Chiral two-dimensional (2D) organic-inorganic hybrid perovskites (OIHPs) attract increasing interest due to the potential applications in spintronic, and optoelectronic devices. However, circularly polarized luminescence (CPL) properties of chiral 2D OIHPs...

Superstructures made from nanoscale clusters with new collective properties are promising in high-tech applications; however, chiral superstructures remain elusive, and the limited intercluster coupling effect at room temperature hampers the tailoring of collective properties. Here, we show that from chiral monomeric copper clusters to two enantiomeric pairs of supercrystals with distinct phases, the absorption band edge red-shifts by over 1.3 eV, with photoluminescence and circularly polarized phosphorescence from visible (572 nm) to near-infrared (NIR, 858 nm). These supercrystals with high NIR quantum yields of up to 45% at room temperature are prototyped for night-vision imaging. In response to solvent and temperature stimuli, chiral supercrystal-to-supercrystal transformations occurred, concomitant with high-contrast optical/chiroptical switching. In situ single-crystal Xray diffraction (SCXRD), steady-state and time-resolved optical spectroscopy, and response experiments combined with theoretical calculations demonstrate that distance-sensitive intercluster orbital interactions contribute to the exceptional collective optical responses. Such chiral supercrystals built from subnanoscale metal clusters with novel collective chiroptical responses would be useful in the fields of information storage and NIR optical devices.

Comprehensive SummaryIn this work, we have successfully obtained a series of novel copper(I)–iodide clusters (CuI NCs) based assembly materials by combining supramolecular pseudorotaxane ligands {[Mebpe+]PF6–@CB[6] (CB[6] = cucurbit[6]uril), L’·PF6} and linkers {BPHF@CB[6], [BPHF = C14H20N4(PF6)2], L·PF6}, including discrete cluster CuI 1 and extended cluster organic frameworks MORF 1 and MORF 2. CuI 1 can be described as a dumbbell‐shaped molecule with its body‐centered site and two vertexes respectively occupied by one [Cu5I6]– cluster and two CB[6] held together by two L’·PF6 ligands. The crystal structures of MORF 1 and MORF 2 are 1D anionic chain and four‐fold interpenetrated 3D cationic diamondoid structure, respectively, which all featured intriguing alternating CB[6] and CuI NCs. Furthermore, CuI 1 exhibits outstanding thermochromic and piezochromic luminescence. MORF 1 and MORF 2 also are detected pressure dependent luminescence properties with an enormous blue‐shift of the near‐infrared (NIR) emission band under high pressure compression. These exciting and smart materials possess great potential in the application field of novel temperature and pressure sensors.

The oriented films of a new enantiomeric pair of 2D organic–inorganic hybrid perovskites demonstrated bright circularly polarized luminescence and a 5-fold enlarged glum of up to 1.0 × 10−2, relative to the solid-state powders.