| This thesis focused on the synthesis methods and applications on π-entended porphyrin, N-confused porphyrin and doubly N-confused porphyrin.Three types of β, β’-edge fused, π-extended porphyrins were designed. 5,10,15,20-tetraphenylporphyrin or 5,10,15,20-tetrakis(4-tert-butylphenyl) porphyrin as starting material, followed by copper metalation, mono-acylation, demetalation, wittig reaction, 2-vinyl and 2-butadienyl porphyrins were afforded. First, Diels–Alder reaction of 2-vinylporphyrin with 1,4-naphthoquinone, asymmetric ring-fused porphyrins were obtained. Bromination, Sonogashira or Heck coupling on the ring-fused porphyrin introduced a carboxylphenylethynyl group or an acrylic acid group to the π-extended porphyrin. Four new porphyrins were obtained. DFT(density-functional calculaitons) showed that naphthoquinone has strong withdrawing effect, when naphthoquinone and anchor group on the opposite positions, electrons were not easy to transfer to TiO2. It is quite fit for the measurement result, which power conversion efficiency very low. Second, Under high temperature, ring-fused porphyrins are obtained by ring-close of 2-butadienyl porphyrins, followed by Sonogashira coupling, introduced two carboxyl groups. Two new porphyrins were obtained. UV-vis spectra show obvious red shift comparing with tetraphenylporphyrin, they are potential photoelectric material; Third, Diels–Alder reaction of 2-vinylporphyrin with dimethyl acetylenedicarboxylate(DMAD), introduced two carboxyl groups; Selective bromination of ring-fused porphyrin at the ?-pyrrolic positions antipotal to the fused benzo ring led to dibromo product. Further ring-fused porphyrin were obtained by Heck reaction, followed by hydrolyzation, four new porphyrins with anchor group are obtained. The photovoltaic properties of these π-extended porphyrins were examined. The relationship between the size of conjugated structures and efficiency was get it. Two kinds of meso-substitute group can affect on efficiency, and the efficiency of di-ring-fused porphyrin is higher than mono-ring-fused porphyrin. All the result can be explained by DFT calculation. Ten porphyrins were characterized by 1H NMR and MALDI-Tof.Two N-confused porphyrins were synthesized for application in dye-sensitised solar cell(DSSC). Two kinds of N-confused porphyrins with anchor groups were synthesized, followed by condensation, dibromination, metalation, coupling, hydrolysis reaction. Due to the different properties on metalation, finally, palladium complexes N-confused porphyrins were afforded. All the compounds were characterized by 1H NMR and high resolution mass spectrum(HR-MS). When those compounds applied in DSSCs, power conversion efficiency very low, combining with DFT calculation, which showed HOMO of N-confused porphyrins could not match the electrolyte, so oxidized dyes were not oxidized to ground dyes. Meanwhile, we do the research on the synthesis of N-confused pentafluoroporphyrin through N-fused pentafluoroporphyrin. Comparing with traditional method, this way enhaced the yield from 2.2% to 4.2%(pyrrole as starting material).A novel doubly N-confused isophlorin has been prepared through nucleophilic ring-opening reaction of N-confused, N-fused porphyrin with benzenethiol. The structure, redox property of doubly N-confused isophlorinare investigated by 1H-NMR, 13C-NMR, 19F-NMR, HR-MS, X-ray analysis. The distinct nonaromaticity of doubly N-confused isophlorin and aromaticity of doubly N-confused porphyrinare proved by HOMA and NICS values, absorption, emission and 1H NMR spectra, respectively. Coordination of the copper, silver, gold(11 group) ion with doubly N-confused porphyrin lead to the formation of Cu(III), Ag(III), Au(III) complex with an unsymmetrical-conjugation, bearing proton donor and acceptor moieties. As a member of the confused porphyrinoids, removing of the arylthio-substituents lead to the genuine “expanded imidazole†that would be attractive for various applications, such as catalysts and organic electronic materials. |
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