Article

pubs.acs.org/JPCC

Probing the Guest-Mediated Structural Mobility in the UiO-66(Zr)

Framework by 2H NMR Spectroscopy
Alexander E. Khudozhitkov,†,‡ Hervé Jobic,§ Daniil I. Kolokolov,*,†,‡ Dieter Freude,∥ Jürgen Haase,∥
and Alexander G. Stepanov*,†,‡
†
Boreskov Institute of Catalysis, Siberian Branch of Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk
630090, Russia
‡
Novosibirsk State University, Pirogova Street 2, Novosibirsk 630090, Russia
§
Institut de Recherches sur la Catalyse et l’Environnement de Lyon, CNRS, Université de Lyon, 2. Av. A. Einstein, 69626
Villeurbanne, France
∥
Fakultät für Physik und Geowissenschaften, Universität Leipzig, Linnéstrasse 5, 04103 Leipzig, Germany
*
S Supporting Information

ABSTRACT: The solid-state 2H NMR technique (analysis of both the spectrum line
shape and the spin−lattice relaxation) was used to probe both slow and fast dynamical
modes of the phenylene fragments of terephthalate linkers of the UiO-66(Zr)
framework affected by the presence of benzene guest in the pores of the material. Such
approach allowed us to probe different motions within a broad range of time scale,
10−3−10−11 s. The internal dynamics in the UiO-66(Zr) framework is represented by
torsional motions of the phenylene fragment of the linker including 2-site 180° flips (π-
flips) of the plane of the phenylene ring and its restricted librations. In the presence of
benzene loaded in the MOF pores the rate of π-flips decreases essentially and the
activation barrier for this motion increases. The activation barrier has been found to
increase almost in a linear fashion on benzene loading. Such observation is surprisingly unique among other MOFs with mobile
linkers, like MIL-53(Al) or MOF-5. The fast librational motion occurs on a scale of ∼1010 Hz and shows no notable dependence
on the guest loading. It has been established that anisotropy of T1 relaxation of the 2H NMR powder pattern of the phenylene
fragments is especially sensitive to the librational motion when this motion is in a range of 107−1011 Hz. Within this range of
libration frequencies, analysis of the anisotropic spin−lattice (T1) relaxation allows quantitative estimation of the rate of
librational motion.

1. INTRODUCTION
Porous metal−organic frameworks (MOFs) constitute a class
of solid materials formed by inorganic nodes (metal cations or
metal oxide clusters) bridged together by organic linkers in a
regular manner. Such composition makes MOFs unique among
other crystalline porous solids because they combine the
ordered nature of a crystal and the flexibility of a polymer
framework, exhibiting a pronounced local mobility of its
building units. This internal structural mobility mediates many
fascinating MOFs properties such as optical1−3 and dielectrical
response,4 the conductivity,5−7 the adsorption, and the
molecular transport of chemical species confined inside their
pores. Since the walls of the MOFs pores and the windows
interconnecting them are constituted by the linkers, their
potential mobility, including rotational and librational motions,
could strongly affect both the morphology and the effective size
of the frameworks inner space. Indeed, recent studies of the
guests mobility in different MOFs have already confirmed the
essential role of the framework flexibility in the molecular
transport.8−13 Hence, characterization and control of the
structural dynamics in MOFs is key for the rational design of
new materials and the search for potential applications of the
existing ones.
There are several strategies to control the structural dynamics
in MOFs, including synthetic modification of the linkers or the
frameworks itself,14,15 temperature regulation, and finally guests
inclusion.16 All three strategies are currently applied to control
the structural dynamics. However, if we are interested in
particular features of already available systems only the last two
options are in the focus. Among the last two, guest introduction
offers more options in controlling the internal dynamics by
varying either the chemical nature of the guest or the guest
loading.
There are a number of investigations of guest-mediated
internal dynamics in MOFs and related materials.16−20 It was
shown that the chemical nature of the guest and the guest
loading could influence the linker rotational dynamics in
different ways. For example, it was shown for the ordered
porous molecular crystal with phenylenes as the mobile
Received: April 6, 2017
Revised: May 4, 2017
Published: May 5, 2017

