Synthesis, functionalisation and post-synthetic modification of bismuth metal-organic frameworks

Article abstract of DOI:10.1039/c7dt01744h

Two new bismuth metal-organic frameworks (Bi-MOFs) were discovered using high throughput experiments employing bismuth(iii) nitrate pentahydrate and triazine-2,4,6-triyl-tribenzoic acid (H₃TATB). The reaction was carried out for long reaction times (～5 d) in a water/DMF-mixture and resulted in the formation of [Bi₂(O)(OH)(TATB)]·H₂O (denoted as CAU-35). By switching to short reaction times and a methanol/DMF-mixture as the solvent, an analogue of CAU-7-BTB with the composition [Bi(TATB)]·DMF·6H₂O (denoted as CAU-7-TATB) was obtained. The use of the amino-functionalised H₃TATB linker (H₃TATB-NH₂) resulted in the formation of a functionalised porous Bi-MOF with the composition [Bi(TATB-NH₂)]·5H₂O·0.5DMF (CAU-7-TATB-NH₂). The structures of CAU-35 and CAU-7-TATB were successfully solved and refined from the PXRD data. CAU-7-TATB-NH₂ was post-synthetically modified using anhydrides (acetic anhydride and valeric anhydride), cyclic anhydrides (succinic anhydride and phthalic anhydride), and 1,3-propane sultone. The degree of conversion ranged from 33% to 79%.

Full text of DOI:10.1039/c7dt01744h

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DOI: 10.1039/C7DT01744H
Dalton Transactions
ARTICLE
Synthesis, functionalisation and post-synthetic modification of
bismuth metal-organic frameworks
Received 00th January 20xx,
Accepted 00th January 20xx
M. Köppen,† O. Beyer,† S. Wuttke, U. Lüning and N. Stocka,*
a
b
c
b,*
DOI: 10.1039/x0xx00000x
Two new bismuth metal-organic frameworks (Bi-MOFs) have been discovered using high throughput experiments
employing bismuth(III) nitrate pentahydrate and triazine-2,4,6-triyl-trisbenzoic acid (H
in a water/DMF-mixture resulted in the formation of [Bi (O)(OH)(TATB)]∙H O (denoted as CAU-35). By switching to short
reaction times and a methanol/DMF-mixture as the solvent, an analogue of CAU-7-BTB with the composition
Bi(TATB)]∙DMF∙6H O (denoted as CAU-7-TATB) was obtained. The use of the amino-functionalised H TATB linker (H TATB-
NH ) resulted in the formation of a functionalised porous Bi-MOF with the composition [Bi(TATB-NH )]∙5H O∙0.5DMF (CAU-
-TATB-NH ). The structures of CAU-35 and CAU-7-TATB were successfully solved and refined from PXRD data. CAU-7-
TATB-NH was post-synthetically modified using anhydrides (acetic anhydride, valeric anhydride), cyclic anhydrides
succinic anhydride, phthalic anhydride) and 1,3-propane sultone. The degree of conversion ranges from 33 % to 79 %.
3
TATB). Long reaction times ( 5 d)
www.rsc.org/
2
2
[
2
3
3
2
2
2
7
2
2
(
synthesised under the same reaction conditions using a
1
1
Introduction
Tuneable properties and high specific surface areas made
metal-organic frameworks (MOFs) one of the main focussed
compounds in chemistry over the last decade. Many different
metal ions have been incorporated into MOF structures, but
for future applications most often abundant and non-toxic
metal ions are the elements of choice. Bismuth compounds
are generally known to be non-toxic, even though bismuth is
the heaviest stable element in nature. So far, only three Bi-
functionalised linker, but very often the conditions must be
optimised again. An additional functional group in the linker
can also lead to a different reaction product due to changes in
the solubility and/or coordination properties. Nevertheless,
the tedious optimisation is often worthwhile because a
functionalised MOF facilitates PSM. Especially amino-
functionalised MOFs and their usage for PSM have resulted in
1
2
9,12,13
many modified framework compounds.
Besides
cyclic anhydrides15 and
carboxylic acid chlorides, there are also known modification
13,14
acetylation with anhydrides,
3
16
MOFs have been published which possess permanent porosity,
17
18
19
reactions with isocyanates, aldehydes, alkylbromides and
4
5
6
i.e. CAU-7, NOTT-220 and CAU-17 . Among these, CAU-7-BTB
20
peptide coupling reagent. The large pool of potential PSM
reactions for amino-functionalised MOFs allows many
possibilities to generate new, functionalised frameworks.
