Variation of Desolvation Behavior in Two Isostructural Metal–Organic Frameworks Based on a Flexible, Racemic Bifunctional Organic Linker

Article abstract of DOI:10.1002/ejic.201600681

A racemic mixture of the chiral ligand 4,4′-(1,2-dihydroxyethane-1,2-diyl)dibenzoic acid was used to prepare two isostructural metal–organic frameworks, CPO-49-Zn and CPO-49-Mn, which contain coordinated solvent molecules at the metal site. The compounds showed different behavior upon desolvation. The dissociation of the solvent molecule from the metal site leads to a single-crystal-to-single-crystal transformation. In CPO-49-Zn, a change of coordination geometry from trigonal bipyramidal to tetrahedral occurs at the zinc atom. In CPO-49-Mn, a rearrangement of coordination mode of a carboxylate group occurs instead, leading to a 4+1 coordination of the manganese cation in the form of a capped distorted tetrahedron. N₂gas adsorption confirms that both desolvated structures are permanently porous. The behavior of the compounds upon heating has also been studied using variable temperature powder X-ray diffraction. The presence of a coordinated solvent molecule in the as-synthesized structures indicates the possibility to access the metal cation with reactive substrates. Both materials were evaluated in the catalytic oxidation of styrene. CPO-49-Mn showed significantly higher conversion than the CPO-49-Zn material.

Full text of DOI:10.1002/ejic.201600681

DOI: 10.1002/ejic.201600681
Full Paper
CLUSTER
ISSUE
Structural Transformations
Variation of Desolvation Behavior in Two Isostructural Metal–
Organic Frameworks Based on a Flexible, Racemic Bifunctional
Organic Linker
Andrey A. Bezrukov,[a] Karl W. Törnroos,[a] and Pascal D. C. Dietzel*[a]
Abstract: A racemic mixture of the chiral ligand 4,4′-(1,2-di- of the manganese cation in the form of a capped distorted
hydroxyethane-1,2-diyl)dibenzoic acid was used to prepare two tetrahedron. N2 gas adsorption confirms that both desolvated
isostructural metal–organic frameworks, CPO-49-Zn and CPO- structures are permanently porous. The behavior of the com-
49-Mn, which contain coordinated solvent molecules at the pounds upon heating has also been studied using variable tem-
metal site. The compounds showed different behavior upon de- perature powder X-ray diffraction. The presence of a coordi-
solvation. The dissociation of the solvent molecule from the nated solvent molecule in the as-synthesized structures indi-
metal site leads to a single-crystal-to-single-crystal transforma- cates the possibility to access the metal cation with reactive
tion. In CPO-49-Zn, a change of coordination geometry from substrates. Both materials were evaluated in the catalytic oxid-
trigonal bipyramidal to tetrahedral occurs at the zinc atom. In ation of styrene. CPO-49-Mn showed significantly higher con-
CPO-49-Mn, a rearrangement of coordination mode of a carb- version than the CPO-49-Zn material.
oxylate group occurs instead, leading to a 4+1 coordination
Introduction
tage of being neutral (as long as the hydroxy groups remain
protonated), which means either a charged framework is cre-
ated or an additional anionic linker has to be present which
takes the role of providing charge balance in the framework.
In the present work, we used 4,4′-(1,2-dihydroxyethane-1,2-
diyl)dibenzoic acid (H4dhdba) (Scheme 1), which contains both
a diol unit and terminal carboxylic acid groups. The hydroxy
group carrying carbon atoms are asymmetric. Thus, an enantio-
merically pure linker could be used to prepare homochiral
MOFs.[8] Previously reported coordination polymer structures
containing the H4dhdba linker are either 1D or 2D coordination
networks without permanent porosity.[9] Derivatives of the
H4dhdba linker, where two protons on hydroxy groups were
substituted with a 1,1′-dimethylmethylene group[10] or two
methyl groups,[11] have also been used in the preparation of
coordination networks.[10–1c] Herein, we successfully employed
a racemic mixture of the H4dhdba linker and Zn and Mn salts to
build two isostructural 3D networks with permanent porosity,
in which the dihydroxy group actually partakes in coordination
of the metal. We also report the behavior of the new materials
upon desolvation, heating and catalysis.
Metal–organic frameworks (MOFs) are inorganic-organic crystal-
line materials where the inorganic part is represented by metal/
metal cluster and organic part is the bridging polydentate
linker.[1] By combining different inorganic and organic parts, it is
possible to obtain a variety of different structures with different
properties for application in various areas, such as adsorption
and catalysis.[2]
Synthesis of permanently porous MOFs with flexible linkers
is often a challenge because the conformational freedom of
the linkers might lead to structural rearrangement and loss of
porosity when the guest molecules are removed from the
pores. On the other side, the flexibility of the linker might result
in new topologies and larger structural diversity than in case of
a rigid bridging ligand.[3] Variable conformational angles around
the metal node may also lead to flexible frameworks.[4]
Derivatives of ethane-1,2-diol with two adjacent hydroxy
groups are attractive units to be incorporated into the MOF
structure, because it might be used in a subsequent post-modi-
fication of the framework if the dihydroxy group does not par-
ticipate in construction of the framework.[5] Previously, 1,2-di(4-
pyridyl)glycol containing two 4-pyridyl groups connected to the
glycol unit was successfully employed in syntheses of 2D[6] and
3D[7] networks. The pyridyl terminated linker has the disadvan-
[a] Department of Chemistry, University of Bergen,
P. O. Box 7803, 5020 Bergen, Norway
E-mail: pascal.dietzel@uib.no
http://www.uib.no/en/persons/Pascal.Dietzel
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under http://dx.doi.org/10.1002/ejic.201600681.
