Ethynyl-Directed Dual C(sp3)–H Activation Polymerization to Construct Regio- and Stereoregular C(sp3)–C(sp3) Bond Polymers

• Published in: Macromolecules 2024-01, Vol.57 (1), p.122-131
• Main Authors: Wang, Jia, Li, Mingzhao, Xu, Liguo, Huang, Die, Qin, Anjun, Wang, Xin
• Format: Article
• Language: English
• ISSN: 0024-9297; 1520-5835
• DOI: 10.1021/acs.macromol.3c02132

The establishment of facile, efficient, and precise synthetic approaches to selectively convert stable C–H bonds to functional polymers has great significance in both chemistry and material science especially by C­(sp3)–H activation. Here, an efficient dual C­(sp3)–H activation polymerization of alkynes and activated methylenes catalyzed by Pd­(PPh3)4/benzoic acid was successfully established with a 100% atom economy and excellent regio- and stereoselectivity. A series of high-weight-average molecular-weight (M w of approximately 66,500) poly­(aryl butene)­s (PABs) with a sole E configuration were generated in remarkable yields (approximately 99%). PABs exhibit good thermal stability, excellent solubility, and great film-forming ability. In addition, the thin PAB films display high refractive indices (RI) of up to 1.7126 at 589 nm. Because this polymerization has a strong functional group tolerance, luminophores can be readily constructed into the main chain to empower PABs with efficient and multicolored luminescence in various states. Notably, PABs containing a tetraphenylethene (TPE) moiety feature unique aggregation-induced emission (AIE) peculiarities, which could specifically and sensitively detect Fe­(III) ions with a low limit of detection (LOD) of 1.585 × 10–6 M.