Dion–Jacobson to Alternating‐Cations‐Interaction Reconstruction toward Narrow Bandgap 2D Aromatic Hybrid Perovskite

Abstract The 2D aromatic Dion–Jacobson (DJ) hybrid perovskites combining advantages of high stability, enhanced light absorption, and favorable charge transport, are regarded as a kind of very promising materials for high‐performance optoelectronic applications. However, due to the rigidity and large size of the aromatic ring, how to further reduce the interlayer distance to achieve better carrier transport and wider light response window still remain extremely challenging. Here, an interesting DJ‐to‐ACI (alternating‐cations‐interaction) reconstruction in 2D aromatic perovskite is first realized by inserting MA⁺ cations into (4‐AP)PbI₄ (1, 4‐AP = 4‐amidinopyridinium), successfully constructing an unprecedented ACI perovskite of (4‐AP)(MA)₂Pb₂I₈ (2, MA = methylamine). Remarkably, such a DJ‐to‐ACI reconstruction not only effectively reduces the interlayer spacing from 3.89 to 3.15 Å but also alleviates the structural distortion, which jointly causes a significant bandgap narrowing from 2.22 to 1.95 eV (smaller than all current 2D monolayered DJ perovskites), hence achieving a broad photodetection window over 660 nm. This work reports a novel narrow bandgap 2D ACI perovskite derived from the aromatic DJ motif, which sheds light on future regulations on the structure and properties of hybrid perovskites.