Metal-Cation-Independent Dynamics of Phenylene Ring in Microporous MOFs: A 2H Solid-State NMR Study | Sciact - CRIS-system of Boreskov Institute of Catalysis

Metal-Cation-Independent Dynamics of Phenylene Ring in Microporous MOFs: A 2H Solid-State NMR Study Full article

Journal

The Journal of Physical Chemistry C
ISSN: 1932-7447 , E-ISSN: 1932-7455

Output data

Year: 2015, Volume: 119, Number: 50, Pages: 28038-28045 Pages count : 8 DOI: 10.1021/acs.jpcc.5b09435

Tags

Activation energy; Crystalline materials; Dynamics; Isomers; Metals; Molecules; Nuclear magnetic resonance spectroscopy; Organic solvents; Organometallics; Positive ions

Authors

Khudozhitkov Alexander E. ^1,2 , Kolokolov Daniil I. ^1,2 , Stepanov Alexander G. ^1,2 , Bolotov Vsevolod A. ³ , Dybtsev Danil N. ^2,3

Affiliations

1	Boreskov Institute of Catalysis, Siberian Branch of Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk 630090, Russia
2	Department of Physical Chemistry, Faculty of Natural Sciences,, Novosibirsk State University, Pirogova Street 2, Novosibirsk 630090, Russia
3	Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, Prospekt Akademika Lavrentieva 3, Novosibirsk 630090, Russia

Funding (2)

1	Russian Foundation for Basic Research	14-03-91333
2	The Ministry of Education and Science of the Russian Federation	14.Z50.31.0006

Mobility of the organic linkers in metal–organic frameworks (MOFs) is an established phenomenon. Knowledge of the details of linker motion in MOFs could provide a great deal of information about the linker structure and the way the guest molecules interact with the organic framework. However, the mobility of the organic linkers is poorly characterized. The extent of the influence of the metal cation or guest molecules on linker motion is still unknown for MOFs with identical topologies. In this work, we have analyzed the rotational dynamics of the phenylene ring fragments of terephthalate (1,4-benzenedicarboxylate, bdc) linkers in the series of MOFs [M2(bdc)2(dabco)]·G (M = Co2+, Ni2+, Cu2+, Zn2+; dabco =1,4-diazabicyclo[2.2.2]octane; G = none or dimethylformamide, DMF). We have established that the reorientational motion of the phenylene rings is performed by π-flipping of the plane of the ring about its C2 axis. The dynamics of the phenylene rings is insensitive to the variation of the metal cation, whereas the loading of the guest DMF molecules provides both a significant decrease of the rate of π-flips and an increase of the activation energy for the motion of the phenylene rings.

Khudozhitkov A.E. , Kolokolov D.I. , Stepanov A.G. , Bolotov V.A. , Dybtsev D.N.
Metal-Cation-Independent Dynamics of Phenylene Ring in Microporous MOFs: A 2H Solid-State NMR Study
The Journal of Physical Chemistry C. 2015. V.119. N50. P.28038-28045. DOI: 10.1021/acs.jpcc.5b09435 WOS Scopus РИНЦ ANCAN OpenAlex

Submitted:	Sep 28, 2015
Accepted:	Nov 16, 2015
Published online:	Dec 3, 2015
Published print:	Dec 17, 2015

Web of science:	WOS:000366878500018
Scopus:	2-s2.0-84951983835
Elibrary:	26928038
Chemical Abstracts:	2015:1840776
Chemical Abstracts (print):	164:22879
OpenAlex:	W2287895672

DB	Citing
Web of science	35
Scopus	36
Elibrary	35
OpenAlex	36