Hong Yuchen, Zhao Yupeng, Ma Lei, Wang Yongtao
College of Chemistry and Bioengineering, Guilin University of Technology, Guilin 541004, China.
Tianjin International Center for Nanoparticles and Nanosystem, Tianjin University, Tianjin 300072, China.
Spectrochim Acta A Mol Biomol Spectrosc. 2025 Jan 5;324:124955. doi: 10.1016/j.saa.2024.124955. Epub 2024 Aug 21.
Designing persistent dual-band afterglow materials with thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP) contributed to solving the problems of homogenization and singularity in long afterglow materials. Here, six aryl acetonitrile (CBM) and aryl dicyanoaniline (AMBT) derivatives, used as host and guest materials respectively, were successfully designed and synthesized based on the isomerization effect. Among of them, 0.1 % m-CBM/p-AMBT showed the longest dual-band TADF (540 ms) and RTP lifetimes (721 ms), as well as persistent afterglow over 8 s, whose fluorescence (Φ), TADF (Φ) and RTP (Φ) quantum yields were 0.11, 0.06 and 0.22 in sequence. More interestingly, some doping systems constructed by CBM and AMBT series compounds showed persistent triple-band emissions composed of TADF, unimolecular and aggregated AMBT series compounds. What's more, Φ, Φ and Φ of 1 % o-AMBT@PMMA film were up to 0.17, 0.17, 0.23 in turn, with TADF, RTP and afterglow lifetimes of 606 ms, 727 ms, and 10 s respectively. TADF and RTP emission of CBM/AMBT series doping systems was attributed to host sensitized guest emission. Besides, the comparison displayed AMBT series compounds had bigger intensity ratios between TADF and RTP emission in PMMA films compared to in CBM series compounds. Finally, a series of data encryption were successfully constructed based on different afterglow lifetimes of the doping systems, and a dynamic anti-counterfeiting pattern was prepared by using different temperature responses of TADF and RTP emissions.
设计具有热激活延迟荧光（TADF）和室温磷光（RTP）的持久性双波段余辉材料，有助于解决长余辉材料中的均匀性和单一性问题。在此，基于异构化效应，成功设计并合成了六种分别用作主体和客体材料的芳基乙腈（CBM）和芳基二氰基苯胺（AMBT）衍生物。其中，0.1%的间位-CBM/对位-AMBT表现出最长的双波段TADF（540毫秒）和RTP寿命（721毫秒），以及超过8秒的持久余辉，其荧光（Φ）、TADF（Φ）和RTP（Φ）量子产率依次为0.11、0.06和0.22。更有趣的是，由CBM和AMBT系列化合物构建的一些掺杂体系表现出由TADF、单分子和聚集态AMBT系列化合物组成的持久三波段发射。此外，1%的邻位-AMBT@PMMA薄膜的Φ、Φ和Φ依次高达0.17、0.17、0.23，TADF、RTP和余辉寿命分别为606毫秒、727毫秒和10秒。CBM/AMBT系列掺杂体系的TADF和RTP发射归因于主体敏化客体发射。此外，比较表明，与CBM系列化合物相比，AMBT系列化合物在PMMA薄膜中的TADF和RTP发射强度比更大。最后，基于掺杂体系不同的余辉寿命成功构建了一系列数据加密，并利用TADF和RTP发射的不同温度响应制备了动态防伪图案。
