2,6-polyaminoazulene
Date Issued
2013
Date
2013
Author(s)
Hou, Cheng-Yi
Abstract
This thesis describe the syntheses and properties of a new series of conjugated polymers: 2,6-linked polyaminoazulene, and its related compounds. Different kinds of monomeric, dimeric and polymeric aminoazulene derivatives have been synthesized via various types of Pd-catalyzed amination, primary and secondary amidation and carbamation. Among these, Buchwald secondary carbamation has been firstly applied to polymer synthesis to afford the BOC-protected polyaminoazulene 48, which could undergo deprotection under acidic conditions to yield the corresponding polyaminoazulene 51.
The photophysical properties of these aminoazulene derivatives suggest that the BOC-protected aminoazulenes show poor conjugation. Little bathochromic shifts of longer wavelength absorption maximum were observed when the degree of polymerization became larger. However, excellent conjugation was observed in the case of unprotected polyaminoazulenes. The longer wavelength absorption maximum of the polymer showed about 200 nm bathochromic shift in comparison with the corresponding monomer, and the energy gap for the polymer was 1.66 eV. The electrochemical behavior of unprotected aminoazulenes have been studied, the HOMO energy increased with the degree of polymerization while the LUMO energy decreased.
Protonation at the C1 or C3 position of aminoazulene derivatives occured under acidic conditions. These processes resulted in enhancement of conjugation of BOC-protected aminoazulenes. In UV-Vis absorption spectra an obvious bathochromic shift of longer wavelength absorption were observed when the degree of polymerization became larger. Furthermore, in the case of unprotected aminoazulenes, the conjugation was not interrupted when protonated, and the HOMO energy are strongly reduced. The longer wavelength absorption maximum of polyaminoazulene 51 was at 591 nm and became 670 nm after protonation, and the band gap were around 1.65 eV both in neutral and acidic conditions.
This study suggests that 2,6-linked polyaminoazulene is quite unique in comparison with other kinds of polyaminoarenes. They are not polyaniline.
Subjects
薁
聚合物
共軛
聚苯胺
偶連
Type
thesis
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