Inside-Out/Outside-In Tunability in Nanosized Lanthanide-Based Molecular Cluster-Aggregates: Modulating the...

Modulating the optical property of a material via structural modification is a powerful tool for obtaining the desired optical output. If a material can be tuned inside (core) and outside (outer shell), then the degree of control is greater toward application. Herein, we present a lanthanide-based nanosized molecular cluster aggregate (MCA) that allows fine-tuning of the inner core via composition control akin to nanoparticles. At the same time, the tunable outer shell enables light-harvesting properties similar to molecular systems. As such {Eu₄Tb₁₆}, {Eu₃Gd₅Tb₁₂}, {Eu₂Gd₁₀Tb₈}, and {Eu₁Gd₁₅Tb₄} compositions were synthesized, and their photophysical properties were investigated in solution and in the solid state. Controlling the composition and spacing of the emitter ions with the optically silent Gd^III ions results in a decrease in the Tb^III → Eu^III energy-transfer process efficiency. Consequently, ratiometric luminescence thermometry performance is fine-tuned to reach a maximum relative sensitivity of 4.17% °C^-1 at 36 °C for the {Eu₄Tb₁₆} MCA. This study demonstrates that the optical properties are intrinsic to individual MCA species rather than a collective intermolecular effect. The color change observed close to room temperature for {Eu₂Gd₁₀Tb₈} suggests potential applications such as multistage anticounterfeiting technology.