The Role of π–f Orbital Interactions in Eu(III) Complexes for an Effective Molecular Luminescent Thermometer
Yuichi Kitagawa, Marina Kumagai, Takayuki Nakanishi, Koji Fushimi, Yasuchika Hasegawa
Abstract
Luminescent Eu(III) complexes with a ligand-to-metal charge transfer (LMCT) state were demonstrated for the development of a molecular thermometer. The Eu(III) complex was composed of three anionic ligands (hfa: hexafluoroacetylacetonate) and a phosphine oxide derivative containing a chrysene framework (diphenylphosphorylchrysene (DPCO)). The chrysene framework induced a rigid coordination structure via intermolecular interactions, resulting in a high thermal stability (decomposition point: 280 °C). The Eu(III) complex also exhibited an extremely high molar absorption coefficient (490000 cm–1 M–1), high intrinsic emission quantum yields (73%), and temperature-dependent energy migration between ligands and Eu(III) ion. The characteristic energy migration system was explained by the presence of the LMCT state based on π–f orbital interactions.