Mirco Natali

Photocatalytic water oxidation: tuning light-induced electron transfer by molecular Co4O4 cores.

Isostructural cubane-shaped catalysts [Co(III)(4)(μ-O)(4)(μ-CH(3)COO)(4)(p-NC(5)H(4)X)(4)], 1-X (X = H, Me, t-Bu, OMe, Br, COOMe, CN), enable water oxidation under dark and illuminated conditions, where the primary step of photoinduced electron transfer obeys to Hammett linear free energy relationship behavior. Ligand design and catalyst optimization are instrumental for sustained O(2) productivity with quantum efficiency up to 80% at λ > 400 nm, thus opening a new perspective for in vitro molecular photosynthesis.

Photocatalytic Water Oxidation by a Mixed‐Valent MnIII3MnIVO3 Manganese Oxo Core that Mimics the Natural Oxygen‐Evolving Center

The functional core of oxygenic photosynthesis is in charge of catalytic water oxidation by a multi-redox Mn(III)/Mn(IV) manifold that evolves through five electronic states (S(i), where i=0-4). The synthetic model system of this catalytic cycle and of its S0→S4 intermediates is the expected turning point for artificial photosynthesis. The tetramanganese-substituted tungstosilicate [Mn(III)3Mn(IV)O3(CH3COO)3(A-α-SiW9O34)](6-)(Mn4POM) offers an unprecedented mimicry of the natural system in its reduced S0 state; it features a hybrid organic-inorganic coordination sphere and is anchored on a polyoxotungstate. Evidence for its photosynthetic properties when combined with [Ru(bpy)3](2+) and S2O8(2-) is obtained by nanosecond laser flash photolysis; its S0→S1 transition within milliseconds and multiple-hole-accumulating properties were studied. Photocatalytic oxygen evolution is achieved in a buffered medium (pH 5) with a quantum efficiency of 1.7%.

Is [Co4(H2O)2(α-PW9O34)2]10− a genuine molecular catalyst in photochemical water oxidation? Answers from time-resolved hole scavenging experiments

Water oxidation catalysts: evolution of [Co(4)(H(2)O)(2)(α-PW(9)O(34))(2)](10-) to catalytically active species is assessed by laser flash photolysis in sacrificial photocatalytic cycles with Ru(bpy)(3)(2+) as a photosensitizer.

Photoinduced Water Oxidation by a Tetraruthenium Polyoxometalate Catalyst: Ion-pairing and Primary Processes with Ru(bpy)32+ Photosensitizer

The tetraruthenium polyoxometalate [Ru(4)(μ-O)(4)(μ-OH)(2)(H(2)O)(4)(γ-SiW(10)O(36))(2)](10-) (1) behaves as a very efficient water oxidation catalyst in photocatalytic cycles using Ru(bpy)(3)(2+) as sensitizer and persulfate as sacrificial oxidant. Two interrelated issues relevant to this behavior have been examined in detail: (i) the effects of ion pairing between the polyanionic catalyst and the cationic Ru(bpy)(3)(2+) sensitizer, and (ii) the kinetics of hole transfer from the oxidized sensitizer to the catalyst. Complementary charge interactions in aqueous solution leads to an efficient static quenching of the Ru(bpy)(3)(2+) excited state. The quenching takes place in ion-paired species with an average 1:Ru(bpy)(3)(2+) stoichiometry of 1:4. It occurs by very fast (ca. 2 ps) electron transfer from the excited photosensitizer to the catalyst followed by fast (15-150 ps) charge recombination (reversible oxidative quenching mechanism). This process competes appreciably with the primary photoreaction of the excited sensitizer with the sacrificial oxidant, even in high ionic strength media. The Ru(bpy)(3)(3+) generated by photoreaction of the excited sensitizer with the sacrificial oxidant undergoes primary bimolecular hole scavenging by 1 at a remarkably high rate (3.6 ± 0.1 × 10(9) M(-1) s(-1)), emphasizing the kinetic advantages of this molecular species over, e.g., colloidal oxide particles as water oxidation catalysts. The kinetics of the subsequent steps and final oxygen evolution process involved in the full photocatalytic cycle are not known in detail. An indirect indication that all these processes are relatively fast, however, is provided by the flash photolysis experiments, where a single molecule of 1 is shown to undergo, in 40 ms, ca. 45 turnovers in Ru(bpy)(3)(3+) reduction. With the assumption that one molecule of oxygen released after four hole-scavenging events, this translates into a very high average turnover frequency (280 s(-1)) for oxygen production.

