Synthesis of phosphonosulfonic acid building blocks as linkers for coordination polymers

Article abstract of DOI:10.1039/c7nj01697b

Ten aromatic building blocks (8-11, 23-28) containing phosphonic and sulfonic acid groups within one molecule were synthesized. Twofold nucleophilic substitution starting from 1,2,4,5-tetrakis(bromomethyl)benzene (1) followed by hydrolysis gave building blocks 8-11. To obtain building blocks 23-28, the respective bromobenzenesulfonic acids 13, 16, 18-20 and 22 had to be synthesized first. Palladium-catalysed cross coupling with triethylphosphite followed by hydrolysis gave the desired building blocks with phosphonic and sulfonic acid groups. Building block 9 was successfully used as a linker for the synthesis of a new La-based CP with the composition [La₂(H₂L)_1.5(H₂O)₄].

Full text of DOI:10.1039/c7nj01697b

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ISSN 1144-0546
PAPER
Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
diarylethene-based metal–organic frameworks
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Synthesis of phosphonosulfonic acid building blocks as linkers for
coordination polymers
O. Beyer,a T. Homburg,b M. Albat,b N. Stockb and U. Lüninga
Received 00th January 20xx,
Accepted 00th January 20xx
Ten aromatic building blocks (
one molecule were synthesized. Twofold nucleophilic substitution starting from 1,2,4,5-
tetrakis(bromomethyl)benzene ( ) followed by hydrolysis gave building blocks 11. To obtain
building blocks 23 28, the respective bromobenzenesulfonic acids 13 16 18-20 and 22 had to be
synthesized first. Palladium-catalysed cross coupling with triethylphosphite followed by hydrolysis
gave the desired building blocks with phosphonic and sulfonic acid groups. Building block was
8-11, 23-28) containing phosphonic and sulfonic acid groups within
DOI: 10.1039/x0xx00000x
www.rsc.org/
1
8-
-
,
,
9
successfully used as a linker for the synthesis of a new La-based CP with the composition
[La2(H2L)1.5(H2O)4].
high proton conduction.4,10
Examples11,12,13 of organic building blocks containing
a
Introduction
phosphonic and a sulfonic acid group are rare, which limits the
investigation of metal phosphonate-sulfonate
Coordination polymers (CP)1 and metal-organic frameworks
(MOF)2 are intensely studied compounds with possible
application in gas storage, gas separation, catalysis, drug
delivery and ion conduction.3,4
frameworks.14,15–18 In case of the known frameworks, very
little is known in terms of proton conduction.19,20 To the best
of our knowledge, only four organic building blocks have been
successfully used up until now. In case of flexible building
blocks, only 2-phosphonoethanesulfonic acid18,21 and 4-
phosphonobutanesulfonic acid17,22 have been investigated.
The majority of known metal phosphonate-sulfonate
frameworks have been obtained using rigid m- or p-
phosphonobenzenesulfonic acid.15,16,19,23
The most investigated frameworks are based on carboxylates
as organic building blocks.5 Considerably less well-studied are
organic phoshonates and sulfonates. This might be because
single crystal growth and the prediction of the coordination
chemistry of metal phosphonates is more difficult and since
they mostly form non-porous dense layered materials. In the
case of metal sulfonates, the relatively weak coordination of
the anions to the metal nodes facilitates the formation of
crystalline products, but often these networks are less robust.
Nevertheless, there is a broad spectrum of phosphonate and
sulfonate frameworks described to date.6
Our research focuses on the synthesis of new rigid and flexible
benzene-based building blocks containing at least one sulfonic
acid and one phosphonic acid group.
Results and discussion
Especially in the field of ion conduction, the use of organic
building blocks with phosphonic or sulfonic acid groups has The synthesis of aromatic building blocks containing both
shown promising results. While metal phosphonates are able sulfonic and phosphonic acid groups (herein called
to build stable frameworks with high proton conductivity7,8
,
phosphonosulfonic acids) can be divided into two approaches.
metal sulfonates seem to be more promising in sulfonate- Either these groups are connected directly to the aromatic ring
carboxylate frameworks.9 In the latter case, the carboxylates or via a flexible spacer unit.
coordinate to metal nodes and the sulfonate remains free. But To obtain flexible phosphonosulfonic acids, 1,2,4,5-
also phosphonate-carboxylate frameworks are known for very tetrakis(bromomethyl)benzene (1) was chosen as the starting
material. Nucleophilic substitution of the bromides with
triethyl phosphite7 or sodium sulfite24 at the benzyl positions
has proven to be an efficient tool to introduce -PO3H2 and
-SO3H groups.
