Xuan Junji, Chen Lingjie, Tian Jintao
National Key Laboratory of Marine Corrosion and Protection, Luoyang Ship Material Research Institute, Luoyang 471023, China.
School of Materials Science and Engineering, Ocean University of China, Qingdao 266100, China.
Int J Mol Sci. 2025 Feb 12;26(4):1531. doi: 10.3390/ijms26041531.
Spiropyran has an attractive and mysterious fluorescence switch and dual-color conversion characteristics, as it exhibits both aggregation-caused quenching (ACQ) in solvents and fluorescence enhancement in polymer matrices. The explanation for this phenomenon has always been of great controversy. Hence, the solvent effect on the emission of spiropyran () was investigated in 16 solvents. By means of molecular orbital theory and the Jablonski diagram, several special parameters (e.g., Hansen solubility parameters and viscosity) were selected for this analysis, with excellent goodness of fit. Subsequently, the main factors that affected the blue shift, red shift, and luminescence efficiency of the emission of the ring-opened form merocyanine () were found to be the hydrogen bonding and polarity, aggregation effect, and viscosity, respectively. A newly modified Jablonski diagram was proposed to clarify the emission behaviors of spiropyran influenced by solvent polarity and isomerization. Meanwhile, the solvent effect could also be extended to a solid polymer matrix (six kinds of polyethylene glycol (PEG) with different molecular weights), which is proposed to be defined as the generalized solvent effect. Accordingly, we have demonstrated that the unique fluorescence properties of spiropyran are dominated by the generalized solvent effect. The security information storage capacity of the simulated quick response (QR) code sensor combined with for anti-counterfeiting was significantly improved to six dimensions in taking advantage of the former theoretical analysis.
螺吡喃具有引人注目的神秘荧光开关和双色转换特性,因为它在溶剂中表现出聚集诱导猝灭(ACQ),而在聚合物基质中表现出荧光增强。对这一现象的解释一直存在很大争议。因此,研究了16种溶剂对螺吡喃()发射的溶剂效应。借助分子轨道理论和雅布隆斯基图,选择了几个特殊参数(如汉森溶解度参数和粘度)进行分析,拟合优度良好。随后发现,影响开环形式部花青()发射的蓝移、红移和发光效率的主要因素分别是氢键和极性、聚集效应和粘度。提出了一种新的修正雅布隆斯基图,以阐明溶剂极性和异构化对螺吡喃发射行为的影响。同时,溶剂效应也可以扩展到固体聚合物基质(六种不同分子量的聚乙二醇(PEG)),这被定义为广义溶剂效应。因此,我们证明了螺吡喃独特的荧光性质受广义溶剂效应支配。利用上述理论分析,结合用于防伪的模拟快速响应(QR)码传感器的安全信息存储容量显著提高到六个维度。