A water-based and high space-time yield synthetic route to MOF Ni2(dhtp) and its linker 2,5-dihydroxyterephthalic acid

Article abstract of DOI:10.1039/c4ta03066d

2,5-Dihydroxyterephthalic acid (H₄dhtp) was synthesized on an 18 g scale by carboxylation of hydroquinone in molten potassium formate. The hydrated form of the Ni₂(dhtp) MOF (also known as CPO-27-Ni and MOF-74(Ni)) was obtained in 92% yield by refluxing for 1 h a water suspension of the H₄dhtp linker with an aqueous solution of nickel acetate. The ensuing characterization of the material (XRD, HRTEM, TGA, N₂ adsorption at 77 K-S_BET = 1233 m² g^-1) confirmed the formation of a metal-organic framework of at least equal quality to the ones obtained from the previously reported routes (CPO-27-Ni and MOF-74(Ni)), with a different morphology (namely, well-separated 1 ??m platelets for the herein reported water-based route). The temperature dependence of the magnetic susceptibility was measured and satisfactorily simulated assuming a Heisenberg (H = -2JΣS_iS_i+1) ferromagnetic intrachain interaction (J = +8.1 cm^-1) and an antiferromagnetic interchain interaction (J′ = -1.15 cm^-1). Overall, the reaction in water appears to follow easily distinguishable steps, the first being the deprotonation of H₄dhtp by an acetate counterion, leading to a soluble nickel adduct of the linker, en route to the MOF self-assembly. This journal is

Full text of DOI:10.1039/c4ta03066d

Volume 2 Number 42 14 November 2014 Pages 17693–18150
Journal of
Materials Chemistry A
Materials for energy and sustainability
www.rsc.org/MaterialsA
ISSN 2050-7488
PAPER
Elsje Alessandra Quadrelli et al.
A water-based and high space-time yield synthetic route to MOF Ni (dhtp)
2
and its linker 2,5-dihydroxyterephthalic acid

Journal of
Materials Chemistry A
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PAPER
A water-based and high space-time yield synthetic
route to MOF Ni (dhtp) and its linker 2,5-
dihydroxyterephthalic acid†
2
Cite this: J. Mater. Chem. A, 2014, 2,
7757
1
ab
a
c
d
Stephane Cadot, Laurent Veyre, Dominique Luneau, David Farrusseng
´
a
and Elsje Alessandra Quadrelli*
2
,5-Dihydroxyterephthalic acid (H
in molten potassium formate. The hydrated form of the Ni
MOF-74(Ni)) was obtained in 92% yield by refluxing for 1 h a water suspension of the H
an aqueous solution of nickel acetate. The ensuing characterization of the material (XRD, HRTEM, TGA,
4
dhtp) was synthesized on an 18 g scale by carboxylation of hydroquinone
(dhtp) MOF (also known as CPO-27-Ni and
dhtp linker with
2
4
2
ꢀ1
N
2
adsorption at 77 K – SBET ¼ 1233 m
at least equal quality to the ones obtained from the previously reported routes (CPO-27-Ni and MOF-
4(Ni)), with a different morphology (namely, well-separated 1 mm platelets for the herein reported
water-based route). The temperature dependence of the magnetic susceptibility was measured and
satisfactorily simulated assuming a Heisenberg (H ¼ ꢀ2JSS i+1) ferromagnetic intrachain interaction (J ¼
g
) confirmed the formation of a metal–organic framework of
7
Received 17th June 2014
Accepted 24th July 2014
i
S
ꢀ1
0
ꢀ1
+
8.1 cm ) and an antiferromagnetic interchain interaction (J ¼ ꢀ1.15 cm ). Overall, the reaction in
water appears to follow easily distinguishable steps, the first being the deprotonation of H dhtp by an
DOI: 10.1039/c4ta03066d
4
www.rsc.org/MaterialsA
acetate counterion, leading to a soluble nickel adduct of the linker, en route to the MOF self-assembly.
