Introducing a longer versus shorter acylhydrazone linker to a metal-organic framework: Parallel mechanochemical approach, nonisoreticular structures, and diverse properties

Article abstract of DOI:10.1021/acs.cgd.9b01031

A 20-?-long diacylhydrazone linker was used for the first time as a building block for the construction of a metal-organic framework (MOF). The terephthalaldehyde di-isonicotinoylhydrazone (tdih) is considerably longer than its 11-?-long monoacylhydrazone

Full text of DOI:10.1021/acs.cgd.9b01031

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Article
Introducing a longer versus shorter acylhydrazone linker
to a metal-organic framework: parallel mechanochemical
approach, non-isoreticular structures and diverse properties
Kornel Roztocki, Monika Szufla, Maciej Hodorowicz, Irena Senkovska, Stefan Kaskel, and Dariusz Matoga
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.9b01031 • Publication Date (Web): 24 Oct 2019
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Introducing a longer versus shorter acylhydrazone linker to a
metal-organic framework: parallel mechanochemical approach,
non-isoreticular structures and diverse properties
Kornel Roztocki,[a] Monika Szufla,[a] Maciej Hodorowicz,[a] Irena Senkovska,[b] Stefan
Kaskel,[b] Dariusz Matoga[a]*
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[a]Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30-387 Kraków, Poland
[b]Department of Inorganic Chemistry, Technische Universität Dresden, Bergstrasse 66,
01062 Dresden, Germany
Abstract
A 20-Å-long diacylhydrazone linker was used for the first time as a building block for the
construction of a metal-organic framework (MOF). The terephthalaldehyde di-
isonicotinoylhydrazone (tdih) is considerably longer than its 11-Å-long mono-acylhydrazone
counterpart, 4-pyridinecarboxaldehyde isonicotinoylhydrazone (pcih), used so far as a MOF
linker. By utilizing the two ditopic hydrazone linkers providing linear connectivity, two non-
isoreticular cadmium-organic frameworks, {[Cd2(oba)2(hydrazone)2]}n (with oba = 4,4’-
oxybis(benzenedicarboxylate) co-linker) were obtained by solution and mechanochemical
methods. In spite of the same secondary building units, the frameworks differ in
dimensionality as well as exhibit various stability and adsorption behavior, that are compared
and discussed. The insights into structure-property relationships are provided by single-crystal
X-ray diffraction (SC-XRD), temperature-dependent powder XRD, thermogravimetric
analysis, CO2 (at 195 K), N2 (at 77 K) and H2O (at 298 K) gas adsorption measurements, as
well as quasi-equilibrated temperature-programmed desorption and adsorption (QE-TPDA).
The work opens possibilities to synthesize new functional materials based on the longer
linker.
Introduction
The considerable interest of academia and industry in the chemistry of metal-organic
frameworks (MOFs)1–3 is driven to a large extent by their well-ordered porosity connected
with structural flexibility and modularity.4,5 These features allow for tunability of MOF
properties beyond conventional solid-state materials, to address plethora of challenging
applications in the fields of drug delivery6,7, electronic devices,8–10 catalysis,11,12
photocatalysis,13 gas adsorption,14–17 water purification18 and others. Tuning of MOF
functionalities can be carried out through a careful selection of appropriate linker precursors
used for the assembly of extended networks. In particular, the first example of a systematic
change of pore size and polarity was demonstrated for an isoreticular series of MOFs based on
Zn4O nodes linked by linear dicarboxylates.19 This series included the prototypal MOF-5 with
terephthalate linkers and comprised other frameworks of the same primitive cubic topology
differing in linker lengths and side groups. This elegant isoreticular approach allowed to
identify the best candidate for methane storage and became a more common strategy
successfully realized in other MOF families. Naturally, the implementation of a given
synthetic strategy may vary in details but the preferable approaches reduce the use of energy
and solvents. In this regard, solvent-free mechanochemistry, relying on grinding of solid
substrates, has recently emerged as a powerful tool for the synthesis of MOFs.20
Following the synthetic challenge to build functional MOFs, we have recently been
exploring the chemistry of metal-organic frameworks based on mixed carboxylate and
acylhydrazone linkers, the latter bearing both hydrogen-bond donor and acceptor groups as
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well as showing coordination versatility towards a diverse range of metals.21–24 In 2016 we
reported the first mixed-linker MOFs based on an acylhydrazone and a dicarboxylate.25 Since
then several articles describing new frameworks from this family and their properties, have
been published. In particular, the carboxylate-acylhydrazone MOFs have been reported to
exhibit numerous interesting behaviors, such as flexibility,26 high mechanical and
hydrothermal stability,27,28 gas adsorption selectivity,25,26,28,29 structural diversity,29
multifunctional catalytic activity30 and sensing potential.31 However, all of the
aforementioned frameworks have been based on the same relatively short (~11 Å) 4-
pyridinecarboxaldehyde isonicotinoylhydrazone (pcih) linkers and different dicarboxylate co-
linkers. Therefore, this work was undertaken with the following motivation: (i) to construct
the first MOF with a longer acylhydrazone linker than pcih used so far, possibly by a solvent-
free method; (ii) to determine and compare its crystal structure and properties with the
analogous pcih-based material; (iii) to verify hypothesis of isoreticular expansion based on
acylhydrazone linkers.
Herein, we present two new cadmium metal-organic frameworks based on
acylhydrazone linkers providing linear connectivity: a shorter pcih or a longer
terephthalaldehyde di-isonicotinoylhydrazone (tdih), each with the same additional
dicarboxylate co-linker. In spite of the same secondary building units, the frameworks have
non-isoreticular structures with different dimensionalities. We present and compare various
alternative methods of synthesis of the two materials including deposition from solutions and
optimized grinding of solid reactants. Both Cd-MOFs exhibit adsorption behaviors that are
untypical of the so far known mixed-linker carboxylate-acylhydrazone MOFs, with CO2/N2
non-selectivity being the major difference. The adsorption properties towards CO2 (at 195 K)
and N2 (at 77 K) gases are discussed along with structural features of the frameworks.
