First Row Transition Metal Complexes Research Articles

Mechanistic Insight of High-Valent First-Row Transition Metal Complexes for Dehydrogenation of Ammonia Borane.

Designing an efficient and cost-effective catalyst for ammonia borane (AB) dehydrogenation remains a persistent challenge in advancing a hydrogen-based economy. Transition metal complexes, known for their C-H bond activation capabilities, have emerged as promising candidates for AB dehydrogenation. In this study, we investigated two recently synthesized C-H activation catalysts, 1 (CoIV-dinitrate complex) and 2 (NiIV-nitrate complex), and demonstrated their efficacy for AB dehydrogenation. Using density functional theory calculations and a detailed analysis, we elucidated the AB dehydrogenation mechanism of these complexes. Our results revealed that both complexes 1 and 2 can efficiently dehydrogenate AB at room temperature, although the abstraction of molecular H2 from these complexes requires slightly elevated temperatures. We utilized H2 binding free energy calculations to identify potentially active sites and observed that complex 2 can release two equivalents of H2 at a temperature slightly higher than room temperature. Furthermore, we investigated AB dehydrogenation kinetics and thermodynamics in iron (Fe)-substituted systems, complexes 3 and 4. Our results showed that the strategic alteration of the central metal atom, replacing Ni in complex 2 with Fe in complex 4, resulted in enhanced kinetics and thermodynamics for AB dehydrogenation in the initial cycle. These results underscore the potential of high-valent first-row transition metal complexes for facilitating AB dehydrogenation at room temperature. Additionally, our study highlights the beneficial impact of incorporating iron into such mononuclear systems, enhancing their catalytic activity.

Strategies and Mechanisms of First-Row Transition Metal-Regulated Radical C-H Functionalization.

Radical C-H functionalization represents a useful means of streamlining synthetic routes by avoiding substrate preactivation and allowing access to target molecules in fewer steps. The first-row transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, and Cu) are Earth-abundant and can be employed to regulate radical C-H functionalization. The use of such metals is desirable because of the diverse interaction modes between first-row transition metal complexes and radical species including radical addition to the metal center, radical addition to the ligand of metal complexes, radical substitution of the metal complexes, single-electron transfer between radicals and metal complexes, hydrogen atom transfer between radicals and metal complexes, and noncovalent interaction between the radicals and metal complexes. Such interactions could improve the reactivity, diversity, and selectivity of radical transformations to allow for more challenging radical C-H functionalization reactions. This review examines the achievements in this promising area over the past decade, with a focus on the state-of-the-art while also discussing existing limitations and the enormous potential of high-value radical C-H functionalization regulated by these metals. The aim is to provide the reader with a detailed account of the strategies and mechanisms associated with such functionalization.

Establishing the origin of Marcus-inverted-region behaviour in the excited-state dynamics of cobalt(III) polypyridyl complexes.

Growing interest in the use of first-row transition metal complexes in a number of applied contexts-including but not limited to photoredox catalysis and solar energy conversion-underscores the need for a detailed understanding of their photophysical properties. A recent focus on ligand-field photocatalysis using cobalt(III) polypyridyls in particular has unlocked unprecedented excited-state reactivities. Photophysical studies on Co(III) chromophores in general are relatively uncommon, and so here we carry out a systematic study of a series of Co(III) polypyridyl complexes in order to delineate their excited-state dynamics. Compounds with varying ligand-field strengths were prepared and studied using variable-temperature ultrafast transient absorption spectroscopy. Analysis of the data establishes that the ground-state recovery dynamics are operating in the Marcus inverted region, in stark contrast to what is typically observed in other first-row metal complexes. The analysis has further revealed the underlying reasons driving this excited-state behaviour, thereby enabling potential advancements in the targeted use of the Marcus inverted region for a variety of photolytic applications.

Alternant Hydrocarbon Diradicals as Optically Addressable Molecular Qubits.

