Isoreticular Chemistry of Group 13 Metal-Organic Framework Compounds Based on V-Shaped Linker Molecules: Exceptions to the Rule?

Article abstract of DOI:10.1021/acs.inorgchem.1c00767

Following the concept of isoreticular chemistry, we carried out a systematic study on Ga-containing metal-organic frameworks (MOFs) using six V-shaped linker molecules of differing sizes, geometries, and additional functional groups. The linkers included three isophthalic acid derivatives (m-H2BDC-R, R = CH3, OCH3, NHCOCH3), thiophene-2,5-dicarboxylic acid (H2TDC), and two 4,4′-sulfonyldibenzoic acid derivatives (H2SDBA, DPSTA). The crystal structures of seven compounds were elucidated by a combination of model building, single-crystal X-ray diffraction (SCXRD), three-dimensional electron diffraction (3D ED), and Rietveld refinements against powder X-ray diffraction (PXRD) data. Four new Ga-MOFs that are isoreticular with their aluminum counterparts, i.e. Ga-CAU-10-R (Ga(OH)(m-BDC-R); R = OCH3, NHCOCH3), Ga-CAU-11 (Ga(OH)(SDBA)), and Ga-CAU-11-COOH (Ga(OH)(H2DPSTC)), were obtained. For the first time large single crystals of a MOF crystallizing in the CAU-10 structure type could be isolated, i.e. Ga-CAU-10-OCH3, which permitted a detailed structural characterization. In addition, the use of 5-methylisophthalic acid and thiophene-2,5-dicarboxylic acid resulted in two new Ga-MOFs denoted Ga-CAU-49 and Ga-CAU-51, respectively, which are not isostructural with any known Al-MOF. The crystal structure of Ga-CAU-49 ([Ga4(m-HBDC-CH3)2(m-BDC-CH3)3(OH)4(H2O)]) contains an unprecedented rod-shaped inorganic building unit (IBU) of the formula ∞1{Ga16(OH)18O60}, composed of corner-sharing GaO5 and GaO6 polyhedra. In Ga-CAU-51 ([Ga(OH)(C5H2O2S)]) chains of alternating cis and trans corner-sharing GaO6 polyhedra form the IBU. A detailed characterization of the title compounds was carried out, including nitrogen gas and water vapor sorption measurements. Ga-CAU-11 was the only compound exhibiting porosity toward nitrogen with a type I isotherm, a specific surface area of aS,BET = 210 m2/g, and a micropore volume of Vmic = 0.09 cm3/g. The new MOF Ga-CAU-51 exhibits exceptional water sorption properties with a reversible S-shaped isotherm and a high uptake around p/p0 = 0.38 of mads = 370 mg/g.

Full text of DOI:10.1021/acs.inorgchem.1c00767

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Article
Isoreticular Chemistry of Group 13 Metal−Organic Framework
Compounds Based on V‑Shaped Linker Molecules: Exceptions to the
Rule?
Timo Rabe, Erik Svensson Grape, Hauke Rohr, Helge Reinsch, Stephan Wöhlbrandt, Alexandra Lieb,
A. Ken Inge, and Norbert Stock*
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ABSTRACT: Following the concept of isoreticular chemistry, we
carried out a systematic study on Ga-containing metal−organic
frameworks (MOFs) using six V-shaped linker molecules of differing
sizes, geometries, and additional functional groups. The linkers
included three isophthalic acid derivatives (m-H2BDC-R, R = CH3,
OCH3, NHCOCH3), thiophene-2,5-dicarboxylic acid (H2TDC),
and two 4,4′-sulfonyldibenzoic acid derivatives (H2SDBA, DPSTA).
The crystal structures of seven compounds were elucidated by a
combination of model building, single-crystal X-ray diffraction
(SCXRD), three-dimensional electron diffraction (3D ED), and Rietveld refinements against powder X-ray diffraction (PXRD) data.
Four new Ga-MOFs that are isoreticular with their aluminum counterparts, i.e. Ga-CAU-10-R (Ga(OH)(m-BDC-R); R = OCH3,
NHCOCH3), Ga-CAU-11 (Ga(OH)(SDBA)), and Ga-CAU-11-COOH (Ga(OH)(H2DPSTC)), were obtained. For the first time
large single crystals of a MOF crystallizing in the CAU-10 structure type could be isolated, i.e. Ga-CAU-10-OCH3, which permitted a
detailed structural characterization. In addition, the use of 5-methylisophthalic acid and thiophene-2,5-dicarboxylic acid resulted in
two new Ga-MOFs denoted Ga-CAU-49 and Ga-CAU-51, respectively, which are not isostructural with any known Al-MOF. The
crystal structure of Ga-CAU-49 ([Ga4(m-HBDC-CH3)2(m-BDC-CH3)3(OH)4(H2O)]) contains an unprecedented rod-shaped
inorganic building unit (IBU) of the formula ∞1 {Ga16(OH)18O60}, composed of corner-sharing GaO5 and GaO6 polyhedra. In Ga-
CAU-51 ([Ga(OH)(C5H2O2S)]) chains of alternating cis and trans corner-sharing GaO6 polyhedra form the IBU. A detailed
characterization of the title compounds was carried out, including nitrogen gas and water vapor sorption measurements. Ga-CAU-11
was the only compound exhibiting porosity toward nitrogen with a type I isotherm, a specific surface area of aS,BET = 210 m2/g, and a
micropore volume of Vmic = 0.09 cm3/g. The new MOF Ga-CAU-51 exhibits exceptional water sorption properties with a reversible
S-shaped isotherm and a high uptake around p/p0 = 0.38 of mads = 370 mg/g.