Scheme 1. 4,4′-(1,2-dihydroxyethane-1,2-diyl)dibenzoic acid (H4dhdba).
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Results and Discussion
pyramidal (τ = 0 for ideal), or trigonal bipyramidal (τ = 1 for
ideal) geometry. Zn2 has octahedral coordination environment
(Figure 1, a). Zn2 is coordinated to both O atoms of the singly
deprotonated diol group of one linker molecule and two oxy-
gen atoms from two carboxylate groups of additional linker
molecules in square planar fashion. The two O atoms which
complete the octahedral coordination environment belong to
formate anions (Figure 1, a). Zn1 is coordinated to the oxygen
atom of the oxido group and two carboxylate oxygens in the
equatorial positions. One axial position of the Zn1 environment
is occupied by an oxygen atom belonging to a formate anion,
while the second axial position is occupied by a DMF molecule
coordinated through its oxygen atom. The octahedral and trigo-
nal bipyramidal polyhedra are connected via common corners
(corresponding to the oxygen atom of the oxido group of the
partially deprotonated diol and the formate anion, respectively)
and form infinite chains along the b axis. Each linker molecule
interconnects three Zn chains: one chain by coordination with
the oxido-hydroxy group and two chains by coordination with
each of its carboxylate groups (Figure 1, b). The coordination
network can be described as rhombic arrangement with 1D
chains of the inorganic secondary building unit in the corners
and each organic linker participating in the formation of two
wall sections. The 1D pore is filled with a second non-coordinat-
ing DMF molecule in addition to the DMF molecule coordinated
to the metal site (Figure 1, b).
The organic linker 4,4′-(1,2-dihydroxyethane-1,2-diyl)dibenzoic
acid (H4dhdba) was synthesized from the 4-formylbenzoic acid
according to the literature procedure[12] (see Experimental Sec-
tion). The synthesis procedure applied by us yielded an equimo-
lar mixture of (S,S)- and (R,R)-stereoisomers. In principle, the
linker has a large degree of conformational freedom around the
C(OH)–C(OH) bond. Originally, we selected the ligand with the
aim to obtain porous coordination networks based on carboxyl-
ate metal bonds in which the hydroxy groups are still available
for post-synthetic functionalization.[7c,13] However, the reaction
conditions of the solvothermal synthesis, led to the formation
of single crystalline products of composition [M2(Hdhdba)-
(HCO2)DMF]·DMF (CPO-49-M, M = Zn, Mn, DMF = N,N-dimethyl-
formamide, CPO stands for Coordination Polymer of Oslo),
which contain partially deprotonated diol groups and addi-
tional formate groups involved in coordination of metal cations
and framework construction. Formate anions are sometimes en-
countered in MOFs as a result of hydrolysis of DMF during the
solvothermal reaction.[14] The manganese and zinc compounds
are isostructural to each other and an analogous cobalt com-
pound.[15] To the best of our knowledge, it is the first MOF
series in which the 1,2-dihydroxy groups of the H4dhdba linker
are partially deprotonated and participate in coordination to
the metal cation in the framework. The crystal structure deter-
mination reveals that one of the guest DMF molecules is coordi-
nated to a metal site, meaning there is a potential opportunity
to obtain open-metal sites in the desolvated structure. The
presence of coordinatively unsaturated metal sites frequently
indicates broad potential for application of the material in ad-
sorption and catalysis.[16]
The two oxygen atoms of the diol group are not equivalent
to each other. One is protonated, while the second is deproto-
nated and bridges two adjacent Zn atoms. The difference in
coordination and protonation is clearly reflected in the Zn–O
distances. The Zn2–O2 distance of the protonated oxygen is
2.268(2) Å, while it is shorter for the deprotonated and conse-
quently stronger coordinated O1 atom [d(Zn1–O1) = 1.924(2) Å
for and d(Zn2–O1) = 2.0094(19) Å, see also Table S2].
Crystal Structure of as-Synthesized CPO-49-Zn and -Mn
As-synthesized CPO-49-Mn is isostructural to as-synthesized
CPO-49-Zn with analogous coordination environments of the
two crystallographically independent Mn atoms (trigonal bi-
pyramidal for Mn1, with τ = 0.86, and octahedral for Mn2). Se-
The single crystal structure of CPO-49-Zn (Table S1) as obtained
after synthesis (as-synthesized) contains two crystallographi-
cally independent Zn atoms in general positions. Zn1 is in a
distorted trigonal bipyramidal coordination environment with lected metal–oxygen distances and oxygen–metal–oxygen an-
τ = 0.80, where τ is an Addison parameter[17] indicating square gles for Zn and Mn structures are listed in Table S2.
Figure 1. a) Secondary inorganic building unit in as-synthesized CPO-49-Zn (parallel to [010]; disorder in the C–C backbone is not shown for clarity), b) As-
synthesized CPO-49-Zn framework structure, viewed along [010] (guest molecules in the pore are represented as sticks for clarity); as-synthesized CPO-49-Mn
is isostructural.
