[M2(μ-OH)2(DHBQ)3] (M = Zr, Hf) - Two New Isostructural Coordination Polymers based on the Unique M2O14 Inorganic Building Unit and 2,5-Dioxido-p-benzoquinone as Linker Molecule

Article abstract of DOI:10.1002/zaac.202000315

Two new isostructural porous coordination polymers (CPs) were obtained under solvothermal reaction conditions using 2,5-dihydroxy-p-benzoquinone (H₂DHBQ) or 1,2,4,5-tetrahydroxybenzene (H₄THB) as linker molecule and Zr⁴⁺ or Hf⁴⁺ salts. Highly crystalline compounds with composition [M₂(μ-OH)₂(DHBQ)₃]·xH₂O (M = Zr⁴⁺ or Hf⁴⁺, x = 0–3.6/3.3) were found in a wide temperature range (120–200 °C) and a reaction time of 70 h. The crystal structures were determined ab initio from powder X-ray diffraction data and the oxidation state of the linker was confirmed spectroscopically. The dinuclear inorganic building unit M₂O₁₄ is new for Zr- and Hf-CPs. For both compounds a full characterization was carried out, i.e. crystal structure determination, spectroscopic measurements, elemental- and thermogravimetric analyses. [M₂(OH)₂(DHBQ)₃] (M = Zr⁴⁺ or Hf⁴⁺) is stable up to 250 and 220 °C, respectively. Water sorption measurements proofed an uptake of 3.6 mol H₂O per mol and 3.3 mol H₂O per mol, respectively.

Full text of DOI:10.1002/zaac.202000315

Title: [M2(µ‑OH)2(DHBQ)3]·(M = Zr, Hf) - two new isostructural
coordination polymers based on the unique M2O14 inorganic
building unit and 2,5-dioxido-p-benzoquinone as linker molecule
Authors: Norbert Stock, Mirjam Patricia Margarete Poschmann, and
Helge Reinsch
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Z. anorg. allg. Chem. 10.1002/zaac.202000315
Link to VoR: https://doi.org/10.1002/zaac.202000315

Zeitschrift für anorganische und allgemeine Chemie
10.1002/zaac.202000315
ARTICLE
[M
2
(µ-OH)
2
(DHBQ)
3
]·(M = Zr, Hf) - two new isostructural coordination polymers based on
the unique M
molecule
2
O14 inorganic building unit and 2,5-dioxido-p-benzoquinone as linker
a
a
a*
Mirjam P. M. Poschmann , Helge Reinsch and Norbert Stock
Dedication to Professor Christoph Janiak on the Occasion of his 60th Birthday
[
7]
Two new isostructural porous coordination polymers (CPs) were
obtained under solvothermal reaction conditions using 2,5-
resulted in some highly porous compounds . The most common
solvent for the synthesis of Zr-CPs is the teratogenic
N,N-dimethylformamide (DMF) that contrasts with the low toxicity
of Zr-salts. Due to this fact researchers recently tried to replace
DMF through less toxic solvents such as formic acid, acetic acid,
acetonitrile and water.[9]–[12] This area of research is often named
“green chemistry” and interest in this topic has increased
drastically during the last few years.[13]–[15]
dihydroxy-p-benzoquinone
(H
2
DHBQ)
or
1,2,4,5-
4
+
4+
tetrahydroxybenzene (H THB) as linker molecule and Zr or Hf
4
salts. Highly crystalline compounds with composition
2 2 3 2
M (µ-OH) (DHBQ) ]·x H
O (M = Zr4+ or Hf , x = 0-3.6/3.3) were
4+
[
found in a wide temperature range (120-200 °C) and a reaction
time of 70 h. The crystal structures were determined ab initio from
powder X-ray diffraction data and the oxidation state of the linker
was confirmed spectroscopically. The dinuclear inorganic building
A limited number of IBUs have been reported for Zr-CPs, which
are summarized in Tab. S1. The most common IBU in carboxylate
based Zr-CPs is the hexanuclear cluster with composition
2
unit M O14 is new for Zr- and Hf-CPs. For both compounds a full
characterisation was carried out, i. e. crystal structure
determination, spectroscopic measurements, elemental- and
6 4 4
O (OH)
}[7] described by KICKELBICK and SCHUBERT[16] 1996
{
Zr
for the first time. Extended forms of this cluster are also known,
namely the dodecanuclear cluster {Zr12 (OH)20(H O)
}[17]–[19] and
. Furthermore,
2 2 3
(OH) (DHBQ)
] (M = Zr4+ or Hf4+)
thermogravimetric analyses. [M
is stable up to 250 and 220 °C, respectively. Water sorption
measurements proofed an uptake of 3.6 mol H O/mol and 3.3 mol
O/mol, respectively.