The synthesis of new rigid phosphonosulfonic acids is based on
combining different synthetic approaches. Previously,
sulfonation of benzenephosphonic acid has been reported to
give
3-phosphonobenzenesulfonic
acid
and
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Journal Name
5-phosphonobenzene-1,3-disulfonic
acid
(
23).13
But Due to very similar reactivities of the bromomethylene groups
sulfonation of aromatic phosphonic acids has two major draw in the starting material and products, a mixture of the starting
backs: long reaction times of up to 35 d and only meta- material and six different phosphonic acid ethyl esters (mono-,
substitution due to the electron withdrawing effect of the di-, tri- and tetra-phosphonic acid diethyl esters) was obtained.
phosphonic acid group. Therefore, Montoneri et al. Column chromatography of the mixture yielded pure mono-
synthesized 4-phosphonobenzenesulfonic acid using
different approach.11 4-Bromobenzenesulfonic acid ethyl ester a mixture of di-substituted
was synthesized from the respective sulfonic acid chloride and and pure tri-substituted phosphonic acid diethyl ester
sodium ethanolate. The obtained arylbromide was converted third fraction. The tetra-substituted phosphonic acid diethyl
with triethyl phosphite and nickel(II) chloride to the respective ester was not isolated. A mixture of the di-substituted esters
arylphosphonic acid diethyl ester. This synthesis is known as and were obtained from the second fraction by
the Tavs reaction.25 Hydrolysis of the diester yielded 4- crystallization. Column chromatography of this mixture yielded
phosphonobenzenesulfonic acid. pure and pure . Fortunately did not crystallize because
Sulfonation of arylbromides and bromination of arylsulfonic separation of from or via column chromatography is
acids were chosen to obtain a large variety of different possible but separation of from was not successful even
a
substituted phosphonic acid diethyl ester
and in the second fraction
in the
5 in the first fraction,
2,
3
4
6
7
2
4
2
4
3
2
3
4
3
4
bromobenzenesulfonic acids. Compared to arylphosphonic after several attempts. Nevertheless, these purification
acids, many different arylbromides are commercially available procedures reduced the yields, especially for the di-substituted
and the electron donating effect of the bromine allows ortho- phosphonic acid diethyl esters
2
and
and para-sulfonation in short reaction times. Following a The H-NMR and 13C-NMR spectra of
modified Tavs reaction using microwave-assisted heating, the and differ only by the chemical shift of the signals. NOESY
4.
1
2
and 4 are very similar
respective phosphonobenzenesulfonic acids were obtained.
experiments of both isomers were performed for unequivocal
assignment. In case of isomer a NOE interaction was
Synthesis of flexible phosphonosulfonic acids
2
observed between the protons of the bromomethylene group
and the phosphonic acid diethyl ester methylene group. Such a
Although
commercially available, it was synthesized from durene
(1,2,4,5-tetramethylbenzene) according to literature
procedure.26 Nucleophilic substitution of
was performed
1,2,4,5-tetrakis(bromomethyl)benzene
(
1
)
is
NOE interaction was not found for isomer
a doublet is observed for the 13C-NMR signal of the methylene
carbon atom connected to the phosphorus atom for isomer
4. Also, a doublet of
a
1
4.
with two equivalents of triethyl phosphite. Two equivalents
were chosen to get di-substituted phosphonic acid ethyl
esters. The remaining bromomethylene groups would allow
nucleophilic substitution with sodium sulfite to introduce the
sulfonic acid groups.
1
4
The coupling constants could be assigned to J and J coupling
with the respective phosphorus atom. For the respective
1
, only a doublet with a J coupling is
carbon atom of isomer
2
observed. The 6J coupling to the second phosphorus atom
seems to be too small.
