Ding Huangting, Sun Yitong, Tang Meng, Wen Jingyi, Yue Shiwen, Peng Ye, Li Fei, Zheng Liyan, Wang Suning, Shi Yonggang, Cao Qiue
School of Chemical Science and Technology, National Demonstration Center for Experimental Chemistry and Chemical Engineering Education, Yunnan University Kunming Yunnan 650091 P. R. China
School of Chemistry and Chemical Engineering, Beijing Institute of Technology Beijing 102488 P. R. China.
Chem Sci. 2023 Mar 28;14(17):4633-4640. doi: 10.1039/d3sc00568b. eCollection 2023 May 3.
Triarylboranes-based pure organic room-temperature phosphorescence (RTP) materials are rarely investigated because of their large steric hindrance and the electron defect of the boron atom. As a result, creating functional triarylborane RTP materials is difficult. Herein, we report the first photo-activated RTP materials with lifetimes/quantum yields ≤0.18 s/6.83% based on donor (D)-π-acceptor (A) from methylene carbazole-functionalized aminoborane (BN)-doped polymethyl methacrylate (BN--Met-Cz@PMMA) under 365 nm UV irradiation (30 s). Incredibly, BN--Met-Cz@PMMA films exhibited unprecedented photo-activated RTP dual-response properties (, air + 365 nm: = 0.18 s, = 6.83%; N + 365 nm: = 0.42 s, = 17.34%). Intriguingly, the BN (D-π-A) system demonstrated good versatility for photo-activated RTP whether the electron-donating group or electron-withdrawing group was placed in the ()-position of the B atom. As a result, a series of photo-activated single-molecule organic RTP materials with multi-color emission, high quantum yields, and ultra-long lifetimes can be prepared rapidly. BN-X@PMMA films showed broad application prospects for information encryption, data erasure, anti-counterfeiting, and water resistance. Our method provides new strategies for the design, synthesis, and application of RTP materials, thereby enriching the types of organic RTP materials and facilitating further developments in this area.
基于三芳基硼烷的纯有机室温磷光（RTP）材料由于其较大的空间位阻和硼原子的电子缺陷而鲜有研究。因此，制备功能性三芳基硼烷RTP材料具有挑战性。在此，我们报道了首例基于供体（D）-π-受体（A）的光激活RTP材料，其寿命/量子产率≤0.18 s/6.83%，该材料由亚甲基咔唑官能化氨基硼烷（BN）掺杂的聚甲基丙烯酸甲酯（BN--Met-Cz@PMMA）在365 nm紫外光照射（30 s）下制得。令人惊讶的是，BN--Met-Cz@PMMA薄膜展现出前所未有的光激活RTP双响应特性（空气 + 365 nm： = 0.18 s， = 6.83%；氮气 + 365 nm： = 0.42 s， = 17.34%）。有趣的是，无论给电子基团还是吸电子基团位于B原子的（）位，BN（D-π-A）体系对于光激活RTP均表现出良好的通用性。因此，可以快速制备出一系列具有多色发射、高量子产率和超长寿命的光激活单分子有机RTP材料。BN-X@PMMA薄膜在信息加密、数据擦除、防伪和防水方面显示出广阔的应用前景。我们的方法为RTP材料的设计、合成和应用提供了新策略，从而丰富了有机RTP材料的类型并推动了该领域的进一步发展。
