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Article
pubs.acs.org/JPCC

Fast Interchange of Coordinated and Guest Dimethylformamide

2 Molecules in the Zinc(II) Lactate Terephthalate MetalOrganic
3 Framework
1

Marsel R. Gallyamov, Danil N. Dybtsev, Denis P. Pischur, Svetlana G. Kozlova, Nikolai K. Moroz,*
5 and Vladimir P. Fedin
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Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 630090 Novosibirsk, Russian
Federation
S Supporting Information
*

ABSTRACT: Mobility of N,N-dimethylformamide (dmf) molecules

in a homochiral metalorganic framework [Zn2(bdc)(S-lac) (dmf)]
dmf (bdc = 1,4-benzenedicarboxylate; S-lac = L-()-lactate) has
been studied using 13C, 1H, and 2H solid-state NMR and DSC
experiments. The compound exhibits a phase transition in the
vicinity of 240 K, associated with disordering of the dmf molecules.
In the high-temperature phase, the dmf molecules undergo intense
diusion accompanied by the exchange between the molecules
coordinated with Zn and guest molecules in the framework pores.
The activation energy of the molecular migration including exchange
between coordinated and guest molecules was estimated to be 37 kJ/
mol.

INTRODUCTION
The postsynthetic modication approach is now widely
recognized as a versatile tool to tune the composition and
structure and to augment the functionalities of porous metal
organic coordination polymers.1,2 Metalorganic frameworks
with nonbridging (terminal) thus labile ligands are valuable
targets for such modication through the ligand exchange,
especially when direct synthetic methods fail to achieve
comparable results.3 A number of terminal ligand exchange
reactions successfully demonstrated an introduction of reactive
or catalytic centers, a modulation of sorption properties, proton
conductivity, as well as a pore modication for metal
nanoparticle stabilization.49 The exchange necessarily takes
place between the coordination environment of the metal
center (inner sphere ligands) and guest solvent molecules
(outer sphere ligands). The systematic study of molecular
substitution between the coordinated and guest solvent
molecules is therefore fundamentally important in the development of the postsynthetic modication methodology. Also, a
catalytic activation of various molecules by porous metal
organic coordination frameworks through the coordination to
the metal cations encourages the investigation of ligand
exchange mechanisms.
In the present investigation we describe the solid-state NMR
study of the ligand exchange between the coordinated and
guest N,N-dimethylformamide (dmf) molecules in a homochiral [Zn2(bdc)(S-lac) (dmf)]dmf porous framework. Dimethylformamide is one of the most popular solvents for the
synthesis of porous metalorganic frameworks. The exchange
XXXX American Chemical Society

of inner- and outer-sphere dmf ligands in molecular complexes

in solutions was extensively studied in the 1980s and
1990s.1014 On the contrary, to the best of our knowledge, a
similar process in crystalline metalorganic frameworks has not
yet received any comparable attention, and our study hopefully
provides an important insight on a way to a better
understanding and control of the ligand substitution in solidstate materials in general.

EXPERIMENTAL SECTION

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Synthesis. The powdered sample of [Zn2(bdc)(S-lac)

(dmf)]dmf (1) was obtained and characterized according to
procedures reported previously.15 The sample 1D with the
deuterated dmf-d7 molecules was obtained by treating 1 in the
dmf-d7 solution at 85 C for 20 h.
NMR Experiments. 13C MAS NMR spectra were obtained
at room temperature and frequency of 125.76 MHz on a Bruker
Avance III 500 MHz narrow-bore magnet spectrometer with a
4 mm HX probe at sample rotation frequency of 10 kHz and
relaxation delay of 100 s. The 90 pulse with length of 4 s was
used. The SPINAL-64 (small phase incremental alternation
with 64 steps) sequence at power of 84.3 W was used for Hdecoupling. The spectra were externally referenced to TMS. 2H
NMR spectra dictated by the quadrupole interactions of
deuterons in 1D were registered at a frequency of 76.77 MHz
Received: March 24, 2015
Revised: October 15, 2015

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in the 200300 K temperature range using a 5 mm solenoid

probe and a solid-echo pulse sequence with the echo delay of
12 s. The wide-line 1H NMR spectra resulting from the
magnetic dipoledipole proton interactions were recorded in
the form of the rst derivative of the absorption line in a low
magnetic eld (0.587 T) and 120300 K temperature range by
sweeping the frequency in the neighborhood of the Larmor
frequency using a homemade NMR spectrometer with signal
accumulation.
DSC Measurements. DSC measurement were carried out
with a dierential scanning calorimeter NETZSCH DSC 204
F1 Phoenix by the heat ow method at a heating rate of 9 K/
min in 10 mL/min Ar ow. The powdered samples with mass
of 1525 mg, placed in opened aluminum crucibles, were used.
The sensitivity and temperature scale were calibrated by
melting of standard samples (C6H12, Hg, In). Netzsch Proteus
Analysis software was applied to determine DSC peak areas and
transition temperatures.