Furthermore, by using of single-crystal X-ray diffraction (SC-XRD), temperature-dependent
powder XRD, thermogravimetric analysis and quasi-equilibrated temperature-programmed
desorption and adsorption (QE-TPDA) method, versatile types of the frameworks' stability are
also investigated and discussed. Our study is the first example of utilization of
terephthalaldehyde di-isonicotinoylhydrazone molecule as a MOF linker. This opens new
synthetic possibilities with other metals and/or co-linkers which may provide interesting
materials for a variety of applications.
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Results and Discussion
Parallel solvent-based and solvent-free syntheses
Two mixed-linker cadmium(II) metal-organic frameworks of various dimensionalities: 2D
{[Cd2(oba)2(pcih)2]∙3DMF}n (1) and 3D {[Cd2(oba)2(tdih)2]∙7H2O∙6DMF}n (2), based on 4,4’-
oxybis(benzenedicarboxylate)
(oba2-)
and
either
4-pyridinecarboxaldehyde
isonicotinoylhydrazone (pcih) or terephthalaldehyde di-isonicotinoylhydrazone (tdih) (Figure
1), were synthesized by parallel solvent-based and solvent-free methods. In the solvent-based
case, relatively high amounts of both organic solvent and energy (heating at 70 oC for approx.
4 days) were consumed to yield single crystals of compounds 1 and 2 suitable for X-ray
diffraction measurements. Alternatively, the two materials were prepared by the solvent-free
mechanochemical method, where solid reagents were ground together in a ball-mill in either a
one-pot or a two-step variant (Figure 1 and Figures S1-S4, Supplementary Information). The
latter approach meets the expectations of green chemistry, i.e. a reaction is fast and no organic
solvent is used. The purity of products 1 and 2 obtained by the two methods was confirmed by
elemental analysis, IR spectroscopy and powder X-ray diffraction (Table S1; Figures S2-S4,
Supplementary Information).
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Figure 1. (a) Linkers/linker precursors used for syntheses of compounds 1 and 2. H2oba: 4,4’-
oxybis(benzenedicarboxylic) acid; pcih: 4-pyridinecarboxaldehyde isonicotinoylhydrazone (in 1); tdih:
terephthalaldehyde di-isonicotinoylhydrazone (in 2). (b) Various synthetic approaches to compounds 1 and 2;
LAG: liquid-assisted grinding.
In the mechanochemical one-pot approach, CdO or Cd(OH)2, H2oba and pcih or tdih
were ground together in the 1:1:1 molar ratio with the addition of a small amount of DMF
(150 µL), and in case of the CdO substrate, with the addition of a catalytic amount of
NH4NO3 (4 wt%). In contrast, the two-step reaction which proceeds via an intermediate
coordination polymer of [Cd(µ-H2O)(oba)(H2O)]n (CCDC1476612),32 does not require
addition of the catalyst. Both products 1 and 2 are obtainable in the two-step variant from a
pre-assembled intermediate which is built of Cd2+ ions that are linked by the oba2-
dicarboxylates and aqua bridges into a 3D framework, wherein each metal centre has a labile
terminal aqua ligand. Analogous behavior was shown for example for archetypical UiO-66
and its NH2 analogue which were easily obtained in a gram-scale milling by utilization of pre-
assembled benzoate or methacrylate precursors.33
In our experiments, cadmium hydroxide was found as the preferable metal substrate.
Firstly, when it was used as the substrate for grinding then independently on the variant used
in the mechanochemical approach, no catalyst was required for the formation of 1 and 2 (see
Figure S2-S3, Supplementary Information and Materials and Method section). Secondly, in
case of the materials obtained from CdO, larger discrepancies were found in their elemental
analyses (Table S1, Supplementary Information), which may indicate the presence of
unreacted CdO as an impurity. The main factor responsible for reactivity is the chemical
character of Cd(OH)2 which is a stronger base than CdO and thus favours deprotonation of H-
2oba. Additionally, in order to get an insight into homogeneity as well as size and morphology
of crystals, scanning electron microscopy (SEM) analysis has been carried out for the samples
obtained in a ball mill from Cd(OH)2 (Figure S5, Supplementary Information). SEM images
of 1 and 2 confirm the homogeneity of the mechanochemically obtained materials which form
plate-shaped crystals of similar size and uniform morphology.
Crystal structures
Single
crystals
of
compounds
{[Cd2(oba)2(pcih)2]∙3DMF}n
(1)
and
{[Cd2(oba)2(tdih)2]∙7H2O∙6DMF}n (2) used for X-ray diffraction (XRD) were grown in a
DMF/H2O mixture (see Materials and Methods section). Despite using the same type of
building blocks for the construction of the two materials, i.e. the H2oba linker precursor and a
pyridyl-functionalized acylhydrazone building block of a linear connectivity (pcih or tdih
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differing in length), resulting products 1 and 2 do not form an isoreticular series. The MOFs
crystallize in monoclinic and triclinic crystal systems with the space groups P and C2/c,
1
respectively. As revealed by XRD experiments, the Cd2+ ions in both frameworks have
disordered pentagonal bipyramidal geometry where central ion is coordinated equatorially by
five oxygen atoms from three different dicarboxylate acids (oba2-) (Figure S6, Supplementary
Information). The coordination sphere is completed by axial N-pyridyl atoms from two
neutral N,N-donor linkers; terephthalaldehyde di-isonicotinoylhydrazone (tdih) and 4-
pyridinecarboxaldehyde isonicotinoylhydrazone (pcih), respectively for 1 and 2 (Figure 2,
Figure S6, Supplementary Information). In both materials the oba2- ligands and Cd2+ ions
form the [Cd2(COO)2] secondary building units (SBUs) with Cd-Cd distances of 3.836 Å (1)
and 3.868 Å (2) in each cluster. The oba2- carboxylates act as μ3-κ2κ2κ1 angular ligands
connecting SBU units into the [Cd2(oba)2]n double chains (1) and layers (2). The double
chains in 1 are further connected by the pcih ligands into the 2D framework of sql topology
(determined by ToposPro software).34 The adjacent layers in 1 interact via strong N-H···O
hydrogen bonds between NH group of the pcih acylhydrazone and carboxylate oxygen atom
[d(N9-H(N9)∙∙∙O47) = 2.85 Ȧ, angle = 171°] forming a two-dimensional pore structure
(Figure 2; Figure S7, Supplementary Information). In contrast, the layers of [Cd2(oba)2]n in
the framework 2 are further linked by the tdih ligand to form a three-dimensional non-
interpenetrated pillar-layered structure. Solvent-accessible voids in the structure, occupied by
DMF and H2O molecules in the as-synthesized material, consist of two intersecting 1D
channels that form a 2D channel system propagating along the (001) plane. Two types of
hydrogen bonds can be distinguished in the as-synthesized compound 2: intraframework and
between the framework and guest molecules. The former includes carboxylate oxygen atoms
interacting with NH groups of the tdih ligands (d(N20-H(N20)···O57)) = 2.89 Ȧ, angle =
170°), whereas the latter involves NH group of the tdih ligands and oxygen atoms of DMF
molecules d((N9-H(N9)···O64)) = 2.84 Ȧ, angle = 164°). The formation of hydrogen bonds in
both MOFs is corroborated by their IR spectra. The spectra show the presence of the ν(NH)
amide bands that are shifted as compared to pure ligands [3218 (1) as compared to 3190 cm-1
(pcih); 3235 (2) as compared to 3249 cm-1 (tdih)]
In spite of identical acylhydrazone linker topology, the use of linear acylhydrazone
linkers of various length leads to non-isoreticular cadmium-organic frameworks 1 and 2.
