Theoretical study of crown ethers with incorporated azobenzene moiety.

A series of crown ethers containing the azobenzene moiety incorporated into crowns of various sizes [Cr(O(6))(,) Cr(O(7)) and Cr(O(8))] and their corresponding alkali metal cation (Li(+), Na(+), K(+), Rb(+)) complexes have been studied theoretically. The density functional theory (DFT) method was employed to elucidate the stereochemical structural natures and thermodynamic properties of all of the target molecules at the B3LYP/6-31 G(d) and LANL2DZ level for the cation Rb(+). The fully optimized geometries had real frequencies, thus indicating their minimum-energy status. In addition, the bond lengths between the metal cation and oxygen atoms, atomic torsion angles and thermodynamic energies for complexes were studied. Natural bond orbital (NBO) analysis was used to explore the origin of the internal forces and the intermolecular interactions for the metal complexes. The calculated results show that the most significant interaction is that between the lone pair electrons of electron-donating oxygens in the cis-forms of azobenzene crown ethers (cis-ACEs) and the LP (1-center valence antibond lone pair) orbitals of the alkali-metal cations (Li(+), Na(+), K(+) and Rb(+)). The electronic spectra for the cis-ACEs [cis-Cr(O(6)), cis-Cr(O(7)) and cis-Cr(O(8))] are obtained by the time-dependent density functional theory (TDDFT) at the B3LYP/6-31 G(d) level. The spectra of the cis-isomers show broad π → π (S(0) → S(2)) absorption bands at 310-340 nm but weaker n → π (S(0) → S(1)) bands at 480-490 nm. The calculated results are in good agreement with the experimental results.