O
8
2
6
[15][20]
chains of condensed hexanuclear clusters
2
-polyhedra[ or corner-sharing ZrO
21]
-
chains of edge-sharing ZrO
octahedra[22] have been reported.
7
6
H
2
Only few results on the synthesis of Zr-CPs employing
catecholate or quinone linker molecules have been published.
COOPER et al. reported the compounds MIL-151 to 154 (MIL =
Matériaux de l′Institut Lavoisier) formed by the reaction of gallic
Introduction
Since the early 1990s the interest in coordination polymers (CPs)
like coordination networks (CNs) as well as metal-organic
frameworks (MOFs) is increasing.[1] Coordination polymers are
built up from inorganic building units (IBUs) interconnected with
linker molecules.[2] The coordination networks, a subclass of the
4
acid, pyrogallic acid or salicylic acid and ZrCl . These compounds
exhibit IBUs that consist of chains of edge sharing ZrO
8
polyhedra[23]. The IBU is given in Figure 1 and the same IBU was
found in the MOF MIL-163.[24]
CPs, exhibit a two- or three-dimensional interconnection to layers
or networks. If the latter have a pore systems and organic linkers
are used they are denoted as metal-organic frameworks
2
-
While CPs with 2,5-dioxylato-1,4-benzoquinone (DHBQ ) as
linker molecule (Fig. 2) and di- and trivalent metal ions such as
Co , Ni , Cu , Mn , Fe , Cr , Ln have been reported[25]–[29]
for zirconium only molecular clusters are known. Thus two studies
2
+
2+
2+
2+
2+
2+
3+
,
MOFs).[2] These compounds have been very intensely
investigated due to their potential application in separation or
(
by MOUCHAHAM et al.[ and IMAZ et al. described compounds
containing the anion [Zr(DHBQ)
]4- that are connected through
hydrogen-bonds into a framework structure. An approach to get
highly crystalline materials of composition M(C )(H O) (M =
Mg, or Zn) was reported by ABRAHAMS et al.[32] who used 1,2,4,5-
tetrahydroxy-benzene (H THB) instead of H DHBQ as a starting
30]
[31]
storage of gases , in catalysis and as drug delivery systems[5][6]
[
3]
[4]
.
4
In recent years, interest in Zr-based CPs has rapidly increased
6
H
2
O
4
2
2
[
7]
due to their high thermal and chemical stability as well as the
[
8]
low toxicity of Zr-salts . Mainly the use of carboxylate linker
molecules was reported but also phosphonate linker molecules
4
2
[
a]
M. P. M. Poschmann, Dr. H. Reinsch, Prof. Dr. N. Stock
Institut für Anorganische Chemie
Christian-Albrechts-Universität
Max-Eyth-Straße 2, 24118 Kiel, Germany
E-mail: stock@ac.uni-kiel.de
Supporting information for this article is given via a link at the end of
the document. CCDC 2025008 and 2025009 contains the
Figure 1 Section of the IBU composed of edge sharing ZrO
found using the ligands gallic acid (H Gal) in MIL-153, -154 or 5,5’-(1,2,4,5-
tetrazine-3,6-diyl)bis(benzene-1,2,3-triol) (H TzGal) in MIL-163: Zr-atoms are
8
polyhedra as
4
2 2 3 2
supplementary crystallographic data for [M (µ-OH) (DHBQ) ]·x H O
6
4+
4+
(
M = Zr or Hf ).
coloured in blue, carbon in black and oxygen in red.[25],[26]
This article is protected by copyright. All rights reserved.

Zeitschrift für anorganische und allgemeine Chemie
10.1002/zaac.202000315
ARTICLE
material (Fig. 2). The higher crystallinity was ascribed by the
authors to a preceding in situ oxidation step leading to the quinone
DHBQ .
Table 1 Selected crystallographic data of the two isostructural compounds
O )
4 3
] (M = Zr4+ or Hf4+).
