Functional Model of Compound II of Cytochrome P450: Spectroscopic Characterization and Reactivity Studies of a FeIV-OH Complex.

Herein, we show that the reaction of a mononuclear FeIII(OH) complex (1) with N-tosyliminobenzyliodinane (PhINTs) resulted in the formation of a FeIV(OH) species (3). The obtained complex 3 was characterized by an array of spectroscopic techniques and represented a rare example of a synthetic FeIV(OH) complex. The reaction of 1 with the one-electron oxidizing agent was reported to form a ligand-oxidized FeIII(OH) complex (2). 3 revealed a one-electron reduction potential of -0.22 V vs Fc+/Fc at -15 °C, which was 150 mV anodically shifted than 2 (Ered = -0.37 V vs Fc+/Fc at -15 °C), inferring 3 to be more oxidizing than 2. 3 reacted spontaneously with (4-OMe-C6H4)3C• to form (4-OMe-C6H4)3C(OH) through rebound of the OH group and displayed significantly faster reactivity than 2. Further, activation of the hydrocarbon C-H and the phenolic O-H bond by 2 and 3 was compared and showed that 3 is a stronger oxidant than 2. A detailed kinetic study established the occurrence of a concerted proton-electron transfer/hydrogen atom transfer reaction of 3. Studying one-electron reduction of 2 and 3 using decamethylferrocene (Fc*) revealed a higher ket of 3 than 2. The study established that the primary coordination sphere around Fe and the redox state of the metal center is very crucial in controlling the reactivity of high-valent Fe-OH complexes. Further, a FeIII(OMe) complex (4) was synthesized and thoroughly characterized, including X-ray structure determination. The reaction of 4 with PhINTs resulted in the formation of a FeIV(OMe) species (5), revealing the presence of two FeIV species with isomer shifts of -0.11 mm/s and = 0.17 mm/s in the Mössbauer spectrum and showed FeIV/FeIII potential at -0.36 V vs Fc+/Fc couple in acetonitrile at -15 °C. The reactivity studies of 5 were investigated and compared with the FeIV(OH) complex (3).

Directed Electron Delivery from a Pb-Free Halide Perovskite to a Co(II) Molecular Catalyst Boosts CO2 Photoreduction Coupled with Water Oxidation.

The development of high-performance photocatalytic systems for CO2 reduction is appealing to address energy and environmental issues, while it is challenging to avoid using toxic metals and organic sacrificial reagents. We here immobilize a family of cobalt phthalocyanine catalysts on Pb-free halide perovskite Cs2AgBiBr6 nanosheets with delicate control on the anchors of the cobalt catalysts. Among them, the molecular hybrid photocatalyst assembled by carboxyl anchors achieves the optimal performance with an electron consumption rate of 300±13 µmol g-1 h-1 for visible-light-driven CO2-to-CO conversion coupled with water oxidation to O2, over 8 times of the unmodified Cs2AgBiBr6 (36±8 µmol g-1 h-1), also far surpassing the documented systems (<150 µmol g-1 h-1). Besides the improved intrinsic activity, electrochemical, computational, ex-/in situ X-ray photoelectron and X-ray absorption spectroscopic results indicate that the electrons photogenerated at the Bi atoms of Cs2AgBiBr6 can be directionally transferred to the cobalt catalyst via the carboxyl anchors which strongly bind to the Bi atoms, substantially facilitating the interfacial electron transfer kinetics and thereby the photocatalysis.

Mapping the Ultrafast Mechanistic Pathways of Co Photocatalysts in Pure Water through Time-Resolved X-ray Spectroscopy.

