Electron Paramagnetic Resonance Absorption Research Articles

Preparation and characterization of MnIIMnIII complexes with relevance to class Ib ribonucleotide reductases

The Mn2 complex [MnII2(TPDP)(O2CPh)2](BPh4) (1, TPDP = 1,3-bis(bis(pyridin-2-ylmethyl)amino)propan-2-ol, Ph =phenyl) was prepared and subsequently characterized via single-crystal X-ray diffraction, X-ray absorption, electronic absorption, and infrared spectroscopies, and mass spectrometry. 1 was prepared in order to explore its properties as a structural and functional mimic of class Ib ribonucleotide reductases (RNRs). 1 reacted with superoxide anion (O2•–) to generate a peroxido-MnIIMnIII complex, 2. The electronic absorption and electron paramagnetic resonance (EPR) spectra of 2 were similar to previously published peroxido-MnIIMnIII species. Furthermore, X-ray near edge absorption structure (XANES) studies indicated the conversion of a MnII2 core in 1 to a MnIIMnIII state in 2. Treatment of 2 with para-toluenesulfonic acid (p-TsOH) resulted in the conversion to a new MnIIMnIII species, 3, rather than causing O—O bond scission, as previously encountered. 3 was characterized using electronic absorption, EPR, and X-ray absorption spectroscopies. Unlike other reported peroxido-MnIIMnIII species, 3 was capable of oxidative O—H activation, mirroring the generation of tyrosyl radical in class Ib RNRs, however without accessing the MnIIIMnIV state.

Single-Site Ni-Grafted TiO2 with Diverse Coordination Environments for Visible-Light Hydrogen Production.

Solar hydrogen production at a high efficiency holds the significant importance in the age of energy crisis, while the micro-environment manipulation of active sites on photocatalysts plays a profound role in enhancing the catalytic performance. In this work, a series of well-defined single-site Ni-grafted TiO2 photocatalysts with unique and specific coordination environments, 2,2'-bipyridine-Ni-O-TiO2 (T-Ni Bpy) and 2-Phenylpyridine-Ni-O-TiO2 (T-Ni Phpy), were constructed with the methods of surface organometallic chemistry combined with surface ligand exchange for visible-light-induced photocatalytic hydrogen evolution reaction (HER). A prominent rate of 33.82 μmol ⋅ g-1 ⋅ h-1 and a turnover frequency of 0.451 h-1 for Ni are achieved over the optimal catalyst T-Ni Bpy for HER, 260-fold higher than those of Ni-O-TiO2 . Fewer electrons trapped oxygen vacancies and a larger portion of long-lived photogenerated electrons (>3 ns, ~52.9 %), which were demonstrated by the electron paramagnetic resonance and femtosecond transient IR absorption, correspond to the photocatalytic HER activity over the T-Ni Bpy. The number of long-lived free electrons injected from the Ni photoabsorber to the conduction band of TiO2 is one of the determining factors for achieving the excellent HER activity.

Enhanced the energy storage performance in AgNbO3‑based antiferroelectric ceramics via manipulation of oxygen vacancy

The applications of silver niobate (AgNbO3)-based antiferroelectric (AFE) ceramics for potential energy storage are limited by the introduction of oxygen vacancies (OVs). The inevitable OVs narrow the band gap and promote grain growth, resulting in poor breakdown strength and low recoverable energy density (Wrec). Here, we report a significant energy density performance of (Ag1-2xSrx)(Nb0.78Ta0.22)O3 AFE ceramics designed by restraining OVs. Electron paramagnetic resonance (EPR) and UVvis absorption spectra experiments demonstrate that the OV content gradually decreases and the band gap increases with increasing Sr content. Donor doping of Sr leads to the generation of silver ion vacancies, thus, the OV concentration decreases to maintain the electrical neutrality of the system. As a result, a high Wrec of ~5.6 J/cm3 together with an energy efficiency of 70.1% at 300 kV/cm is achieved in the (Ag0.92Sr0.04)(Nb0.78Ta0.22)O3 ceramic. This work offers a novel strategy for improving the energy storage properties of AgNbO3-based AFE ceramics.

Magnetic Field Effects in Triplet-Triplet Annihilation Upconversion: Revisiting Atkins and Evans' Theory.

