Synthesis And Property Research Of Meso-porphyrin And β-diketonate Dyes With Push-pull Framework

Three kinds of organic dyes with “push-pull” framework(ferrocene-porphyrin, triphenylamine-porphyrin and β-triphenylamine diketonate) based the ferrocene and triphenylamine as the electron donators, were synthesized systematically. The optical and electrochemical properties were studied,then the potential applications were explored theoretically.(1) vinylferrocene, ethynylferrocene and 4-formylphenylferrocenebased on the ferrocene as the starting materials, were synthesized through different redox reactions. The classical method [2+2] was used to synthesis the porphyrin model through the condensation reaction between the different dipyrroylymethane and aromatic aldehyde. A series of meso-ferrocenyl-porphyrin dyads linked by four different ?-conjugated bridging units(directly bound, vinyl, ethynyl and phenyl) have been synthesized throughthe bromination and coupling reactions, then, the influence of the conjugated linker on both electronic and photochemical properties of the porphyrin chromophore were investigated. The basic structure consists of Fc-Porphyrin where Fc = ferrocene, vinylferrocene, ethynylferrocene or phenylferrocene. Due to the charge transfer intramolecule, there was fluorescence qunench in the new ferrocene-porphyrin. Own to the oxidation of s the ferrocene group can be oxidated by some metal ions(Fe3+, Cu2+, Ce4+), so partial fluorescence recoveried.(2) four kind of 4-formyltriphenylamine were synthesiszed by Ullmann reaction based on the carbazole, phenothiazine, iminostilbene, as the starting materials. The porphyrin model was synthesized through the classical [2+2] method. Then three donor-π-acceptor porphyrin dyes, bearing a variety of rigid triarylamine donor groups were synthesized for application as photosensitizers in TiO2 based dye-sensitized solar cells(DSSCs). Compared with the “naked” porphyrin ZnP, broadened and red-shifted spectral features were exhibited due to introduction of the bulky donor moiety to the ISB-ZnP CZ-ZnP, and IDB-ZnP dyes. Overall, introduction of the triarylamine moieties is demonstrated to promote a better performance than the “naked” porphyrin.(3) Serials triphenylamine derivative were synthesized by coupling reaction, then fourβ-diketonates-BF2 compounds with “Donator-π-Acceptor-π-Donator” type based on triphenylamine group as the electron donator were synthesized and photophysical properties were investigated through the UV-Vis and Emission.With the increasing of the π bridge length, the UV-Vis absorption and emission indicate the regular change in different solvents.The potential application based on the fluorescence probe and cosensitier in DSSCs were studied.