Molecule-matrix-exciton synergistic regulation for efficient TS-FRET multicolor organic room-temperature phosphorescent materials: Photo-Stimuli responsiveness and anti-counterfeiting applications

IF 3.6 3区物理与天体物理 Q2 OPTICS

Journal of Luminescence Pub Date : 2025-09-09 DOI:10.1016/j.jlumin.2025.121527

Yujiao Luo , Yuman Li , Yujiao Zhang , Jie Zhao , Lei Xue , Jian Wang , Wei Shen

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引用次数: 0

Abstract

The development of organic room-temperature phosphorescence (RTP) materials featuring long-lived emission, color-tunability, and stimuli-responsiveness is critical for advanced anti-counterfeiting technologies. This study innovatively proposes a "molecule-matrix-exciton synergistic regulation" strategy to fabricate high-performance, photo-stimuli-responsive multicolor RTP systems. First, carbazole dimer isomers (3,3-CZ/3,9-CZ/2,9-CZ) were selected as luminophores via molecular engineering. Their planar conformation differences and variable hydrogen-bonding sites synergistically stabilized triplet excitons, while poly (vinyl alcohol) (PVA) matrix provided a rigid environment through doping. The 3,3-CZ@PVA film demonstrated exceptional RTP performance, achieving an ultralong phosphorescence lifetime of 1.91 s, a high quantum yield of 39.86 %, and pattern memory retention exceeding 120 h. Second, an efficient triplet-to-singlet Förster resonance energy transfer (TS-FRET) system was constructed. Long-lived RTP donors transferred energy to fluorescent dyes (sodium fluorescein, Fluo; rhodamine B, RhB), enabling precise afterglow color tuning from blue/cyan to green/red. Notably, the RhB/3,3-CZ@PVA 5 % system exhibited an energy transfer efficiency of up to 99.6 %. Furthermore, UV-light-controlled afterglow switching and dynamic pattern storage/erasure were realized via a ³O₂→¹O₂ photoconversion mechanism. By modulating acceptor ratios, anti-counterfeiting labels with lifetime gradients and broad color gamut adjustability were developed, enabling advanced applications such as time-dependent pattern display and dynamic digital encryption. Through multidimensional molecule-matrix-exciton synergy, this work overcomes the limitations of conventional amorphous organic RTP materials, establishing a robust foundation for high-performance, scalable photo-stimuli-responsive multicolor phosphors in intelligent anti-counterfeiting and information encryption.

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高效TS-FRET多色有机室温磷光材料的分子-基质-激子协同调节：光刺激响应和防伪应用

开发具有长寿命发光、颜色可调性和刺激响应性的有机室温磷光（RTP）材料对于先进的防伪技术至关重要。本研究创新性地提出了一种“分子-基质-激子协同调节”策略，以制造高性能、光刺激响应的多色RTP系统。首先，通过分子工程选择咔唑二聚体（3,3- cz /3,9- cz /2,9- cz）作为发光基团。它们的平面构象差异和可变的氢键位点协同稳定了三重态激子，而聚乙烯醇（PVA）基体通过掺杂提供了一个刚性环境。3,3-CZ@PVA薄膜表现出优异的RTP性能，实现了1.91 s的超长磷光寿命，39.86%的高量子产率和超过120 h的模式记忆保留。其次，构建了一个高效的三重态到单重态Förster共振能量转移（TS-FRET）系统。长寿命的RTP供体将能量转移到荧光染料（荧光素钠，Fluo；罗丹明B， RhB）上，使余辉的颜色从蓝色/青色精确地调整到绿色/红色。值得注意的是，RhB/3,3-CZ@PVA 5%体系的能量传递效率高达99.6%。此外，通过3O2→1O2光转换机制实现了紫外光控制的余辉开关和动态图案存储/擦除。通过调制受体比率，防伪标签与寿命梯度和宽色域可调性被开发，使先进的应用，如时间依赖的模式显示和动态数字加密。通过多维分子-基质-激子协同作用，克服了传统非晶有机RTP材料的局限性，为高性能、可扩展的光刺激响应多色荧光粉在智能防伪和信息加密领域的应用奠定了坚实的基础。

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来源期刊

Journal of Luminescence 物理-光学

CiteScore

6.70

自引率

13.90%

发文量

850

审稿时长

3.8 months

期刊介绍： The purpose of the Journal of Luminescence is to provide a means of communication between scientists in different disciplines who share a common interest in the electronic excited states of molecular, ionic and covalent systems, whether crystalline, amorphous, or liquid. We invite original papers and reviews on such subjects as: exciton and polariton dynamics, dynamics of localized excited states, energy and charge transport in ordered and disordered systems, radiative and non-radiative recombination, relaxation processes, vibronic interactions in electronic excited states, photochemistry in condensed systems, excited state resonance, double resonance, spin dynamics, selective excitation spectroscopy, hole burning, coherent processes in excited states, (e.g. coherent optical transients, photon echoes, transient gratings), multiphoton processes, optical bistability, photochromism, and new techniques for the study of excited states. This list is not intended to be exhaustive. Papers in the traditional areas of optical spectroscopy (absorption, MCD, luminescence, Raman scattering) are welcome. Papers on applications (phosphors, scintillators, electro- and cathodo-luminescence, radiography, bioimaging, solar energy, energy conversion, etc.) are also welcome if they present results of scientific, rather than only technological interest. However, papers containing purely theoretical results, not related to phenomena in the excited states, as well as papers using luminescence spectroscopy to perform routine analytical chemistry or biochemistry procedures, are outside the scope of the journal. Some exceptions will be possible at the discretion of the editors.