Nanosecond time-resolved X-ray (tr-XAS) and optical transient absorption spectroscopy (OTA) are applied to study 3 multimolecular photocatalytic systems with [Ru(bpy)3 ]2+ photoabsorber, ascorbic acid electron donor and Co catalysts with methylene (1), hydroxomethylene (2) and methyl (3) amine substituents in pure water. OTA and tr-XAS of 1 and 2 show that the favored catalytic pathway involves reductive quenching of the excited photosensitizer and electron transfer to the catalyst to form a CoII square pyramidal intermediate with a bonded aqua molecule followed by a CoI square planar derivative that decays within ≈8 µs. By contrast, a CoI square pyramidal intermediate with a longer decay lifetime of ≈35 µs is formed from an analogous CoII geometry for 3 in H2 O. These results highlight the protonation of CoI to form the elusive hydride species to be the rate limiting step and show that the catalytic rate can be enhanced through hydrogen containing pendant amines that act as H-H bond formation proton relays.

Precious-Metal-Free CO2 Photoreduction Boosted by Dynamic Coordinative Interaction between Pyridine-Tethered Cu(I) Sensitizers and a Co(II) Catalyst.

Improving the photocatalytic efficiency of a fully noble-metal-free system for CO2 reduction remains a fundamental challenge, which can be accomplished by facilitating electron delivery as a consequence of exploiting intermolecular interactions. Herein, we have designed two Cu(I) photosensitizers with different pyridyl pendants at the phenanthroline moiety to enable dynamic coordinative interactions between the sensitizers and a cobalt macrocyclic catalyst. Compared to the parent Cu(I) photosensitizer, one of the pyridine-tethered derivatives boosts the apparent quantum yield up to 76 ± 6% at 425 nm for selective (near 99%) CO2-to-CO conversion. This value is nearly twice that of the parent system with no pyridyl pendants (40 ± 5%) and substantially surpasses the record (57%) of the noble-metal-free systems reported so far. This system also realizes a maximum turnover number of 11 800 ± 1400. In contrast, another Cu(I) photosensitizer, in which the pyridine substituents are directly linked to the phenanthroline moiety, is inactive. The above behavior and photocatalytic mechanism are systematically elucidated by transient fluorescence, transient absorption, transient X-ray absorption spectroscopies, and quantum chemical calculations. This work highlights the advantage of constructing coordinative interactions to fine-tune the electron transfer processes within noble-metal-free systems for CO2 photoreduction.

Structural and Spectroscopic Characterization of Copper(III) Complexes and Subsequent One-Electron Oxidation Reaction and Reactivity Studies.

The formation of Cu(III) species are often invoked as the key intermediate in Cu-catalyzed organic transformation reactions. In this study, we synthesized Cu(II) (1) and Cu(III) (3) complexes supported by a bisamidate-bisalkoxide ligand consisting of an ortho-phenylenediamine (o-PDA) scaffold and characterized them through an array of spectroscopic techniques, including UV-visible, electron paramagnetic resonance, X-ray crystallography, and 1H nuclear magnetic resonance (NMR) and X-ray absorption spectroscopy. The Cu-N/O bond distances in 3 are ∼0.1 Šreduced compared to 1, implying a significant increase in 3's overall effective nuclear charge. Further, a Cu(III) complex (4) of a bisamidate-bisalkoxide ligand containing a trans-cyclohexane-1,2-diamine moiety exhibits nearly identical Cu-N/O bond distances to that of 3, inferring that the redox-active o-PDA backbone is not oxidized upon one-electron oxidation of the Cu(II) complex (1). In addition, a considerable difference in the 1s → 4p and 1s → 3d transition energy was observed in the X-ray absorption near-edge structure data of 3 vs 1, which is typical for the metal-centered oxidation process. Electrochemical measurements of the Cu(II) complex (1) in acetonitrile exhibited two consecutive redox couples at -0.9 and 0.4 V vs the Fc+/Fc reference electrode. One-electron oxidation reaction of 3 further resulted in the formation of a ligand-oxidized Cu complex (3a), which was characterized in depth. Reactivity studies of species 3 and 3a were explored toward the activation of the C-H/O-H bonds. A bond dissociation free energy (BDFE) value of ∼69 kcal/mol was estimated for the O-H bond of the Cu(II) complex formed upon transfer of hydrogen atom to 3. The study represents a thorough spectroscopic characterization of high-valent Cu complexes and sheds light on the PCET reactivity studies of Cu(III) complexes.