Replacing shorter pcih with longer tdih linker strongly affects conformation of the oba2- co-
linker that is capable of twisting about the C-O and the C-C single bonds. As a result, dihedral
angles between the CdOOC planes of the oba2- co-linker are significantly different in the two
compounds (20.0o and 78.3o for 1 and 2, respectively), and the Cd···Cd distance (via the oba2-
linker) is shorter for 2 (15.09 Å) than for 1 (15.20 Å) [Figure S8, Supplementary
Information]. The main consequence, however, is significantly different angles between axial
axes of neighboring coordination centres, i.e. parallel versus nearly perpendicular
arrangement, for 1 and 2, respectively. This considerable difference leads to different network
dimensionalities and topologies: three-dimensional 3,5-c network of unknown topology for 2
as opposed to two-dimensional sql topology for 1 (according to ToposPro).
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Figure 2. X-ray crystal structures of MOFs 1 (top) and 2 (bottom): (a) cluster coordination spheres of
[Cd2(oba)2(pcih)2] (in 1) and [Cd2(oba)2(tdih)2] (in 2), (b) [Cd2(oba)2]n fragments (1D double chains in 1 and 2D
layers in 2), (c) interlayer (in 1) and intraframework (in 2) hydrogen bonds, (d) contact surface (calculated with
Mercury software by using a probe molecule with a radius of 1.2 Å. In a), b), d) hydrogens atoms are omitted for
clarity.
Thermal stability and adsorption properties
In order to assess thermal stability as well as to determine activation conditions for porous
coordination polymers 1-2, both thermogravimetric (TG) and in situ temperature-dependent
powder X-ray diffraction analyses (TD-PXRD) have been utilized (Figure 3). The TG curves
indicate that the materials are thermally stable approx. up to 300 oC with derivative thermo-
gravimetric (DTG) curves minima of 362 oC (1) and 342 oC (2), wherein upon heating to 280
oC weight losses of 15.7% and 29.1% are observed, respectively. These weight losses
observed for both compounds are associated with removal of guests molecules from channels
of the frameworks, and are in agreement with theoretical values (calculated for 3DMF: 15.6
% (1); for 7H2O and 6DMF: 27.6 % (2)).
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Figure 3. Thermal stability of the as-synthesized (in solution) compounds 1 and 2. TG and DTG curves (left),
and TD-PXRD patterns (right).
Temperature-dependent powder X-ray diffraction patterns confirm thermal stability of
compound 1 determined by thermogravimetric analysis. When the sample is conditioned for
o
10 min at 330 C, first clear changes in the XRD pattern, including the decrease of the
distinguished peak at 2Θ = 6.5o, are observed (Figure 3). In contrast, variable temperature
PXRD patterns recorded for compound 2, indicate that the framework undergoes two phase
o
transitions in the range of 80-160 C. The phase at higher temperatures and below 310 oC is
characterized by two broad reflections which indicates loss of long-range ordering within the
MOF and its predominant amorphous character above 160 oC.
In order to avoid potential decompositions/phase transitions of the frameworks 1-2
indicated by TD-PXRD analysis (Figure 3), further confirmed by adsorption measurement
o
upon thermal activation of 1 at 180 C (Figure S9, Supplementary Information), gentle
activation procedures have been adopted for both compounds before adsorption
measurements. The samples were soaked for a few days in dichloromethane (DCM), with
several replacement of the supernatant by fresh portions of DCM (such samples are referred
to as 1·DCM and 2·DCM, respectively), followed by room-temperature activation for
approx. 16 hours under vacuum (Figure S10, Supplementary Information). The adsorption
experiments reveal that the two MOFs 1 and 2, regardless of the method of their synthesis, are
porous towards both N2 at 77 K and CO2 at 195 K (Figure 4 and Figure S11, Supplementary
Information). This observation is in contrast with previous adsorption behavior in the family
of
mixed-linker
acylhydrazone/carboxylate
metal-organic
frameworks
{[M2(dca)2(pcih)2]·guest}n (M = Zn2+, Cd2+; dca2- – dicarboxylate),25–29 where the adsorption
selectivity towards CO2 versus N2 was explained by the sieving effect and the presence of
Lewis basic NH groups from acylhydrazone moieties that decorated pores walls.27 However,
unlike compounds 1-2, the representatives of this family so far possess only one-dimensional
channels or zero-dimensional voids. Even three-dimensional highly robust MOF
[Cd2(sba)2(pcih)2]n (sda2- - 4,4’-sulfonyldibenzoic carboxylate), which has bigger window size
(4.4 Å) than kinetic diameter of nitrogen (3.64 Å), demonstrates selective adsorption of
CO2.27 Contrary to the previously reported mixed-linker acylhydrazone/carboxylate metal-
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organic frameworks, the as-synthesized materials 1-2 have two-dimensional voids (Figure 2)
constructed by two intersecting channels: i) a bigger one, decorated by polar acylhydrazone -
C(O)=N-NH- groups of the pcih or tdih linkers, and ii) a smaller one, propagating in close
proximity of the oba2- linkers. The latter, more nonpolar channels, provide extra diffusion
pathways for N2 into the frameworks 1-2. The following discussion refers to the data obtained
for the materials synthesized in solution and the corresponding data for the samples
synthesized mechanochemically are shown in Figure S11, Supplementary Information.
