Catalytic CO2 Reduction with Heptacoordinated Polypyridine Complexes: Switching the Selectivity via Metal Replacement.

The discovery of molecular catalysts for the CO2 reduction reaction (CO2 RR) in the presence of water, which are both effective and selective towards the generation of carbon-based products, is a critical task. Herein we report the catalytic activity towards the CO2 RR in acetonitrile/water mixtures by a cobalt complex and its iron analog both featuring the same redox-active ligand and an unusual seven-coordination environment. Bulk electrolysis experiments show that the cobalt complex mainly yields formate (52 % selectivity at an applied potential of -2.0 V vs Fc+ /Fc and 1 % H2 O) or H2 (up to 86 % selectivity at higher applied bias and water content), while the iron complex always delivers CO as the major product (selectivity >74 %). The different catalytic behavior is further confirmed under photochemical conditions with the [Ru(bpy)3 ]2+ sensitizer (bpy=2,2'-bipyridine) and N,N-diisopropylethylamine as electron donor, where the cobalt complex leads to preferential H2 formation (up to 89 % selectivity), while the iron analog quantitatively generates CO (up to 88 % selectivity). This is ascribed to a preference towards a metal-hydride vs. a metal-carboxyl pathway for the cobalt and the iron complex, respectively, and highlights how metal replacement may effectively impact on the reactivity of transition metal complexes towards solar fuel formation.

Bioinspired motifs in proton and CO2 reduction with 3d-metal polypyridine complexes.

The synthesis of active and efficient catalysts for solar fuel generation is nowadays of high relevance for the scientific community, but at the same time poses great challenges. Critical requirements are mainly associated with the kinetic barriers due to the multi-proton and multi-electron nature of the hydrogen evolution reaction (HER) and the CO2 reduction reaction (CO2RR) as well as to selectivity issues. In this regard, natural enzymes can be a source of inspiration for the design of effective and selective catalysts to target such fundamental reactions. In this Feature Article we review some recent works on molecular catalysts for both the HER and the CO2RR performed in our labs and other research teams which mainly address (i) the role of redox non-innocent ligands, to lower the overpotential for catalysis and control the selectivity, and (ii) the role of internal relays, to assist formation of catalytic intermediates via intramolecular routes. The selected exemplars have been chosen to emphasize that, although the molecular structures and the synthetic motifs are different from those of the active sites of natural enzymes, many affinities in terms of catalytic mechanism and functionality are instead present, which account for the observed remarkable performances under operative conditions. The data discussed herein thus demonstrate the great potential and the privileged role of molecular catalysts towards the design and construction of hybrid photochemical systems for solar energy conversion into fuels.

Electro- and photochemical H2 generation by Co(ii) polypyridyl-based catalysts bearing ortho-substituted pyridines.

Cobalt(ii) complexes featuring hexadentate amino-pyridyl ligands have been recently discovered as highly active catalysts for the Hydrogen Evolution Reaction (HER), whose high performance arises from the possibility of assisting proton transfer processes via intramolecular routes involving detached pyridine units. With the aim of gaining insights into such catalytic routes, three new proton reduction catalysts based on amino-polypyridyl ligands are reported, focusing on substitution of the pyridine ortho-position. Specifically, a carboxylate (C2) and two hydroxyl substituted pyridyl moieties (C3, C4) are introduced with the aim of promoting intramolecular proton transfer which possibly enhances the efficiency of the catalysts. Foot-of-the-wave and catalytic Tafel plot analyses have been utilized to benchmark the catalytic performances under electrochemical conditions in acetonitrile using trifluoroacetic acid as the proton source. In this respect, the cobalt complex C3 turns out to be the fastest catalyst in the series, with a maximum turnover frequency (TOF) of 1.6 (±0.5) × 105 s-1, but at the expense of large overpotentials. Mechanistic investigations by means of Density Functional Theory (DFT) suggest a typical ECEC mechanism (i.e. a sequence of reduction - E - and protonation - C - events) for all the catalysts, as previously envisioned for the parent unsubstituted complex C1. Interestingly, in the case of complex C2, the catalytic route is triggered by initial protonation of the carboxylate group resulting in a less common (C)ECEC mechanism. The pivotal role of the hexadentate chelating ligand in providing internal proton relays to assist hydrogen elimination is further confirmed within this novel class of molecular catalysts, thus highlighting the relevance of a flexible polypyridine ligand in the design of efficient cobalt complexes for the HER. Photochemical studies in aqueous solution using [Ru(bpy)3]2+ (where bpy = 2,2'-bipyridine) as the sensitizer and ascorbate as the sacrificial electron donor support the superior performance of C3.

