Conductive Coordination Polymers From Sulfur-Containing Ligands:Design,Syntheses And Electrical Properties

Coordination polymers(CPs)generally contain the porous coordination polymers(PCPs)and the non-porous coordination polymers.PCPs are porous crystalline compounds with many advantages,such as diversities of structure and function,unsaturated metal sites,and large surface area.Because of these nature which had led to various applications in gas storage,catalysis,drug delivery,luminescence sensing,separation and biomedicine,etc.Beside,the applications of PCPs will be greatly enhanced and enriched by further modifying or synthesizing the novel metal-organic coordination polymers.In this work,we propose to design and synthesize the novel PCPs based on rational researchs and studied its features that have remained unexplored.The research contents will be demonstrated in detail as follows:In chapter one,we focused on the explanations about the characteristics and applications of metal-organic framework compounds,a brief description of the main significance of this topic and the research contents were also presented.In chapter two,we mainly designed and synthesized ligand Ll in order to coordinate with EUCl3·6H2O to get three MOFs with different colors and coordination modes at different temperatures.For the first time,a kind of 2-D layered rare earth MOF(denoted as 3-Eu-MOF)was prepared.The semiconductor nature of 3-Eu-MOF was demonstrated by the conductivity at room temperature and activation energy.The conductivity was 2.86x1O-9 S cm-1 at room temperature and the activation energy was 0.25 eV.In chapter three,in order to obtain the UiO-66-2F-2SO3H,the H2O2 was introduced into the pores of UiO-66-2F-2SH which had many thiol groups and chemical stability to completely oxidize the thiol groups to sulfonic acid groups by facile postsynthetic oxidation.Proton conduction tests were used to investigate the proton conductivity at different humidity and temperatures.We found the conductivity of UiO-66-2F-2SO3H was improved by comparing the changes of proton conductivity of the two materials.Then,we analyzed the conductivity enhancement results and explained the transmission mechanism.In chapter four,we designed and synthesized ligand L2 containing a conjugated macrocyclic structure based on the conjugate effect and the ?-? stacking effect of the benzene ring,then reacted with Cu+ to prepare CuPT.The effect of reaction solvent and temperature on the morphology and conductivity of CuPT was investigated,and CuPT-5 with conductivity of 1.26×l0-6 S cm-1 was obtained.It also explored its thermal stability,all of which have paved the way for study of its structure and applications.