Synthesis And Characterization Of Calix[4]resorcinarene-based Hyper-structure Photorefractive Molecules Using Phenothiazine Derivatives As NLO Chromophore

The photorefractive effect refers to spatial modulation of the index refraction due to the functional photorefractive components such as charge transporting agent and nonlinear optical chromophore.Hyper-structure photorefractive molecule is one type of molecule,which functional components are introduced to form a complex molecule.In this thesis,three hyper-structure photorefractive molecules were prepared by introducing three small functional molecules into calix[4]resorcinarene(CRA)core.Their chemical structures,optical properties and thermal properties were characterized through1 H NMR,FT-IR,EA,MALDI-TOF-MS,UV-Vis,TG,DSC,etc.In part 1,phenothiazine modified by nitrophenylacetonitrile serving as electron acceptor PT-CSN-N3-n(n=6,8)were synthesized,then hyper-structure photorefractive molecules CRA-PT-CSN-n(n=6,8)and model compounds RES-PT-CSN were synthesized from PT-CSN-N3-n(n=6,8).The effect of flexibility on the properties of materials were studied by changing the length of alkyl chain introduced to phenothiazine.The chemical structures and some properties were identified by 1H NMR,FT-IR,EA,UV-Vis,DSC/TG.The results showed that the glass transition temperature of CRA-PT-CSN-n(n=6,8)reduced slightly with the increasing of the length of alkyl chain.The element analysis and MALDI-TOF-MS results proved that the grafted rate of chromophores to CRA core was nearly 100%.In Part 2,isophorone was introduced to increase the length of conjugated chain of D-?-A structure,and nonlinear optical chromophore PT-IM-N3 based on phenothiazine was synthesized.Then the hyper-structure photorefractive molecules CRA-PT-IM was prepared via “click chemistry” reaction between functional molecule PT-IM-N3 and CRA-Alkyne,a terminal alkyne-containing molecule CRA derivative.The structures were confirmed by 1H NMR,FT-IR,EA,UV-Vis,etc.The element analysis and MALDI-TOF-MS results showed that the synthesized molecule was correct and the grafted rate of chromophores was nearly 100%.In the last part,the photorefractive properties of as-synthesized materials were tested.First of all,a small molecule PDCST was synthesized which served as standard specimen.Then photorefractive device containing PDCST and other functional groups was prepared.The photorefractive properties of molecule were tested by two-beam-coupling(TBC)method.The result showed that the signal of TBC effect of PDCST was weak without the applied electric field,and the signal enhance with the increase of applied electric field strength.