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Probing Interactions of N-Donor Molecules with Open Metal Sites within Paramagnetic Cr-MIL-101 : a Solid-State NMR Spectroscopic and Density Functional Theory Study

Title data

Wittmann, Thomas ; Mondal, Arobendo ; Tschense, Carsten ; Wittmann, Johannes J. ; Klimm, Ottokar ; Siegel, Renée ; Corzilius, Björn ; Weber, Birgit ; Kaupp, Martin ; Senker, Jürgen:
Probing Interactions of N-Donor Molecules with Open Metal Sites within Paramagnetic Cr-MIL-101 : a Solid-State NMR Spectroscopic and Density Functional Theory Study.
In: Journal of the American Chemical Society. Vol. 140 (14 February 2018) Issue 6 . - pp. 2135-2144.
ISSN 1520-5126
DOI: https://doi.org/10.1021/jacs.7b10148

Abstract in another language

Understanding host–guest interactions is one of the key requirements for adjusting properties in metal–organic frameworks (MOFs). In particular, systems with coordinatively unsaturated Lewis acidic metal sites feature highly selective adsorption processes. This is attributed to strong interactions with Lewis basic guest molecules. Here we show that a combination of 13C MAS NMR spectroscopy with state-of-the-art density functional theory (DFT) calculations allows one to unravel the interactions of water, 2-aminopyridine, 3-aminopyridine, and diethylamine with the open metal sites in Cr-MIL-101. The 13C MAS NMR spectra, obtained with ultrafast magic-angle spinning, are well resolved, with resonances distributed over 1000 ppm. They present a clear signature for each guest at the open metal sites. Based on competition experiments this leads to the following binding preference: water < diethylamine ≈ 2-aminopyridine < 3-aminopyridine. Assignments were done by exploiting distance sum relations derived from spin–lattice relaxation data and 13C{1H} REDOR spectral editing. The experimental data were used to validate NMR shifts computed for the Cr-MIL-101 derivatives, which contain Cr3O clusters with magnetically coupled metal centers. While both approaches provide an unequivocal assignment and the arrangement of the guests at the open metal sites, the NMR data offer additional information about the guest and framework dynamics. We expect that our strategy has the potential for probing the binding situation of adsorbate mixtures at the open metal sites of MOFs in general and thus accesses the microscopic interaction mechanisms for this important material class, which is essential for deriving structure–property relationships.

Further data

Item Type: Article in a journal
Refereed: Yes
Additional notes: ISI:000425475300030
Institutions of the University: Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Anorganic Chemistry III > Chair Anorganic Chemistry III - Univ.-Prof. Dr. Jürgen Senker
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Anorganic Chemistry IV > Chair Anorganic Chemistry IV - Univ.-Prof. Dr. Birgit Weber
Faculties
Faculties > Faculty of Biology, Chemistry and Earth Sciences
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Anorganic Chemistry III
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Anorganic Chemistry IV
Result of work at the UBT: Yes
DDC Subjects: 500 Science > 540 Chemistry
Date Deposited: 16 Feb 2018 09:38
Last Modified: 14 Sep 2018 07:31
URI: https://eref.uni-bayreuth.de/id/eprint/42299