have rarely been described.16 Important pioneering work was
INTRODUCTION
■
carried out by the group of Ferey and Loiseau, reporting
The concept of isoreticular chemistry is well-known for metal−
almost the entirety of frameworks based on Ga3+ with
organic frameworks (MOFs), which are assembled by organic
carboxylate linkers.17−20 In most cases, Al- and Ga-MOFs
form isoreticular frameworks.21−23 The ionic radii of group 13
elements Al3+, Ga3+, and In3+ with a coordination number
(CN) of 6 are 0.675, 0.760, and 0.940 Å, respectively.24 With a
decrease in surface charge density of the metal center, from
[Al(H2O)6]3+ to [Ga(H2O)6]3+ and [In(H2O)6]3+, consid-
erably higher exchange rates during synthesis are found for the
latter metal ions.25 A higher lability usually allows the synthesis
linker molecules and inorganic building units (IBUs).1−3 Such
a modular construction leads to materials that crystallize in
various framework topologies.4 In some cases, components can
be chosen to intentionally create a framework structure with
specific, desired properties. For example, the pore size can be
tailored by substituting smaller for larger metal ions or linker
molecules, e.g. in CAU-215 and MOF-5,6 respectively, or the
water sorption properties can be tuned by variation of the
linker molecules.7 Hence, MOFs are materials of interest for
drug delivery,8 gas storage,9 catalysis,10 and heat trans-
formation11 since these applications rely strongly on specific
host−guest interactions that need to be optimized.12,13
Received: March 12, 2021
Published: June 9, 2021
MOFs containing Al3+ ions have been intensely studied in
the past decade due to the abundance of aluminum salts,14
their high thermal and chemical stability,7 and outstanding
sorption properties.15 In contrast, MOFs built from Ga3+ ions
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of larger single crystals.26 Therefore, the crystal structures of
Ga- and In-MOFs are often elucidated by SCXRD, while the
structures of Al-MOFs are most often determined from PXRD
data.27,28 Structure determination from SCXRD data is
preferable, as it is more straightforward and since a higher
accuracy is achieved due to the lack of overlapping
reflections.29
In recent years we have intensely studied the influence of the
linker size and geometry on the crystal structure of Al-MOFs.16
In particular, the use of V-shaped linker molecules has resulted
in a rich structural chemistry and we were able to demonstrate
that subtle changes in the linker lead to Al-MOFs with very
different properties.30 In line with these investigations and
following our interest in the chemistry of group 13 MOFs, we
have recently started a systematic investigation of Ga-MOFs.
Thus, the use of various substituted naphthyldicarboxylic acids
under similar reaction conditions resulted in the formation of
isostructural Al- and Ga-MOFs.21
EXPERIMENTAL SECTION
■
Materials. Gallium(III) nitrate heptahydrate (Ga(NO3)3·7H2O,
ABCR, 99.99% PURATREM), aluminum(III) nitrate nonahydrate
̈
(Al(NO3)3·9H2O, Grussing, reinst), 5-methoxybenzene-1,3-dicarbox-
ylic acid (m-H2BDC-OCH3, TCI, >95%), 5-methylbenzene-1,3-
dicarboxylic acid (m-H2BDC-CH3, ABCR, 98%), 4,4′-sulfonyldiben-
zoic acid (H2SDBA, Sigma-Aldrich, >98%), 3,3′,4,4′-diphenylsulfo-
netetracarboxylic dianhydride (DPSDA, TCI, >98%), and thiophene-
2,5-dicarboxylic acid (H2TDC, TCI, >98%) are commercially
available and were used without further purification. 5-Acetamide-
benzene-1,3-dicarboxylic acid (m-H2BDC-NHCOCH3) was synthe-
sized from 5-aminobenzene-1,3-dicarboxylic acid (m-H2BDC-NH2,
Sigma-Aldrich, 94%) following the procedure by Moynihan et al.31
and characterized by 1H-NMR spectroscopy (section 2 in the
Supporting Information).