It is important to notice that tri-substituted phosphonic acid
diethyl ester
6 should be used as fast as possible for further
reactions. Ethanol impurities originating from column
chromatography were difficult to remove and tended to react
in a nucleophilic substitution of the bromide after some time.
1
The respective ether was observed via H-NMR spectroscopy
and EI mass spectrometry.
The desired phosphonobenzenesulfonic acids 8, 9, 10 and 11
were obtained by introduction of the sulfonic acid groups and
hydrolysis of the phosphonic acid diethyl esters. Sulfonic acid
groups were introduced by nucleophilic substitution of the
bromides in 2, 4, 5 and 6 with sodium sulfite. The respective
phosphonic acid diethyl esters were dissolved in acetone,
added to a saturated sodium sulfite solution in water and
heated for 12 h. A saturated solution was used to minimize
nucleophilic side reactions with water. After removing
acetone, conc. hydrochloric acid was added to hydrolyze the
phosphonic acid diethyl ester and to decompose sodium
sulfite. After removing the conc. hydrochloric acid,
dimethylsulfoxide was added to dissolve the respective
phosphonobenzenesulfonic acid. The majority of sodium
chloride remained undissolved and was removed by filtration.
The acids were precipitated by adding dichloromethane and
filtered off. Since it is difficult to know whether the respective
acids or sodium salts were obtained, ion exchange was used to
Scheme 1 Nucleophilic substitution of 1,2,4,5-tetrakis(bromomethyl)benzene (1) with
two equivalents of triethyl phosphite. a) P(OEt)3, toluene, 12 h reflux.
2 | J. Name., 2012, 00, 1-3
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sodium
ions.
The
four
desired obtained due to the electron-donating effect of the first
phosphonobenzenesulfonic acids
obtained as colourless solids.
8, 9, 10 and 11 were substituted bromine. Since separation was too difficult,
another
approach
using
was
ipso-sulfonation
tried.27
of
a
trimethylsilylbenzene
3,5-Dibromo-1-
(trimethylsilyl)benzene (14) was treated with trimethylsilyl
chlorosulfonate to give 3,5-dibromobenzenesulfonic acid (16).
The +I effect of the trimethylsilyl group surpasses the +M
effect of the bromine atoms and enables an ipso-substitution.
The addition of aqueous sodium hydroxide is necessary to
hydrolyze the sulfonic acid trimethylsilyl ester intermediate 15
.
Scheme 4 ipso-Sulfonation of 14. a) ClSO3SiMe3, 1,2-dichloroethane, 2 d, 90 °C; b) 1.
NaOH(aq); 2. ion exchange.
Another tri-substituted bromobenzenesulfonic acid was
obtained using a modification of a published procedure.28 1,4-
Dibromobenzene (17) was sulfonated with fuming sulfuric acid
(20-30 % SO3) to give 2,5-dibromobenzenesulfonic acid (18).
After stirring for 2 h at 150 °C, the suspension became a clear
Scheme 2 Nucleophilic substitution of the bromides with sodium sulfite followed by
hydrolysis of the phosphonic acid diethyl esters. a) 1. Na2SO3(aq), acetone, 12 h, 100 °C;
2. HCl(aq), 2 d, 120 °C; 3. ion exchange.
Synthesis of rigid phosphonosulfonic acids
solution.
A
mixture of the mono- and disulfonated
The general procedure for the preparation of different
phosphonobenzenesulfonic acids can be divided into two
steps: synthesis of the bromobenzenesulfonic acids and the
Tavs reaction to introduce the phosphonic acid groups.
