Abstract: We present a detailed solid state NMR characterization of the molecular dynamics of tert ‐butyl alcohol (TBA) confined inside breathing metal‐organic framework (MOF) MIL‐53 (Al). 27 Al MAS NMR demonstrates that TBA adsorption induces the iX phase of MIL‐53 framework structure with partially shrinked channels. 2 H solid‐state NMR shows that the adsorbed alcohol exhibits anisotropic rotations of the methyl groups around two [[EQUATION]] axes and librations of the molecule as a whole about the axis passing through the TBA C–O bond. These librations are realized by two distinct ways: the faster ones with characteristic time τ D ≈10 ‐9 s at 300 K, reflects the molecule orientation change during the translational jump diffusion along the channel; the slower one with τ l ≈10 ‐6 s at 300 K reflects the local librations at a single coordination site, representing framework hydroxyl groups. We provide an estimation of self‐diffusion coefficient of the alcohol in the MOF: D = 3.4×10 ‐10 m 2 s ‐1 at 300 K. It is inferred that both the framework flexibility and the interaction with framework hydroxyl groups define the dynamics of TBA confined in the channels of MIL‐53 (Al).

Cite: Khudozhitkov A.E. , Toktarev A.V. , Arzumanov S.S. , Gabrienko A.A. , Kolokolov D.I. , Stepanov A.G.
Molecular Mobility of Tert‐butyl Alcohol Confined in a Breathing MIL‐53 (Al) Metal‐Organic Framework
ChemPhysChem. 2020. V.21. N17. P.1951–1956. DOI: 10.1002/cphc.202000445 WOS Scopus РИНЦ ANCAN PMID OpenAlex

Dates:

Submitted:	May 28, 2020
Accepted:	Jul 22, 2020
Published online:	Jul 22, 2020
Published print:	Sep 2, 2020

Identifiers:

Web of science:	WOS:000555530700001
Scopus:	2-s2.0-85089031040
Elibrary:	45428028
Chemical Abstracts:	2020:1525176
Chemical Abstracts (print):	182:92808
PMID:	32697428
OpenAlex:	W3043992392

Citing:

DB	Citing
Scopus	3
Web of science	3
Elibrary	3
OpenAlex	3

Altmetrics: