title: Interactions in pseudorotoxanes based on crown ether-secondary ammonium motifs. A theoretical study.
abstract: A theoretical analysis of the nature of the interactions in dibenzo[24]crown-8 (DB24C8)-n-dibutylammonium (DBM)--pseudorotaxane complex at the MP2 and DFT levels shows that the main contribution to the binding energy is the electrostatic interaction with moderate (20-25%) correlation stabilization. The total binding energy in the DB24C8-DBM complex represents a sum of the binding energies of two NH-O and one CH-O hydrogen bonds and the latter constitutes about 25% of the total interaction energy, giving the total binding energy of -41.2 kcal mol(-1) at the BHandHLYP/6-311 + + G** level. Deprotonation of the DB24C8-DBM complex reduces the binding energy by some 50 kcal mol(-1), giving metastable complexes DB24C8-DBA-1 or DB24C8-DBA-2, which will dissociate to give free crown ether and n-dibutylamine because of the strong exchange repulsion that prevails in neutral complexes.
authors.affiliation: Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Apartado Postal 70-360, CU, Coyoacán, 04510, México, México.
authors.forename: Carlos
authors.initials: C
authors.lastname: Ramero
authors.forename: Patricia
authors.initials: P
authors.lastname: Guadarrama
authors.forename: Serguei
authors.initials: S
authors.lastname: Fomine
mesh_terms: D043844:Crown Ethers / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D000644:Quaternary Ammonium Compounds / Q000737:chemistry*; D043862:Rotaxanes / Q000737:chemistry*
chemical_list: D043844:Crown Ethers; D000644:Quaternary Ammonium Compounds; D043862:Rotaxanes