Among the wide diversity of MOFs, the M (dhtp) series (dhtp
2
Introduction
¼
dobdc ¼ 2,5-dioxido-1,4-benzenedicarboxylate [O C–C H O –
2
6
2 2
4
ꢀ
7
Metal–Organic Frameworks (MOFs) have received considerable CO
]
; M ¼ Mg, Mn, Fe, Co, Ni or Zn), called CPO-27-M (CPO
2
attention over the past decade, especially in the eld of gas ¼ Coordination Polymer of Oslo) or MOF-74(M), has been
1
purication and storage as well as catalysis and drug delivery.
extensively studied because of its 1D microporous hexagonal
˚
The growing interest in these materials has recently led to the channel structure with calibrated pores at 12 A which allow an

rst industrial production of MOFs with the ton-scale synthesis optimal interaction between the walls of the solid and guest
2
of aluminum fumarate (Basolite A520®) at BASF facilities
2
molecules. In fact, M (dhtp) offers a permanent porosity upon
which is a promising candidate for methane storage and solvent removal, displaying strong adsorption centers at the
delivery. This transfer to industrial production has been ach- penta-coordinated open metal sites (see Scheme 1 for M ¼ Ni)
ieved, inter alia, through the development of a water-based which allow the selective adsorption/desorption of a wide
8
–10
route, reducing both production costs and environmental diversity of molecules without loss of porosity.
In particular
impact while increasing the production rates. Unfortunately, the nickel member of the M (dhtp) series, which is highly
2
2
–6
11
12
entirely water-based MOF syntheses are still very limited.
tolerant towards moisture and oxygen, is able to reversibly
13
14
adsorb sulfur-containing molecules like H
and selectively adsorb CO and CO over CH
over N even under 3% relative humidity while the efficiency of
2
S
or thiophene,
9,10
2
4
and H
2
and CO
2
1
5
2
a
Equipe Chimie Organom ´e tallique de Surface, C2P2 – UMR 5265 (CNRS – Universit ´e
Lyon 1 – CPE Lyon), CPE Lyon, 43 Boulevard du 11 Novembre 1918, 69616
Villeurbanne Cedex, France. E-mail: quadrelli@cpe.fr
this separation using Mg (dhtp) or zeolites is much more
2
16,17
affected by only a trace amount of water.
methane storage capacity of Ni
Most strikingly, the
b
2
(dhtp) is among the highest
CEA, LETI, MINATEC Campus, 17 rue des Martyrs, 38054 Grenoble Cedex 9, France
3
ꢀ3
ꢁ
18
c
reported for MOFs (214 cm (STP) cm at 25 C, 35 bars),
which makes it a very promising candidate for adsorption and/
(dhtp) is also active as a Lewis-
Laboratoire des Multimat ´e riaux et Interfaces – UMR 5615 (Universit ´e Claude Bernard
Lyon 1), Campus de La Doua, 69622 Villeurbanne Cedex, France
d
Institut de Recherche sur la Catalyse et l'Environnement de Lyon (IRCELYON), 2 Av. or separation applications. Ni
2
19
Albert Einstein, 69626 Villeurbanne cedex, France
Electronic supplementary information (ESI) available: Experimental and
simulated nitrogen adsorption and desorption isotherms at 77 and
thermogravimetric analysis (TGA) under N and O of Ni (dhtp) as well as the
type catalyst and its application for delivering an anticancer
drug as well as its use in antimicrobial NO-delivering patches
†
20
21
K
has been reported.
2
2
2
Overall, MOF syntheses, there included Ni (dhtp) synthetic
2
XRD diffraction pattern of the intermediate isolated along the synthesis
1
2,22,23
routes reported so far
(see the Results section below for
described in the main text. See DOI: 10.1039/c4ta03066d
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yet reported magnetic properties. In addition, we describe a
synthesis method for the H dhtp linker in a single step from
4
hydroquinone (which is a bulk chemical) using a cheap and
organic solvent-free procedure. Indeed, 2,5-dihydroxytereph-
thalic acid is distributed on a gram scale by different chemical
suppliers at a price of about $15 per gram. Although it does not
represent the price at the industrial level, it strongly limits its
synthesis on a kg scale for demonstration purposes.
