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We report how mechanical and dynamical properties in formate-based perovskites can be manipulated by the preparation of an A-site solid-solution. In the series [NH 3 NH 2 ] 1- x  [NH 3 OH]  x  Zn(HCOO) 3 with x  max = 0.48, the substitution of [NH 3 NH 2 ] + by [NH 3 OH] + is accompanied by a series of complex changes in crystal chemistry which are analysed using PXRD, SCXRD, 1 H solid state NMR, DSC and nanoindentation. NMR shows increased motion of [NH 3 NH 2 ] + in [NH 3 NH 2 ] 0.52 [NH 3 OH] 0.48 Zn(HCOO) 3 , which results in a shift of the ferroelectric-to-paraelectric phase transition temperature from T  c = 352 K ( x = 0) to T  c = 324 K ( x = 0.48). Additionally, the loss of hydrogen bonds directly influences the mechanical response of the framework; the elastic moduli and hardnesses decrease by around 25% from E  110 = 24.6 GPa and H  110 = 1.25 GPa for x = 0, to E  110 = 19.0 GPa and H  110 = 0.97 GPa for x = 0.48. Our results give an in-depth insight into the crystal chemistry of ABX 3 formate perovskites and highlight the important role of hydrogen bonding and dynamics.

chemical science

Tuneable mechanical and dynamical properties in the ferroelectric perovskite solid solution [NH3NH2]1−x[NH3OH]xZn(HCOO)3