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We used an equimolar mixture of (R,R)- and (S,S)-stereoiso- tion environment while O3 from the carboxylate enters the co-
mers in the synthesis. There have been cases in which a chiral ordination environment of Mn1, which is demonstrated by the
coordination network was spontaneously resolved from the ra- change of the Mn1–O3 distance from 3.4863(23) Å in the as-
cemic mixture of linkers[18] or even using achiral linkers.[19] synthesized to 2.364(2) Å in the desolvated structure. The coor-
However, we did not observe spontaneous resolution, i.e. the dination geometry of Mn1 changes from trigonal bipyramidal
formation of crystals of opposite chirality in which the dia- (τ = 0.86) to a shape best described as severely distorted square
stereomers are separated. Instead, the stereoisomers are built pyramidal (τ = 0.09) or capped distorted tetrahedron with four
into the framework in equimolar amounts. The asymmetric unit Mn–O distances in the range 1.9988(18)–2.1565(18) Å and one
contains a Hdhdba3– anion, in which the asymmetric C atoms with 2.364(2) Å and O–Mn–O angles in the range 57.84(7)–
of the ethane backbone and the hydrogen atom bonded to 138.48(7)°. Another effect of the rearrangement of the carboxyl-
them are disordered, meaning that there is a mixture of (S,S)- ate coordination mode is that the connection of the Mn coordi-
and (R,R)-diastereomers on the position in the crystal structure. nation polyhedra changes from corner-connected to edge-con-
Because the corresponding oxidohydroxy groups of both nected. This is reflected in larger changes of metal–metal dis-
stereoisomers are not disordered themselves, they are able to tances (M1–M2) for the Mn compound than the Zn compound
coordinate the metal with the α-oxidohydroxy group without as it changes from as-synthesized to desolvated structure (Table
distortion of the overall framework structure. Thus, in principle, S2).
it should be possible to synthesize the analogous homochiral
porous structure using the pure enantiomer of the organic
linker.
Crystal Structure of Desolvated CPO-49-Zn and -Mn
A gentle procedure of removing the solvent from the as-synthe-
sized single crystals was performed by soaking the sample sev-
eral times in chloroform to replace the high boiling DMF with
a more volatile solvent. Afterwards, the chloroform was re-
moved by heating the samples in a dynamic vacuum at 90 °C
overnight. Both samples remained single crystalline, indicating
that the solvent removal proceeded in form of a single-crystal-
to-single-crystal transformation.[20]
The single crystal structure determination confirms that both
compounds are permanently porous. No solvent was located in
the pores as reflected by the absence of significant electron
density in the pore space. Both, desolvated CPO-49-Zn and -Mn,
still contain one-dimensional inorganic secondary building
units composed of condensed coordination polyhedra around
the metal cations which are connected by the organic linkers
into the framework. However, despite the fact that as-synthe-
sized CPO-49-Zn and -Mn are isostructural, the coordination en-
Figure 2. Coordination environment of the two crystallographically unique
transition metal atoms in a) as-synthesized CPO-49-Zn, b) desolvated CPO-
49-Zn, c) as-synthesized CPO-49-Mn, d) desolvated CPO-49-Mn. The corre-
sponding bond lengths are listed in Table S2. Extended structures are repre-
vironment of the metal cations with coordinated solvent rear-
ranges differently for the zinc and manganese compounds. In
CPO-49-Zn, the removal of the coordinated solvent molecule
carrying atom O9 causes a decrease of coordination number of
Zn1 from 5 to 4 and change of coordination geometry from
trigonal bipyramidal to tetrahedral (Figure 2, a–b) with Zn–O
distances in the range 1.913(2)–2.009(2) Å and O–Zn–O angles
in the range 102.20(10)–122.98(10)° (Table S2). The largest abso-
lute change in distance is observed for the Zn1–O7 distance
which decreases from 2.100(2) to 2.009(2) Å in the as-synthe-
sized and desolvated structure, respectively. In contrast, the
Mn1 atom retains the coordination number 5 after the loss of
sented in Figures S1–S2.
Atoms Zn2 and Mn2 are not coordinated by a solvent mol-
ecule. All the coordinating groups are contributed by 4,4′-(1,2-
oxidohydroxidoethane-1,2-diyl)dibenzoate and formate ligands.
The octahedral coordination environment of Zn2 and Mn2 re-
mains essentially unchanged in the desolvated compound.
In congruence to the changes in the chain, the conformation
of the flexible linker rearranges during the desolvation process.
The torsion angle between the C–C bonds changes for both
structures (Table S2).
The conformational flexibility of the organic linker and the
coordinated DMF molecule. This is a result of a change in coor- rigidity of the framework structure influence the ease of change
dination mode by one of the carboxylate groups. In the as- in coordination environment of the metal cation. Removal of
synthesized form, it coordinates Mn1 and Mn2 with each one coordinated solvent in rigid frameworks leads to the presence
of its oxygen atoms, while it rearranges in the desolvated form of coordinatively unsaturated metal sites (open metal sites), for
so that one oxygen atom coordinates both Mn1 and Mn2 (Fig- example, as observed for the CPO-27 series.[21] In the case of
ure 2, c–d). The O9 atom belonging to DMF leaves the coordina- CPO-49-Zn, the removal of the solvent molecule from Zn1 re-
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sults in a change of coordination environment from trigonal pore volume (at p/p0 = 0.5) is 0.30 cm3 g–1 for CPO-49-Zn and
bipyramidal to tetrahedral. An analogous rearrangement in a 0.25 cm3 g–1 for CPO-49-Mn, which corresponds well with calcu-
MOF has been observed for [Zn3(ntb)2(EtOH)2]·4nEtOH,[22] in lated values based on the single crystal structures (see Table S3
which a reversible single-crystal-to-single-crystal transforma- in the Supporting Information).