Results and discussion
Two different synthetic routes have been reported for the
isomorphous family of M (dhtp), both of them requiring
2
organic solvents: tetrahydrofuran (THF) for the CPO-27 material
22
originated from SINTEF's work in Oslo and dimethylforma-
mide (DMF) (or DMF–water or DMF–water–ethanol mixtures)
23
for the MOF-74 developed by Yaghi's group. The general
procedure consists of mixing an aqueous solution of the metal
salt with a solution of 2,5-dihydroxyterephthalic acid in the
appropriate organic solvent inside a Teon-lined autoclave,
followed by heating at the appropriate temperature (ca. 100–110
ꢁ
C) for 2–3 days. The use of dimethylformamide generally
25
reduces both temperature and reaction time but the resulting
MOF then have to be washed several days with methanol
because of the strong coordination of DMF molecules to the
nickel atoms in the framework, which prevents simple removal
by vacuum treatment. If the tetrahydrofuran–water mixture is
used, a relatively large amount of solvent is required as well as
12
long reaction time: in a typical procedure, three days and a
ꢁ
temperature of 110 C were necessary to produce 6.46 g of CPO-
27-Ni (4.10 g expected aer complete water removal) from 100
ml of a THF/water (1 : 1) mixture.
2
2
2
Scheme 1 Representation of the fully desolvated Ni (dhtp) structure
2
The procedure described here for the synthesis of Ni (dhtp)
showing the hexagonal 1D channels (upper picture: view towards the
113) plane, lower picture: view towards the (ꢀ120) plane).
entails only concentrated aqueous solution under atmospheric
pressure, without the addition of organic co-solvent at any point
of the procedure.
(
details), require high dilution factors which imply large
amounts of organic solvents, low production rates and strong
H dhtp synthesis
4
environmental impact. This is mainly ascribed to the difficulty 2,5-Dihydroxyterephthalic acid has been directly synthesized in
in nding a good solvent for both the metal salt and the organic good yields from the inexpensive hydroquinone using an
linker. Therefore, non-optimized small-scale lab syntheses as organic solvent-free procedure (see Scheme 2), derived from a
26
described in the literature have usually space-time yields (STY) patented process and adapted for the laboratory-scale experi-
3
10
between 0.1 and 1 kg per m per day or even lower. While the ment by replacing pressurized CO with an atmospheric-pres-
2
reaction time has been reduced by one order of magnitude sure CO stream. Preformed potassium formate has also been
2
24
using ultrasound or microwave heating, the minimization of replaced by its in situ generation from K CO and HCOOH to
2
3
solvent usage is still a goal to attain with a STY larger than 500 yield the molten salt reaction medium. The yellow crystalline
3
kg per m per day. Beyond this, the development of water-based 2,5-dihydroxyterephthalic acid can be conveniently recovered by
routes for MOF synthesis would strongly facilitate their indus-
trialization. Indeed, organic solvents are more difficult to use at
industrial levels because they shall be handled in specic non-

ammable areas, while water is a cheap, safe and more easily
post-treatable solvent.
Here we report for the rst time the synthesis of Ni (dhtp) in
2
water with high space-time yield. We carefully demonstrate the
quality of the obtained Ni
in short and long ranges, as well as its porous structure and not
2
(dhtp) by a series of characterization
Scheme 2 Reaction scheme for the synthesis of 2,5-dihydroxyter-
ephthalic acid by dicarboxylation of hydroquinone.
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
ltration aer acidication of the reaction crude and washing
with water, and used directly for the MOF synthesis.
