Inorg. Chem. 2022, 61, 30, 11973–11980.https://doi.org/10.1021/acs.inorgchem.2c01730

The participation of organic cations plays an important role in tuning broad-spectra emissions. Herein, we synthesized a series of Mn(II)-based two-dimensional (2D) halide perovskites with arylamine cations of different lengths having the general formula (C₆H₅(CH₂)_xNH₃)₂MnCl₄ (x = 1–4), with the x = 4 compound reported here for the first time. With the increase in the −(CH₂)– in organic cations, the distance between adjacent inorganic layers increases, causing the title compounds to exhibit different structural distortions. As the Mn–Cl–Mn angular distortion increases, the experimental optical band gaps of the title compounds increase correspondingly. When the angle distortion between the octahedrons of the compounds is similar, the band gaps may also be affected by the distortion of the octahedron itself (the bond-length distortion of 2 is greater than that of 4). Under UV-light irradiation at 298 K, all of the compounds exhibit two emission peaks centered at 480–505 and 610 nm, corresponding to the organic-cation emission and the ⁴T₁(G) to ⁶A₁(S) radiative transition of Mn²⁺ ions, respectively. Among these title compounds, (PPA)₂MnCl₄ [(PPA)⁺ = C₆H₅(CH₂)₃NH₃⁺] exhibits the strongest photoluminescence (PL). The study of the title compounds contributes to an in-depth understanding of the relationship between the structural distortion and optical properties of 2D Mn(II)-based perovskite materials.