The reaction between the TTF-fused dipyrido[3,2-a:2',3'-c]phenazine (dppz) ligand (L) and 1 equiv of Ln(hfac)(3)center dot 2H(2)O (hfac(-) = 1,1,1,5,5,5-hexafluoroacetyacetonate) or 1 equiv of Ln(tta)(3)center dot 2H(2)O (tta(-) = 2-thenoyltrifluoroacetonate) (Ln(III) = Dy-III or Yb-III) metallic precursors leads to four mononuclear complexes of formula [Ln(hfac)(3)(L)]center dot C6H14 (Ln(III) = Dy-III (1), Yb-III (2)) and [Ln(tta)(3)(L)]center dot C6H14 (Ln(III) = Dy-III (3), Yb-III (4)), respectively. Their X-ray structures reveal that the Ln(III) ion is coordinated to the bischelating nitrogenated coordination site and adopts a D4d coordination environment. The dynamic magnetic measurements show a slow relaxation of the Dy-III magnetization for 1 and 3 with parameters highlighting a slower relaxation for 3 than for 1 (t0 = 4.14(+/- 1.36) x 10(-6) and 1.32(+/- 0.07) x 10(-6) s with Delta = 39(+/- 3) and 63.7(+/- 0.7) K). This behavior as well as the orientation of the associated magnetic anisotropy axes have been rationalized on the basis of both crystal field splitting parameters and ab initio SA-CASSCF/RASSI-SO calculations. Irradiation of the lowest-energy HOMO -> LUMO ILCT absorption band induces a (2)F-5/2 ->(2)F(7/)2 Yb-centered emission for 2 and 4. For these Yb-III compounds, Stevens operators method has been used to fit the thermal variation of the magnetic susceptibilities, and the resulting MJ splittings have been correlated with the emission lines.