Two series of six beta-diketone, 2-(2,2,2-trifluoroethyl)-1-indone (TFI) containing a trifluorinated alkyl group and a rigid indone group, neodymium and ytterbium complexes, namely, [Ln(TFI)(3)L] [Ln=Nd; L= (H2O)(2) (1), hpy (2) and phen (3); Ln=Yb; L=(H2O)(2) (4), bpy (5) and phen (6); bpy=2,2-bipyridine, phen=1,10-phenanthroline], have been synthesized and isolated. X-ray crystallographic analysis reveals that complex 2 is mononuclear structure in which the central Nd3+ ion is eight-coordinated by six oxygen atoms furnished by three TFI ligands and two nitrogen atoms from ancillary ligand. PXRD analysis suggests that all complexes 1 and 4, 2 and 5, 3 and 6 are isomorphic, respectively The room-temperature PL spectra of complexes 1-6 show strong characteristic NIR luminescence of the corresponding Nd3+ and Yb3+ ions and the substitution of the solvent molecules by bidentate nitrogen ligands essentially enhance the NIR luminescence quantum yields and lifetimes of the complexes. (C) 2013 Elsevier B.V. All rights reserved.