Triphenylene containing blue-light emitting semi-fluorinated aryl ether polymers with excellent thermal and photostability
Triphenylene containing blue-light emitting semi-fluorinated aryl ether polymers with excellent thermal and photostability
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含苯并菲的蓝光发射半氟化芳基醚聚合物，具有优异的热稳定性和光稳定性
DOI：
10.1039/d2qm00099g
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发表时间：
2022
影响因子：
7
通讯作者：
Caldona, Eugene
中科院分区：
文献类型：
--
作者：
Shelar, Ketki Eknath;Le, Nghia;Mukeba, Karl M.;Dey, Sriloy;Farajidizaji, Behzad;Athukorale, Sumudu;Pittman, Charles U.;Webster, Charles Edwin;Donnadieu, Bruno;Caldona, Eugene
将多环芳烃(PAH)单元集成到半氟化聚合物中，具有很高的热稳定性和良好的加工性，在光电、气体分离和先进复合材料中具有潜在的应用前景。商品双酚与含双三氟乙烯基醚(TFVE)的新型三苯基单体在碱促进下的分步缩聚反应，以较高的产率合成了半氟化芳亚乙基醚(FAVE)聚合物。溶液可加工的聚合物形成坚韧的透明薄膜，在溶液中产生依赖于取代的蓝光发射，发射量子产率从7.2-12%(在二氯甲烷中)。虽然主要为非晶态，具有176-243°C的高玻璃化转变温度(Tg)，但粉末X射线衍射研究显示，三苯聚合物具有典型的分子直径和pi堆积反射。聚合物在250℃空气中加热24 h后，表现出良好的热稳定性、溶液光稳定性和显著的热氧化光稳定性。此外，后聚合模型的SCALL偶联提供了一种具有新的光学性质的新型半氟六苯并冠烯聚合物。用Smd(二氯甲烷)-ωB97XD/Bs1(Bs1=6-31G(d‘)对C、H、O和F进行了含时密度泛函理论计算)。这项工作证明了可加工、蓝光发射、热稳定的三苯基链半氟芳基醚聚合物的合成和表征。
Integration of polycyclic aromatic hydrocarbon (PAH) units into semi-fluorinated polymers affords high thermal stability and excellent processability for potential applications in optoelectronic, gas-separation, and advanced composites. Base-promoted step-growth polycondensation of commercial bisphenols with new triphenylene containing bis-trifluorovinyl ether (TFVE) monomers affords semi-fluorinated arylene vinylene ether (FAVE) polymers in good yields. The solution-processable polymers form tough transparent films and produce substitution dependent blue-light emission in solution with emission quantum yields ranging from 7.2–12% (in dichloromethane). Although predominantly amorphous with high glass transition temperatures (Tg) ranging from 176–243 °C, powder X-ray diffraction studies show typical molecular diameter and pi-stacking reflections for triphenylene polymers. The polymers exhibited excellent thermal stability, solution photostability, and remarkable thermal oxidative photostability after heating at 250 °C for 24 h in air. Further, a model post-polymerization Scholl coupling afforded a novel semi-fluorinated hexabenzocoronene polymer with new optical properties. Time-dependent density functional theory (TD-DFT) computations were also performed using SMD (dichloromethane)-ωB97XD/BS1 (BS1 = 6-31G(d′) for C, H, O and F). This work demonstrated the synthesis and characterization of processable, blue-light emitting, thermally stable triphenylene enchained semi-fluorinated aryl ether polymers.