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基于非晶态分子“三重态激子泵”实现的具有时空分辨率加密功能的动态超长室温磷光

Dynamic Ultra-long Room Temperature Phosphorescence Enabled by Amorphous Molecular "Triplet Exciton Pump" for Encryption with Temporospatial Resolution.

作者信息

Deng Huangjun, Li Gaoyu, Xie Haozhi, Yang Zhan, Mao Zhu, Zhao Juan, Yang Zhiyong, Zhang Yi, Chi Zhenguo

机构信息

Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education, Guangdong Engineering Technology Research Center for High-performance Organic and Polymer Photoelectric Functional Films, GBRCE for Functional Molecular Engineering, School of Chemistry, Sun Yat-sen University, 510275, Guangzhou, P. R. China.

School of Materials Science and Engineering, Sun Yat-sen University, 510275, Guangzhou, P. R. China.

出版信息

Angew Chem Int Ed Engl. 2024 Feb 19;63(8):e202317631. doi: 10.1002/anie.202317631. Epub 2024 Jan 11.

Abstract

Organic ultra-long room-temperature phosphorescence (RTP) materials in the amorphous state have attracted widespread attention due to their simple preparation and flexibility to adopt various forms in sensors, bioimaging, and encryption applications. However, the amorphous molecular host for the host-guest RTP systems is highly demanded but limited. Here, a universal molecular host (DPOBP-Br) has been designed by integration of an amorphous moiety of diphenylphosphine oxide (DPO) and an intersystem crossing (ISC) group of 4-bromo-benzophenone (BP-Br). Various commercial fluorescence dyes were doped into the tight and transparent DPOBP-Br film, respectively, resulting in amorphous host-guest systems with ultra-long RTP colors from green to red. It was found that DPOBP-Br acted as a universal "triplet exciton pump" for promoting the generation of triplet excitons in the guest, through energy transfer processes and external heavy-atom effect based on DPOBP-Br. Interestingly, dynamic RTP was achieved by controlling residual oxygen concentration in the amorphous matrix by UV irradiation. Therefore, multi-dimensional anti-counterfeiting coatings were realized even on curved surfaces, simultaneously exhibiting spatial and 2D-time dependence. This work provides a strategy to design new amorphous molecular hosts for RTP systems and demonstrates the advanced information encryption with tempo-spatial resolution based on the dynamic ultra-long RTP of an amorphous system.

摘要

非晶态有机超长室温磷光(RTP)材料因其制备简单且在传感器、生物成像和加密应用中能灵活采用多种形式而受到广泛关注。然而,用于主客体RTP体系的非晶态分子主体要求很高且数量有限。在此,通过整合二苯基氧化膦(DPO)的非晶部分和4-溴二苯甲酮(BP-Br)的系间窜越(ISC)基团,设计了一种通用分子主体(DPOBP-Br)。将各种商用荧光染料分别掺杂到致密且透明的DPOBP-Br薄膜中,得到了具有从绿色到红色超长RTP颜色的非晶主客体体系。研究发现,DPOBP-Br作为一种通用的“三重态激子泵”,通过基于DPOBP-Br的能量转移过程和外部重原子效应,促进客体中三重态激子的产生。有趣的是,通过紫外光照射控制非晶基质中的残余氧浓度,实现了动态RTP。因此,即使在曲面上也实现了多维防伪涂层,同时展现出空间和二维时间依赖性。这项工作提供了一种设计RTP体系新型非晶分子主体的策略,并展示了基于非晶体系动态超长RTP的具有时空分辨率的先进信息加密技术。

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