Luminescent copper(I)‐based compounds have recently attracted much attention since they can reach very high emission quantum yields. Interestingly, Cu(I) clusters can also be emissive, and the extension from small molecules to larger architecture could represent the first step towards novel materials that could be obtained by programming the units to undergo self‐assembly. However, for Cu(I) compounds the formation of supramolecular systems is challenging due to the coordinative diversity of copper centers. This works shows that this diversity can be exploited in the construction of responsive systems. In detail, the changes in the emissive profile of different aggregates formed in water by phosphine‐thioether copper(I) derivatives were followed. Our results demonstrate that the self‐assembly and disassembly of Cu(I)‐based coordination polymeric nanoparticles (CPNs) is sensitive to solvent composition. The solvent‐induced changes are related to modifications in the coordination sphere of copper at the molecular level, which alters not only the emission profile but also the morphology of the aggregates. Our findings are expected to inspire the construction of smart supramolecular systems based on dynamic coordinative metal centers.

We examined the Au–P and Au–X chemical bonding scenario throughout the series of compounds of the general formula [AuX(LP)] wherein LP is triphenylphosphine or a fluorinated phosphine [PPhF = P(C6H5)2(C6F5) 1, P(C6H5)(C6F5)2 2 and P(C6F5)3 3] and X is chloride or a fluorinated thiolate [SRF = SCF3 a, SCH2CF3 b, SC6F5 c, SC6F4(CF3)‐4 d]. We found that the increase of the fluorination degree or the replacement of Cl– by a –SRF ligand decreases the stability of the compound. Furthermore, this substitution shifts the 31P‐NMR signals to low field, which indicates differences in the electronegativity of the phosphorus due to the distinct trans influences of the Cl– and –SRF species. These effects correlate with the charge of the gold atom coordinated to phosphorus. Our investigation shows the high potential of fluorination as a strategy for the modulation of the properties of gold compounds, for example in catalysis, and the applicability of quantum chemical topology studies in the explanation of these features.

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The formation of coordination polymer nanoparticles by a copper(I) coordination compound containing cubane‐like clusters as nodes connected by hybrid thioether‐phosphine ligands has been achieved in aqueous media. The formed particles display a yellow aggregation‐induced emission. The change in the environment triggers a morphological transformation towards elongated aggregates due to changes in the coordination environment, opening the cubane units and causing a cyan emission. More information can be found in the Full Paper by G. Moreno‐Alcántar et al. (DOI: 10.1002/chem.202100865).