CO₂-Involved and Isocyanide-Based Three-Component Polymerization toward Functional Heterocyclic Polymers with Self-Assembly and Sensing Properties

Abstract

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

Fused Heterocyclic Polymers with Aggregation-Induced Emission: Synthesis and Applications

“…developed an isocyanide-based and CO 2 -involved MCP to furnish well-defined poly­(benzoyleneurea)­s. The presence of amide groups allows the polymer to self-assembly into spheres with sizes of 200–1000 nm …”

“…For instance, the soluble salts of gold are harmful for living organisms . Poly­(benzoyleneurea) with a TPE motif ( P2 ) displayed a typical AIE feature, and its highly fluorescent aggregates showed a selective fluorescence response to Au 3+ . As depicted in Figure , this polymer showed excellent selectivity to Au 3+ ions among 13 different kinds of ions.…”

“…(C) Structure of poly­(benzoyleneurea)­s P2 . Reproduced from ref . Copyright 2021 American Chemical Society.…”

Advances in Palladium-Catalyzed Carboxylation Reactions

“…Interestingly, very recently this kind of reactivity has been exploited for the synthesis of new heterocyclic polymers 30 with self-assembly and sensing properties, starting from bis(2-iodoaniline) and diisocyanide monomers, using PdCl 2 and PPh 3 as the catalyst precursor, under 1 atm of CO 2 , in DMA at 80 °C for 18 h ( Scheme 32 ) [ 109 ].…”

Progress in Isocyanide‐Based Step‐Growth Polymerization

“…molecular weights (M w up to 8700) were prepared in good yields (up to 86%) (Scheme 5a). [57] In this reaction, tert-butyl isocyanide undergoes the migratory insertion into the intermediate formed by 2-iodoanilines with Pd(0). CO 2 can be successfully trapped by the intermediate under the catalysis of organobase of 1,8diazabicyclo[5.4.0]undec-7-ene (DBU).…”