tion occurred upon loss of coordinated ethanol. Additional ex-
amples of single-crystal-to-single-crystal transformations with
Zn containing MOFs induced by the loss of coordinated solvent
molecule include the transformation from non-interpenetrated
to interpenetrated structure in [Zn7O2(nbd)5(DMF)2],[23] while
exchange of coordinated solvent led to a change of topology
for [Zn2(mtc)(DMF)4]·2DMF·4H2O, in which complete exchange
of DMF by soaking crystals in CH2Cl2 resulted in a unique 2D
to 3D structural transformation that increased the porosity and
sorption capacity.[24]
In CPO-49-Mn like in CPO-49-Zn, desolvation does not lead
to the formation of an open metal site. However, instead of a
straightforward change in coordination geometry as observed
for the Zn1 atom, a change of carboxylate coordination mode
is observed which leads to the 4+1 coordination of the Mn1
atom and the change in connectivity in the 1D inorganic sec-
Figure 3. Nitrogen adsorption (full circles) and desorption (empty circles) iso-
therms on CPO-49-Zn (blue) and CPO-49-Mn (red) at –196 °C.
ondary building unit. To the best of our knowledge, this is the
first time such a single-crystal-to-single-crystal structural trans-
formation has been observed for a manganese MOF. There are
significantly fewer manganese MOFs reported in the literature
than Zn MOFs and, consequently, fewer examples of single-
crystal-to-single-crystal transformations induced by the loss of
the solvent on the Mn2+ ions. One of the few examples of sin-
gle-crystal-to-single-crystal transformations of manganese-or-
ganic frameworks is the hydration induced transformation of
2D [Mn3(ip)3(bipy)2]·2H2O to 1D [Mn(ip)(bipy)(H2O)2]·H2O.[25]
The simultaneous flexibility of the chain and linker results
in different rearrangements for the Zn and Mn structures. The
difference between Zn1 and Mn1 behavior can be rationalized
with the difference in ionic radii. The Mn2+ ion is larger than
Zn2+, and it prefers a higher coordination number.
The desolvation of the CPO-49-M frameworks appears to be
a reversible process. Resolvation of the bulk material used in
the gas adsorption experiments (which showed good porosity
and can therefore be assumed to be desolvated) with DMF re-
establishes powder X-ray diffraction patterns which correspond
well to the patterns of as-synthesized material for both CPO-
49-Zn and -Mn (Figures S7 and S8).
Thermal Analysis
Thermogravimetric analysis indicates that the CPO-49-M materi-
als undergo two processes during the heating: loss of the sol-
vent (coordinated to metal sites and/or distributed in the pores)
and decomposition of the framework.
For CPO-49-Zn in both O2/Ar (20:80) and Ar atmosphere (Fig-
ure 4), the first mass decrease occurs in the range 32–300 °C
that corresponds to loss of solvent. The second mass decrease
is observed at ca. 440 °C and is typical for the decomposition
of the material. The two processes of solvent loss and decom-
position occur at widely spaced temperatures, in between
which a plateau at ca. 78 mass-% is observed. However, a small
exothermic peak at ca. 250 °C in the DSC signal in O2/Ar may
indicate that the desolvated framework starts to undergo fur-
ther changes at lower temperature than implied by the mass
loss and intense exothermic peak at ca. 440 °C that accompany
the ultimate decomposition of the material and formation of
crystalline ZnO (Figure S9).
Sorption Experiments
Nitrogen sorption confirms the permanence of porosity indi-
cated by the single crystal structures of the desolvated com-
pounds. Both materials display reversible sorption isotherms
(Figure 3), as expected for microporous materials. However, the
shape deviates from an ideal type I isotherm, particularly for
CPO-49-Mn, in that several steps occur above a nitrogen uptake
of 130–150 cm3 (STP) g–1. Such steps are frequently related to
changes of the structure of the adsorbant at the corresponding
pressure. For example, steps occur in the MOFs due to the gate
opening effect.[26] Based on the flexibility of the ligand and the
In the case of CPO-49-Mn, solvent loss and decomposition
contraction observed on transition from the solvated to desolv- of the framework appear to occur at more similar temperatures.
ated crystal structure (≈ 3 % and 7 % for CPO-49-Zn and -Mn, As a consequence, no plateau is observed in the TG trace. In-
respectively), it is reasonable to assign the occurrence of the stead, it shows only a gradual decrease of mass without well
steps to the response of the framework structure to increasing resolved steps until final exothermic combustion. Again, a less
amounts of adsorbate in the pores. Application of the Langmuir intense exothermic peak occurs at ca. 180 °C in O2/Ar (20:80).
equation to the lower pressure region yields specific surface The ultimate mass loss occurs after 400 °C with a significantly
areas of 853 m2 g–1 for CPO-49-Zn and 647 m2 g–1 for CPO-49- more intense exothermic peak in the DSC signal than in case
Mn, respectively. The BET specific surface area is 730 and of the Zn material, fitting well to the observation that the inor-
578 m2 g–1 for CPO-49-Zn and -Mn, respectively. The observed ganic residue is Mn2O3 (Figure S10), i.e. an additional redox
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reflections in the powder pattern degrade visibly above ca.
