Site-selective $d^{10}$/$d^0$ substitution in a $S = 1/2$ spin ladder Ba$_2$CuTe$_{1-x}$W$_x$O$_6$ ($0 \leq x \leq 0.3$)

Charlotte E. Pughe; Otto H. J. Mustonen; Alexandra S. Gibbs; Martin Etter; Cheng Liu; Siân E. Dutton; Aidan Friskney; Neil C. Hyatt; Gavin B. G. Stenning; Heather M. Mutch; Fiona C. Coomer; Edmund J. Cussen

doi:10.1021/acs.inorgchem.1c03655

paper

Site-selective $d^{10}$ / $d^{0}$ substitution in a $S = 1/2$ spin ladder Ba $_{2}$ CuTe $_{1 - x}$ W $_{x}$ O $_{6}$ ( $0 \leq x \leq 0.3$ )

arXiv:2108.02761 · doi:10.1021/acs.inorgchem.1c03655

Abstract

Remarkably, doping isovalent $d^{10}$ and $d^{0}$ cations onto the $B$ '' site in $A_{2} B$ ' $B$ ''O $_{6}$ double perovskites has the power to direct the magnetic interactions between magnetic $B$ ' cations. This is due to changes in orbital hybridization, which favors different superexchange pathways, and leads to the formation of alternative magnetic structures depending on whether $B$ '' is $d^{10}$ or $d^{0}$ . Furthermore, the competition generated by introducing mixtures of $d^{10}$ and $d^{0}$ cations can drive the material into the realms of exotic quantum magnetism. Here, a W $^{6 +}$ $d^{0}$ dopant was introduced to a $d^{10}$ hexagonal perovskite Ba $_{2}$ CuTeO $_{6}$ , which possesses a spin ladder geometry of Cu $^{2 +}$ cations, creating a Ba $_{2}$ CuTe $_{1 - x}$ W $_{x}$ O $_{6}$ solid solution ( $x$ = 0 - 0.3). Neutron and synchrotron X-ray diffraction show that W $^{6 +}$ is almost exclusively substituted for Te $^{6 +}$ on the corner-sharing site within the spin ladder, in preference to the face-sharing site between ladders. This means the intra-ladder interactions are selectively tuned by the $d^{0}$ cations. Bulk magnetic measurements suggest this suppresses magnetic ordering in a similar manner to that observed for the spin-liquid like material Sr $_{2}$ CuTe $_{1 - x}$ W $_{x}$ O $_{6}$ . This further demonstrates the utility of $d^{10}$ and $d^{0}$ dopants as a tool for tuning magnetic ground states in a wide range of perovskites and perovskite-derived structures.

arXiv comment26+24 pages, 7+20 figures

Site-selective $d^{10}$ / $d^{0}$ substitution in a $S = 1/2$ spin ladder Ba $_{2}$ CuTe $_{1 - x}$ W $_{x}$ O $_{6}$ ( $0 \leq x \leq 0.3$ )

Abstract

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Site-selective d10/d0 substitution in a S=1/2 spin ladder Ba2​CuTe1−x​Wx​O6​ (0≤x≤0.3)

Abstract

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Site-selective $d^{10}$ / $d^{0}$ substitution in a $S = 1/2$ spin ladder Ba $_{2}$ CuTe $_{1 - x}$ W $_{x}$ O $_{6}$ ( $0 \leq x \leq 0.3$ )