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At least 91 records · Page 5

Catalyst-Specific Accelerated Stress Tests in Proton Exchange Membrane Low-Temperature Electrolysis for Intermittent Operation

Device-level stress tests are developed that focus on anode catalyst layer degradation and future anticipated operating conditions, including intermittent load and reduced platinum group metal content. Square-wave cycles with an upper load limit of 2.5 A cm -2 are utilized to screen commercial iridium (Ir) materials. Performance losses are primarily due to decreasing kinetics and are accompanied by catalyst migration into the membrane, worsening catalyst/ionomer integration, and weakening of the catalyst/membrane interface. For ruthenium-containing catalysts, the in situ performances are higher but durabilities lower than Ir baselines, and any performance advantage is lost within the test. Increased loss is likely due to the higher dissolution rate; microscopy confirmed greater degrees of ruthenium migration. For Ir metal or mixed oxides, ex situ activity improvements generally did not translate to in situ performance. The durability, however, is significantly lower and the loss rate increased from 3 (oxide) to 9 (metal) μ V cycle -1 . These results are consistent with historical findings in literature, rationalize the continued use of iridium oxide as a baseline catalyst, and demonstrate that traditional catalyst development approaches may not improve device-level durability when focused on low-cost applications. A shift in focus may therefore be more effective at improving catalyst utilization and lessening load requirements.

08 HYDROGEN↗

New findings and current controversies in the reaction of ruthenium red and ammonium cerium(iv) nitrate: focus on the precipitated compound

Finding the true catalyst has always been a challenging step toward the exploration, understanding, and design of catalytic systems for water-oxidation reaction. Many homogeneous and heterogeneous transition metal complexes have been reported that can undergo a complete transformation to the true catalysts during water-oxidation reaction. Furthermore, the transformation of the previously-explored ruthenium red ([(NH 3 ) 5 RuORu(NH 3 ) 4 ORu(NH 3 ) 5 ]Cl 6 ) catalyst in the presence of ammonium cerium(IV) nitrate is reported. For the first time, it is reported that a heterogeneous nano-sized ruthenium–cerium compound is formed by the electrostatic interaction of [(NH 3 ) 5 RuORu(NH 3 ) 4 ORu(NH 3 ) 5 ], 6+/7+ nitrate ions, and the products of the reduction of ammonium cerium(IV) nitrate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanistic investigation of the aerobic oxidation of 2-pyridylacetate coordinated to a Ru(ii) polypyridyl complex

A new ruthenium polypyridyl complex, [Ru(bpy) 2 (acpy)] + (acpy = 2-pyridylacetate, bpy = 2,2'-bipyridine), was synthesized and fully characterized. Distinct from the previously reported analog, [Ru(bpy) 2 (pic)] + (pic = 2-pyridylcarboxylate), the new complex is unstable under aerobic conditions and undergoes oxidation to yield the corresponding α-keto-2-pyridyl-acetate (acpyoxi) coordinated to the Ru II center. The reaction is one of the few examples of C–H activation at mild conditions using O 2 as the primary oxidant and can provide mechanistic insights with important implications for catalysis. Theoretical and experimental investigations of this aerobic oxidative transformation indicate that it takes place in two steps, first producing the α-hydroxo-2-pyridyl-acetate analog and then the final product. The observed rate constant for the first oxidation was in the order of 10 -2 h -1 . The reaction is hindered in the presence of coordinating solvents indicating the role of the metal center in the process. Theoretical calculations at the M06-L level of theory were performed for multiple reaction pathways in order to gain insights into the most probable mechanism. Our results= indicate that O 2 binding to [Ru(bpy) 2 (acpy)] + is favored by the relative instability of the six-ring chelate formed by the acpy ligand and the resulting Ru III -OO˙- superoxo is stabilized by the carboxylate group in the coordination sphere. C–H activation by this species involves high activation free energies (ΔG ‡ = 41.1 kcal mol -1 ), thus the formation of a diruthenium μ-peroxo intermediate, [(Ru III (bpy) 2 (O-acpy)) 2 O 2 ] 2+ via interaction of a second [Ru(bpy) 2 (acpy)] + was examined as an alternative pathway. The dimer yields two Ru IV =O centers with a low ΔG ‡ of 2.3 kcal mol -1 . The resulting Ru IV =O species can activate C–H bonds in acpy (ΔG ‡ = 23.1 kcal mol -1 ) to produce the coordinated α-hydroxo-2-pyridylacetate. Further oxidation of this intermediate leads to the α-keto-2-pyridyl-acetate product. The findings provide new insights into the mechanism of C–H activation catalyzed by transition-metal complexes using O 2 as the sole oxygen source.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Controlling the Ru Island Decoration on Ni Nanoparticles to Tune the Activity for 5-Hydroxylmethylfurfural (HMF) Oxidation

