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.

Room‐temperature syntheses of metal–organic frameworks (MOFs) are of interest to meet the demand of the sustainable chemistry and are a pre‐requisite for the incorporation of functional compounds in water‐stable MOFs. However, only few routes under ambient conditions have been reported to produce metal(IV)‐based MOFs. Reported here is a new versatile one‐step synthesis of a series of highly porous M6‐oxocluster‐based MOFs (M=Zr, Hf, Ce) at room temperature, including 8‐ or 12‐connected micro/mesoporous solids with different functionalized organic ligands. The compounds show varying degrees of defects, particularly for 12‐connected phases, while maintaining the chemical stability of the parent MOFs. Proposed here are first insights into in situ kinetics observations for efficient MOF preparation. Remarkably, the synthesis has a high space‐time yield and also provides the possibility to tune the particle size, therefore paving the way for their practical use.

Zr(IV)-based metal-organic frameworks (MOFs) such as the Zr(IV) trimesate MOF-808 are promising materials for catalytic applications. In this work, we report an aqueous solution-based room temperature strategy to produce well-defined monodispersed MOF-808 nanocrystals down to 35 nm with a high space-time yield, up to 2516 g/ m 3 / day, and an excellent crystallinity and porosity. The resulting nanocrystals show remarkable colloidal dispersion during one day in a wide range of nanoparticles concentrations. As a result, 35 nm MOF-808 colloidal-level nanocrystals exhibit the highest rate of selective peptide bond and protein hydrolysis among reported Zr(IV)-based MOFs. This result may open new opportunities for highly efficient peptide or protein hydrolysis using scalable nano-catalyst.