Rigidifying Fluorescent Linkers by Metal鈥揙rganic Framework Formation for Fluorescence Blue Shift and Quantum Yield Enhancement
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- 作者：Zhangwen Wei ; Zhi-Yuan Gu ; Ravi K. Arvapally ; Ying-Pin Chen ; Roy N. McDougald ; Jr. ; Joshua F. Ivy ; Andrey A. Yakovenko ; Dawei Feng ; Mohammad A. Omary ; Hong-Cai Zhou
- 刊名：Journal of the American Chemical Society
- 出版年：2014
- 出版时间：June 11, 2014
- 年：2014
- 卷：136
- 期：23
- 页码：8269-8276
- 全文大小：481K
- 年卷期：v.136,no.23(June 11, 2014)
- ISSN：1520-5126
文摘
We demonstrate that rigidifying the structure of fluorescent linkers by structurally constraining them in metal鈥搊rganic 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 卤 0.5%) under Ar, representing ca. 3600 cm鈥? 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.