An efficient organobase (DABCO)-catalysed hydroxyl–yne click polymerization is successfully developed under mild conditions.

Fixing carbon dioxide (CO2) into useful polymeric materials has attracted broad interest since carbon dioxide is an abundant, inexpensive, nontoxic, and renewable C1 resource. Nevertheless, the polymerization of CO2 and alkynes attracted less attention because the propagation step involving CO2 is a major obstacle. Herein, we overcome this obstacle by developing a facile and efficient Ag2WO4-catalyzed polymerization of CO2, diynes, and alkyl dihalides under mild reaction conditions. Soluble and thermally stable poly­(alkynoate)­s with high weight-average molecular weights (up to 31 400) were obtained in high yields (up to 95%). Thanks to its unique reaction mechanism, this step-growth polymerization can produce an ethynyl group terminated telechelic polymer that can be used as macromonomer to prepare poly­(alkynoate)­s with higher molecular weights by either continually adding alkyl dihalide into the reaction solution or mixing the isolated telechelic polymers with alkyl dihalide and catalytic system under a CO2 atmosphere. The resultant polymers show versatile properties. The tetraphenylethene, silole, and tetraphenylpyrazine moieties that feature the aggregation-induced emission (AIE) characteristics can be facilely incorporated into the polymer main chains to make them AIE active with high absolute quantum yields up to 61% in the film state. Their containing ester linkages endow the polymers degradable under basic conditions, and the alkynoate repeating units enable them to be postfunctionalized by the powerful amino–yne click reaction to generate nitrogen-containing stereo- and regioregular polymers with unity grafting ratio. Thus, this work not only establishes a powerful polymerization to directly fix CO2 but also provides poly­(alkynoate)­s with versatile properties.

Through mimicking the synthesis of hereditary-information-containing nucleic acids, scientists are committed to synthesizing sequence-defined macromolecules. Herein, a protecting-group-free, metal-free, and atom-economical chemistry combining hydroxyl-yne and thiol-ene click reactions was developed to efficiently synthesize sequence-defined oligo-(monothioacetals) (overall yield of 54% for an 11-step synthesis) from readily available starting compounds and monomers under ambient conditions. The sequences of linear oligo(monothioacetals) could be easily decoded via a tandem ESI-MS/MS technique, making them new kinds of digital macromolecules with a high data storage density (0.013 bit/Da). Moreover, star oligo(monothioacetals) could also be facilely generated through divergent and convergent strategies and their combination. An unprecedented sequence-defined miktoarm star oligo(monothioacetal) was obtained, which could serve as a new nonlinear digital macromolecule to achieve 2D information matrix encoding and hold great potential to be applied for information encryption, anticouterfeiting, secret communication, etc. Thus, this work provides a powerful stepwise iterative approach to facilely access sequence-defined linear and topological oligo(monothioacetals) for high-density data storage.

A highly efficient, spontaneous, and atom-economic polymerization of aroylacetylenes and amines at room temperature in air was established, and poly(β-enaminone)s with high molecular weights were produced in nearly quantitative yields. Moreover, singly E-configuration polymers can be obtained efficiently with secondary amines, while absolute Z-configuration products were prepared when using primary amines. In addition, the poly(β-enaminone)s can be degraded by primary amines in aqueous system to obtain definite compounds, proving their wide application prospects as degradable nitrogen containing polymers. File list (2) download file view on ChemRxiv manuscript.docx (1.14 MiB) download file view on ChemRxiv Supporting Information.pdf (2.80 MiB)

Triphenylamine-functionalized tetraphenylpyrazines were facilely prepared and their multi-functional properties were thoroughly investigated.

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Branched poly[1,4-butylene carbonate-co-terephthalate]s (PBCTs) have been synthesized by the addition of a small amount of glycerol propoxylate (1) or pentaerythritol (2) in the polycondensation of 1,4-butanediol, dimethyl carbonate, and dimethyl terephthalate. To avoid gel formation, the feed amount of 1 or 2 was carefully controlled at below 0.5 mol % for 1 and below 0.3 mol % for 2. When feed of 1 or 2 was used, a high-molecular weight melt state (M w 180,000 g/mol) was reached in a total reaction time of 5.5 to 6.5 h with a yield higher than 90%. The generated PBCTs were a semicrystalline polymer (T g 5 C and T m 120 C) when the terephthalate content (F [TPA] ) was 45 to 50 mol %. The crystallization rate

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