Fashioning Fluorous Organic Spacers for Tunable and Stable Layered Hybrid Perovskites

Two dimensional (2D) organic–inorganic hybrid perovskites have recently attracted enormous attention due to their higher environmental stability with respect to three-dimensional (3D) perovskites and larger structural tunability. The layered structure relaxes constraints on the dimensions of the organic cations that alternate the inorganic sheets, opening up a large choice on the organics, ultimately enabling the creation of tunable layered perovskites. Here, we report on a series of fluorous cations, varying in size and shape, as building blocks for a new family of fluorous 2D lead-iodide perovskites. These display a large tunability in the optical and dielectric properties depending on the structure of the fluorous cations. Importantly, despite the invariant inorganic framework, the 2D perovskite electronic structure is strongly affected by the cation size. The longer the cation, the smaller the 2D perovskite band gap and the exciton binding energy (reducing from 400 meV down to 130 meV). Such variation is induced by the strain in the inorganic sheet, resulting in a more dispersed valence and conduction bands, in turn yielding a smaller band gap. In addition, a smaller effective mass for the 2D perovskite with the longest cation is calculated, for which improved transport properties are anticipated. Importantly, the fluorous moiety confers extreme stability to the 2D perovskite and enhances the hydrophobic character of the perovskite surface, which remains perfectly stable for more than one month in ambient conditions.