Page 60 - ILLS Annual Report 2018

CHEMISTRY AND CHRYSTALLOGRAPHY
Laura Cañadillas Delgado. Spanish ILL & Centro Universitario de la Defensa de Zaragoza, Spain
‘Our research is based on the synthesis and characterisation of multifunctional metal-organic materials, aimed at looking for clues for the design of new materials with desired assets.
The determination of complete structural models including H and other light atoms is needed to determine their properties. Neutron diffraction provides us with unique information about the magnetic structures of these compounds, making it a crucial tool in this field.’
Nuclear and magnetic structure determination of the multiferroic perovskite-like [CH3NH3] [Co(COOH) ] compound
Single-crystal diffractometer D19 and powder diffractometer D1B
BL04-MSPD beamline at ALBA synchrotron
Co-ordination polymers have attracted intense interest in recent years, not only from a fundamental point of view but also from the possibility of developing new functional materials. We have focused our efforts on finding new multiferroic materials where electric and magnetic order coexist. In order to achieve this objective we have prepared a metal-organic compound, constructed from a 3D-framework, with counterions located
in its cavities. This approach has proved
an effective method for combining two or more properties in the same compound in order to produce multifunctional materials.
Figure 1
Top) Representation of the perovskite-like structure of compound 1.
Bottom) View of the asymmetric unit at 135 K and at 45 K in ORTEP representation (50 % ellipsoid probability), together with the atom numbering, obtained from the single-crystal neutron refinement at 135 and 45 K, respectively. The cobalt, nitrogen, oxygen, carbon and hydrogen atoms
are represented in pink, blue, red, black and light grey, respectively. The transparent mode represents the atoms generated by symmetry operations.
AUTHORS
L. Mazzuca, O. Fabelo and J. Rodriguez-Carvajal (ILL)
L. Canadillas-Delgado (ILL and Centro Universitario de la Defensa of
Zaragoza, Spain)
J. Alberto Rodríguez-Velamazán (ILL and CSIC-Universidad of Zaragoza, Spain) J. Luzón (Centro Universitario de la Defensa and CSIC-Universidad of Zaragoza, Spain)
O. Vallcorba (Alba Synchrotron, Cerdanyola del VallHs, Spain)
V. Simonet and C.V. Colin (CNRS and UJF, Grenoble, France)
ARTICLE FROM
Chem. Eur. J. (2018)—doi: 10.1002/chem.201703140
REFERENCES
[1] L. Mazzuca, L. Cañadillas-Delgado, O. Fabelo, J.A. Rodríguez-Velamazán, J. Luzón, O. Vallcorba, V. Simonet, C.V. Colin and J. Rodríguez-Carvajal, Chem. Eur. J. 24 (2018) 388
[2] M. Azuma, K. Takata, T. Saito, S. Ishiwata, Y. Shimakawa and M. Takano, J. Am. Chem. Soc. 127 (2005) 8889
[3] Y.-H Chu, L.W. Martin, M.B. Holcomb, M. Gajek, S.-J.Han, Q. He,
N. Balke, C.-H Yang, D. Lee, W. Hu, Q. Zhan, P.-L. Yang, A. Fraile-Rodríguez, A. Scholl, S.X. Wang and R. Ramesh, Nat. Mater. 7 (2008) 478
[4] O.M. Yaghi, M. O’Keeffe, N.W. Ockwig, H.K. Chae, M. Eddaoudi and J. Kim, Nature 423 (2003) 705
[5] (a) R. Ramesh, Nature 46 (2009) 1218; (b) E. Pardo, C. Train, H.B. Liu, L.M. Chamoreau, B. Dkhil, K. Boubekeur, F. Lloret, K. Nakatani, H. Tokoro, S. Ohkoshi and M. Verdaguer, Angew. Chem. 51 (2012) 8356
[6] D. Ganyushin and F. Neese, J. Chem. Phys. 125 (2006) 024103
In this article, we show how combining molecule-based counterions within a 3D-framework constructed from metal centres connected through organic linkers, gives rise to a
final crystal structure that looks like the well-known Perovskite compounds. However, due to the presence of the organic linkers, this compound is transparent and has a relatively low density, making it of interest for various possible applications. Moreover, the synthesised [CH3NH3][Co(COOH)3] compound combines two different ferroic-orders [1] and is a multiferroic
of type I [2] material, so electric and magnetic properties are weakly correlated. Multiferroic materials in which electric order coexists in the same phase in which long-range magnetic order occurs, albeit at substantially lower temperatures, are an exciting starting point for the design of new devices based on these
new materials [3]. Multiferroic behaviour of this type can be achieved using hybrid inorganic/organic frameworks in which an adequate combination of magnetic transition metal ions
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ANNUAL REPORT 2018