The first synthesis of well‐defined poly(methylene‐co‐1,1‐diphenylpropenenylene) (C1‐co‐C1’), equivalent to poly(ethylene‐co‐diphenylbutadiene) copolymer was accomplished by C1 copolymerization of novel diphenylpropenyl triphenyl arsonium ylides (Ph2AY) and dimethylsulfoxonium methylide (Me2SY) using B‐thexylborepane as an initiator. All polymerization conditions, including feed ratio, temperature, and reaction time, were optimized. A series of photoluminescent poly(ethylene‐co‐diphenylbutadiene) were synthesized at different feed ratios, opening a new synthetic horizon for poly(ethylene‐co‐disubstitutedbutadiene). Notably, a new C1 segment, resulting from a double bond rearrangement, was confirmed by NMR, resulting in an unprecedented two‐monomer three‐structure random terpolymer. An unexpected red‐shift phenomenon in the fluorescence spectra was observed with an increase in the ratio of Ph2AY in the copolymer. This shift is attributed to the aggregation of diphenylbutadiene segment, akin to through‐space conjugation (TSC), likely induced by a decrease in the crystallinity of copolymers. Furthermore, another disubstituted allylic triphenyl arsonium ylides, (E)‐2‐phenylbutenyl triphenyl arsonium ylide (MePhAY) was also synthesized and investigated. These additional compounds expand knowledge and potential applications of such copolymerization techniques in advanced materials.

中文翻译：

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硼催化砷和亚磺鎓叶立德的 C1 共聚得到未描述的结构和荧光性质

通过新型二苯基丙烯基三苯基砷叶立德的 C1 共聚，首次合成了明确的聚（亚甲基 - 共 - 1,1 - 二苯基丙烯基）（C1 - 共 - C1'），相当于聚（乙烯 - 共 - 二苯基丁二烯）共聚物(Ph2AY) 和二甲基亚砜 (Me2SY)，使用 B-己基硼烷作为引发剂。所有聚合条件，包括进料比、温度和反应时间均经过优化。以不同的投料比合成了一系列光致发光聚（乙烯-二苯基丁二烯），开辟了聚（乙烯-二取代丁二烯）的合成新视野。值得注意的是，核磁共振证实了由双键重排产生的新 C1 片段，从而产生了前所未有的双单体三结构无规三元共聚物。随着共聚物中 Ph2AY 比例的增加，观察到荧光光谱出现意想不到的红移现象。这种转变归因于二苯基丁二烯链段的聚集，类似于空间共轭（TSC），可能是由共聚物结晶度的降低引起的。此外，还合成并研究了另一种二取代的烯丙基三苯基砷叶立德，(E)-2-苯基丁烯基三苯基砷叶立德（MePhAY）。这些额外的化合物扩展了此类共聚技术在先进材料中的知识和潜在应用。