Journal of Physical Chemistry, Vol.99, No.49, 17497-17500, 1995
Application of the Parity Rule of Through-Bond Coupling to the Design of Superbridges That Exhibit Greatly Enhanced Electronic Coupling
A treatment based on the parity rule of through-bond (TB) coupling is described which provides qualitative insight into the origin of interference effects in TB coupling through multistrand saturated hydrocarbon bridges. We demonstrate how the parity rule may be used to modify bridges in which TB coupling is enhanced by as much as 2 orders of magnitude. For example, HF/3-21G calculations on dienes constructed with these "superbridges" give a pi+,pi-splitting energy of 0.2 eV for the 14- and 15-bond systems in which the double bonds are 17 Angstrom apart.