Structural Diversity in Multicomponent Nanocrystal Superlattices Comprising Lead Halide Perovskite Nanocubes

[Image: see text] Nanocrystal (NC) self-assembly is a versatile platform for materials engineering at the mesoscale. The NC shape anisotropy leads to structures not observed with spherical NCs. This work presents a broad structural diversity in multicomponent, long-range ordered superlattices (SLs) comprising highly luminescent cubic CsPbBr(3) NCs (and FAPbBr(3) NCs) coassembled with the spherical, truncated cuboid, and disk-shaped NC building blocks. CsPbBr(3) nanocubes combined with Fe(3)O(4) or NaGdF(4) spheres and truncated cuboid PbS NCs form binary SLs of six structure types with high packing density; namely, AB(2), quasi-ternary ABO(3), and ABO(6) types as well as previously known NaCl, AlB(2), and CuAu types. In these structures, nanocubes preserve orientational coherence. Combining nanocubes with large and thick NaGdF(4) nanodisks results in the orthorhombic SL resembling CaC(2) structure with pairs of CsPbBr(3) NCs on one lattice site. Also, we implement two substrate-free methods of SL formation. Oil-in-oil templated assembly results in the formation of binary supraparticles. Self-assembly at the liquid–air interface from the drying solution cast over the glyceryl triacetate as subphase yields extended thin films of SLs. Collective electronic states arise at low temperatures from the dense, periodic packing of NCs, observed as sharp red-shifted bands at 6 K in the photoluminescence and absorption spectra and persisting up to 200 K.