Experimental and theorectial study of the photophysics and structures of europium cryptates incorporating 3,3′-bi-isoquinoline-2,2′-dioxide

A detailed photophysical study of [Eusubset of(biqO(2).2.2)(CF3SO3)](CF3SO3)(2)(CH3CNH2O)-C-.-H-. (Eusubset of1) and two other types of cryptates incorporating three 3,3'-biisoquinoline-2,2'-dioxide units has been performed. Structural crystallographic data of Eusubset of1, electronic structure calculations and theoretical models were used to obtain the intramolecular energy transfer rates and the appropriate set of rate equations, which was solved numerically. Quantum yields and decay lifetimes were obtained from these results and compared to the experimental data. The role of the ligand-to-metal charge transfer (LMCT) states was ascertained. A theoretical ligand field and intensity analysis was carried out and the results agree very well with the emission spectra. The molecular structures of the lanthanide cryptates were successfully modelled by the Y-III ion using the restricted Hartree-Fock (RHF) method, with the advantage of dealing with closed-shell systems. These molecular structures were used to explain the drastic differences in the photophysics of the three Eu-III cryptates.