Different approaches to obtain tri- and tetra-substituted
bromobenzenesulfonic acids will be discussed.
dibromobenzenes was obtained in a ratio of 3:2. Optimization
of the reaction conditions in favor of the mono-sulfonated
product 18 was not successful. Using a weaker sulfonation
agent like conc. sulfuric acid led to unexplainable side
reactions. Reducing the reaction time favored mono-
sulfonation but at the same time not all starting material 17
was converted. Nevertheless, 2,5-dibromobenzenesulfonic
acid (18) was obtained after separation from the disulfonated
5-Bromobenzene-1,3-disulfonic acid (13) was synthesized by
bromination of benzenedisulfonic acid disodium salt (12). The
starting material 12 was dissolved in conc. sulfuric acid and
brominated with N-bromosuccinimide (NBS). Unbrominated
starting material and dibrominated benzenedisulfonic acid
were obtained as byproducts depending on the reaction time
and the amount of NBS used. Starting material 12 could be
separated by transferring product 13 into the organic layer
with tetra-n-butylammonium cations. Surprisingly, the starting
material 12 stayed in the aqueous layer. Since this was not the
case for the dibrominated byproduct, the reaction conditions
were optimized to prevent double-bromination. Stirring
starting material 12 with 1.1 equivalents of NBS for 12 h at
room temperature showed satisfying results. Cation-exchange
after workup yielded the desired 5-bromobenzene-1,3-
disulfonic acid (13).
byproducts 19 and 20
.
Scheme 5 Mono-sulfonation of 1,4-dibromobenzene (17). a) 1. Fuming sulfuric acid (20
- 30 % SO3), 2 h, 150 °C; 2. ion exchange.
As described in the literature29, double-sulfonation of 1,4-
dibromobenzene (17) gives two isomers which are perfect
precursor
for
the
synthesis
of
tetra-substituted
phosphonobenzenesulfonic acids.
Scheme 3 Bromination of benzenedisulfonic acid disodium salt (12). a) 1. NBS, conc.
sulfuric acid, 12 h, room temp.; 2. ion exchange.
Scheme 6 Double-sulfonation of 1,4-dibromobenzene (17) to obtain isomers 19 and 20.
a) 1. Fuming sulfuric acid (20 - 30 % SO3), 24 h, 200 °C; 2. ion exchange.
In a similar approach, benzenesulfonic acid was reacted with
NBS to obtain 3,5-dibromobenzenesulfonic acid (16). But only By increasing the reaction time to 24 h and raising the
a mixture of different dibrominated benzenesulfonic acids was temperature to 200 °C, only the disulfonated isomers 2,5-
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dibromobenzene-1,3-disulfonic
acid
(
19)
and
2,5-
dibromobenzene-1,4-disulfonic acid
(20) were obtained.
Contrary to the literature, both isomers were characterized.
Double-sulfonation was also possible for 1,3-dibromobenzene
(
21). Treatment with fuming sulfuric acid (65 % SO3) gave 4,6-
dibromobenzene-1,3-disulfonic acid (22). No disulfonated
isomer was observed as well as any mono- or triple-
sulfonation.
Scheme 8 Tavs reaction and hydrolysis to obtain 23 and 24. a) 1.NBu4OH; 2. P(OEt)3,
PdCl2, MW; 3. HCl(aq); 4. ion exchange.
An unexpected side reaction reduced the yields of the three
Scheme 7 Double-sulfonation of 1,3-dibromobenzene (21). a) 1. Fuming sulfuric acid
phosphonobenzenesulfonic acids 25, 26 and 27 significantly.
(65 % SO3), 5 h, 120 °C; 2. ion exchange.
An ethylphosphinic acid ethylester group was partly
introduced instead of the desired phosphonic acid diethyl
ester group.
The second step to obtain the tri- and tetra-substituted
phosphonobenzenesulfonic acids involves the introduction of
phosphonic acid groups. Conversion of the described
bromobenzenesulfonic acids in a modified Tavs reaction25 gave
the respective phosphonic acid diethyl esters. The most
common reaction conditions for arylbromides and aryliodides
in a Tavs reactions are: high temperature (up to 200 °C),
nickel(II) chloride as catalyst and triethyl phosphite as reagent
and solvent. In addition, changing the catalyst to palladium(II)
chloride and using microwave-assisted heating showed
promising results in the literature.30 Palladium(II) chloride gave
better yields for bromoaryls in general and in the presence of a
sterically demanding group in the ortho-position. Microwave-
assisted heating was chosen because the necessary high
temperatures (≥ 200°C) are easier to accomplish and the
reaction time is much shorter compared to ordinary heating.
