Pentanuclear iron complex for water oxidation: spectroscopic analysis of reactive intermediates in solution and catalyst immobilization into the MOF-based photoanode.

Photoelectrochemical water splitting can produce green hydrogen for industrial use and CO2-neutral transportation, ensuring the transition from fossil fuels to green, renewable energy sources. The iron-based electrocatalyst [FeII4FeIII(µ-3-O)(µ-L)6]3+ (LH = 3,5-bis(2-pyridyl)pyrazole) (1), discovered in 2016, is one of the fastest molecular water oxidation catalysts (WOC) based on earth-abundant elements. However, its water oxidation reaction mechanism has not been yet fully elucidated. Here, we present in situ X-ray spectroscopy and electron paramagnetic resonance (EPR) analysis of electrochemical water oxidation reaction (WOR) promoted by (1) in water-acetonitrile solution. We observed transient reactive intermediates during the in situ electrochemical WOR, consistent with a coordination sphere expansion prior to the onset of catalytic current. At a pre-catalytic (~+1.1 V vs. Ag/AgCl) potential, the distinct g~2.0 EPR signal assigned to FeIII/FeIV interaction was observed. Prolonged bulk electrolysis at catalytic (~+1.6 V vs. Ag/AgCl) potential leads to the further oxidation of Fe centers in (1). At the steady state achieved with such electrolysis, the formation of hypervalent FeV=O and FeIV=O catalytic intermediates was inferred with XANES and EXAFS fitting, detecting a short Fe=O bond at ~1.6 Å. (1) was embedded into MIL-126 MOF with the formation of (1)-MIL-126 composite. The latter was tested in photoelectrochemical WOR and demonstrated an improvement of electrocatalytic current upon visible light irradiation in acidic (pH=2) water solution. The presented spectroscopic analysis gives further insight into the catalytic pathways of multinuclear systems and should help the subsequent development of more energy- and cost-effective catalysts of water splitting based on earth-abundant metals. Photoelectrocatalytic activity of (1)-MIL-126 confirms the possibility of creating an assembly of (1) inside a solid support and boosting it with solar irradiation towards industrial applications of the catalyst.

Introducing proton/electron mediators enhances the catalytic ability of an iron porphyrin complex for photochemical CO2 reduction.

A novel iron porphyrin complex with hydroquinone moieties as proton/electron mediators at meso positions was designed and synthesised. The complex serves as an efficient catalyst for photochemical CO2 reduction, and its turnover frequency (TOF = 1.3 × 104 h-1) was the highest among those of comparable systems with sufficient durability.

Iron-Complex-Based Supramolecular Framework Catalyst for Visible-Light-Driven CO2 Reduction.

Molecule-based heterogeneous photocatalysts without noble metals are one of the most attractive systems for visible-light-driven CO2 reduction. However, reports on this class of photocatalysts are still limited, and their activities are quite low compared to those containing noble metals. Herein, we report an iron-complex-based heterogeneous photocatalyst for CO2 reduction with high activity. The key to our success is the use of a supramolecular framework composed of iron porphyrin complexes bearing pyrene moieties at meso positions. The catalyst exhibited high activity for CO2 reduction under visible-light irradiation (29100 µmol g-1 h-1 for CO production, selectivity 99.9%), which is the highest among relevant systems. The performance of this catalyst is also excellent in terms of apparent quantum yield for CO production (0.298% at 400 nm) and stability (up to 96 h). This study provides a facile strategy to create a highly active, selective, and stable photocatalyst for CO2 reduction without utilizing noble metals.

Visible-Light-Driven Hydroacylation of Unactivated Alkenes Using Readily Available Acyl Donors.

Herein, we report visible-light-driven hydroacylation of unactivated alkenes. We employed benzimidazolines as new acyl donors and achieved perfect regioselectivity, high functional-group tolerance, and excellent substrate generality. We also performed mechanistic experiments to elucidate the detailed reaction mechanism. This is the first example of (1) hydroacylation of unactivated alkenes using (2) easily prepared acyl donors under (3) visible-light irradiation. Our findings offer a new strategy to synthesize a wide variety of ketones under mild conditions.

Brønsted Acid/Base Site Isolated in a Pentanuclear Scaffold.

Invited for the cover of this issue is the group of Shigeyuki Masaoka at Osaka University. The image depicts a Brønsted acid/base pair based on a pentanuclear scaffold, and the formation thermodynamically metastable state of H+ by the steric isolation of a Brønsted acid/base site. Read the full text of the article at 10.1002/chem.202203253.

Brønsted Acid/Base Site Isolated in a Pentanuclear Scaffold.

