The structural complexity of composite biomaterials and biomineralized particles arises from the hierarchical ordering of inorganic building blocks over multiple scales. Although empirical observations of complex nanoassemblies are abundant, the physicochemical mechanisms leading to their geometrical complexity are still puzzling, especially for nonuniformly sized components. We report the self-assembly of hierarchically organized particles (HOPs) from polydisperse gold thiolate nanoplatelets with cysteine surface ligands. Graph theory methods indicate that these HOPs, which feature twisted spikes and other morphologies, display higher complexity than their biological counterparts. Their intricate organization emerges from competing chirality-dependent assembly restrictions that render assembly pathways primarily dependent on nanoparticle symmetry rather than size. These findings and HOP phase diagrams open a pathway to a large family of colloids with complex architectures and unusual chiroptical and chemical properties.

High quantum yield, photoluminescence tunability, and sensitivity to the environment are hallmarks that make carbon nanodots interesting for fundamental research and applications. Yet, the underlying electronic transitions behind their bright photoluminescence are strongly debated. Despite carbon-dot interactions with their environment should provide valuable insight into the emitting transitions, they have hardly been studied. Here, we investigate these interactions in a wide range of solvents to elucidate the nature of the electronic transitions. We find remarkable and systematic dependence of the emission energy and kinetics on the characteristics of the solvent, with strong response of the photoexcited dots to hydrogen bonding. These findings suggest that the fluorescence originates from the radiative recombination of a photoexcited electron migrated to surface groups with holes left in the valence band of the crystalline core. Furthermore, the results demonstrate the fluorescence tunability to inherently derive from dot-to-dot polydispersity, independent of solvent interactions.

The assembly of semiconductor nanoparticles, quantum dots (QDs), into dense crystalline nanostructures holds great promise for future optoelectronic devices. However, knowledge of the sub-nanometer scale driving forces underlying the kinetic processes of nucleation, growth, and final densification during QD assembly remains poor. Emulsion-templated assembly has recently been shown to provide good control over the bulk condensation of QDs into highly ordered 3D supercrystals. Here, emulsion-templated assembly is combined with in situ small-angle X-ray scattering to obtain direct insight into the nanoscale interactions underlying the nucleation, growth, and densification of QD supercrystals. At the point of supercrystal nucleation, nanoparticles undergo a hard-sphere-like crystallization into a hexagonal-close-packed lattice, slowly transforming into a face-centered-cubic lattice. The ligands play a crucial role in balancing steric repulsion against attractive van der Waals forces to mediate the initial equilibrium assembly, but cause the QDs to be progressively destabilized upon densification. The rich detail of this kinetic study elucidates the assembly and thermodynamic properties that define QD supercrystal fabrication approaching single-crystal quality, paving the way toward their use in optoelectronic devices.

Carbon dots (CDs) are carbon-based fluorescent nanoparticles that can exhibit excitation-dependent photoluminescence (PL) "tunable" throughout the entire visible range, interesting for optoelectronic and imaging applications. The mechanism underlying this tunable emission remains largely debated, most prominently being ascribed to dot-to-dot variations that ultimately lead to excitation-dependent ensemble properties. Here, single-dot spectroscopy is used to elucidate the origin of the excitation-dependent PL of CDs. It is demonstrated that already single CDs exhibit excitation-dependent PL spectra, similar to those of the CD ensemble. The single dots, produced by a facile one-step synthesis from chloroform and diethylamine, exhibit emission spectra with several characteristic peaks differing in emission peak position and spectral width and shape, indicating the presence of distinct emission sites on the CDs. Based on previous work, these emission sites are related to the sp subregions in the carbon core, as well as the functional groups on the surface. These results confirm that it is possible to integrate and engineer different types of electronic transitions at the nanoscale on a single CD, making these CDs even more versatile than organic dyes or inorganic quantum dots and opening up new routes toward light-emission engineering.

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