A Multimodal Ratiometric Luminescent Thermometer Based on a Single-Dysprosium Metal-Organic Framework

The design of high-performance luminescent MOF thermometers with multi-operation modes has been long sought but remains a formidable challenge. In this work, for the first time, we present a multimodal luminescent ratiometric thermometer based on the single-lanthanide metal-organic framework (MOF) DyTPTC-2Me (H₄TPTC-2Me = 2',5'-dimethyl-[1,1':4',1″-terphenyl]-3,3″,5,5″-tetracarboxylic acid). It not only has the characteristic luminescence of Dy³⁺ in which the atomic transitions from the ⁴I_15/2 and ⁴F_9/2 states (thermally coupled energy levels, TCELs) are included but also emits ligand fluorescence due to the efficient energy back-transfer of Dy³⁺ to the ligand, thus allowing accurate non-invasive determination of temperature by different modes. In particular, the TCEL-based emissions of the Dy³⁺ ions give ideal signals for measuring the temperature in the 303-423 K range. The emissions of the ligand and Dy³⁺ (⁴F_9/2 → ⁶H_13/2) are used for temperature sensing in the range of 423 to 503 K. Both two modes feature promising thermometric performance, including high relative sensitivity, high temperature resolution, and excellent repeatability. Their combination is thus beneficial to achieve more accurate temperature detection over a broad temperature range, which can broaden the application scope of the ratiometric luminescent thermometers.