Synthesis,Functional Modification And Properties Of Coordination Polymers Based On Dicarboxylate Ligands

In recent decades,the synthesis and design of coordination polymers(CPs)has attracted tremendous attention due to their fascinating structures and potential applications.Among them,luminescent CPs have received great interest because they can be applied as chemosensors for the sensitive detection of metal ions,small molecules,explosives,toxic anions,and so on.In this thesis,using series of dicarboxylate ligands decorated with functional groups(nitro,methoxyl or hydroxy),eight novel coordination polymers(1-8)have been synthesized and characterized.Some of the complexes can be utilized in the detection of metal ions,anions or nitro benzenes.The main contents of the thesis are devided into the following parts:1.Two Eu(III)/Tb(III)complexes(1-2)were synthesized with L_NO2ligand:Complexes1 and 2 are both three-dimensional(3D)frameworks based on infinite rod-shaped Ln ^III-C-O-C carboxylate SBUs.The structures exhibit 1D channels decorated with functional groups.Fluorescence measurements show that complex 1 can serve as a fast and recyclable fluorescence sensor for nitroaromatics detection via a turn-off response with low detection limits.The fluorescence quenching of 1 for nitroaromatics is presumably due to the following reasons:the photo-induced electronic transfer mechanism and the competitive adsorption mechanism.2.Four Co(II)complexes(3-6)were syntheized with L_OHligand:Four Co(II)complexes of different dimensionality have been obtained by solvothermal reactions of Co(II)with L_OHin the presence of N-containing ligands.Complex 3 consists of infinite 1D linear chains,which are stacked in parallel to form a 3D supramolecular architecture.Complexes 4 and 5 are both(4,4)-connected 2 D layered networks based on trinuclear[Co₃(COO)₆N₂]clusters.Complex 6 contains 2D layers based on binuclear clusters,which are further linked into a layer-pillared 3D framework by the4,4'-bipy.Complexes 4 and 5 can be used as fluorescent sensors in the detection of Fe³⁺,Cr²O₇^2-and NB.3.Two Zn(II)complexes(7-8)were synthesized with L_OMe/L_OHligands:Complex 7and 8 are both 3D anionic frameworks with large 3D intersecting channels.The former is based on eight nuclear[Zn₈O₃(CO₂)₁₂]clusters and the latter is based on trinuclear[Zn₃O(CO₂)₄(H₂O)]clusters.Flourescent studies reveal that complex 7 has highly selective and sensitive detection for Fe³⁺and NB in EtOH.