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Thirteen boronated cyanometallates [M(CN-BR

The dynamics of photodissociation and recombination in heme proteins represent an archetypical photochemical reaction widely used to understand the interplay between chemical dynamics and reaction environment. We report a study of the photodissociation mechanism for the Fe(II)-S bond between the heme iron and methionine sulfur of ferrous cytochrome c. This bond dissociation is an essential step in the conversion of cytochrome c from an electron transfer protein to a peroxidase enzyme. We use ultrafast X-ray solution scattering to follow the dynamics of Fe(II)-S bond dissociation and 1s3p (Kβ) X-ray emission spectroscopy to follow the dynamics of the iron charge and spin multiplicity during bond dissociation. From these measurements, we conclude that the formation of a triplet metal-centered excited state with anti-bonding Fe(II)-S interactions triggers the bond dissociation and precedes the formation of the metastable Fe high-spin quintet state., The dissociation mechanism of the heme axial ligand in heme proteins is not yet fully understood. The authors investigate the photodissociation dynamics of the bond between heme Fe and methionine S in ferrous cytochrome c using femtosecond time-resolved X-ray solution scattering and X-ray emission spectroscopy, simultaneously tracking electronic and nuclear structure changes.

Earth-abundant oxygen evolution catalysts (OECs) with extended stability in acid can be constructed by embedding active sites within an acid-stable metal-oxide framework. Here, we report stable NiPbO(x) films that are able to perform oxygen evolution reaction (OER) catalysis for extended periods of operation (>20 h) in acidic solutions of pH 2.5; conversely, native NiO(x) catalyst films dissolve immediately. In situ X-ray absorption spectroscopy and ex situ X-ray photoelectron spectroscopy reveal that PbO(2) is unperturbed after addition of Ni and/or Fe into the lattice, which serves as an acid-stable, conductive framework for embedded OER active centers. The ability to perform OER in acid allows the mechanism of Fe doping on Ni catalysts to be further probed. Catalyst activity with Fe doping of oxidic Ni OEC under acid conditions, as compared to neutral or basic conditions, supports the contention that role of Fe(3+) in enhancing catalytic activity in Ni oxide catalysts arises from its Lewis acid properties.

Complexes with the formula [M(diimine)(CN-BR3)4]2–, where diimine = bipyridine (bpy), phenanthroline (phen), 3,5-trifluoromethylbipyridine (flpy), R = Ph, C6F5, and M = FeII, RuII, were synthesized...

Iron porphyrin carbenes (IPCs) are important reaction intermediates in engineered carbene transferase enzymes and homogeneous catalysis. However, discrepancies between theory and experiment complicate the understanding of IPC electronic structure. In the literature, this has been framed as whether the ground state is an open- vs closed-shell singlet (OSS vs CSS). Here we investigate the structurally dependent ground and excited spin-state energetics of a free carbene and its IPC analogs with variable trans axial ligands. In particular, for IPCs, multireference ab initio wave function methods are more consistent with experiment and predict a mixed singlet ground state that is dominated by the CSS (Fe(II) ← {:C(X)Y}0) configuration (i.e., electrophilic carbene) but that also has a small, non-negligible contribution from an Fe(III)–{C(X)Y}−• configuration (hole in d(xz), i.e., radical carbene). In the multireference approach, the “OSS-like” excited states are metal-to-ligand charge transfer (MLCT) in nature and are energetically well above the CSS-dominated ground state. The first, lowest energy of these “OSS-like” excited states is predicted to be heavily weighted toward the Fe(III)–{C(X)Y}−• (hole in d(yz)) configuration. As expected from exchange considerations, this state falls energetically above a triplet of the same configuration. Furthermore, potential energy surfaces (PESs) along the IPC Fe–C(carbene) bond elongation exhibit increasingly strong mixings between CSS/OSS characters, with the Fe(III)–{C(X)Y}−• configuration (hole in d(xz)) growing in weight in the ground state during bond elongation. The relative degree of electrophilic/radical carbene character along this structurally relevant PES can potentially play a role in reactivity and selectivity patterns in catalysis. Future studies on IPC reaction coordinates should evaluate contributions from ground and excited state multireference character.

Herein, we report a Cu-catalyzed enantioselective allylic alkylation using a γ-butyrolactone-derived silyl ketene acetal. Critical to the development of this work was the identification of a novel mono-picolinamide ligand with the appropriate steric and electronic properties to afford the desired products in high yields (up to 96%) and high ee (up to 95%). Aryl, aliphatic, and unsubstituted allylic chlorides bearing a broad range of functionality are well-tolerated. Spectroscopic studies reveal that a Cu(I) species is likely the active catalyst, and DFT calculations suggest ligand sterics play an important role in determining Cu coordination and thus catalyst geometry.

Quantum coherence of S = 1/2 transition metal-based quantum bits (qubits) is strongly influenced by the magnitude of spin-phonon coupling. While this coupling is recognized as deriving from dynamic distortions about the first coordination sphere of the metal, a general model for understanding and quantifying ligand field contributions has not been established. Here we derive a general ligand field theory model to describe and quantify the nature of spin-phonon coupling terms in S = 1/2 transition metal complexes. We show that the coupling term for a given vibrational mode is governed by: (1) the magnitude of the metal-based spin-orbit coupling constant, (2) the magnitude and gradient in the ligand field excited state energy, which determines the magnitude of ground state orbital angular momentum, and (3) dynamic relativistic nephelauxetic contributions reflecting the magnitude and gradient in the covalency of the ligand-metal bonds. From an extensive series of density functional theory (DFT) and time-dependent DFT (TDDFT) calculations calibrated to a range of experimental data, spin-phonon coupling terms describing minimalistic D4h/D2d [CuCl4]2- and C4v [VOCl4]2- complexes translate to and correlate with experimental quantum coherence properties observed for Cu(ii)- and V(iv)-based molecular qubits with different ligand sets, geometries, and coordination numbers. While providing a fundamental framework and means to benchmark current qubits, the model and methodology described herein can be used to screen any S = 1/2 molecular qubit candidate and guide the discovery of room temperature coherent materials for quantum information processing.

