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Ruthenium complexes containing the pentapyridyl ligand 6,6′′-(methoxy(pyridin-2-yl)methylene)di-2,2′-bipyridine (L-OMe) of general formula trans-[RuII(X)(L-OMe-κ-N5)]n+ (X=Cl, n=1, trans-1+; X=H2O, n=2, trans-22+) have been isolated and characterized in solution (by NMR and UV/Vis spectroscopy) and in the solid state by XRD. Both complexes undergo a series of substitution reactions at oxidation state RuII and RuIII when dissolved in aqueous triflic acid–trifluoroethanol solutions as monitored by UV/Vis spectroscopy, and the corresponding rate constants were determined. In particular, aqueous solutions of the RuIII-Cl complex trans-[RuIII(Cl)(L-OMe-κ-N5)]2+ (trans-12+) generates a family of Ru aquo complexes, namely trans-[RuIII(H2O)(L-OMe-κ-N5)]3+ (trans-23+), [RuIII(H2O)2(L-OMe-κ-N4)]3+ (trans-33+), and [RuIII(Cl)(H2O)(L-OMe-κ-N4)]2+ (trans-42+). Although complex trans-42+ is a powerful water oxidation catalyst, complex trans-23+ has only a moderate activity and trans-33+ shows no activity. A parallel study with related complexes containing the methyl-substituted ligand 6,6′′-(1-pyridin-2-yl)ethane-1,1-diyl)di-2,2′-bipyridine (L-Me) was carried out. The behavior of all of these catalysts has been rationalized based on substitution kinetics, oxygen evolution kinetics, electrochemical properties, and density functional theory calculations. The best catalyst, trans-42+, reaches turnover frequencies of 0.71 s−1 using CeIV as a sacrificial oxidant, with oxidative efficiencies above 95 %.

We explore the potential of various hydroquinone/quinone redox couples as electron relays in a homogenous water reduction system between a Re-based photosensitizer and a sacrificial electron donor [tris-(2-carboxyethyl)-phosphine, TCEP]. By using transient IR spectroscopy, flash photolysis as well as stopped-flow techniques covering timescales from picoseconds to 100 ms, we determine quenching rates and cage escape yields, the kinetics of the follow-up chemistry of the semiquinone, the recombination rates, as well as the re-reduction rates by TCEP. The overall quantum yield of hydrogen production is low, and we show that the limiting factors are the small cage escape yields and, more importantly, the slow regeneration rate by TCEP in comparison to the undesired charge recombination with the reduced water reduction catalyst.

Complexes with purely pyridine-based macrocycles are rarely studied in photo(electro)catalysis. We synthesized and investigated macrocycles, in which two 2,2'-bipyridine (bpy) units are linked twice by two cyano-methylene groups, to yield the basic tetradentate, bipyridine based ligand framework (pyr). The protons in the bridges were substituted to obtain derivatives with one (pyr-alk) or two (pyr-alk2) alkyl-chains, respectively. We present the crystal structures of the mono-pentylated and the cis-dibutylated ligands. The corresponding Co(II) complexes [Co(II)(OH2)2(pyr)], [Co(II)Br(HOMe)(pyr-bu)], [Co(II)Br2(cis-pyr-bu2)] and [Co(II)Br2(trans-pyr-bu2)] were prepared, their physico-chemical properties elucidated and their crystal structures determined. X-ray analyses revealed for the latter three complexes distorted octahedral coordination and a fairly planar {Co(II)(pyr)} macrocyclic scaffold. The axial bromides in [Co(II)Br(HOMe)(pyr-bu)], [Co(II)Br2(cis-pyr-bu2)] and [Co(II)Br2(trans-pyr-bu2)] are weakly bound and dissociate upon dissolution in water. While the alkylated complexes are paramagnetic and feature Co(II) d(7) high spin configurations, the unsubstituted complex [Co(II)(OH2)2(pyr)] displays a rare Co(II) low spin configuration. The electronic ground states of [Co(II)Br2(cis-pyr-bu2)] and [Co(II)Br2(trans-pyr-bu2)] are similar, as evident from the almost identical UV/vis spectra. Electrochemical analyses show redox-non-innocent ligand frameworks. All complexes are highly robust and efficient H(+) reducing catalysts. In the presence of [Ru(bpy)3]Cl2 as a photosensitizer and TCEP/NaHasc as a sacrificial electron donor and shuttle, turnover numbers (TONs, H2/Co) up to 22 000 were achieved.

