Self-assembly of a Ru(II)-deuteroporphyrin lipoic acid derivative on Au(111) surfaces

The synthesis of a new carbonyl ruthenium(II) deuteroporphyrin-IX lipoic acid derivative (Ru(PLip)(CO)) (4) and its self-assembly on Au(111) surfaces were accomplished. Ru(PLip)(CO) 4 was prepared by reduction of the ester groups of carbonyl-ruthenium(II) deuteroporphyrindimethylester 1 and further esterification with D, L-alpha-lipoic acid 3. The self-assembly of Ru(PLip)(CO) 4 was confirmed by X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). The S2p XP spectrum of SAM formed by Ru(PLip)(CO) showed the S2p(3/2) peak at 162.4 eV which corresponds to thiolated species bounded to gold. The influence of the interaction of porphyrin moieties on SAM stability was studied. The reductive desorption voltammogram of Ru(PLip)(CO) 4 self-assembled on gold showed an intense reduction peak at -1.02 V while when pyridine was coordinated to the central ruthenium(II) the reductive desorption peak was shifted to -0.85 V. The capacity of the modified Ru(PLip)(CO) gold electrode to detect nitric oxide (NO) was investigated by cyclic voltammetry. An irreversible reduction peak which increased with time on NO exposure was registered at -0.69 V indicating NO coordination to ruthenium(II).