240 °C (Figure S11), in tune with the exothermic peak observed
in the DSC measurement.
Figure 4. Simultaneous thermogravimetric analysis (blue) and differential
scanning calorimetry (red) of a) CPO-49-Zn in O2/Ar (20:80), b) CPO-49-Mn in
O2/Ar (20:80), c) CPO-49-Zn in Ar, d) CPO-49-Mn in Ar.
process takes place in the form of oxidation of Mn2+ to Mn3+
.
While the final decomposition step occurs at almost the same
temperature for the zinc compound in Ar and O2/Ar mixture
atmospheres, this step occurs at slightly higher temperature in
Ar than in O2/Ar mixture for the manganese compound.
Figure 5. 2D variable temperature powder X-ray diffraction plot of a) CPO-49-
Zn in Ar flow, b) CPO-49-Mn in He flow. Note the significant change in pat-
terns of CPO-49-Mn before and after the gas flow through the capillary was
switched on (the first pattern of CPO-49-Mn on the bottom was measured
without flow). Representative powder X-ray diffraction patterns with reflec-
tion labels are shown on the right. At 220 °C, radiation damage was observed
for the Mn sample and the sample was moved 0.5 mm upstream and perpen-
dicular to the beam which lead to a significantly improved pattern, but also
introduced a discontinuity in evolution of the patterns between the corre-
sponding scans.
Variable Temperature Powder X-ray Diffraction
Powder X-ray diffraction under operation conditions is a power-
ful technique to obtain additional information about how a
crystalline metal–organic framework reacts to external stim-
uli.[27] Thermogravimetric analysis gives information only about
the mass change, but it does not provide any information about
changes in crystal structure of the material during heating. Vari-
able temperature powder X-ray diffraction in inert gas flow pro-
vides this complementary information.
In the case of CPO-49-Zn, the powder diffraction patterns
before and after flow through the sample cell commenced look
almost identical (Figure S13 and S14). A phase that is derived
from as-synthesized CPO-49-Zn exists in the temperature inter-
val from room temperature to ca. 150 °C. We observe a smooth
change of lattice parameters for this phase up to ca. 100 °C
(Figure 6, a). From ca. 100 °C upwards, a second phase starts to
manifest while the first phase disappears. This discontinuous
phase transition happens in the temperature range ca. 100–
150 °C. The second phase has additional reflections at 2θ ≈ 2.1
We would like to point out that the second phase does not
correspond to the single crystal structure of desolvated CPO-
49-Zn (Figure S15). The simulated powder pattern from the de-
solvated single crystal CPO-49-Zn actually looks very similar to
the powder pattern of solvated as-synthesized CPO-49-Zn. We
ascribe this to the use of the gentle desolvation procedure (de-
scribed above) which led to complete removal of the solvent
from the pores at 90 °C, which is below the temperature where
the phase transition starts to happen. The desolvated single
crystals and the bulk material used in the adsorption experi-
ments were treated in this way.
The main difference between the powder patterns of as-syn-
and 3.2°, i.e. at lower angles than the first reflection of the room thesized and desolvated CPO-49-Zn is the relative intensity of
temperature phase. This would be in accordance with a de- the [002] reflection. It seems to be characteristic for the amount
crease of symmetry of the structure or an increase in volume of solvent present in the structure. While it is almost as intense
of the unit cell. Despite the fact that the second phase has one as the reflection with maximum intensity in the powder pattern
very intense reflection, there are only few reflections at higher of solvated structure, it has dropped to approximately 1/3 of
angle which are well resolved. With the quality of the data avail- its intensity in the powder pattern of the desolvated structure
able, attempts to index this phase were unsuccessful. Although (Figure 5, a and S16). This decrease in intensity gradually occurs
thermogravimetric data showed ultimate mass loss for CPO-49- in the temperature range from 25–100 °C, concomitantly with
Zn after 450 °C, it was found that Zn sample has lost all crystalli- the decrease of the framework solvation in that temperature
nity at about 350 °C (Figure 5, a). In fact, the intensities of the interval. However, at 100 °C not all molecules of the high-boil-
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ing DMF have been removed in the variable temperature pow- for catalysis because of the potentially accessible coordination
der X-ray diffraction experiment, meaning that the intensity of site at the cation. CPO-49-Zn and -Mn discussed here contain a
the [002] reflection did not decrease to quite as low levels as racemic mixture of the linker, and therefore cannot be used as
expected from simulated powder pattern of the single crystal the catalysts in enantioselective reactions. However, if one
structure determination.
wished to do so the homochiral coordination polymer with the
chiral linker could be synthesized in all likelihood, as discussed
above. Here, we limited ourselves to test the potential catalytic
activity of CPO-49-M using the oxidation of styrene (as model
molecule bearing a C=C double bond) with tert-butyl hydroper-
oxide.
The as-synthesized sample of CPO-49-Mn, installed in the
variable temperature setup but before the inert gas flow was
switched on, corresponds well with the theoretical powder pat-
tern calculated from the single crystal structure determination
(Figure S18 and S19). The first pattern collected after the gas
flow was switched on already shows dramatic shifts in reflection
While CPO-49-Zn showed only limited conversion, CPO-49-
positions, reflecting significant changes in lattice parameters. Mn showed high conversion after a few hours (Figure 7). This
Apparently, the cell volume decreases by ca. 6 % already upon result corresponds well with a previous study, in which styrene
commencement of the desolvation process (Figure S20). After oxidation was catalyzed by the open metal site frameworks
this first sharp change, the diffraction patterns change more CPO-27-M (M-MOF-74), and where the CPO-27-Mn framework
smoothly in the temperature range from room temperature to showed the highest conversion, while the CPO-27-Zn frame-
220 °C, in congruence with continuous changes of the lattice work showed the lowest conversion among the -Mn, -Mg, -Ni,
parameters (Figure 6, b). Unfortunately, we observed radiation -Zn, -Co frameworks.[30]
damage of the sample at 220 °C, as indicated by the decrease
of intensity and change of the color of the sample in the beam.
