1,10-phenanthroline is grafted to indium tin oxide (ITO) and titanium dioxide nanoparticle (TiO₂) semiconductors by electroreduction of 5-diazo-1,10-phenanthroline in 0.1 M H₂SO₄. The lower and upper potential limits (−0.20 and 0.15 V_SCE, respectively) were set to avoid reduction and oxidation of the 1,10-phenanthroline (phen) covalently grafted at C5 to the semiconductor. The resulting semiconductor-phen ligand (ITO-phen or TiO₂-phen) was air stable, and was bonded to Ru- or Ir- by reaction with cis-[Ru(bpy)₂(CH₃CN)₂]²⁺ (bpy = 2,2′-bipyridine) or cis-[Ir(ppy)₂(CH₃CN)₂]⁺ (ppy = ortho-C_phenyl metalated 2-phenylpyridine) in CH₂Cl₂ and THF solvent at 50 °C. Cyclic voltammetry, X-ray photoelectron spectroscopy, solid-state UV–vis, and inductively coupled plasma–mass spectrometry all confirmed that the chromophores SC-[(phen)Ru(bpy)₂]²⁺ and SC-[(phen)Ir(ppy)₂]⁺ (SC = ITO or TiO₂) formed in near quantitative yields by these reactions. The resulting photoanodes were active and relatively stable to photoelectrochemical oxidation of hydroquinone and triethylamine under neutral and basic conditions.

中文翻译：

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具有共价键的Ru和Ir聚吡啶基可见光生色团的光阳极的模块化结构

通过在0.1 MH ₂ SO _4中电还原5-重氮-1,10-菲咯啉将1,10-菲咯啉接枝到氧化铟锡（ITO）和二氧化钛纳米颗粒（TiO ₂）半导体上。设置电位上限和下限（分别为-0.20和0.15 V _SCE），以避免在C5共价接枝到半导体上的1,10-菲咯啉（phen）的还原和氧化。所得的半导体-phen配体（ITO-phen或TiO ₂ -phen）是空气稳定的，并通过与顺式[Ru（bpy）₂（CH ₃ CN）₂ ] ²⁺（ bpy = 2,2'-联吡啶）或顺式-[Ir（ppy）₂（CH ₃ CN）₂ ] ⁺（ppy =邻-C_苯基金属化的2-苯基吡啶）在CH ₂ Cl ₂和THF溶剂中，在50°C下。循环伏安法，X射线光电子能谱，固态紫外可见光谱和电感耦合等离子体质谱法都证实了发色团SC-[（phen）Ru（bpy）₂ ] ²⁺和SC-[（phen）Ir （ppy）₂ ] ⁺（SC = ITO或TiO ₂通过这些反应以接近定量的收率形成。所得的光阳极在中性和碱性条件下对氢醌和三乙胺的光电化学氧化具有活性且相对稳定。