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Small-moment paramagnetism and extensive twinning in the topochemically reduced phase Sr 2 ReLiO 5.5

DOI: 10.1039/C8DT03463J DOI Help

Authors: Nijat Hasanli (University of Oxford) , Nicolas Gauquelin (University of Twente) , Johan Verbeeck (University of Antwerp) , Joke Hadermann (University of Antwerp) , Michael A. Hayward (University of Oxford)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Dalton Transactions , VOL 57

State: Published (Approved)
Published: October 2018
Diamond Proposal Number(s): 13284

Abstract: Reaction of the cation-ordered double perovskite Sr2ReLiO6 with dilute hydrogen at 475 °C leads to the topochemical deintercalation of oxide ions from the host lattice and the formation of a phase of composition Sr2ReLiO5.5, as confirmed by thermogravimetric and EELS data. A combination of neutron and electron diffraction data reveals the reduction process converts the –Sr2O2–ReLiO4–Sr2O2–ReLiO4– stacking sequence of the parent phase into a –Sr2O2–ReLiO3–Sr2O2–ReLiO4–, partially anion-vacant ordered sequence. Furthermore a combination of electron diffraction and imaging reveals Sr2ReLiO5.5 exhibits extensive twinning – a feature which can be attributed to the large, anisotropic volume expansion of the material on reduction. Magnetisation data reveal a strongly reduced moment of μeff = 0.505μB for the d1 Re6+ centres in the phase, suggesting there remains a large orbital component to the magnetism of the rhenium centres, despite their location in low symmetry coordination environments.

Subject Areas: Chemistry

Instruments: I11-High Resolution Powder Diffraction