Coordination-inspired assembly of binary nanocrystal superlattices featuring a diamond-like sublattice

We present a coordination-inspired strategy for assembling binary nanocrystal superlattices (BNSLs) using CdSe nanotetrapods as symmetry-encoding building blocks. Exploiting their intrinsic tetrahedral geometry, which mimics the sp 3 hybridization of carbon atoms in a diamond lattice, we encode spatially defined binding sites that guide regioselective coassembly with spherical nanocrystals. By tuning the size ratio between components, we achieve both three-dimensional and two-dimensional BNSLs with long-range structural order. Notably, in NaCl-type BNSLs, the CdSe tetrapod sublattice defines a hypothetical porous network that is topologically analogous to a diamond lattice—an architecture difficult to realize using isotropic nanocrystals. The key advantage of this approach lies in its ability to translate molecular coordination principles into nanoscale assembly, thereby enabling access to architecturally complex and topologically rich lattices. A potential limitation, however, is the need for precise control over component size and shape to ensure high-quality ordering. By integrating molecular coordination concepts with nanocrystal assembly, this work establishes nanotetrapods as versatile symmetry-directing building blocks for the rational design of next-generation superlattices. This work establishes nanotetrapods as symmetry-directing building blocks for designing architecturally complex BNSLs, bridging molecular coordination chemistry with nanocrystal assembly.