In this work, we present the results of the systematic
investigation of the system Bi /TATB /H
which led to two different Bi-MOFs of the composition
(O)(OH)(TATB)] (CAU-35, TATB
trisbenzoate, Scheme 1) and [Bi(TATB)] (CAU-7-TATB). The
latter was also obtained using a functionalised linker with one
amino group per linker molecule (CAU-7-TATB-NH
Bi-MOF was investigated in several PSM reactions.
3
-
(
[Bi(BTB)], BTB = 1,3,5-benzenetrisbenzoate, Scheme 1) has
been proven to be catalytically active in the
hydroxymethylation of furane derivatives. In addition, Bi-
4
5
MOFs have also been studied for application in gas storage,
3+
3-
2 3
O/DMF/CH OH,
7
8
photocatalysis and photoluminescence.
The introduction of functional groups into the MOF scaffold is
common way to adjust their chemical and physical
3
-
[
Bi
2
= 1,3,5-triazine-2,4,6-
a
properties and thereby extend their possible field of
applications. This can be achieved either by directly using a
functionalised linker in the MOF synthesis or via post-synthetic
2
), and this
9
,10
modification (PSM). An isoreticular MOF can sometimes be
a.Institut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, Max-
Eyth-Str. 2, 24118 Kiel, Germany.
b.
Otto-Diels-Institut für Organische Chemie, Christian-Albrechts-Universität zu Kiel,
Otto-Hahn-Platz 4, 24118 Kiel, Germany.
Department of Chemistry and Center for NanoScience (CeNS), LMU München,
c.
Butenandtstraße 11, 81377 München, Germany
†
These authors contributed equally to this work.
*
correspondence to: luening@oc.uni-kiel.de, stock@ac.uni-kiel.de
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
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Dalton Transactions
In CAU-35, the structure is build up by a linear inorganic
View Article Online
DOI: 10.1039/C7DT01744H
7
-polyhedra, which are connected
building unit (IBU) with BiO
to a chain of composition {Bi
2
O6.5} (Fig. S22). The connection of
these IBUs to a network is reminiscent to a distorted
honeycomb net with one additional linker inside the distorted
hexagonal pore (Fig. 2 and 3). According to the Rietveld
analysis, two oxygen atoms are observed in the IBU of CAU-35
that are not part of a linker molecule. One is coordinating to
3
+
2-
4
four Bi ions (µ -O ion) and the other oxygen atom is
3+
-
3
bridging three Bi ions (µ -OH ion). Since the structure is
3 3 3 2
Scheme 1 Molecular structure of the organic linkers H BTB, H TATB and H TATB-NH .
solved and refined from PXRD data, we were not able to
unequivocally locate the position of the proton. Charge
balance by dimethylammonium ions in the pores, which can be
formed by hydrolysis of DMF during the synthesis, can be
excluded based on the characterisation data (IR spectroscopy
Results and discussion
3+
3-
The systematic investigation of the system Bi /TATB
O/DMF/CH
/H
2
3
OH was carried out using our high-throughput as well as TG and elemental analysis). The irregular, distorted
To study the influence of different reaction shape of the BiO
-polyhedra is caused by the lone electron pair
21
set-up.
parameters on the product formation the molar ratio and of the Bi ions.
7
3+
22
concentration of starting materials, the solvent (-mixtures) and CAU-35 exhibits moderate sorption properties, with a specific
2
reaction temperatures/times were varied.
BET surface area of 77 m /g and a micropore volume of 0.06
3
Depending on the reaction conditions, two different products cm /g (Fig. S23). A detailed characterisation of this compound,
3 3 2 3
were obtained using Bi(NO ) ·5H O and H TATB. CAU-35 is including N
2
sorption, IR, TG and elemental analysis data, is
formed when water/DMF-mixtures and long reaction times are given in the Supporting Information (page S26-S28).
used in a conventional solvothermal synthesis. On the other
hand, short reaction times and methanol/DMF-mixtures in a
microwave-assisted synthesis led to CAU-7-TATB. The
conditions for the synthesis of CAU-7-TATB-NH
similar.