Unveiling the impact of the light-source and steric factors on [2+2] heterocycloaddition reactions.

Information gained from in-depth mechanistic investigations can be used to control the selectivity of reactions, leading to the expansion of the generality of synthetic processes and the discovery of new reactivity. Here, we investigate the mechanism of light-driven [2+2] heterocycloadditions (Paternò-Büchi reactions) between indoles and ketones to develop insight into these processes. Using ground-state UV-Vis absorption and transient absorption spectroscopy (TAS), together with DFT calculations, we found that the reactions can proceed via an exciplex or electron-donor-acceptor (EDA) complex, which are key intermediates in determining the stereoselectivity of the reactions. We used this discovery to control the diastereoselectivity of the reactions, gaining access to previously inaccessible diastereoisomeric variants. When moving from 370 to 456 nm irradiation, the EDA complex is increasingly favoured, and the diastereomeric ratio (d.r.) of the product moves from >99:<1 to 47:53. In contrast, switching from methyl to ipropyl substitution favours the exciplex intermediate, reversing the d.r. from 89:11 to 16:84. Our study shows how light and steric parameters can be rationally used to control the diastereoselectivity of photoreactions, creating mechanistic pathways to previously inaccessible stereochemical variants.

Modulable Photocatalyzed Strategies for the Synthesis of α-C-Glycosyl Alanine Analogues via the Giese Reaction with Dehydroalanine Derivates.

Herein, we present the α-selective Giese reaction between pyranosyl/furanosyl bromides and dehydroalanine analogues, which provides access to a library of highly valuable α-C-glycosyl alanines. The key C-glycosyl radical is generated through photocatalysis by either the new generation copper(I) complex [(DPEPhos)(bcp)Cu]PF6 or [Ru(bpy)3](BF4)2. The reactions proceed smoothly, affording the desired α-C-glycosyl alanines in up to 99% yield when diethyl 1,4-dihydro-2,6-dimethyl-3,5-pyridinedicarboxylate [Hantzsch ester (HE)] is used as an additive. N,N-Diisopropylethylamine (DIPEA) has been selected as a reductant in both protocols. A mechanistic study by means of transient absorption spectroscopy unveils a halogen-atom transfer (XAT) process in C-glycosyl radical formation.

Self-assembly of benzophenone-diphenylalanine conjugate into a nanostructured photocatalyst.

The conjugation of photoactive benzophenone with diphenylalanine yielded a self-assembling photocatalyst that was probed in the E → Z photoisomerisation of stilbene derivatives.

A Proton-Coupled Electron Transfer Strategy to the Redox-Neutral Photocatalytic CO2 Fixation.

Herein, we report our study on the design and development of a novel photocarboxylation method. We have used an organic photoredox catalyst (PC, 4CzIPN) and differently substituted dihydropyridines (DHPs) in combination with an organic base (1,5,7-triazabicyclodec-5-ene, TBD) to access a proton-coupled electron transfer (PCET) based manifold. In depth mechanistic investigations merging experimental analysis (NMR, IR, cyclic voltammetry) and density-functional theory (DFT) calculations reveal the key activity of a H-bonding complex between the DHP and the base. The thermodynamic and kinetic benefits of the PCET mechanism allowed the implementation of a redox-neutral fixation process leading to synthetically relevant carboxylic acids (18 examples with isolated yields up to 75%) under very mild reaction conditions. Finally, diverse product manipulations were performed to demonstrate the synthetic versatility of the obtained products.

Air- and Water-Stable Heteroleptic Copper (I) Complexes Bearing Bis(indazol-1-yl)methane Ligands: Synthesis, Characterisation, and Computational Studies.

