Center for AIE Research, Shenzhen Key Laboratory of Polymer Science and Technology, Guangdong Research Center for Interfacial Engineering of Functional Materials, College of Materials Science and Engineering, Shenzhen University, Shenzhen, 518061, China.
HKUST Shenzhen Research Institute, Shenzhen, 518057, China.
Adv Mater. 2023 Jul;35(28):e2301874. doi: 10.1002/adma.202301874. Epub 2023 May 30.
Amorphous polymers with ultralong room-temperature phosphorescence (RTP) are highly promising for various applications. Particularly, polymer-based RTP materials with multiple functions such as color-tunability or stimulus-response are highly desirable for multilevel anti-counterfeiting but are rarely reported. Herein, a facile strategy is presented to achieve a series of polymer-based RTP materials with ultralong lifetime, multicolor afterglow, and reversible response to UV irradiation by simply embedding pyridine-substituted triphenylamine derivatives into the polymer matrix poly(vinyl alcohol) (PVA) and poly(methyl methacrylate) (PMMA), respectively. Notably, the pyridine group with the capabilities of promoting intersystem crossing and forming hydrogen-bonding interactions is essential for triggering ultralong RTP from the doping PVA system, among which the doping film TPA-2Py@PVA exhibits excellent RTP property with an ultralong lifetime of 798.4 ms and a high quantum yield of 15.2%. By further co-doping with the commercially available fluorescent dye, multicolor afterglow is obtained via phosphorescence energy transfer. Meanwhile, the doped PMMA system exhibits reversible photoactivated ultralong RTP properties under continuous UV irradiation. Finally, potential applications of these doped PVA and PMMA systems with ultralong lifetime, multicolor afterglow, and photoactivated ultralong RTP in multidimensional anti-counterfeiting are demonstrated.
具有超长室温磷光(RTP)的无定形聚合物在各种应用中极具前景。特别是具有多种功能的聚合物基 RTP 材料,如可调色彩或刺激响应,对于多层次防伪是非常理想的,但很少有报道。在此,通过将吡啶取代的三苯胺衍生物分别嵌入聚合物基质聚乙烯醇(PVA)和聚甲基丙烯酸甲酯(PMMA)中,提出了一种简便的策略来实现一系列具有超长寿命、多色余辉和对紫外光照射可逆响应的聚合物基 RTP 材料。值得注意的是,具有促进系间窜越和形成氢键相互作用能力的吡啶基团对于从掺杂 PVA 体系中引发超长 RTP 是必不可少的,其中掺杂膜 TPA-2Py@PVA 表现出优异的 RTP 性能,超长寿命为 798.4 ms,量子产率为 15.2%。通过进一步共掺杂市售荧光染料,通过磷光能量转移获得多色余辉。同时,掺杂的 PMMA 体系在连续紫外光照射下表现出可逆的光致超长 RTP 性能。最后,展示了这些具有超长寿命、多色余辉和光致超长 RTP 的掺杂 PVA 和 PMMA 体系在多维防伪中的潜在应用。