Comparing the reactivity of an oxoiron(IV) cation radical and its oxoiron(V) tautomer towards C-H bonds.

An oxoiron(IV) cation radical is generated upon two-electron oxidation of an iron(III) complex bearing an electron-rich methoxy substituted bTAML framework and thoroughly characterized via multiple spectroscopic techniques and density functional theory (DFT). Reactivity studies demonstrate faster rates for oxidation of strong aliphatic sp3 C-H bonds than for its corresponding oxoiron(V) valence tautomer.

Heterogeneous Electrochemical Ammonia Oxidation with a Ru-bda Oligomer Anchored on Graphitic Electrodes via CH-π Interactions.

Molecular catalysts can promote ammonia oxidation, providing mechanistic insights into the electrochemical N2 cycle for a carbon-free fuel economy. We report the ammonia oxidation activity of carbon anodes functionalized with the oligomer {[RuII(bda-κ-N 2 O 2)(4,4'-bpy)]10(4,4'-bpy)}, Rubda-10, where bda is [2,2'-bipyridine]-6,6'-dicarboxylate and 4,4'-bpy is 4,4'-bipyridine. Electrocatalytic studies in propylene carbonate demonstrate that the Ru-based hybrid anode used in a 3-electrode configuration transforms NH3 to N2 and H2 in a 1:3 ratio with near-unity faradaic efficiency at an applied potential of 0.1 V vs Fc+/0, reaching turnover numbers of 7500. X-ray absorption spectroscopic analysis after bulk electrolysis confirms the molecular integrity of the catalyst. Based on computational studies together with electrochemical evidence, ammonia nucleophilic attack is proposed as the primary pathway that leads to critical N-N bond formation.

Characterization of Reaction Intermediates Involved in the Water Oxidation Reaction of a Molecular Cobalt Complex.

Molecular cobalt(III) complexes of bis-amidate-bis-alkoxide ligands, (Me4N)[CoIII(L1)] (1) and (Me4N)[CoIII(L2)] (2), are synthesized and assessed through a range of characterization techniques. Electrocatalytic water oxidation activity of the Co complexes in a 0.1 M phosphate buffer solution revealed a ligand-centered 2e-/1H+ transfer event at 0.99 V followed by catalytic water oxidation (WO) at an onset overpotential of 450 mV. By contrast, 2 reveals a ligand-based oxidation event at 0.9 V and a WO onset overpotential of 430 mV. Constant potential electrolysis study and rinse test experiments confirm the homogeneous nature of the Co complexes during WO. The mechanistic investigation further shows a pH-dependent change in the reaction pathway. On the one hand, below pH 7.5, two consecutive ligand-based oxidation events result in the formation of a CoIII(L2-)(OH) species, which, followed by a proton-coupled electron transfer reaction, generates a CoIV(L2-)(O) species that undergoes water nucleophilic attack to form the O-O bond. On the other hand, at higher pH, two ligand-based oxidation processes merge together and result in the formation of a CoIII(L2-)(OH) complex, which reacts with OH- to yield the O-O bond. The ligand-coordinated reaction intermediates involved in the WO reaction are thoroughly studied through an array of spectroscopic techniques, including UV-vis absorption spectroscopy, electron paramagnetic resonance, and X-ray absorption spectroscopy. A mononuclear CoIII(OH) complex supported by the one-electron oxidized ligand, [CoIII(L3-)(OH)]-, a formal CoIV(OH) complex, has been characterized, and the compound was shown to participate in the hydroxide rebound reaction, which is a functional mimic of Compound II of Cytochrome P450.