© XXXX American Chemical Society A DOI: 10.1021/acs.jpcc.7b03259

J. Phys. Chem. C XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry C
fragments that the exposure of the material to a relatively low
quantity of I2 vapor decreased the rotation rate by 104 times.18
In the case of ZIF-8 (see Figure 1a) the linker’s mobility is
Figure 1. (a) ZIF-8 framework pores are connected by very narrow
windows (∼3.4 Å) composed by 2-methylimidazolate linkers that
normally lie in the window plane, almost closing the window. (b)
Pores of MIL-53 (Al) represent 1D channels composed by
terephthalate linkers orthogonal to the channels cross section. (c)
Pores of UiO-66(Zr) are connected by windows composed by
terephthalate linkers with the phenylene fragment partially turned out
of the windows plane. (d) Plane of the phenylene fragment in UiO-
66(Zr) exhibits relatively slow 2-site 180° flips and much faster local
restricted librations about the C2 symmetry axis.
B DOI: 10.1021/acs.jpcc.7b03259
Article
altered notably only when the guest occupies the window
between the pores, resulting in the change of the linker
librational dynamics in a step-like manner.21 A different
example is MIL-53(Al) (see Figure 1b), where the strong
effect of xylene guest on the rotation of the phenylene fragment
of terephthalate linker was observed only after saturation with
guest molecules.20
Further systematic studies are needed to clarify the general
regularities of the effect of the guest molecules on the rotational
motion of the MOFs linkers. The study of the effect of
progressive guest loading could be of particular interest.
The framework of UiO-66(Zr) consists of tetrahedral- and
octahedral-type cages of 8 and 11 Å diameter, interconnected
by windows, with dimensions similar to those in ZIF-8 (see
Figure 1a and 1c). However, since the phenylene fragments of
terephthalate linkers that form these windows are turned out of
the windows plane (like in MIL-53(Al), see Figure 1b and 1c)
the aperture is larger, about 5−7 Å.22 Such topology allows
UiO-66(Zr) to show remarkable adsorption/separation proper-
ties8,23 and the ability to host very large molecules like xylenes
or certain drugs (caffeine, ibuprofen).15,24 In fact, the
phenylene fragments in UiO-66(Zr) are remarkably mobile,15,25
capable to perform 180° 2-site flips (π-flips) around its C2
symmetry axis (Figure 1d). Additionally, during such rotations
the phenylene rings are crossing the window plane, shrinking its
effective aperture to a great extent. If fast enough, this process
could effectively control the migration of the guests within the
framework. In this regard, the UiO-66(Zr) could be considered
as a convenient model to study the effects of controllable guest
adsorption on the structural mobility in MOFs.
As a guest molecule, benzene appears to be a good model
candidate as it is relatively large with a size comparable to the
window’s aperture. It is the simplest aromatic compound
capable of having π−π interactions with the aromatic ring of the
phenylene fragment of the terephthalate linker.
In the present work we investigate the dynamics of the UiO-
66(Zr) phenylene fragments in the presence of benzene with
solid-state 2H NMR in a broad range of characteristic
times.17,18,26,27 The low natural abundance of the 2H isotope
requires substitution of protium for deuterium in phenylene
fragments. This does not affect the torsional dynamics of the
phenylenes, because the electronic structure of the linker or its
effective size is not notably changed.
We report on the experimental observation of the slow and
fast dynamical modes of the UiO-66(Zr) framework affected by
benzene guest with different loading. The slow rotational
modes are probed by the line shape analysis of the 2H NMR
spectrum. The fast libration modes are investigated by analysis
of the 2H NMR spin−lattice relaxation time.
2. EXPERIMENTAL SECTION
2.1. Materials. The synthesis and activation of deuterated
UiO-66(Zr) was performed as reported earlier,22 with
deuterated terephthalic acid as a reactant.
2.2. 2H NMR Experiment. 2H NMR experiments were
performed at the Larmor frequency ω0/2π = 61.424 MHz on a
Bruker Avance-400 spectrometer using a high-power probe
with a 5 mm horizontal solenoid coil. All 2H NMR spectra were
obtained by a Fourier transform of a quadrature-detected and
phase-cycled quadrupole echo after two phase-alternating 90°
pulses in the pulse sequence (90°x − τ − 90°y − τ − acquisition
− t), where τ = 20 μs and t is a repetition time of the sequence
during accumulation of the NMR signal.28 The duration of the
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π/2 pulse was 1.6 μs. Spectra were typically obtained with 32−
1000 scans with a repetition time ranging from 1 to 5 s.
Inversion−recovery experiments for measurements of spin−
lattice relaxation times (T1) were carried out using the pulse
sequence
180°x − tv − 90°x − τ − 90° y − τ − acquisition − t
(1)
where tv was the variable delay between the 180° and the 90°
pulses. The repetition time t was always longer than 5-fold of
the obtained relaxation time T1.
The temperature of the samples was controlled with a flow of
nitrogen gas by a variable-temperature unit BVT-3000 with a
precision of about 1 K. The sample was allowed to equilibrate
at least 15 min at the temperature of the experiment before the
NMR signal was acquired.
Modeling of spectra line shape and spin−lattice relaxation
was performed with a homemade FORTRAN program based
on the standard formalism.21,29−31
2.3. 2H NMR Sample Preparation. In order to prepare the
sample for the NMR experiments, 0.08 g of UiO-66(Zr)
powder was loaded in a 5 mm (o.d.) glass tube and connected
to a vacuum line. The sample was then heated up to 503 K and Figure 2. 2H NMR experimental (left) and simulated (right) spectra
kept at this temperature for 24 h under vacuum to a final of UiO-66(Zr) loaded with 12 molecules of benzene per unit cell. T
pressure above the sample of 10−2 Pa. After cooling back to (in Kelvin) is the measuring temperature, and kfm is the mean flipping
room temperature, the material was exposed to the previously rate constant.
degassed benzene vapors in the calibrated volume. The
adsorbate was condensed on the sample by cooling it at liquid
nitrogen temperature. The quantity of adsorbed benzene
corresponded to 12 molecules per unit cell (molecules/uc)
(∼1 molecules per UiO-66(Zr) cage) and 22 molecules/uc
(maximum loading capacity). After adsorption, the neck of the
tube was sealed off, while the lower part of the glass tube was
held in liquid nitrogen in order to prevent sample heating by
the flame. Finally, the sample was heated for 20 h at 373 K to
get a uniform distribution of molecules over the pore void of
the studied material.