For that reason the sample was moved 0.5 mm upstream which
led to a significantly improved pattern. Although this operation
resulted in a small discontinuity of the evolution of pattern and
lattice parameters, the change of lattice parameters follow the
previous trend. The high temperature phase corresponds well
to the empty one from the desolvated single crystal structure
of CPO-49-Mn (see Figure S21 and S22). The Mn sample has
completely lost its crystallinity at approximately 300 °C (Fig-
ure 5, b).
Figure 7. Kinetics curves for catalytic experiments of oxidation of styrene with
tert-butyl hydroperoxide with CPO-49-Zn as the catalyst (red), CPO-49-Mn as
the catalyst (blue), blank experiment without the catalyst (grey) and leaching
test (green, CPO-49-Mn catalyst was centrifuged off after 1 h).
After the catalytic reaction run, the powder diffraction pat-
tern of CPO-49-Zn remained more resolved than that of CPO-
49-Mn (Figure S23), i.e. while the zinc compound was less react-
ive in the catalytic test, its long range structure was also less
affected by the oxidative environment. The loss of long range
structure of CPO-49-Mn was accompanied with a significant
loss of specific surface area (Figure S24). The pore volume de-
creased by approximately 80 %. ICP analysis of the supernatant
solution indicates that there is no leaching of Mn2+ ions into the
solution which means the catalytic activity is of heterogeneous
nature.
Figure 6. Evolution of lattice parameters with temperature for a) CPO-49-Zn
CPO-49-Mn was also tested for reusability. After 10 hours
catalytic reaction the solid was separated by centrifugation and
used in a new catalytic run. The catalyst still showed significant
conversion of styrene, although a drop of conversion from ca.
73 to about 59 % is observed between runs 2 and 3 (Figure 8),
probably due to mechanical loss of the catalyst. A leaching test
was also performed for CPO-49-Mn (Figure 7). After initial con-
(only up to 100 °C; there is no data available for the second crystalline, but
non-indexed phase appearing at temperatures above 100 °C), b) CPO-49-Mn
(for the full temperature range in which a crystalline phase was observed).
Catalysis
Oxidation of double bonds is an important reaction in organic version after 1 h reaction, CPO-49-Mn was centrifuged off from
chemistry. Enantioselective epoxidation[28] is especially of inter- the reaction mixture and the conversion of styrene in superna-
est, because chiral epoxides can be transformed into other chi- tant was monitored over the time. An increase of conversion
ral molecules.[29] The CPO-49-M materials are good candidates over time is still observed after the removal of the solid catalyst.
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This is likely due to thermal conversion: the slope of styrene Experimental Section
conversion after removal of the solid catalyst is comparable
with the slope of the blank experiment.
Materials: All chemicals, reagents and solvents were purchased
from Sigma–Aldrich and used as received without further purifica-
tion, if it is not stated specifically. Hexane, toluene, THF and CH2Cl2
for inert syntheses were dried using Solvent Purification System
(MBraun SPS-800). Manipulations under inert atmosphere were per-
formed either in glove box (MBraun) or using Schlenk line tech-
nique. The gases were purchased from Yara Praxair and were of
99.999 % purity or higher.
Crystallography: Suitable crystals for diffraction experiments were
mounted in a minimum amount of Parabar 10312 oil (Hampton
Research) in a nylon loop. As-synthesized single crystals were
mounted at ambient conditions. Desolvated single crystals were
mounted in the glove-box and transferred into the cryostream in a
sealed shuttle. Intensity data was collected with a Bruker AXS TXS
rotating anode system with an APEXII Pt135 CCD detector using
graphite-monochromated Mo-Kα radiation (λ = 0.71073 Å). Data col-
lection and data processing were done using APEX2,[31]
SAINT,[32] and SADABS[33] version 2008/1, whereas structure solution
and final model refinement were performed using SHELXS[34] ver-
sion 2013/1 or SHELXT[35] version 2014/4 and SHELXL[36] version
2014/7.
Figure 8. Recycling of the CPO-49-Mn in styrene oxidation reaction; reaction
time is 10 h.
Based on the experimental results above, we concluded that
the catalytic reaction is of heterogeneous nature. The catalytic
activity of CPO-49-Mn persisted despite a large loss of its struc-
tural order and surface area, indicating that the active sites on
the outer surface of the material are possibly involved in the
conversion of substrates. The material is reusable and shows
activity in at least 4 catalytic runs of styrene oxidation.
CCDC 1483106 (for CPO-49-Zn as-synthesized), 1483107 (for CPO-
49-Zn desolvated), 1483108 (for CPO-49-Mn as-synthesized), and
1483109 (for CPO-49-Mn desolvated) contain the supplementary
crystallographic data for this paper. These data can be obtained
free of charge from The Cambridge Crystallographic Data Centre.