Ni 2,2’–bipyridine (bpy) complexes are commonly employed photoredox catalysts of bond-forming reactions in organic chemistry. However, the mechanisms by which they operate are still under investigation. One potential mode of catalysis is via entry into Ni(I)/Ni(III) cycles, which can be made possible by light-induced, excited state Ni(II)–C bond homolysis. Here we report experimental and computational analyses of a library of Ni(II)-bpy aryl halide complexes, Ni(Rbpy)(R′Ph)Cl (R = MeO, t-Bu, H, MeOOC; R′ = CH3, H, OMe, F, CF3), to illuminate the mechanism of excited state bond homolysis. At given excitation wavelengths, photochemical homolysis rates span two orders of magnitude across these structures and correlate linearly with Hammett parameters of both bpy and aryl ligands, reflecting structural control over key metal-to-ligand charge transfer (MLCT) and ligand-to-metal charge transfer (LMCT) excited state potential energy surfaces (PESs). Temperature- and wavelength-dependent investigations reveal moderate excited state barriers (ΔH‡ ~4 kcal mol-1) and a minimum energy excitation threshold (~55 kcal mol-1, 525 nm), respectively. Correlations to electronic structure calculations further support a mechanism in which repulsive triplet excited state PESs featuring a critical aryl-to-Ni LMCT lead to bond rupture. Structural control over excited state PESs provides a rational approach to utilize photonic energy and leverage excited state bond homolysis processes in synthetic chemistry.

Developing quantum bits (qubits) exhibiting room temperature electron spin coherence is a key goal of molecular quantum information science. At high temperatures, coherence is often limited by electron spin relaxation, measured by T1. Here we develop a simple and powerful model for predicting relative T1 relaxation times in transition metal complexes from dynamic ligand field principles. By considering the excited state origins of ground state spin-phonon coupling, we derive group theory selection rules governing which vibrational symmetries can induce decoherence. Thermal weighting of the coupling terms produces surprisingly good predictions of experimental T1 trends as a function of temperature and explains previously confounding features in spin-lattice relaxation data. We use this model to evaluate experimental relaxation rates across S = 1/2 transition metal qubit candidates with diverse structures, gaining new insights into the interplay between spin-phonon coupling and molecular symmetry. This methodology elucidates the specific vibrational modes giving rise to decoherence, providing insight into the origin of room temperature coherence in transition metal complexes. We discuss the outlook of symmetry-based modeling and design strategies for understanding molecular coherence.

The photogeneration of X2 is the key to achieving an efficient HX-splitting photocycle, as it is more thermodynamically and kinetically challenging than its H2 half reaction counterpart. Here we report a strategy that enables Cl2 photoelimination from low-valent binuclear d9–d9 and d9–d10 Ni complexes. We demonstrate the importance a of metal–metal bond interaction for M–X bond photoactivation with a combination of TD-DFT computations together with spectroscopy and photocrystallography, exemplifying a design principle for future developments of 3d metal complexes for HX photocatalysis.

Iron alloying of oxidic cobaltate catalysts results in catalytic activity for oxygen evolution on par with Ni-Fe oxides in base but at much higher alloying compositions. Zero-field 57Fe Mössbauer spectroscopy and X-ray absorption spectroscopy (XAS) are able to clearly identify Fe4+ in mixed-metal Co-Fe oxides. The highest Fe4+ population is obtained in the 40–60% Fe alloying range, and XAS identifies the ion residing in an octahedral oxide ligand field. The oxygen evolution reaction (OER) activity, as reflected in Tafel analysis of CoFeOx films in 1 M KOH, tracks the absolute concentration of Fe4+. The results reported herein suggest an important role for the formation of the Fe4+ redox state in activating cobaltate OER catalysts at high iron loadings., The capturing of high valent iron in a catalytic reaction is important but difficult task. Here, the authors report identification of a high-valent Fe(IV)-species with different spectroscopic tools such as Mössbauer spectroscopy and X-ray absorption spectroscopy during the course of an oxygen evolving reaction.

One of the most oft-employed methods for C-C bond formation involving the coupling of vinyl-halides with aldehydes catalyzed by Ni and Cr (Nozaki-Hiyama-Kishi, NHK) has been rendered more practical using an electroreductive manifold. Although early studies pointed to the feasibility of such a process, those precedents were never applied by others due to cumbersome setups and limited scope. Here we show that a carefully optimized electroreductive procedure can enable a more sustainable approach to NHK, even in an asymmetric fashion on highly complex medicinally relevant systems. The e-NHK can even enable non-canonical substrate classes, such as redox-active esters, to participate with low loadings of Cr when conventional chemical techniques fail. A combination of detailed kinetics, cyclic voltammetry, and in situ UV-vis spectroelectrochemistry of these processes illuminates the subtle features of this mechanistically intricate process.

