Dong Xi-Yan, Si Yubing, Yang Jin-Sen, Zhang Chong, Han Zhen, Luo Peng, Wang Zhao-Yang, Zang Shuang-Quan, Mak Thomas C W
Green Catalysis Center, and College of Chemistry, Zhengzhou University, 450001, Zhengzhou, China.
College of Chemistry and Chemical Engineering, Henan Polytechnic University, 454003, Jiaozuo, China.
Nat Commun. 2020 Jul 22;11(1):3678. doi: 10.1038/s41467-020-17200-w.
Ratiometric luminescent oxygen sensing based on dual fluorescence and phosphorescence emission in a single matrix is highly desirable, yet the designed synthesis remains challenging. Silver-chalcogenolate-cluster-based metal-organic frameworks that combine the advantages of silver clusters and metal-organic frameworks have displayed unique luminescent properties. Herein, we rationally introduce -NH groups on the linkers of a silver-chalcogenolate-cluster-based metal-organic framework (Agbpy-NH) to tune the intersystem crossing, achieving a dual fluorescence-phosphorescence emission from the same linker chromophore. The blue fluorescence component has a 100-nm gap in wavelength and 8,500,000-fold difference in lifetime relative to a yellow phosphorescence component. Agbpy-NH quantifies oxygen during hypoxia with the limit of detection of as low as 0.1 ppm and 0.3 s response time, which is visualized by the naked eye. Our work shows that metal cluster-based MOFs have great potential in luminescent sensing, and the longer-lived charge-separated states could find more photofunctional applications in solar energy transformation and photocatalysis.
基于单一基质中双荧光和磷光发射的比率发光氧传感是非常理想的，但设计合成仍然具有挑战性。结合银簇和金属有机框架优点的硫属银酸盐簇基金属有机框架展现出独特的发光特性。在此，我们在硫属银酸盐簇基金属有机框架（Agbpy-NH）的连接体上合理引入-NH基团来调节系间窜越，从而实现来自同一连接体发色团的双荧光-磷光发射。蓝色荧光组分与黄色磷光组分相比，波长相差100纳米，寿命相差8500000倍。Agbpy-NH在缺氧期间对氧气进行定量检测，检测限低至0.1 ppm，响应时间为0.3秒，肉眼即可观察到。我们的工作表明，基于金属簇的金属有机框架在发光传感方面具有巨大潜力，寿命更长的电荷分离态在太阳能转化和光催化等光功能应用中可能会有更多发现。
