Department of Chemistry, University of Liverpool, Liverpool L69 7ZD, UK.
J Am Chem Soc. 2010 Mar 31;132(12):4119-30. doi: 10.1021/ja906041f.
The carboxylate ligand 1,3,6,8-tetrakis(p-benzoic acid)pyrene (TBAPy)-based on the strongly fluorescent long-lifetime pyrene core-affords a permanently microporous fluorescent metal-organic framework, [In(2)(OH)(2)(TBAPy)].(guests) (1), displaying 54% total accessible volume and excellent thermal stability. Fluorescence studies reveal that both 1 and TBAPy display strong emission bands at 471 and 529 nm, respectively, upon excitation at 390 nm, with framework coordination of the TBAPy ligands significantly increasing the emission lifetime from 0.089 to 0.110 ms. Upon desolvation, the emission band for the framework is shifted to lower energy: however, upon re-exposure to DMF the as-made material is regenerated with reversible fluorescence behavior. Together with the lifetime, the emission intensity is strongly enhanced by spatial separation of the optically active ligand molecules within the MOF structure and is found to be dependent on the amount and chemical nature of the guest species in the pores. The quantum yield of the material is found to be 6.7% and, coupled with the fluorescence lifetime on the millisecond time scale, begins to approach the values observed for Eu(III)-cryptate-derived commercial sensors.
基于强荧光长寿命芘核心的羧酸配体 1,3,6,8-四(对苯二甲酸)芘(TBAPy)提供了一种永久微孔荧光金属有机骨架[In(2)(OH)(2)(TBAPy)]·(客体)(1)，显示出 54%的总可及体积和优异的热稳定性。荧光研究表明，1 和 TBAPy 在 390nm 激发下分别在 471nm 和 529nm 处显示出强发射带，TBAPy 配体的骨架配位显著将发射寿命从 0.089ms 增加到 0.110ms。在去溶剂化后，骨架的发射带向低能量移动；然而，当重新暴露于 DMF 时，所制得的材料通过可逆荧光行为得以再生。与寿命一起，发射强度通过 MOF 结构中光学活性配体分子的空间分离得到强烈增强，并发现其依赖于孔中客体物种的数量和化学性质。该材料的量子产率为 6.7%，与毫秒时间尺度上的荧光寿命相结合，开始接近 Eu(III)-cryptate 衍生的商业传感器观察到的值。