Methods. The reactions were carried out using either conven-
tional heating or microwave-assisted heating. Syntheses in conven-
tional ovens were performed in custom-made steel autoclaves
equipped with Teflon liners with a total volume of 2 or 20 mL.32
For the microwave-assisted reactions in Biotage Initiator and Initiator
+ microwave systems, 20 mL glass reactors were employed. Initial
characterization by PXRD was done on a STOE Stadi P-Combi
diffractometer equipped with a MYTHEN 1K detector and using Cu
Kα1 radiation. PXRD data for structure determination and refinement
were collected on a STOE Stadi MP instrument with a MYTHEN 1K
detector and a flat sample spinner using Cu Kα1 radiation. SCXRD
data were collected on a STOE imaging plate detector system (IPDS)
using graphite-monochromated Mo Kα radiation. The temperature-
dependent PXRD data (TD PXRD) were collected with a STOE
capillary furnace in 0.5 mm quartz capillaries. Humidity-dependent
PXRD (HD PXRD) data were collected on a PANalytical Empyrean
diffractometer (Cu Kα1/2 radiation). IR spectra were recorded on a
Bruker ALPHA-FT-IRA220/D-01 spectrometer equipped with an
ATR unit. The thermogravimetric (TG) analyses were done using a
NETZSCH STA 409 CD analyzer (air flow 75 mL/min, heating rate
4 K/min) and on a Linseis STA PT 1000 (nitrogen flow 80 mL/min
or air flow 80 mL/min, heating rate 4 K/min). The carbon, hydrogen,
nitrogen, and sulfur contents were determined by elemental analysis
on a HEKAtech Euro EA Elemental Analyzer. The crystal structure
database33 (CSD) search was carried out in the MOF subset list34
employing the programs ConQuest35 and Mercury.36 Calculations of
pore diameters or theoretical specific surface areas were conducted
using PLATON37 or Zeo++.38 Three-dimensional electron diffraction
(3D-ED) data were collected on a JEOL JEM2100 instrument
equipped with a Timepix detector from Amsterdam Scientific
Instruments. Topological analyses were carried out using ToposPro39
and Systre.40
Herein we present our latest results on the systematic study
on the use of V-shaped linker molecules, differing in size, linker
geometry, and functional groups (Figure 1). In addition to
Figure 1. V-shaped linker molecules and their angles between the
carboxylic acid groups as used in the synthesis of Al- and Ga-MOFs:
4,4′-sulfonyldibenzoic acid (H2SDBA), thiophene-2,5-dicarboxylic
acid (H2TDC), 5-methoxybenzene-1,3-dicarboxylic acid (m-
H2BDC-OCH3), 5-acetamidebenzene-1,3-dicarboxylic acid (m-
H2BDC-NHCOCH3) and 5-methylbenzene-1,3-dicarboxylic acid
(m-H2BDC-CH3).
Synthesis. A summary of reaction parameters for the syntheses of
all compounds is given in Table 1. It includes solvents, metal to linker
molar ratio (M:L), reaction temperature (T) and time (t), as well as
the heating method (MW, microwave-assisted reaction; conv,
conventional heating). The synthetic procedure for every reaction
started with weighing in the organic linker, and then the solvent was
establishing the synthesis parameters, chemical and physical
properties, and crystal structures of one Al-MOF and five new
Ga-MOFs, we compare the structural chemistry of Al- and Ga-
MOFs.
Table 1. Overview of the Synthesis Parameters for Ga-CAU-10-OCH3, Al-CAU-10-NHCOCH3, Ga-CAU-10-NHCOCH3, Ga-
a
CAU-11, Ga-CAU-11-COOH, Ga-CAU-49, and Ga-CAU-51
compound
solvent
solvent ratio
1:9
T/°C, t/h
M:L ratio
heating
Ga-CAU-10-OCH3
Al-CAU-10-NHCOCH3
Ga-CAU-10-NHCOCH3
Ga-CAU-11
Ga-CAU-11-COOH
Ga-CAU-49
water−toluene
water
water
water
water
water−toluene
water−AcOH
140, 3
160, 48
120, 4
120, 2
180, 24
120, 24
120, 4
1:0.6
1:1
1:1
1:0.9
1:1.3
1:0.1
1:1
conv/MW
conv
MW
MW
conv
1:0.8
1:5
conv
MW
Ga-CAU-51
a
Abbreviations: AcOH, acetic acid; DMF, N,N-dimethylformamide; MW, microwave-assisted heating; conv, conventional heating. Exact quantities
of starting materials are provided in section 2 of the Supporting Information.
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filled in the respective reactor. Subsequently, additives and the
aqueous gallium(III) or aluminum(III) nitrate solution were added to
the reaction mixture. Finally, the reaction vessel was closed and
subjected to a temperature−time program in a conventional or
microwave oven. The detailed synthesis procedures (including the
exact amounts of starting materials), the results of the CHNS
analyses, and synthesis yields can be found in section 2 in the
Supporting Information.
Structure Determination of Ga-CAU-10-OCH3 and Ga-CAU-
49. The crystal structures of Ga-CAU-10-OCH3 (Figure S3) and Ga-
CAU-49 were determined by SCXRD. Single crystals of both
compounds were selected under a polarizing microscope, and data
collection was carried out at 293 K. The single-crystal structures were
solved using the program SHELXT41 and refined with SHELXL42
using Olex243 as the GUI. All hydrogen atoms were added via AFIX
instructions and refined using a riding model.