2
Ni (dhtp) synthesis
The procedure for Ni
2
(dhtp) synthesis consists of mixing an
ꢁ
aqueous solution of nickel(II) acetate (warmed at 80 C to allow
high concentration of the metal, typically 1 M) with a suspen-
sion containing 1.02 equivalent of 2,5-dihydroxyterephthalic
ꢀ1
acid in water (ca. 25 g L ). Upon adding the nickel-containing
solution to the linker suspension, the reaction mixture imme-
diately turns into a clear emerald green solution. When this
solution is heated at reux temperature, a yellow solid quickly
precipitates. Aer 1 h reuxing, washing with water and drying
Fig. 2 Experimental N
2
adsorption (blue diamonds) and desorption
2
(purple squares) isotherms at 77 K of Ni (dhtp) synthesized in aqueous
solution; in the inset: calculated pore size distribution from the
ꢁ
at 80 C, the nal product is recovered as a yellow powder with
simulated adsorption isotherm reported in the ESI, Fig. S1.†
almost full conversion with respect to the nickel salt, the
limiting reagent of the procedure (calculated yield: 91.6%).
2
ꢀ1
area of 1218 m g (BET method) reported in the literature for
X-ray diffraction
12
the CPO-27-Ni material. The adsorption/desorption isotherms
30
The X-ray powder diffraction (XRD) pattern of the product aer are satisfactorily tted with the NLDFT simulation method
full rehydration shows a highly crystalline material (see Fig. 1 (see Fig. S1†), which allows us to obtain a pore size distribution
˚
for experimental and simulated diffractograms).
plot (see the inset of Fig. 2) with a mean pore diameter of 11.7 A,
˚
12
The highest intensity peaks of the material obtained from in agreement with the calculated value of 11.85 A, and an
ꢁ
ꢁ
3
ꢀ1
the aqueous procedure are found at 2q ¼ 6.8 and 11.8 (cor- estimated pore volume of 0.823 cm g
.
˚
˚
responding to d ¼ 12.99 A and 7.48 A). These measurements
hkl
are in good agreement with the published CPO-27-Ni crystal-
22
ꢁ
ꢁ
Magnetic susceptibility
The magnetic behavior of the Co and Fe members of the
(dhtp) isomorphous family of MOFs has already been
reported, but not, to the best of our knowledge that of Ni (dhtp),
for which only a theoretical investigation is available. At room
temperature, the product of the magnetic susceptibility and the
lographic data: 2q ¼ 6.80 and 11.79 , corresponding to dhkl
¼
˚
˚
31
32
1
2.99 A and 7.50 A, that is the (ꢀ120) and (030) planes,
respectively. The X-ray powder diffraction pattern was tted by
M
2
27
28
the Le Bail full prole tting method using the FullProf and
2
29
33
Winplotr soware. Fig. 1 shows good agreement between the
recorded powder pattern (red) and the simulated one (black).
No supplementary peaks were observed in the difference curve
2
temperature (cT), of a fully rehydrated Ni (dhtp) obtained from
3
ꢀ1
(blue) which conrms the purity of the obtained sample.
the water based route, is 2.67 cm K mol . Upon cooling, cT
3
ꢀ1
increases and reaches the maximum value of 3.57 cm K mol
Permanent microporosity
at 20 K and then drops abruptly below this temperature. This
behavior is in agreement with the ferromagnetic coupling of
ꢀ1 nickel(II) ions (S ¼ 1) along the chain running parallel to the c
The reversible N
2
adsorption and desorption performed at 77 K
2
(
(
(
see Fig. 2 and S1†) lead to specic surface areas of 1233 m g
Brunauer–Emmett–Teller (BET) method) and 1355 m
Langmuir method), in line with the highest specic surface
31,32
2
ꢀ1 axis, as previously observed for Co(II) and Fe(II) analogs.
To
g
extract the value of the magnetic interaction, the data were
simulated for [Ni (dhtp)(H O) ]$8H O assuming Heisenberg
i+1) using the Fisher
2
2
2
2
interactions between spins (H ¼ ꢀ2JSS
i
S
analytical expression for the magnetic susceptibility of an
innite chain of classical spins S ¼ 1 with an interchain
magnetic interaction in the molecular eld approximation
0
34,35
(
ZJ ).
interaction J ¼ +8.1 cm and an antiferromagnetic interchain
32
The best t (Fig. 3A) gives a ferromagnetic intrachain
ꢀ
1
0
ꢀ1
interaction J ¼ ꢀ1.15 cm with Z ¼ 3 as previously suggested
ꢀ1
ꢀ
6
and g ¼ 2.02. A small TIP has been included (150 ꢂ 10 cm ).
