Electronic properties of mono-substituted tetraferrocenyl porphyrins in solution and on a gold surface: assessment of the influencing factors for photoelectrochemical applications.

Two unsymmetric meso-tetraferrocenyl-containing porphyrins of general formula Fc3 (FcCOR)Por (Fc=ferrocenyl, R=CH3 or (CH2)5 Br, Por=porphyrin) were prepared and characterized by a variety of spectroscopic methods, whereas their redox properties were investigated using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) approaches. The mixed-valence [Fc3 (FcCOR)Por](n+) (n=1,3) were investigated using spectroelectrochemical as well as chemical oxidation methods and corroborated with density functional theory (DFT) calculations. Inter-valence charge-transfer (IVCT) transitions in [Fc3 (FcCOR)Por](+) were analyzed, and the resulting data matched closely previously reported complexes and were assigned as Robin-Day class II mixed-valence compounds. Self-assembled monolayers (SAMs) of a thioacetyl derivative (Fc3 (FcCO(CH2)5 SCOCH3 )Por) were also prepared and characterized. Photoelectrochemical properties of SAMs in different electrolyte systems were investigated by electrochemical techniques and photocurrent generation experiments, showing that the choice of electrolyte is critical for efficiency of redox-active SAMs.