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.

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1 results in hybrid improper ferroelectrics in Keywords: hybrid improper ferroelectrics

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

1 results in Keywords: hybrid improper ferroelectrics