Assembly Of Coordination Complexes Of 1,3,5-Tri-4-pyridyl-1,2-ethenylbenzene:Structures And Properties

Coordination polymers(CPs)have the advantages of adjustability and designability in structures and properties control.Thus they have been widely studied in the fields of gas storage and capture,drug delivery,molecule sensing,photocatalytic degradation and fluorescent detection.These materials have become hot topics in the fields of chemistry and materials recently.In this thesis,we constructed a series of CPs based on a highly conjugated ligand,1,3,5-tri-4-pyridyl-1,2-ethenylbenzene(tpeb)and Zn(NO3)2,Cd(NO3)2,Co(NO3)2,Ni(NO3)2 together with various auxiliary carboxylic acids.We have studied their performances in photocatalytic degradation of dyes and detection of trace small toxic molecules in water.Main achievements are summarized as follows:1.Solvothermal reactions of M(NO3)2(M=Zn,Cd),with tpeb in the presence of various carboxylic acids including 4-HIBA,1,4-H2BDC,2,5-H2FDC,2,5-H2DBTPA,1,2-H2CHDC and 1,5-H2PDC gave rise to eight CPs,viz,[Zn(tpeb)2(4-IBA)2]·2H2O(1),{[Cd(NO3)(tpeb)(4-IBA)]H2O}n(2),{[Cd2(N03)2(tpeb)2(1,4-BDC)]}n(3),{[Cd2(tpeb)2(2,5-FDC)2]·2H20}n(4),[Cd(tpeb)(2,5-DBTPA)2]n(5),{[Cd2(H20)2(tpeb)2(1,2-CHDC)2]·H2O}n(6),[Zn(tpeb)(1,2-CHDC)]n(7)and{[Zn(tpeb)(1,5-PDC)]H2O}n(8).Compound 1 is a discrete mononuclear complex while compound 2 is a 2D waterfall-like network.Compounds 3,4 and 5 contain similar 1D chains,which are linked by 1,4-BDC,2,5-FDC,and 2,5-DBTPA bridges,respectively,forming either 2D(2 and 3)networks or a 3D(4)framework.Compound 6 holds a 2D wave-like layer structure while compounds 7 and 8 contain similar 2D fish-scale networks.Among them,water-stable 6 proved to be a highly efficient and conveniently recyclable(five rounds)photo-catalyst for degrading CR in water under visible light irradiation.The mechanism of degradation was also verified by free radical capture experiment.2.Solvothermal reactions of Co(NO3)2/Ni(NO3)2,with tpeb in the presence of various carboxylic acids including 2,5-H2TDC,2,5-H2FDC,2,2’-H2BPDBA,2,5-H2DBTPA and 4,4’-H2DBDPE gave rise to six CPs,including[Co2(tpeb)2(2,5-TDC)2]n(9),[Co2(tpeb)2(2,5-FDC)2]m(10),{[Co(tpeb)(2,2’-BPDBA)]·MeCN}n(11),[Co(tpeb)(2,5-DBTPA)]n(12),[Ni(tpeb)(2,5-DBTPA)]n(13)and{[Ni2(tpeb)3(4,4’-DBDPE)2]·2MeCN·2H2O}n(14).Compounds 9 and 10 share similar 2D double-layer structures which are constructed by 1D[Cd(tpeb)]n chains bridging different five-membered heterocycle dicarboxylates.Compound 11 is a 3D structure obtained by wave-like[Co(tpeb)]n planes linking with 1D[Co(2,2’-BPDBA)]n chains.Compounds 12 and 13 are 3D networks formed by the cross-connection of 1D[M(2,5-DBTPA)]n(M=Co,Ni)chains through tpeb ligands.Compound 14 is a 3D network connected by tpeb ligands with ID[Ni(4,4’-DBDPE)]n chains in two vertical directions.Among them,11 can be used as an efficient fluorescent probe for detection of p-nitrophenol in water.