Supramolecular Assembly of Multielement Ribbon-like Structures Derived from Halide Perovskites

Halide perovskites are crucial materials with broad applications owing to their exceptional optoelectronic properties. Vacancy-ordered double perovskites, featuring highly tunable transition metal sites, enable controllable optoelectronic properties through multielement compositional design. In this study, we introduced 18-crown-6 into the vacancy-ordered double perovskites system and developed two-dimensional ribbon-like single crystals (18C6@K)2{PtSnTeIrRe}1Cl6 via an antisolvent supramolecular assembly method, demonstrating morphology modulation through multielement composition design. The crystals crystallize in the centrosymmetric space group P1¯. The dumbbell-shaped structural units (crown ether@A)2MX6 pack along a and b axes to form a 2-dimensional (2D) monolayer, and these monolayers further stack along the c axis to generate the ribbon-like single crystals. Energy-dispersive X-ray spectroscopy (EDX) qualitatively confirmed the uniform distribution of the five transition metals throughout the crystal, while inductively coupled plasma atomic emission spectroscopy (ICP–AES) quantitatively verified their atomic ratios. We further investigated the origin of the morphology, distinct from the previously reported cube-like single crystals with the R3¯ space group. When acetonitrile was used as the solvent, three-dimensional crystals with R3¯ symmetry were obtained, whereas dimethylformamide (DMF) was essential for forming two-dimensional ribbon-like single crystals. The essential role of DMF could be ascribed to its capability to maintain a higher concentration of the building blocks. Moreover, Ir4+ and Pt4+ cations also played critical roles in inducing the two-dimensional ribbon-like morphology. The three-element (18C6@K)2{PtSnTe}1Cl6 single crystals exhibited bright yellow emission under 375 nm laser excitation, demonstrating the tunability of optoelectronic properties of this class of material.