2 2
[M (OH) (C
6
H
2
2
-
[
Zr (OH) (C
2
2
6
H
2
O
4 3
) ]
2 2 6 2 4 3
[Hf (OH) (C H O ) ]
Herein we present two new isostructural porous Zr- and Hf-CPs
with a previously unknown IBU that were obtained using the linker
crystal system
space group
a / Å
orthorhombic
Cccm
orthorhombic
Cccm
molecules 2,5-dihydroxy-p-benzoquinone (H
tetrahydroxy-benzene (H THB).
2
DHBQ) or 1,2,4,5-
4
21.5158(6)
6.7672(2)
15.6894(4)
3.73
21.4455(6)
6.7348(2)
15.6205(5)
3.75
b / Å
c / Å
p
R / %
R
wp / %
5.31
5.26
GoF
2.80
2.71
Figure 2 Redox chemistry of THB4- (left) and DHBQ2- (right).
R
Bragg / %
3.68
2.41
Results and Discussion
the van der Waals radii into account, along the b-axis are too
small to be filled with molecules like N with a kinetic diameter of
.64 Å (Fig. 4, bottom left). The bond lengths are summarised
in Table. S6. The distance between C-atoms varies between
.28(6)-1.49(5) Å as expected for single and double bonds in the
linker molecule (in all three possible oxidation states (Fig. 2)).
From this structural data we cannot identify the oxidation state of
the linker, unequivocally, but based on the results of the IR- and
UV/Vis- spectroscopic measurements the presence of DHBQ2-
ions can be deduced. Due to the bridging character of the OH-
group the M-O1 bond (2.06(2)/2.09(2) Å) is slightly smaller than
the other M-O bonds (2.177(9)-2.240(9) Å). Standard deviations
are slightly higher for the linker molecule containing C4-C6 and
O4 and O5 atoms compared to the linker molecule containing C1-
C3 atoms.
2
Two new isostructural porous CPs of composition
[36]
3
2 6 2 4 3
(C H O )
], with M = Zr4+ or Hf , were obtained at 120
4+
[
M
2
(OH)
or 200 °C using acetic acid, HCl, ZrCl
4
4
or HfCl and the linker
1
molecules 2,5-dihydroxy-p-benzoquinone or 1,2,4,5-tetra-
hydroxybenzene, respectively. During the synthesis optimization
using our high-throughput set-up a slightly higher crystallinity of
the products was observed using H
instead of H DHBQ in a molar ratio of Zr : L : HCl : HOAc =
.5 : 1 : 42 : 306 for H DHBQ and 1 : 1 : 33 : 67 for H THB,
respectively. These results are line with the previously reported
4
THB as starting material
2
1
2
4
.
[32]
study of ABRAHAMS et al. . While in the chemical system
4
+
Zr /H
S2-3) most of the syntheses with HfCl
pure products. During synthesis optimization products with
highest crystallinity could be obtain using high amounts of H THB
4
THB/acetic acid several byproducts were observed (Fig.
4
and H THB led to phase
4
4
and low amounts of HCl (Fig. S4) corresponding to a molar ration
of Hf : L : HCl : HOAc = 1 : 2 : 27 : 78.
The structure solution and refinement were carried out using
powder X-ray diffraction data from a [Zr (OH) (C H O ) ] sample.
2 2 6 2 4 3
Indexing, structure solution and Rietveld refinements were
performed using TOPAS Academic 4.1[33], EXPO 2009[34] and
Materials Studios[35]. Details are described in the SI. The final
Rietveld refinements against powder X-ray diffraction data of
[
2 2 6 2 4 3 2 2 6 2 4 3
Zr (OH) (C H O ) ] and [Hf (OH) (C H O ) ] are given in
Figure 3 and S6. The crystallographic data of the Rietveld
refinements are summarised in Table 1.
4
+
The structure exhibits an unusual IBU including M -ions that are
coordinated by eight oxygen-atoms forming distorted
a
trigondodecahedron the same polyhedra as reported for
MIL-151 - 154 and MIL-163[23],[24]. Two of these polyhedra are
linked by two µ-OH groups forming a dinuclear IBU (Fig. 4, top
right). Although these were confirmed by IR spectroscopy,
hydrogen atoms could not be refined but were added for charge
balance. Each IBU is connected to six surrounding IBUs by six
linker molecules (Fig. 4, top middle) to form a 3D network (Fig. 4,
bottom right). The 1D channels with 1.9 x 2.3 Å diameter, taking
2 2 6 2 4 3
Figure 3 Final plot of the Rietveld refinement of [Zr (OH) (C H O ) ]. The
observed PXRD pattern (black), the calculated curve (red) and the difference
plot (blue) are shown. The allowed peak positions are marked as black ticks
below the curve.
