Synthesis And Characterization Of Calixresorcinarene Derivatives Containing Ru Complex Or Cacbazole

Calixarene are oligomers formed by methylene rings substituted phenols, which have adjustable sizes of the hydrophobic cavity, and the phenolic hydroxyl and aromatic ring are easily derivatized. Furthermore, ruthenium metal complex dyes such as N3show strong broad absorption in the visible region. Currently, the energy conversion efficiency of the dye-sensitized solar cell has reached10～11%, which used bipyridine ruthenium complexes "N3" or terpyridine ruthenium complexes "black dye" as sensitizer. At the same time, the dyes exposed to natural light can withstand108cycles which is equivalent to20-year service life, and they have high thermal stability. Aiming to prepare novel light-absorption material and hole-transporting materials for solar cell, Ruthenium complexes and carbazole moieties were introduced into calixresorcinarene (CRA) via the modification of phenolic hydroxyl groups, respectively.In the first part of this paper, CRA with eight high reactive phenolic hydroxyl groups was first synthesized. Then the terpyridine-containing CRA (Tpy-CRA) was prepared via Williamson etherification reaction by the reaction of calixarene CRA with trepyridine chloride (Tpy-Cl) using ammonium halide as catalysts under alkaline conditions. After that, Tpy-CRA was reacted with ruthenium small molecule and other appropriate ligands. The resulting calixarene derivatives is the ruthenium metal complex dyes, which was named as Ru-Tpy-CRA. Ru-Tpy-CRA showed strong broad absorption in the visible region380nm to650nm, and could be used as photosensitivity for dye-sensitized solar cell.In the second part, carbazole bromide CZ-Br was firstly synthesized. Then carbazole-containing CRA derivatives CZ-CRA was synthesized via the Williamson etherification etherification of CZ-Br with CRA. CZ-CRA showed good solubility in common solvents and high thermal stability, and could be used as hole-transporting materials for solid-state dye-sensitized solar cell.The chemical structures of the intermediates and target products were confirmed by’H-NMR, IR, EA, etc. And their relative molecular weight, thermal stability and optical absorption properties were measured by GPC, TG, DSC and UV-vis, respectively.