The Barbier reaction, a widely utilized reaction for carbon–carbon bond formation, has played important roles in modern organic chemistry for more than a century. Here, we show its successful introduction to polymer chemistry. Through one-pot Barbier polyaddition (both A2+B2 type and AB type) of monomers containing an organic halide and a benzoyl group, a series of phenylmethanol group containing polymers, including polymonophenylmethanol (PMPM), polydiphenylmethanol (PDPM), and polytriphenylmethanol (PTPM), have been synthesized. Para-PTPM exhibits interesting aggregation-induced emission, tunable thermo-responsive over a wide temperature range, sensory, luminescence enhancement of fluorescent dye in solid-state and processing properties. This significantly expands the libraries of monomer and polymer, and opens up an avenue for the design and application of functional polymer materials.

Self-assembly of block copolymers (BCPs) in solution is a powerful technology to achieve a broad range of structures, such as spheres, cylinders, vesicles, and other hierarchical structures. However, the BCP self-assembly library is limited, especially with respect to tubular structures. Here we show a versatile strategy to expand the morphology library of block copolymer solution self-assemblies with tubular structures (including tubular dumbbells and tubules) via self-assembly of the most common diblock copolymers P4VP-b-PS BCPs in methanol. No special chemistry is needed in this strategy, which proves the universality of this method. The novelty of the strategy is to keep the BCPs both highly asymmetric and with very high molecular weight. The underlying formation mechanism and kinetics of these tubular structures were elucidated. The prepared tubular structures expand the structure library of BCP solution self-assemblies and open up a new avenue for the further applications of a variety of tubular materials.

CO 2 utilization has been a hot research topic in academic and industrial respects. Besides converting CO 2 into chemicals and fuels, incorporating it into the polymers to construct functional materials is another promising strategy. However, the CO 2 -involved polymerization techniques should be further developed. In this work, a facile and efficient CO 2 -involved multicomponent polymerization is successfully developed. The reaction of monomers of CO 2 , isocyanides and 2-iodoanilines readily produces soluble and thermally stable poly(benzoyleneurea)s with well-defined structures under mild conditions. Thanks to the formed amide groups in the heterocyclic units in the main-chains, the resultant polymers could self-assemble into spheres with sizes between 200 and 1000 nm. The polymers containing tetraphenylethylene (TPE) unit show the unique aggregation-enhanced emission (AEE) features, which could be used to visualize the self-assembly process and morphologies under UV irradiation, and serve as fluorescence probe to selectively and sensitively detect Au 3+ ions. Notably, the polymers containing cis-and trans-TPE units exhibit different behaviors in self-assembly and limit of detection for Au 3+ ions due to the different intermolecular interactions. Thus, this work not only provides a new strategy for CO 2 utilization but also furnishes a series of functional heterocyclic polymers for diverse applications. File list (3) download file view on ChemRxiv Manuscript.docx (18.84 MiB) download file view on ChemRxiv Manuscript -Anjun Qin.pdf (1.92 MiB) download file view on ChemRxiv Supporting information.pdf (2.46 MiB) CO 2 -Involved and Isocyanide-based Threecomponent Polymerization toward Functional