The concept of Brønsted-Lowry acids and bases is long and widely recognized as the most reasonable theory to explain the behavior of H+ ions. Here, we report a Brønsted acid/base pair that does not follow this theory. Two heteronuclear metal complexes, in which Brønsted acid/base sites are sterically isolated, were synthesized and characterized. These sterically isolated sites exhibited anomalous behavior, wherein the H+ species encapsulated in the Brønsted acid site did not undergo a deprotonation reaction, and the corresponding protonation reaction at the Brønsted base site failed to proceed. As a result, two states that are in a relationship of a Brønsted acid/base pair stably exist over a wide pH range without any interconversion, generating a thermodynamically metastable state. Additionally, these two states exhibited distinct electron transfer abilities and reactivities. The system presented in this study is in sharp contrast with the traditional concept of Brønsted-Lowry acids and bases.

A Catalytic Alkylation of Ketones via sp3 C-H Bond Activation.

We identified a ternary hybrid catalyst system composed of an acridinium photoredox catalyst, a thiophosphoric imide (TPI) catalyst, and a titanium complex catalyst that promoted an intermolecular addition reaction of organic molecules with various ketones through sp3 C-H bond activation. The thiyl radical generated via single-electron oxidation of TPI by the excited photoredox catalyst abstracted a hydrogen atom from organic molecules such as toluene, benzyl alcohol, alkenes, aldehydes, and THF. The thus-generated carbon-centered radical species underwent addition to ketones and aldehydes. This intrinsically unfavorable step was promoted by single-electron reduction of the intermediate alkoxy radical by catalytically generated titanium(III) species. This reaction provided an efficient and straightforward route to a broad range of tertiary alcohols and was successfully applied to late-stage functionalization of drugs or their derivatives. The proposed mechanism was supported by both experimental and theoretical studies.

Visible light-driven CO2 reduction with a Ru polypyridyl complex bearing an N-heterocyclic carbene moiety.

A novel Ru polypyridyl complex with an N-heterocyclic carbene ligand was successfully synthesised and characterised. The complex exhibited an intense absorption band in the visible-light region derived from the strong electron-donating character of the carbene ligand, and efficiently catalysed the visible light-driven CO2 reduction with the reaction rate of 36.7 h-1.

Copper(II) tetrakis(pentafluorophenyl)porphyrin: highly active copper-based molecular catalysts for electrochemical CO2 reduction.

We report a highly active copper-based catalyst for electrochemical CO2 reduction. Electrochemical analysis revealed that the maximum turnover frequency for CO2 to CO conversion reached 1 460 000 s-1 at an overpotential (η) of 0.85 V. Surprisingly, this value is more than 1 000 000 times higher than those of other reported copper-based molecular catalysts.

Photochemical hydrogen production based on the HCOOH/CO2 cycle promoted by a pentanuclear cobalt complex.

The first catalytic cycle for hydrogen production based on the photochemical two-electron reduction of carbon dioxide (CO2) and the dehydrogenation of formic acid at ambient temperature was demonstrated using a pentanuclear cobalt complex (Co5). A series of mechanistic studies were performed to elucidate the mechanism responsible for the promotion of the photocatalytic cycle by Co5.

Bridging coordination of acenaphthylene to a Pd3 chain or a Pd4 sheet cluster.

The coordination behaviour of multinuclear clusters to fused arene ligands is of continuous interest due to its relevance to metal catalysts supported by graphitic carbon materials. Herein, we report the bridging coordination behaviour of acenaphthylene to a Pd3 or a Pd4 cluster. A bis-acenaphthylene Pd3 chain cluster and an acenaphthylene-COT Pd4 sheet cluster were isolated, and the µ3-π-coordination mode or the µ4-oxidative π-addition mode of the acenaphthylene ligand in each cluster was elucidated by X-ray structure analysis.

Quick and Easy Method to Dramatically Improve the Electrochemical CO2 Reduction Activity of an Iron Porphyrin Complex.

The development of artificial molecular catalysts for CO2 reduction is the key to solving energy and environmental problems. Although chemical modifications can generally improve the catalytic activity of this class of compounds, they often require complicated synthetic procedures. Here, we report a simple procedure that dramatically enhances electrochemical CO2 reduction activity. A one-step counteranion-exchange reaction increased the solubility of a commercially available catalyst, iron(III) tetraphenylporphyrin chloride, in a variety of solvents, allowing the investigation of its catalytic performance under various conditions. Surprisingly, the turnover frequency for CO evolution in acetonitrile (MeCN) reached 7 300 000 s-1 , which is the highest among those of current best-in-class molecular catalysts. This excellent catalytic activity originates from the unique reaction between the generated FeI species and CO2 in MeCN during catalysis. The present study offers a "quick and easy" method for obtaining an efficient catalytic system for electrochemical CO2 reduction.

