Introducing Intermolecular Cation‐π Interactions for Water‐Stable Low Dimensional Hybrid Lead Halide Perovskites

Abstract

AbstractOptoelectronically active hybrid lead halide perovskites dissociate in water. To prevent this dissociation, here, we introduce long‐range intermolecular cation‐π interactions between A‐site cations of hybrid perovskites. An aromatic diamine like 4,4′‐trimethylenedipyridine, if protonated, can show a long‐range cation‐π stacking, and therefore, serves as our A‐site cation. Consequently, 4,4′‐trimethylenedipyridinium lead bromide [(4,4′‐TMDP)Pb2Br6], a one‐dimensional hybrid perovskite, remains completely stable after continuous water treatment for six months. Mechanistic insights about the cation‐π interactions are obtained by single‐crystal X‐ray diffraction and nuclear magnetic resonance spectroscopy. The concept of long‐range cation‐π interaction is further extended to another A‐site cation 4,4′‐ethylenedipyridinium ion (4,4′‐EDP), forming water‐stable (4,4′‐EDP)Pb2Br6 perovskite. These water‐stable perovskites are then used to fabricate white light‐emitting diode and for light up‐conversion through tunable third‐harmonic generation. Note that the achieved water stability is the intrinsic stability of perovskite composition, unlike the prior approach of encapsulating the unstable perovskite material (or device) by water‐resistant materials. The introduced cation‐π interactions can be a breakthrough strategy in designing many more compositions of water‐stable low‐dimensional hybrid perovskites.