Synthesis And Characterization Of Calix[4]Resorcinarene Derivatives Containing Photoelectricity Functional Groups Via A Flexable Spacer

Calix[4]resorcinarene (CRA) is one of the most attractive macrocyclic compounds prepared easily from the acid catalyzed reaction of resorcinols and aldehydes. The calix[4]resorcinarene derivatives show considerable potential for practical application in many fields because of their particular molecular structure, facile preparation and functionalization, relatively good solubility and thermostability. If the light-emitting group, photosensitive group or azo photorefractive group were linked onto the calixarene matrix, the corresponding CRA derivatives photoelectric material can be prepared. If the linkages are flexable spacer, the CRA derivatives can maintain similar photoelectric properties to small molecules.There are many excellent organic dyes in dye-sensitized solar cell, most of them have-COOH group in the end of the molecules. If these dyes could be linked onto the calixarene matrix, some new organic polymer photovoltaic materials could be prepared. Considered coumarin dye is a kind of excellent photosensitive metrrials, we firstly chose coumarin-3-carboxylic acid as model compound to explore the feasibility. However, if the coumarin-COC1was directly reacted with CRA, we couldn’t get target product resulted from the steric hindrance of CRA. Then, CRA was modified, and the the hychoxy active site was extended two carbon atoms outward to get CRA-OH. When CRA-OH reacted with coumarin-COC1, CRA-CM could be easily prepared. CRA-CM showed good solubility in common solvents and thermal stability, and could be used as photosensitivity for dye-sensitized solar cells.Hyper-structured molecule (HSM) photorefractive materials contain different photorefractive function components through chemical bonds to form a complex three-dimensional molecular structure. The photorefractive effect of molecular is achieved by the synergy of the different functional components. As the CRA itself has a three-dimensional structure, CRA matrix can easily keep the material in the amorphous state, and avoid NLO chromophores crystallization. At the same time, CRA drrivatives have much more substituents, greater molecular weight, and better film-forming property. Calixarene photorefractive materials CRA-CZ(100-x)-Azo(X)(x=0,25,50,100) containing hole-transporting and chromophores groups were prepared via the esterization of CRA-COC1and CZ-OH (carbazole with hydroxyl group) and CZ-Azo-OH (nitro azo carbozole chromophores). CRA-CZ(100-x)-Azo(X) showed good solubility in common solvents and thermal stability, and narrow molecular weight distribution, which could be used as HSM photorefractive material.In conclusion, the phenol hydroxyl of CRA was extended two carbon atoms outward through chemical modification, and convert to the hydroxyl or carboxyl. Then the modified CRA was reacted with the functional monomer with the carboxyl or hydroxyl, some new CRA derivatives photoelectric material were successfully prepared.