Boron-Catalyzed Polymerization of Phenyl-Substituted Allylic Arsonium Ylides toward Nonconjugated Emissive Materials from C3/C1 Monomeric Units,ACS Macro Letters

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Boron-Catalyzed Polymerization of Phenyl-Substituted Allylic Arsonium Ylides toward Nonconjugated Emissive Materials from C3/C1 Monomeric Units
ACS Macro Letters ( IF 5.1 ) Pub Date : 2021-10-04 , DOI: 10.1021/acsmacrolett.1c00514
Pibo Liu _{1,

2} , Nikos Hadjichristidis ₂

Affiliation

Two novel allylic arsonium ylide monomers with a phenyl (steric and electronic effect) group at different positions were synthesized and used in boron-catalyzed polymerization to produce a series of well-defined polymers, poly(2-phenyl-propenylene-co-2-phenyl-propenylidene) (P2-PhAY) and poly(3-phenyl-propenylene-co-3-phenyl-propenylidene) (P3-PhAY), with unusual structures but a controllable molecular weight and relatively low polydispersity. The backbone of these polymers consists of a mixture of C1 (chain grows by one carbon atom at a time) and C3 (chain grows by three carbon atoms at a time) monomeric units, as determined by ¹H, ¹³C, and ¹H–¹³C HSQC 2D NMR. Based on the experimental results and density functional theoretical (DFT) calculations, we were able to propose a mechanism that takes into account not only the steric hindrance, but also the electron effect of the phenyl group. In addition, a nontraditional intrinsic luminescence was observed from the nonconjugated P2-PhAY and P3-PhAY; such unexpected emission is attributed to the formation of C3-unit clusters, as evidenced by ultraviolet–visible and fluorescence spectroscopy.

中文翻译：

苯基取代的烯丙基砷叶立德的硼催化聚合从 C3/C1 单体单元制备非共轭发光材料

合成了两种在不同位置具有苯基（空间和电子效应）基团的新型烯丙基砷叶立德单体，并将其用于硼催化聚合，以生产一系列定义明确的聚合物，聚（2-苯基-丙烯-共-2-苯基-亚丙烯）（P2-PhAY）和聚（3-苯基-亚丙烯-共-3-苯基-亚丙烯）（P3-PhAY），具有不同寻常的结构，但分子量可控且多分散性相对较低。这些聚合物的主链由 C1（链一次增长一个碳原子）和 C3（链一次增长三个碳原子）单体单元的混合物组成，由¹ H、¹³ C 和¹ H确定– ¹³C HSQC 2D NMR。基于实验结果和密度泛函理论 (DFT) 计算，我们能够提出一种机制，该机制不仅考虑了空间位阻，还考虑了苯基的电子效应。此外，从非共轭 P2-PhAY 和 P3-PhAY 观察到非传统的本征发光；这种意想不到的发射归因于 C3 单元簇的形成，紫外 - 可见光和荧光光谱证明了这一点。

更新日期：2021-10-19

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