Synthesis And Characterization Of Hyper-structure Photorefractive Molecules With Calix[4] Resorcinarene Core And Disperse Red Chromophores Arms

Photorefractive(PR)effect is seen in some materials that combine photoconductivity and nonlinear optical(NLO)response to modulate the refractive index of the medium.In this thesis,two disperse red photorefractive NLO chromphores and a charge transport molecule were designed and synthesized,and were introduced into the CRA core to prepare star-shaped hyper-structure refractivemolecules through click reaction.The chemical structures and some properties of all the intermediates and final products were characterized.In the first part,synthesis and characterization of model compounds R-DR1 and R-DR1-Et.Two chromophore molecules with azido group DR1-N3 and DR1-Et-N3 were synthesized through nucleophilic substitution and diazotization.At the same time,the core molecule R-Alkyne was synthesized through resorcinol and propargyl bromide.Finally,two model molecules R-DR1 and R-DR1-Et were synthesized through the click reaction between DR1-N3,DR1-Et-N3 and R-Alkyne,respctively.The chemical structure and the performance of all the intermediates and final products were characterized by 1H NMR,FT-IR,EA,HR-MS,UV-Vis,DSC/TG and other methods.In the second part,synthesis and characterization of hyper-structure molecule CRA-DR1(X)-Cz(100-X)(x=100,50).The core molecule CRA-Alkyne was synthesized by CRA and propargyl bromide.Carbzole-based derivative of Cz-N3 was synthesized as the charge transfer molecule.The hyper-sructure photorefractive molecules were prepared through click reaction by addition of the functional molecules DR1-N3 and Cz-N3 in a certain ratio.The chemical structure and the performance of all the intermediates and final products were characterized by 1H NMR,FT-IR,EA,GPC,MALDI-TOF-MS,UV-Vis,DSC/TG.EA and MALDI-TOF-MS showed that the introuduced rate of the functional molecules is nearly 100%.GPC results indicated that the molecular dispersity index is below 1.18.TG results showed that all of the hyper-structure photorefractive molecules havegood thermal stability,and their temperature of decomposition were near 300?.In the third part,synthesis and characterization of hyper-structure molecule CRA-DR1-Et(X)-Cz(100-X)(x=100,50).The chromophore DR1-Et-N3 and charge transport molecule Cz-N3 were introduced to the core of CRA-Alkyne via click reaction to synthesis hyper-structure molecules.The chemical structure and the performance of the final products were characterized by 1H NMR,FT-IR,EA,GPC,MALDI-TOF-MS,UV-Vis,DSC/TG.EA and MALDI-TOF-MS showed that the introuduced rate of the functional molecules is nearly 100%.GPC results indicated that the molecular dispersity index is below 1.24.TG results showed that the decomposed temperature of the star-shaped hyper-structure photorefractive molecules are relatively high,and all of them have good thermal stability.In the last part,the photorefractive properties of the as-synthesized molecules were characterized by two-beam coupling(TBC)experiment using ECz as a plasticizer and PCBM as a sensitizer.Without the external electric field,the TBC gain values of R-DR1 and CRA-DR1 based composities were 98.4 cm-1and 117.3cm-1,respectively,which is also one of the best performance in molecular glasses under the same test conditions.