Transfer of Cl Ligands between Adsorbed Iron Tetraphenylporphyrin Molecules

Iron tetraphenylporphyrin chloride (FeTPPCl) adsorbed on a Au(111) substrate is investigated using low-temperature scanning tunneling microscopy. Cl is controllably transferred between the Fe center of a selected molecule and the tip of the microscope without disrupting the surrounding molecular pattern. Cl abstraction from FeTPPCl is triggered by removing an electron from the highest occupied molecular orbital. Density functional calculations suggest that the reaction involves a change in the oxidation state of the Fe ion.