These conditions were adapted for all the Tavs reactions
performed. Nevertheless, some optimizations had to be
carried out to get satisfying results. Since acidity of the sulfonic
acid might be problematic for the reaction and the workup,
the respective tetra-n-butylammonium sulfonates were used.
In contrast to sodium sulfonates, the organic sulfonates
possess a better solubility and have a lower melting point.
Both aspects ensure that the sulfonate mixes and reacts with
triethyl phosphite. The synthesis of sulfonic acid esters, as
described by Montoneri et al.11, becomes irrelevant. The tetra-
n-butylammonium sulfonates are easy and fast to obtain by
treating the respective sulfonic acid with tetra-n-
butylammonium hydroxide.
Scheme 9 The observed ethylphosphinic acid ethylester group.
1H-NMR spectra showed characteristic signals for an ethyl
group connected directly to a phosphorus atom and a second
set of aromatic signals. For all three cases, integration of the
signals showed that the byproduct possesses one
ethylphosphinic acid ethylester group and one phosphonic
acid diethyl ester group. It remains unclear why and how this
side reaction takes place. But it was observed only when a
sulfonate group was in ortho position to a bromine atom.
After ester hydrolysis, the phosphinic acid byproducts could be
separated
diphosphonobenzenesulfonic
diphosphonobenzene-1,4-disulfonic acid
by
recrystallization.
Pure
25),
26
2,5-
2,5-
acid
(
(
)
and 4,6-
diphosphonobenzene-1,3-disulfonic acid (27) were obtained.
This procedure was successfully used for the conversion of tri-
substituted bromobenzenesulfonic acids 13 and 16
.
Subsequent hydrolysis of the respective phosphonic acid
diethyl esters with conc. hydrochloric acid gave
5-phosphonobenzene-1,3-disulfonic
acid
(
23)
and
3,5-diphosphonobenzenesulfonic acid (24).
Scheme 10 Synthesis of phosphonobenzenesulfonic acids 25, 26 and 27. a) 1.NBu4OH;
2. P(OEt)3, PdCl2, MW; 3. HCl(aq); 4. ion exchange.
4 | J. Name., 2012, 00, 1-3
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Different side reactions were observed during the synthesis of and six oxygen atoms from five or four different linker
2,5-diphosphonobenzene-1,3-disulfonic acid (28). The Tavs molecules for La1 and La2, respectively. Due to statistical
reaction at the bromine in the 5-position works very well but incorporation of phosphonate and sulfonate groups the
the conversion of the bromine in the 2-position is very slow. structure was refined with an occupancy of 0.5 for sulfur and
1H-NMR spectra suggested that either the bromine atom did phosphorus atoms at each position. All sulfonate/phosphonate
not react at all or it was substituted by a hydrogen atom. The groups coordinate two La3+ ions in a [2, 1 1 0] fashion and
desired product 28 was obtained in a mixture which mainly connect the linker molecule to six La3+ ions, four monodentate
contains byproducts 29 and 23. 2,5-Diphosphonobenzene-1,3- and two chelating (Fig. S3). Every La3+ ion is bound to two
disulfonic acid (28) could be obtained by recrystallization in other La3+ ions by three sulfonic/phosphonic groups, forming
low yield.
chains along the b axis (Figure 2).
Scheme 11 Synthesis of 2,5-diphosphonobenzene-1,3-disulfonic acid (28) with non-
isolated byproducts 29 and 23. a) 1.NBu4OH; 2. P(OEt)3, PdCl2, MW; 3. HCl(aq); 4. ion
exchange.
Figure
2 Excerpt of the structure of [La4(H2L)3(H2O)8]. Chains are formed by
Synthesis of a La-based coordination polymer
interconnections of La3+ ions through sulfonate/phosphonate groups. LaO8 polyhedra in
light blue and sulfonate/phosphonate groups as purple tetrahedra.
