The magnitude of [C-H...O] hydrogen bonding in molecular and supramolecular assemblies.
Ab initio calculations at the MP2/6-311++G** level on model systems (N-methylpyridinium complexes of dimethyl ether and dimethyl phosphate anion) provide quantitative measures of the large stabilization energies that arise from [C-H...O] contacts in charged systems. These attractive interactions control (i) the self-assembly of bipyridinium-based catenanes and rotaxanes in solution, (ii) the self-organization of left-handed Z-DNA with alternating [dC-dG] sequences in the solid state, and (iii) the binding of pyridinium derivatives with single- and double-stranded DNA. Slightly attractive interactions occur between the donor ether and phosphate moieties and a neutral pyridine molecule in the gas phase. Electrostatic potential and solvation calculations demonstrate that [C-H...O] interactions which involve a cationic [C-H] donor are dominated by electrostatic terms.
Raymo
F M
FM
Center for Supramolecular Science, Department of Chemistry, University of Miami, 1301 Memorial Drive, Coral Gables, Florida 33146-0431, USA.
Bartberger
M D
MD
Houk
K N
KN
Stoddart
J F
JF
D004247:DNA / Q000737:chemistry; D006860:Hydrogen Bonding; D046911:Macromolecular Substances; D008958:Models, Molecular; D009690:Nucleic Acid Conformation; D011726:Pyridinium Compounds / Q000737:chemistry*; D055672:Static Electricity
D046911:Macromolecular Substances; D011726:Pyridinium Compounds; D004247:DNA