Using carboxylate-protected silver nanoclusters (Ag-carboxylate NCs) as a model, we separately investigated the contribution of the ligand shell and the metal core to understand the nature of photoluminescence of Ag NCs. A new Ag(0)NCs@Ag(I)-carboxylate complex core-shell structural model has been proposed. The emission from the Ag-carboxylate NCs could be attributed to ligand-to-metal-metal charge transfer from Ag(I)-carboxylate complexes (the oxygen atom in the carboxylate ligands to the Ag(I) ions) to the Ag atoms and subsequent radiative relaxation. Additionally, we found that the emission wavelength of the Ag NCs depends on the excitation wavelength implying a strong coupling between surface plasmon and emitter in Ag NCs. The strong coupling between the surface plasmon and the emitter determines the quantum yield and lifetime. The emission mechanism of Ag NCs and its relation to the organic templates and metal cores were clearly clarified. The results should stimulate additional experimental and theoretical research on the molecular-level design of luminescent metal probes for optoelectronics and other applications.

Recently, metal nanoclusters (MNCs) emerged as a new class of luminescent materials and have attracted tremendous interest in the area of luminescence-related applications due to their excellent luminous properties (good photostability, large Stokes shift) and inherent good biocompatibility. However, the origin of photoluminescence (PL) of MNCs is still not fully understood, which has limited their practical application. In this mini-review, focusing on the origin of the photoemission emission of MNCs, we simply review the evolution of luminescent mechanism models of MNCs, from the pure metal-centered quantum confinement mechanics to ligand-centered p band intermediate state (PBIS) model via a transitional ligand-to-metal charge transfer (LMCT or LMMCT) mechanism as a compromise model.

The fluorescence-phosphorescence dual solvoluminescence (SL) of water-soluble metal nanoclusters (NCs) at room temperature was successfully achieved by a simple solvent-stimulated strategy. The strong interaction between carboxylate ligands and the metal core at the nanoscale interface not only induces rigid conformations of carbonyl groups but also affords a perfect carbonyl cluster that acts as an exact chromophore of metal NCs for aggregation-induced emission (AIE) mechanics. The clustering of carbonyl groups bearing on the polymer backbone chain is promoted by newly discovered n → π* noncovalent interactions. The efficient delocalization of electrons in overlapped C═O double bonds between neighboring carbonyl groups triggered by strong n → π* interactions in the polymer cluster accounts for its unique SL properties, especially the abnormal phosphorescence. This was further confirmed by controlled experiments for the presence of intersystem crossing (ISC) transitions. The results provide novel insights for understanding the complex SL process and open up a new way to study the inherent mechanism of SL by broadening the application of metal NCs.

The availability of a range of excited states has endowed low dimensional quantum nanostructures with interesting luminescence properties. However, the origin of photoluminescence emission is still not fully understood, which has limited its practical application. Here we judiciously manipulate the delicate surface ligand interactions at the nanoscale interface of a single metal nanocluster, the superlattice, and mesoporous materials. The resulting interplay of various noncovalent interactions leads to a precise modulation of emission colors and quantum yield. A new p-band state, resulting from the strong overlapping of p orbitals of the heteroatoms (O, N, and S) bearing on the targeting ligands though space interactions, is identified as a dark state to activate the triplet state of the surface aggregated chromophores. The UV-Visible spectra calculated by time-dependent density functional theory (TD-DFT) are in quantitative agreement with the experimental adsorption spectra. The energy level of the p-band center is very sensitive to the local proximity ligand chromophores at heterogeneous interfaces.

The synthesis of highly uniform mesoporous silica nanospheres (MSNs) with dendritic pore channels, particularly ones with particle sizes below 200 nm, is extremely difficult and remains a grand challenge. By a combined synthetic strategy using imidazolium ionic liquids (ILs) with different alkyl lengths as cosurfactants and Pluronic F127 nonionic surfactants as inhibitors of particle growth, the preparation of dendritic MSNs with controlled diameter between 40 and 300 nm was successfully realized. An investigation of dendritic MSNs using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and nitrogen physisorption revealed that the synthesis of dendritic MSNs at larger size (100-300 nm) strongly depends on the alkyl lengths of cationic imidazolium ILs; while the average size of dendritic MSNs can be controlled within the range of 40-100 nm by varying the amount of Pluronic F127. The Au@MSNs can be used as a catalyst for the reduction of 4-nitrophenol by NaBH4 into 4-aminophenol and exhibit excellent catalytic performance. The present discovery of the extended synthesis conditions offers reproducible, facile, and large-scale synthesis of the monodisperse spherical MSNs with precise size control and, thus, has vast prospects for future applications of ultrafine mesostructured nanoparticle materials in catalysis and biomedicine.