Beyond AIE (aggregation-induced emission) phenomena in small molecules, supramolecules with AIE properties have evolved in the AIE family and accelerated the growth of supramolecular application diversity. Inspired by its mechanism,...

Tunable fluorescence emission materials play a critical role in many fields such as biology and chemistry. With respect to metallo‐supramolecular assemblies, the construction of 3D tunable‐fluorescent supramolecular assemblies with 2,2′:6′,2″‐terpyridine (tpy) is still in its infancy. In this study, two luminous 3D supramolecular prisms self‐assembled with two terpyridine‐based tetraphenylethylene (TPE) ligands and metal Zn(II) are prepared, and the influence of hydrophobic alkyl chains on tunable fluorescence is further explored. By exploiting hydrophobic properties, the prism SA exhibits tunable visible‐light emission in the molecular‐aggregated state. Moreover, SA forms left‐hand and right‐hand helical nanofibers by hierarchical self‐assembly. However, the prism SB without hydrophobic chains does not exhibit tunable fluorescence emission, and only random spherical aggregates after hierarchical self‐assembly are formed. This study can aid to further strengthen the understanding about the effect of hydrophobic segments on photophysical properties and hierarchical self‐assembly of discrete supramolecular architectures.

Inspired by the architecture of single-atom catalysts, where the monodispersed metal atoms are widely distributed but stabilized by various coordination circumstances, the biomimetic design and synthesis of metalloporphyrin-containing nanocages have been demonstrated in this study. The nanocages were fabricated through a coordination-driven self-assembly process, and the Mn­(III) porphyrin-based one was found to have exclusively peroxidase-like activity at pH 6.0 with neither oxidase nor catalase-like activity under the routine conditions. Benefiting from this, we demonstrated the wide applicability and convenient usage of an Mn­(III)-containing supramolecular nanocage (Mn-PC) in the one-step detection of H2O2, sarcosine, and glucose through various oxidase-involved reactions, with a satisfactory detection limit and eligible specificity. Real samples including H2O2 in lens care solution, sarcosine in human urine, and glucose in human serum were also assayed, showing an adequate recovery rate. Such a specific activity originates from the super-consistent microstructure of each catalytic unit, which means that the active site of manganese porphyrin was “protected” by the confinement of the nanocage. This also helps to sustain the super long-term activity even after 545 days of storage. Furthermore, the intrinsic electronic structure of the Mn­(III)-containing supramolecular nanocage endows the ability in electrochemical detection of H2O2 and glucose. Our smart design toward the supramolecular nanocages with a defined structure and quantity contributes to the construction of the ingenious sensing platform and has guiding significance for architectural design of nanozymes.

In this study, two trigonal prisms based on the 1,3,5-triazine motif (SA and SB), distinguished by hydrophobic groups, were prepared by the self-assembly of tritopic terpyridine ligands and Zn(II) ions. SA and SB exhibited high luminescence efficiencies in the solid state, overcoming the fluorescence quenching of the 1,3,5-triazine group caused by π–π interactions. Notably, SA and SB exhibited different luminescence behaviors in the solution state and aggregation state. SB with 12 alkyl chains exhibited extremely weak fluorescence in a dilute solution, but its fluorescence intensity and photoluminescence quantum yield (PLQY) were significantly enhanced in the aggregated state (with the increase in the water fraction), especially in the solid state. Different from the gradually enhanced efficiency of SB, the PLQY of SA gradually decreased with the increase in aggregation but still maintained a high luminescence efficiency. These two complexes exhibited different modes to solve the fluorescence quenching of 1,3,5-triazine in the solid state. The hierarchical self-assembly of SB exhibited nanorods owing to the hydrophobic interactions of alky chains, while SA aggregated into spheres under the influence of π–π interactions.