High-spin molecules allow for bottom-up qubit design and are promising platforms for magnetic sensing and quantum information science. Optical addressability of molecular electron spins has also been proposed in first-row transition-metal complexes via optically detected magnetic resonance (ODMR) mechanisms analogous to the diamond-nitrogen-vacancy color center. However, significantly less progress has been made on the front of metal-free molecules, which can deliver lower costs and milder environmental impacts. At present, most luminescent open-shell organic molecules are π-diradicals, but such systems often suffer from poor ground-state open-shell characters necessary to realize a stable ground-state molecular qubit. In this work, we use alternancy symmetry to selectively minimize radical-radical interactions in the ground state, generating π-systems with high diradical characters. We call them m-dimers, referencing the need to covalently link two benzylic radicals at their meta carbon atoms for the desired symmetry. Through a detailed electronic structure analysis, we find that the excited states of alternant hydrocarbon m-diradicals contain important symmetries that can be used to construct ODMR mechanisms leading to ground-state spin polarization. The molecular parameters are set in the context of a tris(2,4,6-trichlorophenyl)methyl (TTM) radical dimer covalently tethered at the meta position, demonstrating the feasibility of alternant m-diradicals as molecular color centers.

Ultrafast Photophysics of Ni(I)-Bipyridine Halide Complexes: Spanning the Marcus Normal and Inverted Regimes.

Owing to their light-harvesting properties, nickel-bipyridine (bpy) complexes have found wide use in metallaphotoredox cross-coupling reactions. Key to these transformations are Ni(I)-bpy halide intermediates that absorb a significant fraction of light at relevant cross-coupling reaction irradiation wavelengths. Herein, we report ultrafast transient absorption (TA) spectroscopy on a library of eight Ni(I)-bpy halide complexes, the first such characterization of any Ni(I) species. The TA data reveal the formation and decay of Ni(I)-to-bpy metal-to-ligand charge transfer (MLCT) excited states (10-30 ps) whose relaxation dynamics are well described by vibronic Marcus theory, spanning the normal and inverted regions as a result of simple changes to the bpy substituents. While these lifetimes are relatively long for MLCT excited states in first-row transition metal complexes, their duration precludes excited-state bimolecular reactivity in photoredox reactions. We also present a one-step method to generate an isolable, solid-state Ni(I)-bpy halide species, which decouples light-initiated reactivity from dark, thermal cycles in catalysis.

Reversible Photoinduced Ligand Substitution in a Luminescent Chromium(0) Complex.

Light-triggered dissociation of ligands forms the basis for many compounds of interest for photoactivated chemotherapy (PACT), in which medicinally active substances are released or "uncaged" from metal complexes upon illumination. Photoinduced ligand dissociation is usually irreversible, and many recent studies performed in the context of PACT focused on ruthenium(II) polypyridines and related heavy metal complexes. Herein, we report a first-row transition metal complex, in which photoinduced dissociation and spontaneous recoordination of a ligand unit occurs. Two scorpionate-type tridentate chelates provide an overall six-coordinate arylisocyanide environment for chromium(0). Photoexcitation causes decoordination of one of these six ligating units and coordination of a solvent molecule, at least in tetrahydrofuran and 1,4-dioxane solvents, but far less in toluene, and below detection limit in cyclohexane. Transient UV-vis absorption spectroscopy and quantum chemical simulations point to photoinduced ligand dissociation directly from an excited metal-to-ligand charge-transfer state. Owing to the tridentate chelate design and the substitution lability of the first-row transition metal, recoordination of the photodissociated arylisocyanide ligand unit can occur spontaneously on a millisecond time scale. This work provides insight into possible self-healing mechanisms counteracting unwanted photodegradation processes and seems furthermore relevant in the contexts of photoswitching and (photo)chemical information storage.

Approaching the Complete Basis Set Limit for Spin-State Energetics of Mononuclear First-Row Transition Metal Complexes.

