4.8 Article

Double Double to Double Perovskite Transformations in Quaternary Manganese Oxides

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 41, Pages 22248-22252

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202108586

Keywords

double perovskites; high-pressure chemistry; magnetic properties; solid-state structures

Funding

  1. EPSRC
  2. King Abdulaziz City for Science and Technology (KACST)

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Controlling cation ordering in perovskites is crucial for their structural, physical, and chemical properties. Under pressure, thermal transformations can achieve fully disordered cations in double perovskites, leading to a switch in magnetic properties. Comparing different polymorphs of materials can help explore the effects of cation order and disorder on properties like ferroelectricity and conductivity.
Control of cation ordering in ABX(3) perovskites is important to structural, physical and chemical properties. Here we show that thermal transformations of AA ' BB ' O-6 double double perovskites, where both A and B sites have 1:1 cation order, to (A(0.5)A '(0.5))(2)BB ' O-6 double perovskites with fully disordered A/A ' cations can be achieved under pressure in CaMnMnWO6 and SmMnMnTaO6, enabling both polymorphs of each material to be recovered. This leads to a dramatic switch of magnetic properties from ferrimagnetic order in double double perovskite CaMnMnWO6 to spin glass behaviour in the highly frustrated double perovskite polymorph. Comparison of double double and double perovskite polymorphs of other materials will enable effects of cation order and disorder on other properties such as ferroelectricity and conductivity to be explored.

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