Local structure of the metal–organic perovskite dimethylammonium manganese(ii) formate

Abstract

We report total neutron scattering measurements on the metal-organic perovskite analogue dimethylammonium manganese(ii) formate, (CD3)2ND2[Mn(DCO2)3]. Reverse Monte Carlo modelling shows that, in both the disordered high-temperature and ordered low-temperature phases, the ammonium moiety forms substantially shorter hydrogen bonds (N...O = 2.4 Å and 2.6 Å) than are visible in the average crystal structures. These bonds result from a pincer-like motion of two adjacent formate ions about the dimethylammonium ion in such a way that the framework can adjust independently to the positions of nearest-neighbour dimethylammonium ions. At low temperatures the shortest hydrogen bond is less favourable, apparently because it involves a greater distortion of the framework. Furthermore, in the high-temperature phase, in addition to the three disordered nitrogen positions expected from the average crystal structure, there appear to be also smaller probability maxima between these positions, corresponding to orientations in which the dimethylammonium is hydrogen-bonded to the two oxygen atoms of a single formate ion. The spontaneous strain across the phase transition reveals a contraction of the framework about the dimethylammonium cation, continuing as the material is cooled below the transition temperature. These results provide direct evidence of the local atomic structure of the guest-framework hydrogen bonding, and in particular the distortions of the framework responsible for the phase transition in this system.

Magnetic field-temperature phase diagram of multiferroic [(CH3)2NH2]Mn(HCOO)3<

“…2(b) as well as recent magneto-infrared and neutron scattering work. 43,45 Taken together, these findings suggest that [(CH 3 ) 2 NH 2 ]Mn(HCOO) 3 is sensitive to magnetic field above T N due to a remnant of the saturation field. In the absence of thermal fluctuations (well into the canted antiferromagnetic state), it is likely that dielectric polarization will be greatly enhanced under magnetic field.…”

Methylammonium Lead Trihalide Perovskite Solar Cell Semiconductors Are Not Organometallic: A Perspective

“…As such, the A‐site cation has filled with the [HC(NH 2 ) 2 ], , C 3 H 8 N + , and [NH 4 ] + cations, and the M‐site with a variety of metal ions. Examples of some of these include the [(CH 2 ) 2 NH 2 ][M(HCOO) 3 ] (M = Mg, Mn, Fe, Co, Ni, Cu, Zn), [(CH 2 ) 3 NH 2 ][Mn(HCOO) 3 ], [HC(NH 2 ) 2 M(HCOO) 3 ] (M = Mg, Mn, Zn), [NH 4 ][M(HCOO) 3 ] (M = Sc to Zn), [N(CH 3 ) 4 )][Mn(N 3 ) 3 ], (CD 3 ) 2 ND 2 [Mn(DCO 2 ) 3 ], [C 3 H 8 N][M(HCOO) 3 ], and [C 2 H 5 NH 3 ][Na 0.5 Fe 0.5 (HCOO) 3 ] . In all these cases, the HCOO − organic anion replaces the halogen Y − in AMY 3 .…”

Phonon mode links ferroicities in multiferroic [(CH3)2NH2]Mn(HCOO)3Hughey1, Clune2, Yokosuk3 et al. 2017Phys. Rev. B18030View full textAdd to dashboardCite

“…In this system, T C = 185 K, below which the ferroelectric polarization P is 1.5 µC/cm 2 ; ferroelectric domain walls have been visualized [6,8,9]. The low temperature antiferromagnetic state (T N = 8.5 K) is non-collinear and arises from the non-centrosymmetric nature of the formate bridge [6,[10][11][12][13][14]. Curiously, cross-coupling between the electric and magnetic orders [8,15,16] extends to relatively high temperatures [8,9], demonstrating that a low ordering temperature may not be a barrier to strong magnetoelectric coupling -although the precise mechanism for this effect has not yet been resolved.…”