Convergence to the complete basis set (CBS) limit is analyzed for the problem of spin-state energetics in mononuclear first-row transition metal (TM) complexes by taking under scrutiny a benchmark set of 18 energy differences between spin states for 13 chemically diverse TM complexes. The performance of conventional CCSD(T) and explicitly correlated CCSD(T)-F12a/b calculations in approaching the CCSD(T)/CBS limits is systematically studied. An economic computational protocol is developed based on the CCSD-F12a approximation and (here proposed) modified scaling of the perturbative triples term (T#). This computational protocol recovers the relative spin-state energetics of the benchmark set in excellent agreement with the reference CCSD(T)/CBS limits (mean absolute deviation of 0.4, mean signed deviation of 0.2, and maximum deviation of 0.8 kcal/mol) and enables performing canonical CCSD(T) calculations for mononuclear TM complexes sized up to ca. 50 atoms, which is illustrated by application to heme-related metalloporphyrins. Furthermore, a good transferability of the basis set incompleteness error (BSIE) is demonstrated for spin-state energetics computed using CCSD(T) and other wave function methods (MP2, CASPT2, CASPT2/CC, NEVPT2, and MRCI + Q), which justifies efficient focal-point approximations and simplifies the construction of multimethod benchmark studies.

The performance and efficiency of twelve range-separated hybrid DFT functionals for calculation of the magnetic exchange coupling constants of di-nuclear first row transition metal complexes

The performance and efficiency of twelve range-separated hybrid functionals are compared with each other in calculating magnetic exchange coupling constant (J) data on eleven di-nuclear first-row transition metal complexes having di-copper (Cu) and di-vanadium (V) as their central atoms. The J values are then compared with the experimental findings. In addition to that we also computed the B3LYP results of these complexes. We compared them with the results obtained from range-separated functionals as well as with the experimental results to understand their performances in predicting the magnetic exchange coupling constant. When computing, we reoptimized all the structures of the complexes taken from the crystal data, and then the values of Js were determined. The performances are predicted in terms of four statistical error matrices, namely, the mean absolute error (MAE), mean fractional error (MFE), mean signed error (MSE), root mean square error (RMSE) in cm−1.

Mapping the mechanisms of oxidative addition in cross-coupling reactions catalysed by phosphine-ligated Ni(0).

The complexes of first-row transition metals can undergo elementary reactions by multiple pathways due to their propensity to undergo both one- and two-electron redox steps. Classic and recent studies of the oxidative addition of aryl halides to Ni(0)-a common step in widely practised cross-coupling processes-have yielded contradictory conclusions about stepwise, radical versus concerted mechanisms, but such information is crucial to the design of catalysts based on earth-abundant metals. Here we show that the oxidative addition of aryl halides to Ni(0) ligated by monophosphines occurs by both mechanisms and delineate how the branching of radical and non-radical pathways depends on the electronic properties of both the ligand and reactant arene as well as the identity of the halide. The one-electron pathway occurs by outer-sphere electron transfer to form an aryl radical rather than the often-proposed halogen atom transfer.

Controlling the Photophysical Properties of a Series of Isostructural d6 Complexes Based on Cr0, MnI, and FeII.