This article is protected by copyright. All rights reserved.

Zeitschrift für anorganische und allgemeine Chemie
10.1002/zaac.202000315
ARTICLE
2 2 6 2 4 3
Figure 4 Crystal structure of [M (OH) (C H O ) ]: Asymmetric unit (top left), dinuclear cluster with (top middle) and without coordinating linker molecules (top right),
space-filling model along b-axis (bottom left) and ball-and-stick model of the CN (bottom right) including the unit cell.
The results of the elemental analyses (Tab. 2) and the
thermogravimetric measurements (Fig.
5
and S7) are in
Table 2 Comparison of the results of the CH-analysis with the theoretical
data of [M (OH) (C ] (with M = Zr and Hf). Samples were dried for
several hours at 70 °C before the measurement.
agreement with the composition of both compounds obtained
from the crystal structure. Small deviations can be attributed to
the different amounts of adsorbed water molecules molecules in
the samples due to different temperatures used to dry the reaction
2
2
6 2 4 3
H O )
C / %
H / %
calc./ obs.
calc./ obs.
products.
Hf (OH)
Further VT-PXRD measurements of [Zr
Decomposition
] takes place at 250 and 220 °C, respectively.
(OH) (C ] were
of
[Zr
2
(OH)
2
(C
6
H
2
O
4
)
3
]
and
[
Zr
2
(OH)
2
(C
6
H
2
O
4
)
3
]
34.3 / 33.5
26.9 / 26.3
1.3 / 1.6
1.0 / 1.5
[
2
2 6 2 4 3
(C H O )
2
2
6 2 4 3
H O )
[Hf
2
(OH)
2
(C
6 2 4 3
H O ) ]
performed and no phase transition was observed up to
decomposition temperature (Fig. S8).
2 2 6 2 4 3
(OH) (C H O )
] (M = Zr4+ or Hf ) are presented
4+
IR-spectra of [M
in Figure 6. The bands with low intensity at 3638 cm and
3
-1
-1
645 cm , confirm the presence of bridging µ-OH groups,
respectively. Furthermore the bands corresponding to the OH
deformation vibrations at 815 cm-1 (Zr-OH) and 835 cm (Hf-OH),
as well as the M-O stretching bands at 488 cm-1 (Zr-O) and
-1
4
93 cm-1 (Hf-O) were observed in the IR spectra. The bands in
the range of 1000-1700 cm-1 are caused by C=O, C-O, C=C and
C-C vibration modes and cannot be assigned unequivocally due
to strong overlap of the bands.
To confirm the oxidation state of the linker molecule UV/Vis
spectra were recorded. The UV/Vis-spectra of the two title
2 2 6 2 4 3 2
Figure 5 Left: TGA plot for [Zr (OH) (C H O ) ] · 2.5 H O showing the weight
loss event occurring on evaporation of water molecules (7 %; expected 7 %)
and above 250 °C the total structure decomposition (59 %; expected 57 %).
compounds and H
to literature only the π-π* transitions of H
2
DHBQ are shown in Figure 7 (left). According
DHBQ at 281 nm and
43 nm were observed[37]. For the CPs these bands are shifted to
2
Right: TGA plot for [Hf
occurring on evaporation of water molecules (3 %; expected 2 %) and above
20 °C the total structure decomposition (48 %; expected 47 %). The lower
amount of adsorbed water in the pores compared to TGA-analysis of the
2 2 6 2 4 3 2
(OH) (C H O ) ] · H O showing the weight loss event
4
3
5
64 nm and 532 nm for [Zr (OH)
2
2 6 2 4 3
(C H O ) ] and 346 nm and
2
30 nm for [Hf (OH) (C H O ) ]. No additional bands were
2
2
6 2 4 3
observed in the spectra confirming the absence of any radical
anions.
Zr-compound can be attributed to
measurement.
a drying-step at 70 °C before the
This article is protected by copyright. All rights reserved.