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Figure 4. Physisorption isotherms of N2 (77 K) and CO2 (195 K) for materials 1 and 2 synthesized in solution.
The CO2 (195 K) and N2 (77 K) physisorption isotherms for framework 1 after activation
show maximum loading of 128 cm3·g-1 at p/po = 0.99 and 148 cm3·g-1 at p/p0 = 0.98,
respectively. These values, according to the Gurvich rule35 (for both gases) correspond to a
total pore volume of 0.23 cm3·g-1 (Table 1).
Table 1. Porosity parameters for 1-2 calculated by Zeo++ software and obtained from CO2 (195 K) adsorption
isotherms.
MOF
pws [Å] *
6.01
mpd [Å] *
4.05
Vpt [cm3∙g-1 ]* Vpe [cm3∙g-1 ] *
1
2
0.23
0.32
0.23#
6.94
9.07
0.32##
*probe radius = 1.6 Å, pws-pore window size, mpd- maximum pore diameter, Vpt-theoretical pore volume, Vpe- experimental
pore volume (based on limiting loading in adsorption isotherms for CO2)
# p/po ~1.0, uptake 128 cm3∙g-1
## p/po ~ 1.0, uptake 181 cm3∙g-1
This is in agreement with the theoretical pore volume of 0.23 cm3·g-1 calculated for the
[Cd2(oba)2(pcih)2] framework by the Zeo++ software36 using the probe with a radius of 1.6 Å
(corresponding to carbon dioxide diameter of 3.30 Å). The slight hysteresis for CO2 between
adsorption and desorption branches is caused by weak interactions of the adsorptive with
polar acylhydrazone -C(O)=N-NH- groups of the pcih linkers. The framework 1 belongs to a
rare family of interdigitated 2D coordination polymers of general formula [M2(adc)2(lig)2]n
(adc – angular dicarboxylate, lig – neutral N-donor ligand), whose members show selective
CO2 (195K) adsorption over N2 (77 K). The utilization of the longer bent dicarboxylate, as
compared e.g. to isophthalates, is responsible for the second highest CO2 uptake as well as for
the loss of CO2 over N2 selectivity in this family (Table 2). In spite of the highest void volume
of 1 in this group, the CO2 uptake is lower than for [Zn2(iso)2(dptztz)2]n. This is caused by a
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structural transformation of [Zn2(iso)2(dptztz)2]n that led to creation of additional free space
and enhanced adsorption. In general, the lack of straightforward correlation between
theoretical pore volumes and CO2 uptakes for compounds without groups known for strong
interactions with CO2, indicates the occurrence of structural changes upon adsorption.
In order to verify reversibility of adsorption, the second run of N2 (77 K) has been carried out
on the sample evacuated at room temperature after the first run (Figure S12, Supplementary
Information). The total uptake of N2 is almost unchanged in the second run (147 cm3·g-1) as
compared to the first (148 cm3·g-1), however in the first stage of the adsorption branch, at p/po
~ 0.05, the capacity drops from 141 to 130 cm3·g-1. These phenomena can be explained by
increasing disorder of interdigitated layers of 1 upon subsequent activation process, which as
a result causes more steric hindrances and limits gas diffusion into pores. This explanation is
additionally supported by PXRD patterns recorded for samples that were soaked in DCM,
thermally activated, and after N2 adsorption (Figure S10, Supplementary Information)29 The
latter confirms that the structure of 1 remains unchanged after N2 adsorption.
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Table 2. Examples of mixed-linker (dicarboxylate/N,N-donor)
coordination polymers with layered interdigitated structures.
MOF
CO2 uptake Theoretical Ref.