Controlling the island decoration on metal nanoparticle supports is a major opportunity for improving the catalytic activity and an attractive synthetic challenge. The structure of the decorating metal determines how it interacts with the metal support and how it effectively catalyzes the reactants and the intermediates. In this work, we demonstrate that a slow-growth method maximizes the formation of Ru islands on faceted, branched Ni nanoparticles, thereby controlling the number of Ru–Ni atomic interactions and improving the catalytic activity. The Ru islands on branched Ni nanoparticles with the highest loading of Ru (9%) exhibited the highest activity for the electro-oxidation of biomass-derived 5-hydroxymethylfurfural (HMF). In conclusion, these results demonstrate the ability to synthetically control the second metal decoration to tune metal–support interactions, thereby enhancing the catalytic activity.

5-hydroxymethylfurfural↗

Synthesis, Characterization, and Water Oxidation Activity of Isomeric Ru Complexes

The synthesis and characterization of the isomeric ruthenium complexes with the general formula cis- and trans-[Ru(trpy)(qc)X] n+ (trpy is 2,2':6',2"-terpyridine, qc is 8-quinolinecarboxylate, cis-1 and trans-1, X = Cl, n = 0; cis-2 and trans-2, X=OH2, n = 1) with respect to the relative disposition of the carboxylate and X ligands are reported. For comparison purposes, another set of ruthenium complexes with general formula cis- and trans-[Ru(trpy)(pic)(OH 2 )]+ (pic is 2-picolinate (cis-3, trans-3)) have been prepared. The complexes with a qc ligand show a more distorted geometry compared to the complexes with a pic ligand. In all of the cases, the trans isomers show lower potential values for all of the redox couples relative to the cis isomers. Furthermore, complexes cis-2 and trans-2 with six-member chelate rings show higher catalytic activity than cis-3 and trans-3. Overall, it was shown that the electronic perturbation to the metal center exerted by different orientation and geometry of the ligands significantly influences both redox properties and catalytic performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Plasma-Initiated Graft Polymerization of Acrylic Acid onto Fluorine-Doped Tin Oxide as a Platform for Immobilization of Water-Oxidation Catalysts

The discovery of new and versatile strategies for the immobilization of molecular water-oxidation catalysts (WOCs) is crucial for developing clean energy conversion devices [e.g., (photo)electrocatalytic cells for water splitting]. The traditional approach for surface attachment to transparent conductive oxides [e.g., fluorine doped tin oxide (FTO)] is via synthetic modification of the ligand architecture to incorporate functional groups such as carboxylic acids (-COOH) or phosphonates (-PO 3 H 2 ) prior to immobilization. However, challenges arising from desorption and the cumbersome derivatizations steps have limited the scope and applications of surface-bound WOCs. Herein, we report the successful immobilization of underivatized Ru(II)-based WOCs (Ru–Cat1 = [Ru(tpy) (bpy) (H 2 O)] 2+ (tpy = 2,2':6'2"–terpyridine and bpy = 2,2;-bipyridine) and Ru–Cat2 = [Ru(Mebimpy) (bpy) (H 2 O)] 2+ (Mebimpy = 2,6-bis(1-methylbenzimidazol-2-yl) pyridine)) and the Ru(II) polypyridyl chromophore Ru–C3 = [Ru(bpy) 3 ] 2+ onto a FTO plasma-grafted poly(acrylic acid) surface (PAA|FTO). Various characterization techniques such as attenuated total reflectance Fourier transform infrared spectroscopy, scanning electron microscopy, atomic force microscopy, and cyclic voltammetry measurements provide evidence for the plasma-induced grafted PAA|FTO film and immobilization. Surface stability and electrocatalytic properties of these new hybrid composite films upon cycling were investigated at different pH values. Immobilized Ru–Cat1 and Ru–Cat2 onto PAA|FTO displayed pH-dependent (RuIII/RuII) couples and onset potentials indicative of PCET (proton-coupled electron transfer) reactions. Based on cyclic voltammetry results and spectroscopic monitoring, the immobilized WOCs Ru–Cat1 and Ru–Cat2 exhibited a higher surface stability in neutral aqueous solutions relative to Ru–C3 upon electrochemical oxidation. Furthermore, we attribute the surface PCET and stability to the presence of a water ligand in the coordination sphere of immobilized Ru–Cat1 and Ru–Cat2 which can H-bond with negatively charged carboxylate groups of the cross-linked PAA brushes. Our findings demonstrate that the plasma-grafted polymeric network onto FTO offers a versatile platform to directly anchor unmodified homogeneous WOCs or chromophores for potential applications in solar-to-fuel energy conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ru-CoO heterostructured nanoparticles supported on nitrogen and sulfur codoped graphene nanosheets as effective electrocatalysts for hydrogen evolution reaction in alkaline media

