We report the use of a nickel-thiolate hexameric cluster, Ni6(SC2H4Ph)12, for photocatalytic hydrogen production from water. The nickel cluster was synthesized ex-situ and characterized by various techniques. Single crystal X-ray analysis, (1)H NMR, 2D COSY, ESI-MS, UV-visible spectroscopy, and TGA provided insight into the structure and confirmed the purity and stability of the cluster. Cyclic voltammetry helped confirm hydrogen evolution reaction (HER) activity of this catalyst. Photoreactions carried out using an iridium photosensitizer, Ir(F-mppy)2(dtbbpy)[PF6], and TEA as the sacrificial reductant revealed the high activity of the Ni6 cluster as a water reducing catalyst. High TONs (3750) and TOFs (970 h(-1)) were obtained at optimum catalyst concentration (0.025 mM), with low concentrations of catalyst yielding up to 30,000 turnovers. Quenching studies, along with the evidence obtained from the electrochemical analysis, showed that this water reduction system proceeds through a reductive quenching mechanism. Mercury poisoning studies confirmed that no active, metallic colloids were formed during the photocatalytic reaction.

The relatively unexplored luminophore architecture [Ir(N^N^N)(C^N)L](+) (N^N^N = tridentate polypyridyl ligand, C^N = 2-phenylpyridine derivative, and L = monodentate anionic ligand) offers the stability of tridentate polypyridyl coordination along with the tunability of three independently variable ligands. Here, a new family of these luminophores has been prepared based on the previously reported compound [Ir(tpy)(ppy)Cl](+) (tpy = 2,2':6',2″-terpyridine and ppy = 2-phenylpyridine). Complexes are obtained as single stereoisomers, and ligand geometry is unambiguously assigned via X-ray crystallography. Electrochemical analysis of the materials reveals facile HOMO modulation through ppy functionalization and alteration of the monodentate ligand's field strength. Emission reflects similar modulation shifting from orange to greenish-blue upon replacement of chloride with cyanide. Many of the new compounds exhibit impressive room temperature phosphorescence with lifetimes near 3 μs and quantum yields reaching 28.6%. Application of the new luminophores as photosensitizers for photocatalytic hydrogen generation reveals that their photostability in coordinating solvent is enhanced as compared to popular [Ir(ppy)2(bpy)](+) (bpy = 2,2'-bipyridine) photosensitizers. Yet, the binding of their monodentate ligand emerges as a source of instability during the redox processes of cyclic voltammetry and mass spectrometry. DFT modeling of electronic structure is provided for all compounds to elucidate experimental properties.

In the evaluation of systems designed for catalytic water oxidation, ceric ammonium nitrate (CAN) is often used as a sacrificial electron acceptor. One of the sources of failure for such systems is oxidative decay of the catalyst in the presence of the strong oxidant CAN (E ox = +1.71 V). Little progress has been made in understanding the circumstances behind this decay. In this study we show that a 2-(2′hydroxphenyl) derivative (LH) of 1,10-phenanthroline (phen) in the complex [Ru(L)(tpy)] + (tpy = 2,2′;6′,2″-terpyridine) can be oxidized by CAN to a 2-carboxy-phen while still bound to the metal. This complex is, in fact, a very active water oxidation catalyst. The incorporation of a methyl substituent on the phenol ring of LH slows down the oxidative decay and consequently slows down the catalytic oxidation. An analogous system based on bpy (2,2′-bipyridine) instead of phen shows much lower activity under the same conditions. Water molecule association to the Ru center of [Ru(L)(tpy)] + and carboxylate donor dissociation were proposed to occur at the trivalent state. The resulting [Ru III −OH 2 ] was further oxidized to [Ru IV O] via a PCET process.

Chemiluminescent iridium-based sensors which demonstrate oxygen dependent responses have been developed. The molecular probes, named IrCL-1, IrCL-2 and IrCL-3 consist of oxygen-sensitive iridium complexes attached to a spiroadamantane 1,2 dioxetane and operate via energy transfer from the chemiexcited benzoate to the corresponding iridium(III) complex. Complexing the iridium-(III) center with π-extended ligands results in emission in the biologically relevant, near-infrared (NIR) region. All probes demonstrate varying oxygen tolerance, with IrCL-1 being the most oxygen sensitive. These probes have been further utilized for in vitro ratiometric imaging of oxygen, as well as for intraperitoneal, intramuscular and intratumoral imaging in live mice. To our knowledge, these are the first iridiumbased chemiluminescent probes that have been employed for in vitro ratiometric oxygen sensing, and for in vivo tumor imaging.

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