At 2 K, the magnetization vs. magnetic eld (Fig. 3B) rst
increases linearly with the magnetic eld. Then, around 2.8 T, a
transition is observed, progressively moving towards the
B
expected value for two nickel(II) ions (z2 m ). This eld-induced
transition may be ascribed to the fact that the small antiferro-
magnetic interchain interactions are overtaken by the strength
of the magnetic eld, in line with what has already been
Fig. 1 View of the experimental powder XRD pattern (red dots) and
the simulated one (black line) by the Le Bail method. The difference
curve is shown in blue.
31
reported for CPO-27-Co.
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˚
measured 12.5 A distance between two contiguous lines
observed in the micrograph can be explained as corresponding
˚
to the 12.99 A spacing between two (ꢀ120) planes in the CPO-27-
22
Ni crystallographic structure (see Fig. S3†).
At lower magnication, the micrographs showed platelets of
about 1 mm width (see the inset in Fig. 4A), distinctively
different in morphology with respect to the crystallites obtained
12
by us following the CPO-27-Ni procedure (see Fig. 4B).
This lower symmetry morphology with the presence of
agglomerates appears representative of the morphology
induced by the CPO-27 route, based on the comparison with
36
existing literature micrographs of CPO-27-Ni. As recently
37
reviewed, the existence of a correlation between the compo-
sition of the solvent mixture and the crystallinity, or the shape
of the resulting MOF crystals has already been established for
some MOFs. The use of water as a co-solvent in such a strategy
was directly addressed in a study on MIL-96(Al) shape-selected
38
crystallite growth. The solvent appears in most cases to act as a
modulator of crystal nucleation processes. To the best of our
knowledge, such a phenomenon had not yet been observed for a
2
member of the M (dhtp) family.
Mechanistic considerations
Substantial interest also lies in understanding the mechanism
by which the MOF self-assembles from the metal ion and the
2 2 2 2
Fig. 3 (A) Temperature dependence of cT for [Ni (dhtp)(H O) ]$8H O.
The solid line is the best fit of experimental data with the parameters
reported in the text; (B) magnetization curves for [Ni (dhtp)(H O) ]$
O.
2
2
2
8H
2
Thermal behavior
2
Thermogravimetric analysis under N of another aliquot of the
Ni
2
(dhtp) material exposed to moist air at room temperature for
22
thirty minutes displays both of the expected phenomena,
namely: rstly a loss of water molecules present inside the pores
of the MOF or coordinated to the nickel atom, a phenomenon
ꢁ
occurring up to 200 C and leading to the fully dehydrated
ꢁ
phase, Ni (dhtp), which is stable up to 360 C, and secondly the
2
thermal decomposition of the MOF material (see Fig. S2A†). The
ꢁ
water content estimated from the weight loss up to 200 C is
equivalent to about 8 molecules of water per Ni
gesting an almost complete rehydration of the sample toward
its fully hydrated form [Ni (dhtp)(H O) ]$8H O reported in the
2
(dhtp), sug-
2
2
2
2
12
literature. As already reported, the thermogram obtained
under O2 is quite similar, with decomposition occurring at
ꢁ
ꢁ
lower temperature (280 vs. 360 C under N , see Fig. S2B†).
2
2
Morphology of the Ni (dhtp) synthesized in water
The well-formed 1D channels of the Ni (dhtp) material obtained
from the aqueous synthetic route were observed using a high-
resolution transmission electron microscope (see Fig. 4A). The electron micrograph of Ni
2
Fig. 4 A and inset) High-resolution transmission electron micrograph
at different magnifications of Ni
2
(dhtp) obtained in water; (B) scanning
12
2
(dhtp) obtained in THF–water (1 : 1).
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39
linker precursor. While we are unable to account for the 98% (Sigma-Aldrich) and HCl 37% (VWR Chemicals) were used
crystallization mechanism that underpins the synthesis of without further purication.
