Liu Songen, Zhang Yi, Li Jianqiu, Wang Conghui, Chen Yong, Liu Yu
College of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, P. R. China.
ACS Appl Mater Interfaces. 2024 Jan 31;16(4):5149-5157. doi: 10.1021/acsami.3c17214. Epub 2024 Jan 21.
Water/light regulated room-temperature phosphorescence (RTP) of polypseudorotaxane supramolecular gel is constructed by threading the poly(ethylene glycol)--poly(propylene glycol)--poly(ethylene glycol) (PEG-PPG-PEG) chain with the bromoaromatic aldehyde into mono-(6-ethylenediamine-6-deoxygenated)-β-cyclodextrin (ECD) cavities and further assembling with negatively charged Laponite XLG (CNS) and diarylethene derivative (DAE) through electrostatic interaction. This hydrogel exhibits significant blue fluorescence emission; instead, after lyophilization to xerogel, the system exhibits both blue fluorescence and yellow RTP based on the rigid network structure of the xerogel, which restricts the vibration of the phosphor and suppresses the nonradiative relaxation process. Interestingly, the addition of excess ECDs to the gel system can enhance the RTP emission. Furthermore, the reversible luminescence behavior can be adjusted by the photoresponsive isomerism of DAE and humidity. This polypseudorotaxane supramolecular gel system provides a novel strategy for constructing tunable RTP materials.
通过将聚(乙二醇)-聚(丙二醇)-聚(乙二醇)(PEG-PPG-PEG)链与溴代芳醛穿入单(6-乙二胺-6-脱氧)-β-环糊精(ECD)空腔,并进一步通过静电相互作用与带负电荷的锂皂石XLG(CNS)和二芳基乙烯衍生物(DAE)组装,构建了水/光调节的聚准轮烷超分子凝胶的室温磷光(RTP)。这种水凝胶表现出显著的蓝色荧光发射;相反,冻干成干凝胶后,基于干凝胶的刚性网络结构,该体系同时表现出蓝色荧光和黄色RTP,这限制了磷光体的振动并抑制了非辐射弛豫过程。有趣的是,向凝胶体系中加入过量的ECD可以增强RTP发射。此外,可逆发光行为可以通过DAE的光响应异构化和湿度来调节。这种聚准轮烷超分子凝胶体系为构建可调谐RTP材料提供了一种新策略。