Synthetic Procedures: [TiCl3·3THF]: [TiCl3·3THF] was synthesized
according to a literature procedure.[37] In a glove box, (TiCl3)3·AlCl3
(20 g, 0.0335 mol) was suspended in toluene (20 mL) in a Schlenk
flask. The flask was subsequently transferred to a fume hood and
operated using standard Schlenk techniques under Ar. The reaction
mixture was cooled down to –50 °C and dry THF (150 mL, 1.8 mol)
was added via cannula transfer. The purple suspension was then
heated for 14 h under reflux. The green reaction mixture was cooled
to room temperature and filtered under Ar atmosphere. The prod-
uct was washed with dry hexane and dried in vacuo. The resulting
blue powder (yield: 34 g, 94 %) was stored under Ar at 2–8 °C.
Conclusions
We have managed to prepare two new isostructural frameworks
using Zn2+ and Mn2+ cations and a flexible bifunctional linker.
The hydroxy groups of this linker are involved in coordination
to the metal, leading to permanently porous frameworks with
1D channels.
H4dhdba Linker: 4,4′-(1,2-Dihydroxyethane-1,2-diyl)dibenzoic acid
was synthesized based on a slightly modified literature proce-
dure.[12] [TiCl3·3THF] (34.0 g, 91.7 mmol) were dissolved in dry
CH2Cl2 (50 mL) under Ar in a flask. In another flask, 4-formylbenzoic
acid (13.7 g, 91.3 mmol) were suspended in dry CH2Cl2 (100 mL)
under Ar. The titanium chloride complex solution was added to 4-
formylbenzoic acid suspension via cannula transfer. The reaction
mixture was stirred for 2.5 h under inert conditions at room temper-
ature. Then, water (150 mL) was added to quench the reaction. The
resulting white precipitate was filtered and washed with water and
ethanol under ambient atmosphere. Twice, the product was sus-
pended in methanol (50 mL), sonicated with ultrasound and fil-
tered. The obtained white solid was dried in dynamic vacuum over-
night at 110 °C (yield: 8.7 g, 63 %). 1H NMR (400 MHz, [D6]DMSO,
25 °C): δ = 4.74 (s, 2 H, CH), 5.61 (s, 2 H, OH), 7.23 (d, JH,H = 8.3 Hz,
4 H, Ph-H), 7.76 (d, JH,H = 8.3 Hz, 4 H, Ph-H), 12.85 (s, 2 H, COOH)
ppm. Elemental analysis (C16H14O6·0.2H2O): calcd. C 62.83, H 4.75;
found C 62.59, H 4.48.
The high crystallinity and crystal size of the materials allowed
observation of the single-crystal-to-single-crystal transforma-
tions in the compound upon removal of DMF solvent from the
pore, including the solvent molecules coordinated to the metal
site. Both isostructural frameworks undergo a rearrangement of
coordination environment and circumvent the formation of an
open metal site. In case of the manganese compound, a rear-
rangement of the carboxylate group takes place leading to a
4+1 coordination environment.
Even though the racemic mixture of the linker was used in
the synthesis, the structure allows one to anticipate that a
homochiral MOF could be built from the enantiomerically pure
linker. The presence of a solvent accessible metal site means
the material could potentially be evaluated in asymmetric catal-
ysis. In initial catalytic tests, the Mn compound showed higher
conversion than the Zn compound.
Another promising way of the development of this MOF se-
ries is to elongate the linker molecule by increasing the number
of phenyl rings in order to obtain larger pores.[10b,11c] That will
potentially affect the pore size and lead to higher surface area
and better accessibility of the internal pore volume.
CPO-49-Zn Synthesis: In a typical experiment, zinc(II) nitrate hexa-
hydrate (90 mg, 0.3 mmol) and 4,4′-(1,2-dihydroxyethane-1,2-
diyl)dibenzoic acid (30 mg, 0.1 mmol) were placed in a glass vial
(Schott, 22 mL). DMF (3 mL) and H2O (0.05 mL) were added. The
mixture was stirred at room temperature until the formation of a
Eur. J. Inorg. Chem. 2016, 4430–4439
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clear solution and subsequently placed in a preheated oven at
Variable temperature powder X-ray diffraction experiments with
110 °C for 1 d. The precipitate consisting of colorless crystals was synchrotron radiation were performed at beamline BM01A of the
filtered and washed with DMF, yield 50 mg, 81 % calculated on
linker basis for Zn2C17H12O8·2DMF. Elemental analysis (Zn2C17H12O8·
1.75C3H7NO·0.2H2O): calcd. C 44.06, H 4.10, N 4.04; found C 43.95,
H 3.96, N 4.10.
Swiss-Norwegian Beamlines (SNBL) at the European Synchrotron
Radiation Facility (ESRF) using a custom experimental setup,
adapted from literature.[38] The sample was put into a 0.5 mm capil-
lary. Glass fibers were placed on the downstream side of the sample
to prevent the sample from being blown out of the capillary. A flow
of inert gas was applied through the capillary while the sample was
heated with a hot air blower with a rate of 2 °C min–1 in the range
from room temperature to 200 °C and with a rate of 5 °C min–1
above 200 °C until the decomposition of the sample. Data was col-
lected using a diffractometer equipped with a Pilatus 2M detector.