2
are very
CAU-35
During the high-throughput experiments with H
bismuth(III) nitrate pentahydrate,
composition [Bi (O)(OH)(TATB)], denoted as CAU-35, was
3
TATB and
a
product with the
2
discovered. The crystal structure of this compound was
successfully solved and refined from PXRD data. Details about
the solution and refinement are given in the Supporting
Information (page S20), the Rietveld plot is shown in Fig. 1.
Fig. 2 Crystal structure of CAU-35 (view along [001]). The unit cell dimension is
represented by the box.
CAU-7-TATB
[
Bi(TATB)]∙DMF∙6H
2
O (CAU-7-TATB (as), as = as synthesised)
TATB and bismuth(III) nitrate
was obtained employing H
3
pentahydrate using short reaction times (20 min) and a
mixture of methanol and DMF as the solvent. In contrast to
CAU-7-BTB, which was first obtained using H
3
BTB as the linker
4
(Scheme 1), structural transformation upon activation of
CAU-7-TATB (as) is observed. The PXRD pattern of CAU-7-TATB
as) is very similar to the one of CAU-7-BTB. Indexing of the
(
PXRD pattern led to a monoclinic unit cell, which was
confirmed by a LeBail fit (Table S1, Fig. S1). When the as
synthesised sample is treated at 120 °C for 1 d, the crystal
structure changes to the orthorhombic high temperature (ht)
phase of CAU-7-TATB. High resolution PXRD data of CAU-7-
Fig. 1 Rietveld plot of the refinement of CAU-35. Measured and calculated PXRD data,
the difference of both and the allowed reflections are shown in black, red, blue and as
black bars, respectively.
2
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TATB (ht) allowed a Rietveld refinement of the structure (Tab. effect, high resolution scanning electron microVsicewopAreticle(SOEnMline)
S1, Fig. S3). To obtain a guest free sample of CAU-7-TATB (ht) micrographs were taken of two sampDleOsI: 1w0.i1t0h39s/Cig7nDiTfi0c1a7n44tlHy
activation was carried out in a glass capillary, which was different BET surface areas. Surprisingly, no differences could
heated at 120 °C under reduced pressure for 1 h. In be detected (Fig. S13-S16).
comparison to the structure of CAU-7-BTB, in CAU-7-TATB (ht)
(
Fig. 3) less rotation of the benzoate groups is observed with Post-synthetic modification of CAU-7-TATB-NH
2
respect to the central aromatic ring, and thus the rings are
more co-planar. This observation is typical for triazine based
linkers, due to the missing steric hindrance of the hydrogen
2
The possibility of PSM reactions using CAU-7-TATB-NH was
explored using some typical literature procedures.9 For this
purpose eight synthesis batches of CAU-7-TATB-NH
combined to ensure data consistency and all PSM reactions
were performed using this mixture. CAU-7-TATB-NH was
2
were
23
atoms. The analysis of the nitrogen sorption isotherm of
2
CAU-7-TATB led to a specific BET surface area of 813 m /g and
2
3
a micropore volume of 0.31 cm /g (Fig. S7). These are lower
treated with methanesulfonyl chloride, acetyl chloride, ethyl
isocyanate, several anhydrides and two different sultones.
After treatment with methanesulfonyl chloride and acetyl
2
than the published values for CAU-7-BTB (ABET = 1150 m /g,
3
4
V
mic = 0.43 cm /g), but correlate well with the theoretical
2
3
values (ABET = 867 m /g, Vmic = 0.32 cm /g), which are
calculated using the program Materials Studio.24
chloride, a clear solution was obtained. Since CAU-7-TATB-NH
2
is not stable against HCl, the reaction was performed in the
presence of pyridine or triethyl amine to capture the HCl which
is formed during the acetylation of the amino group.
Nevertheless, dissolution of the material was observed.
Different observations were made for the treatment of CAU-7-
2
TATB-NH with ethyl isocyanate. In this case, a degradation of
the structure was observed (Fig. S33). In all three cases, it
remains unclear why the degradation takes place.