temperature behavior of the dipoledipole interactions of

protons of dmf-h7 as well as quadrupole interactions of
deuterons of dmf-d7, both of which are essentially responsive to
molecular mobility, is required to understand the nature of this
exchange.
1
H NMR. The room-temperature static 1H NMR spectra for
1 and 1D are plotted in Figure 2. The integralintensity ratio

RESULTS AND DISCUSSION

Coordinated and Guest dmf Molecules. According to
the low-temperature (100 K) X-ray data15 of the metalorganic
framework [Zn2(bdc)(S-lac) (dmf)], 5-coordinated Zn2+ ions,
having a trigonal-bipyramidal coordination environment, are
linked together by S-lac and bdc anions. The pore system is
composed of intersected channels of ca. 5 diameter, lled
with both coordinated and guest dmf molecules with
interatomic ZnO distances 2.102 and 5.288 , respectively,
and the OO distance between those dmfs is 4.211 (see the
Supporting Information, section SI 1, Figure S1). The dmf
molecules seem to play some structure-supporting role since
heating of 1 at 100 C in vacuum results in a gradual solvent
molecule release and partial deterioration of the crystallinity of
the compound.
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C NMR. The 13C MAS NMR spectra obtained at ambient
temperatures (Figure 1) give no way to recognize two types of

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Figure 2. Room-temperature wide-line 1H NMR spectra normalized

on the same sample mass for 1 and 1D. The spectral component
assigned to the dmf molecules is shown dashed.

for these spectra I1/I1D = 2.68(5) is in close proximity to the

value of 2.75 expected for total dmf-d7 dmf-h7 substitution
when the number of protons per formula 8(bdc and S-lac) + 2
7(dmf) = 22 decreases to 8, while the substitution of only
guest dmf molecules would give I1/I1D = 1.47. Then, the
spectrum of 1D may be considered as the spectral component
belonging to bdc and S-lac species. Ignoring, for a rst
approximation, a distinction in intermolecular dipolar coupling
in both samples, the dierence spectrum of 1 and 1D may be
assigned to the dmf molecules in 1.
The temperature evolution of the dmf 1H NMR spectra
obtained with the above procedure is illustrated in Figure 3a.
The temperature increase from 120 to 230 K results in a
gradual narrowing of the spectra, apparently, due to molecular
librations. A sharp spectrum narrowing in the interval of 240
300 K is indicative of an eective suppression of the dipolar
coupling as a result of development of the rotational or/and
translational diusion. The formation of a single narrow
resonance line in this range suggests that both guest and
coordinated dmf molecules are involved in the molecular
motion. That is possible if a fast (in the NMR time scale)
solvent exchange takes place. From the temperature dependence of the NMR line width (Figure 3b), the activation energy
of the molecular motion, Ea, was estimated to be 37(3) kJ/mol
(see the Supporting Information, section SI 4). This value must
be considered as an upper limit of the ligand exchange
activation energy since the molecular mobility includes
migrations between dierent structural positions in the
framework pores as well as the exchange between the
coordinated and guest molecules. The characteristic frequencies
of the ligand exchange exceed 104 s1 above 250 K. Notice that
the 1H NMR spectra of 1D, i.e., the spectra of the bdc and S-lac
linkers, remain practically unchanged at all temperatures.
DSC Measurements. The character of the above-described
spectrum changes suggests a phase transition in the vicinity of
240 K. The phase transitions associated with an orientational
disordering of polar molecules were found in a variety of
porous MOFs.1620 In order to determine the actual existence

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Figure 1. Carbonyl and methyl fragments of the H-decoupled C

MAS NMR spectrum (96 transients) for 1 at room temperature (for
the complete spectrum see the Supporting Information, section SI 2).