RESULTS AND DISCUSSION
■
Seven new group 13 MOFs containing Al3+ or Ga3+ ions and
V-shaped linker molecules differing in size, linker geometry,
and additional functional groups (Figure 1) have been
obtained by solvothermal syntheses (Table 1) employing
conventional as well as microwave-assisted heating. Reactions
were carried out using the metal nitrates and the solvents
water, acetic acid, and toluene. The Ga-CAU-11 type
compounds, containing the larger, more flexible linker
molecules, i.e. 4,4′-sufonyldibenzoic acid H2SDBA and
DPSDA, were synthesized under hydrothermal reaction
conditions similar to those reported for Al-CAU-11 by Reimer
et al. in 2015.45
When the more rigid and smaller isophthalic acid derivatives
(m-H2BDC-X, X = CH3, OCH3, NHCOCH3) were used,
MOFs exhibiting different crystal structure types, depending
on the metal ion employed, were obtained. While the reactions
with Al3+ salts exclusively led to the formation of CAU-10 type
structures, a larger structural variability was observed for the
Ga-MOFs. Thus, we were able to obtain the first Ga-CAU-10
type compounds with m-H2BDC-NHOCH3 and m-H2BDC-
OCH3, while the use of m-H2BDC-CH3 resulted in a new,
more complex crystal structure (Ga-CAU-49). The use of
toluene proved to be advantageous in these syntheses,
although we can only speculate on its role during the
crystallization. Thus, it could influence the solubility of the
starting materials or the final MOFs. It is worth mentioning
that the Ga-CAU-49 and Ga-CAU-10-OCH3 syntheses
resulted in coarse crystalline products containing single crystals
of suitable size for structure determination by SCXRD. This
observation is in line with previous reports on the synthesis of
Al- and Ga-MOFs showing that larger crystals are more
frequently obtained with Ga3+ salts.48,49 This phenomenon is
related to the higher lability of Ga3+ complexes in comparison
to Al3+ complexes.25
Structure Determination of M-CAU-10-NHCOCH3 (M = Al3+,
Ga3+), Ga-CAU-11, Ga-CAU-11-COOH, and Ga-CAU-51. The
crystal structures of Ga-CAU-11, M-CAU-10-NHCOCH3 (M = Al3+,
Ga3+), and Ga-CAU-51 were determined from PXRD data. Structure
models of Ga-CAU-11 and M-CAU-10-NHCOCH3 (M = Al3+, Ga3+)
were derived in Materials Studio44 using crystallographic information
on Al-CAU-1145 and Al-CAU-10-OCH3.7 After indexing of the PXRD
patterns with TOPAS academic,46 the unit cell dimensions were
imposed in Materials Studio and Al3+ ions were substituted by Ga3+.
The structure models were optimized using the universal force field as
implemented in the software. A suitable structure model for Ga-CAU-
51 was derived from 3D electron diffraction data recorded on small
single crystals (ca. 1.5 μm; section 4, Figure S3, and Table S2 in the
Supporting Information). The structure refinement was performed
using the Rietveld method implemented in the TOPAS academic
software suit.47 Details are provided in section 5 in the Supporting
Information. The final Rietveld refinement plot of Ga-CAU-51 is
shown in Figure 2, whereas all other Rietveld plots are presented in
When H2TDC was employed, a small, rigid linker with a
larger opening angle between the two carboxylate groups in
comparison to m-H2BDC-X (148 vs 120°) another new, highly
porous Ga-MOF, denoted Ga-CAU-51, could be isolated from
an acetic acid and water (5/1) mixture under solvothermal
reaction conditions. Further details on the synthesis of each
title compound are given in section 2 in the Supporting
Information).
The crystal structure determinations of the title compounds
were carried out from single-crystal and powder diffraction
data. A comparison of the structures of Al- and Ga-MOFs
obtained with the same linker molecules reveals that
isostructural compounds, i.e. CAU-10 and CAU-11, were
observed when the linker molecules m-H2BDC-OCH3, m-
H2BDC-NHCOCH3, and H2SDBS were used (Figure 3).
However, when linker molecules m-H2BDC-CH3 and H2TDC
were employed, compounds with distinct, new framework
structures, denoted Ga-CAU-49 and Ga-CAU-51, respectively,
were obtained.
Since the structures of CAU-11 and CAU-10 have been
reported previously, their structural descriptions are given in
section 5 in the Supporting Information. The focus of the
following sections will be on the new crystal structures of Ga-
CAU-49 and Ga-CAU-51.
Figure 2. Final Rietveld refinement plot for Ga-CAU-51. The
observed curve is shown in black, the calculated curve in red, the
difference curve in blue, and the positions of allowed reflections are
shown as black ticks.
the Supporting Information. For Ga-CAU-11-COOH only a Pawley
fit was performed (Figure S11 and Table S8). Results of the crystal
structure refinements are summarized in Table 2. In addition to the
Ga compounds, structural data information on the isostructural Al-
MOFs is also included. The asymmetric units and bond lengths are
given in section 5, Figures S4−S18, and Tables S3−S14 in the
Supporting Information. The CCDC entries 2067831−2067836
contain the full crystallographic data for Al-CAU-10-NHCOCH3,
Ga-CAU-10-OCH3, Ga-CAU-51, Ga-CAU-10-NHCOCH3, Ga-CAU-
49, and Ga-CAU-11, respectively. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre.