Light driven water oxidation by a single site cobalt salophen catalyst

A salophen cobalt(II) complex enables water oxidation at neutral pH in photoactivated sacrificial cycles under visible light, thus confirming the high appeal of earth abundant single site catalysis for artificial photosynthesis.

Efficient photocatalytic hydrogen generation from water by a cationic cobalt(II) porphyrin

Efficient photocatalytic hydrogen evolution is obtained from 1 M phosphate buffer at pH 7 in the presence of a Ru(bpy)3(2+) sensitizer, an ascorbic acid sacrificial donor, and a water-soluble Co(II) porphyrin catalyst. Spectroscopic investigation of the system by stationary and time-resolved techniques enables a complete characterization of the photoinduced dynamics.

Photocatalytic Hydrogen Evolution with a Self‐Assembling Reductant–Sensitizer–Catalyst System

A noble-metal-free system for photochemical hydrogen production is described, based on ascorbic acid as sacrificial donor, aluminium pyridyl porphyrin as photosensitizer, and cobaloxime as catalyst. Although the aluminium porphyrin platform has docking sites for both the sacrificial donor and the catalyst, the resulting associated species are essentially inactive because of fast unimolecular reversible electron-transfer quenching. Rather, the photochemically active species is the fraction of sensitizer present, in the aqueous/organic solvent used for hydrogen evolution, as free species. As shown by nanosecond laser flash photolysis experiments, its long-lived triplet state reacts bimolecularly with the ascorbate donor, and the reduced sensitizer thus formed, subsequently reacts with the cobaloxime catalyst, thereby triggering the hydrogen evolution process. The performance is good, particularly in terms of turnover frequencies (TOF=10.8 or 3.6 min(-1), relative to the sensitizer or the catalyst, respectively) and the quantum yield (Φ=4.6%, that is, 9.2% of maximum possible value). At high sacrificial donor concentration, the maximum turnover number (TON=352 or 117, relative to the sensitizer or the catalyst, respectively) is eventually limited by hydrogenation of both sensitizer (chlorin formation) and catalyst.

Nondestructive Photoluminescence Read‐Out by Intramolecular Electron Transfer in a Perylene Bisimide‐Diarylethene Dyad

A novel, highly stable photochromic dyad 3 based on a perylene bisimide (PBI) fluorophore and a diarylethene (DAE) photochrome was synthesized and the optical and photophysical properties of this dyad were studied in detail by steady-state and time-resolved ultrafast spectroscopy. This photochromic dyad can be switched reversibly by UV-light irradiation of its ring-open form 3 o leading to the ring-closed form 3 c, and back reaction of 3 c to 3 o by irradiation with visible light. Solvent-dependent fluorescence studies revealed that the emission of ring-closed form 3 c is drastically quenched in solvents of medium (e.g., chloroform) to high (e.g., acetone) polarities, while the emission of the ring-open form 3 o is appreciably quenched only in highly polar solvents like DMF. The strong fluorescence quenching of 3 c is attributed to a photoinduced electron-transfer (PET) process from the excited PBI unit to ring-closed DAE moiety, as this process is thermodynamically highly favorable with a Gibbs free energy value of -0.34 eV in dichloromethane. The electron-transfer mechanism for the fluorescence quenching of ring-closed 3 c is substantiated by ultrafast transient measurements in dichloromethane and acetone, revealing stabilization of charge-separated states of 3 c in these solvents. Our results reported here show that the new photochromic dyad 3 has potential for nondestructive read-out in write/read/erase fluorescent memory systems.

Porphyrin–cobaloxime dyads for photoinduced hydrogen production: investigation of the primary photochemical process

Three porphyrin-cobaloxime dyads, suitable for application in photoinduced hydrogen generation with sacrificial donors, are characterized by ultrafast spectroscopy in order to clarify the primary photochemical events.

A Co(II)–Ru(II) dyad relevant to light-driven water oxidation catalysis

Artificial photosynthesis aims at efficient water splitting into hydrogen and oxygen, by exploiting solar light. As a priority requirement, this process entails the integration of suitable multi-electron catalysts with light absorbing units, where charge separation is generated in order to drive the catalytic routines. The final goal could be the transposition of such an asset into a photoelectrocatalytic cell, where the two half-reactions, proton reduction to hydrogen and water oxidation to oxygen, take place at two appropriately engineered photoelectrodes. We herein report a covalent approach to anchor a Co(II) water oxidation catalyst to a Ru(II) polypyridine photosensitizer unit; photophysical characterisation and the catalytic activity of such a dyad in a light activated cycle are reported, and implications for the development of regenerative systems are discussed.