Development of first-row transition metal complexes with similar luminescence and photoredox properties as widely used RuII polypyridines is attractive because metals from the first transition series are comparatively abundant and inexpensive. The weaker ligand field experienced by the valence d-electrons of first-row transition metals challenges the installation of the same types of metal-to-ligand charge transfer (MLCT) excited states as in precious metal complexes, due to rapid population of energetically lower-lying metal-centered (MC) states. In a family of isostructural tris(diisocyanide) complexes of the 3d6 metals Cr0, MnI, and FeII, the increasing effective nuclear charge and ligand field strength allow us to control the energetic order between the 3MLCT and 3MC states, whereas pyrene decoration of the isocyanide ligand framework provides control over intraligand (ILPyr) states. The chromium(0) complex shows red 3MLCT phosphorescence because all other excited states are higher in energy. In the manganese(I) complex, a microsecond-lived dark 3ILPyr state, reminiscent of the types of electronic states encountered in many polyaromatic hydrocarbon compounds, is the lowest and becomes photoactive. In the iron(II) complex, the lowest MLCT state has shifted to so much higher energy that 1ILPyr fluorescence occurs, in parallel to other excited-state deactivation pathways. Our combined synthetic-spectroscopic-theoretical study provides unprecedented insights into how effective nuclear charge, ligand field strength, and ligand π-conjugation affect the energetic order between MLCT and ligand-based excited states, and under what circumstances these individual states become luminescent and exploitable in photochemistry. Such insights are the key to further developments of luminescent and photoredox-active first-row transition metal complexes.

Synthesis and Investigations of the Antitumor Effects of First-Row Transition Metal(II) Complexes Supported by Two Fluorinated and Non-Fluorinated β-Diketonates.

The 3d transition metal (Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II)) complexes, supported by anions of sterically demanding β-diketones, 1,3-dimesitylpropane-1,3-dione (HLMes) and 1,3-bis(3,5-bis(trifluoromethyl)phenyl)-3-hydroxyprop-2-en-1-one (HLCF3), were synthesized and evaluated for their antitumor activity. To assess the biological effects of substituents on phenyl moieties, we also synthesized and investigated the analogous metal(II) complexes of the anion of the less bulky 1,3-diphenylpropane-1,3-dione (HLPh) ligand. The compounds [Cu(LCF3)2], [Cu(LMes)2] and ([Zn(LMes)2]) were characterized by X-ray crystallography. The [Cu(LCF3)2] crystallizes with an apical molecule of solvent (THF) and features a rare square pyramidal geometry at the Cu(II) center. The copper(II) and zinc(II) complexes of diketonate ligands, derived from the deprotonated 1,3-dimesitylpropane-1,3-dione (HLMes), adopt a square planar or a tetrahedral geometry at the metal, respectively. We evaluated the antitumor properties of the newly synthesized (Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II)) complexes against a series of human tumor cell lines derived from different solid tumors. Except for iron derivatives, cellular studies revealed noteworthy antitumor properties, even towards cancer cells endowed with poor sensitivity to the reference drug cisplatin.

Application of first-row transition metal complexes bearing 1,2,3-triazolylidene ligands in catalysis and beyond.

Triazole-derived N-heterocyclic carbenes, triazolylidenes (trz) have become an interesting alternative to the ubiquitous Arduengo-type imidazole-derived carbenes, in part because they are stronger donors, and in other parts due to their versatile synthesis through different types of click reactions. While the use of trz ligands has initially focused on their coordination to precious metals for catalytic applications, the recent past has seen a growing interest in their impact on first-row transition metals. Coordination of trz ligands to such 3d metals is more challenging due to the orbital mismatch between the carbene and the 3d metal center, which also affects the stability of such complexes. Here we summarize the strategies that have been employed so far to overcome these challenges and to prepare first-row transition metal complexes containing at least one trz ligand. Both properties and reactivities of these trz complexes are comprehensively compiled, with a focus on photophysical properties and, in particular, on the application of these complexes in homogeneous catalysis. The diversity of catalytic transformations entailed with these trz 3d metal complexes as well as the record-high performance in some of the reactions underpins the benefits imparted by trz ligands.

Electrocatalytic formate and alcohol oxidation by hydride transfer at first-row transition metal complexes.

The electrocatalytic oxidation of carbon-based liquid fuels, such as formic acid and alcohols, has important applications for our renewable energy transition. Molecular electrocatalysts based on transition metal complexes provide the opportunity to explore the interplay between precise catalyst design and electrocatalytic activity. Recent advances have seen the development of first-row transition metal electrocatalysts for these transformations that operate via hydride transfer between the substrate and catalyst. In this Frontier article, we present the key contributions to this field and discuss the proposed mechanisms for each case. These studies also reveal the remaining challenges for formate and alcohol oxidation with first-row transition metal systems, for which we provide perspectives on future directions for next-generation electrocatalyst design.