Ni (dhtp) in water, the observation of some intermediates
2
during the synthesis appears facilitated by the mild conditions
reported here. During the synthesis, we observed the complete
dissolution of the otherwise sparingly soluble acid linker at
room temperature (see Fig. S4A to C†). We assign such disso-
lution to the deprotonation of 2,5-dihydroxyterephthalic acid
Characterization techniques
Powder X-ray diffraction data were collected from the “Centre de
Diffractom ´e trie Henri Longchambon”, site CLEA, Villeurbanne,
on a Bruker D8 Advance Diffractometer (Cu Ka radiation, 33 kV,
ꢁ
45 mA). Diffraction data were recorded in the range of 4–70 2q.
(pK
a
estimated at ca. 2.2‡) by the acetate counterion of the
High-resolution transmission electron micrographs were
recorded at the “Centre Technologique des Microstructures”,
UCBL, Villeurbanne, on a Jeol 2100F transmission electron
microscope. The acceleration voltage was 200 kV. Scanning
electron micrographs were recorded at the “Centre Tech-
nologique des Microstructures”, UCBL, Villeurbanne, on a FEI
Quanta 250 FEG scanning electron microscope. Nitrogen
adsorption/desorption measurements were carried out at 77 K
nickel salt present in the aqueous solution (pK of acetic acid ¼
a
40
4
.76). If this emerald green mother solution is stored for a few
minutes at room temperature, pastel green crystals start
precipitating (see Fig. S4D†) whose X-ray diffraction pattern is
different from that of CPO-27-Ni (see Fig. S5†). The nal MOF
can be observed only when the mixture is heated above ca. 80
ꢁ
C, and its formation is complete within 1 h if the heating is
ꢁ
carried out at 100 C (Fig. S4E†).
using a BELSORB-max from BEL JAPAN system. Before N
2
ꢀ
5
adsorption, the samples were outgassed at 2.5 ꢂ 10 Pa; 423 K
1
13
Conclusions
for 3 h. H and C liquid NMR spectra were recorded on a
Bruker DSX 300 NMR spectrometer. Magnetic-susceptibility
data (2–300 K) were collected with a Quantum Design MPMS
SQUID magnetometer under an applied magnetic eld of 0.1 T
on a powdered polycrystalline sample pressed in a PTFE sample
holder equipped with a piston to avoid dehydration. The
magnetization isotherm was collected at 2 K between 0 and 5 T.
All data were corrected with the contribution of the sample
holder and diamagnetism of the sample estimated with Pascal's
In conclusion, we have reported a novel synthetic route to
Ni (dhtp): in water, under air, at atmospheric pressure, with
2
high space-time-yield and from an affordable linker, therefore
complementing this already well-remarked member of the MOF
material family with an additional attractive feature. A pertinent
parameter to compare the performance of the aqueous route
described herein with respect to the previously reported ones in
organic solvents is the space-time yield expressed in terms of
35
constants. The analysis of magnetic data was carried out by
10,41,42
isolated MOF weight/volume of solvent used/time unit.
simulation of cT thermal dependence including intramolecular
While the total volume of all solvents used should be taken into
consideration, the available published data allow us to calculate
this value by only taking into account the volume used during
the synthesis itself (and not the ones used for the washing
steps). The procedure reported here yields a production rate of
0
interactions (J), intermolecular interactions (zJ ) in the molec-
ular eld approximation and a temperature independent para-
magnetism (TIP) according to the following expression:
2
kgiso FðJ; TÞ
c ¼
þ TIP
4J
ꢀ
1
ꢀ1
0
2
8.5 g L
h
, that is a 50-fold increase with respect to the
12kT ꢀ 16ZJ FðJ; TÞ
ꢀ
1
ꢀ1
published route (0.6 g L
dehydrated Ni
h
considering the weight of fully
ð1 ꢀ uÞ
kT
where Fð J; TÞ ¼ 2
and u ¼ 4J ꢀ coth
12
3
2
(dhtp)). Expressed in kg per m per day, the
ð1 þ uÞ
kT
industrially pertinent unit, the space-time yield of the water-
based route described here could be extrapolated to 680 kg per
Unless otherwise specied, all analyses were performed on
fully rehydrated Ni
2
(dhtp) samples. The rehydration procedure
3
m per day; such a gure should be considered only as a very
ꢁ
consisted of exposing the material (previously dried at 80 C
overnight and stored in a dry box) to water-saturated air for 24 h
at room temperature.