at 195 K
[cm3·g-1]
pore volume*
[cm3·g-1]
Cd2(oba)2(pcih)2
128
0.23
this
work
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Cd2(iso)2(pcih)2
88
66
91
94
96
138
58
77
44
33
89
77
57
58
0.08
0.14
0.09
0.09
0.15
0.19
0.08
0.17
0.18
0.18
0.18
0.17
0
Cd2(tBu-iso)2(pcih)2
Zn2(iso)2(pcih)2
Zn2(OH-iso)2(pcih)2
Zn2(CH3-iso)2(pcih)2
Zn2(iso)2(dptztz)2
Zn2(iso)2(bpy)2 CID-1
Zn2(azdc)2(bpy)2 CID-13
Zn2(iso)2(bpb)2 CID-21
Zn2(iso)2(bpt)2 CID-22
Zn2(iso)2(bpa)2 CID-23
Zn2(ndc)2(bpy)2 CID-3
Zn2(NO2-iso)2(bpy)2 CID-5
Zn2(CH3O-iso)2(bpy)2 CID-6
0.11
Xiso2-= 5-substituted isophthalate (X = H, CH3, OCH3, OH, NH2, NO2, tBu)
bpy = 4,4'-bipyridyl
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bpndc2- = benzophenone-4,4’ -dicarboxylate
bpb = 1,4- bis(4-pyridyl)benzene
bpt = 3,6-bis(4-pyridyl)-1,2,4,5-tetrazine
bpa = 1,4-bis(4-pyridyl)acetylene)
dptztz = 2,5-di(4-pyridyl)thiazolo[5,4-d]thiazole
azdc2- = 1,6-azulenedicarboxylate
ndc2- = 2,6-naphthalenedicarboxylate
*calculated from X-ray crystal structures
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Replacement of the pcih linker with the longer tdih diacylhydrazone ligand, utilized as a
linker in MOFs for the first time, leads to 3D acylhydrazone-carboxylate framework 2 which
has the highest theoretical pore volume of 0.32 cm3·g-1, the highest CO2 (195 K) uptake of
181 cm3·g-1 as well as the highest maximum pore diameter (9.1 Å) and window size (6.94 Å)
of all mixed-linker acylhydrazone-carboxylate frameworks reported to date. However, this is
still far from the values found in the literature for MOFs that show excellent CO2 storage
capacities (e.g. at 293K and 40 bar: MOF-5, 495 cm3/g; MOF-177, 759 cm3/g; IRMOF-6, 443
cm3/g).42 The experimental pore volume calculated from the CO2 adsorption branch at p/p0 =
0.99 equals to 0.32 cm3·g-1 (Vpe)CO2 and is in a agreement with the value calculated
geometrically (Table 1). However, the analogous value of (Vpe)N2 = 0.496 cm3·g-1, calculated
at p/p0 = 0.99 (320 cm3·g-1) from the N2 (77 K) adsorption isotherm, surpasses (Vpe)CO2 by
nearly 50%. To verify whether it is not an experimental error, a few adsorption-desorption
cycles were performed as well as different batches of compounds were verified (Figure S13,
Supplementary Information). The result is repeatable and the discrepancy between calculated
Vpe values for various adsorbates will be subject of further more detailed investigations.
In order to get a fuller insight into adsorption processes, water vapor adsorption
isotherms and isobars have been measured for activated MOFs 1 and 2 (Figures 5 and Figure
S14). The isotherms recorded at 298 K for both MOFs have shown their instability towards
this small adsorptive demonstrating by large untypical hysteresis, long time of measurement
(even 5 days) as well as the highest H2O uptake for lower p/p0 (105 cm3·g-1 at p/p0 = 0.94 for
1; and 225 cm3·g-1 at p/p0 = 0.94 for 2) than for maximal partial pressure (103 cm3·g-1 for 1;
and 199 cm3·g-1 for 2). To investigate the stability in liquid H2O, frameworks 1-2 have been
immersed in water at ambient temperature for 1-6 days, and after this treatment, the water-
loaded MOFs were soaked in DMF or DMF/H2O (9:1 v/v) solution, to study their guest
exchange reversibility. The framework 1 undergoes fully reversible phase transition (Figure
S15, Supplementary Information), which according to our previous study of interdigitated
frameworks, is caused by a reversible change of relative arrangement of adjacent layers,
induced by exchange of guest molecules.28 However, this MOF is not stable during repeatable
cycles of water adsorption-desorption, which is demonstrated by loss of porosity (Figure S16,
Supplementary Information). In contrast, material 2 after soaking in water, has undergone
irreversible transformation to a highly water stable phase {[Cd2(oba)2(tdih)2]∙13H2O}n
(2·H2O) that shows characteristic narrow band at ~ 3500 cm-1 in IR spectrum, ascribed to the
presence of highly ordered water molecules engaged in strong hydrogen bonds with
acylhydrazone groups (Figure S17, Supplementary Information). Analogous hydrogen bonds
involving an acylhydrazone group and water guest molecules have been observed in the
structure of [Cd2(sba)2(pcih)2]n.27
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Figure 5. The as-synthesized (in solution) MOF 2: QE-TPDA profiles of water vapor desorption-adsorption cycles at 2250 Pa
(left), desorption-adsorption isobars (middle) and stability of porosity upon repeated water vapor desorption-adsorption cycle
(right).
The stability of the [Cd2(oba)2(tdih)2] phase obtained via thermal activation of
{[Cd2(oba)2(tdih)2]∙13H2O}n (2·H2O) as well as its porosity towards H2O have been
elucidated by QE-TPDA (quasi-equilibrated temperature-programmed desorption and
adsorption), which clearly demonstrated that H2O loading of the [Cd2(oba)2(tdih)2] framework
does not change after 22 cycles (Figure 5). The maximal amount of water adsorbed in isobaric
conditions (~150 cm3·g-1; 12.1% by mass) is in agreement with the data obtained from
thermogravimetric and elemental analyses for the water-loaded material 2 (Figure S18,
Supplementary Information and Experimental section).
Conclusion
By utilizing two ditopic acylhydrazone linkers providing linear connectivity: shorter 4-
pyridinecarboxaldehyde isonicotinoylhydrazone or longer terephthalaldehyde di-
isonicotinoylhydrazone, two non-isoreticular cadmium-organic frameworks have been
obtained. The frameworks possess the same secondary building units including Cd2 cluster
but differ in dimensionality. The Cd-MOFs exhibit sorption behavior untypical of the so far
known mixed-linker carboxylate-acylhydrazone MOFs, without CO2/N2 selectivity,
commonly observed in this framework family. This phenomenon is explained by the
coexistence of two types of channels in their structures, not observed for previous MOFs, that
provide extra diffusion pathways for adsorptives. The frameworks immersed in water undergo
either reversible or irreversible phase transitions, for shorter- or longer-linker MOF
respectively; whereas the latter gives the longer-linker framework ability to reversibly absorb
water vapor. The first use of a diacylhydrazone building block for the construction of metal-
organic frameworks opens new synthetic possibilities e.g. with other metals and co-linkers
and this work is currently in progress.
Experimental
Materials and Methods
4-pyridinecarbaldehyde isonicotinoylhydrazone (pcih) was prepared according to the
published method.25 All other reagents and solvents were of analytical grade (Sigma Aldrich,
POCH, Polmos) and were used without further purification.
Carbon, hydrogen and nitrogen were determined by conventional microanalysis with
the use of an Elementar Vario MICRO Cube elemental analyzer.