3. RESULTS AND DISCUSSION

We first consider the motion occurring in the slower time
domain (10−3−10−7 s) for UiO-66(Zr) phenylene fragments by
monitoring the evolution with the temperature of the 2H NMR
line shape. The experimental results for evolution of the 2H
NMR line shape for different benzene loadings are given in
Figures 2 and 3.
In both cases the experimental results show the evolution of
the spectra line shapes from an axially symmetric Pake-powder
pattern with quadrupole constant Q0 = 176 ± 2 kHz and
asymmetry parameter η = 0, typical for almost immobile
Figure 3. 2H NMR experimental (left) and simulated (right) spectra
phenylenes (τC ≫ Q0−1 ≈ 5 × 10−6 s at T < 253 K), up to an of UiO-66(Zr) loaded with 22 molecules of benzene per unit cell. T
averaged anisotropic pattern with effective quadrupole constant (in Kelvin) is the measuring temperature, and kfm is the mean flipping
Q1 ≈ 80 ± 2 kHz and remarkably high asymmetry parameter η rate constant.
≈ 0.8 at T > 381 K. Such pattern is characteristics of the 2-site
180° flips (π-flips) of the plane of the phenylene ring about the
C2 symmetry axis in the fast motional regime (τC ≪ Q0−1 ≈ 5 ×
10−6 s). The decrease of the effective quadrupolar constant Q1 The progressive increase of the π-flips rate (characterized by
by 10% compared to the value expected for π-flips within the the flipping rate constant kfm) upon increasing the temperature
phenylene geometry is indicative of the presence of additional is reflected in increasing intensity of the central part of the
fast librations of the plane of the phenylene ring about the same spectrum. This simple observation can be used to estimate the
symmetry axis.25,32 guest’s influence on the phenylene dynamics. Figure 4 shows
Qualitatively the observed mobility is fully consistent with that an increase of the loading of benzene in the MOF pores
the previously reported dynamics in the guest-free UiO- results in a notable decrease of the phenylene fragment flipping
66(Zr).25 rate compared to the guest-free case under similar conditions.
C DOI: 10.1021/acs.jpcc.7b03259
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comparison of the phenylene dynamics for different loadings of

benzene and to quantify their hindering we can consider only
the mean flipping rate constant kfm. For instance, at 315 K
(Figure 4), the loading of 12 molecules/uc results in a decrease
of the flipping rate kfm by 11 times and the saturation of the
MOF pores with 22 molecules/uc slows down the rotation
additionally by 4 times, i.e., we observe indeed a progressive
and notable dependence of the flipping rate constant kfm on the
concentration of the loaded benzene. More details of the effect
of benzene loading on the phenylene flipping rate are shown in
Figure 5.
Figure 4. Effect of benzene loading on the phenylene fragment line
shape and the rate of its π-flips at 315 K. Unloaded guest-free UiO-
66(Zr) (a); benzene loading of 12 (b) and 22 molecules/uc (c).
Corresponding rate constants kfm (in Hz units) are shown above each
spectrum.