The synthesis of the two penta-pyridyl type ligands pyridine-2,6-diylbis(dipyridin-2-ylmethanol) (PPy, 1) and bis-2,2''-bipyridine-6-yl(pyridine-2-yl)methanol (aPPy, 2) is described. Both ligands coordinate rapidly to the 3d element cations Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II), thereby yielding complexes of the general composition [MBr(1)](+) and [MBr(2)](+), respectively. Further, the X-ray structures of selected complexes with ligands 1 and 2 are described. They show metal center dependent structural features and complexes with 2 exhibiting distinctly distorted octahedral geometries. Moreover, photocatalytic water reduction with [Co(II)Br(PPy)]Br (1c) and [Co(II)Br(aPPy)]Br (2c) as water reducing catalysts (WRC) was investigated. Both complexes showed catalytic activity in water when in presence of ascorbic acid as sacrificial electron donor and [Re(py)(bpy)(CO)3](+) (3) as photosensitizer (PS). Turnover numbers, TONs (H2/Co), up to 11,000 were achieved. Complex 2c was more active than 1c, whereas none of the other complexes showed any activity.

Non-covalent binding of water reduction catalysts and photosensitizers to hydrophobic silica particles represents a general approach for heterogenizing molecular water splitting components., Heterogeneous photocatalytic hydrogen production with a non-covalently immobilized molecular ruthenium based photosensitizer (PS) and a cobalt polypyridyl based water reducing catalyst (WRC) is reported. PS and WRC were derivatized with C18-alkyl chains and immobilized by adsorption on hydrophobic fumed silica. The resulting loaded support was suspended in water with anionic or cationic surfactants and subjected to heterogeneous photocatalytic H2 production with ascorbate as sacrificial electron donor (SED). No leaching was observed under catalytic conditions, thus catalysis was truly heterogeneous. The catalytic performance of immobilized PS and WRC clearly exceeded that of homogeneous catalysis at low concentrations. At high concentration, diffusion and light limitation lead to lower reaction rates, but the same stability as for homogeneous reactions was still achieved. WRC concentration variations indicated a relatively high stability (up to 1300 H2/Co) and mobility of amphiphilic catalysts on the hydrophobic silica surface. Comparison of fumed silica with porous and non-porous silica showed, that a high BET surface area along with a good accessibility from the reaction media are crucial for catalytic performance. Mechanistic investigations by transient absorption spectroscopy displayed reductive quenching of excited PS by ascorbate followed by on particle electron transfer to WRC as reaction pathway. Particles with additional cationic surfactants exhibited a significantly higher catalytic performance as compared to anionic surfactants. Non-covalent anchoring of correspondingly derivatized WRCs or PSs to reversed-phase silica offers a rapid and versatile transition from homogeneous to heterogeneous molecular proton reduction.

The mechanism of photocatalytic hydrogen production was studied with a three-component system consisting of fac-[Re(py)(CO)3bipy](+) (py = pyridine, bipy = 2,2'-bipyridine) as photosensitizer, [Co(TPY-OH)(OH2)](2+) (TPY-OH = 2-bis(2-pyridyl)(hydroxy)methyl-6-pyridylpyridine), a polypyridyl-based cobalt complex, as water reduction catalyst (WRC), and triethanolamine (TEOA) as sacrificial electron donor in aqueous solution. A detailed mechanistic picture is provided, which covers all processes from excited state quenching on the time scale of a few nanoseconds to hydrogen release taking place between seconds and minutes at moderately basic reaction conditions. Altogether these processes span 9 orders of magnitude in time. The following reaction sequence was found to be the dominant pathway for hydrogen generation: After reductive quenching by TEOA, the reduced photosensitizer (PS) transfers an electron to the Co(II)-WRC. Protonation of Co(I) yields Co(III)H which is reduced in the presence of excess Co(I). Co(II)H releases hydrogen after a second protonation step, which is detected time-resolved by a clark-type hydrogen electrode. Aside from these productive steps, the role of side and back reactions involving TEOA-derived species is assessed, which is particularly relevant in laser flash photolysis measurements with significantly larger transient concentrations of reactive species as compared to continuous photolysis experiments. Most notable is an equilibrium reaction involving Co(I), which is explained by a nucleophilic addition of Co(I) to the oxidation product of TEOA, an electrophilic iminium ion. Quantum chemical calculations indicate that the reaction is energetically feasible. The calculated spectra of the adduct are consistent with the spectroscopic observations.

Ascorbate acts as a reversible electron shuttle between tris(2-carboxyethyl) phosphine (TCEP) and Re(I) or Ru(II) photosensitizers. Oxidized ascorbate is recycled up to 50 times by the TCEP → TCEP[double bond, length as m-dash]O redox process which enables 30 000 TONs per WRC in photocatalytic hydrogen production, thus exceeding the performance with pure ascorbate by far.

Synthesis, characterization and activity in homogeneous photocatalytic hydrogen production of a cobalt polypyridyl complex are reported. TONs up to 9000 H(2)/Co could be achieved. Immobilization of the complex on a swellable resin yielded a recyclable heterogeneous catalyst.