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Detection of adsorbates on emissive MOF surfaces with X-ray photoelectron spectroscopy

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Abstract

Luminescent metal–organic frameworks (MOFs) have been explored extensively as potential probes for nitroaromatic molecules, which are common constituents of explosive devices. Guest encapsulation within MOF pores is often cited as the prerequisite for emission changes, but the evidence for this signal transduction mechanism is often inadequate. Using the unique bipyridyl ligand AzoAEpP (2,2′-bis[N,N′-(4-pyridyl)ethyl]diaminoazobenzene), we constructed two luminescent pillared paddle-wheel Zn2+ MOFs using aryl dicarboxylate ligands 1,4-naphthalenedicarboxylic acid (ABMOF-1) and benzene 1,4-dicarboxylic acid (ABMOF-2). While both MOFs exhibit luminescence, 2,4-dinitrophenol only extinguishes ABMOF-1 emission. Since the size of the pores in ABMOF-1 precludes guest inclusion, we used X-ray photoelectron spectroscopy (XPS) to confirm the surface interaction and obtain insight into the nature of the quenching process. XPS experiments utilized a fluorinated nitroaromatic molecule, 4-trifluoromethyl-2,6-dinitrophenol, that extinguishes ABMOF-1 emission, and verified surface adsorption through a series of angle-resolved (ARXPS) and argon-ion sputter depth profile experiments. By further developing these techniques, we hope to develop a general approach for distinguishing between the various intermolecular interactions between MOFs and analytes that lead to changes in luminescence.

Graphical abstract: Detection of adsorbates on emissive MOF surfaces with X-ray photoelectron spectroscopy

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Publication details

The article was received on 05 Nov 2018, accepted on 02 Mar 2019 and first published on 04 Mar 2019


Article type: Paper
DOI: 10.1039/C8DT04404J
Citation: Dalton Trans., 2019, Advance Article

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    Detection of adsorbates on emissive MOF surfaces with X-ray photoelectron spectroscopy

    J. Yan, A. D. Carl, A. R. Maag, J. C. MacDonald, P. Müller, R. L. Grimm and S. C. Burdette, Dalton Trans., 2019, Advance Article , DOI: 10.1039/C8DT04404J

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