Similarly to the guest-free case, the motional model used to

fit the experimental patterns includes two motions of the
phenylene fragment about the C2 axis: the π-flips and the local
librations restricted within a sector 2φlib (see Figure 1d). The
librational motion characterized by the rate constant klib is
assumed to be very fast (klib ≫ Q0), and thus, its effect on the
line shape is parametrized only by the libration angle φlib. In
contrast, the π-flips have a fixed geometry of the motion but
somewhat more complex behavior of the rate factor: at each
temperature the π-flips are characterized by a distribution of the
flipping rate constant k.25,33 This distribution in the flipping
rates was accounted for by the presence of the defects in the Figure 5. Arrhenius plots for the mean rate constants kfm of π-flipping
UiO-66(Zr) framework, namely, by the absence of each 1/12 of motion of UiO-66(Zr). Guest-free material (data of ref 25) (○).
the carboxylic linkers at each Zr cluster.22,34 As a result, at a Material loaded with benzene: 12 (□) and 22 molecules/uc (Δ).
given temperature the π-flips are defined by the mean flipping
rate constant kfm and the distribution width for the rate Figure 5 clearly shows that in the presence of benzene the
constants σ. Our recent investigation of the guest-free flipping motion is slowing down with increasing benzene
material25 showed that a log-normal33 distribution for the loading. Arrhenius plots give the following parameters for the
rate constants was an appropriate model for description of the rate constants kfm: E12 = 38.5 ± 1.5 kJ mol−1 and k012 = (2 ± 1)
π-flipping motion. × 1012 Hz for phenylene π-flips with benzene loading of 12
The simulated patterns presented in Figures 2 and 3 show molecules/uc; E22 = 48.0 ± 1.5 kJ mol−1 and k022 = (6 ± 3) ×
that such model fits very well with UiO-66(Zr) loaded with 1012 Hz for the flips with benzene loading of 22 molecules/uc.
benzene guests as well. The main fitting results are given in For guest-free material the following parameters were found
Table 1. earlier in ref 25; E = 30 ± 2 kJ mol−1 and k0 = (0.5 ± 0.8) ×
Let us first consider π-flips. Similar to the guest-free 1012 s−1. A comparison of these parameters shows that the main
material25 the rate constant distribution width σ is equal to 5. effect of increasing benzene loading consists in a slow down of
This is expected as it is mainly related to the inhomogeneity the rotation rate and an increase of the activation energy for
inside the framework itself and should be identical for the phenylene π-flips. The pre-exponential factor does not change
material prepared under exactly the same conditions. For a strongly.
We introduce the pore occupancy factor α = n/Nmax, where n
Table 1. Effect of Different Benzene Loading on the Flipping is the actual loading and Nmax is the maximum loading for a
Rate Constant kfm and the Libration Angle Amplitude φlib given molecular species. Then we can compare the guest
for Phenylene Fragments of UiO-66(Zr) loading dependence of the rotation barrier for different systems.
In the present case the dependence is almost linear (see Figure
12 C6H6 molecules/uc 22 C6H6 molecules/uc 6a). This is in fact not a trivial observation, as for the recently
T, K kfm × 10−3, Hz φlib kfm × 10−3, Hz φlib studied MIL-53(Al) filled with xylene20 the dependence is
253 8 <5° 1 <5° almost step-like (see Figure 6b), i.e., a notable change in the
273 50 <5° 5 <5° activation barrier occurs only when the pores are fully saturated
298 150 <5° 15 <5° with the xylene guest.
315 300 10° 70 10° Thus, the UiO-66(Zr) MOF offers a framework topology
337 800 12° 300 12° with an example of an almost linear relationship between the
359 2500 15° 650 15° activation barrier of the phenylene fragment rotation and the
381 5400 17° 2000 17° benzene−guest loading: the more benzene loaded the higher
the activation barrier for phenylene π-flips.
a
The estimated errors are ±10% for kfm and ±10% for φlib (for T ≥ We further performed a more detailed analysis of the fast
315 K). σ ≈ 5 in both cases. librational modes. As mentioned above (see Table 1) the
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Figure 6. Dependence of the rotation barrier on the occupancy factor