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the dmf molecules: any splitting of the resonance lines,

associated with chemical inequality of the coordinated and
guest dmf molecules, is not observed in any of the carbonyl
(163.3 ppm) and methyl (30.8; 36.7 ppm) resonances. The
half-widths of these lines are about 100 Hz. That means that
the expected splitting is less than 0.5 ppm which seems rather
surprising, particularly for carbonyl groups, half of which have
short ZnO contacts. On the other hand, this fact may be
associated with the existence of the exchange between the
coordinated and guest molecules, averaging chemical shifts over
all dmf molecules. Therefore, the investigation of the
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spectra are presented in the Supporting Information, section SI

5). With the exception of very low temperatures, the spectrum
of the stationary dmf-d7 molecule with rapidly reorienting CD3
groups is expected as a superposition of two doublet lines with
the integral intensity ratio of 6:1 and diered widely from
quadrupole splitting, corresponding to the movable methyl
deuterons and xed formyl deuterons, respectively.21 The
spectra of this sort are observed in the low-temperature phase
of 1D up to 230 K (Figure 5a). From spectrum simulations, the

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Figure 3. (a) Wide-line 1H NMR absorption spectra of the dmf

molecules in 1 at various temperatures (see also the Supporting
Information, section SI 3, Figure S3). (b) Temperature dependence of
the spectrum rms width () and t to experimental data, calculated
for Ea = 37 kJ/mol and preexponential factor of 8 1011 s1 (solid
line). A related dependence for bdc and S-lac species (sample 1D) is
added for comparison ().
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of a phase transition, thermodynamic properties of the title

compound were investigated by DSC in the temperature range
from 213 to 285 K (Figure 4). The thermal anomaly with the

Figure 5. Experimental () and simulated (solid lines) 2H NMR

spectra for 1D at 220 (a) and 300 (b) K. The dashed lines are the
weighted contributions of dierent deuteron groups. Inset: Temperature dependence of the spectrum rms width in the high-temperature
phase; the relative dependence calculated for the activation parameters
determined from the 1H NMR measurements is shown solid.
Figure 4. Temperature dependence of the DSC signal for [Zn2(bdc)(S-lac) (dmf)]dmf.
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quadrupole coupling constants at 220 K were estimated to be

46 and 138 kHz for the methyl and formyl deuterons,
respectively, which are in reasonable agreement with the earlier
dmf-d7 NMR study (a decrease close to 10% of both constants
in our case may be assigned to the above-mentioned molecular
librations).21 The development of molecular motion in the
high-temperature phase changes the spectrum shape remarkably, and above 280 K, the spectrum takes the form indicative
of substantial averaging of the quadrupolar couplings (Figure
5b). The spectrum transformation, as a function of the dmfjump frequency with interaction parameters estimated for the
low-temperature phase, may in principle be described basing on
known stochastic approaches. 22 However, the lack of
information about dmf orientations in the disordered hightemperature phase presents obstacles to such a description, and
we interpreted the spectrum ne structure observed above 280
K in terms of quadrupolar couplings averaged by the molecular
motion. Under diusion in the low-symmetry crystal, the
eective, time-averaged quadrupole coupling tensors of the two
methyl groups of the planar (or dynamically planar) dmf-d7
molecule may become nonequivalent if the set of the

maximum position at 253.0 K and Tonset = 248.6 K was

observed. The thermal eect was estimated to be 5.3(5) J/g
corresponding to an entropy increase S = 9.511.5 J K1
mol1. This entropy growth could be assigned to the increase of
the number of the guest dmf positions by exp(S/R) = 34
times. The observed anomaly is oset to high temperatures by
several degrees as compared with that in the NMR measurements. This shift may be explained by the dierences in the
operating conditions of the static NMR and dynamic DSC
measurements rather than by the inaccuracy in the NMR
temperature scale, not exceeding by our estimates 0.1 K in the
considered temperature region. It could be assumed that the
intense diusive mobility of the guest dmf molecules, including
their exchange with the dmf ligands, is an inherent characteristic of the disordered high-temperature phase only.
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H NMR. Some of the supporting evidence for fast exchange
between coordinated and guest molecules comes from analysis
of the static 2H NMR spectra for 1D (the 2H MAS NMR
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orientation quadrupole coupling tensors in all sites visited