Production of clean hydrogen energy from water splitting is vital for the future fuel industry, and nanocomposites have emerged as effective catalysts for the hydrogen evolution reaction (HER). In this study, Ru-CoO@SNG nanocomposites are prepared by controlled pyrolysis where Ru-CoO heterostructured nanoparticles are supported on nitrogen and sulfur codoped graphene oxide nanosheets. With a large surface area, the obtained composites exhibit a remarkable electrocatalytic activity toward HER in 1.0M KOH with an overpotential of only -90mV to reach the current density of 10 mA cm -2 , in comparison to -60mV for commercial Pt/C benchmark, along with high stability. Mechanistically, codoping of sulfur and nitrogen facilitates the dispersion of the nanoparticles, and the formation of Ru-CoO heterostructures increases the active site density, reduces the electron-transfer kinetics and boosts the catalytic performance. Further, results from this study highlight the unique potential of structural engineering in enhancing the electrocatalytic performance of heterostructured nanocomposites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Universal Reversible Hydrogen Potential for Electrocatalytic Ammonia Splitting Reactions in Nonaqueous Solvents from Unified pH Measurements

In this work, we introduce a new approach of using differential potentiometric measurements in four nonaqueous solvents─MeCN, THF, DMF, and PC─to determine the universal pH abs H 2 O values aligned to the aqueous pH scale for dilute NH 4 + /NH 3 solutions. Knowledge of the pH abs H 2 O values allows simple determination of the reversible hydrogen potential in any given solvent relative to the aqueous standard hydrogen electrode (SHE) and, most importantly, ensures comparability across different solvents. As an independent method, Open Circuit Potenial measurements were carried out in the same solvents titrated with NH 4 + /NH 3 to obtain alternative values for the reversible hydrogen potential in these solvents. The close agreement of these two methods, as well as calculated potentials from literature values when available, substantiates the new, simpler, and more robust approach to determine the reversible hydrogen potential introduced here. We further use the reversible hydrogen potential values established here to report, for the first time, the overpotential for ammonia oxidation as a function of solvent, with a recently discovered ruthenium catalyst.

ammonia↗

Computational analysis of metal–metal bonded dimetal tetrabenzoate redox potentials in the context of ammonia oxidation electrocatalysis

