Characteristic stacked structures and luminescent properties of dinuclear lanthanide complexes with pyrene units

A novel design strategy of stacked organic fluorophores using dinuclear lanthanide (Ln(III)) complexes is demonstrated for the formation of excimer. The dinuclear Ln(III) complexes are composed of two Ln(III) (Eu(III) or Gd(III)) ions, six hexafluoroacetylacetonate (hfa), and two pyrene-based phosphine oxide ligands. Single-crystal analysis revealed a rigid pyrene-stacked structure via CH-F (pyrene/hfa) intramolecular interactions. The rigid aggregation structures of the two-typed organic ligands around Ln(III) resulted in high thermal stability (decomposition temperature: 340°C). The aggregated ligands exhibited excimer-type green emission from the stacked pyrene-center. The change in the Ln(III) ion promotes effective shifts of excimer emissions (Gd(III):500 nm, Eu(III):490 nm). The organic aggregation system using red-luminescent Eu(III) also provides temperature-sensitive ratiometric emission composed of π-π* and 4f-4f transitions by energy migration between aggregated ligands and Eu(III).