Multireference electronic structure calculations consistent with known experimental data have elucidated a novel mechanism for photo-triggered Ni(II)–C homolytic bond dissociation in Ni 2,2’-bipyridine (bpy) photoredox catalysts. Previously, a thermally assisted dissociation from the lowest energy triplet ligand field excited state was proposed and supported by density functional theory (DFT) calculations that reveal a barrier of ~30 kcal mol-1. In contrast, multireference ab initio calculations suggest this process is disfavored, with barrier heights of ~70 kcal mol-1, and highlight important ligand noninnocent contributions to excited state relaxation and bond dissociation processes that are not captured with DFT. In the multireference description, photo-triggered Ni(II)–C homolytic bond dissociation occurs via initial population of a singlet Ni(II)-to-bpy metal-to-ligand charge transfer (1MLCT) excited state followed by intersystem crossing and aryl-to-Ni(III) charge transfer, overall a formal two-electron transfer process driven by a single photon. This results in repulsive triplet excited states from which spontaneous homolytic bond dissociation can occur, effectively competing with relaxation to the lowest energy, nondissociative triplet Ni(II) ligand field excited state. These findings guide important electronic structure considerations for the experimental and computational elucidation of the mechanisms of ground and excited state cross-coupling catalysis mediated by Ni heteroaromatic complexes.

Recent interest in transition-metal complexes as potential quantum bits (qubits) has reinvigorated the investigation of fundamental contributions to electron spin relaxation in various ligand scaffolds. From quantum computers to chemical and biological sensors, interest in leveraging the quantum properties of these molecules has opened a discussion of the requirements to maintain coherence over a large temperature range, including near room temperature. Here we compare temperature-, magnetic field position-, and concentration-dependent electron spin relaxation in copper(II) phthalocyanine (CuPc) and vanadyl phthalocyanine (VOPc) doped into diamagnetic hosts. While VOPc demonstrates coherence up to room temperature, CuPc coherence times become rapidly T₁-limited with increasing temperature, despite featuring a more covalent ground-state wave function than VOPc. As rationalized by a ligand field model, this difference is ascribed to different spin–orbit coupling (SOC) constants for Cu(II) versus V(IV). The manifestation of SOC contributions to spin–phonon coupling and electron spin relaxation in different ligand fields is discussed, allowing for a further understanding of the competing roles of SOC and covalency in electron spin relaxation.

Complexes with the formula [M(diimine)(CN-BR

A dicobalt(II) complex, [Co2(mBDCA-5t)](2-) (1), demonstrates a cofacial arrangement of trigonal monopyramidal Co(II) ions with an inter-metal separation of 6.2710(6) A. Reaction of 1 with potassium superoxide generates an encapsulated Co-O-Co core in the dianionic complex, [Co2O(mBDCA-5t)](2-) (2); to form the linear Co-O-Co core, the inter-metal distance has diminished to 3.994(3) A. Co K-edge X-ray absorption spectroscopy data are consistent with a +2 oxidation state assignment for Co in both 1 and 2. Multireference complete active space calculations followed by second-order perturbation theory support this assignment, with hole equivalents residing on the bridging O-atom and on the cryptand ligand for the case of 2. Complex 2 acts as a 2-e(-) oxidant toward substrates including CO and H2, in both cases efficiently regenerating 1 in what represent net oxygen-atom-transfer reactions. This dicobalt system also functions as a catalase upon treatment with H2O2.

Sulfur's balancing act in cytochrome c Cytochrome c enzymes have two distinct functions that depend on the position of a methionine residue. When the sulfur in the methionine side chain coordinates with iron in the enzyme's active site, the protein is optimized for electron transfer; otherwise, it is poised for peroxidase activity. Mara et al. used ultrafast x-ray absorption and emission spectroscopy to probe the energetics of this Fe-S bond (see the Perspective by Bren and Raven). By breaking the bond transiently with light and then timing its reformation, they determined that the surrounding protein environment boosts the bond strength by 4 kilocalories per mole—just enough to toggle between each functional state at a practical rate. Science , this issue p. 1276 ; see also p. 1236

The Co4O4 cubane is a representative structural model of oxidic cobalt oxygen-evolving catalysts (Co-OECs). The Co-OECs are active when residing at two oxidation levels above an all-Co(III) resting state. This doubly oxidized Co(IV)2 state may be captured in a Co(III)2(IV)2 cubane. We demonstrate that the Co(III)2(IV)2 cubane may be electrochemically generated and the electronic properties of this unique high-valent state may be probed by in situ spectroscopy. Intervalence charge-transfer (IVCT) bands in the near-IR are observed for the Co(III)2(IV)2 cubane, and spectroscopic analysis together with electrochemical kinetics measurements reveal a larger reorganization energy and a smaller electron transfer rate constant for the doubly versus singly oxidized cubane. Spectroelectrochemical X-ray absorption data further reveal systematic spectral changes with successive oxidations from the cubane resting state. Electronic structure calculations correlated to experimental data suggest that this state is best represented as a localized, antiferromagnetically coupled Co(IV)2 dimer. The exchange coupling in the cofacial Co(IV)2 site allows for parallels to be drawn between the electronic structure of the Co4O4 cubane model system and the high-valent active site of the Co-OEC, with specific emphasis on the manifestation of a doubly oxidized Co(IV)2 center on O–O bond formation.

Significance Iron-doped nickel oxide films are the most active nonnoble metal oxygen evolution reaction (OER) catalysts in alkaline electrolyte. Since Corrigan’s original discovery of enhanced activity with Fe doping in nickel oxides, the chemical basis for this synergy remains unclear. Recent studies suggest iron to assume a high valent oxidation state, thus promoting OER. We provide evidence for an alternative role of Fe 3+ as a Lewis acid in the host nickel oxide. We observe that Fe 3+ promotes the formation of Ni 4+ , which leads to enhanced catalytic activity. This result is consistent with Fe 3+ to be one of the strongest Lewis acidic metals by any measure of Lewis acidity, including hard–soft acid base theory, metal ion pK a s, and chemical inertness.