Metal–metal bonded complexes are promising candidates for catalyzing redox transformations. Of particular interest is the oxidation of ammonia to dinitrogen, an important half reaction for the potential utilization of ammonia as a fuel or hydrogen carrier. This work computationally explores 30 different metal–metal bonded dimers (5 different metal centers and 6 different benzoate ligand derivatives) to explore the tunability of the redox potential when ammonia is bound to the complexes as an axial ligand, modeling the first step in ammonia oxidation electrocatalysis. We calculate the redox potentials of these compounds, making reference to experimental data when appropriate, identifying two degrees of tunability: a coarse adjustment, changing the metal center, allows for a wide range of redox potentials to be accessed (from +1.0 to –2.0 V vs. ferrocene/ferrocenium in acetonitrile solution) and a fine adjustment, the para-substituent of the benzoate derivative, which affects the redox potential in a smaller range based on the electron donating/withdrawing effects of the substituent. Ruthenium and osmium tetrabenzoate catalysts are prime candidates for next generation ammonia oxidation catalysts because their redox potentials fall within the direct ammonia fuel cell “viability zone” bracketed by the thermodynamic potentials of oxygen reduction (ORR) and nitrogen reduction (NRR). Rhodium tetrabenzoate species fall above the ORR potential, suggesting ammonia oxidation promoted by Rh 2 catalysts could instead be used to facilitate hydrogen production through coupling to hydrogen evolution at a cathode. The redox potentials of rhenium and iridium tetrabenzoate catalysts fall below the NRR potential suggesting that these compounds could be further investigated in the context of electrochemical ammonia synthesis. Each redox event studied involves electron transfer from the M–M δ* orbital regardless of choice of metal or benzoate ligand derivative; this leads us to believe that the chemical reactivity of the various studied compounds will be similar in the context of ammonia oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Effect of Material Properties on Oxygen Evolution Activity and Assessing Half-Cell Screening as a Predictive Tool in Electrolysis

Iridium-based oxygen evolution catalysts are screened in this study for activity and stability with rotating disk electrode (RDE) half-cells. This study focuses on the electrochemical and materials approaches needed to characterize oxygen evolution catalysts, and include testing for activity, stability, composition, oxide content, and structure. Findings also discuss recommendations for data interpretation and detail the difficulties of comparing catalysts across materials sets with different elemental and oxide compositions, and linking RDE activity to device-level performance. The materials evaluated are a mixture of oxides and metals, and several methods are used to quantify metal content, qualitatively assess oxide content, and determine total surface area. Oxygen evolution activities and stabilities are compared, where a wide range of results are reported. In general, higher RDE performances are found for catalysts that contained larger amounts of ruthenium and metals. Higher durability, however, is found for catalysts that only contained iridium and a higher proportion of oxides. Additionally, catalysts are evaluated for performance in membrane electrode assemblies to assess RDE as a predictive tool in electrolysis. While activity trends within individual material sets generally held between ex- and in-situ testing, RDE tends to overestimate the activity of more metallic catalysts when compared to device-level performance. These results stress the need for multiple metal/oxide baselines for mixed catalysts, to better project in-situ kinetics.

36 MATERIALS SCIENCE↗

Expanding and quantifying the crystal chemistry of the flexible ligand 15aneN5

Tetraazamacrocycles have been very extensively exploited as transition metal ligands for a variety of purposes, including catalysis, medical imaging, pharmaceuticals, etc. However, the pentaazamacrocycles are much less commonly used for similar purposes because of poor availability, difficulties in their synthesis, and less well-known metal coordination properties. 1,4,7,10,13-pentaazacyclopentadane (15aneN5) was initially synthesized by a published synthetic route, which we simplified and shortened with minimal drop in yield. Eight different transition metal complexes were made using typical complexation methods. X-ray crystallography of multiple novel complexes yielded insight into the flexibility in coordination geometry of this interesting macrocycle as well as the first crystal structures of 15aneN5 with Cr 3+ , Mn 3+ , Fe 3+ , Co 3+ , Cu 2+ , and Ru 2+ . A parameter to quantify the coordination geometry adopted by the ligand was devised and applied to all known crystal structures of its metal complexes. Lastly, oxidation of 15aneN5 to a novel diimine macrocycle was observed during complexation with ruthenium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemical cells for direct oxide reduction, and related methods

A method of direct oxide reduction includes forming a molten salt electrolyte in an electrochemical cell, disposing at least one metal oxide in the electrochemical cell, disposing a counter electrode comprising a material selected from the group consisting of osmium, ruthenium, rhodium, iridium, palladium, platinum, silver, gold, lithium iridate, lithium ruthenate, a lithium rhodate, a lithium tin oxygen compound, a lithium manganese compound, strontium ruthenium ternary compounds, calcium iridate, strontium iridate, calcium platinate, strontium platinate, magnesium ruthenate, magnesium iridate, sodium ruthenate, sodium iridate, potassium iridate, and potassium ruthenate in the electrochemical cell, and applying a current between the counter electrode and the at least one metal oxide to reduce the at least one metal oxide. Related methods of direct oxide reduction and related electrochemical cells are also disclosed.

Tripathy, Prabhat K.↗

Oxygen Atom Transfer as an Alternative Pathway for Oxygen–Oxygen Bond Formation

Fundamental understanding of catalytic mechanisms of water oxidation is a prerequisite for the design and development of efficient and rugged water oxidation catalysts. In this work, a detailed mechanistic study of the water oxidation mechanism of the [Ru II (npm)(4-pic) 2 (H 2 O)] 2+ (npm = 4-t-butyl-2,6-di(1',8'-naphthyrid-2'-yl)-pyridine, pic = 4-picoline) complex, [Ru II –OH 2 ] 2+ , reveals oxygen atom transfer from highly reactive ruthenium oxo intermediates to noncoordinating nitrogen atoms of the ligand as a novel route for oxygen evolution via storage of oxidizing equivalents as N-oxide groups on the ligand framework. Theoretical calculations show that the initial complex, [RuII–OH 2 ] 2+ , is transformed to a di-N-oxide [Ru II –OH 2 ,(-NO) 2 ] 2+ complex upon oxidation via facile OAT steps from Ru V =O species and that [Ru V =O,(-NO) 2 ] 3+ represents the most likely reactive species for the critical O–O bond formation. Furthermore, a new stepwise mechanism for oxygen evolution is introduced, which proceeds via coupling of Ru–O and N–O moieties producing a peroxide intermediate, [Ru V –OO–N,(-NO)] 3+ , and can compete with the water nucleophilic attack pathway for the oxygen evolution reaction. In this mechanism, a water molecule is oxidatively activated to an “oxygen atom” which is “stored” at a noncoordinating pyridine. Oxidative activation of a second water molecule, facilitated by coordination expansion of the intermediate N-oxide, generates the second oxygen atom required to produce a dioxygen molecule.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nature of Reactive Hydrogen for Ammonia Synthesis over a Ru/C12A7 Electride Catalyst

Recently, there have been renewed interests in exploring new catalysts for ammonia synthesis under mild conditions. Electride-based catalysts are among the emerging ones. Ruthenium particles supported on an electride composed of a mixture of calcium and aluminum oxides (C12A7) have attracted great attention for ammonia synthesis due to their facile ability in activating N2 under ambient pressure. However, the exact nature of the reactive hydrogen species and the role of electride support still remain elusive for this catalytic system. Here, we report for the first time that the surface-adsorbed hydrogen, rather than the hydride encaged in the C12A7 electride, plays a major role in ammonia synthesis over the Ru/C12A7 electride catalyst with the aid of in situ neutron scattering techniques. Combining in situ neutron diffraction, inelastic neutron spectroscopy, density functional theory (DFT) calculation, and temperature-programmed reactions, the results provide direct evidence for not only the presence of encaged hydrides during ammonia synthesis but also the strong thermal and chemical stability of the hydride species in the Ru/C12A7 electride. Steady state isotopic transient kinetic analysis (SSITKA) of ammonia synthesis showed that the coverage of reactive intermediates increased significantly when the Ru particles were promoted by the electride form (coverage up to 84%) of the C12A7 support rather than the oxide form (coverage up to 15%). Such a drastic change in the intermediate coverage on the Ru surface is attributed to the positive role of electride support where the H2 poisoning effect is absent during ammonia synthesis over Ru. The finding of this work has significant implications for understanding catalysis by electride-based materials for ammonia synthesis and hydrogenation reactions in general.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A general strategy and a consolidated mechanism for low-methane hydrogenolysis of polyethylene over ruthenium

