Qiu Juan, Li Qingrun, Lei Nana, Chen Xiao
Key Laboratory of Colloid and Interface Chemistry, Shandong University, Ministry of Education, Jinan 250100, China.
School of Chemical Engineering and Technology, North University of China, Taiyuan 030051, China.
ACS Omega. 2020 Mar 18;5(12):6895-6902. doi: 10.1021/acsomega.0c00261. eCollection 2020 Mar 31.
Using the ionic self-assembly (ISA) strategy to combine Eu-containing polyoxometalates (Eu-POMs) and organic molecules mainly through noncovalent electrostatic interactions can protect Eu-POMs from solvent quenching of luminescence and enhance their processability. For this reason, a cationic polyelectrolyte, branched polyethyleneimine (PEI), and a Eu-POM, Na(EuWO)·32HO (EuW), were used here to construct luminescence-enhanced spherical aggregates with diameters ranging from 50 to 200 nm. At a fixed concentration of EuW, the phase behavior and luminescence properties of the mixture could be modulated by the PEI concentration. Such ISA-induced aggregates could effectively shield water molecules and result in better photophysical properties. Compared to bare EuW, the absolute quantum yield and lifetime of luminescence for aggregates increased 10 and 5 times, respectively. Meanwhile, the sensitivity of the EuW coordination structure to the environment made it possible for obtained aggregates being used to detect either copper cations or permanganate anions due to their strong specific quenching effects to luminescence. Such a new type of luminescent soft material not only provided a reference for exploring the luminescence enhancement mechanism of lanthanide through self-assembly in aqueous solution but also exhibited potential in detection by luminescence analysis.
利用离子自组装(ISA)策略,主要通过非共价静电相互作用将含铕多金属氧酸盐(Eu-POMs)与有机分子相结合,可以保护Eu-POMs免受发光的溶剂猝灭,并提高其可加工性。因此,本文使用阳离子聚电解质支化聚乙烯亚胺(PEI)和Eu-POM Na(EuWO)·32HO(EuW)来构建直径范围为50至200nm的发光增强球形聚集体。在EuW浓度固定的情况下,混合物的相行为和发光性质可通过PEI浓度进行调节。这种由ISA诱导的聚集体可以有效地屏蔽水分子,并产生更好的光物理性质。与裸露的EuW相比,聚集体的绝对量子产率和发光寿命分别提高了10倍和5倍。同时,EuW配位结构对环境的敏感性使得所获得的聚集体能够用于检测铜阳离子或高锰酸根阴离子,因为它们对发光具有强烈的特异性猝灭作用。这种新型发光软材料不仅为探索水溶液中通过自组装增强镧系元素发光机制提供了参考,而且在发光分析检测方面也具有潜力。