Metathesis cyclopolymerization of substituted 1,6‐heptadiyne and dual conductivity of doped polyacetylene bearing branched triazole pendants

Abstract

The branched triazole group is synthesized by click chemistry via a controlled approach of slow addition of AB 2 compound to a B 2 core, and used as the substituent for 1,6heptadiyne monomer. Metathesis cyclopolymerization of monomer is performed well in dichloromethane without the weakly coordinating additive, indicating that the branched triazole itself can stabilize the living propagating chain, to generate branched triazole pendant-contained polyacetylene with trans-double bonds and five-membered ring repeating units along the conjugated backbone. The LiTFSI doped polyacetylenes display ionic conductivities of 2.5-1.8 3 10 26 S cm 21 ; by further doping with iodine, polyacetylenes show the improved ionic and electronic conductivities of 1.3 3 10 25 and 2.1 3 10 27 S cm 21 at 30 8C, respectively. Therefore, these doped polyacetylenes may act as the new electrolyte materials. V C 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 485-494

Living β-selective cyclopolymerization using Ru dithiolate catalysts

“…10 Although the early-stage catalysts produced ill-defined regiorandom polyenes,1 the Buchmeiser group successfully demonstrated the first selective CP to generate five-membered rings via exclusive α-addition using Mo-based Schrock catalysts,23–27 and later, Ru-based Buchmeiser catalysts 17–22,28,29. Afterward, our group reported α-selective living CP to prepare various soluble polyacetylenes with complex architectures,30–33 and the Xie group demonstrated CP of functionalized monomers to generate polyacetylenes exerting high ionic conductivity,34–36 by using a user-friendly, fast-initiating third-generation Grubbs catalyst 11–14…”

Toward Perfect Regiocontrol for β-Selective Cyclopolymerization Using a Ru-Based Olefin Metathesis Catalyst

“…Cyclopolymerization (CP) of terminal diynes via an olefin metathesis is one of the most efficient and powerful tools for the synthesis of conjugated polymers . Although the promises of CP were introduced to the polymer science community with extensive studies using ill-defined catalysts, such as Ziegler-type catalysts, , MoCl 5 , and WCl 6 , − the first breakthrough came with the development of well-defined catalysts by the Schrock group, who provided a mechanistic understanding of CP and structural analyses of the resulting conjugated polyenes. , Recently, this field was revisited by polymer chemists because modified Grubbs catalysts − developed by the Buchmeiser group, and even user-friendly Grubbs catalysts − based on Ru promoted excellent CP with outstanding reactivity and tolerance toward air, moisture, and many functional groups. − Therefore, various macromolecules with interesting architectures have been prepared, thereby extending the scope of CP. − …”

Enhanced Ionic and Electronic Conductivity of Polyacetylene with Dendritic 1,2,3‐Triazolium‐Oligo(ethylene glycol) Pendants

“…Poly(ionic liquid)s (PILs) are peculiar polyelectrolytes combining the unique properties of ionic liquids (e.g., thermal stability, versatile anion exchange, and chemical stability) with polymer materials (e.g., mechanical, stability, processability, durability, and tunable architecture from macromolecular design) . Compared with neutral polymers, PILs usually have higher ionic conductivity (σ i ). In recent years, PILs were extensively studied basing on various cations (e.g., phosphonium, pyrrolidinium, imidazolium, and 1,2,4‐triazolium) and anions (e.g., halides, triflate, and tosylate).…”

“…Recently, MCP was also proved to fit well to the ionic 1,6‐heptadiyne derivatives, generating ionic PAs (iPAs) . On the basis of our previous work, we combined the dendritic 1,2,3‐triazolium moiety with oligo(ethylene glycol) (OEG) group, instead of the ill‐defined branched 1,2,3‐triazolium or dendronized neutral 1,2,3‐triazole and alkyl group, as the pendant of the PA backbone to synthesize the dendronized trans ‐iPAs with well‐defined ionic density and five‐membered ring microstructure via MCP, and the iPA solution was doped with the solution of bis(trifluoromethane)sulfonimide lithium (LiTFSI) and I 2 at different molar ratios of dopant to polymer, which is different from the previous doping procedure of immerging the polymer film in dopant solution, affording a fully mixed and soluble doped‐iPA solution, and aiming to gain the iPAs with improved ionic and electronic dual conductive performance.…”