high upper estimate, since we have tested our method only on
an 18 g scale and have not included the time-intensive washing
and drying steps necessary for the ton-scale batches. At the
same time, such a gure bodes well for the industrial potential
of this route, given the reported industrial space-time yields of
Preparation of 2,5-dihydroxyterephthalic acid from
hydroquinone
3
3
1
60 kg per m per day for Basolite A100®, 225 kg per m per day
3
for Basolite C300® and over 300 kg per m per day for Basolite In a 500 ml 2-neck round-bottom ask equipped with a
41
M050®.
2 3
condenser, K CO (97.7 g, 0.7 mol) was introduced. Formic acid
(42.3 g, 0.9 mol) was added drop by drop under vigorous
magnetic stirring, releasing a large amount of CO
strong exothermicity. The mixture was then heated up to 210 C,
leading to a thick melt of potassium formate, bicarbonate and
2
and causing
Experimental section
Materials and methods
ꢁ
Nickel(II) acetate tetrahydrate 99%, (Sigma-Aldrich), hydroqui- carbonate. The condenser was then removed and the reactor
none (Aldrich Chemie), anhydrous K CO (Acros), formic acid was ushed for 30 min with a continuous stream of argon. The
2
3
argon line was then replaced by a 500 ml round-bottom ask

lled with 300 g of dry ice. Hydroquinone (22.24 g, 0.2 mol) was
‡
Calculated using Advanced Chemistry Development (ACD/Labs) Soware V11.02
(
© 1994–2014 ACD/Labs).
added in a single portion to the melt and the condenser was
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placed back on the top of the reactor. The reaction mixture was XRD measurements, to Erwann Jeanneau from the “Centre de
ꢁ
then vigorously stirred for 6 h at 210 C under the CO stream Diffractom ´e trie Henri Longchambon” for the Le Bail renement
2
generated by the dry ice. Aer 6 h, the yellow reaction mixture of the PXRD pattern, and to Ruben Checa from the “Laboratoire
was dispersed in 300 ml of boiling water, leading to a suspen- des Multimat ´e riaux et Interfaces” (Universit ´e Claude Bernard
sion of white crystals in a dark-brown solution. This suspension Lyon 1) for magnetic susceptibility measurements.
was cooled to RT and ltered. The off-white powder obtained
was nally suspended in 200 ml of water and acidied with 40
ml of HCl 37%, causing the suspension to turn canary yellow.
Notes and references
This suspension was stirred for 1 h, ltered and washed 3 times
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with 50 ml portions of deionized water. The yellow product
ꢁ
obtained was dried at 80 C, yielding 20.8 g (105 mmol, 52.5%
based on hydroquinone) of 2,5-dihydroxyterephthalic acid
1
13
which was characterized by H and C NMR spectroscopy (see
Fig. S6A and B†).
1
6
13
H NMR (300 MHz, DMSO-d ) d ¼ 7.28 ppm (2H, S); C NMR
6
(
300 MHz, DMSO-d ) d ¼ 170.62; 152.26; 119.37; 117.52 ppm.
5
Y. Pan, Y. Liu, G. Zeng, L. Zhao and Z. Lai, Chem. Commun.,
011, 47, 2071–2073.