Zeitschrift für anorganische und allgemeine Chemie
10.1002/zaac.202000315
ARTICLE
Conclusions
4
+
The systematic investigation of the systems M /linker/HCl/HOAc
with M4 = Zr or Hf , linker = H
+
4+
4+
2 4
DHBQ or H THB in acetic acid
as the solvent led to the discovery of two new isostructural porous
2 2 6 2 4 3
CPs with composition [M (OH) (C H O )
] (M = Zr4+ or Hf ). The
4+
crystal structure was elucidated from PXRD data and the
presence of DHBQ2- linker molecules was demonstrated. Both
compounds contain dinuclear edge-sharing polyhedra {M
the IBU, which has not been previously reported for Zr- or Hf-CPs.
The use of H THB as starting material instead of its oxidized form
DHBQ leads to reaction products with higher crystallinity. This
2
O14} as
4
H
2
is probably due to an in-situ oxidation step. Both compounds show
an incorporation of about 3.5 mol/mol water molecules, which
demonstrates their porosity and makes these compounds the first
Zr- and Hf-based porous CPs with the quinone linker molecule
2,5-dioxido-p-benzoquinone. It is notable that no acetate ions are
] (M = Zr4+ or Hf4+) and the two linker
2 2 6 2 4 3
(OH) (C H O )
incorporated into the final crystal structure although acetic acid
had to be used as the solvent. This is in contrast to the chemistry
Figure 6 IR-spectra of [M
molecules employed in this study.
of zirconium carboxylates, where acetic acid acts as
a
O (M = Zr4
+
To determine the porosity of [M
2
(OH)
2
(C
6
H
2
O
4
)
3
]·x H
2
modulator[ or as a co-ligand , which can lead to the formation
38]
[39]
4
+
-2
or Hf ) samples were dried under reduced pressure (10 kPa) at
of defect sites.[
15][40][41]
2
00 °C and used for nitrogen and water sorption measurements
at 77 K and 25 °C, respectively. As expected, the isotherm of
Zr (OH) (C ] confirms the sample to be nonporous against
Experimental Section
[
2
2
6 2 4 3
H O )
nitrogen (Fig. S9). The isotherms of water sorption measurements
are given in Figure 7 (right) and Figure S10. They show a
continuous water-uptake without any well-defined steps, which is
probably due to the small pore size. The maximum capacity for
Materials and methods
All chemicals were used as received without further purification.
The high-throughput powder X-ray diffraction (PXRD)
measurements for phase identification were performed using a
Stoe Stadi P X-ray diffractometer containing an xy-stage and a
Mythen detector and operating in transmission geometry (CuKα1
radiation). PXRD patterns for structure determination were
measured using a Stoe Stadi MP X-ray diffractometer operating
in Debye Scherrer geometry using a Mythen detector (CuKα1
radiation). Thermogravimetric (TG) analyses were carried out
using a Linseis STA 1600 analyzer with a heating rate of 4 K∙min-1
under flowing air (flow rate 100 sccm/min). For elemental
analyses a EuroVector Euro EA elemental analyser was used and
infrared spectra were measured on a Bruker ALPHA-P A220/D-
water uptake is 3.6 mol/mol for [Zr
2 2 6 2 4 3
(OH) (C H O ) ] and
3
.3 mol/mol for [Hf (OH) (C ]. PXRD-measurements of the
2
2
6 2 4 3
H O )
samples after the sorption measurements confirmed the stability
of the samples (Fig. S11). Although the pores of
4
+
4+
[
M
2
(OH)
seems to be flexible enough to incorporate water molecules at
5 °C.
2 6 2 4 3
(C H O ) ] (M = Zr or Hf ) are very small, the structure
2
0
(
1 FTIR spectrometer operating with an attenuated total reflection
ATR) unit. For sorption measurements a BELSORP-max (Bel
Japan Inc.) devices and a temperature of 298 K (for water
sorption) and 77 K (for N -sorption) were used. Before sorption
2
measurements, the samples were treated under reduced
pressure (10-2 kPa) and elevated temperature.
Figure 7 Left: UV/Vis-spectra of [Zr
2
(OH)
(OH) (C
with NaCl as white standard). Right: Water sorption measurement of
(OH) (C ] (black) and [Hf (OH) (C ] (red) (right) . Adsorption
is shown with filled, desorption with empty rectangles.
