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笼状聚集诱导发光体:机械激活触发的多色和白色发射

Caged AIEgens: Multicolor and White Emission Triggered by Mechanical Activation.

作者信息

Sun Yunyan, Wang Kecheng, Huang Xiao, Wei Shixuan, Contreras Enrique, Jain Prashant K, Campos Luis M, Kulik Heather J, Moore Jeffrey S

机构信息

Department of Chemistry, University of Illinois Urbana-Champaign, Urbana, Illinois 61801, United States.

Beckman Institute for Advanced Science and Technology, University of Illinois Urbana-Champaign, Urbana, Illinois 61801, United States.

出版信息

J Am Chem Soc. 2024 Oct 2;146(39):27117-27126. doi: 10.1021/jacs.4c09926. Epub 2024 Sep 22.

DOI:10.1021/jacs.4c09926
PMID:39306733
Abstract

Aggregation-induced emission luminogens (AIEgens) that respond to mechanical force are increasingly used as force probes, memory devices, and advanced security systems. Most of the known mechanisms to modulate mechanoresponsive AIEgens have been based on changes in aggregation states, involving only physical alterations. Instances that employ covalent bond cleavage are still rare. We have developed a novel mechanochemical uncaging strategy to unveil AIEgens with diverse emission characteristics using engineered norborn-2-en-7-one (NEO) mechanophores. These mechanophores were covalently integrated into polymer molecules and activated in both the solution and solid states. This activation resulted in highly tunable fluorescence upon immobilization through solidification or aggregation, producing blue, green, yellow, and orange-red emissions. By designing the caged and uncaged forms as donor-acceptor pairs for Förster resonance energy transfer (FRET), we achieved multicolor mechanofluorescence, effectively broadening the color spectrum to include white emission. Additionally, we computationally explored the electronic structures of activated NEOs, providing insights into the observed regiochemical effects of the substituents. This understanding, together with the novel luminogenic characteristics of the caged and activated species, provides a highly tunable reporter that traces progress with continuous color evolution. This advancement paves the way for future applications of mechanoresponsive materials in areas like damage detection and bioimaging.

摘要

对机械力有响应的聚集诱导发光发光体(AIEgens)越来越多地被用作力探针、存储设备和先进的安全系统。大多数已知的调节机械响应性AIEgens的机制都基于聚集状态的变化,仅涉及物理改变。采用共价键断裂的情况仍然很少见。我们开发了一种新型的机械化学解笼策略,使用工程化的降冰片-2-烯-7-酮(NEO)机械基团来揭示具有不同发射特性的AIEgens。这些机械基团被共价整合到聚合物分子中,并在溶液和固态中均被激活。这种激活通过固化或聚集固定后产生高度可调谐的荧光,产生蓝色、绿色、黄色和橙红色发射。通过将笼合形式和解笼形式设计为用于Förster共振能量转移(FRET)的供体-受体对,我们实现了多色机械荧光,有效地拓宽了光谱范围以包括白色发射。此外,我们通过计算探索了活化NEOs的电子结构,深入了解了观察到的取代基区域化学效应。这种理解,连同笼合和活化物种的新型发光特性,提供了一种高度可调谐的报告分子,可随着颜色的持续演变追踪进展情况。这一进展为机械响应材料在损伤检测和生物成像等领域的未来应用铺平了道路。

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