In situ alkylation or protonation reactions on the thiazolyl-N donors of benzothiazole (btz) and its derivative 2-aminobenzothiazole (abtz) occurred to form four structure directing agents (SDAs), which feature different structure directing abilities and hydrophobicities. The thiazolyl-N alkylated and protonated btz cations direct to form an α-type (AgI) iodoargentate chain in (Etbtz)(AgI) (1), (Prbtz)(AgI) (2), and (Hbtz)(AgI) (3), respectively, while the thiazolyl-N protonated abtz cation directs to form a new type of (AgI) anionic chain in (Habtz)(AgI) (4). Compounds 1 and 4 represent the first noncentrosymmetric (NCS) hybrid iodoargentates with organic S-containing N-heterocycle derivative cations as SDAs. Further, 1 exhibits high water stability and is second harmonic generation (SHG) active with a response about twice that of KDP (KHPO). Importantly, the water stability studies indicate that hybrid iodoargentates with hydrophobic N-alkylated SDAs are more stable in water than those with relative hydrophilic N-protonated SDAs.

Layered heterostructures of different 2D building blocks have invigorated the booming of 2D materials toward high-performance optoelectronic devices. However, contrary to the typical artificial multi-component form, the engineering of non-artificial layered heterostructure into single-phase crystals and resultant properties are largely overlooked. Here, for the first time, an inch-sized single crystal of a non-artificial layered heterostructure is exploited, (PbBr 2 ) 2 (AMTP) 2 PbBr 4 (1, AMTP is 4-ammoniomethyltetrahydropyran), serving as polarization-sensitive candidate. Notably, it adopts an interleaved architecture of 2D perovskite slabs with the distinct non-perovskite lattice, thus forming a self-assembled perovskite-intergrowth layered heterostructure. This motif leads to new electronic transitions distributed across two sublattices and affords an inherent in-plane anisotropy ratio of ≈1.6, beyond some known inorganic materials (e.g., GeSe: 1.44; GeAs: 1.49). Combining this inplane anisotropy and wide bandgap (≈2.9 eV), lateral crystal array of 1 enables shortwave polarized-light detection with ultrahigh responsivity and detectivity under weak illumination compared to some inorganic polarized detectors. As the first demonstration of inch-sized single crystals of non-artificial layered heterostructure, this study affords a new platform to explore candidates toward high-performance optoelectronic devices.

Dion–Jacobson (DJ) phase of 2D hybrid perovskites has recently attracted intensive attention owing to their remarkable optoelectronic properties and superior structural stability. In spite of great endeavors, only a few DJ‐type multilayered hybrid perovskites are obtained and most of them are constructed by very small organic spacer cations (e.g., Cs+ and CH3NH3+). It is still challenging to incorporate larger spacing moieties inside the perovskite cages for accomplishing excellent photoelectric properties. Herein, a newly tailored member of DJ‐type 2D perovskites, (HIS)(DMA)Pb2Br7 (1, where HIS2+ is histammonium and DMA+ is dimethylammonium), of which the perovskite cavities display a remarkable structural distortion to accommodate relatively larger secondary DMA+ cation as the “perovskitizer” is acquired. The monolayers of divalent HIS2+ organic cations directly link to inorganic sheets through NH∙∙∙Br hydrogen bonds, thus eliminating the van der Waals gap in 2D Ruddlesden–Popper counterparts and enabling superior phase stability. As a result, crystal‐based array photodetector of 1 shows fascinating photoactive activities of high detectivity (1.2 × 1013 Jones), large responsivity (18.1 A W−1), and antifatigue behavior, along with polarization‐sensitive detection based on the intrinsic anisotropy. Such findings disclose the potential of 1 for efficient photodetection, and definitely enrich the booming family of 2D hybrid perovskites.