2
(C
6
H
2
O
4
)
3
] synthesized with H
4
THB
Synthesis
(black) and H
2
DHBQ (red), [Hf
2
2
6
H
2
O
4
)
3
] (blue) and H DHBQ (green)
2
[
42]
(
In house high-throughput (HT) multiclaves
were used to
4
+
[
Zr
2
2
6
H
O )
2 4 3
2
2
6 2 4 3
H O )
systematically study the systems M /linker/additive/solvent, with
4+
4+
4+
M
= Zr or Hf , linker = H
HCl, NaOH, NaF and solvent = mainly DMF, water, acetic acid,
methanol and toluene. The linker H THB was synthesized as
previously described[32]. Details can be found in the ESI,
section S3. Only the use of acetic acid, ZrCl and HCl lead to a
4 2
THB or H DHBQ, additive = mainly
] (M = Zr4+ or Hf ) in different
4+
Stability of [M (OH) (C H O )
2 2 6 2 4 3
solvents was investigated. Both compounds showed high stability
while stored at RT under air for one year and during short-term
treatment with toluene, acetone, DMF, ethanol and water. Details
are given in section S8 in the supporting information.
4
4
highly crystalline product and is therefore described hereafter.
A total of 112 syntheses with 2,5-dihydroxy-p-benzoquinone
(H DHBQ) and acetic acid as solvent were carried out using a
2
This article is protected by copyright. All rights reserved.

Zeitschrift für anorganische und allgemeine Chemie
10.1002/zaac.202000315
ARTICLE
[
[
10]
11]
H. Reinsch, N. Stock, Dalton Trans. 2017, 46, 8339-8349.
steel multiclave equipped with 24 Teflon reactors with a maximum
solvent volume of 2 mL each. 260 syntheses with 1,2,4,5-
tetrahydroxybenzene (H THB) were performed using a steel
4
multiclave equipped with 48 Teflon reactors with a maximum
volume of 400 µL each. Acetic acid to HCl ratios were tested fixing
the solvent volume at 1 mL and 200 µL, respectively. During the
optimization process, i. e. by varying the chemical and process
parameters, the optimized synthesis conditions were found using
S. Leubner, R. Stäglich, J. Franke, J. Jacobsen, J. Gosch, R. Siegel, H.
Reinsch, G. Maurin, J. Senker, P.G. Yot, N. Stock, Chem. – Eur. J. 2020,
26, 3877-3883.
[
[
[
12]
13]
14]
J. Jacobsen, L. Wegner, H. Reinsch, N. Stock, Dalton Trans. 2020, 49,
11396-11402.
Z. Hu, Y. Peng, Z. Kang, Y. Qian, D. Zhao, Inorg. Chem. 2015, 54,
4862-4868.
G. Zahn, H.A. Schulze, J. Lippke, S. König, U. Sazama, M. Fröba, P.
Behrens, Microporous Mesoporous Mater. 2015, 203, 186-194.
S. Leubner, H. Zhao, N. Van Velthoven, M. Henrion, H. Reinsch, D.E.
De Vos, U. Kolb, N. Stock, Angew. Chem. Int. Ed. 2019, 58, 10995-
[15]
H
2
DHBQ and H
and 200 °C. The highest crystallinity was observed employing
THB as the linker molecule and a reaction temperature of
20 °C. For the Hf-based CP only the linker molecule H THB and
4
THB. The temperature was varied between 120
11000.
[
16]
G. Kickelbick, U. Schubert, Chem. Ber. 1997, 130, 473-478.
P. Ji, K. Manna, Z. Lin, X. Feng, A. Urban, Y. Song, W. Lin, J. Am.
Chem. Soc. 2017, 139, 7004-7011.
S. Waitschat, H. Reinsch, M. Arpacioglu, N. Stock, CrystEngComm
2018, 20, 5108-5111.
I.L. Malaestean, M.K. Alıcı, C. Besson, A. Ellern, P. Kögerler,
CrystEngComm 2013, 16, 43-46.
S. Waitschat, H. Reinsch, N. Stock, Chem. Commun. 2016, 52, 12698-
12701.
V. Guillerm, F. Ragon, M. Dan-Hardi, T. Devic, M. Vishnuvarthan, B.
Campo, A. Vimont, G. Clet, Q. Yang, G. Maurin, G. Férey, A. Vittadini,
S. Gross, C. Serre, Angew. Chem. Int. Ed. 2012, 51, 9267-9271.
T. Rhauderwiek, H. Zhao, P. Hirschle, M. Döblinger, B. Bueken, H.
Reinsch, D.D. Vos, S. Wuttke, U. Kolb, N. Stock, Chem. Sci. 2018, 9,
H
4
[17]
1
4
[
[
[
[
18]
19]
20]
21]
a reaction temperature of 120 °C were used. The optimized
synthesis conditions are given below. For the syntheses with
H THB reaction “scale-up” to 1 mL reaction volume was
4
performed. An overview of the high-throughput syntheses is given
in the ESI, section S4.
