Controlling multiple orderings in metal thiocyanate molecular perovskites Ax{Ni[Bi(SCN)6]}

We report four new A-site vacancy ordered thiocyanate double double perovskites, A1–x{Ni[Bi(SCN)6](1–x)/3}, 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