The entatic or rack-induced state is a core concept in bioinorganic chemistry. In its simplest form, it is present when a protein scaffold places a transition metal ion and its first coordination sphere into an energized geometric and electronic structure that differs significantly from that of the relaxed form. This energized complex can exhibit special properties. Under this purview, however, entatic states are hardly unique to bioinorganic chemistry, and their effects can be found throughout a variety of important chemistries and materials science applications. Despite this broad influence, there are only a few examples where entatic effects have been quantified. Here we extend the entatic concept more generally to photophysical processes by developing a combined experimental and computational methodology to quantify entatic states across an entire class of functional molecules, e.g., Cu-based photosensitizers. These metal complexes have a broad range of applications, including solar electricity generation, solar fuels synthesis, organic light emitting diodes (OLEDs), and photoredox catalysis. As a direct consequence of quantifying entatic states, this methodology allows the disentanglement of steric and electronic contributions to excited state dynamics. Thus, before embarking on the syntheses of new Cu-based photosensitizers, the correlations described herein can be used as an estimate of entatic and electronic contributions and thus guide ligand design and the development of next-generation transition metal complexes with improved or tailored excited state dynamics. Lastly, entatic energies in some Cu photosensitizers are the largest yet quantified and are found here to approach 20 kcal/mol relative to the conformationally flexible [Cu(phen)₂]⁺. These energetics are significant relative to typical chemical driving forces and barriers, highlighting the utility in extending entatic state descriptors to new classes of molecules and materials with interesting functional properties involving the coupling between electron and vibrational dynamics.

Magnetization dynamics of transition metal complexes manifest in properties and phenomena of fundamental and applied interest [e.g., slow magnetic relaxation in single molecule magnets, quantum coherence in quantum bits (qubits), and intersystem crossing (ISC) rates in photophysics]. While spin–phonon coupling is recognized as an important determinant of these dynamics, additional fundamental studies are required to unravel the nature of the coupling and, thus, leverage it in molecular engineering approaches. To this end, we describe here a combined ligand field theory and multireference ab initio model to define spin–phonon coupling terms in S = 2 transition metal complexes and demonstrate how couplings originate from both the static and dynamic properties of ground and excited states. By extending concepts to spin conversion processes, ligand field dynamics manifest in the evolution of the excited state origins of zero-field splitting (ZFS) along specific normal mode potential energy surfaces. Dynamic ZFSs provide a powerful means to independently evaluate contributions from spin-allowed and/or spin-forbidden excited states to spin–phonon coupling terms. Furthermore, ratios between various intramolecular coupling terms for a given mode drive spin conversion processes in transition metal complexes and can be used to analyze the mechanisms of ISC. Variations in geometric structure strongly influence the relative intramolecular linear spin–phonon coupling terms and will define the overall spin state dynamics. While the findings of this study are of general importance for understanding magnetization dynamics, they also link the phenomenon of spin–phonon coupling across fields of single molecule magnetism, quantum materials/qubits, and transition metal photophysics.

A direct, catalytic conversion of benzene to phenol would have wide-reaching economic impacts. Fe zeolites exhibit a remarkable combination of high activity and selectivity in this conversion, leading to their past implementation at the pilot plant level. There were, however, issues related to catalyst deactivation for this process. Mechanistic insight could resolve these issues, and also provide a blueprint for achieving high performance in selective oxidation catalysis. Recently, we demonstrated that the active site of selective hydrocarbon oxidation in Fe zeolites, named α-O, is an unusually reactive Fe(IV)=O species. Here, we apply advanced spectroscopic techniques to determine that the reaction of this Fe(IV)=O intermediate with benzene in fact regenerates the reduced Fe(II) active site, enabling catalytic turnover. At the same time, a small fraction of Fe(III)-phenolate poisoned active sites form, defining a mechanism for catalyst deactivation. Density-functional theory calculations provide further insight into the experimentally defined mechanism. The extreme reactivity of α-O significantly tunes down (eliminates) the rate-limiting barrier for aromatic hydroxylation, leading to a diffusion-limited reaction coordinate. This favors hydroxylation of the rapidly diffusing benzene substrate over the slowly diffusing (but more reactive) oxygenated product, thereby enhancing selectivity. This defines a mechanism to simultaneously attain high activity (conversion) and selectivity, enabling the efficient oxidative upgrading of inert hydrocarbon substrates. ispartof: Proceedings of the National Academy of Sciences of the United States of America vol:115 issue:48 pages:12124-12129 ispartof: location:United States status: published

The nature of the photoexcited state of octabutoxy nickel(II) phthalocyanine (NiPcOBu

Two distinct [Cu-O-Cu]^(2+) sites with methane monooxygenase activity are identified in the zeolite Cu-MOR, emphasizing that this Cu-O-Cu active site geometry, having a ∠Cu-O-Cu ∼140°, is particularly formed and stabilized in zeolite topologies. Whereas in ZSM-5 a similar [Cu-O-Cu]^(2+) active site is located in the intersection of the two 10 membered rings, Cu-MOR provides two distinct local structures, situated in the 8 membered ring windows of the side pockets. Despite their structural similarity, as ascertained by electronic absorption and resonance Raman spectroscopy, the two Cu-O-Cu active sites in Cu-MOR clearly show different kinetic behaviors in selective methane oxidation. This difference in reactivity is too large to be ascribed to subtle differences in the ground states of the Cu-O-Cu sites, indicating the zeolite lattice tunes their reactivity through second-sphere effects. The MOR lattice is therefore functionally analogous to the active site pocket of a metalloenzyme, demonstrating that both the active site and its framework environment contribute to and direct reactivity in transition metal ion-zeolites.