Reactions were performed under hydrothermal conditions
using La(NO3)3·6H2O and the flexible linker
bis(phosphonomethyl)-benzene-1,4-diyl]bis(methylsulfonic
acid).31
new La-based CP with the composition
9 (H6L, [2,5-
Each chain is interconnected via the organic moieties to three
other chains and a double layer in the a-b plane with diamond
shaped pores along the b axis is formed (Figure 3). Taking the
van der Waals radii into account, the diameter of the pores is
3.8 Å (Fig. S5). They are interconnected by smaller pores along
the c axis to form a three dimensional network of infinite
channels that amounts to 30 % of the crystal space. This is
shown by the calculation of the Connolly surface (Fig. S4).
A
[La4(H2L)3(H2O)8] was obtained. The crystal structure of this
compound was determined from single-crystal X-ray
diffraction data and phase purity was confirmed by powder X-
ray diffraction (Fig. S1 and Fig. S2). The compound
[La4(H2L)3(H2O)8] crystallizes in the monoclinic space group
C2/m. The asymmetric unit contains two La3+ ions and two
linker molecules on special positions and four water molecules
(Figure 1).
Figure 3 Excerpt of the structure of [La4(H2L)3(H2O)8]. Double layer, in the a-b plane
with diamond shaped pores along the b axis. The orange sphere with a diameter of
6.8 Å is used for easier visualisation. LaO8 polyhedra in light blue and
sulfonic/phosphonic groups as purple tetrahedra.
Figure 1 Extended asymmetric unit of compound [La4(H2L)3(H2O)8] with 50% thermal
ellipsoids. La-O bonds are presented by dashed lines. H atoms are omitted for clarity.
[Symmetry code: (i) x + 0.5, y + 0.5, z; (ii) x + 0.5, y - 0.5, z; (iii) x,1 - y, z; (iv) x, - y, z;
(v) x, y - 1, z]
Considering the IR-spectra as well as the synthetic conditions,
the pores are filled with disordered water molecules. Based on
the distances between oxygen atoms in the crystal structure,
the presence of hydrogen bonds can be postulated. Thus, the
double layers are connected by hydrogen bonds between the
oxygen atoms O1 and O2 which are two coordinating water
Both La3+ ions (La1 and La2) are eightfold coordinated in a
distorted square antiprismatic fashion by two water molecules
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metal-organic frameworks. Synthesis, characterization,
and applications, Wiley-VCH Verlag GmbH & Co. KGaA,
Weinheim, 2016; c) H.-C. Zhou, J. R. Long and O. M. Yaghi,
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Kitagawa, Chem. Soc. Rev., 2014, 43, 5415–5418.
molecules connected to La1 and La2, respectively, and O10
(Tab. S2). The latter oxygen atom (O10) belongs to
a
sulfonate/phosphonate group. Due to charge balancing, two
protons must be present in the structure. Since these could
not be localised, we postulate that –PO3H groups are formed,
which is supported by IR spectroscopy (Fig. S6). The presence
of hydrogen acceptor and donor groups in combination with
the coordinating water molecules within the pores makes this
CP a potential candidate for proton conduction.
3
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Schierle-Arndt and J. Pastré, J. Mater. Chem., 2006, 16,
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Up to now only two mixed-linker lanthanum arylphosphonato-
sulfonates have been reported.32 The pure tetrasulfono or
tetraphosphono
linker
molecules
and
1,2,4,5-
tetrakis(sulfonomethyl)-benzene
1,2,4,5-tetrakis
(phosphonomethyl)-benzene have also been reported but only
one lanthanum tetraphosphonate (PCMOF-5) has been
prepared with the latter linker. The compound crystallizes in a
three dimensional framework structure. As observed in the
title compound, the La3+ ions exhibit a distorted square
antiprismatic coordination environment. In PCMOF-5, one of
the four functional groups does not coordinate to the metal
ion but protrudes into the pore making the pore surface highly
acidic.7
4
5
P. Ramaswamy, N. E. Wong and G. K. H. Shimizu, Chem.
Soc. Rev., 2014, 43, 5913–5932.
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a) G. K. H. Shimizu, R. Vaidhyanathan and J. M. Taylor, Chem.
