Luminescent Ln³⁺-based silsesquioxanes with a -diketonate antenna ligand: toward the design of efficient temperature sensors

We report the synthesis and single-crystal X-ray diffraction, magnetic, and luminescence measurements of a novel family of luminescent cage-like tetranuclear silsesquioxanes (PhSiO1.5)(8)(LnO(1.5))(4)(O)(C5H8O2)(6)(EtOH)(2)(CH3CN)(2)& sdot;2CH(3)CN (where Ln = Tb, 1; Tb/Eu, 2; and Gd, 3), featuring seven-coordinated lanthanide ions arranged in a one-capped trigonal prism geometry. Compounds 1 and 2 exhibit characteristic Tb3+ and Tb3+/Eu3+-related emissions, respectively, sensitized by the chelating antenna acetylacetonate (acac) ligands upon excitation in the UV and visible spectral regions. Compound 3 is used to assess the energies of the triplet states of the acac ligand. For compound 1, theoretical calculations on the intramolecular energy transfer and multiphonon rates indicate a thermal balance between the D-5(4) Stark components, while the mixed Tb3+/Eu3+ analog 2, with a Tb:Eu ratio of 3:1, showcases intra-cluster Tb3+-to-Eu3+ energy transfer, calculated theoretically as a function of temperature. By utilizing the intensity ratio between the D-5(4)-> F-7(5) (Tb3+) and D-5(0)-> F-7(2) (Eu3+) transitions in the range 11-373 K, we demonstrate the realization of a ratiometric luminescent thermometer with compound 2, operating in the range 11-373 K with a maximum relative sensitivity of 2.0% K-1 at 373 K. These findings highlight the potential of cage-like silsesquioxanes as versatile materials for optical sensing-enabled applications.