Solid-phase synthesis and photoactivity of Ru-polypyridyl visible light chromophores bonded through carbon to semiconductor surfaces

Abstract

1,10-Phenanthroline (phen) was grafted to either indium tin oxide (ITO), fluorine-doped tin oxide (FTO), or titanium dioxide (TiO₂) semiconductors (SC's) by electrochemical reduction of 5-diazo-phen. The phen ligand is bonded to the semiconductor at C5, and it can be handled in air. The semiconductor-phen (SC-phen) complexes displace both CH₃CN ligands from either cis-[Ru(Mebipy)₂(CH₃CN)₂]²⁺ (Mebipy = 4,4′-methyl-2,2′-bipyridine), cis-[Ru(^tBubipy)₂(CH₃CN)₂]²⁺ (^tBubipy = 4,4′-tert-butyl-2,2′-bipyridine), or cis-[Ru(pheno)(bipy)(CH₃CN)₂]²⁺ (bipy = 2,2′-bipyridine; pheno = 1,10-phenanthroline-5,6-dione) dissolved in DCM/THF (4 h, 70 °C) to form the corresponding surface-bound SC-[(phen)Ru(bipyridyl)₂]²⁺ chromophores. The identities of the SC-[(phen)Ru(Mebipy)₂]²⁺, SC-[(phen)Ru(^tBubipy)₂]²⁺, and SC-[(phen)Ru(pheno)(bipy)]²⁺ (SC = ITO, FTO or TiO₂) chromophores were confirmed by X-ray photoelectron spectroscopy (XPS); inductively coupled plasma mass spectrometry (ICP-MS); UV-vis and reflectance infrared spectroscopies; and cyclic voltammetry (CV). The data were compared to analogous Ru-polypyridyl control compounds dissolved in solution. A facile ketone-amine condensation solid-phase synthesis reaction between SC-[(phen)Ru(pheno)(bipy)]²⁺ and [Ru(1,10-phenthroline-5,6-diamine)(bipy)₂]²⁺ in ethanol (80 °C, 1 h) formed the dinuclear, bound chromophore SC-[(phen)(bipy)Ru(tpphz)Ru(bipy)₂]⁴⁺ (tpphz = tetrapyrido[3,2-a:2′,3′-c:3′′,2′′-h:2′′′,3′′′-j]phenazine). Photoelectrochemical oxidation of hydroquinone and triethylamine under acidic, neutral, or basic conditions showed that the SC-chromophore photoanodes are active, and that TiO₂-[(phen)Ru(Mebipy)₂]²⁺ is the most active and stable under basic- and neutral conditions. The dinuclear chromophore SC-[(phen)(bipy)Ru(tpphz)Ru(bipy)₂]⁴⁺ was most active and stable under potentiostatic conditions in acid.