Polar Structure and Two-Dimensional Heisenberg Antiferromagnetic Properties of Arylamine-Based Manganese Chloride Layered Organic–Inorganic Perovskites

Abstract

The breaking of inversion symmetry can enhance the multifunctional properties of layered hybrid organic–inorganic perovskites. However, the mechanisms by which inversion symmetry can be broken are not well-understood. Here, we study a series of MnCl 4 -based 2D perovskites with arylamine cations, namely, (C 6 H 5 C x H 2 x NH 3 ) 2 MnCl 4 ( x = 0, 1, 2, 3), for which the x = 0, 1, and 3 members are reported for the first time. The compounds with x = 1, 2, and 3 adopt polar crystal structures to well above room temperature. We argue that the inversion symmetry breaking in these compounds is related to the rotational degree of freedom of the organic cations, which determine the hydrogen bonding pattern that links the organic and inorganic layers. We show that the tilting of MnCl 6 octahedra is not the primary mechanism involved in inversion symmetry breaking in these materials. All four compounds show 2D Heisenberg antiferromagnetic behavior. A ferromagnetic component develops in each case below the long-range magnetic ordering temperature of ∼42–46 K due to spin canting.

Polar Ferromagnet Induced by Fluorine Positioning in Isomeric Layered Copper Halide Perovskites

“…More significantly, meta- F-substitution in (3-FbaH) 2 CuCl 4 leads to a polar material, with the symmetry being broken by subtle displacements in the positions of the 3-FbaH moieties, with resulting advantages in H-bonding opportunities to the [CuCl 4 ] ∞ layers. This symmetry-breaking mechanism seems related to, but distinct from, that recently seen in some manganese chloride layered perovskites 46 where the rotational degree of freedom of extra-cyclic chains is suggested to be responsible. In addition, in this case, we see that the F-substitution of the phenyl ring also plays a key role.…”

Triphenylene-ethylammonium tetrachlorometallate salts: multicolumnar mesophases, thermochromism and Langmuir films

“…In the solid state, these structures consist of an alternation of anionic metal halide layers partitioned by arrays of cations. The inorganic regions of the copper, 39 nickel, 40 and manganese 41,42 compounds consist of distorted MCl 6 octahedra featuring MCl 4 layers of square planar metal centres sharing bridging chloro ligands, and two apical terminal Cl ligands on each metal centre. 43 At variance with those, reported tetrahedral [CoCl 4 ] 2− groups were found in the cobaltate salts.…”

Unraveling Correlated Electronic States in Layered Manganese-Based Perovskites

“…Another study by Septiany et al 12 discussed the effects of methylene group on magnetic properties in manganese-based 2D perovskites. They found that the bond angles in PPA-Mn had indeed shifted from 180°, compared to PEA-Mn.…”

“…Furthermore, changes in the dimensional structure of the perovskites could bring major alterations to the material properties. − In three-dimensional materials, any disparities present within the materials are uniform in all three geometrical axes; therefore, no noticeable changes would be observed via highly sensitive angular-dependent probing such as X-ray absorption spectroscopy (XAS). − On the other hand, materials belonging to low-dimensional structures are organized in different arrangements with their distinct behavior. Two-dimensional materials are constructed of entities arranged within the same plane, leading to the materials exhibiting a unique angular-dependent response upon probing by X-ray irradiation. − This combination of highly sensitive spectroscopy and the peculiar behavior of 2D materials could provide more insight into the structural phase transition.…”

“…24,25 The role of cation and ligand size have shown a tremendous effect on the crystal structure and behavior of HOIPs, including electronic and optical properties. 4,12,24 Bigger cation size resulted in higher lattice parameter and reduced carrier mobility, which would eventually hinder its conductivity. Moreover, this change is also reflected in the anharmonicity observed by the Raman shift.…”