Out-of-plane polarization in a layered manganese chloride hybrid

We investigate possible mechanisms to induce electric polarization in layered organic-inorganic hybrids. Specifically, we investigate the structural phase transitions of PEA(2)MnCl(4) (PEA = phenethylamine) using temperature dependent single-crystal X-ray diffraction analysis, including the symmetry analysis of the observed space groups. Our results show that PEA(2)MnCl(4) transforms from a high-temperature centrosymmetric structure with space group I4/mmm to a low-temperature polar Pca2(1) phase via an intermediate phase with polar space group Aea2. We study the mechanism responsible for the I4/mmm to Aea2 polar phase transition and find that it is different from previously proposed mechanisms in similar systems. The transition is governed by the opening of a small dihedral angle between the phenyl ring planes of two adjacent PEA molecules, which consequently become crystallographically inequivalent in the Aea2 phase. This molecular rotation induces a significant difference in the lengths of the ethylammonium tails of the two molecules, which coordinate the inorganic layer asymmetrically and are consequently involved in different hydrogen bonding patterns. Consequently, the negatively charged chlorine octahedron that coordinates the Mn(2+)cation deforms. This deformation moves the Mn2+ off-center along the out-of-plane-axis, contributing to the polar nature of the structure. Notably, the polar axis is out-of-plane with respect to the inorganic sheets. This is in contrast to other layered organic-inorganic hybrids as well as conventional layered perovskites, such as the Aurivillius phases, where in-plane polarization is observed. Our findings add to the understanding of possible mechanisms that can induce ferroelectric behavior in layered organic-inorganic hybrids. (C) 2018 Author(s).