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

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