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Rigidifying Fluorescent Linkers by Metal–Organic Framework Formation for Fluorescence Blue Shift and Quantum Yield Enhancement

Wei, Zhangwen, Gu, Zhi-Yuan, Arvapally, Ravi K., Chen, Ying-Pin, McDougald, Roy N., Ivy, Joshua F., Yakovenko, Andrey A., Feng, Dawei, Omary, Mohammad A., Zhou, Hong-Cai·2014·Journal of the American Chemical Society

DOI 10.1021/ja5006866

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Abstract

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.

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See all 657

Authors: Wei, Z., Gu, Z.-Y., Arvapally, R. K., Chen, Y.-P., McDougald, R. N., Ivy, J. F., Yakovenko, A. A., Feng, D., Omary, M. A., & Zhou, H.-C.
Venue: Journal of the American Chemical Society
Publisher: American Chemical Society (ACS)
Published: 2014-05-28
Volume: 136
Issue: 23
Pages: 8269-8276
ISSN: 0002-7863 (ISSN-L)
1520-5126
DOI: 10.1021/ja5006866
OpenAlex: W2048428864
Cited by: 657
References: 66
FWCI: 20.74
Type: journal article
Language: en
Open access: closed

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Rigidifying Fluorescent Linkers by Metal–Organic Framework Formation for Fluorescence Blue Shift and Quantum Yield Enhancement

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