Abstract
From extraction experiments and $$ \gamma $$ -activity measurements, the extraction constant corresponding to the equilibrium $$ {\text{Eu}}^{ 3+ } \left( {\text{aq}} \right) + 3 {\text{A}}^{ - } \left( {\text{aq}} \right) + {\mathbf{1}}\left( {\text{nb}} \right) \Leftrightarrow {\mathbf{1}} \cdot {\text{Eu}}^{ 3+ } \left( {\text{nb}} \right) + 3 {\text{A}}^{ - } \left( {\text{nb}} \right) $$ taking place in the two-phase water–nitrobenzene system ( $$ {\text{A}}^{ - } = \text {CF}_{3} \text{SO}_{3}^{ - } $$ ; 1 = macrocyclic lactam receptor—see Scheme 1; aq = aqueous phase, nb = nitrobenzene phase) was evaluated as $$ { \log } K_{{{\text{ex}} }} ({\mathbf{1}} \cdot {\text{Eu}}^{ 3+ } ,{\text{ 3A}}^{ - } )\; = \; - 4. 9 \pm 0. 1 $$ . Further, the stability constant of the 1·Eu3+ cationic complex in nitrobenzene saturated with water was calculated for a temperature of 25 °C: $$ { \log } \beta_{{{\text{nb}} }} ({\mathbf{1}} \cdot {\text{Eu}}^{ 3+ } ) \; = \; 8. 2 \pm 0. 1 $$ . Finally, using DFT calculations, the most probable structure of the cationic complex species 1·Eu3+ was derived. In the resulting 1·Eu3+ complex, the “central” cation Eu3+ is bound by five bond interactions to two ethereal oxygen atoms and two carbonyl oxygens, as well as to one carbon atom of the corresponding benzene ring of the parent macrocyclic lactam receptor 1 via cation-π interaction.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have