Effect of Redox-Inactive Metal Ion-Nickel(III) Interactions on the Redox Properties and Proton-Coupled Electron Transfer Reactivity.

Mononuclear nickel(II) and nickel(III) complexes of a bisamidate-bisalkoxide ligand, (NMe4)2[NiII(HMPAB)] (1) and (NMe4)[NiIII(HMPAB)] (2), respectively, have been synthesized and characterized by various spectroscopic techniques including X-ray crystallography. The reaction of redox-inactive metal ions (Mn+ = Ca2+, Mg2+, Zn2+, Y3+, and Sc3+) with 2 resulted in 2-Mn+ adducts, which was assessed by an array of spectroscopic techniques including X-ray absorption spectroscopy (XAS), electron paramagnetic resonance (EPR), and reactivity studies. The X-ray structure of Ca2+ coordinated to Ni(III) complexes, 2-Ca2+T, was determined and exhibited an average Ni-Ca distance of 3.1253 Å, close to the metal ions' covalent radius. XAS analysis of 2-Ca2+ and 2-Y3+ in solution further revealed an additional coordination to Ca and Y in the 2-Mn+ adducts with shortened Ni-M distances of 2.15 and 2.11 Å, respectively, implying direct bonding interactions between Ni and Lewis acids (LAs). Such a short interatomic distance between Ni(III) and M is unprecedented and was not observed before. EPR analysis of 2 and 2-Mn+ species, moreover, displayed rhombic signals with gav > 2.12 for all complexes, supporting the +III oxidation state of Ni. The NiIII/NiII redox potential of 2 and 2-Mn+ species was determined, and a plot of E1/2 of 2-Mn+ versus pKa of [M(H2O)n]m+ exhibited a linear relationship, implying that the NiIII/NiII potential of 2 can be tuned with different redox-inactive metal ions. Reactivity studies of 2 and 2-Mn+ with different 4-X-2,6-ditert-butylphenol (4-X-DTBP) and other phenol derivatives were performed, and based on kinetic studies, we propose the involvement of a proton-coupled electron transfer (PCET) pathway. Analysis of the reaction products after the reaction of 2 with 4-OMe-DTBP showed the formation of a Ni(II) complex (1a) where one of the alkoxide arms of the ligand is protonated. A pKa value of 24.2 was estimated for 1a. The reaction of 2-Mn+ species was examined with 4-OMe-DTBP, and it was observed that the k2 values of 2-Mn+ species increase by increasing the Lewis acidity of redox-inactive metal ions. However, the obtained k2 values for 2-Mn+ species are much lower compared to the k2 value for 2. Such a variation of PCET reactivity between 2 and 2-Mn+ species may be attributed to the interactions between Ni(III) and LAs. Our findings show the significance of the secondary coordination sphere effect on the PCET reactivity of Ni(III) complexes and furnish important insights into the reaction mechanism involving high-valent nickel species, which are frequently invoked as key intermediates in Ni-mediated enzymatic reactions, solar-fuel catalysis, and biomimetic/synthetic transformation reactions.

Deciphering the photophysical kinetics, electronic configurations and structural conformations of iridium-cobalt hydrogen evolution photocatalysts.

Picosecond optical and X-ray absorption spectroscopies with time-dependent density functional theory revealed the reaction pathways, electronic and structural conformations of Ir-Co hydrogen evolution photocatalysts. The dyad bearing 2-phenylpyridine ancillary ligands produced more photoreduced Co(II) than its 2-phenylisoquinoline analogue. These findings are important for designs of earth-abundant photosensitizers for photocatalytic applications.

Magnetic, Mechanically Interlocked Porphyrin-Carbon Nanotubes for Quantum Computation and Spintronics.

