The effect of multiple substituents on sandwich and T-shaped pi-pi interactions.
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.
Ringer
Ashley L
AL
Center for Computational Molecular Science and Technology, School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia, 30332-0400, USA.
Sinnokrot
Mutasem O
MO
Lively
Ryan P
RP
Sherrill
C David
CD
D001554:Benzene / Q000737:chemistry*; D002627:Chemistry, Physical / Q000379:methods; D019281:Dimerization; D008956:Models, Chemical; D008968:Molecular Conformation
D001554:Benzene