Facile synthesis of a hydrazone-based zinc(ii) complex for ferroptosis-augmented sonodynamic therapy.

Sonodynamic therapy (SDT), as a novel non-invasive cancer treatment modality derived from photodynamic therapy (PDT), has drawn much attention due to its unique advantages for the treatment of deep tumors. Zinc-based complexes have shown great clinical prospect in PDT due to their excellent photodynamic activity and biosafety. However, their application in SDT has lagged seriously behind. Exploring efficient zinc-based complexes as sono-sensitizers remains an appealing but significantly challenging task. Herein, we develop a hydrazone ligand-based zinc complex (ZnAMTC) for SDT of tumors in vitro and in vivo. ZnAMTC was facilely synthesized via a two-step reaction from low-cost raw materials without tedious purification. It shows negligible dark toxicity and can produce singlet oxygen (1O2) under ultrasound (US) irradiation, exhibiting high sono-cytotoxicity to various cancer cells. Mechanism studies show that ZnAMTC can effectively reduce the levels of glutathione (GSH) and glutathione peroxidase 4 (GPX4) under US irradiation and later cause ferroptosis of cancer cells. In vivo studies further demonstrate that ZnAMTC exhibits efficient tumor growth inhibition under US irradiation and has good biosafety. This work provides useful insights into the design of first-row transition metal complexes for SDT application.

Screening of First-Row Transition Metal Complexes for Aqueous Redox Flow Batteries: Experimental and Density Functional Theory Approaches

The development of redox flow batteries took new directions in the last decades. From initial metal-based systems, it evolved towards organic and hybrid approaches in aqueous media. Furthermore, redox targeting flow batteries are an emerging alternative to the traditional redox flow battery architecture which offer improved energy density via an added electroactive solid ‘booster’. Whatever the system, there is a need of soluble electroactive species with potentials allowing large cell potentials within the water stability window or imperative redox potentials matching between soluble redox mediator and the solid for redox targeting. Transition metal complexes are a promising class of redox electroactive centers due to the tunability of their solubility and electrochemical potential, and the ability to take into account sustainability1. Recent reports underlined for instance that either the modification of the ligand2 or using heteroleptic complexes3, can lead to iron complexes with solubilities higher than 1 M and potentials higher than 1 V vs SHE. Furthermore, reliable and time-efficient prediction tools for the redox potentials of transition metal complexes are needed to help the search for new potential systems. While density functional theory usually provides a good trade-off between computational cost and accuracy, calculations on transition metal complexes often result in large errors. We thus developed a procedure and compared different solvation methods and levels of theory using an initial experimental data set based on aqueous iron complexes with bidentate ligands (Figure 1).In the present contribution, we will illustrate this coordination approach through a screening of new complexes based on non-toxic and affordable transition metal complexes. In this perspective, electrochemical characterization at different pH, coupled with NMR and UV-Visible studies will be presented, to screen for new candidates as electrolyte in redox flow batteries. Finally, we will show how the calculations corrected using a simple linear regression using training data yields a good prediction of redox potentials (mean average error =0.09 V).

Homologous acetone carboxylases select Fe(II) or Mn(II) as the catalytic cofactor.