In contrast, the treatment with anhydrides like acetic
anhydride and valeric anhydride was successful and resulted in
2 2
the formation of CAU-7-TATB-NH -AA and CAU-7-TATB-NH -
VA, respectively (Scheme 2). Both MOFs maintain their
structure according to PXRD data (Fig. S32). The degree of
conversion was determined by comparing the relative integrals
1
in the H-NMR-spectra after digestion of the MOF (Fig. S26 and
S27). The degree of conversion drops from 79 % for CAU-7-
TATB-NH
2 2
-AA to 47 % for CAU-7-TATB-NH -VA, which may be
attributed to the longer alkyl chain of valeric anhydride.
Fig. 3 Crystal structure of CAU-7-TATB (view along [001]). The unit cell dimension is
represented by the box.
CAU-7-TATB-NH
Reactions carried out under very similar synthesis conditions
to those of CAU-7-TATB with H TATB-NH as the linker resulted
in successful formation of the CAU-7 analogue [Bi(TATB-NH )]
5H O∙0.5DMF (CAU-7-TATB-NH ), which is, to the best of our
2
3
2
2
∙
2
2
knowledge, the first example of a functionalised Bi-MOF.
Whereas for CAU-7-TATB two different phases (as and ht)
were discovered, for CAU-7-TATB-NH only one phase with an
2
orthorhombic crystal structure was observed (Table S4, Fig.
S10). Since synthesis scale-up could not be carried out, several
2
batches of CAU-7-TATB-NH were synthesised under identical
reaction conditions. In order to get sufficiently large amounts
of the compound for a systematic PSM study, the exact same
starting materials were used in every synthesis.
Although the characterisation of the different batches by
PXRD, elemental- and thermogravimetric analysis, as well as
the infrared spectroscopy did not indicate any impurity
(Supporting Information, page S16-S17 and page S36-S38)
large variation in the nitrogen adsorption properties (ABET in a
2
range of 104-627 m /g) were observed. To get insight into this
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Dalton Transactions
modified MOFs are available in the Supporting Information
View Article Online
DOI: 10.1039/C7DT01744H
(page S29-S38).
Experimental
Chemicals and experimental details
The chemicals were purchased from Aldrich, Alfa Aesar or
Walter CMP and used without further purification. Syntheses
were carried out under solvothermal conditions in a Biotage
Initiator microwave oven or in self-made high-throughput
21
autoclaves with in PTFE inserts of 2 mL volume.
Powder X-ray diffraction (PXRD) was performed on a STOE
Stadi P Combi (λ = 1.5406 Å) equipped with a MYTHEN
26
detector. FOX was used for structure solution from PXRD
27
data and TOPAS Academic 4.1 for LeBail fits and Rietveld
refinement.
Sorption measurements were performed on a BELsorp max or
BELsorp mini, infrared spectroscopy on a Bruker Alpha-P
spectrometer and elemental analyses on a HEKAtech Euro
Elemental Analyzer. The scanning electron microscopy (SEM)
experimentswere performed on a Jeol JSM-6500F with EDX-
Detector and Inca-software (Oxford Instruments).
NMR spectra were recorded on Bruker DRX 500 or AV 600
instruments and assignments were supported by COSY, HSQC
and HMBC. Even when spectra were obtained as broad-band
1
3
13
decoupled C-NMR, the type of C signal is always listed as
singlet, doublet, etc. Degree of conversion by post-synthetic
modification reaction was determined by comparing the
1
relative integrals in H-NMR-spectra of digested material.
6
Digestion was achieved by adding a mixture of DMSO-d and
Scheme
2 Post-synthetic modification of CAU-7-TATB-NH
2
with the respective DCl (37 %) to the MOF.
anhydrides and 1,3-propane sultone. Degree of conversion in %.
Crystallographic information files
2
Despite the limited stability of CAU-7-TATB-NH towards acids,
The crystallographic information is available in the Cambridge
Structural Database (CSD) as CCDC 1549690 (CAU-7-TATB (ht))
and CCDC 1549691 (CAU-35).
