Quenching of the luminescent excited state of Eu3+ ions by C-H high-vibrational modes was studied by deuteration of the encapsulating ligand and the solvent. Novel polydentate hemispherands providing nine donor atoms, which form overall neutral complexes with rare earth ions, were synthesized in nine steps, allowing the easy incorporation of deuterium atoms (11a-d . Eu3+). The introduction of tert-butyl groups at the aromatic rings of the ligand further increased the solubility of the complexes in organic solvents (29 . Eu3+ and 34 . Eu3+). Photophysical studies, viz., luminescence spectra and lifetime measurements, revealed that significant quenching of the Eu3+ excited state is induced by nearby C-K vibrational modes. Substitution of these quenching C-H modes for C-D bonds in the azacrown bridge leads to an enhancement of the luminescent lifetime by a factor of 1.5. C-H high-vibrational modes of the pendant arms which are at a larger distance to the Eu3+ ion than the azacrown bridge hydrogen atoms (determined from the MD calculations) are less efficient quenchers. The number of coordinating methanol molecules to 11a . Eu3+, 29 . Eu3+, and 34 . Eu3+ estimated by the "Horrocks equation" is 0.9, 1.2, and 1.9, respectively, as was predicted by MD calculations. Moreover, the experimental data show that quenching of the excited state of well-shielded Eu3+ ions by the C-H modes of the ligand is of the same order of magnitude as quenching by one O-H mode.