Selective turn-on ammonia sensing enabled by high-temperature fluorescence in metal-organic frameworks with open metal sites

Natalia B. Shustova, Anthony F. Cozzolino, Sebastian Reineke, Marc Baldo, Mircea Dincǎ

Research output: Contribution to journalArticle

303 Scopus citations

Abstract

We show that fluorescent molecules incorporated as ligands in rigid, porous metal-organic frameworks (MOFs) maintain their fluorescence response to a much higher temperature than in molecular crystals. The remarkable high-temperature ligand-based fluorescence, demonstrated here with tetraphenylethylene- and dihydroxyterephthalate-based linkers, is essential for enabling selective and rapid detection of analytes in the gas phase. Both Zn2(TCPE) (TCPE = tetrakis(4-carboxyphenyl)ethylene) and Mg(H2DHBDC) (H 2DHBDC2- = 2,5-dihydroxybenzene-1,4-dicarboxylate) function as selective sensors for ammonia at 100 C, although neither shows NH3 selectivity at room temperature. Variable-temperature diffuse-reflectance infrared spectroscopy, fluorescence spectroscopy, and X-ray crystallography are coupled with density-functional calculations to interrogate the temperature-dependent guest-framework interactions and the preferential analyte binding in each material. These results describe a heretofore unrecognized, yet potentially general property of many rigid, fluorescent MOFs and portend new applications for these materials in selective sensors, with selectivity profiles that can be tuned as a function of temperature.

Original languageEnglish
Pages (from-to)13326-13329
Number of pages4
JournalJournal of the American Chemical Society
Volume135
Issue number36
DOIs
StatePublished - Sep 11 2013

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