Crystal structure and thermochemical properties of bis(1-octylammonium) tetrachlorocuprate

Chiral organic ammonium cations ((R)-2-methylphenethylammonium (R-MPhA) and (R)-3,7-dimethyloctylammonium (R-DMOA)) cations were combined with [MX 4 ] 2− anions (M = Cu and Pb, X = Cl and Br) to form two-dimensional (2D) perovskites: (R-MPhA) 2 CuCl 4 (1a), (R-MPhA) 2 CuBr 4 (1b), (R-DMOA) 2 CuCl 4 (2a), (R-DMOA) 2 CuBr 4 (2b), (R-DMOA) 2 PbCl 4 (2c), and (R-DMOA) 2 PbBr 4 (2d). The point shearing of the MX 4 octahedron formed 2D perovskite layers, which were sandwiched by the bilayer molecular assembly of chiral organic ammonium cations. We found that the flexible and polar organic R-MPhA and R-DMOA cations in the 2D perovskites played an important role in the phase transition behavior and dielectric responses. Salts 2a−2d showed similar solid−solid (S1−S2) phase transitions, for which the temperatures decreased in the order of CuCl 4 (2a) > PbCl 4 (2c) > CuBr 4 (2b) > PbBr 4 (2d). The occupation volume of one R-DMOA per MX 4 octahedron determined the dynamic crystalline space for the motional freedom of chiral ammonium in the 2D perovskite layer. Although thermally activated dielectric fluctuations were observed in salts 2a, 2b, and 2c, only an order−disordertype dielectric phase transition was observed in salt 2d. Interband optical transitions were observed in the CuCl 4 and CuBr 4 2D perovskites, whereas sharp exciton absorptions were observed in the 2D PbCl 4 and PbBr 4 layers in perovskite salts 2c and 2d.

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Crystal structure and thermochemical properties of bis(1-octylammonium) tetrachlorocuprate

Cited by 2 publications

References 13 publications

Low-temperature heat capacities, and thermodynamic properties of solid–solid phase change material bis(1-octylammonium) tetrachlorocuprate

Low-temperature heat capacities, and thermodynamic properties of solid–solid phase change material bis(1-octylammonium) tetrachlorocuprate

Dynamics of Chiral Cations in Two-Dimensional CuX₄ and PbX₄ Perovskites (X = Cl and Br)

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Crystal structure and thermochemical properties of bis(1-octylammonium) tetrachlorocuprate

Cited by 2 publications

References 13 publications

Low-temperature heat capacities, and thermodynamic properties of solid–solid phase change material bis(1-octylammonium) tetrachlorocuprate

Low-temperature heat capacities, and thermodynamic properties of solid–solid phase change material bis(1-octylammonium) tetrachlorocuprate

Dynamics of Chiral Cations in Two-Dimensional CuX4 and PbX4 Perovskites (X = Cl and Br)

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Dynamics of Chiral Cations in Two-Dimensional CuX₄ and PbX₄ Perovskites (X = Cl and Br)