Subppm Amine Detection via Absorption and Luminescence Turn-On Caused by Ligand Exchange in Metal Organic Frameworks

Luminescent metal–organic frameworks (LMOFs) are promising materials for lighting and sensing applications. Herein, exposure of the highly luminescent Zn2(bpdc)2(bpee) MOF (H2bpdc = 4,4′-biphenyldicarboxylic acid and bpee = 1,2-bipyridylethene) to subppm amine contents turns on a new absorption band...

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Bibliographic Details
Published in:Analytical chemistry (Washington) 2019-12, Vol.91 (24), p.15853-15859
Main Authors: Sousaraei, Ahmad, Queirós, Carla, Moscoso, Francisco G, Lopes-Costa, Tania, Pedrosa, Jose M, Silva, Ana M. G, Cunha-Silva, Luís, Cabanillas-Gonzalez, Juan
Format: Article
Language:English
Subjects:
Absorption
Absorption spectra
Amines
Aqueous solutions
Chemistry
Exchanging
Fourier transforms
Infrared analysis
Infrared spectra
Ligands
Luminescence
Membranes
Metal-organic frameworks
Photoluminescence
Photons
Polydimethylsiloxane
Siloxanes
Thermogravimetric analysis
Vapor phases
Wavelengths
X ray powder diffraction
X-ray diffraction
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Summary:Luminescent metal–organic frameworks (LMOFs) are promising materials for lighting and sensing applications. Herein, exposure of the highly luminescent Zn2(bpdc)2(bpee) MOF (H2bpdc = 4,4′-biphenyldicarboxylic acid and bpee = 1,2-bipyridylethene) to subppm amine contents turns on a new absorption band unambiguously ascribed to free bpee molecules concomitant with the gradual appearance of a new photoluminescence band at shorter wavelengths. These findings combined with Fourier-transform infrared spectra, powder X-ray diffraction and thermogravimetric analysis of exposed LMOF powders confirm that bpee ligands are exchanged by amines and released inside the LMOF, triggering absorption and luminescence features which can be exploited for highly sensitive amine recognition. This principle was demonstrated in mixed matrix membranes (MMMs) prepared by a simple solvent-free method consisting of mixing Zn2(bpdc)2(bpee) with dimethylvinyl-terminated dimethylsiloxane and dimethylhydrogen siloxane. This method enabled the production of free-standing, permeable, and highly transparent MMMs which showed enormous potential and sensitivity to the detection of amines in gas phase and aqueous medium.
ISSN:0003-2700
1520-6882
DOI:10.1021/acs.analchem.9b04291