Hybrid Organic–Inorganic Antiperovskites

Abstract Substitution of A‐site and/or X‐site ions of ABX 3 ‐type perovskites with organic groups can give rise to hybrid perovskites, many of which display intriguing properties beyond their parent compounds. However, this method cannot be extended effectively to hybrid antiperovskites. Now, the design of hybrid antiperovskites under the guidance of the concept of Goldschmidt's tolerance factor is presented. Spherical anions were chosen for the A and B sites and spherical organic cations for the X site, and seven hybrid antiperovskites were obtained, including (F 3 (H 2 O) x )(AlF 6 )(H 2 dabco) 3 , ((Co(CN) 6 )(H 2 O) 5 )(MF 6 )(H 2 dabco) 3 (M=Al 3+ , Cr 3+ , or In 3+ ), (Co(CN) 6 )(MF 6 )(H 2 pip) 3 (M=Al 3+ or Cr 3+ ), and (SbI 6 )(AlF 6 )(H 2 dabco) 3 . These new structures reveal that all ions at A, B, and X sites of inorganic antiperovskites can be replaced by molecular ions to form hybrid antiperovskites. This work will lead to the synthesis of a large family of hybrid antiperovskites.