Near-infrared luminescence of Nd3+ and Yb3+ complexes using a polyfluorinated pyrene-based β-diketonate ligand

A new polyfluorinated beta-diketonate ligand containing a pyrene chromophore, namely, 4,4,5,5,6,6,6-heptafluoro-3-hydroxy-1-(pyren-1-yl)hex-2-en-1-one (Hhfpyr) has been designed and employed for the development of a series of near-infrared (NIR) emitting lanthanide complexes (Nd3+ and Yb3+) in the absence and presence of an ancillary ligand, 4,7-diphenyl-1,10-phenanthroline (bath). The isolated NIR-emitting lanthanide complexes [Nd(hfpyr)(3)(H2O)(1), Nd(hfpyr)(3)(bath)(2), Yb(hfpyr)(3)(H2O)(3) and Yb(hfpyr) 3(bath) 4] have been characterized by various spectroscopic techniques and evaluated their photoluminescence properties. The photophysical properties disclosed that the developed pyrene-based b-diketonate ligand is well suited for the sensitization of Nd3+ as well as Yb3+ emissions, thanks to the favourable position of the triplet state (T-1) of the ligand (Delta E = T-1-F-4(3/2) = 4700 cm (1) for Nd3+ and Delta E = T-1-F-2(5/2) = 6200 cm(-1) for Nd3+), as evidenced from the phosphorescence spectra of the corresponding Gd3+ complexes. Most importantly, the displacement of solvent molecules from the coordination sphere of the NIR emitting lanthanide binary complexes (1 and 3) with an ancillary ligand markedly enhances the quantum yields (Phi(overall) = 0.45 for 1 to 1.07% for 2 and from 1.69 for 3 to 3.08% for 4) and excited state lifetime values (tau = 2.80 for 1 to 6.16 mu s for 2 and from 6.88 for 3 to 13.45 mu s for 4). Notably, Yb3+ ternary compound 4 with promising NIR luminescence properties was embedded into PMMA matrices, giving rise to a series of PMMA-supported hybrid materials (PMMA@4), where the thermal stability and the film-forming properties were significantly enhanced.