Atomic-scale reproducibility and tunability endorse magnetic molecules as candidates for spin qubits and spintronics. A major challenge is to implant those molecular spins into circuit geometries that may allow one, two, or a few spins to be addressed in a controlled way. Here, the formation of mechanically bonded, magnetic porphyrin dimeric rings around carbon nanotubes (mMINTs) is presented. The mechanical bond places the porphyrin magnetic cores in close contact with the carbon nanotube without disturbing their structures. A combination of spectroscopic techniques shows that the magnetic geometry of the dimers is preserved upon formation of the macrocycle and the mMINT. Moreover, the metallic core selection determines the spin location in the mMINT. The suitability of mMINTs as qubits is explored by measuring their quantum coherence times (Tm). Formation of the dimeric ring preserves the Tm found in the monomer, which remains in the µs scale for mMINTs. The carbon nanotube is used as vessel to place the molecules in complex circuits. This strategy can be extended to other families of magnetic molecules. The size and composition of the macrocycle can be tailored to modulate magnetic interactions between the cores and to introduce magnetic asymmetries (heterometallic dimers) for more complex molecule-based qubits.

Surface-Promoted Evolution of Ru-bda Coordination Oligomers Boosts the Efficiency of Water Oxidation Molecular Anodes.

A new Ru oligomer of formula {[RuII(bda-κ-N2O2)(4,4'-bpy)]10(4,4'-bpy)}, 10 (bda is [2,2'-bipyridine]-6,6'-dicarboxylate and 4,4'-bpy is 4,4'-bipyridine), was synthesized and thoroughly characterized with spectroscopic, X-ray, and electrochemical techniques. This oligomer exhibits strong affinity for graphitic materials through CH-π interactions and thus easily anchors on multiwalled carbon nanotubes (CNT), generating the molecular hybrid material 10@CNT. The latter acts as a water oxidation catalyst and converts to a new species, 10'(H2O)2@CNT, during the electrochemical oxygen evolution process involving solvation and ligand reorganization facilitated by the interactions of molecular Ru catalyst and the surface. This heterogeneous system has been shown to be a powerful and robust molecular hybrid anode for electrocatalytic water oxidation into molecular oxygen, achieving current densities in the range of 200 mA/cm2 at pH 7 under an applied potential of 1.45 V vs NHE. The remarkable long-term stability of this hybrid material during turnover is rationalized based on the supramolecular interaction of the catalyst with the graphitic surface.

Characterization and reactivity study of non-heme high-valent iron-hydroxo complexes.

A terminal FeIIIOH complex, [FeIII(L)(OH)]2- (1), has been synthesized and structurally characterized (H4L = 1,2-bis(2-hydroxy-2-methylpropanamido)benzene). The oxidation reaction of 1 with one equiv. of tris(4-bromophenyl)ammoniumyl hexachloroantimonate (TBAH) or ceric ammonium nitrate (CAN) in acetonitrile at -45 °C results in the formation of a FeIIIOH ligand radical complex, [FeIII(L˙)(OH)]- (2), which is hereby characterized by UV-visible, 1H nuclear magnetic resonance, electron paramagnetic resonance, and X-ray absorption spectroscopy techniques. The reaction of 2 with a triphenylcarbon radical further gives triphenylmethanol and mimics the so-called oxygen rebound step of Cpd II of cytochrome P450. Furthermore, the reaction of 2 was explored with different 4-substituted-2,6-di-tert-butylphenols. Based on kinetic analysis, a hydrogen atom transfer (HAT) mechanism has been established. A pK a value of 19.3 and a BDFE value of 78.2 kcal/mol have been estimated for complex 2.

Structure and excited-state dynamics of dimeric copper(i) photosensitizers investigated by time-resolved X-ray and optical transient absorption spectroscopy.

