Several complexes and silica-based nanohybrids of rare-earth ions (Eu3+, Gd3+) have been synthesized from dimethyl 4-azidopyridine-2,6-dicarboxylate (4) following the Click chemistry approach. A complete spectroscopic study indicates that such compounds exhibit strong sensitization by the antenna effect from both UV and NIR excitations. The Gd3+-based materials show phosphorescence under ambient conditions, which originates from the lowest-energy intra-ligand triplets. Fine analysis of the NIR excitation spectra using time resolved photoluminescence spectroscopy (TRS) indicates that the spectral repartition of the triplet T1 state differs notably between the complexes and the NPs embedding the complexes. Moreover the dependence of Eu3+ luminescence vs. incident beam power in the NIR region diverges from pure quadratic dependence expected in the framework of the two-photon absorption process. The results are discussed considering the occurrence of a direct singlet-to-triplet optical absorption transition (S0[RIGHTWARDS ARROW]T1) upon NIR excitation.