Jun-Feng Yang,Yun-Fei Liu,Lin-Lin Wei,Kai-Kai Qiao,Yan-Qiu Zhao,Lei Shi
The Minisci-type dehydrogenative coupling of N-heteroaromatic rings with inert C–H or Si–H partners via visible-light-catalyzed hydrogen atom transfer has been reported. This methodology allows the coupling reactions to be carried out in water as a solvent under air atmospheric conditions with visible-light illumination. A wide range of inert C–H and Si–H partners could be directly coupled with various N-aromatic heterocycles to deliver products in good to excellent yields.
The heteroatom-containing polymers are important components of advanced functional materials. Among the tremendous synthetic methodologies, polymerization via C–H activation is a powerful tool for the preparation of functional heteroatom-containing polymers, which should be further enriched, especially via C(sp3)–H activation. In this work, a new atom economic Pd(0)/benzoic acid catalyzed polymerization of internal diynes and secondary diamines via C(sp3)–H activation; i.e., C(sp3)–H polyamination of internal alkynes was successfully established. A series of regio- and stereoregular functional poly(allylic tertiary amine)s with high weight-average molecular weights (Mw, up to 25 600) were synthesized in excellent yields (up to 98%). The resultant polymers possess good solubility and film-forming ability, and their thin films exhibit high refraction indices (RI) with the range of 1.7207–1.6797 at 632.8 nm. Moreover, all the poly(allylic tertiary amine)s are emissive in solution and solid states. Thanks to the tolerance to functional groups of this polymerization, the tetraphenylethene (TPE) moiety could be facilely incorporated to endow the resultant polymers with the unique aggregation-enhanced emission (AEE) characteristics. Thus, this work not only establishes a powerful C(sp3)–H polyamination but also provides a strategy to facilely prepare functional nitrogen-containing acetylenic polymers.
Hyperbranched polymers have been widely applied in various fields because of their good solubility, high reactive end groups, and low viscosity, etc. Therefore, it is of great importance to develop new strategies to build multifunctional hyperbranched polymers with novel architectures. In this work, a C(sp 3 )─H activation-based polymerization of internal alkynes and bifunctional secondary amines is successfully established, and multifunctional hyperbranched polyamines (hb-PAs) with 100% E -isomers and high molecular weights ( M w up to 76 500) are prepared in good yields (up to 82%). The hb-PAs containing tetraphenylethylene moiety show unique aggregation-enhanced emission properties and can be used for explosive detection with a low limit of detection (9.14 × 10 −8 m ). Notably, the hb-PAs display high refractive indices (up to 1.7607) that can be further modulated to 1.7825 by the coordination of its peripheral ethynyl group with metallic cobalt. Moreover, the hyperbranched structure endows the hb-PAs with much better properties than their linear counterparts, such as higher photoluminescence quantum yields and refractive indices. In addition, the hb-PAs can be modified by a C(sp 3 )─H activation reaction of internal alkynes and alcohols. This work not only prepares a series of functional nitrogen-containing hyperbranched polymers but also promotes the application of C(sp 3 )─H activation in polymer chemistry.
危险品化学品经营许可证（带存储）