IR spectra were recorded on a Thermo Scientific Nicolet iS10 FT-IR
spectrophotometer equipped with an iD7 diamond ATR attachment.
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Thermogravimetric analyses (TGA) were performed on a Mettler-Toledo TGA/SDTA
851e instrument at a heating rate of 10 °C min−1 in a temperature range of 25 – 600 °C
(approx. sample weight of 8-14 mg). The measurement was performed at atmospheric
pressure under argon flow.
7
Powder X-ray diffraction (PXRD) patterns were recorded at room temperature (295 K)
on a Rigaku Miniflex 600 diffractometer with Cu-Kα radiation (λ = 1.5418 Å) in a 2θ range
from 3° to 45° with a 0.02° step at a scan speed of 2.5° min−1. Temperature-dependent powder
X-ray diffraction experiments were performed using Anton Paar BTS 500 heating stage from
30 to 350 C. At each temperature samples were conditioned for 10 minutes prior to the
measurement.
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Nitrogen and carbon dioxide adsorption/desorption studies were performed on a
BELSORP-max adsorption apparatus (MicrotracBEL Corp.); 77 K was achieved by liquid
nitrogen bath and 195 K was achieved by dry ice/isopropanol bath. Water vapor isotherms
were recorded on Hydrosorb (Quantachrome). Prior to the sorption measurements the samples
1 and 2 (synthesized either in solution or by mechanochemical methods from Cd(OH)2) were
soaked with DCM for 5 – 7 days. After that the samples were evacuated at 80 °C (1) or RT
(2) for 16 h. For some experiments, indicated in the manuscript, sample 1 was evacuated at
180 °C for 20 h.
1
The H NMR spectrum was recorded with a Bruker Avance III 600 at 300 K. The
chemical shifts (δ) are reported in parts per million (ppm) on a scale downfield from
1
tetramethylsilane. The H NMR spectra were referenced internally to the residual proton
resonance in DMSO-d6 (δ 2.49 ppm).
Scanning electron microscope (SEM) analysis was performed on the SU8020 scanning
electron microscope (HITACHI, Japan) with an accelerating voltage of 1-2 kV. The samples
of 1 and 2 (mechanosynthesized from Cd(OH)2) were sputtered with gold prior to
measurements.
In order to determine stability of porosity of 1 and 2 upon adsorption of water
molecules we used a quasi-equilibrated temperature-programmed desorption and adsorption
(QE-TPDA) technique.43,44 Prior to the experiment a sample of 6.1 mg (1·DCM) and 5.9 mg
(2·H2O) were activated by heating in a flow (6.75 cm3/min) of pure helium (purity 5.0, Air
o
Products) to 120 °C (1·DCM) and 200 C (2·H2O) at 5 °C/min and then cooled down. After
activation the flow was switched to helium containing steam saturated at 25 °C and room
temperature sorption began. After stabilization of the TCD signal, 9 (1) and 21 (2) desorption-
adsorption cycles were measured with linear temperature program (5 °C /min rate). Maximum
o
temperature was equal to 120 C (1) and 200 °C (2) for each cycle. To make sure that
adsorption process fully ended, 90 minutes of RT isothermal sorption was applied after each
finished desorption-adsorption cycle. The maxima obtained in experiment correspond to
desorption and the minima to adsorption, while together they form the QE-TPDA profiles
(Figure 5 and Figure S16, Supplementary Information). Sorption capacities were determined
by integrating desorption maxima over the range from 25 °C to 120 °C and recalculating the
obtained areas by adequate calibration constant.45 Desorption and adsorption isobars were
calculated from the first desorption/adsorption cycle (Figure 5 and Figure S16, Supplementary
Information).46
Syntheses
Synthesis of {[Cd2(oba)2(pcih)2]∙3DMF}n (1) in solution:
4-Pyridinecarboxaldehyde isonicotinoylhydrazone (pcih) (67.9 mg, 0.300 mmol),
Cd(NO3)24H2O (92.5 mg, 0.295 mmol) and 4,4’-oxybis(benzenedicarboxylic) acid (H2oba)
(77.4 mg, 0.300 mmol) were dissolved in DMF (16 mL) and H2O (1.8 mL) by sonification
(60 s) and heated at 70 C for 4 days. Colorless crystals of 1 were filtered off, washed with
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DMF and dried in oven at 60 C for 0.5 hour. Yield: 159.9 mg (73.7 %). Anal. Calc. for
C61H57N11O15Cd2: C 51.92, H 4.21, N 10.92. Found: C 51.49, H 03.90, N 10.72. FTIR (ATR,
cm-1): ν(COO)as 1402s, ν(COO)s 1559m/1532s, ν(C=O)DMF 1675s, ν(C=N)pcih 1594s,
ν(CH)pcih 3071w, ν(NH) 3218m. Synthesis of single crystals suitable for SC-XRD
measurement: Pcih (22.6 mg, 0.100 mmol), Cd(NO3)24H2O (31.3mg, 0.100 mmol) and
H2oba (25.8 mg, 0.1 mmol) were dissolved in DMF (9.0 mL) by sonification (60 s), next H2O
(9.0 mL) was added and the mixture was heated at 70 C for 4 days.
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Synthesis of {[Cd2(oba)2(pcih)2]∙3H2O}n (1·H2O): {[Cd2(oba)2(pcih)2]∙3DMF }n (1) (100 mg)
was immersed in 15 mL water for 2 days at room temperature. Cream-colored powder was
filtered off, washed with H2O and dried in air at ambient conditions for 0.5 hour. Anal. Calc.
For {[Cd2(oba)2(pcih)2]∙3H2O}n :C 50.22, H 3.40, N 9.01. Found: C 50.31, H 3.11, N 8.95%.
