A Close View of the Organic Linker in a MOF: Structural Insights from a Combined 1H NMR Relaxometry and Computational Investigation
Научная публикация
| Общая информация |
Язык:
Английский,
Жанр:
Статья (Full article),
Статус опубликования:
Опубликована,
Оригинальность:
Оригинальная
|
| Журнал |
PCCP: Physical Chemistry Chemical Physics
ISSN: 1463-9076
, E-ISSN: 1463-9084
|
| Вых. Данные |
Год: 2020,
Том: 22,
Номер: 27,
Страницы: 15222-15230
Страниц
: 9
DOI:
10.1039/d0cp01863e
|
| Ключевые слова |
TEREPHTHALATE PHENYLENES; ROTATIONAL-DYNAMICS; HEAT TRANSFORMATION; FRAMEWORKS; N-14; RELAXATION; MOBILITY; SEPARATION; STORAGE |
| Авторы |
Pizzanelli Silvia
1
,
Monti Susanna
1
,
Gordeeva Larisa G.
2,3
,
Solovyeva Marina V.
2,3
,
Freni Angelo
1
,
Forte Claudia
1
|
| Организации |
| 1 |
CNR-ICCOM, Institute of the Chemistry of Organometallic Compounds, via G. Moruzzi 1, 56124 Pisa, Italy
|
| 2 |
Boreskov Institute of Catalysis, Ac. Lavrentiev av. 5, Novosibirsk 630090, Russia
|
| 3 |
Novosibirsk State University, Pirogova str. 1, Novosibirsk 630090, Russia
|
|
Информация о финансировании (4)
|
1
|
Российский фонд фундаментальных исследований
|
18-29-04033
|
|
2
|
European Cooperation in Science and Technology
|
CA15209
|
|
3
|
Tuscany Region
|
2014-2020 FELIX project
|
|
4
|
BENEFICENTIA Stiftung
|
|
The organic linker in a metal organic framework (MOF) affects its adsorption behavior and performance, and its structure and dynamics play a role in the modulation of the adsorption properties. In this work, the combination of 1H nuclear magnetic resonance (NMR) longitudinal relaxometry and theoretical calculations allowed details of the structure and dynamics of the organic linker in the NH2-MIL-125 MOF to be obtained. In particular, fast field cycling (FFC) NMR, applied here for the first time on MOFs, was used to disclose the dynamics of the amino group and its electronic environment through the analysis of the 14N quadrupole relaxation peaks, observed in the frequency interval 0.5–5 MHz, at different temperatures from 25 to 110 °C. The line width of the peaks allowed a lower boundary on the rotational correlation time of the N–H bonds to be set, whereas relevant changes in the amplitudes were interpreted in terms of a change in the orientation of the 14N averaged electric field gradient tensor. The experimental findings were complemented by quantum chemistry calculations and classical molecular dynamics simulations.