Mobility and Reactivity of 4-Substituted TEMPO Derivatives in Metal–Organic Framework MIL-53(Al) | Sciact - CRIS-система Института катализа

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

Журнал

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

Вых. Данные

Год: 2016, Том: 120, Номер: 19, Страницы: 10698-10704 Страниц : 7 DOI: 10.1021/acs.jpcc.6b02966

Ключевые слова

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

Авторы

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

Организации

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

Информация о финансировании (3)

1	Российский научный фонд	14-13-00826
2	Российский фонд фундаментальных исследований	14-03-00224
3	Федеральное агентство научных организаций России	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 CAPlusCA OpenAlex

Поступила в редакцию:	22 мар. 2016 г.
Принята к публикации:	29 апр. 2016 г.
Опубликована online:	9 мая 2016 г.
Опубликована в печати:	19 мая 2016 г.

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

БД	Цитирований
Web of science	26
Scopus	26
РИНЦ	26
OpenAlex	23