Dirhodium-Based Supramolecular Framework Catalyst for Visible-Light-Driven Hydrogen Evolution.

The direct conversion of solar energy to clean fuels as alternatives to fossil fuels is an important approach for addressing the global energy shortage and environmental problems. Here, we introduce a new dirhodium-complex-based framework assembly as a heterogeneous molecule-based photocatalyst for hydrogen evolution using visible light. Two dirhodium complexes bearing visible-light-harvesting BODIPY (boron dipyrromethene, BDP) moieties were newly designed and synthesized. The obtained complexes were self-assembled to framework structures (supramolecular framework catalysts), which are stabilized intermolecular noncovalent interactions. These frameworks retained excellent visible-light-harvesting properties of BDP moieties. Investigation of the catalytic performance of the supramolecular framework catalysts revealed that the supramolecular framework catalyst with heavy atoms at BDP moieties exhibited excellent performance in the formation of hydrogen with a reaction rate of 275.8 µmol g-1 h-1 under irradiation of visible light, whereas the supramolecular framework catalyst without heavy atoms at BDP moieties was inactive. Moreover, the system has the additional benefits of high durability (up to 96 h), reusability, and facile removal from the reaction mixture. We also disclosed the effect of heavy atoms at BDP moieties on the catalytic activity and proposed a reaction mechanism.

Design of molecular water oxidation catalysts with earth-abundant metal ions.

The four-electron oxidation of water (2H2O → O2 + 4H+ + 4e-) is considered the main bottleneck in artificial photosynthesis. In nature, this reaction is catalysed by a Mn4CaO5 cluster embedded in the oxygen-evolving complex of photosystem II. Ruthenium-based complexes have been successful artificial molecular catalysts for mimicking this reaction. However, for practical and large-scale applications in the future, molecular catalysts that contain earth-abundant first-row transition metal ions are preferred owing to their high natural abundance, low risk of depletion, and low costs. In this review, the frontier of water oxidation reactions mediated by first-row transition metal complexes is described. Special attention is paid towards the design of molecular structures of the catalysts and their reaction mechanisms, and these factors are expected to serve as guiding principles for creating efficient and robust molecular catalysts for water oxidation using ubiquitous elements.

Photoconductive Coordination Polymer with a Lead-Sulfur Two-Dimensional Coordination Sheet Structure.

Coordination polymers with metal-sulfur (M-S) bonds in their nodes have interesting optical properties and can be used as photocatalysts for water splitting. A wide range of inorganic-organic hybrid materials with M-S bonds have been prepared in recent years. However, there is a dearth of structural information because of their low crystallinity, which has hampered the understanding of their underlying chemistry and physics. Thus, we conducted a structural study of a novel, highly crystalline coordination polymer with M-S bonds. Theoretical calculations were performed to elucidate its photoconductivity mechanism. The photoconductive, three-dimensional coordination polymer [Pb(tadt)]n (denoted as KGF-9; tadt = 1,3,4-thiadiazole-2,5-dithiolate) was synthesized and confirmed to have a three-dimensional structure containing a two-dimensional Pb-S framework by single-crystal X-ray diffraction. We also performed diffuse-reflectance ultraviolet-visible-near-infrared spectroscopy, time-resolved microwave conductivity, and photoelectron yield spectroscopy measurements on the bulk powder samples, as well as first-principles calculations. Additionally, direct-current photoconductivity measurements were conducted on a single-crystal sample.

Modulation of Self-Assembly Enhances the Catalytic Activity of Iron Porphyrin for CO2 Reduction.

Electrochemical reduction of CO2 in aqueous media is an important reaction to produce value-added carbon products in an environmentally and economically friendly manner. Various molecule-based catalytic systems for the reaction have been reported thus far. The key features of state-of-the-art catalytic systems in this field can be summarized as follows: 1) an iron-porphyrin-based scaffold as a catalytic center, 2) a dinuclear active center for the efficient activation of a CO2 molecule, and 3) a hydrophobic channel for the accumulation of CO2 . This article reports a novel approach to construct a catalytic system for CO2 reduction with the aforementioned three key substructures. The self-assembly of a newly designed iron-porphyrin complex bearing bulky substituents with noncovalent interaction ability forms a highly ordered crystalline solid with adjacent catalytically active sites and hydrophobic pores. The obtained crystalline solid serves as an electrocatalyst for CO2 reduction in aqueous media. Note that a relevant iron-porphyrin complex without bulky substituents cannot form a porous structure with adjacent active sites, and the catalytic performance of the crystals of this relevant iron-porphyrin complex is substantially lower than that of the newly developed catalytic system. The present study provides a novel strategy for constructing porous crystalline solids for small-molecule conversions.

