Site-Selective d10/d0 Substitution in an S = 1/2 Spin Ladder Ba2CuTe1-xWxO6 (0 ≤ x ≤ 0.3).
Stenning, Gavin BG
Mutch, Heather M
Coomer, Fiona C
American Chemical Society (ACS)
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Pughe, C., Mustonen, O. H., Gibbs, A. S., Etter, M., Liu, C., Dutton, S. E., Friskney, A., et al. (2022). Site-Selective d10/d0 Substitution in an S = 1/2 Spin Ladder Ba2CuTe1-xWxO6 (0 ≤ x ≤ 0.3).. Inorg Chem, 61 (9), 4033-4045. https://doi.org/10.1021/acs.inorgchem.1c03655
Isovalent nonmagnetic d10 and d0 B″ cations have proven to be a powerful tool for tuning the magnetic interactions between magnetic B' cations in A2B'B″O6 double perovskites. Tuning is facilitated by the changes in orbital hybridization that favor different superexchange pathways. This can produce alternative magnetic structures when B″ is d10 or d0. Furthermore, the competition generated by introducing mixtures of d10 and d0 cations can drive the material into the realms of exotic quantum magnetism. Here, Te6+ d10 was substituted by W6+ d0 in the hexagonal perovskite Ba2CuTeO6, which possesses a spin ladder geometry of Cu2+ cations, creating a Ba2CuTe1-xWxO6 solid solution (x = 0-0.3). We find W6+ is almost exclusively substituted for Te6+ on the corner-sharing site within the spin ladder, in preference to the face-sharing site between ladders. The site-selective doping directly tunes the intraladder, Jrung and Jleg, interactions. Modeling the magnetic susceptibility data shows the d0 orbitals modify the relative intraladder interaction strength (Jrung/Jleg) so the system changes from a spin ladder to isolated spin chains as W6+ increases. This further demonstrates the utility of d10 and d0 dopants as a tool for tuning magnetic interactions in a wide range of perovskites and perovskite-derived structures.
E.J.C., O.H.J.M., and C.P. acknowledge financial support from Leverhulme Trust Research Project Grant RPG-2017-109. O.H.J.M. is grateful for funding via Leverhulme Trust Early Career Fellowship ECF-2021-170. A.S.G. acknowledges funding through EPSRC Early Career Fellowship EP/T011130/1. The authors thank the Science and Technology Facilities Council for beam time allocated at ISIS. The authors are grateful for access to the MPMS3 instrument at the Materials Characterisation Laboratory at ISIS. The authors acknowledge DESY (Hamburg, Germany), a member of the Helmholtz Association HGF, for the provision of experimental facilities. Parts of this research were carried out at PETRA III beamline P02.1. Components of this research utilized the HADES/MIDAS facility at the University of Sheffield established with financial support from EPSRC and BEIS, under Grant EP/T011424/1. (62) Use of the National Synchrotron Light Source II, Brookhaven National Laboratory, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract DE-AC02-98CH10886 and beam time proposal number 303200. The authors are grateful to Bruce Ravel for assistance with acquisition of W L3 XAS data. Heat capacity measurements were performed using the Advanced Materials Characterisation Suite, funded by EPSRC Strategic Equipment Grant EP/M000524/1. S.E.D. acknowledges funding from the Winton Programme for the Physics of Sustainability (Cambridge) and EPSRC (EP/T028580/1).
Engineering and Physical Sciences Research Council (EP/M000524/1)
Engineering and Physical Sciences Research Council (EP/P024947/1)
External DOI: https://doi.org/10.1021/acs.inorgchem.1c03655
This record's URL: https://www.repository.cam.ac.uk/handle/1810/337111
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Licence URL: https://creativecommons.org/licenses/by/4.0/