α for (a) UiO-66(Zr) loaded with benzene (□) and (b) MIL-53(Al)
loaded with p-xylene (○). Data for MIL-53(Al) are adopted from ref
20.
Figure 7. Evolution of 2H NMR line shape of phenylene fragments of
geometry of the librations remains almost unchanged compared UiO-66(Zr) framework in dependence of the recovery time tv in
to the guest-free case. The amplitude of these restricted inversion−recovery pulse sequence (1) at 359 K. (a) Experimental line
librations given by the libration angle φlib progressively shape for UiO-66 with benzene loading of 12 molecules/uc. (b)
increases up to 17° at 380 K. The observed progression is in Simulation of the line shape implying phenylene reorientation by π-
agreement with the harmonic nature of the librational potential flips with kfm = 2.5 × 106 Hz. (c) Simulation of the line shape implying
as was discussed in detail for the guest-free ZIF-8 MOF.21 phenylene reorientation by π-flips with kfm = 2.5 × 106 Hz and
librations with klib = 3 × 1010 Hz and φlib = 15°.
Unfortunately, analysis of 2H NMR line shape does not provide
information about the rate of the librational motion.
In order to get information about the rates of the phenylene
librations we further analyzed the spin−lattice relaxation T1.
Analysis of the anisotropy of the T1 relaxation allows us to
define both the mechanism and the rate of anisotropic
motions.35,36 2H NMR patterns of phenylene fragments for
partially relaxed spectra were simulated. (Approaches used to
perform simulations of the partially relaxed spectra are provided
in the SI.) In these simulations, the rate constant kfm and
geometries of both motions are known from line shape analysis;
the recovery time tv is taken from the experiment.
Two models were tested for simulation of partially relaxed
spectra. In the first model only the π-flips were taken into
account. The second model was comprised of both rotational
by π-flips and librational motions.
The tv dependences of the 2H NMR line shape of
experimental and simulated spectra are presented in Figure 7.
As can be seen from Figure 7b, the motional model, where only
the π-flips are taken into account, does not provide a
correspondence of simulated partially relaxed spectra to the
experimental ones. T1 of simulated spectra is about 3 times
Figure 8. Evolution of 2H NMR line shape of phenylene fragments of
larger compared to experimental ones. UiO-66 framework in dependence of the recovery time tv at 359 K. (a)
Within a frame of the second model, where both π-flips and Experimental line shape for UiO-66 with 22 molecules/uc of benzene
librations with the rate constant klib are taken into account, a loading. (b) Simulation of the line shape implying phenylene
satisfactory agreement of experimental and simulated partially reorientation by π-flips with kfm = 6.5 × 105 Hz. (c) Simulation of
relaxed spectra is well reached at klib = 3 × 1010 Hz (see Figure the line shape implying phenylene reorientation by π-flips with kfm =
7c). 6.5 × 105 Hz and librations with klib = 3 × 1010 Hz and φlib = 15°.
Analysis of the evolution of the 2H NMR line shape of
partially relaxed spectra with recovery time tv for the sample to confirm the existence of fast librational motion, identified
with a higher loading of benzene (Figure 8) shows that unlike earlier by analysis of the 2H NMR line shape,25 and allows us to
the π-flips motion (rate constants kfm), the libration motion estimate its rate constants for phenylene fragments in UiO-
(including klib and φlib parameters) is not sensitive to the guest 66(Zr).
loading (cf. Figures 7c and 8c). At this point it is essential to discuss the limitations of this
The results presented above show that analysis of partially approach. Any dynamical mode in 2H NMR should have its
relaxed spectra in the inversion−recovery experiment allows us strongest impact on T1 relaxation at k ≈ ω0/2π (resonance
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frequency of the 2H, ω0/2π ≈ 6 × 107 Hz in our case). The
question arises about the maximum distinguishable klib. The
answer lies within careful analysis of the anisotropic T1
relaxation. In solids T1 always depends on the observation
polar angles (θ, φ). Thus, in the general case, each position in
the spectrum could have multiple contributions arising from
different sets of (θ, φ) resonating at the same frequency. Thus,
a multiexponential relaxation can be expected. Consequently,
for a powder spectrum a fully consistent approach is to
calculate the line shape anisotropy for each recovery time tν, as
it was performed above. This approach fails when we analyze
the T1 dependence of a certain parameter. Fortunately, at