four reactions were carried out to introduce pendant
carboxylic and sulfonic acid groups into the framework. By
2
treating CAU-7-TATB-NH with cyclic anhydrides such as
succinic and phthalic anhydride, two functionalised MOFs with
free carboxylic acid groups were obtained (Scheme 2). Succinic
Syntheses of the organic linkers
2
anhydride resulted in the formation of CAU-7-TATB-NH -SA The synthesis of H
3 3 2
TATB28 and functionalised H
TATB-NO
29
with 67 % conversion and phthalic anhydride gave CAU-7- were performed according to literature procedures. The nitro-
TATB-NH -PA with 35 % conversion (Fig. S28 and S29). To group of H
TATB-NO was reduced by sodium dithionite to
introduce pendant sulfonic acid groups into the framework, obtain H
TATB-NH . For synthetic details and characterisation
2
3
2
3
2
ring-opening reactions using 1,3-propane sultone or 1,4- see Supporting Information.
butane sultone were performed. In both cases, the MOF
maintained its structure after the reaction but only the Syntheses of the metal-organic frameworks
treatment with 1,3-propane sultone led to a conversion of the
Synthesis of [Bi(TATB)] (CAU-7-TATB):
H
3
TATB (30.0 mg, 68.0
2
amino groups. The respective CAU-7-TATB-NH -PS was
µmol) and ground Bi(NO ) ·5 H O (28.7 mg, 59.2 µmol) were
3 3 2
obtained with a conversion of 33 % (Fig. S30). It should be
mentioned that the sulfonic acid group within the framework
most likely might be deprotonated due to internal
neutralisation. The investigation of the same PSM reaction on
a different MOF proved that a zwitterionic form is preferred
and the acidity is attributed to the ammonium group.25
mixed in a 30 mL glass vial and MeOH (6 mL) and DMF (6 mL)
were added. The sealed vial was shaken and heated in a
microwave-assisted synthesis at 120 °C for 20 min while
stirring with 600 rpm. The solid product was filtered off and
washed with DMF (5 mL) and MeOH (5 mL). A white powder
3
was obtained in a yield of 30.8 mg (55% based on H TATB).
Phase purity was confirmed by PXRD (Fig. S1) and elemental
2
Nevertheless, these results show that CAU-7-TATB-NH is
capable of bearing acidic groups within the pores. Analytical
1
data ( H-NMR, PXRD, TGA, elemental analysis, IR) for all
4
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analysis (calc. (%) for BiC24
H 3.77, N 6.76; meas. (%): C 37.29, H 2.93, N 7.84).
12 3 6 3 7 2
View Article Online
H N O ·C H NO·6H O: C 39.14, anhydride, succinic anhydride, phthalic anhydride and 1,3-
DOI: 10.1039/C7DT01744H
propane sultone to give the respective modified Bi-MOFs with
degrees of conversion varying from 33 to 79 %.
Synthesis of [Bi(TATB-NH
2
)] (CAU-7-TATB-NH
2 3 2
): H TATB-NH
(
100 mg, 219 µmol) and ground Bi(NO
3
)
3
·5 H O (76.8 mg, 158
2
Acknowledgements
We thank A. Ken Inge and Helge Reinsch for helpful
discussions.
µmol) were mixed in a 30 mL glass vial and MeOH (10 mL) and
DMF (10 mL) were added. The sealed vial was shaken and
heated in a microwave-assisted synthesis at 120 °C for 20 min
while stirring with 600 rpm. The solid product was filtered off
and washed with DMF (5 mL) and MeOH (5 mL). A yellow
powder was obtained in a yield of 118 mg (68% based on Notes and references
H
3
TATB-NH
and elemental analysis (calc. (%) for BiC24
0.5C NO·5H O: C 38.82, H 3.39, N 7.99; meas. (%): C 39.74,
2
). Phase purity was confirmed by PXRD (Fig. S10)
1
H. Furukawa, K. E. Cordova, M. O'Keeffe and O. M. Yaghi,
Science, 2013, 341, 1230444.
A. C. McKinlay, R. E. Morris, P. Horcajada, G. Férey, R. Gref,
P. Couvreur and C. Serre, Angew. Chem., 2010, 122, 6400–
13 4 6
H N O
·
H
3 7
2
2
H 1.85, N 7.99).
6
406, Angew. Chem. Int. Ed., 49, 6260–6266.
Y. Yang, R. Ouyang, L. Xu, N. Guo, W. Li, K. Feng, L. Ouyang,
Z. Yang, S. Zhou and Y. Miao, J. Coord. Chem., 2014, 68
79–397.