In this report we describe the synthesis of a new phenanthroline ligand, 2,9-di(2,4,6-tri-isopropyl-phenyl)-1,10-phenanthroline (bL2) and its use as the blocking ligand in the preparation of two new heteroleptic Cu(i)diimine complexes. Analysis of the CuHETPHEN single crystal structures shows a distinct distortion from an ideal tetrahedral geometry around the Cu(i) center, forced by the secondary phenanthroline ligand rotating to accommodate the isopropyl groups of bL2. The increased steric bulk of bL2 as compared to the more commonly used 2,9-dimesityl-1,10-phenanthroline blocking ligand prohibits intramolecular ligand-ligand interaction, which is unique among CuHETPHEN complexes. The ground state optical and redox properties of CuHETPHEN complexes are responsive to the substitution on the blocking ligand even though the differences in structure are far removed from the Cu(i) center. Transient optical spectroscopy was used to understand the excited state kinetics in both coordinating and non-coordinating solvents following visible excitation. Substitution of the blocking phenanthroline ligand has a significant impact on the ^3MLCT decay and can be used to increase the excited state lifetime by 50%. Electronic structure calculations established relationships between ground and excited state properties, and general entatic state concepts are discussed for copper photosensitizers. This work contributes to the growing library of CuHETPHEN complexes and broadens the fundamental understanding of their ground and excited state properties.

This review focuses on the unique spectroscopic features of the blue copper active sites. These reflect a novel electronic structure that activates the site for rapid long-range electron transfer in its biological function. The role of the protein in determining the geometric and electronic structure of this site is defined, as is its contribution to function. This has been referred to as the entatic/rack-induced state. These concepts are then extended to cytochrome c, which is also determined to be in an entatic state.

The Co-OEC (oxygen-evolving catalyst) is an exemplary OEC that has provided a wealth of kinetics information on the proton-coupled electron transfer mechanism of O–O bond formation. Whereas electrochemical kinetics studies establish a high-valent Co(IV)2 oxidation state as a prerequisite for catalysis, this species cannot be spectroscopically examined in thin-film Co-OECs owing to its short lifetime and dilution against a largely Co(III) background. A molecular model of this high-valent active species is provisioned in the form of a doubly oxidized Co(III)2(IV)2 cubane. In situ X-ray absorption spectroscopic examination of this high-valent state of the cubane provides direct insights into the electronic structure of a Co(IV)2 site and into its role in the mechanism of O–O bond formation.

Developing light-harvesting and photocatalytic molecules made with iron could provide a cost effective, scalable, and environmentally benign path for solar energy conversion. To date these developments have been limited by the sub-picosecond metal-to-ligand charge transfer (MLCT) electronic excited state lifetime of iron based complexes due to spin crossover-the extremely fast intersystem crossing and internal conversion to high spin metal-centered excited states. We revitalize a 30 year old synthetic strategy for extending the MLCT excited state lifetimes of iron complexes by making mixed ligand iron complexes with four cyanide (CN-;) ligands and one 2,2′-bipyridine (bpy) ligand. This enables MLCT excited state and metal-centered excited state energies to be manipulated with partial independence and provides a path to suppressing spin crossover. We have combined X-ray Free-Electron Laser (XFEL) Kβ hard X-ray fluorescence spectroscopy with femtosecond time-resolved UV-visible absorption spectroscopy to characterize the electronic excited state dynamics initiated by MLCT excitation of [Fe(CN)4(bpy)]2-. The two experimental techniques are highly complementary; the time-resolved UV-visible measurement probes allowed electronic transitions between valence states making it sensitive to ligand-centered electronic states such as MLCT states, whereas the Kβ fluorescence spectroscopy provides a sensitive measure of changes in the Fe spin state characteristic of metal-centered excited states. We conclude that the MLCT excited state of [Fe(CN)4(bpy)]2- decays with roughly a 20 ps lifetime without undergoing spin crossover, exceeding the MLCT excited state lifetime of [Fe(2,2′-bipyridine)3]2+ by more than two orders of magnitude.

Type one (T1) Cu sites deliver electrons to catalytic Cu active sites: the mononuclear type two (T2) Cu site in nitrite reductases (NiRs) and the trinuclear Cu cluster in the multicopper oxidases (MCOs). The T1 Cu and the remote catalytic sites are connected via a Cys-His intramolecular electron-transfer (ET) bridge, which contains two potential ET pathways: P1 through the protein backbone and P2 through the H-bond between the Cys and the His. The high covalency of the T1 Cu-S(Cys) bond is shown here to activate the T1 Cu site for hole superexchange via occupied valence orbitals of the bridge. This covalency-activated electronic coupling (H_(DA)) facilitates long-range ET through both pathways. These pathways can be selectively activated depending on the geometric and electronic structure of the T1 Cu site and thus the anisotropic covalency of the T1 Cu-S(Cys) bond. In NiRs, blue (π-type) T1 sites utilize P1 and green (σ-type) T1 sites utilize P2, with P2 being more efficient. Comparing the MCOs to NiRs, the second-sphere environment changes the conformation of the Cys-His pathway, which selectively activates HDA for superexchange by blue π sites for efficient turnover in catalysis. These studies show that a given protein bridge, here Cys-His, provides different superexchange pathways and electronic couplings depending on the anisotropic covalencies of the donor and acceptor metal sites.