Acetone carboxylases (ACs) catalyze the metal- and ATP-dependent conversion of acetone and bicarbonate to form acetoacetate. Interestingly, two homologous ACs that have been biochemically characterized have been reported to have different metal complements, implicating different metal dependencies in catalysis. ACs from proteobacteria Xanthobacter autotrophicus and Aromatoleum aromaticum share 68% sequence identity but have been proposed to have different catalytic metals. In this work, the two ACs were expressed under the same conditions in Escherichia coli and were subjected to parallel chelation and reconstitution experiments with Mn(II) or Fe(II). Electron paramagnetic and Mössbauer spectroscopies identified signatures, respectively, of Mn(II) or Fe(II) bound at the active site. These experiments showed that the respective ACs, without the assistance of chaperones, second metal sites, or post-translational modifications facilitate correct metal incorporation, and despite the expected thermodynamic preference for Fe(II), each preferred a distinct metal. Catalysis was likewise associated uniquely with the cognate metal, though either could potentially serve the proposed Lewis acidic role. Subtle differences in the protein structure are implicated in serving as a selectivity filter for Mn(II) or Fe(II).IMPORTANCEThe Irving-Williams series refers to the predicted stabilities of transition metal complexes where the observed general stability for divalent first-row transition metal complexes increase across the row. Acetone carboxylases (ACs) use a coordinated divalent metal at their active site in the catalytic conversion of bicarbonate and acetone to form acetoacetate. Highly homologous ACs discriminate among different divalent metals at their active sites such that variations of the enzyme prefer Mn(II) over Fe(II), defying Irving-Williams-predicted behavior. Defining the determinants that promote metal discrimination within the first-row transition metals is of broad fundamental importance in understanding metal-mediated catalysis and metal catalyst design.

Photothermal catalytic conversion of water and inert nitriles to amide activated by in-situ formed transition-metal-complex nanodots

Photothermal catalytic N-acetylation of aniline has been a promising strategy to synthesize amides, which combined the advantages of thermal catalysis and photocatalysis. Herein, we demonstrate a high-performance strategy to synthesize amides catalyzed by the in-situ formed first-row transition-metal (Fe, Co, Ni, Mn et al.) complexes nanodots (TMC NDs) under solar light excitation without using noble metals or strong acids. The dual-functional nitriles substrates acted as the ligands to coordinate with transition-metal salts affording photosensitive TMC NDs with high solar-to-thermal energy conversion efficiency. Intramolecular charge transitions reduced the energy barrier of nitriles activation by weakening CN bond and triggered near-field temperature rise via the electron–phonon scattering non-radiative pathway. The reaction system exhibited good tolerance to different functional groups, affording a series of amide derivatives. Such a dynamic coordination reaction mode and the in-situ formed TMC NDs opens new avenues toward solar-heat conversion via photon–phonon coupling in the field of chemical synthesis.

Markovnikov-Selective Cobalt-Catalyzed Wacker-Type Oxidation of Styrenes into Ketones under Ambient Conditions Enabled by Hydrogen Bonding.

The replacement of palladium catalysts for Wacker-type oxidation of olefins into ketones by first-row transition metals is a relevant approach for searching more sustainable protocols. Besides highly sophisticated iron catalysts, all the other first-row transition metal complexes have only led to poor activities and selectivities. Herein, we show that the cobalt-tetraphenylporphyrin complex is a competent catalyst for the aerobic oxidation of styrenes into ketones with silanes as the hydrogen sources. Remarkably, under room temperature and air atmosphere, the reactions were exceedingly fast (up to 10 minutes) with a low catalyst loading (1 mol %) while keeping an excellent chemo- and Markovnikov-selectivity (up to 99 % of ketone). Unprecedently high TOF (864 h-1 ) and TON (5,800) were reached for the oxidation of aromatic olefins under these benign conditions. Mechanistic studies suggest a reaction mechanism similar to the Mukaiyama-type hydration of olefins with a change in the last fundamental step, which controls the chemoselectivity, thanks to a unique hydrogen bonding network between the ethanol solvent and the cobalt peroxo intermediate.

First-Row Transition Metal Complexes Incorporating the 2-(2'-pyridyl)quinoxaline Ligand (pqx), as Potent Inflammatory Mediators: Cytotoxic Properties and Biological Activities against the Platelet-Activating Factor (PAF) and Thrombin.