2
Synthesis of [Bi (O)(OH)(TATB)] (CAU-35):
3
4
H
3
TATB (5.0 mg, 11.3 µmol) and ground Bi(NO
mg, 11.3 µmol) were mixed in a 2 mL PTFE inserts and H
800 µL) and DMF (200 µL) were added. The autoclave was
3 3 2
) ·5 H O (5.5
,
2
O
3
(
M. Feyand, E. Mugnaioli, F. Vermoortele, B. Bueken, J. M.
Dieterich, T. Reimer, U. Kolb, D. de Vos and N. Stock,
Angew. Chem., 2012, 124, 10519–10522, Angew. Chem.
Int. Ed., 2012, 51, 10373–10376.
M. Savage, S. Yang, M. Suyetin, E. Bichoutskaia, W. Lewis,
A. J. Blake, S. A. Barnett and M. Schröder, Chem. - Eur. J.,
2014, 20, 8024–8029.
A. K. Inge, M. Köppen, J. Su, M. Feyand, H. Xu, X. Zou, M.
O'Keeffe and N. Stock, J. Am. Chem. Soc., 2016, 138, 1970–
1976.
a) G. Wang, Y. Liu, B. Huang, X. Qin, X. Zhang and Y. Dai,
Dalton Trans., 2015, 44, 16238–16241; b) G. Wang, Q. Sun,
Y. Liu, B. Huang, Y. Dai, X. Zhang and X. Qin, Chem. - Eur. J.,
2015, 21, 2364–2367.
sealed and heated to 120 °C in 12 h. The temperature was kept
for 36 h and subsequently the reactor was slowly cooled to
room temperature in 60 h. The solid product was filtered off
and washed with DMF (1 mL) and H
was obtained. Phase purity was confirmed by PXRD (Fig. S17)
and elemental analysis (calc. (%) for Bi ·H O:
2
O (1 mL). A white powder
5
6
7
2
C
24
H
13
N
3
O
8
2
C 31.77, H 1.67, N 4.63; meas. (%): C 32.77, H 1.41, N 4.97).
Post-synthetic modification procedure
2
Prior to the modification reactions, CAU-7-TATB-NH was dried
for 12 h at 60 °C in a vacuum oven. 15 equivalents of the
respective anhydride or sultone were added to a suspension of
2
CAU-7-TATB-NH (130 mg, 195 µmol) in dichloromethane
(6 mL). The reaction mixture was stirred under reflux for 72 h.
These conditions were chosen to ensure highest degree of
conversion. The solid was separated by centrifugation and
washed with dichloromethane (2 x 10 mL), ethanol (2 x 10 mL)
and water (2 x 10 mL). After drying for 4 d at 60 °C in a vacuum
oven, 10 mg of the solid was digested with a mixture of DMSO-
8
M. Feyand, M. Köppen, G. Friedrichs and N. Stock, Chem. -
Eur. J., 2013, 19, 12537–12546.
S. M. Cohen, Chem. Rev., 2012, 112, 970–1000.
0 a) S. M. Cohen, J. Am. Chem. Soc., 2017, 139, 2855–2863;
b) K. K. Tanabe and S. M. Cohen, Chem. Soc. Rev., 2011,
9
1
d
6
(595 µL) and DCl (37 %, 5 µL). The conversion was
40, 498–519.
1
determined by H-NMR spectroscopy (see Supporting
Information).
1
1
1
1
1 M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wachter, M.
O'Keeffe and O. M. Yaghi, Science, 2002, 295, 469–472.
2 A. Klinkebiel, N. Reimer, M. Lammert, N. Stock and U.
Lüning, Chem. Commun., 2014, 50, 9306–9308.
Conclusions
3 H. Hintz and S. Wuttke, Chem. Mater., 2014, 26, 6722–
3
In summary, we used the triazine-based H TATB linker for the
6
728.
4 a) S. J. Garibay and S. M. Cohen, Chem. Commun., 2010,
, 7700–7702; b) K. K. Tanabe, Z. Wang and S. M. Cohen,
synthesis of two new Bi-MOFs. Depending on the solvent
mixture and the reaction time, either a MOF with CAU-7
structure (CAU-7-TATB) or a new MOF (CAU-35) was obtained.