Crystal Structures. Ga-CAU-49. The reaction of gallium-
(III) nitrate with m-H2BDC-CH3 in toluene and water (1/1)
results in the compound Ga-CAU-49 with the composition
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Table 2. Crystallographic Parameters of Ga-CAU-10-OCH3, Al-CAU-10-NHCOCH3, Ga-CAU-10-NHCOCH3, Ga-CAU-11,
Ga-CAU-49, and Ga-CAU-51 (tw = This Work)
M-CAU-10-OCH3
M-CAU-10-NHOCH3
M-CAU-11
Ga-CAU-49
Ga3+ (tw)
Ga-CAU-51
Ga3+ (tw)
7
45
metal ion (M)
Al3+
Ga3+ (tw)
SCXRD
Al3+ (tw)
PXRD
Ga3+ (tw)
PXRD
Al3+
Ga3+ (tw)
PXRD
refinement from (data) PXRD
PXRD
SCXRD
3DED/
PXRD
cryst syst
space group
tetragonal
I41/a
tetragonal
I41/a
tetragonal
I41/a
orthorhombic
I41/a
orthorhombic
Pnma
orthorhombic
Pnma
monoclinic
C2/c
monoclinic
P21/c
a/Å
b/Å
c/Å
β/deg
V/Å3
Rwp
21.3609(3)
21.3609(3)
10.5699(2)
21.570(3)
21.570(3)
10.790(2)
21.4594(4)
21.4594(4)
10.7902(4)
21.7251(3)
21.7251(3)
10.8522(3)
6.6111(5)
12.888(1)
20.020(1)
6.7288(4)
12.8292(9)
20.4174(18)
37.335(8)
11.524(2)
24.123(5)
97.11(3)
1762.5(2)
5.4
12.5726(8)
15.777(1)
14.025(1)
102.538(7)
2715.7(4)
4.3
4822.9(2)
7.6
5020.2(2)
4968.9(2)
5.8
5122.0(2)
3.8
10300(4)
1705.8(5)
7.7
RBragg
4.3
4.1
2.9
1.4
2.8
1.7
GOF
2.0
6.1
3.8
not reported
3.1
2.7
no. of rflns collected
no. of indep rflns
R indices (I > 2σ(I))
20185
2822
43557
11577
R1 = 0.0524
wR2 = 0.1356
R1 = 0.0555
wR2 = 0.1377
2822/0/159
R1 = 0.0647
wR2 = 0.1520
R1 = 0.0944
wR2 = 0.1681
11577/0/705
R indices (all data)
no. ofdata/restraints/
params
GooF
1.079
1.036
Figure 3. Overview of the group 13 MOFs obtained in this study (AlO6 polyhedra are displayed in gray). Isostructural compounds (CAU-10 and
CAU-11) are observed when the linker molecules H2SBDS, m-H2BDC-OCH3, and m-H2BDC-NHCOCH3 are employed (MO6 polyhedra, M =
Al3+, Ga3+ is displayed in green), while distinct, new framework structures are observed with m-H2BDC-CH3 and H2TDC as linker molecules. The
latter MOFs are denoted Ga-CAU-49 and Ga-CAU-51, respectively (GaO6 polyhedra and GaO5 polyhedra displayed in pale blue and pink,
respectively).
[Ga4(m-HBDC-CH3)2(m-BDC-CH3)3(OH)4(H2O)]. Ga-
CAU-49 crystallizes in a new and very complex crystal
structure containing an unprecedented IBU of the formula
1∞{Ga16(OH)18O60}, composed of corner-sharing GaO5 and
GaO6 polyhedra. This is, to the best of our knowledge, the first
time a trigonal-bipyramidal coordination geometry has been
observed in a Ga-MOF, while for coordination polymers and
complexes this coordination geometry is well-known.50,51 The
hexagonal arrangement of the IBUs is shown in Figure 4. Five
symmetry-independent Ga3+ ions and linker molecules are
observed in the asymmetric unit, and the Ga3+ ions form
1∞{Ga16(OH)18O60} chains, which are extending along the ac
diagonal of the unit cell (Figure 4d). In contrast to other Al-
and Ga-MOFs the IBU contains 5-fold-coordinated Ga3+ ions.
The IBU is formed by corner-sharing GaO5 and GaO6
polyhedra shown in pink and blue, respectively, in Figure 4.
Each IBU is connected through the linker molecules to six
other IBUs, which leads to a heptanodal 3,3,4,4,4,5,5-c net
(Figure S24). The choice of nodes when deconstructing the
inorganic building units of Ga-CAU-49 and Ga-CAU-51 was
made as described by O’Keeffe and Yaghi,52 where the point of
extension of each linker was used as a node. Elaborate
structural details can be found in section 5 in the Supporting
Information. Water molecules are represented by O6 and O7
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Figure 4. Crystal structure architecture of Ga-CAU-49 with its IBU in
different perspective views (a−c) and the repetitive sequence of Ga3+
ions in the IBU marked in pink for CN = 5 and blue for CN = 6 as
well as (d) the hexagonal connection pattern between the IBUs.