A series of four novel heteroleptic Cu(I) complexes, bearing bis(1H-indazol-1-yl)methane analogues as N,N ligands and DPEPhos as the P,P ligand, were synthesised in high yields under mild conditions and characterised by spectroscopic and spectrometric techniques. In addition, the position of the carboxymethyl substituent in the complexes and its effect on the electrochemical and photophysical behaviour was evaluated. As expected, the homoleptic copper (I) complexes with the N,N ligands showed air instability. In contrast, the obtained heteroleptic complexes were air- and water-stable in solid and solution. All complexes displayed green-yellow luminescence in CH2Cl2 at room temperature due to ligand-centred (LC) phosphorescence in the case of the Cu(I) complex with an unsubstituted N,N ligand and metal-to-ligand charge transfer (MLCT) phosphorescence for the carboxymethyl-substituted complexes. Interestingly, proper substitution of the bis(1H-indazol-1-yl)methane ligand enabled the achievement of a remarkable luminescent yield (2.5%) in solution, showcasing the great potential of this novel class of copper(I) complexes for potential applications in luminescent devices and/or photocatalysis.

Synthesis and Characterization of Iridium(III) Complexes with Substituted Phenylimidazo(4,5-f)1,10-phenanthroline Ancillary Ligands and Their Application in LEC Devices.

In this work, we report on the synthesis and characterization of six new iridium(III) complexes of the type [Ir(C^N)2(N^N)]+ using 2-phenylpyridine (C1-3) and its fluorinated derivative (C4-6) as cyclometalating ligands (C^N) and R-phenylimidazo(4,5-f)1,10-phenanthroline (R = H, CH3, F) as the ancillary ligand (N^N). These luminescent complexes have been fully characterized through optical and electrochemical studies. In solution, the C4-6 series exhibits quantum yields (Ф) twice as high as the C1-3 series, exceeding 60% in dichloromethane and where 3MLCT/3LLCT and 3LC emissions participate in the phenomenon. These complexes were employed in the active layer of light-emitting electrochemical cells (LECs). Device performance of maximum luminance values of up to 21.7 Lx at 14.7 V were observed for the C2 complex and long lifetimes for the C1-3 series. These values are counterintuitive to the quantum yields observed in solution. Thus, we established that the rigidity of the system and the structure of the solid matrix dramatically affect the electronic properties of the complex. This research contributes to understanding the effects of the modifications in the ancillary and cyclometalating ligands, the photophysics of the complexes, and their performance in LEC devices.

Rethinking Electronic Effects in Photochemical Hydrogen Evolution Using CuInS2@ZnS Quantum Dots Sensitizers.

Molecular catalysts based on coordination complexes for the generation of hydrogen via photochemical water splitting exhibit a large versatility and tunability of the catalytic properties through chemical functionalization. In the present work, we report on light-driven hydrogen production in an aqueous solution using a series of cobalt polypyridine complexes as hydrogen evolving catalysts (HECs) in combination with CuInS2@ZnS quantum dots (QDs) as sensitizers, and ascorbate as the electron donor. A peculiar trend in activity has been observed depending on the substituents present on the polypyridine ligand. This trend markedly differs from that previously recorded using [Ru(bpy)3]2+ (where bpy = 2,2'-bipyridine) as the sensitizer and can be ascribed to different kinetically limiting pathways in the photochemical reaction (viz. protonation kinetics with the ruthenium chromophore, catalyst activation via electron transfer from the QDs in the present system). Hence, this work shows how the electronic effects on light-triggered molecular catalysis are not exclusive features of the catalyst unit but depend on the whole photochemical system.

Beyond Water Oxidation: Hybrid, Molecular-Based Photoanodes for the Production of Value-Added Organics.