2D frames were integrated azimuthal with the Bubble tool.[39]
The sample used in the synchrotron experiment was prepared using
a slightly different experimental procedure: zinc(II)-nitrate hexa-
hydrate (90 mg, 0.3 mmol) and 4,4′-(1,2-dihydroxyethane-1,2-
diyl)dibenzoic acid (90 mg, 0.3 mmol) were placed in a glass vial
(Schott, 22 mL). DMF (9 mL) was added. The mixture was stirred
at room temperature until the formation of a clear solution and
subsequently placed in a preheated oven at 110 °C for 1 d. The
colorless precipitate was filtered and washed with DMF.
Powder X-ray diffraction data and variable temperature powder X-
ray diffraction data was analyzed using TOPAS 4.2.[40]
CPO-49-Mn Synthesis: The single crystals measured were obtained
using the following experimental procedure: 4,4′-(1,2-dihydroxy-
ethane-1,2-diyl)dibenzoic acid (60 mg, 0.2 mmol) was placed in a
glass vial (Schott, 22 mL). DMF (9 mL) was added and the mixture
was stirred at room temperature until formation of a clear solution.
A solution of manganese(II) acetate tetrahydrate (98 mg, 0.4 mmol)
in H2O (0.9 mL) was added. The formation of a white suspension
was observed. The reaction mixture was stirred for 5 min before it
was placed in a preheated oven at 160 °C for 3 d. Colorless crystals
(yield: 10–15 mg) and formation of a brown precipitate was ob-
served.
Catalysis: Catalytic reactions were performed in a Biotage micro-
wave vial capped with a septum. In a typical catalytic reaction styr-
ene (0.2 mmol), tert-butyl hydroperoxide solution (70 wt.-% in H2O,
0.6 mmol), as-synthesized CPO-49-M (0.01 mmol) and toluene
(0.1 mmol) as standard were used. Reaction was run in acetonitrile
(1 mL) as a solvent. After addition of the components, the vial was
sealed with the septum and placed in a pre-heated bath. The reac-
tion was heated at 60 °C for the specified time period under contin-
uous stirring. Aliquots (50 μL) of the reaction mixture were taken at
specified time intervals, diluted in acetonitrile (1 mL) and immedi-
ately analyzed using GC–MS. GC–MS analysis was performed with
a Shimadzu GC–MS–QP2010 Ultra gas chromatograph mass spec-
trometer equipped with AOC-20i auto sampler and Rxi-5Sil-MS
The experimental procedure was subsequently optimized to yield
pure bulk samples which also contain single crystals of sufficient
size for crystal structure determination: 4,4′-(1,2-dihydroxyethane- (fused silica, 30.0 m × 0.25 mm × 1.00 μm) column. The following
1,2-diyl)dibenzoic acid (60 mg, 0.2 mmol) was placed in a glass vial
(Schott, 22 mL). DMF (3 mL) was added and the mixture was stirred
at room temperature until formation of a clear solution. Formic acid
(0.2 mmol) and a solution of manganese(II) acetate tetrahydrate
(98 mg, 0.4 mmol) in H2O (0.3 mL) were added in this order. The
formation of a white suspension was observed after addition of
manganese(II) acetate solution. The reaction mixture was stirred for
5 min. The atmosphere in the reactor was changed to Ar and the
reactor was placed in a preheated oven at 160 °C for 3 d. That
procedure resulted in higher, but still moderate yield of 40 mg and
absence of brown impurity (33 % yield calculated on linker basis for
Mn2C17H12O8·2DMF). Crystals were filtered and washed with DMF.
Elemental analysis (Mn2C17H12O8·1.9C3H7NO·0.2H2O): calcd. C 45.70,
H 4.34, N 4.46; found C 45.60, H 4.21, N 4.53.
temperature program was used: the temperature was held at 50 °C
for 1 min, then raised to 230 °C with a ramp of 9 °C min–1. Injector
and interface temperatures were 230 °C. Ion source temperature
was 200 °C.
In addition, the catalytic reaction was performed in larger scale by
a factor of 3.5. The solid residue from the reaction was used in the
N2 adsorption measurement and supernatant solution for the ICP
measurements. The supernatant solution obtained after the centrif-
ugation of catalytic reaction mixture was evaporated in vacuum.
The residue obtained in this way was dissolved in 20 mL of 2 %
nitric acid. This solution was analyzed by inductively coupled
plasma optical emission spectrometry (ICP-OES) using an iCAP7600
instrument.
Desolvation of the Samples and Gas Adsorption: Gas adsorption
measurements were carried out on a BELSORP-max instrument.
Samples were pre-treated by soaking in chloroform for several
times and subsequently heated in a dynamic vacuum at 90 °C over-
night. Samples were transferred into the glove-box, where sample
cells were filled and transferred to the instrument under inert at-
mosphere using quick seals. Prior to the sorption experiment, the
samples were again heated overnight in a dynamic vacuum at
90 °C.
Acknowledgments
We are grateful to Dr. D. Chernyshov, Dr. V. Dyadkin and A.
Mikheykin for kind assistance with the measurements at the
SNBL@ESRF. This research was supported by the Research Coun-
cil of Norway through grants ISP-KJEMI 209339 and SYNKNOYT
227702 and 247734.
Keywords: Metal–organic frameworks · Adsorption ·
Heterogeneous catalysis
Thermal Analysis: A Netzsch STA 449 F1 Jupiter was used for simul-
taneous thermogravimetric-differential scanning calorimetry meas-
urements. Measurements were performed in a flow of pure Ar or
O2/Ar (20:80) mixture and a heating rate of 2 °C min–1
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© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim