Ru(iii)- and Rh(iii)-cyclam macrocyclic complexes as selective oxygen electroreduction catalysts: no ligand μ-bonds or complex heating treatments are needed.

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The interaction of the 4,5-bis(diphenylthiophosphinoyl)-1,2,3-triazolate (SPTz −) with different gold surfaces was investigated (nanoparticles, an electrode, and flat sheets). Studies on binding affinity of this dithiophosphin-triazolate on a gold electrode were performed by cyclic voltammetry (CV). Voltammograms exhibit two reductive desorption and only one oxidative readsorption, indicating that once reabsorbed, the molecule achieves a unique conformation. The morphology and average size of modified gold nanoparticles were studied by transmission electron microscopy (TEM) (av. diameter of 5.9 ± 1.8 nm). Further characterization was made by UV-visible (UV-vis) spectroscopy showing surface plasmon resonance (SPR) at about 580 nm. The bonding configurations of SPTz − on gold have also been investigated by comparing the FT-IR and FT-Raman spectra. The 31 P{ 1 H} NMR spectrum of capped nanoparticles exhibited two sharp signals at 30.3 and 29.6 ppm and a very broad signal at 72.7 ppm. X-ray photoelectron spectroscopy (XPS) showed SPTz − can accomplish a strong interaction with gold nanoparticles through bonds involving a sulfur atom and a nitrogen from the triazole ring with a free terminal PS group, forming self-assembled monolayers (SAM). This may allow subsequent functionalization through free S/N atoms of the formed SAMs. The SPTz − packing led to a reduction in packing density that permits large spaces between adsorbed headgroups and the inclusion of carbon and oxygen impurities from small molecules; nevertheless, oxidized sulfur or nitrogen species were not detected, indicating the chemical stability of the obtained SAMs.