The political and environmental problems related to the massive use of fossil fuels prompted researchers to develop alternative strategies to obtain green and renewable fuels such as hydrogen. The light-driven water splitting process (i.e., the photochemical decomposition of water into hydrogen and oxygen) is one of the most investigated strategies to achieve this goal. However, the water oxidation reaction still constitutes a formidable challenge because of its kinetic and thermodynamic requirements. Recent research efforts have been focused on the exploration of alternative and more favorable oxidation processes, such as the oxidation of organic substrates, to obtain value-added products in addition to solar fuels. In this mini-review, some of the most intriguing and recent results are presented. In particular, attention is directed on hybrid photoanodes comprising molecular light-absorbing moieties (sensitizers) and catalysts grafted onto either mesoporous semiconductors or conductors. Such systems have been exploited so far for the photoelectrochemical oxidation of alcohols to aldehydes in the presence of suitable co-catalysts. Challenges and future perspectives are also briefly discussed, with special focus on the application of such hybrid molecular-based systems to more challenging reactions, such as the activation of C-H bonds.

Recent findings and future directions in photosynthetic hydrogen evolution using polypyridine cobalt complexes.

The production of hydrogen gas using water as the molecular substrate currently represents one of the most challenging and appealing reaction schemes in the field of artificial photosynthesis (AP), i.e., the conversion of solar energy into fuels. In order to be efficient, this process requires a suitable combination of a light-harvesting sensitizer, an electron donor, and a hydrogen-evolving catalyst (HEC). In the last few years, cobalt polypyridine complexes have been discovered to be competent molecular catalysts for the hydrogen evolution reaction (HER), showing enhanced efficiency and stability with respect to previously reported molecular species. This perspective collects information about all relevant cobalt polypyridine complexes employed for the HER in aqueous solution under light-driven conditions in the presence of Ru(bpy)32+ (where bpy = 2,2'-bipyridine) as the photosensitizer and ascorbate as the electron donor, trying to highlight promising chemical motifs and aiming towards efficient catalytic activity in order to stimulate further efforts to design molecular catalysts for hydrogen generation and allow their profitable implementation in devices. As a final step, a few suggestions for the benchmarking of HECs employed under light-driven conditions are introduced.

Insights into the light-driven hydrogen evolution reaction of mesoporous graphitic carbon nitride decorated with Pt or Ru nanoparticles.

Ru or Pt nanoparticles have been prepared following the organometallic approach and deposited onto the surface of mesoporous graphitic carbon nitride (mpg-CN). Three different Ru-based samples have also been compared to investigate the effect of 4-phenylpyridine as a stabilizing agent. The photocatalytic performance towards the hydrogen evolution reaction (HER) has been tested showing that all hybrid systems clearly outperform the photocatalytic activity of bare mpg-CN. In particular, Pt-decorated mpg-CN yields the largest H2 production upon visible-light irradiation (870 µmol h-1 g-1, TOF = 14.1 h-1, TON = 339 after 24 h) when compared with the Ru-based samples (137-155 µmol h-1 g-1, TOFs between 2.3-2.7 h-1, TONs between 54-57 after 24 h). Long-term photochemical tests (up to 65 h irradiation) show also an improved stability of the Pt-based samples over the Ru counterpart. Photophysical experiments aimed at rationalizing the photocatalytic performance of the different hybrid systems elucidate that the enhanced activity of the Pt-decorated mpg-CN over the Ru-based analogues arises from improved electron transfer kinetics from mpg-CN to the metal nanoparticles.

Basicity as a Thermodynamic Descriptor of Carbanions Reactivity with Carbon Dioxide: Application to the Carboxylation of α,ß-Unsaturated Ketones.