Electrochemical Polymerization Provides a Function-Integrated System for Water Oxidation.

Water oxidation is a key reaction in natural and artificial photosynthesis. In nature, the reaction is efficiently catalyzed by a metal-complex-based catalyst surrounded by hole-transporting amino acid residues. However, in artificial systems, there is no example of a water oxidation system that has a catalytic center surrounded by hole transporters. Herein, we present a facile strategy to integrate catalytic centers and hole transporters in one system. Electrochemical polymerization of a metal-complex-based precursor afforded a polymer-based material (Poly-1). Poly-1 exhibited excellent hole-transporting ability and catalyzed water oxidation with high performance. It was also revealed that the catalytic activity was almost completely suppressed in the absence of the hole-transporting moieties. The present study provides a novel strategy for constructing efficient molecule-based systems for water oxidation.

Pentanuclear Scaffold: A Molecular Platform for Small-Molecule Conversions.

Small-molecule conversions involving multielectron transfer processes enable the conversion of earth-abundant materials into valuable chemicals and are regarded as a solution for environmental and energy shortage problems. In this context, the development of artificial catalysts that promote these reactions is an important research target. In nature, metalloenzymes that contain multinuclear metal complexes as active sites are known to efficiently catalyze reactions under mild conditions. Therefore, using multinuclear metal complexes as artificial catalysts can be an attractive strategy for small-molecule conversions involving multielectron transfer processes. However, multinuclear-metal-complex-based catalysts for these reactions have not been well established. In this Account, we describe our recent advances in the development of multinuclear metal complexes as catalysts for small-molecule conversion, mainly focusing on water oxidation. As small-molecule conversions involving multielectron transfer processes consists of two essential processes, (1) the transfer of multiple electrons and (2) the formation/cleavage of covalent bond(s), catalysts for these reactions should facilitate both steps. Therefore, we assumed that the assembly of redox-active metal ions and the cooperative effect of neighboring coordinatively unsaturated metal ions can promote these processes. On the basis of this assumption, we employed a pentanuclear metal complex as a molecular scaffold for the catalyst. The scaffold has a pentanuclear structure with quasi-D3 symmetry and consists of a [M3(µ3-X)] core (X = O2- or OH-) wrapped by two [M(µ-bpp)3] units (Hbpp = 3,5-bis(2-pyridyl)pyrazole). The metal ions in the triangular core are coordinatively unsaturated, whereas the metal ions at the apical positions are coordinatively saturated. In other words, the pentanuclear scaffold possesses multiple redox-active centers and coordinatively unsaturated sites. It should also be noted that the electron transfer ability of the complex changes dramatically depending on the identity of the constituent metal ions. The iron derivative of the pentanuclear scaffold was found to serve as an electrocatalyst for water oxidation (2H2O → O2 + 4e- + 4H+) with a high reaction rate and excellent robustness. The substitution of metal ions in the pentanuclear scaffold to cobalt ions resulted in the development of a catalyst for CO2 reduction. Furthermore, we investigated the effect of substituents on the ligands of the pentanuclear iron complex and succeeded in precisely manipulating the electron transfer possess. These results clearly demonstrate that the pentanuclear scaffold is an attractive platform for catalysts for small-molecule conversions. Additionally, the intrinsic features of the multinuclear catalytic system, which are totally different from those of conventional mononuclear-metal-complex-based catalysts, are disclosed. In reactions mediated by multinuclear complexes, the multinuclear core can initially accumulate the charge required for catalysis to reach the catalytically active state. Subsequently, the catalyst in the active state reacts with the substrate, initiating electron transfer to the substrate and rearrangement of covalent bonds in the substrate to afford the product. In such a mechanism, the desired number of electrons can be transferred to the substrates in an on-demand fashion, and the formation of undesired chemical species in the targeted catalysis may be prevented. This feature of multinuclear-metal-complex-based catalysts will achieve demanding small-molecule conversions with a high reaction rate, selectivity, and durability.

Effect of metal ion substitution on the catalytic activity of a pentanuclear metal complex.

A pentanuclear cobalt complex that consists of five cobalt ions and six bpp- ligands (Co5, Hbpp = 3,5-bis(2-pyridyl)pyrazole) was synthesized and crystallographically characterized. Electrochemical measurements indicate that Co5 has multielectron transfer ability. We also found that Co5 reduces CO2 to CO under photoirradiation in the presence of a photosensitizer.