Understanding the formation mechanism of the [Cu2O](2+) active site in Cu-ZSM-5 is important for the design of efficient catalysts to selectively convert methane to methanol and related value-added chemicals and for N2O decomposition. Spectroscopically validated DFT calculations are used here to evaluate the thermodynamic and kinetic requirements for formation of [Cu2O](2+) active sites from the reaction between binuclear Cu(I) sites and N2O in the 10-membered rings Cu-ZSM-5. Thermodynamically, the most stable Cu(I) center prefers bidentate coordination with a close to linear bite angle. This binuclear Cu(I) site reacts with N2O to generate the experimentally observed [Cu2O](2+) site. Kinetically, the reaction coordinate was evaluated for two representative binuclear Cu(I) sites. When the Cu-Cu distance is sufficiently short (4.2 Å), N2O can bind in a "bridged" μ-1,1-O fashion and the oxo-transfer reaction is calculated to proceed with a low activation energy barrier (2 kcal/mol). This is in good agreement with the experimental Ea for N2O activation (2.5 ± 0.5 kcal/mol). However, when the Cu-Cu distance is long (5.0 Å), N2O binds in a "terminal" η(1)-O fashion to a single Cu(I) site of the dimer and the resulting E(a) for N2O activation is significantly higher (16 kcal/mol). Therefore, bridging N2O between two Cu(I) centers is necessary for its efficient two-electron activation in [Cu2O](2+) active site formation. In nature, this N2O reduction reaction is catalyzed by a tetranuclear CuZ cluster that has a higher E(a). The lower E(a) for Cu-ZSM-5 is attributed to the larger thermodynamic driving force resulting from formation of strong Cu(II)-oxo bonds in the ZSM-5 framework.

Metal-sulfenate centers are known to play important roles in biology and yet only limited examples are known due to their instability and high reactivity. Herein we report a copper-sulfenate complex characterized in a protein environment, formed at the active site of a cavity mutant of an electron transfer protein, type 1 blue copper azurin. Reaction of hydrogen peroxide with Cu(I)-M121G azurin resulted in a species with strong visible absorptions at 350 and 452 nm and a relatively low electron paramagnetic resonance gz value of 2.169 in comparison with other normal type 2 copper centers. The presence of a side-on copper-sulfenate species is supported by resonance Raman spectroscopy, electrospray mass spectrometry using isotopically enriched hydrogen peroxide, and density functional theory calculations correlated to the experimental data. In contrast, the reaction with Cu(II)-M121G or Zn(II)-M121G azurin under the same conditions did not result in Cys oxidation or copper-sulfenate formation. Structural and computational studies strongly suggest that the secondary coordination sphere noncovalent interactions are critical in stabilizing this highly reactive species, which can further react with oxygen to form a sulfinate and then a sulfonate species, as demonstrated by mass spectrometry. Engineering the electron transfer protein azurin into an active copper enzyme that forms a copper-sulfenate center and demonstrating the importance of noncovalent secondary sphere interactions in stabilizing it constitute important contributions toward the understanding of metal-sulfenate species in biological systems.

A dianionic, square planar cobalt(II) complex reacts with O2 in the presence of acetonitrile to give a cyanomethylcobalt(III) complex formed by C–H bond cleavage. Interestingly, PhIO and p-tolyl azide react similarly to give the same cyanomethylcobalt(III) complex. Competition studies with various hydrocarbon substrates indicate that the rate of C–H bond cleavage greatly depends on the pKa of the C–H bond, rather than on the C–H bond dissociation energy. Kinetic isotope experiments reveal a moderate KIE value of ca. 3.5 using either O2 or PhIO. The possible involvement of a cobalt(IV) oxo species in this chemistry is discussed.

The formation of high-valent states is a key factor in making highly active transition-metal-based catalysts of the oxygen evolution reaction (OER). These high oxidation states will be strongly influenced by the local geometric and electronic structures of the metal ion, which are difficult to study due to spectroscopically active and complex backgrounds, short lifetimes, and limited concentrations. Here, we use a wide range of complementary X-ray spectroscopies coupled to DFT calculations to study Co(III)_4O_4 cubanes and their first oxidized derivatives, which provide insight into the high-valent Co(IV) centers responsible for the activity of molecular and heterogeneous OER catalysts. The combination of X-ray absorption and 1s3p resonant inelastic X-ray scattering (Kβ RIXS) allows Co(IV) to be isolated and studied against a spectroscopically active Co(III) background. Co K- and L-edge X-ray absorption data allow for a detailed characterization of the 3d-manifold of effectively localized Co(IV) centers and provide a direct handle on the t_(2g)-based redox-active molecular orbital. Kβ RIXS is also shown to provide a powerful probe of Co(IV), and specific spectral features are sensitive to the degree of oxo-mediated metal-metal coupling across Co_4O_4. Guided by the data, calculations show that electron-hole delocalization can actually oppose Co(IV) formation. Computational extension of Co_4O_4 to CoM_3O_4 structures (M = redox-inactive metal) defines electronic structure contributions to Co(IV) formation. Redox activity is shown to be linearly related to covalency, and M(III) oxo inductive effects on Co(IV) oxo bonding can tune the covalency of high-valent sites over a large range and thereby tune E^0 over hundreds of millivolts. Additionally, redox-inactive metal substitution can also switch the ground state and modify metal-metal and antibonding interactions across the cluster.

