A water-soluble TbIII complex as a temperature-sensitive luminescent probe

Abstract

The water soluble [Tb(dipicCbz)3]3− (dipicCbz = 4-(9H-carbazol-9-yl-)pyridine-2,6-dicarboxylato) complex was isolated and evaluated as a temperature sensor in water. The 1:3 (TbIII:dipicCbz2−) stoichiometry in solution was confirmed by luminescence titration and high-resolution mass spectrometry. The quantum yield of sensitized emission is 3.8% ± 0.4% at 25.0 ± 0.1 °C, and the emission intensity depends on the temperature in the range of 5–70 °C with a relative thermal sensitivity of 3.4% °C−1 at 35 °C and temperature resolution < 0.01 °C in the range of 30–40 °C. The reversibility of this behavior was demonstrated for three heating–cooling cycles. Calculations of the energy gap between donor and acceptor show that the temperature dependence of the emission intensity is due to back-energy transfer from the Tb 5D4 excited state to the triplet and twisted intramolecular charge transfer (TICT) states of the dipicCbz. The assignment of one of the energy levels as a TICT state was confirmed by the temperature-dependent behavior of the phosphorescence band.