2
Synthesis of Ni (dhtp) in water
2
6
Q. Yang, S. Vaesen, F. Ragon, A. D. Wiersum, D. Wu, A. Lago,
T. Devic, C. Martineau, F. Taulelle, P. L. Llewellyn, H. Jobic,
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In a 500 ml round-bottom ask equipped with a condenser, a
suspension of dihydroxyterephthalic acid (10.31 g, 51 mmol) in
deionized water (400 ml) was heated to reux under strong
ꢁ
magnetic stirring (oil bath at 160 C). In a separate ask, nickel
7
S. J. Geier, J. A. Mason, E. D. Bloch, W. L. Queen,
M. R. Hudson, C. M. Brown and J. R. Long, Chem. Sci.,
acetate tetrahydrate (25.14 g, 100 mmol) was dissolved in
ꢁ
deionized water (100 ml) at 80 C. The light green nickel solu-
2013, 4, 2054–2061.
tion obtained was added in one portion to the boiling dihy-
droxyterephthalic acid suspension under continuous stirring
leading almost instantaneously to a homogeneous emerald
green solution. Aer a few minutes, a yellow precipitate started
to form. The reaction mixture was further reuxed for 1 h. The
8
9
X. Wu, Z. Bao, B. Yuan, J. Wang, Y. Sun, H. Luo and S. Deng,
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E. J. Garc ´ı a, J. P. S. Mowat, P. A. Wright, J. P ´e rez-Pellitero,
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26636–26648.

nal suspension was ltered and the yellow microcrystalline
1
0 G. D. Pirngruber and P. L. Llewellyn, in Metal-Organic
Frameworks – Applications from Catalysis to Gas Storage, ed.
D. Farrusseng, Wiley-VCH Verlag GmbH & Co. KGaA, 2011,
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powder was washed three times with 100 ml portions of warm
ꢁ
deionized water before being dried overnight at 80 C. 17.90 g of
this material were isolated and characterized by powder XRD,
HRTEM and TGA. The microporosity was determined by N2
adsorption at 77 K aer activation of a 105.7 mg aliquot for 20 h
1
1
1
1 D. Yu, A. O. Yazaydin, J. R. Lane, P. D. C. Dietzel and
R. Q. Snurr, Chem. Sci., 2013, 4, 3544–3556.
ꢁ
ꢀ5
at 150 C; 5 ꢂ 10 mbar. The weight loss observed during this
2 P. D. C. Dietzel, P. A. Georgiev, J. Eckert, R. Blom, T. Strassle
and T. Unruh, Chem. Commun., 2010, 46, 4962–4964.
3 S. Chavan, F. Bonino, L. Valenzano, B. Civalleri, C. Lamberti,
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activation process was used to determine the water content in
the isolated material (4.42 water molecules per Ni
2
(dhtp) unit).
Isolated yield: 91.6% based on 17.90 g of [Ni
2
(dhtp)$4.42 H O].
2
Author contributions
14 D. Peralta, G. Chaplais, A. Simon-Masseron, K. Barthelet and
G. D. Pirngruber, Energy Fuels, 2012, 26, 4953–4960.
The manuscript was written through contributions of all
authors.
1
1
1
1
1
5 J. Liu, J. Tian, P. K. Thallapally and B. P. McGrail, J. Phys.
Chem. C, 2012, 116, 9575–9581.
6 A. C. Kizzie, A. G. Wong-Foy and A. J. Matzger, Langmuir,
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Funding sources
7 J. Liu, Y. Wang, A. I. Benin, P. Jakubczak, R. R. Willis and
M. D. LeVan, Langmuir, 2010, 26, 14301–14307.
8 J. A. Mason, M. Veenstra and J. R. Long, Chem. Sci., 2014, 5,
“Centre National de la Recherche Scientique” (CNRS), “Ecole
Sup ´e rieure de Chimie, Physique et Electronique de Lyon” (CPE
Lyon) and “Universit ´e Claude Bernard Lyon 1” (UCBL) are
kindly acknowledged for support.
32–51.
9 L. Mitchell, B. Gonzalez-Santiago, J. P. S. Mowat, M. E. Gunn,
P. Williamson, N. Acerbi, M. L. Clarke and P. A. Wright,
Catal. Sci. Technol., 2013, 3, 606–617.
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We are grateful to Ruben Vera from the “Centre de Diffractom ´e -
trie Henri Longchambon” (Universit ´e Claude Bernard Lyon 1) for
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