Inflammatory mediators constitute a recently coined term in the field of metal-based complexes with antiplatelet activities. Our strategy targets Platelet-Activating Factor (PAF) and its receptor, which is the most potent lipid mediator of inflammation. Thus, the antiplatelet (anti-PAF) potency of any substance could be exerted by inhibiting the PAF-induced aggregation in washed rabbit platelets (WRPs), which internationally is a well-accepted methodology. Herein, a series of mononuclear (mer-[Cr(pqx)Cl3(H2O]) (1), [Co(pqx)Cl2(DMF)] (2) (DMF = N,N'-dimethyl formamide), [Cu(pqx)Cl2(DMSO)] (3) (DMSO = dimethyl sulfoxide), [Zn(pqx)Cl2] (4)) and dinuclear complexes ([Mn(pqx)(H2O)2Cl2]2 (5), [Fe(pqx)Cl2]2 (6) and [Ni(pqx)Cl2]2 (7)) incorporating the 2-(2'-pyridyl)quinoxaline ligand (pqx), were biologically evaluated as inhibitors of the PAF- and thrombin-induced aggregation in washed rabbit platelets (WRPs). The molecular structure of the five-co-ordinate analog (3) has been elucidated by single-crystal X-ray diffraction revealing a trigonal bipyramidal geometry. All complexes are potent inhibitors of the PAF-induced aggregation in WRPs in the micromolar range. Complex (6) displayed a remarkable in vitro dual inhibition against PAF and thrombin, with IC50 values of 1.79 μM and 0.46 μM, respectively. Within the series, complex (5) was less effective (IC50 = 39 μM) while complex (1) was almost 12-fold more potent against PAF, as opposed to thrombin-induced aggregation. The biological behavior of complexes 1, 6 and 7 on PAF's basic metabolic enzymatic pathways reveals that they affect key biosynthetic and catabolic enzymes of PAF underlying the anti-inflammatory properties of the relevant complexes. The in vitro cytotoxic activities of all complexes in HEK293T (human embryonic kidney cells) and HeLa cells (cervical cancer cells) are described via the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) assay. The results reveal that complex 3 is the most potent within the series.

Direct Evidence for Excited Ligand Field State-based Oxidative Photoredox Chemistry of a Cobalt(III) Polypyridyl Photosensitizer.

Increasing interest in sustainable chemistry coupled with the quest to explore new reactivity has spurred research on first-row transition metal complexes for potential applications in a variety of settings. One of the more active areas of research is photoredox catalysis, where the synthetically tunable nature of their electronic structures provides a rich palette of options for tailoring their reactivity to a desired chemical transformation. Understanding the mechanism of excited-state reactivity is critical for the informed development of next-generation catalysts, which in turn requires information concerning the propensity of their electronic excited states to engage in the desired electron or energy transfer processes. Herein we provide direct evidence of the highly oxidizing nature of the lowest-energy ligand-field (LF) excited state of a first-row d6-low-spin Co(III) photosensitizer [Co(4,4'-Br2bpy)3]3+ (where 4,4'-Br2bpy is 4,4'-dibromo-2,2'-bipyridine). The redox potential associated with the LF excited state of the Co(III) complex was bracketed by performing bimolecular quenching studies by using a series of simple organic electron donors. Time-resolved absorption spectroscopy confirmed a dynamic quenching process attributed to reductive quenching of the lowest-energy ligand-field excited state of the Co(III) chromophore. Analysis of the Stern-Volmer plots for each chromophore-quencher pair revealed a limiting value of Ered* ∼ 1.25 V vs Fc/Fc+ for the metal-centered excited state, which is significantly stronger than that of more commonly employed transition metal-based photoredox agents such as [Ru(bpy)3]2+ (Ered* = 0.32 V vs Fc/Fc+) and [Ir(ppy)2(bpy)]+ (Ered* = 0.27 V vs Fc/Fc+). These results suggest that this class of chromophores could find utility in applications requiring the activation of oxidatively resistant organic substrates for photoredox catalysis.