Coordination Variations within Binuclear Copper Dioxygen-Derived (Hydro)Peroxo and Superoxo Species; Influences upon Thermodynamic and Electronic Properties.

Copper ion is a versatile and ubiquitous facilitator of redox chemical and biochemical processes. These include the binding of molecular oxygen to copper(I) complexes where it undergoes stepwise reduction-protonation. A detailed understanding of thermodynamic relationships between such reduced/protonated states is key to elucidate the fundamentals of the chemical/biochemical processes involved. The dicopper(I) complex [CuI2(BPMPO-)]1+ {BPMPOH = 2,6-bis{[(bis(2-pyridylmethyl)amino]methyl}-4-methylphenol)} undergoes cryogenic dioxygen addition; further manipulations in 2-methyltetrahydrofuran generate dicopper(II) peroxo [CuII2(BPMPO-)(O22-)]1+, hydroperoxo [CuII2(BPMPO-)(-OOH)]2+, and superoxo [CuII2(BPMPO-)(O2•-)]2+ species, characterized by UV-vis, resonance Raman and electron paramagnetic resonance (EPR) spectroscopies, and cold spray ionization mass spectrometry. An unexpected EPR spectrum for [CuII2(BPMPO-)(O2•-)]2+ is explained by the analysis of its exchange-coupled three-spin frustrated system and DFT calculations. A redox equilibrium, [CuII2(BPMPO-)(O22-)]1+ ⇄ [CuII2(BPMPO-)(O2•-)]2+, is established utilizing Me8Fc+/Cr(η6-C6H6)2, allowing for [CuII2(BPMPO-)(O2•-)]2+/[CuII2(BPMPO-)(O22-)]1+ reduction potential calculation, E°' = -0.44 ± 0.01 V vs Fc+/0, also confirmed by cryoelectrochemical measurements (E°' = -0.40 ± 0.01 V). 2,6-Lutidinium triflate addition to [CuII2(BPMPO-)(O22-)]1+ produces [CuII2(BPMPO-)(-OOH)]2+; using a phosphazene base, an acid-base equilibrium was achieved, pKa = 22.3 ± 0.7 for [CuII2(BPMPO-)(-OOH)]2+. The BDFEOO-H = 80.3 ± 1.2 kcal/mol, as calculated for [CuII2(BPMPO-)(-OOH)]2+; this is further substantiated by H atom abstraction from O-H substrates by [CuII2(BPMPO-)(O2•-)]2+ forming [CuII2(BPMPO-)(-OOH)]2+. In comparison to known analogues, the thermodynamic and spectroscopic properties of [CuII2(BPMPO-)] O2-derived adducts can be accounted for based on chelate ring size variations built into the BPMPO- framework and the resulting enhanced CuII-ion Lewis acidity.

End-On Copper(I) Superoxo and Cu(II) Peroxo and Hydroperoxo Complexes Generated by Cryoreduction/Annealing and Characterized by EPR/ENDOR Spectroscopy.

In this report, we investigate the physical and chemical properties of monocopper Cu(I) superoxo and Cu(II) peroxo and hydroperoxo complexes. These are prepared by cryoreduction/annealing of the parent [LCuI(O2)]+ Cu(I) dioxygen adducts with the tripodal, N4-coordinating, tetradentate ligands L = PVtmpa, DMMtmpa, TMG3tren and are best described as [LCuII(O2•-)]+ Cu(II) complexes that possess end-on (η1-O2•-) superoxo coordination. Cryogenic γ-irradiation (77 K) of the EPR-silent parent complexes generates mobile electrons from the solvent that reduce the [LCuII(O2•-)]+ within the frozen matrix, trapping the reduced form fixed in the structure of the parent complex. Cryoannealing, namely progressively raising the temperature of a frozen sample in stages and then cooling back to low temperature at each stage for examination, tracks the reduced product as it relaxes its structure and undergoes chemical transformations. We employ EPR and ENDOR (electron-nuclear double resonance) as powerful spectroscopic tools for examining the properties of the states that form. Surprisingly, the primary products of reduction of the Cu(II) superoxo species are metastable cuprous superoxo [LCuI(O2•-)]+ complexes. During annealing to higher temperatures this state first undergoes internal electron transfer (IET) to form the end-on Cu(II) peroxo state, which is then protonated to form Cu(II)-OOH species. This is the first time these methods, which have been used to determine key details of metalloenzyme catalytic cycles and are a powerful tools for tracking PCET reactions, have been applied to copper coordination compounds.

Impact of Intramolecular Hydrogen Bonding on the Reactivity of Cupric Superoxide Complexes with O-H and C-H Substrates.

The dioxygen reactivity of a series of TMPA-based copper(I) complexes (TMPA=tris(2-pyridylmethyl)amine), with and without secondary-coordination-sphere hydrogen-bonding moieties, was studied at -135 °C in 2-methyltetrahydrofuran (MeTHF). Kinetic stabilization of the H-bonded [( (X1)(X2) TMPA)CuII (O2.- )]+ cupric superoxide species was achieved, and they were characterized by resonance Raman (rR) spectroscopy. The structures and physical properties of [( (X1)(X2) TMPA)CuII (N3- )]+ azido analogues were compared, and the O2.- reactivity of ligand-CuI complexes when an H-bonding moiety is replaced by a methyl group was contrasted. A drastic enhancement in the reactivity of the cupric superoxide towards phenolic substrates as well as oxidation of substrates possessing moderate C-H bond-dissociation energies is observed, correlating with the number and strength of the H-bonding groups.

Nanostructured CeO2 photocatalysts: optimizing surface chemistry, morphology, and visible-light absorption.

Emerging photocatalytic applications of cerium dioxide (CeO2) include green hydrogen production, CO2 conversion to fuels, and environmental remediation of various toxic molecules. These applications leverage the oxygen storage capacity and tunable surface chemistry of CeO2 to photocatalyze the chosen reaction, but many open questions remain regarding the fundamental physics of photocatalysis over CeO2. The commonly ascribed 'bandgap' of CeO2 (∼3.1 eV) differs fundamentally from other photocatalytic oxides such as TiO2; UV light excites an electron from the CeO2 valence band into a 4f state, generating a polaron as the lattice distorts around the localized charge. Researchers often disregard the distinction between the 4f state and a traditional, delocalized conduction band, resulting in ambiguity regarding mechanisms of charge transfer and visible-light absorption. This review summarizes modern literature regarding CeO2 photocatalysis and discusses commonly reported photocatalytic reactions and visible light-sensitization strategies. We detail the often misunderstood fundamental physics of CeO2 photocatalysis and supplement previous work with original computational insights. The exceptional progress and remaining challenges of CeO2-based photocatalysts are highlighted, along with suggestions for further research directions based on the observed gaps in current understanding.