Guests Like Gear Levers: Donor Binding to Coordinatively Unsaturated Metal Sites in MIL-101 Controls the Linkers Rotation Full article
| Journal |
Chemistry - A European Journal
ISSN: 0947-6539 , E-ISSN: 1521-3765 |
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| Output data | Year: 2019, Volume: 25, Number: 20, Pages: 5163-5168 Pages count : 7 DOI: 10.1002/chem.201900585 | ||||||
| Tags | metal-organic frameworks; structural mobility; coordinatively unsaturated metal sites; Solid State NMR spectroscopy; rotation control | ||||||
| Authors |
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| Affiliations |
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Funding (2)
| 1 | Federal Agency for Scientific Organizations | 0303-2016-0003 |
| 2 | Russian Foundation for Basic Research | 18-29-04009 |
Abstract:
We present investigation of the effect of electron‐donor guests on the framework mobility in the metal‐organic framework (MOF) MIL‐101(Cr) monitored by solid state 2H NMR. In a guest free material, the mobile phenylene fragments of the terephthalate (TP) linkers populate two fractions with notably different kinetic parameters for torsional motion. Two fractions of rotational motion are indicative of non‐equivalence of TP linker binding to Cr3O trimer, the primary building unit of the MIL‐101 framework. It is established that the interaction of the guest molecules with coordinatively unsaturated metal sites (CUS) of the MOF dramatically decreases torsional barriers for the linker motions, enhancing the rotation rate. This result is opposite to a more conventional slowing down effect on the linker rotation of the guests not selectively interacting with the adsorption sites inside framework of the MOFs. The effect of coordination on both the torsional barrier and the rotation rate depends notably on the particular guest interacting with CUS. The found effects of the guest on the rotational motion represent a basis for developing the strategy for ruling and controlling the linker rotation in MOFs with CUS. It is shown if water occupies CUS, another guest (tert‐butanol, cyclohexanone) fails to competitively coordinate to the site.
Cite:
Khudozhitkov A.E.
, Arzumanov S.S.
, Kolokolov D.I.
, Kholdeeva O.A.
, Freude D.
, Stepanov A.G.
Guests Like Gear Levers: Donor Binding to Coordinatively Unsaturated Metal Sites in MIL-101 Controls the Linkers Rotation
Chemistry - A European Journal. 2019. V.25. N20. P.5163-5168. DOI: 10.1002/chem.201900585 WOS Scopus РИНЦ ANCAN PMID OpenAlex
Guests Like Gear Levers: Donor Binding to Coordinatively Unsaturated Metal Sites in MIL-101 Controls the Linkers Rotation
Chemistry - A European Journal. 2019. V.25. N20. P.5163-5168. DOI: 10.1002/chem.201900585 WOS Scopus РИНЦ ANCAN PMID OpenAlex
Dates:
| Submitted: | Feb 7, 2019 |
| Accepted: | Feb 27, 2019 |
| Published online: | Feb 27, 2019 |
| Published print: | Apr 5, 2019 |
Identifiers:
| Web of science: | WOS:000468855200009 |
| Scopus: | 2-s2.0-85063268286 |
| Elibrary: | 38689922 |
| Chemical Abstracts: | 2019:581005 |
| Chemical Abstracts (print): | 170:482129 |
| PMID: | 30811710 |
| OpenAlex: | W2917651480 |