during the motion for one group is distinguished from that for
the other group. If this is the case, the expected spectrum will
consist of three doublet lines with the intensity ratio 3:3:1. In
the case of the exchange between the guest and coordinated
molecules, these lines must be common for both types of
molecules. With this in mind, we attempted to describe the
high-temperature spectra in the framework of the fast-motion
approach as a superposition of three components corresponding to the dierent motion-averaged quadrupole tensors. This
procedure implies the consideration of three independent
parameters for each spectral component: quadrupole coupling
constant - q; asymmetry parameter - ; a Lorentzian broadening
of spectral lines, associated with uctuations of the quadrupole
coupling in the course of the molecular jumps, - . The number
of tting parameters may be reduced to 5 assuming that (i) the
values are the same for all resonance lines and that (ii) the
motion-induced transformation of the quadrupole tensor of the
formyl deuteron is similar to that for the methyl deuterons
trans to the formyl deuteron since the directions of the main
axes of both axial tensors in the starting (motionless) dmf
positions are close to parallel. In other words, we supposed
that, for these tensors, the values are the same and the ratio of
the quadrupole coupling constants is identical to that in the
low-temperature phase. As could be seen from Figure 5b, the
solvent exchange model with the above simplications allowed
us to obtain a satisfactory t to the experimental data. From the
spectra simulation, the following parameters of the eective
interactions were obtained: q = 35.8 kHz, = 0.79 for the
formyl deuteron; q = 11.9 kHz, = 0.79 and q = 6.4 kHz, =
0.65 for the methyl deuterons in trans- and cis-position to the
formyl deuteron, respectively. In the high-temperature phase,
the temperature behavior of the widths of 2H spectra
considered as a whole is similar to that observed for the 1H
NMR spectra and may be assigned to the same activation
energy of the molecular motion (inset in Figure 5).
The mobility of outer-sphere molecules and the metal
coordination sphere susceptibility toward the ligand exchange
in the solid state are generally considered to be lower than
those in solution. On the other hand, the metalorganic
framework structure may stabilize unusual coordination
numbers and polyhedrons, such as the trigonal bipyramidal
environment of the Zn(II) cation in our case, supposedly
susceptible to a local ligand rearrangements. Also, the guestaccessible space in the channels of [Zn2(bdc)(S-lac) (dmf)] is
more capacious than the average volume of the dmf molecule,23
which may suggest an ability of guest molecules to displace
from their equilibrium positions and enter into the ligand
substitution reaction. As a result, the estimated activation
energy for the solvent dmf exchange in 1 (Ea < 37 kJ/mol) is
even lower than the typical value for the dmf ligand substitution
in solutions, such as Ea = 54.3 kJ/mol for [Zn(Me6tren)dmf]2+
(Me6tren = 2,2,2-tris(N,N-dimethylamino)triethylamine) featuring the same 5-coordinated Zn(II) cation.10 The mechanism
of the dmf exchange in 1 remains uncertain and may involve
the temporary association of a guest dmf molecule to the Zn2+
coordination sphere (the associative mechanism) as well as
temporary detachment of the dmf ligand into the framework
pore (the dissociative mechanism). These mechanisms imply
the changes of coordination number of metal cations from 5 to
6 or 4 in the transition states, respectively, which are both very
common for Zn2+ coordination chemistry. It is quite likely,
however, that the actual solvent exchange process combines

both these extreme mechanisms and proceeds through

simultaneous shortening of Zndmf (guest) and elongation
of Zndmf (ligand) distances resulting in an intermediate 4 +
2 coordination of Zn2+ cation. Noteworthy, the abovementioned exchange is registered for the disordered hightemperature phase. Whether this disorder state is a prerequisite
for such facile solvent exchange or not remains an open
question.

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CONCLUSION
The mobility of solvent N,N-dimethylformamide molecules in
the metalorganic framework [Zn2(bdc)(S-lac) (dmf)]dmf
(bdc = 1,4-benzenedicarboxylate; S-lac = S-lactate) has been
studied with 13C, 1H, and 2H NMR as well as DSC methods.
The compound demonstrates a phase transition around T =
240 K, associated with the orderdisorder state of the dmf
molecules. Above this temperature the solvent molecules
exhibit intensive diusion movement, accompanied by the
fast exchange between the coordinated and guest dmf
molecules in the framework pores. By our estimates, the
characteristic frequencies of the solvent interchange exceed 104
s1 above 250 K. The activation energy of the molecular
migration including the diusion and interchange processes was
estimated to be 37 kJ/mol.

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ASSOCIATED CONTENT

* Supporting Information

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The Supporting Information is available free of charge on the

ACS Publications website at DOI: 10.1021/acs.jpcc.5b06349.
Coordinated and guest dmf molecules in [Zn2(bdc)(Slac) (dmf)]dmf (SI 1); 13C MAS NMR for [Zn2(bdc)(Slac) (dmf)]dmf; wide-line 1H NMR spectra for the
samples 1 and 1D; activation parameters for the dmf
migration; 2H MAS NMR spectra of the dmf-d7
molecules in the sample 1D (PDF)

AUTHOR INFORMATION

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Corresponding Author

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*E-mail: moroz@niic.nsc.ru.

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Notes

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The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
DND and VPF acknowledge the grant of the Government of
the Russian Federation (PN 14.Z50.31.0006, leading scientist
M. Schroder).

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