Tuneable mechanical and dynamical properties in the ferroelectric perovskite solid solution [NH(3)NH(2)](1–x)[NH(3)OH](x)Zn(HCOO)(3)

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.