| Summary: | 碩士 === 國立臺灣科技大學 === 材料科學與工程系 === 101 === The novel cyclophanediene-based monomer containing perfluorohexyl substituents were synthesized and further confirmed by NMR, HRMS and solid-state crystallography studies. These cyclophanedienes have potential to polymerize giving p-phenylenevinylene-based conjugated polymers via ring-opening metathesis polymerization; serve as suitable models for the study of their through-space charge transfer properties.
Perfluorohexyl and octyloxy asymmetrically substituted cyclophanediene monomers: 4,7-dioctyloxy-12,15-diperfluorohexyl-[2.2]paracyclophane-1,9-diene 13a and 5,8-dioctyloxy-12,15-diperfluorohexyl-[2.2]paracyclophane-1,9-diene 13b had been synthesized in this research. Only the pseudo-geminal isomer 13a was able to be polymerized by using second generation Grubbs catalyst as an initiator to give poly(2,5-dioctyloxy-2,5-diperfluorohexyl-p-phenylenevinylene)s P1 which showed the presence of all-trans vinylene of the polymer backbone and with narrow molecular weight. The ring-opening metathesis reaction of pseudo-ortho isomer 13b did not proceed. The reason for this was postulated that the catalyst is unable to coordinate with 13b successfully due to the substituted groups shielding both forms of the alkenes. Tetraperfluorohexyl substituted paracyclophanediene monomers were tried to be synthesized, but only the pseudo-ortho isomer “5,8,12,15-tetraperfluorohexyl-[2.2]paracyclophane-1,9-diene 17b” had been observed and which performs extremely poor solubility in common organic solvents.
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