The structure of CAU-35 was successfully solved and refined
from PXRD data, the structure of CAU-7-TATB was confirmed
by a Rietveld analysis of the PXRD data. Additionally, a new
4
6
J. Am. Chem. Soc., 2008, 130, 8508–8517; c) Z. Wang, K. K.
Tanabe and S. M. Cohen, Inorg. Chem., 2009, 48, 296–306.
5 a) S. J. Garibay, Z. Wang and S. M. Cohen, Inorg. Chem.,
1
2
010, 49, 8086–8091; b) K. K. Tanabe and S. M. Cohen,
amino-substituted
synthesised and used for the synthesis of the first
functionalised Bi-MOF, denoted CAU-7-TATB-NH . This MOF
H
3
TATB linker (H
3
TATB-NH
2
)
was
Angew. Chem., 2009, 121, 7560–7563, Angew. Chem. Int.
Ed., 48, 7424–7427.
2
was successfully treated with acetic anhydride, valeric
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
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Ple aDs ea l dt oo nn To rt a and sj ua sc tt imo na sr gins
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ARTICLE
Dalton Transactions
1
1
1
6 a) A. Modrow, D. Zargarani, R. Herges and N. Stock, Dalton
View Article Online
DOI: 10.1039/C7DT01744H
Trans., 2012, 41, 8690–8696; b) M. Savonnet, S. Aguado,
U. Ravon, D. Bazer-Bachi, V. Lecocq, N. Bats, C. Pinel and
D. Farrusseng, Green Chem., 2009, 11, 1729.
7 a) S. Bernt, V. Guillerm, C. Serre and N. Stock, Chem.
Commun., 2011, 47, 2838–2840; b) E. Dugan, Z. Wang, M.
Okamura, A. Medina and S. M. Cohen, Chem. Commun.,
2
008, 3366–3368.
8 a) A. D. Burrows and L. L. Keenan, CrystEngComm, 2012,
, 4112; b) C. J. Doonan, W. Morris, H. Furukawa and O.
1
4
M. Yaghi, J. Am. Chem. Soc., 2009, 131, 9492–9493; c) M.
J. Ingleson, J. P. Barrio, J.-B. Guilbaud, Y. Z. Khimyak and
M. J. Rosseinsky, Chem. Commun., 2008, 2680–2682.
9 K. M. L. Taylor-Pashow, J. Della Rocca, Z. Xie, S. Tran and
W. Lin, J. Am. Chem. Soc., 2009, 131, 14261–14263.
1
2
0 H. Hintz and S. Wuttke, Chem. Commun., 2014, 50, 11472–
1
1475.
2
2
1 N. Stock and S. Biswas, Chem. Rev., 2012, 112, 933–969.
2 A. C. Wibowo, M. D. Smith and H.-C. Zur Loye, Chem.
Commun., 2011, 47, 7371–7373.
2
2
3 A. Klinkebiel, O. Beyer, B. Malawko and U. Lüning, Beilstein
J. Org. Chem., 2016, 12, 2267–2273.
4 a) Materials Studio 5.5.3, Accelrys Software Inc., 2010; b)
T. Düren, F. Millange, G. Férey, K. S. Walton and R. Q.
Snurr, J. Phys. Chem. C, 2007, 111, 15350–15356.
5 H. Liu, F.-G. Xi, W. Sun, N.-N. Yang and E.-Q. Gao, Inorg.
Chem., 2016, 55, 5753–5755.
2
2
6 V. Favre-Nicolin and R. Černý, J. Appl. Crystallogr., 2002,
35, 734–743.
2
2
7 A. Coelho, TOPAS Academic 4.1, Coelho Software, 2007.
8 M. Krüger, H. Reinsch, A. K. Inge and N. Stock,
Microporous Mesoporous Mater., 2017, 249, 128-136.
9 E. Mühlbauer, A. Klinkebiel, O. Beyer, F. Auras, S. Wuttke,
U. Lüning and T. Bein, Microporous Mesoporous Mater.,
2
2
015, 216, 51–55.
6
| J. Name., 2012, 00, 1-3
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Dalton Transactions
View Article Online
DOI: 10.1039/C7DT01744H
Two new Bi-MOFs were discovered, synthesised and characterised and the amino-functionalised Bi-MOF
was post-synthetically modified using anhydrides and 1,3-propane sultone.

Dalton Transactions
Page 8 of 8
View Article Online
DOI: 10.1039/C7DT01744H