Time-resolved X-ray (tr-XAS) and optical transient absorption (OTA) spectroscopy in the picosecond time scale coupled with Density Functional theory (DFT) and X-ray absorption near-edge structure (XANES) calculations are applied to study three homoleptic Cu(i) dimeric chromophores with ethyl and longer propyl spacers, denoted as [Cu2(mphenet)2]Cl2 (C1), [Cu2(mphenet)2](ClO4)2 (C2) and [Cu2(mphenpr)2](ClO4)2 (C3) (where mphenet = 1,2-bis(9-methyl-1,10-phenanthrolin-2-yl)ethane and mphenpr = 1,3-bis(9-methyl-1,10-phenanthrolin-2-yl)propane). Tr-XAS analysis after light illumination at ∼ 100 ps illustrate the formation of a flattened triplet excited state in all 3 complexes. Optical transient absorption (OTA) analysis for C1 monitored in water and C2 and C3 measured in acetonitrile reveals distinct excited-state lifetimes of 169 ps, 670 ps and 1600 ps respectively. These differences are associated to changes in the solvent (comparing C1 and C2) and the flexibility of the ligand to adapt after Cu flattening upon excitation (C2 and C3). Our results are important for the improved structural dynamics of these types of Cu-based dimeric compounds, and can guide the integration of these chromophores into more complex solar energy conversion schemes.

Water oxidation electrocatalysis using ruthenium coordination oligomers adsorbed on multiwalled carbon nanotubes.

Photoelectrochemical cells that utilize water as a source of electrons are one of the most attractive solutions for the replacement of fossil fuels by clean and sustainable solar fuels. To achieve this, heterogeneous water oxidation catalysis needs to be mastered and properly understood. The search continues for a catalyst that is stable at the surface of electro(photo)anodes and can efficiently perform this reaction at the desired neutral pH. Here, we show how oligomeric Ru complexes can be anchored on the surfaces of graphitic materials through CH-π interactions between the auxiliary ligands bonded to Ru and the hexagonal rings of the graphitic surfaces, providing control of their molecular coverage. These hybrid molecular materials behave as molecular electroanodes that catalyse water oxidation to dioxygen at pH 7 with high current densities. This strategy for the anchoring of molecular catalysts on graphitic surfaces can potentially be extended to other transition metals and other catalytic reactions.

Redox Metal-Ligand Cooperativity Enables Robust and Efficient Water Oxidation Catalysis at Neutral pH with Macrocyclic Copper Complexes.

Water oxidation catalysis stands out as one of the most important reactions to design practical devices for artificial photosynthesis. Use of late first-row transition metal (TM) complexes provides an excellent platform for the development of inexpensive catalysts with exquisite control on their electronic and structural features via ligand design. However, the difficult access to their high oxidation states and the general labile character of their metal-ligand bonds pose important challenges. Herein, we explore a copper complex (12-) featuring an extended, π-delocalized, tetra-amidate macrocyclic ligand (TAML) as water oxidation catalyst and compare its activity to analogous systems with lower π-delocalization (22- and 32-). Their characterization evidences a special metal-ligand cooperativity in accommodating the required oxidative equivalents using 12- that is absent in 22- and 32-. This consists of charge delocalization promoted by easy access to different electronic states at a narrow energy range, corresponding to either metal-centered or ligand-centered oxidations, which we identify as an essential factor to stabilize the accumulated oxidative charges. This translates into a significant improvement in the catalytic performance of 12- compared to 22- and 32- and leads to one of the most active and robust molecular complexes for water oxidation at neutral pH with a kobs of 140 s-1 at an overpotential of only 200 mV. In contrast, 22- degrades under oxidative conditions, which we associate to the impossibility of efficiently stabilizing several oxidative equivalents via charge delocalization, resulting in a highly reactive oxidized ligand. Finally, the acyclic structure of 32- prevents its use at neutral pH due to acidic demetalation, highlighting the importance of the macrocyclic stabilization.

Analysis of the Active Species Responsible for Water Oxidation Using a Pentanuclear Fe Complex.

