上海科技大学章跃标研究小组提出了用于比例荧光湿度传感的光互变三维共价有机框架。相关论文于2025年3月6日发表于国际顶尖学术期刊《美国化学会杂志》上。

该课题组提出将氢醌荧光团整合到结晶、多孔、光互变动态3D共价有机框架（COF）中，以显示客体诱导的荧光开启、发射红移增强和缩短的寿命，用于比例荧光湿度传感。理论和光谱研究为多互变异构体的构象动力学、局部激发耦合的电荷转移和基态上坡调节提供了机理见解。研究组阐明了灵敏、快速、稳定和自校准的比例荧光传感，用于广泛的湿度范围，受益于这种光互变3D COF的结构和化学稳定性和结晶度。这些发现为设计功能多孔材料提供了分子见解，该材料集成了主客体相互识别和光电响应，用于环境监测和生物医学诊断应用的多重分子传感。

据介绍，光诱导质子转移是设计光催化剂、白光发射器、生物成像和荧光传感材料必不可少的光化学过程。然而，在液体和致密固体中，有意控制激发态/基态并精细地操纵激发态分子内质子转移（ESIPT）途径是一个重大挑战。

附：英文原文

Title: A Phototautomeric 3D Covalent Organic Framework for Ratiometric Fluorescence Humidity Sensing

Author: Xuan Yao, Youchang Zhang, Yu Qiu, Wentao Jiang, Hao Chen, Tengwu Zeng, Lei Wei, Shan Jiang, Yingbo Zhao, Yanhang Ma, Yue-Biao Zhang

Issue&Volume: March 6, 2025

Abstract: Photoinduced proton transfer is an essential photochemical process for designing photocatalysts, white light emitters, bioimaging, and fluorescence sensing materials. However, deliberate control of the excited/ground states and meticulous manipulation of the excited state intramolecular proton transfer (ESIPT) pathway constitute a significant challenge in liquids and dense solids. Here, we present the integration of a hydronaphthoquinone fluorophore into a crystalline, porous, phototautomeric dynamic 3D covalent organic framework (COF) to show guest-induced fluorescence turn-on, emission redshift enhancement, and shortened lifetimes for ratiometric fluorescence humidity sensing. Theoretical and spectroscopic studies provide mechanistic insights into the conformational dynamics, charge transfer coupled with local excitation, and ground-state uphill regulation for the multiple tautomers. We illustrate the sensitive, rapid, steady, and self-calibrated ratiometric fluorescence sensing for a wide range of humidity benefiting from the architectural and chemical robustness and crystallinity of such a phototautomeric 3D COF. These findings provide molecular insights into the design of functional porous materials that integrate host–guest mutual recognition and photoelectronic response for multiplex molecular sensing for environmental monitoring and biomedical diagnostics applications.

DOI: 10.1021/jacs.4c17776

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c17776