Syntheses,Characterization And Property Studies On Porphyrinic、Fullerenic Polynorbornenes

In this thesis, a series of norbornene monomers with porphyrin, fullerene and long-chain alkyl function group have been designed and synthesized, and copolymers were obtained via ROMP (ring-opening metathesis polymerization) using a Grubbs’ initiator. The photophysics, electrochemistry and optoelectronic conversion in copolymers have been studied. The details were obtained as following:1. Designed and synthesized a series of porphyrinic(NB-H2P), zinc protoporphyrinic(NB-ZnP), fullerenic(NB-C60), long-chainalkyl norbornene (NB-C14) monomer through chemical modification, copolymers were obtained efficiently via ROMP (ring-opening metathesis polymerization) using a Grubbs’ initiator, the yield is over95%。2. The properties of PNB-ZnPm-co-C14ncopolymer and PNB-ZnP homopolymer have been investigated by UV-vis absorption spectroscopy, steady-state fluorescence spectroscopy, lifetime measurements and electrochemistry, the data demonstrate that copolymer PNB-ZnPm-co-C14n、homopolymer PNB-ZnP retain the properties of porphyrin monomer. The oxidation-reduction potential of Copolymer PNB-ZnPx-co-C60y-co-C14z is simple addition of NB-ZnP’s and NB-C60’s oxidation-reduction potential, which demonstrate no interaction between zinc protoporphyrin chromophores and fullerene in ground state. However, the fluorescence was strongly quenched when PNB-ZnPx-co-C60y-co-C14z is excited compared to NB-ZnP monomer, which indicated the electron transfer reactions from the zinc protoporphyrin moiety to fullerene is efficient in copolymer PNB-ZnPx-co-C6Oy-co-C14z.3. A series of copolymer PNB-ZnPm-co-C60n were prepared via ROMP (ring-opening metathesis polymerization) using a Grubbs’initiator. The FTO electrode modified with the copolymers PNB-ZnPm-co-C60n showed a capacity to produce steady and reversible photocurrent at the irradiation of100.0mWcm-2white light. The photocurrent and photovoltage intensity increases with the increasing NB-C60molar proportion in copolymer. on one hand, copolymer PNB-ZnP25-co- C6075possess better optoelectronic conversion ability compared to copolymer PNB-H2P25-co-C6075under the same test conditions, and on the other, PNB-H2P25-co-C6075showed outstanding properties compared to the mixture of NB-H2P and NB-C60under the same molarity.