  Engineering the electronic structure of organics through interface
manipulation, particularly the interface dipole and the barriers to charge
carrier injection, is of essential importance to improved organic devices. This
requires the meticulous fabrication of desired organic structures by precisely
controlling the interactions between molecules. The well-known principles of
organic coordination chemistry cannot be applied without proper consideration
of extra molecular hybridization, charge transer and dipole formation at the
interfaces. Here we identify the interplay between energy level alignment,
charge transfer, surface dipole and charge pillow effect and show how these
effects collectively determine the net force between adsorbed porphyrin 2H-TPP
on Cu(111). We show that the forces between supported porphyrins can be altered
by controlling the amount of charge transferred across the interface accurately
through the relative alignment of molecular electronic levels with respect to
the Shockley surface state of the metal substrate, and hence govern the
self-assembly of the molecules.