,
6
Soc. Rev., 2009, 38, 1430–1449; b) K. J. Gagnon, H. P. Perry and
A. Clearfield, Chem. Rev., 2012, 112, 1034–1054; c) Z.-Y. Du, Y.-
H. Sun, X. Xu, G.-H. Xu and Y.-R. Xie, Eur. J. Inorg. Chem., 2010,
4865–4869; d) C. Zitzer, T. W. T. Muesmann, J. Christoffers and
M. S. Wickleder, New J. Chem., 2015, 39, 6117-6124; e) C.
Zitzer, T. W. T. Muesmann, J. Christoffers, M. S. Wickleder,
Chem. Asian J., 2015, 10, 1354-1362; f) P. Deria, W. Bury, I.
Hod, C.-W. Kung, O. Karagiaridi, J. T. Hupp and O. K. Farha,
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Conclusions
In summary, ten aromatic building blocks (8-11, 23-28) with
phosphonic and sulfonic acid groups were synthesized in batch
sizes and up to several grams. For the literature-known
building block 23, complete characterization and a new
synthetic route was provided. Building blocks
flexible methylene unit between each functional group and the
benzene ring. The more rigid building blocks 23 28 have their
8-11 possess a
-
7
8
J. M. Taylor, K. W. Dawson and G. K. H. Shimizu, J. Am.
Chem. Soc., 2013, 135, 1193–1196.
functional groups directly connected to the benzene ring. Due
to the coordinating ability of phosphonic and sulfonic acid
groups, all ten building blocks might be used as linkers for CP
a) J. M. Taylor, R. K. Mah, I. L. Moudrakovski, C. I. Ratcliffe,
R. Vaidhyanathan and G. K. H. Shimizu, J. Am. Chem. Soc.,
2010, 132, 14055–14057; b) S. Pili, S. P. Argent, C. G.
Morris, P. Rought, V. Garcia-Sakai, I. P. Silverwood, T. L.
Easun, M. Li, M. R. Warren, C. A. Murray, C. C. Tang, S.
or MOF synthesis. First attempts used flexible building block
9
as a linker in hydrothermal reactions with La(NO3)3·6H2O. A
new La-based CP with the composition [La4(H2L)3(H2O)8] was
discovered. Single-crystal X-ray diffraction data showed free
hydrogen acceptor and donor groups within the pores. These
results indicate the potential of these new organic building
blocks for the preparation of proton conducting materials.
Yang and M. Schroder, J. Am. Chem. Soc., 2016, 138
6352–6355; c) S. Kim, K. W. Dawson, B. S. Gelfand, J. M.
Taylor and G. K. H. Shimizu, J. Am. Chem. Soc., 2013, 135
,
,
963–966; d) M. Feyand, C. F. Seidler, C. Deiter, A.
Rothkirch, A. Lieb, M. Wark and N. Stock, Dalton Trans.,
2013, 42, 8761–8770.
9
a) L.-J. Zhou, W.-H. Deng, Y.-L. Wang, G. Xu, S.-G. Yin and
Q.-Y. Liu, Inorg. Chem., 2016, 55, 6271–6277; b) S.-N.
Zhao, X.-Z. Song, M. Zhu, X. Meng, L.-L. Wu, S.-Y. Song, C.
Wang and H.-J. Zhang, Dalton Trans., 2015, 44, 948–954;
c) X.-Y. Dong, R. Wang, J.-B. Li, S.-Q. Zang, H.-W. Hou and
T. C. W. Mak, Chem. Commun., 2013, 49, 10590–10592; d)
W. J. Phang, H. Jo, W. R. Lee, J. H. Song, K. Yoo, B. Kim and
C. S. Hong, Angew. Chem., 2015, 127, 5231–5235, Angew.
Chem. Int. Ed., 2015, 54, 5142–5146; e) T. Kundu, S. C.
Sahoo and R. Banerjee, Chem. Commun., 2012, 48, 4998–
5000.
Acknowledgement
This
project
was
supported
by
the
Deutsche
Forschungsgemeinschaft (STO 643/10-1).
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New Journal of Chemistry
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DOI: 10.1039/C7NJ01697B
Ten benzene based linkers containing sulfonic and phosphonic acids have been synthesized. One
lanthanum MOF was isolated and characterized.