Flexible Polymer-Assisted Mesoscale Self-Assembly of Colloidal CsPbBr₃ Perovskite Nanocrystals into Higher Order Superstructures with Strong Inter-Nanocrystal Electronic Coupling

Surface-passivating ligands, although ubiquitous to colloidal nanocrystal (NC) syntheses, play a role in assembling NCs into higher order structures and hierarchical superstructures, which has not been demonstrated yet for colloidal CsPbX₃ (X = Cl, Br, and I) NCs. In this work, we report that functional poly­(ethylene glycols) (PEG₆-Y, Y = −COOH and −NH₂) represent unique surface-passivating ligands enabling the synthesis of near-uniform CsPbBr₃ NCs with diameters of 3.0 nm. The synthesized NCs are assembled into individual pearl necklaces, bundled pearl necklaces, lamellar, and nanorice superstructures, <i>in situ</i>. It is believed a variety of forces, including van der Waals attractions between hydrophilic PEG tails in a nonpolar solvent and dipole–dipole attraction between NCs, drive mesoscale assembly to form superstructures. Furthermore, postsynthetic ligand treatment strengthens the argument for polymer-assisted mesoscale assembly as pearl necklace assemblies can be successfully converted into either lamellar or nanorice structures. We observe an ∼240 meV bathochromic shift in the lowest energy absorption peak of CsPbBr₃ NCs when they are present in the lamellar and nanorice assemblies, representing strong inter-NC electronic coupling. Moreover, pearl necklace structures are spontaneously assembled into micrometer length scale twisted ribbon hierarchical superstructures during storage of colloidal CsPbBr₃ NCs. The results show that the self-assembled superstructures of CsPbBr₃ NCs are now feasible to prepare via template-free synthesis, as self-assembled structures emerge in the bulk solvent, a process that mimics biological systems except for the use of nonbiological surface ligands (PEG₆-Y). Taken together, emergent optoelectronic properties and higher order superstructures of CsPbBr₃ NCs should aid their potential use in solid-state devices and simplify scalable manufacturing

One-Pot Cascade Approach to Phen­anthridine-Fused Qui­nazo­linimi­niums from Heteroenyne-Allenes

A one-pot cascade method to obtain functionalized phen­anthri­dine-fused quinazoliniminiums from a variety of heteroenyne-allenes is described. This protocol involves formation of C–N and C–C bonds in a single step in the presence of a Lewis acid and trace water to afford pentacyclic title compounds in moderate to good yields