The water-soluble tin(IV) tetrakis(2-N-hydroxyethyl-4-pyridinium)porphyrin 1 photocatalyst was synthesized in good yield and its structure determined by single crystal X-ray crystallography. Electrochemical measurements on tin(IV) porphyrin 1 reveal a range of complex redox processes that are highly dependent on the pH and electrode used. The cathodic processes at ca. -0.6 to -0.8 V were assigned to electrochemical processes on the pyridyl moiety following differential pulse voltammetry and spectroelectrochemical investigation into the electrochemical properties of tin(IV) porphyrin. Photocatalytic experiment on tin(IV) porphyrin 1 under anaerobic conditions using triethanolamine (TEAO) as a sacrifical donor reveal a phlorin species as the main product which rapidly disappears upon exposure to oxygen. These results suggest that tin(IV) porphyrin π-radical anion is perhaps not the species responsible for the apparent ability tin(IV) porphyrins to photocatalytically reduce various substrates, including water to hydrogen.

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A novel tetra-alkyne terminated tin(IV) porphyrin 3 was synthesized in good yields and characterized using NMR spectroscopy, high resolution mass spectrometry and X-ray crystallography, the latter revealing interactions with hexane molecules that stabilize the crystal structure of the tin(IV) porphyrin 3. It was then linked to a conductive fluorine-doped tin oxide (FTO) surfaces using Huisgen [3+2] click chemistry. The attachment of the tin(IV) porphyrin to the FTO surface 6 was characterized by X-ray photoelectron spectroscopy (XPS), indicating the presence of the 1,2,3-triazole unit. Electrochemical measurements of the tin(IV) porphyrin modified FTO surface 7 show that it is still electrochemically active with oxidation (Epa) and reduction peaks (Epc) for the ferricyanide redox couple observed at Epc and Epa of -0.144 and +0.568 V vs. Ag | AgCl respectively, representing a modest shift of ca . +/- 0.1–0.15 V, compared to unmodified FTO.

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