Terpyridyl-Imidazole Based Ligand Coordinated to Ln(Hexafluoroacetyl acetonate)₃ Core: Synthesis, Structural Characterization, Luminescence Properties, and Thermosensing Behaviors in Solution and PMMA Film

Abstract

A new array of ternary lanthanide complexes of the form [Ln(hfa)3(tpy-HImzphen)] have been synthesized and thoroughly characterized wherein Ln = LaIII (1), EuIII (2), SmIII (3), and TbIII (4); hfa = hexafluoroacetylacetonate; and tpy-HImzphen = 2-(4-[2,2′:6′,2″]terpyridin-4′-yl-phenyl)-1H-phenanthro[9,10-d]imidazole. Incorporation of tpy-HImzphen onto the Ln-hfa moiety induced a bathochromic shift of the absorption window of the complexes into the visible region. Extensive investigations of the luminescence characteristics have been conducted both at RT and at 77 K to understand the deactivation pathways of the complexes. Both steady-state and time-resolved emission spectral behaviors indicate four distinctive behaviors upon incorporation of tpy-HImzphen onto the lanthanide core, viz., a huge red-shift of the ligand-centered peak for LaIII; almost complete energy transfer for EuIII; very little energy transfer for SmIII, while reverse energy transfer in the case of TbIII. In addition, the EuIII-complex exhibits its excellence in luminescence thermometry in the solution state as well as in poly(methyl methacrylate) (PMMA) thin films. The thermosensitive luminescence response in solution was further utilized to mimic set–reset flip-flop logic operation. A plausible energy transfer scheme has been devised to explain dissimilar luminescence behaviors in the complexes. The role of LMCT was also considered for the observed thermosensing property of the Eu(III) complex.