Synthesis of [Zr
75 µmol) H DHBQ and 11.6 mg (50 µmol) ZrCl
ml Teflon insert and mixed with 875 µl glacial acetic acid and
2
(OH)
2
(C
6
H O
2 4
)
3
] with H
2
DHBQ: 10.5 mg
[
[
22]
23]
(
2
4
were added to a
5467-5478.
2
1
2
1
L. Cooper, N. Guillou, C. Martineau, E. Elkaim, F. Taulelle, C. Serre, T.
Devic, Eur. J. Inorg. Chem. 2014, 6281-6289.
G. Mouchaham, L. Cooper, N. Guillou, C. Martineau, E. Elkaïm, S.
Bourrelly, P.L. Llewellyn, C. Allain, G. Clavier, C. Serre, T. Devic,
Angew. Chem. Int. Ed. 2015, 54, 13297-13301.
75 µl HCl (37%). The reactor was closed, heated for 70 h at
00 °C and thereafter cooled down to room temperature within
0 h. The dark grey-brown product was filtered off and washed
[24]
with methanol four times.
Synthesis of [Zr (OH)
THB and 35 mg (150 µmol) ZrCl
[
[
[
25]
26]
27]
J. Park, A.C. Hinckley, Z. Huang, D. Feng, A.A. Yakovenko, M. Lee, S.
Chen, X. Zou, Z. Bao, J. Am. Chem. Soc. 2018, 140, 14533-14537.
B.F. Abrahams, A.M. Bond, T.H. Le, L.J. McCormick, A. Nafady, R.
Robson, N. Vo, Chem. Commun. 2012, 48, 11422.
M. Atzori, S. Benmansour, G. Mínguez Espallargas, M. Clemente-León,
A. Abhervé, P. Gómez-Claramunt, E. Coronado, F. Artizzu, E. Sessini,
P. Deplano, A. Serpe, M.L. Mercuri, C.J. Gómez García, Inorg. Chem.
2
2
(C
6
H O
2 4
)
3
]
with
H
4
THB: 21.3 mg
were placed in a
(
150 µmol) H
4
4
2 ml Teflon insert and mixed with 582 µl glacial acetic acid and
418 µl HCl (37%). The reactor was sealed, heated for 70 h at
120 °C and thereafter cooled down to room temperature within
10 h. The dark grey-brown was filtered off and washed with
2013, 52, 10031-10040.
[
28]
B.F. Abrahams, J. Coleiro, K. Ha, B.F. Hoskins, S.D. Orchard, R.
Robson, J. Chem. Soc. Dalton Trans. 2002, 1586-1594.
C.J. Kingsbury, B.F. Abrahams, D.M. D’Alessandro, T.A. Hudson, R.
Murase, R. Robson, K.F. White, Cryst. Growth Des. 2017, 17, 1465-
1470.
G. Mouchaham, N. Roques, C. Duhayon, I. Imaz, J.-P. Sutter, New J.
Chem. 2013, 37, 3476-3487.
I. Imaz, G. Mouchaham, N. Roques, S. Brandès, J.-P. Sutter, Inorg.
Chem. 2013, 52, 11237-11243.
B.F. Abrahams, A.D. Dharma, B. Dyett, T.A. Hudson, H. Maynard-
Casely, C.J. Kingsbury, L.J. McCormick, R. Robson, A.L. Sutton, K.F.
White, Dalton Trans. 2016, 45, 1339-1344.
A. Coelho, TOPAS Academic, Coelho Software, 2007.
A. Altomare, M. Camalli, C. Cuocci, C. Giacovazzo, A. Moliterni, R.
Rizzi, J. Appl. Crystallogr. 2009, 42, 1197-1202.
methanol four times (yield: 19 mg).
