Rigidifying Fluorescent Linkers by Metal-Organic Framework Formation for Fluorescence Blue Shift and Quantum Yield Enhancement
Rigidifying Fluorescent Linkers by Metal-Organic Framework Formation for Fluorescence Blue Shift and Quantum Yield Enhancement
复制标题
DOI：
10.1021/ja5006866
复制
发表时间：
2014-06-11
影响因子：
15
通讯作者：
Zhou, Hong-Cai
中科院分区：
文献类型：
--
作者：
Wei, Zhangwen;Gu, Zhi-Yuan;Zhou, Hong-Cai
我们证明，通过在结构上限制它们在金属有机框架（MOFs），以控制它们的构象有效地调谐荧光能量和提高量子产率的荧光连接体的结构刚性化。因此，一种新的基于四苯乙烯的锆MOF在Ar下在470 nm处表现出深蓝色荧光发射，具有单位量子产率（99.9 +/- 0.5%），代表约100 nm。3600 cm（-1）的蓝移和与连接体前体相比加倍的辐射衰减效率。当将固体MOF从低温加热到环境温度时，发生荧光寿命和相对强度的异常增加。这些不寻常的光致发光特性的起源归因于扭曲的连接体构象，分子内位阻和框架刚性。
We demonstrate that rigidifying the structure of fluorescent linkers by structurally constraining them in metal-organic frameworks (MOFs) to control their conformation effectively tunes the fluorescence energy and enhances the quantum yield. Thus, a new tetraphenylethylene-based zirconium MOF exhibits a deep-blue fluorescent emission at 470 nm with a unity quantum yield (99.9 +/- 0.5%) under Ar, representing ca. 3600 cm(-1) blue shift and doubled radiative decay efficiency vs the linker precursor. An anomalous increase in the fluorescence lifetime and relative intensity takes place upon heating the solid MOF from cryogenic to ambient temperatures. The origin of these unusual photoluminescence properties is attributed to twisted linker conformation, intramolecular hindrance, and framework rigidity.