Density functional theory study on the "Molecular Taekwondo" process of pyrene-armed calix[4]azacrowns

作者：Li, Ling; Li, Mi; Wang, Xueye^*; Wang, Qin

来源：Computational and Theoretical Chemistry, 2014, 1031: 40-49.

DOI：10.1016/j.comptc.2013.12.028

• Calix[4]azacrowns
• Density functional theory (DFT)
• Frontier orbital analysis
• Natural bond orbitals (NBO)
• Time-dependent density functional theory (TD-DFT)

New calixarene derivatives pyrene-armed calix[4]azacrowns L (L-1 and L-2) bearing a crown ether and an azacrown ether as two binding sites are calculated systemically using density functional theory (DFT). The optimized structures and electronic properties, such as HOMO and LUMO energies, band gaps of the free ligands L (L-1 and L-2), the complexes L/M+ (Ag+, K+ and Cs+) and the di-cation complexes L center dot Ag+center dot M+ have been performed at B3LYP/6-31G(d) and Lanl2DZ level. Natural bond orbital (NBO) analysis is discussed on the basic of the optimized geometric structures. The results demonstrate that metal-it and metal-metal ion repulsive interactions are main driving forces of the coordination and the influence of the solvent effect is significant. Moreover, the interesting "Molecular Taekwondo" processes evolving between Ag+-K+ and Ag+-Cs+ pairs have been studied through the fluorescence change. Time-dependent density functional theory (TD-DFT) calculations on the emission spectra of the ligand L-1 and compounds L-1/M+ are investigated and discussed, which further evidences the existence of the metal ion exchange process.

• 出版日期2014-3-1
• 单位厦门大学; 湘潭大学