New Variants of (110)‐Oriented Layered Lead Bromide Perovskites, Templated by Formamidinium or Pyrazolium

Abstract Four new hybrid lead(II) halide perovskites, γ‐(FA)2PbBr4, (FA)1.5(AA)0.5PbBr4, (PY)(GA)PbBr4 and (PY)(TZ)PbBr4 ((FA)=formamidinium, (AA)=acetamidinium, (PY)=pyrazolium, (GA)=guanidinium and (TZ)=1,2,3‐triazolium), adopt (110)‐oriented layered perovskite structures. While (PY) is found to template the formation of ‘conventional’ (110)‐oriented structure types (i. e. containing staggered [PbBr4]∞ layers), (FA) is shown to facilitate formation of much less common variants based 3 : 1 ordering of the interlayer species or 3×2 step‐like corrugation of the perovskite‐like layers themselves.