Linker molecules are deleted for reasons of simplicity. GaO5 trigonal
bipyramids are shown in pink, and GaO6 octahedra are shown in blue.
in the crystal structure of Ga-CAU-49 (Figure S16). Since
there are various distances in the range of d(O···O) =
2.64(3)−3.04(2) Å between O6, O7 and adjacent oxygen
atoms, H-bonding is anticipated.
Figure 5. Crystal structure of Ga-CAU-51 ([Ga(OH)(TDC)]) with
(a) the arrangement of its cis,trans corner-sharing polyhedra, which
are connected through thiophene-2,5-dicarboxylate ions to form the
framework structure (b) containing square-shaped channels along
[100] with a channel diameter of ca. 6.2 Å, and (c, d) pore walls in the
crystal structure of Ga-CAU-51 depicted as Connolly surface models
in Materials Studio.44 GaO6 octahedra are shown in blue, oxygen
atoms in red, carbon atoms in black, and sulfur atoms in yellow.
Ga-CAU-51. Employing H2TDC and gallium(III) nitrate in
an acetic acid and water (5/1) mixture led to the crystallization
of the new compound Ga-CAU-51 ([Ga(OH)(TDC)]). The
crystal structure of Ga-CAU-51 contains chains of alternating
cis,trans corner-sharing GaO6 polyhedra as the IBU (Figure
5a). These chains are interconnected by thiophene-2,5-
dicarboxylate ions, forming square-shaped one-dimensional
channels along [100] with a diameter of ca. 6.2 Å. This IBU
has been described once for another Ga-MOF53 and was also
reported for the Al compounds MOF-303 and MOF-573, of
composition [Ga(OH)(PzDC)], with PzDC2− = 1H-3,5-
pyrazoledicarboxylate.54,55 Further details on the structure
and structure determination are given in (section 5 and Table
S15 in the Supporting Information. A topological analysis of
the framework gives the previously described tetranodal
5,5,5,5-c net xhh.56
Table 3 and Figure 3 summarize the structural details of
MOFs based on the V-shaped linker molecules presented in
Figure 1: i.e., framework name, IBU, and topology. For most of
the linker molecules isostructural products are observed when
Al3+ ions are replaced by Ga3+. Due to the different ionic radii
(r(Ga3+) = 0.620 Å, r(Al3+) = 0.535 Å), larger metal−oxygen
distances and unit cell parameters are found for the Ga-MOFs.
The Ga−O (1.90(2)−2.05(6) Å) and Al−O (1.84(2)−
1.86(2) Å) distances of the title compounds are in good
agreement with the values reported in the literature (Figures
S27 and S28), and the Al3+ and Ga3+ ions are found prevalently
in an octahedral (CN = 6) coordination geometry. However,
with Ga-CAU-49 and Ga-CAU-51, Ga-MOFs were discovered
that do not have isostructural Al-MOFs. The use of m-H2BDC-
CH3 results, as expected, in the formation of Al-CAU-10-CH3,
which contains chains of cis corner-sharing AlO6 polyhedra,
while in Ga-CAU-49 an unprecedented IBU with Ga3+ ions in
octahedral and trigonal-bipyramidal coordination geometries is
observed. With H2TDC, i.e. the linker with the largest angle
∠(O2C,C,CO2) = 148° within the study, two Al-MOFs are
known, the framework polymorphs Al-MIL-53-TDC57 and
CAU-23.58 The former exhibits low long-range ordering, which
was proven by NMR spectroscopy.57 In contrast CAU-23 is a
highly crystalline material containing chains of (trans)4(cis)4
corner-sharing AlO6 polyhedra.58 In combination with the
larger Ga3+ ions only a highly crystalline compound was
observed with chains of alternating cis−trans corner-sharing
GaO6 polyhedra. The crystal structure of Ga-CAU-51
resembles somewhat those of MOF-303 and MOF-573,54,55
which were recently reported but for which no detailed
crystallographic information was presented.
Thermal analysis. The temperature-dependent properties
of all title compounds were investigated by thermogravimetric
(TG) and temperature-dependent (TD) PXRD analyses. The
TG curves are presented in Figures S37−S43 and in Figure 6.
The presence of solvent molecules in the crystal structures of
Ga-CAU-49, Ga-CAU-10-OCH3, and Ga-CAU-51 was con-
firmed, and all compounds decompose above 350 °C, leading
to the formation of crystalline β-Ga2O3 or X-ray amorphous
Al2O3 (Table S23). As has previously been described, the Al-
MOFs exhibit higher thermal stabilities in comparison to their
isostructural Ga-MOFs.21 This trend is also confirmed by TD
PXRD measurements (Figures S44−S50). Figure 6 shows a
correlation between the TG (left) and TD PXRD measure-
ments (right) of Ga-CAU-51. The initial mass loss in the TG
curve, up to a temperature of ca. 100 °C, is attributed to the
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Table 3. V-Shaped Linker Molecules Used in This Study and Their Corresponding Al and Ga Compound Framework Type
a
Structures, IBUs, and Topological Net Symbols
framework type/IBU/net symbol
linker molecule
H2SDBS
m-H2BDC-OCH3
m-H2BDC-NHCOCH3
m-H2BDC-CH3
2,5-H2TDC
angle between carboxylate groups (deg)
Al compound
Ga compound
102
120
120
120
148
Al-CAU-11/trans/sql
Al-CAU-10/cis/lzh
Al-CAU-10/cis/lzh
Al-CAU-10/cis/lzh
Al-MIL-53/trans/sra
Al-CAU-23/(trans)4(cis)4/−
Ga-CAU-11/trans/sql
Ga-CAU-10/cis/lzh
Ga-CAU-10/cis/lzh
Ga-CAU-49/cis,trans/−
Ga-CAU-51/cis,trans/xhh
a
For CAU-23 and Ga-CAU-49 no net symbols (three-letter names) have yet been assigned.