Water splitting with sunlight is today one of the most promising strategies that can be used to start the imperatively needed transition from fossil to solar fuels. To achieve this, one of the key reactions that need to be mastered is the electrocatalytic oxidation of water to dioxygen. Great developments have been achieved using transition metal complexes mainly based on Ru, but for technological applications it is highly desirable to be able to use earth-abundant transition metals. The intrinsic chemistry of first row transition metals and in particular the lability of their M-L bonds in water imposes serious challenges for the latter to work as real molecular catalysts. The present work addresses this issue based on a molecular pentanuclear Fe5 complex and describes the different protocols and tests that need to be carried out in order to identify the real active species, responsible for the generation of dioxygen.

Tracking the Light-Induced Excited-State Dynamics and Structural Configurations of an Extraordinarily Long-Lived Metastable State at Room Temperature.

Time-resolved X-ray (Tr-XAS) and optical transient absorption (OTA) spectroscopy on the pico-microsecond timescale coupled with density functional theory calculations are applied to study the light-induced spin crossover processes of a Fe-based macrocyclic complex in solution. Tr-XAS analysis after light illumination shows the formation of a seven-coordinated high-spin quintet metastable state, which relaxes to a six-coordinated high-spin configuration before decaying to the ground state. Kinetic analysis of the macrocyclic complex reveals an unprecedented long-lived decay lifetime of approximately 42.6 µs. Comparative studies with a non-macrocyclic counterpart illustrate a significantly shortened approximately 568-fold decay lifetime of about 75 ns, and highlight the importance of the ligand arrangement in stabilizing the reactivity of the excited state. Lastly, OTA analysis shows the seven-coordinated high-spin state to be formed within approximately 6.2 ps. These findings provide a complete understanding of the spin crossover reaction and relaxation pathways of the macrocyclic complex, and reveal the importance of a flexible coordination environment for their rational design.

The Coordination Behaviour of CuI Photosensitizers Bearing Multidentate Ligands Investigated by X-ray Absorption Spectroscopy.

A systematic series of four novel homo- and heteroleptic CuI photosensitizers based on tetradentate 1,10-phenanthroline ligands of the type X^N^N^X containing two additional donor moieties in the 2,9-position (X=SMe or OMe) were designed. Their solid-state structures were assessed by X-ray diffraction. Cyclic voltammetry, UV-vis absorption, emission and X-ray absorption spectroscopy were then used to determine their electrochemical, photophysical and structural features in solution. Following, time-resolved X-ray absorption spectroscopy in the picosecond time scale, coupled with time-dependent density functional theory calculations, provided in-depth information on the excited state electron configurations. For the first time, a significant shortening of the Cu-X distance and a change in the coordination mode to a pentacoordinated geometry is shown in the excited states of the two homoleptic complexes. These findings are important with respect to a precise understanding of the excited state structures and a further stabilization of this type of photosensitizers.

Electrochemically and Photochemically Induced Hydrogen Evolution Catalysis with Cobalt Tetraazamacrocycles Occurs Through Different Pathways.

Cobalt complexes containing equatorial tetraazamacrocyclic ligands are active catalysts for the hydrogen evolution reaction in pure aqueous conditions. We investigated the effect of different groups directly linked to the macrocyclic ligand (-NH-, -NCH3 -, or -N(CH2 OH)-). In electrochemically induced hydrogen evolution catalysis at pH 4, the rate determining step is the protonation of the reduced CoI species that gives a cobalt hydride (CoIII -H), a key intermediate towards the H-H bond formation. In sharp contrast, under photochemical conditions using [Ru(bpy)3 ]2+ (bpy=2,2'-bipyridine) as a photosensitizer and ascorbate as sacrificial electron donor, the formation of a Co0 species that quickly protonates to give a CoII -H is proposed. In this scenario, the rate determining step is the H-H bond formation that occurs in an intermolecular fashion from the CoII -H species and a water molecule. Both mechanisms are supported by DFT calculations, which allowed us to estimate the pKa values of the CoIII -H and CoII -H species and transition states based on intramolecular and intermolecular H-H bond formation from CoII -H.