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An unusual thermally sensitive anion-cation interaction, which is characteristic of the anion [Eu(FOD)4 ]- , occurs in the complex [CHOL][Eu(FOD)4 ] (1; CHOL=choline; FOD=1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedionate) and affects both quantum yield and thermochromic behavior. This prompted the design of an Eu3+ -based ratiometric thermometer that functions at temperatures up to 95 °C through a thermally excited state absorption of the Eu3+ ion. The reusable temperature-sensitive luminescent complex showed a range of relative