Tb（TPI）（ndc）_0.5·2H₂O]·DMF}_n（7）,{[Eu（TPI）（ndc）0.5·2H₂O]·DMF}n（8）,{[Eu（TPT）（ndc）0.5·2H₂O]·DMF}n（9）.Compounds 7-9 are isostructural three-dimensional structure.The fluorescence properties of the compounds 7-9 were studied.Compounds 7-9 show their own characteristic emission peaks,but the intensity is different.Compound 8 was selected for a series of fluorescence sensing experiments.The results show that compound 8 can be used as a good sensing material for detection Fe³⁺by fluorescence quenching and detection DMSO by fluorescence discoloration.In addition,the fluorescence of compound 8 also has a pH response.