J. Christoffers, M. S. Wickleder et al.
ARTICLE
–
1
is the crucial step for the implementation of this acid in build- (10 K·min ) up to 800 °C under flowing argon using the thermo ana-
lyzer METTLER TOLEDO SDTA 851e. The data were processed with
ing metal-organic frameworks. In this paper we have demon-
the software of the analyzer.[
17]
strated this on the example of the first lanthanide trisulfonates
[
La(BTS)(H O) ] and [RE(BTS)(H O) ] (RE = Nd, Sm, Eu),
2 5 2 4
which show layer type structures with one of the sulfonate
groups remaining uncoordinated. Thermoanalytical investiga- Acknowledgement
tions show that after dehydration these compounds are stable
The authors are grateful to Wolfgang Saak for collecting the X-ray
up to nearly 550 °C. This is a significantly higher decomposi-
tion temperature compared to the related carboxylates and
proves that sulfonic acids are good candidates to build ther-
mally robust frameworks.
data.
References
[
1] a) Reviews: S. Kaskel, Nachr. Chem. 2005, 53, 394–399; b) U.
Mueller, M. Schubert, F. Teich, H. Puetter, K. Schierle-Arndt, J.
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Angew. Chem. 2008, 120, 8285–8289; Angew. Chem. Int. Ed.
2008, 47, 8164–8168.
Experimental Section
Preparation of [La(BTS)(H O) ] and [RE(BTS)(H O) ]
2
5
2
4
(RE = Nd, Sm, Eu)
3
For the synthesis of each compound a solution of H BTS (0.1 g) in
water (10 mL) was used. At a temperature of 50 °C, the rare earth [2] Review: J. L. C. Rowsell, O. M. Yaghi, Angew. Chem. 2005, 117,
4748–4758; Angew. Chem. Int. Ed. 2005, 44, 4670–4679.
3
hydroxides RE(OH) (RE = La, Nd, Sm, Eu) were slowly added to
[
[
[
3] G. K. H. Shimizu, R. Vaidhyanathan, J. M. Taylor, Chem. Soc.
these solutions until neutrality was achieved. After cooling, the solu-
tions were kept under ambient conditions and block-shaped single
crystals separated from the solutions after a few days. They showed
the colors of the respective rare earth ions (lanthanum: colorless, neo-
dymium: violet, samarium: yellow, europium: light yellow) and were
collected by filtration. With respect to their powder XRD patterns the
products are single phased.
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4] H. Li, M. Eddaoudi, M. O’Keeffe, O. M. Yaghi, Nature 1999,
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Energy Fuels 2009, 23, 2785–2789.
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7] a) Review: M. S. Wickleder, Chem. Rev. 2002, 102, 2011–2087;
b) M. S. Wickleder, Z. Anorg. Allg. Chem. 2001, 627, 1675–1682.
X-ray Crystallography
[
8] CCDC-766201
[La(BTS)(H O)
data for this paper. These data can be obtained free of charge via
([Eu(BTS)(H
2
O)
4
])
and
CCDC-766202
For the structure determinations, single crystals of [La(BTS)(H
2 5
O) ]
(
2
5
]) contain the supplementary crystallographic
and [Eu(BTS)(H O) ], respectively, were glued onto glass fibers and
2
4
intensity data were collected with an image plate diffractometer (STOE
IPDS I) for the europium compound and a CCD diffractometer
www.ccdc.cam.ac.uk,
or
by
emailing
data_re-
quest@ccdc.cam.ac.uk, or by contacting The Cambridge Crystal-
lographic Data Centre, 12, Union Road, Cambridge CB2 1EZ,
UK; Fax: +44-1223-336033.
(
BRUKER APEX II) for the lanthanum compound. The structure solu-
¯
tion and refinement was successful in space group P1 (La) and P2
(
respectively.
1
/n
Eu) using the programs SHELXS97 and SHELXL97, [9] G. A. Jeffrey, An Introduction to Hydrogen Bonding, Oxford Uni-
[12, 13]
versity Press, Oxford, 1997.
A numerical absorption correction was applied to
[14, 15]
[10] H. A. Eick, J. Am. Chem. Soc. 1958, 80, 43–44.
the data with the help of the programs X-RED and X-SHAPE.
[
11] W. Nowacki, Z. Kristallogr. 1938, 99, 339–341.
12] G. M. Sheldrick, SHELXS97, Program for the Solution of Crystal
Structures, Göttingen 1997.
Details of the data collection and the crystallographic parameters are
summarized in Table 2. For all compounds X-ray powder diffraction
measurement were performed on fine powdered samples of the sub-
stances using a flat sample holder. Reflections were detected in the
[
[13] G. M. Sheldrick, SHELXL93, Program for the Refinement of
Crystal Structures, Göttingen 1993.
range from 5° to 90° with the diffractometer STADI P (STOE) using [14] X-RED 1.07, Data Reduction for STADI4 and IPDS, Stoe & Cie
Cu-K
α
radiation (λ = 154.18 pm). Lattice parameter refinement was
Darmstadt 1996.
[
16]
performed with the help of the diffractometer software.
The same [15] X-SHAPE 1.01, Crystal Optimization for Numerical Absorption
Correction, Stoe & Cie Darmstadt 1996.
technique and the same powder diffractometer were used for the char-
acterization of the residues of the thermal decomposition.
POW
POWPOW
[
16] VISUAL X
3.01
, Software Package for the STOE Pow-
der Diffraction System, Stoe & Cie, Darmstadt, Germany, 1996.
17] Thermal analysis for the analyzer SDTA 851e, METTLER
TOLEDO, Germany, 2006.
[
Thermal Analysis
For the investigation of the thermal behavior the respective compound
Received: September 12, 2010
Published Online: December 2, 2010
(about 10 mg) was placed into a corundum container that was heated
2
00
www.zaac.wiley-vch.de
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2011, 195–200