positions corresponding to θ = 90° (the “horns”) the
dependence of the second polar angle φ vanishes, which
opens up the possibility to analyze individual T1 behavior for
anisotropic line shapes in a simple fashion.
The current case of UiO-66(Zr) presents an additional
challenge: because of the intrinsic structural defects the rate
constant k of π-flips is characterized by a rather broad
distribution width σ (σ ≈ 5, covers 2−3 order of magnitude).
Consequently, at each spectral position the T1 relaxation would
have different contributions governed by its individual flipping
rate. However, we can still try to use the standard procedure
(i.e., plotting the intensity I at a given position in the spectrum
against the recovery time tν) to estimate an “effective” T̃ 1 and
analyze its dependence of the librations rate klib.
We computed for different klib values the set of partially
recovered spectra with tν taken from the actual experiment and
analyzed the arising intensity I = I(tν) at spectral position
corresponding to θ = 90° (marked by arrows at Figure 8) by
the usual inversion−recovery experiments equation I = I0[1−2
exp(−t/T̃ 1)]. The T̃ 1 (klib) dependence is shown in Figure 9.
Figure 9. Calculated dependence of the effective T̃ 1 on the libration
rate constant klib. T1 was obtained by analyzing the partially relaxed
spectra which were simulated under the conditions kfm = 2.5 × 106 Hz,
σ ≈ 5. Dashed line corresponds to the T1 relaxation calculated at the
same spectral position if only π-flips were considered, klib = 0.
Calculations were performed for the sample with a benzene loading of
12 molecules/uc.
It follows from Figure 9 that despite the large error bars
arising due to the oversimplified data treatment, T̃ 1 is actually
sensitive to the klib change compared to the π-flips-only model,
at least up to 1012 Hz. Additionally, our simulation tests have
also evidenced that within the current model the T1 anisotropy
allows one to differentiate π-flips with rates up to ∼1011 Hz.
F DOI: 10.1021/acs.jpcc.7b03259
Article
Thus, apparently the range of 106 < klib < 1011 Hz defines the
limits of the quantitative 2H NMR T1 relaxation analysis in the
system with 2 motional modes in play. Shifting to higher
magnetic field should shift the klib limit to higher rates. This
approach to characterization of fast motions can be applied in
addition to other recently reported methods of probing ultrafast
structural dynamics in MOFs.37,38
Finally, it should be noted that the observed fast librations
with klib ≈ 1010 Hz and their remarkable amplitude (±15° at
359 K) could affect notably the mobility of any guest molecules
with size comparable to the UiO-66(Zr) cavity windows and
therefore have to be taken into account when such cases are
investigated, especially by computational methods.
4. CONCLUSION
We applied solid-state 2H NMR spectroscopy to probe
experimentally the slow and fast dynamical modes of the
UiO-66(Zr) framework mediated by benzene guests. The
modes are represented by the 2-site π-flips and the restricted
librations. We have shown that in the presence of benzene the
activation barrier for the slower large amplitude π-flips motion
strongly depends on the benzene loading in an almost linear
fashion. Such observation is surprisingly unique among other
MOFs with mobile linkers (like MIL-53 or MOF-5). The fast
librational modes occur on a ∼1010 Hz scale and do not have a
notable dependence of the guest loading. It has been
established that the anisotropic T1 of the 2H NMR powder
pattern for phenylene fragments is especially sensitive to
librational motion when this motion is in a range of 108−1011
Hz. Within this range of libration frequencies, analysis of the
anisotropic spin−lattice (T1) relaxation allows quantitative
analysis of the rate of librational motion.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jpcc.7b03259.
Simulation of the partially recovered 2H NMR spectra
arising during T1 relaxation measurements and exper-
imental partially recovered 2H NMR spectra without
intensity normalization (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: kdi@catalysis.ru.
*E-mail: stepanov@catalysis.ru. Phone: +7 9529059559. Fax:
+7 383 330 8056.
ORCID
Daniil I. Kolokolov: 0000-0002-1434-095X
Alexander G. Stepanov: 0000-0003-2754-5273
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by Russian Academy of Sciences
within the framework of budget project No.0303-2016-0003 for
Boreskov Institute of Catalysis. It was supported by the
Deutsche Forschungsgemeinschaft (grant HA 1893/16).
J. Phys. Chem. C XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry C
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