Abstract A novel noncentrosymmetric (NCS) polar fluoride sulfate, CsSbF2SO4, was obtained by ionothermal synthesis. A meticulously designed co‐substitution approach was used to successfully replace the [TiO6]8− and [PO4]3− functional groups in KTiOPO4 (KTP) with [SbO4F2]7− and [SO4]2− units, respect...
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