The influence of the degree of π-conjugation in biaroylmethane ligands upon Eu3+ luminescence efficiency in corresponding neutral tris-complexes was investigated in depth. The data obtained by both steady-state and time-resolved luminescence measurements gave an inside into electronic energy transfer mechanisms in the abovementioned complexes. It was shown that extension of the π-system in the naphthalene moiety in comparison to the phenyl one lead to a substantial decrease of both the S1 and T1 energy of the corresponding symmetrical β-diketones, which, in turn, led to a decrease of the total quantum yield of respective Eu3+ complexes. The obtained results are of interest for the rational design of highly luminescent complexes with NIR-emitting lanthanides, as the resonant levels energies are low and can hardly be sensitized by common ligands.
