Post-functionalization of disubstituted polyacetylenes via click chemistry

Abstract

We report a synthetic design and the experimental exploration of preparation of disubstituted polyacetylenes (PAs, P3) through 1,3-dipolar cycloaddition of azides with precursor PA bearing alkyne pendants. The precursor PA (P2) was derived by desilylation of the pristine PA with trimethylethynylsilane side chains (P1). P1 was obtained by polymerization of a dual-alkyne containing monomer with one of the alkynes end-capping by trimethylsilane (M) under the promotion of WCl 6 -Ph 4 Sn catalyst. Two synthetic routes, i.e. two-steps (from P1 to P3 via precursor P2) and one-pot (from P1 to P3 without separation and purification of P2) were tried and the results indicated that one-pot strategy is more facile and resultant P3-1 showed higher purity and higher molecular weight than the resultant of P3-2. By using the techniques such as GPC, FTIR and 1 H NMR spectroscopy the polymerization behavior and the structures of the polymers were well characterized. disubstituted polyacetylene, click chemistry, one-pot method, selective polymerization

A throughway to functional poly(disubstituted acetylenes): a combination of the activated ester strategy with click reaction

“…But this route requires a protection-deprotection procedure, which results in low reaction efficiency and low yield. 15 Introducing alkyne into PDSA by the activated ester strategy…”

“…The precursor PDSA (P0) was prepared according to the procedures described elsewhere. 15 The average molecular weight was 14.5 kDa and poly-dispersion index (PDI) was 1.79, as estimated by GPC technique using monodisperse polystyrene samples as the internal calibration.…”

Molecular iodine in monomer and polymer designing

“…[21] It was advanced that the halogen exchange reaction provided a clean and easy separation of the silylated monomer from a reaction mixture in a high purity.…”

From China to the world: Science China Chemistry celebrates the International Year of Chemistry

“…Notably, 5,5,11,11-tetraisopropyl-5,11H-benzosilolo[3,2-c]silafluorene in microcrystals exhibited violet fluorescence ( max = 396 nm) with a quantum yield of 0.70" [25]. Jingzhi Sun, Ben Zhong Tang, and coworkers reported post-functionalization of disubstituted polyacetylenes via click chemistry [26]. Mina Han and Takumu Honda showed the correlation between the structures and trans ↔ cis isomerization characteristics of azobenzenes.…”

“…"The substituted PAs have been found to show photoconductivity, optical nonlinearity, magnetic susceptibility, photo-and electroluminescence, liquid crystallinity, biocompatibility, chain helicity" [26]. Loh and Brinatti highlighted the modern applications of calorimetry in the investigation of other complex (chemical) systems, including the determination of thermodynamic parameters associated with surfactant/polymer interaction and providing important information on molecular features of these processes [35].…”