Judiciously designed phthalocyanines (Pcs), such as silicon-Pc bis(3,5-diphenyl)benzoate (1c), with axial substituents which prevent aggregation, can self-assemble to form ordered nanoporous films on electrode surfaces. In this paper, complementary techniques such as Scanning Kelvin Nanoprobe (SKN) microscopy, Atom Force Microscopy (AFM) and electrochemical measurements are used to demonstrate that films formed by silicon-Pc bis(3,5-diphenyl)benzoate allow size- and charge- selective transport of probe molecules through well-defined intermolecular cavities. In contrast, the analogs silicon-Pc bis(4-tert-butylbenzoate) (1a) and silicon-Pc bis(3-thienyl)acetate (1b) have different film morphologies when solvent-cast in the same manner and block the electrode surface. The role of the different axial substituents in orienting the molecules on the substrate is discussed.
Role of Axial Ligation in Gating the Reactivity of Dimethylplatinum(III) Diimine Radical Cations