Polyethylene (PE) is one of the most environment-threatening plastic waste. Its Ru-catalyzed hydrogenolysis is rapid but produces too much methane. Here, in this study, low-density PE hydrogenolysis is performed at mild conditions and short times over Ru-doped zirconia catalysts (Ru-XZr, X = Ti, Nb, Ce, W, V, Mo, Fe) to determine low-methane catalysts. Methane is produced via direct terminal C-C scission and surface cascade of consecutive C-C scissions, with the latter sensitive to hydrogen availability and dominant in hydrogen-lean conditions. Reactivity studies, characterization and theory reveal that the most effective dopant oxides (W, V, and Mo) are intermediately reducible, as they store and supply extra hydrogen to Ru via reverse hydrogen spillover. This hydrogen readily hydrogenates and desorbs long alkyl surface intermediates that would otherwise produce cascade methane. Our proposed mechanism reconciles the low methane production achieved by increasing the hydrogen pressure or reducing the particle size and exposes the key selectivity descriptors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Integrated CO 2 capture and hydrogenation in presence of Ru–Na 2 ZrO 3 : An in-situ study

Integrated CO 2 capture and conversion (ICCC) by hydrogenation is a promising strategy to utilize carbon dioxide and this work add to the effort to elucidate the catalytic hydrogenation mechanism using Ru based dual functional materials (DFM). Ru-Na 2 ZrO 3 DFMs, obtained through different wet methods, were evaluated for the first time and the relationship between Ru and support systematically investigated. The thermally stable and cyclable Ru-Na 2 ZrO 3 -a (obtained without filtration step) exhibited CO 2 conversion of 80% and a higher yield of CO at 400°C compared to previously tested DFM, while the Na depleted/Zr rich Ru-Na 2 ZrO 3 -b resulted in 90% selectivity to CH 4 with yield of 1.11 mmol/g at the same temperature. The in-situ experiments have provided conclusive evidence showing that CO 2 hydrogenation on the two Ru DFMs is fundamentally different. In Ru-Na 2 ZrO 3 -a, the monoclinic Na 2 ZrO 3 support acted as the active centre (not as promoter) for CO 2 bridging binding and hydrogenation to CH 4 at the metal-support interface through associative formate pathway with limited further reduction to methane due to lack of H 2 spillover from the small and well dispersed Ru NPs, which results in CO desorption. Conversely, abundant clusters of larger Ru NPs in Ru-Na 2 ZrO 3 -b, led to CH 4 production due to co-existent Ru on-top direct dissociation of CO 2 (preferential) and monodentate formate adsorption and further methanation. Alkali zirconates doped metals, and their synthesis method could thus play a crucial role in designing tuneable heterogeneous catalysis in C 1 chemistry, which could significantly benefit the environment by lowering CO 2 levels, encouraging cleaner industrial practices, supporting a circular economy, and converting waste CO 2 into valuable products.

36 MATERIALS SCIENCE↗

Spectroscopic and Theoretical Studies of Ruthenium Complexes with a Noninnocent N 2 S 2 Ligand in Different Redox States

Herein we report an electronic structure investigation of neutral and oxidized Ru complexes containing a redox noninnocent N 2 S 2 ligand derived from o-phenylenediamide (L1). UV–vis spectroelectrochemistry (SEC) studies were conducted on the square pyramidal complex [Ru I I(L1)(PPh 3 )] (1) and the six-coordinate complexes [Ru I I(μ-BH 3 )(L1)(PPh 3 )] (2) – which has BH 3 bound in a metal–ligand cooperative (MLC) fashion across Ru and L1 – and [Ru II (L1)(PPh 3 )(MeCN)] (3). The SEC results yielded spectra assigned to singly and doubly oxidized 1 and 3, revealing electronic structure changes as a function of oxidation state and in response to the presence and absence of bound MeCN. By contrast, the SEC results of 2 showed that it rapidly loses MLC-bound BH 3 upon oxidation. The SEC results for 1 and 3 were compared to single-crystal XRD data and UV–vis, EPR, and P K-edge, S K-edge, and Ru L 3 -edge X-ray absorption spectroscopy (XAS) data collected on isolated samples of chemically oxidized 3. The data revealed that the first two oxidations are primarily localized on the ligand, which was supported by DFT and TDDFT calculations. DFT calculations for the doubly oxidized species revealed a singlet ground state with a singlet–triplet gap of 8.9 kcal/mol. CASPT2 calculations corroborated the DFT calculations and further revealed that the singlet ground state is multiconfigurational with 21% radical character. Collectively, the results establish redox formalisms and the underlying electronic structure of Ru complexes containing a noninnocent tetradentate ligand in different oxidation states.

electronic structure↗