The utilization of carbon dioxide as a raw material represents nowadays an appealing strategy in the renewable energy, organic synthesis, and green chemistry fields. Besides reduction strategies, carbon dioxide can be exploited as a single-carbon-atom building block through its fixation into organic scaffolds with the formation of new C-C bonds (carboxylation processes). In this case, activation of the organic substrate is commonly required, upon formation of a carbanion C-, being sufficiently reactive toward the addition of CO2. However, the prediction of the reactivity of C- with CO2 is often problematic with the process being possibly associated with unfavorable thermodynamics. In this contribution, we present a thermodynamic analysis combined with density functional theory calculations on 50 organic molecules enabling the achievement of a linear correlation of the standard free energy (ΔG0) of the carboxylation reaction with the basicity of the carbanion C-, expressed as the pKa of the CH/C- couple. The analysis identifies a threshold pKa of ca 36 (in CH3CN) for the CH/C- couple, above which the ΔG0 of the carboxylation reaction is negative and indicative of a favorable process. We then apply the model to a real case involving electrochemical carboxylation of flavone and chalcone as model compounds of α,ß-unsaturated ketones. Carboxylation occurs in the ß-position from the doubly reduced dianion intermediates of flavone and chalcone (calculated ΔG0 of carboxylation in ß = -12.8 and -20.0 Kcalmol-1 for flavone and chalcone, respectively, associated with pKa values for the conjugate acids of 50.6 and 51.8, respectively). Conversely, the one-electron reduced radical anions are not reactive toward carboxylation (ΔG0 > +20 Kcalmol-1 for both substrates, in either α or ß position, consistent with pKa of the conjugate acids < 18.5). For all the possible intermediates, the plot of calculated ΔG0 of carboxylation vs. pKa is consistent with the linear correlation model developed. The application of the ΔG0 vs. pKa correlation is finally discussed for alternative reaction mechanisms and for carboxylation of other C=C and C=O double bonds. These results offer a new mechanistic tool for the interpretation of the reactivity of CO2 with organic intermediates.

Photoinduced Water Oxidation in Chitosan Nanostructures Containing Covalently Linked RuII Chromophores and Encapsulated Iridium Oxide Nanoparticles.

The luminophore Ru(bpy)2 (dcbpy)2+ (bpy=2,2'-bipyridine; dcbpy=4,4'-dicarboxy-2,2'-bipyridine) is covalently linked to a chitosan polymer; crosslinking by tripolyphosphate produced Ru-decorated chitosan fibers (NS-RuCh), with a 20 : 1 ratio between chitosan repeating units and RuII chromophores. The properties of the RuII compound are unperturbed by the chitosan structure, with NS-RuCh exhibiting the typical metal-to-ligand charge-transfer (MLCT) absorption and emission bands of RuII complexes. When crosslinks are made in the presence of IrO2 nanoparticles, such species are encapsulated within the nanofibers, thus generating the IrO2 ⊂NS-RuCh system, in which both RuII photosensitizers and IrO2 water oxidation catalysts are within the nanofiber structures. NS-RuCh and IrO2 ⊂NS-RuCh have been characterized by dynamic light scattering, scanning electronic microscopy, and energy-dispersive X-ray analysis, which indicated a 2 : 1 ratio between RuII chromophores and IrO2 species. Photochemical water oxidation has been investigated by using IrO2 ⊂NS-RuCh as the chromophore/catalyst assembly and persulfate anions as the sacrificial species: photochemical water oxidation yields O2 with a quantum yield (Φ) of 0.21, definitely higher than the Φ obtained with a similar solution containing separated Ru(bpy)3 2+ and IrO2 nanoparticles (0.05) or with respect to that obtained when using NS-RuCh and "free" IrO2 nanoparticles (0.10). A fast hole-scavenging process (rate constant, 7×104  s-1 ) involving the oxidized photosensitizer and the IrO2 catalyst within the IrO2 ⊂NS-RuCh system is behind the improved photochemical quantum yield of IrO2 ⊂NS-RuCh.

Water-Assisted Concerted Proton-Electron Transfer at Co(II)-Aquo Sites in Polyoxotungstates With Photogenerated RuIII (bpy)33+ Oxidant.

The cobalt substituted polyoxotungstate [Co6 (H2 O)2 (α-B-PW9 O34 )2 (PW6 O26 )]17- (Co6) displays fast electron transfer (ET) kinetics to photogenerated RuIII (bpy)33+ , 4 to 5 orders of magnitude faster than the corresponding ET observed for cobalt oxide nanoparticles. Mechanistic evidence has been acquired indicating that: (i) the one-electron oxidation of Co6 involves Co(II) aquo or Co(II) hydroxo groups (abbreviated as Co6(II)-OH2 and Co6(II)-OH, respectively, whose speciation in aqueous solution is associated to a pKa of 7.6), and generates a Co(III)-OH moiety (Co6(III)-OH), as proven by transient absorption spectroscopy; (ii) at pH>pKa , the Co6(II)-OH→RuIII (bpy)33+ ET occurs via bimolecular kinetics, with a rate constant k close to the diffusion limit and dependent on the ionic strength of the medium, consistent with reaction between charged species; (iii) at pH

Rationalizing Photo-Triggered Hydrogen Evolution Using Polypyridine Cobalt Complexes: Substituent Effects on Hexadentate Chelating Ligands.

