Thick-Layer Lead Iodide Perovskites with Bifunctional Organic Spacers Allylammonium and Iodopropylammonium Exhibiting Trap-State Emission

作者：Eugenia S. Vasileiadou, Xinyi Jiang, Mikaël Képénékian, Jacky Even, Michael C. De Siena, Vladislav V. Klepov, Daniel Friedrich, Ioannis Spanopoulos, Qing Tu, Imra S. Tajuddin, Emily A. Weiss, Mercouri G. Kanatzidis · 发表于：Journal of the American Chemical Society · 年份：2022 · DOI：10.1021/jacs.2c00571 · 被引用次数：39 · 研究领域：Perovskite Materials and Applications、2D Materials and Applications、Coral and Marine Ecosystems Studies

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) 2 MA n –1 Pb n I 3 n +1 ( n = 3–4), [(AA) x (IdPA) 1– x ] 2 MA n –1 Pb n I 3 n +1 ( n = 1–4), and (IdPA) 2 MA n –1 Pb n I 3 n +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) 2 MA 2 Pb 3 I 10 crystallizes in the space group P 2 1 / 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) 2 MA 2 Pb 3 I 10 and the alloyed [(AA) x (IdPA) 1– x ] 2 MA 2 Pb 3 I 10 crystallize in the RP structure, both in space group P 2 1 / c . The adjacent I···I interlayer distance in (AA) 2 MA 2 Pb 3 I 10 is ∼5.6 Å, drawing the [Pb 3 I 10 ] 4– layers closer together among all reported n = 3 RP lead iodides. (AA) 2 MA 2 Pb 3 I 10 presents band-edge absorption and photoluminescence (PL) emission at around 2.0 eV that is slightly red-shifte...