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

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.

Authors:
; ; ; ; ; ; ; ;  [1]
  1. UNT
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
DOE - BASIC ENERGY SCIENCES
OSTI Identifier:
1140201
Resource Type:
Journal Article
Journal Name:
J. Am. Chem. Soc.
Additional Journal Information:
Journal Volume: 136; Journal Issue: (23) ; 06, 2014
Country of Publication:
United States
Language:
ENGLISH
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY

Citation Formats

Wei, Zhangwen, Gu, Zhi-Yuan, Arvapally, Ravi K., Chen, Ying-Pin, Ivy, Joshua F., Yakovenko, Andrey A., Feng, Dawei, Omary, Mohammad A., and Zhou, Hong-Cai. Rigidifying Fluorescent Linkers by Metal–Organic Framework Formation for Fluorescence Blue Shift and Quantum Yield Enhancement. United States: N. p., 2014. Web. doi:10.1021/ja5006866.
Wei, Zhangwen, Gu, Zhi-Yuan, Arvapally, Ravi K., Chen, Ying-Pin, Ivy, Joshua F., Yakovenko, Andrey A., Feng, Dawei, Omary, Mohammad A., & Zhou, Hong-Cai. Rigidifying Fluorescent Linkers by Metal–Organic Framework Formation for Fluorescence Blue Shift and Quantum Yield Enhancement. United States. https://doi.org/10.1021/ja5006866
Wei, Zhangwen, Gu, Zhi-Yuan, Arvapally, Ravi K., Chen, Ying-Pin, Ivy, Joshua F., Yakovenko, Andrey A., Feng, Dawei, Omary, Mohammad A., and Zhou, Hong-Cai. 2014. "Rigidifying Fluorescent Linkers by Metal–Organic Framework Formation for Fluorescence Blue Shift and Quantum Yield Enhancement". United States. https://doi.org/10.1021/ja5006866.
@article{osti_1140201,
title = {Rigidifying Fluorescent Linkers by Metal–Organic Framework Formation for Fluorescence Blue Shift and Quantum Yield Enhancement},
author = {Wei, Zhangwen and Gu, Zhi-Yuan and Arvapally, Ravi K. and Chen, Ying-Pin and Ivy, Joshua F. and Yakovenko, Andrey A. and Feng, Dawei and Omary, Mohammad A. and Zhou, Hong-Cai},
abstractNote = {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.},
doi = {10.1021/ja5006866},
url = {https://www.osti.gov/biblio/1140201}, journal = {J. Am. Chem. Soc.},
number = (23) ; 06, 2014,
volume = 136,
place = {United States},
year = {Wed Jun 11 00:00:00 EDT 2014},
month = {Wed Jun 11 00:00:00 EDT 2014}
}