Figure 6. TG curve (left) and TD PXRD measurement (right) of Ga-CAU-51, with major events marked by red lines at ca. 100 and 350 °C.
desorption of water molecules from the framework. This
correlates well with the first major event detected by TD
PXRD, seen as a change in relative intensities and a slight shift
in reflection positions. Ga-CAU-51 decomposes above ca. 350
°C, as confirmed by both techniques.
Sorption Measurements. All of the title compounds were
studied regarding their sorption properties with nitrogen or
water at 77 and 298 K, respectively (Table S25). The nitrogen
isotherms are presented in Figures S51−S57. No considerable
nitrogen uptake was detected except for Ga-CAU-11, which
shows a type I shaped isotherm, which is typical for
microporous materials (Figure S54).59 Ga-CAU-11 exhibits a
specific surface area of as,BET = 210 m2/g and a micropore
volume of Vm = 0.09 cm3/g.
Figure 7. Water sorption isotherm of Ga-CAU-51 at 298 K. Filled
symbols represent adsorption and empty symbols desorption.
Water sorption isotherms of all title compounds and their
PXRD patterns after the sorption measurements are presented
in Figures S59−S64 and Figures S65−S71 in the Supporting
the steep uptakes in the isotherm. Three framework forms
were identified by PXRD measurements (Figure S73): the
activated form of Ga-CAU-10-NHCOCH3 (red), an inter-
mediate wet form (blue), and the as-synthesized form (green).
A structure determination could only be carried out for the
activated form, as it exhibits a highly ordered framework. Thus,
the deviation between calculated (calculated by PLATON mads
= 99 mg/g) and experimental uptakes (mads = 55 mg/g) is
related to structural changes upon water adsorption. Since the
structural flexibility of CAU-10 MOFs has been studied quite
extensively in the past, it is plausible to assume that rotation of
the linker molecules occurs upon water sorption.30
Information, respectively. In the following paragraphs, only the
results of Ga-CAU-51 and Ga-CAU-10-NHCOCH3 are
presented in Figures 7 and 8, since they exhibit the highest
H2O uptake and the most distinct structural changes,
respectively. For Ga-CAU-51 a sigmoidal-shaped isotherm
with a steep rise at p/p0 = 0.38 and a high maximum uptake of
mads = 370 mg/g is found (calculated by PLATON,37 mads=
402 mg/g).
In contrast, only a small water uptake is observed for Ga-
CAU-10-NHCOCH3, but two distinct steps are found,
indicating a structural change in the framework upon water
adsorption.59 Therefore, humidity-dependent PXRD measure-
ments were carried out, showing two major changes in the
PXRD pattern of Ga-CAU-10-NHCOCH3 as depicted in
Figure 8. These changes are located at relative humidity values
of ca. 30−40% and 60−70%, matching the starting points of
CONCLUSION
■
The syntheses, structure determinations, and full character-
izations of one new Al-MOF and five Ga-MOFs containing
different V-shaped linker molecules are reported. We were able
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ASSOCIATED CONTENT
■
sı
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.inorgchem.1c00767.
Thermogravimetric measurement of Ga(NO3)3·xH2O,
detailed synthesis procedures for Ga-CAU-10-OCH3, 5-
acetamideisophthalic acid, Al-CAU-10-NHCOCH3, Ga-
CAU-10-NHCOCH3, Ga-CAU-11, Ga-CAU-11-
COOH, Ga-CAU-49, and Ga-CAU-51 and results of
the CHNS analysis, SEM of Ga-CAU-10-OCH3 single
crystals, 3D electron diffraction measurements of Ga-
CAU-51 ([Ga(OH)(C5H2O2S)]), Rietveld and Pawley
refinements, asymmetric units, and selected bond
lengths for Ga-CAU-10-OCH3, Al-CAU-10-NHCOCH3,
Ga-CAU-10-NHCOCH3, and Ga-CAU-11, Le Bail
refinement, asymmetric unit, and selected bond lengths
for Ga-CAU-11-COOH, asymmetric unit and selected
bond lengths for Ga-CAU-49, Rietveld refinement,
asymmetric unit, and selected bond lengths for Ga-
CAU-51, crystal structure descriptions of CAU-10,
CAU-11, and Ga-CAU-49, CCDC database research,
IR spectroscopy, thermogravimetric measurements,
temperature-dependent PXRD, and sorption isotherms
(PDF)
Accession Codes
CCDC 2067831−2067836 contain the supplementary crys-
tallographic data for this paper. These data can be obtained
free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by
emailing data_request@ccdc.cam.ac.uk, or by contacting The
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
Figure 8. (a) PXRD patterns at relative humidity values between 7
and 90%, measured at 298 K. Three colors represent PXRD data of
the activated sample (red), an intermediate wet form (blue), and the
as-synthesized phase (green). (b) Water sorption isotherm for Ga-
CAU-10-NHCOCH3 measured at 298 K. Filled symbols represent
adsorption and empty symbols desorption. The color of the data
points refers to the color used for the different structures of Ga-CAU-
10-NHCOCH3.
