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Abstract— Excited state emission and absorption decay measurements have been made on the cage‐type cryptate complexes [M bpy.bpy.bpy]n+, where Mn+= Na+, La3+, Eu3+, Gd3+ or Tb3+ and [bpy.bpy.bpy] is a tris‐bipyridine macrobicyclic cryptand. Excitation has been performed in the high intensity 1π‐π* cryptand band with maximum at about 300 nm. Experiments have been carried out in H2O or D2O solutions and at 300 and 77 K to evaluate the rate constants of radiative and nonradiative decay processes. For Mn+= Na+, La3+ and Gd3+ the lowest excited state of the cryptate is a 3ππ* level of the cryptand which decays in the microsecond time scale at room temperature in H2O solution and in the second‐millisecond time scale at 77 K in MeOH‐EtOH. For Mn+= Eu3+, the lowest excited state is the luminescent 5D0 Eu3+ level which in H2O solution is populated with 10% efficiency and decays to the ground state with rate constants 2.9 × 103 s_1 at room temperature and 1.2 × 103 s−′ at 77 K. The relatively low efficiency of 5D0 population upon 1ππ* excitation is attributed to the presence of a ligand‐to‐metal charge transfer level through which 1ππ* decays directly to the ground state. For Mn+= Tb3+ the lowest excited state is the luminescent 5D4 Tb3+ level. The process of 5D4 population upon 1ππ* excitation is ˜100% efficient, but at room temperature it is followed by a high‐efficiency, activated back energy transfer from the 5D4 Tb3+ level to the 3ππ* ligand level because of the relatively small energy gap between the two levels (1200 cm_1) and the intrinsically long lifetime of 5D4. At 77 K back energy transfer cannot take place and the 5D4 Tb3* level deactivates to the ground state with rate constant 5.9 × 102 s‐′ (H2O solution). The relevance of these results toward the optimization of Eu3+ and Tb3+ cryptates as luminescent probes is discussed.

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