Site-selective d10/d0 substitution in an S = 1/2 spin ladder Ba2CuTe1–xWxO6 (0 ≤ x ≤ 0.3)
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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.
Pughe , C , Mustonen , O H J , Gibbs , A S , Etter , M , Liu , C , Dutton , S E , Friskney , A , Hyatt , N C , Stenning , G B G , Mutch , H M , Coomer , F C & Cussen , E J 2022 , ' Site-selective d 10 /d 0 substitution in an S = 1 / 2 spin ladder Ba 2 CuTe 1–x W x O 6 (0 ≤ x ≤ 0.3) ' , Inorganic Chemistry , vol. 61 , no. 9 , pp. 4033-4045 . https://doi.org/10.1021/acs.inorgchem.1c03655
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DescriptionE.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. T S.E.D. acknowledges funding from the Winton Programme for the Physics of Sustainability (Cambridge) and EPSRC (EP/T028580/1).
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