Pressure tuning of hydrogen bond ordering in the metal-organic framework [(CH3)2NH2]Mn(HCOO)3

The influence of pressure on the hydrogen bond ordering in the perovskite metal-organic framework [(CH3)2NH2]Mn(HCOO)3 has been investigated by dielectric, pyroelectric adn magnetic measurements in a piston-cylinder cell. Under ambient pressure the ordering of hydrogen bonds takes place at TC = 188 K and induces a first-order ferroelectric phase transition. With increasing pressure to p = 3.92 kbar, the order-disorder transition shifts to a lower temperature and retains the first-order ferroelectric nature. However, under higher pressures, the ordering process of hydrogen bonds is split into two transitions: a broad antiferroelectric transition at high temperature and a first-order ferroelectric transition at low temperature. With increasing pressure, the antiferroelectric phase is enhanced whereas the ferroelectric phase is greatly suppressed, which implies that compression of the perovskite framework favors antiparallel arrangement of the hydrogen bonds. The canted anti-ferromagnetic transition was almost unchanged when pressure up to 10.85 kbar. Our study demonstrated that the perovskite metal-organic frameworks are more sensitive to external pressure than conventional perovskite oxides so that their electric properties can be easily tuned by pressure.