Four novel polypyridine cobalt(II) complexes were developed based on a hexadentate ligand scaffold bearing either electron-withdrawing (-CF3 ) or electron-donating (-OCH3 ) groups in different positions of the ligand. Experiments and theoretical calculations were combined to perform a systematic investigation of the effect of the ligand modification on the hydrogen evolution reaction. The results indicated that the position, rather than the type of substituent, was the dominating factor in promoting catalysis. The best performances were observed upon introduction of substituents on the pyridine moiety of the hexadentate ligand, which promoted the formation of the Co(II)H intermediate via intramolecular proton transfer reactions with low activation energy. Quantum yields of 11.3 and 10.1 %, maximum turnover frequencies of 86.1 and 76.6 min-1 , and maximum turnover numbers of 5520 and 4043 were obtained, respectively, with a -OCH3 and a -CF3 substituent.

Photoinduced Electron vs. Concerted Proton Electron Transfer Pathways in SnIV (l-Tryptophanato)2 Porphyrin Conjugates.

Aromatic amino acids such as l-tyrosine and l-tryptophan are deployed in natural systems to mediate electron transfer (ET) reactions. While tyrosine oxidation is always coupled to deprotonation (proton-coupled electron-transfer, PCET), both ET-only and PCET pathways can occur in the case of the tryptophan residue. In the present work, two novel conjugates 1 and 2, based on a SnIV tetraphenylporphyrin and SnIV octaethylporphyrin, respectively, as the chromophore/electron acceptor and l-tryptophan as electron/proton donor, have been prepared and thoroughly characterized by a combination of different techniques including single crystal X-ray analysis. The photophysical investigation of 1 and 2 in CH2 Cl2 in the presence of pyrrolidine as a base shows that different quenching mechanisms are operating upon visible-light excitation of the porphyrin component, namely photoinduced electron transfer and concerted proton electron transfer (CPET), depending on the chromophore identity and spin multiplicity of the excited state. The results are compared with those previously described for metal-mediated analogues featuring SnIV porphyrin chromophores and l-tyrosine as the redox active amino acid and well illustrate the peculiar role of l-tryptophan with respect to PCET.

Photoelectrochemical hydrogen evolution using CdTexS1-x quantum dots as sensitizers on NiO photocathodes.

The design of active photocathodes for the hydrogen evolution reaction (HER) is a crucial step in the development of dye-sensitized photoelectrochemical cells (DS-PECs) aimed at solar-assisted water splitting. In the present work, we report on the use of orange CdTexS1-x quantum dots (QDs) with an average diameter of ca. 3.5 nm, featuring different capping agents (MAA, MPA, and MSA) for the sensitization of electrodes based on nanostructured NiO. Photoelectrochemical characterization of the resulting NiO|QDs electrodes in the presence of [CoIII(NH3)5Cl]Cl2 as an irreversible electron acceptor elects MAA-capped QDs as the most active sample to achieve substantial photocurrent densities thanks to both improved surface coverage and injection ability. Functionalization of the NiO|QDs electrodes with either heterogeneous Pt or the molecular nickel bis(diphosphine) complex (1) as the hydrogen evolving catalysts (HECs) yields active photocathodes capable of promoting hydrogen evolution upon photoirradiation (maximum photocurrent densities of -16(±2) and -20(±1) µA·cm-2 for Pt and 1 HECs, respectively, at 0 V vs. NHE, 70-80% faradaic efficiency, maximum IPCE of ca. 0.2%). The photoelectrochemical activity is limited by the small surface concentration of the QD sensitizers on the NiO surface and the competitive light absorption by the NiO material which suggests that the match between dye adsorption and the available surface area is critical to achieving efficient hydrogen evolution by thiol-capped QDs.