Synthesis of terephthalaldehyde di-isonicotinoylhydrazone (tdih)
Isonicotinic acid hydrazide (1.37 g, 10.0 mmol) was added to ethanol (20 mL), and the
mixture was heated to boiling. Terephthalaldehyde (0.67 g, 5.0 mmol) suspended in ethanol
(20 mL) was added. The reaction mixture was refluxed for 1.5 hours, then allowed to cool and
stand overnight, producing a white crystalline solid, which was filtered off, washed with 10
mL of ethanol and dried in air. Yield: 1.26 g (94.6 %). Anal. Calc. for C20H16N 6O2: C 64.51,
H 4.33, N 22.57 %. Found: C 64.16, H 4.37, N 22.11%. ν(C=N) 1544m, ν(C=O) 1653s, ν(CH)
1
3070w, ν(NH) 3249m. H-NMR and IR spectra are attached in the SI file (Figures S15-S16,
Supplementary Information).
Synthesis of {[Cd2(oba)2(tdih)2]∙7H2O∙6DMF}n (2) in solution
Tdih (55.9 mg, 0.150 mmol), Cd(NO3)24H2O (46.3 mg, 0.150 mmol) and H2oba (38.6 mg,
0.150 mmol) were dissolved in DMF (16.2 mL) and H2O (1.8 mL) by sonification (60 s) and
heated at 70 C for 96 hours. Yellow crystals of 2 were filtered off, washed with DMF and
dried in oven at 60C and 500 mbar for 0.5 hour. Yield: 127.8 mg (85.5 %). Anal. Calc. for
C86H104N18O27Cd2: C 50.47, H 5.12, N 12.32 %. Found: C 51.51, H 4.77, N 12.71 %. FTIR
(ATR, cm-1): ν(COO)s 1395shm, 1407m; ν(COO)as 1534m, 1558m; ν(C=O)tdih 1658s;
ν(C=O)DMF 1674s, ν(CH)tdih 3070w, ν(NH) 3235w.
Synthesis of {[Cd2(oba)2(tdih)2]∙13H2O}n (2·H2O): {[Cd2(oba)2(tdih)2]7∙H2O∙6DMF }n (2)
(200 mg) was immersed in 18 mL water for 1-3 days at room temperature. Cream-colored
powder was filtered off, washed with H2O and dried in air at ambient conditions for 0.5 hour.
Anal. Calc. For {[Cd2(oba)2(tdih)2]∙13H2O}n : C 47.59, H 4.35, N 9.79,. Found: C 47.76, H
4.24, N 9.76%.
One-pot mechanosynthesis of {[Cd2(oba)2(pcih)2]∙3DMF}n (1) and
{[Cd2(oba)2(tdih)2]∙7H2O∙6DMF}n (2)
Pcih (67.8 mg, 0.300 mmol) or tdih (111.7 mg, 0.300 mmol), CdO (38.5 mg, 0.300 mmol),
H2oba (77.5 mg, 0.300 mmol) and NH4NO3 (7.4 mg, 0. 093 mol, 4 wt% for 1 and 9.1 mg, 114
mol, 4 wt% for 2) were ground together with an addition of DMF (120 μL, η = 0.65 μL∙mg-1
for 1; 150 μL, η = 0.66 μL∙mg-1 for 2 ) in an agate milling ball (40 min, 15 Hz). After that the
product was washed several times with DMF. The same approach was used to synthesize 1
and 2 from Cd(OH)2, but reaction was carried out without NH4NO3 and Cd(OH)2 (43.9 mg ,
0.300 mmol) was used instead of CdO.
Stepwise
mechanosynthesis
of
{[Cd2(oba)2(pcih)2]∙3DMF}n
(1)
and
{[Cd2(oba)2(tdih)2]∙7H2O∙6DMF}n (2)
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CdO (38.5 mg, 0.300 mmol) and H2oba (77.5 mg, 0.300 mmol) were ground together with an
addition of 150 μL H2O (η = 1.30 μl∙mg-1) an agate milling ball (40 min, 15 Hz). After that
pcih (67.8 mg, 0.300 mmol) (1) or tdih (111.7 mg, 0.300 mmol) (2) and 156 μL DMF (η =
0.85 μL∙mg-1) for 1; 190 μL DMF (η = 0.83 μL∙mg-1) for 2 were added to the intermediate
products and grinding was carried out for 40 min (15 Hz). The same approach was used to
synthesize 1 and 2 from Cd(OH)2, but Cd(OH)2 (43.9 mg, 0.300 mmol) was used instead of
CdO.
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Crystallographic data collection and structure refinement
Diffraction intensity data for single crystals of compounds 1 and 2 were collected at 100 K on
a KappaCCD (Nonius) diffractometer with graphite-monochromated Mo Kα radiation (λ =
0.71073 Å). Cell refinement and data reduction were performed using firmware.47,48 Positions
of all of non-hydrogen atoms were determined by direct methods using SIR-97.49 All non-
hydrogen atoms were refined anisotropically using weighted full-matrix least-squares on F2.
Refinement and further calculations were carried out using SHELXL 2014/7.50,51 All
hydrogen atoms joined to carbon atoms were positioned with an idealized geometries and
refined using a riding model with Uiso(H) fixed at 1.5 Ueq of C for methyl groups and
1.2 Ueq of C for other groups. The hydrogen atoms of the water (O66) molecule in 2 are
indeterminate, H atoms attached to the N atoms were found in the difference-Fourier map and
refined with an isotropic thermal parameter. Additionally, the crystal structure data shows that
one DMF solvent molecule is heavily disordered and was removed using the SQUEEZE
procedure implemented in the PLATON package.50 In case of other two DMF solvent
molecules atoms were refined using DFIX and DANG instructions.51,52 The SQUEZZE
procedure was also applied for 1 due to the presence of disordered guest molecules. The
figures were made using CCDC1852965 (1) and CCDC1581727 (2) cif files that contain the
supplementary crystallographic data. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Table 3. Crystal data and structure refinement parameters for {[Cd2(oba)2(pcih)2]∙3DMF}n (1) and
{[Cd2(oba)2(tdih)2]∙7H2O∙6DMF}n (2).