Synthesis of [Hf (OH) (C ]: 42 mg (300 µmol) H
8 mg (150 µmol) HfCl were added to a 2 ml Teflon inlet and
[29]
2
2
6
H
2
O )
4 3
4
THB and
[
[
[
30]
31]
32]
4
4
mixed with 666 µl glacial acetic acid and 334 µl HCl (37%). The
reactor was closed, heated for 70 h at 120 °C and thereafter
cooled down to room temperature within 10 h. The dark grey-
brown product was filtered off and washed with acetone four times
[
[
33]
34]
(
yield: 24 mg).
[
[
35]
36]
Materials Studios, Accelrys Inc., San Diego, 2009.
C. Scholes, S. Kentish, G. Stevens, Recent Pat. Chem. Eng. 2008, 1,
52-66.
Keywords: metal organic frameworks (MOFs); zirconium;
hafnium; crystal structure; dihydroxybenzoquinone
[
[
[
37]
38]
39]
M. Ahmed, Z.H. Khan, Spectrochim. Acta. A. Mol. Biomol. Spectrosc.
2000, 56, 965-981.
[
[
1]
2]
Q. Wang, D. Astruc, Chem. Rev. 2020, 120, 1438-1511.
S.R. Batten, N.R. Champness, X.-M. Chen, J. Garcia-Martinez, S.
Kitagawa, L. Öhrström, M. O’Keeffe, M.P. Suh, J. Reedijk, Pure Appl.
Chem. 2013, 85, 1715-1724.
H. Wu, Y.S. Chua, V. Krungleviciute, M. Tyagi, P. Chen, T. Yildirim, W.
Zhou, J. Am. Chem. Soc. 2013, 135, 10525-10532.
S. Leubner, V.E. Bengtsson, K. Synnatschke, J. Gosch, A. Koch, H.
Reinsch, H. Xu, C. Backes, X. Zou, N. Stock, J. Am. Chem. Soc. 2020,
[
3]
B. Li, H.-M. Wen, W. Zhou, B. Chen, J. Phys. Chem. Lett. 2014, 5, 3468-
1
42, 15995-16000.
O.V. Gutov, M.G. Hevia, E.C. Escudero-Adán, A. Shafir, Inorg. Chem.
015, 54, 8396-8400.
3479.
[40]
[41]
[42]
[
[
4]
5]
L. Jiao, Y. Wang, H.-L. Jiang, Q. Xu, Adv. Mater. 2018, 30, 1703663.
P. Horcajada, C. Serre, M. Vallet‐Regí, M. Sebban, F. Taulelle, G.
Férey, Angew. Chem. Int. Ed. 2006, 45, 5974-5978.
2
S.M. Shaikh, P.M. Usov, J. Zhu, M. Cai, J. Alatis, A.J. Morris, Inorg.
Chem. 2019, 58, 5145-5153.
N. Stock, Microporous Mesoporous Mater. 2010, 129, 287-295.
[
[
6]
7]
J. An, S.J. Geib, N.L. Rosi, J. Am. Chem. Soc. 2009, 131, 8376-8377.
Y. Bai, Y. Dou, L.-H. Xie, W. Rutledge, J.-R. Li, H.-C. Zhou, Chem. Soc.
Rev. 2016, 45, 2327-2367.
[
[
8]
9]
C. Allègre, G. Manhès, É. Lewin, Earth Planet. Sci. Lett. 2001, 185, 49-
69.
H. Reinsch, Eur. J. Inorg. Chem. 2016, 2016, 4290-4299.
This article is protected by copyright. All rights reserved.

Zeitschrift für anorganische und allgemeine Chemie
10.1002/zaac.202000315
ARTICLE
Entry for the Table of Contents (Please choose one layout)
Layout 1:
FULL PAPER
Two new isostructural porous
coordination polymers were
Mirjam P. M. Poschmann, Dr. Helge
Reinsch, Prof. Dr. Norbert Stock
synthesized from ZrCl
and the linker molecules H
THB in acetic acid as solvent. The
structure was determined from PXRD
data and full characterisation was
performed.
4
or HfCl
4
, HCl
DHBQ or
Page No. – Page No.
2
H
4
Synthesis and characterisation
of two new isostructural
coordination polymers based
on the unique M
building unit (M = Zr, Hf) and
,5-Dioxylato-1,4-
2
O14 inorganic
2
benzoquinone as linker
molecule
Additional Author information for the electronic version of the article.
Author:
Author:
Author:
ORCID identifier
ORCID identifier
ORCID identifier
This article is protected by copyright. All rights reserved.