Mobility and Reactivity of 4-Substituted TEMPO Derivatives in Metal–Organic Framework MIL-53(Al) | Sciact - CRIS-system of Boreskov Institute of Catalysis

Mobility and Reactivity of 4-Substituted TEMPO Derivatives in Metal–Organic Framework MIL-53(Al) Full article

Journal

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

Output data

Year: 2016, Volume: 120, Number: 19, Pages: 10698-10704 Pages count : 7 DOI: 10.1021/acs.jpcc.6b02966

Tags

Crystalline materials; Electron spin resonance spectroscopy; Java programming language; Magnetic resonance; Molecular dynamics; Organic polymers; Organometallics; Paramagnetic resonance; Probes; Reaction kinetics; Structural dynamics

Authors

Poryvaev A.S. ^1,2 , Sheveleva A.M. ^1,2 , Kolokolov D.I. ^2,3 , Stepanov A.G. ^2,3 , Bagryanskaya E.G. ^2,4 , Fedin M.V. ^1,2

Affiliations

1	International Tomography Center SB RAS, 630090 Novosibirsk, Russia
2	Novosibirsk State University, 630090 Novosibirsk, Russia
3	Boreskov Institute of Catalysis SB RAS, Lavrentiev av. 5, 630090 Novosibirsk, Russia
4	N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, 630090 Novosibirsk, Russia

Funding (3)

1	Russian Science Foundation	14-13-00826
2	Russian Foundation for Basic Research	14-03-00224
3	Federal Agency for Scientific Organizations	0333-2014-0001 (V.44.1.1)

Postsynthetic adsorption of stable nitroxide radical probes in diamagnetic nano/mesoporous metal–organic frameworks (MOFs) allows application of electron paramagnetic resonance (EPR) for studying structure, functions, and corresponding guest–host interactions in such MOFs. This approach was recently demonstrated using (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) embedded in structurally flexible MIL-53(Al), with the mobility and reactivity of TEMPO reflecting structural dynamics of MOF. In the present work we embed three derivatives of TEMPO (4-oxo-TEMPO, 4-hydroxo-TEMPO, 4-acetamido-TEMPO) in MIL-53(Al) and investigate structural “breathing” of this MOF with temperature to gain deeper understanding of underlying guest–host interactions. Different substituents in the piperidine ring lead to different mobility and reactivity of corresponding nitroxides. The obtained EPR data and molecular dynamics calculations show that the efficiency of nitroxide radical reaction with μ2-hydroxo group of MIL-53(Al) strongly correlates with the character of its molecular motion, and the reversibility of this reaction upon structural “breathing” is a general phenomenon. On the basis of these findings, practical suggestions on selecting spin probes for in-MOF EPR studies are formulated.

Poryvaev A.S. , Sheveleva A.M. , Kolokolov D.I. , Stepanov A.G. , Bagryanskaya E.G. , Fedin M.V.
Mobility and Reactivity of 4-Substituted TEMPO Derivatives in Metal–Organic Framework MIL-53(Al)
The Journal of Physical Chemistry C. 2016. V.120. N19. P.10698-10704. DOI: 10.1021/acs.jpcc.6b02966 WOS Scopus РИНЦ ANCAN OpenAlex

Submitted:	Mar 22, 2016
Accepted:	Apr 29, 2016
Published online:	May 9, 2016
Published print:	May 19, 2016

Web of science:	WOS:000376417500064
Scopus:	2-s2.0-84971233968
Elibrary:	27158015
Chemical Abstracts:	2016:697094
Chemical Abstracts (print):	164:581500
OpenAlex:	W2346758998

DB	Citing
Web of science	29
Scopus	29
Elibrary	28
OpenAlex	28