The nature of the organic cation in two-dimensional (2D) hybrid lead iodide perovskites tailors the structural and technological features of the resultant material. Herein, we present three new homologous series of (100) lead iodide perovskites with the organic cations allylammonium (AA) containing an unsaturated C═C group and iodopropylammonium (IdPA) containing iodine on the organic chain: (AA)₂MA_n_-1Pb_nI_3n+1 (n = 3-4), [(AA)_x(IdPA)_1-x]₂MA_n_-1Pb_nI_3n+1 (n = 1-4), and (IdPA)₂MA_n_-1Pb_nI_3n+1 (n = 1-4), as well as their perovskite-related substructures. We report the in situ transformation of AA organic layers into IdPA and the incorporation of these cations simultaneously into the 2D perovskite structure. Single-crystal X-ray diffraction shows that (AA)₂MA₂Pb₃I₁₀ crystallizes in the space group P2₁/c with a unique inorganic layer offset (0, <1/2), comprising the first example of n = 3 halide perovskite with a monoammonium cation that deviates from the Ruddlesden-Popper (RP) halide structure type. (IdPA)₂MA₂Pb₃I₁₀ and the alloyed [(AA)_x(IdPA)_1-x]₂MA₂Pb₃I₁₀ crystallize in the RP structure, both in space group P2₁/c. The adjacent I···I interlayer distance in (AA)₂MA₂Pb₃I₁₀ is ∼5.6 Å, drawing the [Pb₃I₁₀]^4- layers closer together among all reported n = 3 RP lead iodides. (AA)₂MA₂Pb₃I₁₀ presents band-edge absorption and photoluminescence (PL) emission at around 2.0 eV that is slightly red-shifted in comparison to (IdPA)₂MA₂Pb₃I₁₀. The band structure calculations suggest that both (AA)₂MA₂Pb₃I₁₀ and (IdPA)₂MA₂Pb₃I₁₀ have in-plane effective masses around 0.04m₀ and 0.08m₀, respectively. IdPA cations have a greater dielectric contribution than AA. The excited-state dynamics investigated by transient absorption (TA) spectroscopy reveal a long-lived (∼100 ps) trap state ensemble with broad-band emission; our evidence suggests that these states appear due to lattice distortions induced by the incorporation of IdPA cations.

	Year	Citations

About