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Controlling Multiple Orderings in Metal Thiocyanate Molecular Perovskites Ax{Ni[Bi(SCN)6]}

preprint
submitted on 03.12.2020, 13:12 and posted on 04.12.2020, 12:18 by Jie Yie Lee, Sanliang Ling, Stephen Argent, Mark Senn, Laura Cañadillas-Delgado, Matthew Cliffe

We report four new A-site vacancy ordered thiocyanate double double perovskites,

A1􀀀xfNi[Bi(SCN)6]1􀀀x3 }, A = K+, NH4+, CH3(NH3)+ (MeNH3+) and C(NH2)3+ (Gua+), including the first examples of thiocyanate perovskites containing organic A-site cations. We show, using a combination of X-ray and neutron diffraction, that the structure of these frameworks depends on the A-site cation, and that these frameworks possess complex vacancy-ordering patterns and cooperative octahedral tilts distinctly different from atomic perovskites. Density functional theory calculations uncover the energetic origin of these complex orders and allow us to propose a simple rule to predict favoured A-site cation orderings for a given tilt sequence. We use these insights, in combination with symmetry mode analyses, to show that these complex orders offer a new route to non-centrosymmetric perovskites which render them as excellent candidates for

piezo- and ferroelectric applications.

Funding

Novel Multiferroic Perovskites through Systematic Design

Engineering and Physical Sciences Research Council

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Royal Society UF160265

Proposal for a Tier 2 Centre - HPC Midlands Plus

Engineering and Physical Sciences Research Council

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HIGH END COMPUTING MATERIALS CHEMISTRY CONSORTIUM

Engineering and Physical Sciences Research Council

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ILL 5-12- 344

Diamond Light Source CY21755-I19

Diamond Light Source EE18786-I11

History

Email Address of Submitting Author

matthew.cliffe@nottingham.ac.uk

Institution

University of Nottingham

Country

United Kingdom

ORCID For Submitting Author

0000-0002-0408-7647

Declaration of Conflict of Interest

None

Version Notes

Version one

Licence

Exports