Synthesis And Properties Research Of Two Kinds Of Linear Hydrogen-Bonded Supramolecular Polymers With Ion Responses And Photo-responses

Supramolecular polymers(SPs)are polymeric arrays of monomeric units that are held together by highly directional and reversible non-covalent interactions,which exhibit polymeric properties in solution and bulk.The reversible feature of the non-covalent interactions endows SP with unique properties that traditional polymers don't equipp,such as reversibility,self-healing and stimuli responsibility.Among them,stimuli-responsive SPs have been developed rapidly,for example,linear SPs which response to ions and light stimuli.This dissertation is divided into the following two parts:1.Synthesis and properties of ionic stimuli-responsive linear supramolecular polymers.A symmetric hexaazatriphenlene(HAT)derivative that bears six urea side chains was designed and synthesized,which can co-assemble with Cl-or Br-ions to form linear SPs driven by the multiple N-H… hydrogen bonds.Thanks to the binding ability of HAT core(for metal ions or protons)and the urea groups(for halogen anions),such anion-bridged SPs also exhibited both Ag+ ion and selective proton-anion ion pair responses,which were proved by various techniques including 1H NMR,UV-Vis and fluorescence spectroscopies,transmission electron microscopy(TEM)as well as semi-empirical calculations.2.Synthesis and properties of visible light responsive linear hydrogen-bonded supramolecular polymers.The monomer molecule had been obtained by incorporating a tetrafluoro-substituted azobenzene(TFAB)motif with two terminal 2-ureido-4-pyrimidones(UPy)unite,which can undergo the linear polymerization processes driven by the quadruple hydrogen bonding interactions of UPy units in chloroform,when the TFAB was in its trans-conformation.However,supramolecular macrocycles were more favorable when the trans-TFAB monomer is isomerized to the cis-TFAB monomer trigged by visible light with ?>500 nm,and the cis-TFAB monomer can isomerize back to the trawps-TFAB monomer when another visible light with ? = 410 nm was employed.Therefore,the formation of supramolecular polymers can be reversibly controlled by the alternative irradiation of TFAB unit with visible light at?>500 nm and ? = 410 nm.The structure of TFAB monomer can be proved by 1H NMR,13H NMR and High resolution mass spectrometry,whose reversible visible light irradiated cis-trans isomerization behaviors were investigated in chloroform as well.The construction of linear hydrogen-bond SPs with trans-TFAB monomer and the visible light responsive properties can be revealed by the systematic studies of 2D DOSY,dynamic light scattering(DLS),SEM as well as viscosity measurement,which are currently in progress.