Developing photocatalytic systems for water splitting to generate oxygen and hydrogen is one of the biggest chemical challenges in solar energy utilization. In this work, we report the first example of heterogeneous photocatalysts for hydrogen evolution based on in-chain cobalt-chelating conjugated polymers. Two conjugated polymers chelated with earth-abundant cobalt ions were synthesized and found to evolve hydrogen photocatalytically from water. These polymers are designed to combine functions of the conjugated backbone as a light-harvesting antenna and electron-transfer conduit with the in-chain bipyridyl-chelated transition metal centers as catalytic active sites. In addition, these polymers are soluble in organic solvents, enabling effective interactions with the substrates as well as detailed characterization. We also found a polymer-dependent optimal cobalt chelating concentration at which the highest photocatalytic hydrogen production (PHP) activity can be achieved.

The short Cu 2+ –S(Met) bond in pseudoazurin (PAz) results in the presence of two relatively intense S p (π) and S p (σ) charge transfer (CT) transitions. This has enabled resonance Raman (rR) data to be obtained for each excited state. The rR data show very different intensity distribution patterns for the vibrations in the 300–500 cm − 1 region. Time-dependent density functional theory (TDDFT) calculations have been used to determine that the change in intensity distribution between the S p (π) and S p (σ) excited states reflects the differential enhancement of S(Cys) backbone modes with Cu–S(Cys)–C β out-of-plane (oop) and in-plane (ip) bend character in their respective potential energy distributions (PEDs). The rR excited state distortions have been related to ground state reorganization energies (λs) and predict that, in addition to M–L stretches, the Cu–S(Cys)–C β oop bend needs to be considered. DFT calculations predict a large distortion in the Cu–S(Cys)–C β oop bending coordinate upon reduction of a blue copper (BC) site; however, this distortion is not present in the X-ray crystal structures of reduced BC sites. The lack of Cu–S(Cys)–C β oop distortion upon reduction corresponds to a previously unconsidered constraint on the thiolate ligand orientation in the reduced state of BC proteins and can be considered as a contribution to the entatic/rack nature of BC sites.

The type 1 (T1) or blue Cu (BC) proteins are a highly studied group of electron transfer (ET) active sites in bioinorganic chemistry. In this review, we cover several more recent results which extend the understanding of the geometric and electronic structure of these interesting Cu ET sites. Spectroscopic methods in tandem with density functional theory (DFT) and time dependent-DFT (TD-DFT) calculations have been used in studies of S → Se variants as well as a series of metal-varied model complexes (M = Mn 2+ → Zn 2+ ). The ligand and metal perturbations further defined the origins of the unique spectral features of BC proteins. These unique spectral features show different temperature dependencies in different T1 sites, and contrasts drawn between their behaviors define the role of the protein in tuning the geometric and electronic structure of the BC site for function. This has been termed the ‘entatic’ or ‘rack-induced’ state in bioinorganic chemistry.

Density functional theory (DFT) and time-dependent DFT (TDDFT) have been used to explore the potential energy landscapes in the class II (in Robin and Day classification) mixed-valence biferrocenium mono-cation (BF^+) in an effort to evaluate factors affecting optical and thermal intramolecular electron transfer rates. Both energy- and spectroscopy-based benchmarks were used to explore the adiabatic potential energy surfaces (PESs) of the mixed-valence BF^+ cation along with the optimization of appropriate ground-, excited-, and transition-state geometries. The calculation of Mossbauer isomer shifts and quadrupole splittings, UV-vis excitation energies, and the electronic coupling matrix element, H_(ab), corroborate the PES analyses. The adiabatic electron transfer pathway is also analyzed with respect to several possible vibronic coordinates. The degree of the electronic coupling between iron sites, the value of H_(ab), and the nature of the electron transfer pathway correlate with the amount of Hartree-Fock exchange involved in the DFT calculation with hybrid (approximately 20% of Hartree-Fock exchange) methods providing the best agreement between theory and experiment. DFT (B3LYP) predicted values of H_(ab) (839, 1085, and 1265 cm^(-1)) depend on the computational method and are in good agreement with experimental data.

Six structurally related cyano ferrocenes have been examined by temperature-dependent Mossbauer effect spectroscopy (MES) to yield information concerning the isomeric shift (IS), quadrupole splitting (QS), and related parameters characterizing the iron atom in these compounds. The IS is related to the s-electron density at the Fe nucleus, while the QS is related to the symmetry and magnitude of the electrostatic field. In addition, these data can yield information related to the dynamics of the metal atom and are in excellent agreement with X-ray crystal data. Density functional theory (DFT) calculations have been used to obtain values for the three principal components of the electric field gradient tensor as well as the electron density at the metal atom site. The results of the DFT calculations and the MES data are found to be in exceptionally good agreement in these compounds.

