Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
A close view of the organic linker in a MOF : structural insights from a combined 1H NMR relaxometry and computational investigation. / Pizzanelli, Silvia; Monti, Susanna; Gordeeva, Larisa G. и др.
в: Physical Chemistry Chemical Physics, Том 22, № 27, 21.07.2020, стр. 15222-15230.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - A close view of the organic linker in a MOF
T2 - structural insights from a combined 1H NMR relaxometry and computational investigation
AU - Pizzanelli, Silvia
AU - Monti, Susanna
AU - Gordeeva, Larisa G.
AU - Solovyeva, Marina V.
AU - Freni, Angelo
AU - Forte, Claudia
N1 - Publisher Copyright: © 2020 the Owner Societies. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.
PY - 2020/7/21
Y1 - 2020/7/21
N2 - 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.
AB - 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.
KW - TEREPHTHALATE PHENYLENES
KW - ROTATIONAL-DYNAMICS
KW - HEAT TRANSFORMATION
KW - FRAMEWORKS
KW - N-14
KW - RELAXATION
KW - MOBILITY
KW - SEPARATION
KW - STORAGE
UR - http://www.scopus.com/inward/record.url?scp=85088246709&partnerID=8YFLogxK
U2 - 10.1039/d0cp01863e
DO - 10.1039/d0cp01863e
M3 - Article
C2 - 32601632
AN - SCOPUS:85088246709
VL - 22
SP - 15222
EP - 15230
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 27
ER -
ID: 24870290