title: The effect of multiple substituents on sandwich and T-shaped pi-pi interactions.
abstract: Sandwich and T-shaped configurations of substituted benzene dimers were studied by second-order perturbation theory to determine how substituents tune pi-pi interactions. Remarkably, multiple substituents have an additive effect on the binding energy of sandwich dimers, except in some cases when substituents are aligned on top of each other. The energetics of substituted T-shaped configurations are more complex, but nevertheless a simple model that accounts for electrostatic and dispersion interactions (and direct contacts between substituents on one ring and hydrogen atoms on the other), provides a good match to the quantum mechanical results. These results provide insight into the manner by which substituents csan be utilized in supramolecular design.
authors.affiliation: Center for Computational Molecular Science and Technology, School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia, 30332-0400, USA.
authors.forename: Ashley L
authors.initials: AL
authors.lastname: Ringer
authors.forename: Mutasem O
authors.initials: MO
authors.lastname: Sinnokrot
authors.forename: Ryan P
authors.initials: RP
authors.lastname: Lively
authors.forename: C David
authors.initials: CD
authors.lastname: Sherrill
mesh_terms: D001554:Benzene / Q000737:chemistry*; D002627:Chemistry, Physical / Q000379:methods; D019281:Dimerization; D008956:Models, Chemical; D008968:Molecular Conformation
chemical_list: D001554:Benzene