Xia Cong-Xin, Wang Ning, Sun Pan-Pan, Tang Shao-Xiong, Xu Xing-Dong, Tan Ye-Bang, Xin Xia
National Engineering Research Center for Colloidal Materials, Key Laboratory of Special Functional Aggregated Materials of Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, P. R. China.
Soft Matter. 2020 Aug 12;16(31):7390-7399. doi: 10.1039/d0sm01148g.
Highly emissive fluorophores based on polyaromatic hydrocarbons with tunable emission properties and aggregated structures play a very important role in relevant functional studies. In this study, a novel alkynylpyrene derivative 1 was synthesized, which exhibits unimolecular to excimer emission in methanol with an increasing concentration accompanied by the formation of nanovesicles via the π-π stacking, hydrogen bond and hydrophobic interaction. The self-assembly behavior as well as emission properties of 1 in aprotic polar solvents (ACN, acetone, DMF and DMSO) can also be adjusted by the volume fraction of the poor solvent H2O, which can induce 1 self-assembly to excimer state and could be applied in information transfer. Moreover, upon visible light irradiation, photoswitchable performance of nanovesicles of 1 was observed in which the emission markedly changes from yellow to blue; this is attributed to the cycloaddition reaction of alkynyl groups and singlet oxygen, which can be generated without the addition of external photosensitizers. The multi-responsive and fluorescence behavior of the alkynylpyrene derivative show that the self-assembly can be used to expand the development of this type of fluorophores, and the novel photoinduced tunability of the fluorescence emission provides an effective strategy to obtain high-performance transmitting and sensing materials.
基于具有可调发射特性和聚集结构的多环芳烃的高发射荧光团在相关功能研究中发挥着非常重要的作用。在本研究中，合成了一种新型炔基芘衍生物1，其在甲醇中随着浓度增加呈现单分子发射到准分子发射，同时通过π-π堆积、氢键和疏水相互作用形成纳米囊泡。1在非质子极性溶剂（乙腈、丙酮、二甲基甲酰胺和二甲基亚砜）中的自组装行为以及发射特性也可通过不良溶剂水的体积分数进行调节，水可诱导1自组装到准分子状态并可应用于信息传递。此外，在可见光照射下，观察到1的纳米囊泡具有光开关性能，其发射从黄色显著变为蓝色；这归因于炔基与单线态氧的环加成反应，该反应无需添加外部光敏剂即可产生。炔基芘衍生物的多响应和荧光行为表明，自组装可用于拓展此类荧光团的发展，而新型的光致荧光发射可调性为获得高性能传输和传感材料提供了有效策略。