AUTHOR INFORMATION
■
Corresponding Author
Norbert Stock − Institute of Inorganic Chemistry, Christian-
Albrechts-Universität zu Kiel, 24118 Kiel, Germany;
orcid.org/0000-0002-0339-7352; Email: stock@ac.uni-
kiel.de
to confirm the previously reported high tendency of Ga-MOFs
to crystallize in frameworks isoreticular with Al-MOFs. Thus,
isostructural compounds were acquired in four out of six cases,
i.e. Ga-CAU-10-R (R = OCH3, NHCOCH3), Ga-CAU-11, and
Ga-CAU-11-COOH, while for the linker molecules m-H2BDC-
CH3 and H2TDC exceptions to this rule are observed. This led
to the discovery of the new Ga-MOFs Ga4(m-HBDC-
CH3)2(m-BDC−CH3)3(OH)4(H2O) (Ga-CAU-49) and Ga-
(OH)(TDC) (Ga-CAU-51). Ga-CAU-49 exhibits an unpre-
Authors
Timo Rabe − Institute of Inorganic Chemistry, Christian-
Albrechts-Universität zu Kiel, 24118 Kiel, Germany
Erik Svensson Grape − Department of Materials and
Environmental Chemistry, Stockholm University, Stockholm
10691, Sweden; orcid.org/0000-0002-8956-5897
Hauke Rohr − Institute of Inorganic Chemistry, Christian-
Albrechts-Universität zu Kiel, 24118 Kiel, Germany
Helge Reinsch − Institute of Inorganic Chemistry, Christian-
Albrechts-Universität zu Kiel, 24118 Kiel, Germany;
orcid.org/0000-0001-5288-1135
Stephan Wöhlbrandt − Institute of Inorganic Chemistry,
Christian-Albrechts-Universität zu Kiel, 24118 Kiel,
Germany
Alexandra Lieb − Institute of Chemistry, Otto-von-Guericke-
University in Magdeburg, 39106 Magdeburg, Germany
A. Ken Inge − Department of Materials and Environmental
Chemistry, Stockholm University, Stockholm 10691, Sweden;
orcid.org/0000-0001-9118-1342
1
cedented, rod-shaped IBU ∞{Ga16(OH)18O60} forming a
complex 3D crystal structure with Ga3+ ions in an uncommon
trigonal-bipyramidal coordination environment. Ga-CAU-10-R
(R = OCH3, NHCOCH3) are the first CAU-10 type
compounds made from Ga3+ ions, which led to single crystals
of suitable size for a structure determination through SCXRD
in the case of Ga-CAU-10-OCH3. Ga-CAU-51 exhibits
exceptional water sorption properties with a maximum uptake
of 370 mg/g. This work not only highlights the important role
of isoreticular chemistry with regard to group 13 element
MOFs but also shows how Ga3+ ions can be employed in
solvothermal syntheses to discover compounds with new
frameworks. Perhaps in the future the isostructural Al-MOFs
will be synthetically accessible, but the right synthesis
conditions must be found.
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.inorgchem.1c00767
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(16) The Chemistry of Metal-organic Frameworks: Synthesis, Character-
ization, and Applications; Schilling, L. H., Reinsch, H., Stock, N., Eds.;
Wiley-VHC: 2016.
Notes
The authors declare no competing financial interest.
(17) Volkringer, C.; Loiseau, T.; Guillou, N.; Férey, G.; Elkaïm, E.;
Vimont, A. XRD and IR structural investigations of a particular
breathing effect in the MOF-type gallium terephthalate MIL-53(Ga).
Dalton Trans. 2009, 2241−2249.
ACKNOWLEDGMENTS
■
Jannik Benecke, Jannick Jacobsen, Mirjam Poschmann, Lisa
Mahnke, Dana Krause, Felix Steinke, Jonas Gosch, and the
team for spectroscopic measurements of the department of
inorganic chemistry (University of Kiel) are thanked for their
support with various measurements. The project was
supported by the Deutsche Forschungsgemeinschaft (STO
643/10-1). E.S.G. and A.K.I. acknowledge support from the
Swedish Foundation for Strategic Research (SSF).
(18) Volkringer, C.; Loiseau, T.; Férey, G.; Morais, C. M.; Taulelle,
F.; Montouillout, V.; Massiot, D. Synthesis, crystal structure and 71Ga
solid state NMR of a MOF-type gallium trimesate (MIL-96) with μ3-
oxo bridged trinuclear units and a hexagonal 18-ring network.
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J.; Férey, G.; Haouas, M.; Taulelle, F.; Audebrand, N.; Latroche, M.
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NOTE ADDED AFTER ASAP PUBLICATION
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