A time-dependent density functional theory (TDDFT) approach coupled with 14 different exchange-correlation functionals was used for the prediction of vertical excitation energies in zinc phthalocyanine (PcZn). In general, the TDDFT approach provides a more accurate description of both visible and ultraviolet regions of the UV-vis and magnetic circular dichroism (MCD) spectra of PcZn in comparison to the more popular semiempirical ZINDO/S and PM3 methods. It was found that the calculated vertical excitation energies of PcZn correlate with the amount of Hartree-Fock exchange involved in the exchange-correlation functional. The correlation was explained on the basis of the calculated difference in energy between occupied and unoccupied molecular orbitals. The influence of PcZn geometry, optimized using different exchange-correlation functionals, on the calculated vertical excitation energies in PcZn was found to be relatively small. The influence of solvents on the calculated vertical excitation energies in PcZn was considered for the first time using a polarized continuum model TDDFT (PCM-TDDFT) method and was found to be relatively small in excellent agreement with the experimental data. For all tested TDDFT and PCM-TDDFT cases, an assignment of the Q-band as an almost pure a_(1u) (HOMO)-->e_g (LUMO) transition, initially suggested by Gouterman, was confirmed. Pure exchange-correlation functionals indicate the presence of six ^1_Eu states in the B-band region of the UV-vis spectrum of PcZn, while hybrid exchange-correlation functionals predict only five ^1E_u states for the same energy envelope. The first two symmetry-forbidden n-->pi* transitions were predicted in the Q0-2 region and in the low-energy tail of the B-band, while the first two symmetry-allowed n-->π* transitions were found within the B-band energy envelope when pure exchange-correlation functionals were used for TDDFT calculations. The presence of a symmetry-forbidden but vibronically allowed n-->π* transition in the Q_(0-2) spectral envelope explains the long-time controversy between the experimentally observed low-intensity transition in the Q_(0-2) region and previous semiempirical and TDDFT calculations, which were unable to predict any electronic transitions in this area. To prove the conceptual possibility of the presence of several degenerate ^1E_u states in the B-band region of PcZn, room-temperature UV-vis and MCD spectra of zinc tetra-tert-butylphthalocyanine (Pc^tZn) in non-coordinating solvents were recorded and analyzed using band deconvolution analysis. It was found that the B-band region of the UV-vis and MCD spectra of Pc^tZn can be easily deconvoluted using six MCD Faraday A-terms and two MCD Faraday B-terms with energies close to those predicted by TDDFT calculations for ^1E_u and ^1A_(2u) excited states, respectively. Such a good agreement between theory and experiment clearly indicates the possibility of employing a TDDFT approach for the accurate prediction of vertical excitation energies in phthalocyanines within a large energy range.

A dicobalt(II) complex, [Co2(mBDCA-5t)](2-) (1), demonstrates a cofacial arrangement of trigonal monopyramidal Co(II) ions with an inter-metal separation of 6.2710(6) A. Reaction of 1 with potassium superoxide generates an encapsulated Co-O-Co core in the dianionic complex, [Co2O(mBDCA-5t)](2-) (2); to form the linear Co-O-Co core, the inter-metal distance has diminished to 3.994(3) A. Co K-edge X-ray absorption spectroscopy data are consistent with a +2 oxidation state assignment for Co in both 1 and 2. Multireference complete active space calculations followed by second-order perturbation theory support this assignment, with hole equivalents residing on the bridging O-atom and on the cryptand ligand for the case of 2. Complex 2 acts as a 2-e(-) oxidant toward substrates including CO and H2, in both cases efficiently regenerating 1 in what represent net oxygen-atom-transfer reactions. This dicobalt system also functions as a catalase upon treatment with H2O2.

Endothermic halogen elimination reactions, in which molecular halogen photoproducts are generated in the absence of chemical traps, are rare. Inspired by the proclivity of mononuclear Ni(III) complexes to participate in challenging bond-forming reactions in organometallic chemistry, we targeted Ni(III) trihalide complexes as platforms to explore halogen photoelimination. A suite of Ni(III) trihalide complexes supported by bidentate phosphine ligands has been synthesized and characterized. Multinuclear NMR, EPR, and electronic absorption spectroscopies, as well as single-crystal X-ray diffraction, have been utilized to characterize this suite of complexes as distorted square pyramidal, S = 1/2 mononuclear Ni(III) complexes. All complexes participate in clean halogen photoelimination in solution and in the solid state. Evolved halogen has been characterized by mass spectrometry and quantified chemically. Energy storage via halogen elimination was established by solution-phase calorimetry measurements; in all cases, halogen elimination is substantially endothermic. Time-resolved photochemical experiments have revealed a relatively long-lived photointermediate, which we assign to be a Ni(II) complex in which the photoextruded chlorine radical interacts with a ligand-based aryl group. Computational studies suggest that the observed intermediate arises from a dissociative LMCT excited state. The participation of secondary coordination sphere interactions to suppress back-reactions is an attractive design element in the development of energy-storing halogen photoelimination involving first-row transition metal complexes.

Halogen photoelimination reactions constitute the oxidative half-reaction of closed HX-splitting energy storage cycles. Here, we report high-yielding, endothermic Cl_2 photoelimination chemistry from mononuclear Ni(III) complexes. On the basis of time-resolved spectroscopy and steady-state photocrystallography experiments, a mechanism involving ligand-assisted halogen elimination is proposed. Employing ancillary ligands to promote elimination offers a strategy to circumvent the inherently short-lived excited states of 3d metal complexes for the activation of thermodynamically challenging bonds.

Influence of molecular geometry, type of exchange-correlation functional, and contraction scheme of basis set applied at the iron nuclei have been tested in the calculation of ^(57)Fe Mössbauer isomer shifts and quadrupole splittings for a wide range of ligand types, as well as oxidation and spin states, in inorganic and organometallic systems. It has been found that uncontraction of the s-part of Wachter's full-electron basis set at the iron nuclei does not appreciably improve the calculated isomer shifts. The observed correlations for all tested sets of geometries are close to each other and predominantly depend on the employed exchange-correlation functional with B3LYP functional being slightly better as compared to BPW91. Both hybrid (B3LYP) and pure (BPW91) exchange-correlation functionals are suitable for the calculation of isomer shifts in organometallic compounds. Surprisingly, it has been found that the hybrid B3LYP exchange-correlation functional completely fails in accurate prediction of quadrupole splittings in ferrocenes, while performance of the pure BPW91 functional for the same systems was excellent. This observation has been explained on the basis of relationship between the amount of Hartree-Fock exchange involved in the applied exchange-correlation functional and the calculated HOMO-LUMO energy gap in ferrocenes. On the basis of this explanation, use of only pure exchange-correlation functionals has been suggested for accurate prediction of Mössbauer spectra parameters in ferrocenes.