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Switch‐On Fluorescence of a Perylene‐Dye‐Functionalized Metal–Organic Framework through Postsynthetic Modification
Authors:Dr. Christian Dietl  Henrik Hintz  Dr. Bastian Rühle  Prof. Dr. Jörn Schmedt auf der Günne  Prof. Dr. Heinz Langhals  Dr. Stefan Wuttke
Affiliation:1. Department of Chemistry and Center for NanoScience (CeNS), University of Munich (LMU), Butenandtstrasse?11 (E), 81377 München (Germany);2. Department of Chemistry/Biology, University of Siegen, Adolf‐Reichwein‐Stra?e?2, 57076 Siegen (Germany)
Abstract:
A perylene dye was introduced directly as a linker into a metal–organic framework (MOF) during synthesis. Depending on the dye concentration in the MOF synthesis mixture, different fluorescent materials were generated. The successful incorporation of the dye was proven by using 13C and 27Al MAS NMR spectroscopy, by solution NMR spectroscopy after digestion of the MOF sample, and by synthesizing a reference dye without connecting groups, which could coordinate on the metal–oxo cluster inside the MOF. Fluorescence quenching effects of the MOF linker, 2‐aminoterephthalate, were observed and overcome by postsynthetic modification with acetic anhydride. We show here for the first time that amino groups, which can be used as anchoring points for covalent attachment of other molecules, are responsible for fluorescence quenching. Thus, a very promising strategy to implement switchable fluorescence into MOFs is shown here.
Keywords:dyes  fluorescence  metal–  organic frameworks  NMR spectroscopy  synthetic methods
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