2
Compound
1
CdC26H18N4O6
594.84
Empirical formula
Formula weight
Crystal size (mm)
CdC43H45N9O11
976.28
0.400 × 0.300 × 0.200
Triclinic
0.300 x 0.200 x 0.030
Monoclinic
C2/c
Crystal system
1
P
Space group
Unit cell dimensions
9.6614(2)
12.2246(3)
15.1946(3)
110.712(2)
102.063(2)
93.664(2)
1622.79(7)
100(2)
a (Å)
40.7755(7)
8.8797(2)
29.8769(5)
90
b (Å)
c (Å)
α (°)
β (°)
109.734(1)
90
γ (°)
Volume (Å3)
10182.3(3)
100(2)
8
Temperature (K)
Z
2
Density (calculated) (g/cm3)
Absorption coefficient (mm-1)
F(000)
1.274
1.217
0.710
0.490
596
4016
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2.947 to 29.431
Theta range for data collection (°)
Index ranges
2.354 to 27.485
-52≤h≤52, -11≤k≤11, -
38≤l≤38
-13≤h≤13, -16≤k≤17, -21≤l≤21
78072
Reflection measured
Reflections unique
20787
9086 [R(int) = 0.0484]
11632 [R(int) = 0.0351]
8927
Reflections observed [I > 2sigma (I)] 7659
Completeness
94.7% to theta = 29.431°
99.5% to theta = 27.485°
none
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Absorption correction
Max. and min. transmission
MULTI-SCAN
1.000, 0.788
0.985, 0.889
Full-matrix least-squares on
2
Refinement method
Full-matrix least-squares on F
2
F
Data / restraints / parameters
9086 / 1 / 338
11632 / 3 / 543
1.061
2
1.076
Goodness-of-fit on F
Final R indices [I>2sigma(I)]
R1 = 0.0293, wR2 = 0.0622
R1 = 0.0416, wR2 = 0.0680
R1 = 0.0673, wR2 = 0.1726
R1 = 0.0887, wR2 = 0.1838
R indices (all data)
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Associated Contents
The Supporting Information is available free of charge on the RSC Publication website at
DOI:... IR spectra, PXRD patterns, N2 adsorption isotherms, TG curves additional structure
drawings and X-ray crystal data (CCDC 1852965, 1581727 and 1476612) for 1, 2 and [Cd(µ-
H2O)(oba)(H2O)]n respectively.
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Acknowledgements
The National Science Centre (NCN, Poland) is gratefully acknowledged for the financial
support (Grant no. 2015/17/B/ST5/01190) of this research. KR additionally thanks the
National Science Centre (NCN, Poland) for a doctoral scholarship within ETIUDA funding
scheme (Grant no. 2018/28/T/ST5/00333). The research was carried out partially with the
equipment purchased thanks to the financial support of the European Regional Development
Fund in the framework of the Polish Innovation Economy Operational Program (contract no.
POIG.02.01.00-12-023/08).
Corresponding Author
*E-mail: dariusz.matoga@uj.edu.pl
References
(1)
Book on MOFs: D. Farrusseng (Ed.), Metal-Organic Frameworks, Wiley- VCH
Verlag & Co. KGaA, Weinheim, 2011. Metal-Organic Frameworks L.R. (Ed.).
(2)
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For Table of Contents Use Only
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Introducing a longer versus shorter acylhydrazone linker to a
metal-organic framework: parallel mechanochemical approach,
non-isoreticular structures and diverse properties
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Kornel Roztocki,[a] Monika Szufla,[a] Maciej Hodorowicz,[a] Irena Senkovska,[b] Stefan
Kaskel,[b] Dariusz Matoga[a]*
[a]Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30-387 Kraków, Poland
[b]Department of Inorganic Chemistry, Technische Universität Dresden, Bergstrasse 66,
01062 Dresden, Germany
*Corresponding author: dariusz.matoga@uj.edu.pl
TABLE OF CONTENTS GRAPHIC:
SYNPOSIS:
Two varied length ditopic hydrazone linkers providing linear connectivity have been used
with a dicarboxylate co-linker to prepare metal-organic frameworks of different
dimensionality, stability and gas adsorption adsorption.
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a
b
)
)
1
2
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7
8
H2oba
O
O
pcih
tdih
H
pcih
N
CdO LAG DMF or,
Cd(OH)2 LAG DMF or,
H
N
O
N
N
H2oba
Cd(NO3)2 in solution DMF/H2O
O
11.4 Å
2
{[Cd2(oba)2(pcih)2]∙g}n ( )
{[Cd2(oba)2(tdih)2]∙g}n ( )
9
O
10
11
12
13
14
15
16
17
18
19
20
21
22
23
O
H
pcih
LAG DMF
tdih
LAG DMF
tdih
3
[Cd(µ-H2O)(oba)(H2O)]n ( )
H
N
NH
O
N
N
N
N
O
LAG H2O
19.8 Å
H2oba + CdO or Cd(OH)2
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T / oC
330
1
15.7 %
310
290
280
260
240
220
200
180
160
140
120
100
80
1
2
3
4
5
6
7
8
calculated
3DMF
15.6 %
9
362 oC
10
11
12
13
14
15
16
17
18
19
20
21
22
23
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28
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30
31
32
33
34
35
36
37
38
39
40
41
42
60
40
100
200
300
400
500
600
5
10
15
20
25
30
35
40
T / oC
2Q / o
100
80
60
40
20
2
T / oC
330
28.7 %
310
280
260
240
220
200
180
160
140
120
100
80
calculated
7H2O 6DMF
27.6 %
342 oC
60
20
100
200
300
400
500
600
5
10
15
20
25
30
35
40
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1
2
320
280
240
200
160
120
80
140
120
100
80
60
40
20
0
10
11
12
13
14
15
16
17
18
19
20
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CO2 (195 K) adsorption
CO2 (195 K) desorption
N2 (77 K) adsorption
N2 (77 K) desorption
CO2 (195 K) adsorption
CO2 (195 K) desorption
N2 (77 K) adsorption
N2 (77 K) desorption
40
0
0.0
0.2
0.4
0.6
0.8
1.0
0.0
0.2
0.4
0.6
0.8
1.0
p/p0
p/p0
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Cd2+
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