Supramolecular Assembly of Halide Perovskite Building Blocks

Abstract

The structural diversity and tunable optoelectronic properties of halide perovskites originate from the rich chemistry of metal halide ionic octahedron [MX6] n-(M = Pb 2+ , Sb 3+ , Te 4+ , Sn 4+ , Pt 4+ , etc.; X = Cl -, Br -, I -). The properties of the extended perovskite solids are dictated by the assembly, connectivity, and interaction of these octahedra within the lattice environment. Hence, the ability to manipulate and control the assembly of the octahedral building blocks is paramount for constructing new perovskite materials. Here, we propose a systematic supramolecular strategy for the assembly of [MX6] noctahedra into a solid extended network. Interaction of alkali metal-bound crown ethers with [M(IV)X6] 2octahedron resulted in a structurally and optoelectronically tunable "dumbbell" structural unit in solution. Single crystals with diverse packing geometries and symmetries will form as the solid assembly of this new supramolecular building block. This supramolecular assembly route introduces a new general strategy for designing halide perovskite structures with potentially new optoelectronic properties.

How to GIWAXS: Grazing Incidence Wide Angle X‐Ray Scattering Applied to Metal Halide Perovskite Thin Films

“…[101][102][103][104] For example, depending on the synthetic approach employed, [105] the dimensions of the archetypal 3D perovskite can be limited in one or more spatial directions, yielding nano-scale building blocks with local order spanning 3D to 0D (Figure 13A). Recently, Yang et al [106] reported a supramolecular route which constitutes an entirely new general strategy for designing and tailoring the halide perovskite structures; starting with a "dumbbell" supramolecular building block in solution, crystals are assembled through interactions of alkali metalbound crown ethers with the [M(IV)X 6 ] 2− octahedra. Notably, such crystal architectures are not solely limited to alkali metal- Adapted with permission.…”

“…Recently, Yang et al. [ 106 ] reported a supramolecular route which constitutes an entirely new general strategy for designing and tailoring the halide perovskite structures; starting with a “dumbbell” supramolecular building block in solution, crystals are assembled through interactions of alkali metal‐bound crown ethers with the [M(IV)X 6 ] 2− octahedra. Notably, such crystal architectures are not solely limited to alkali metal‐bound crown ethers, but also among analogous structures like vacancy‐ordered double halide perovskites.…”

“…A) Overview of the different structural motifs of metal halide perovskite structures, ranging from (top row) extended corner sharing BX 6 octahedral building blocks with different dimensionality, to the construction of (bottom row) 2D [ 113 ] and 3D [ 114 ] superlattice‐type structures expressing long‐range order (i.e., beyond the nominal few octahedral units), and the supramolecular assembly of BX6 octahedra. [ 106 ] Adapted with permission. [ 113 ] Copyright 2020, Royal Society of Chemistry.…”

Photophysical studies for Cu(i)-based halides: broad excitation bands and highly efficient single-component warm white-light-emitting diodes

“…[1][2][3][4] Different combinations of organic cations and metal-halide clusters enable rich structures with various physical and optical properties. [5][6][7][8][9][10] In addition, hybrid metal halides have many advantages such as high defect tolerance, adjustable energy bands and convenient synthesis methods, making them a great commercial prospect in solid-state lighting (SSL), scintillators, anti-counterfeit encryption, etc. 1,[11][12][13][14][15] Due to the unique 6s 2 lone-pair electronic conguration of Pb 2+ , lead-based metal halides tend to show excellent optoelectronic performance.…”

Octahedral Distortion and Excitonic Behavior of Cs3Bi2Br9 Halide Perovskite at Low Temperature

“…Such ionic octahedra are the basic structural and functional units of metal halide perovskites . The assembly, connection, and interaction of octahedra in metal halide perovskites are critical to creating novel optical, electronic, and chemical properties . Thus, a fundamental understanding of the behavior of the [MX 6 ] n − octahedron is essential for establishing a basis for the rational synthesis and potential applications of metal halide perovskites.…”