In their seminal description of magnetic field effects on chemiluminescent fluid solutions, Atkins and Evans considered the spin-dependent interactions between two triplets, incorporating the effects of the diffusion of the molecules in the liquid phase. Their results, crucial for the advancement of photochemical upconversion, have received renewed attention due to the increasing interest in triplet-triplet annihilation for photovoltaic and optoelectronic applications. Here we revisit their approach, using a modern formulation of open quantum system dynamics and extend their results. We provide corrections to the theory of the magnetic field response of the fluorescent triplet pair state with singlet multiplicity. These corrections are timely, as improvements in the precision and range of available experimental methods are supported by the determination of quantitatively accurate rotational and interaction model parameters. We then extend Atkins and Evans' theory to obtain the magnetic field response of triplet pair states with triplet and quintet multiplicity. Although these states are not optically active, transitions between them are becoming imperative to study the working mechanism of spin-mediated upconversion and downconversion processes, thanks to advances in electron spin resonance and time-resolved transient absorption spectroscopy.

EPR Spectrum Analysis of DPPH and MnCl2

This paper presents the findings of electron paramagnetic resonance (EPR) spectroscopy experiments conducted on two different samples: 2,2-diphenyl-1-picrylhydrazyl (DPPH) and Manganese Chloride (MnCl2) dissolved in H2O. The experiments were conducted at Dr. D. Petasis EPR lab located in Allegheny College, Meadville, PA, USA. A Varian X-Band spectrometer was utilized for the analysis of the EPR absorption spectra. The primary objective was to determine the g-values and hyperfine structure of the two samples, which can be crucial in characterizing their electronic properties. The g-values obtained for both DPPH and MnCl2 were found to be remarkably close to the theoretically calculated values, suggesting the high accuracy and success of the experiments. This agreement validates the reliability of the EPR measurements and demonstrates the precision of the instruments and experimental procedures employed. For the MnCl2 sample, a hyperfine structure with 6 visible EPR lines was observed. By analyzing the number of EPR lines, the nuclear spin of the Mn(II) ion was determined to be I = 5/2, consistent with the expected value for Mn(II). The hyperfine constant (A) was also calculated from the field position differences between adjacent lines, providing further insights into the sample's magnetic properties. Comparisons were made between the obtained g-values and hyperfine constant with the expected values for Mn(II) in the literature, confirming the accuracy of the measurements and reinforcing the credibility of the experimental data. Overall, the EPR spectroscopy experiments conducted on DPPH and MnCl2 in H2O have provided valuable information about the electronic and magnetic properties of these paramagnetic materials. The results demonstrate the effectiveness of EPR spectroscopy as a powerful experimental technique for investigating various bio-chemical samples and understanding the effects of solvents on the EPR spectra of compounds. The close agreement between the experimental and theoretical values for the g-factors and hyperfine constants reinforces the reliability of the data obtained from the EPR experiments.

A Conserved Second Sphere Residue Tunes Copper Site Reactivity in Lytic Polysaccharide Monooxygenases.

Lytic polysaccharide monooxygenases (LPMOs) are powerful monocopper enzymes that can activate strong C-H bonds through a mechanism that remains largely unknown. Herein, we investigated the role of a conserved glutamine/glutamate in the second coordination sphere. Mutation of the Gln in NcAA9C to Glu, Asp, or Asn showed that the nature and distance of the headgroup to the copper fine-tune LPMO functionality and copper reactivity. The presence of Glu or Asp close to the copper lowered the reduction potential and decreased the ratio between the reduction and reoxidation rates by up to 500-fold. All mutants showed increased enzyme inactivation, likely due to changes in the confinement of radical intermediates, and displayed changes in a protective hole-hopping pathway. Electron paramagnetic resonance (EPR) and X-ray absorption spectroscopic (XAS) studies gave virtually identical results for all NcAA9C variants, showing that the mutations do not directly perturb the Cu(II) ligand field. DFT calculations indicated that the higher experimental reoxidation rate observed for the Glu mutant could be reconciled if this residue is protonated. Further, for the glutamic acid form, we identified a Cu(III)-hydroxide species formed in a single step on the H2O2 splitting path. This is in contrast to the Cu(II)-hydroxide and hydroxyl intermediates, which are predicted for the WT and the unprotonated glutamate variant. These results show that this second sphere residue is a crucial determinant of the catalytic functioning of the copper-binding histidine brace and provide insights that may help in understanding LPMOs and LPMO-inspired synthetic catalysts.

Intrinsic point defects (vacancies and antisites) in CdGeP2 crystals

Cadmium germanium diphosphide (CdGeP2) crystals, with versatile terahertz-generating properties, belong to the chalcopyrite family of nonlinear optical materials. Other widely investigated members of this family are ZnGeP2 and CdSiP2. The room-temperature absorption edge of CdGeP2 is near 1.72 eV (720 nm). Cadmium vacancies, phosphorous vacancies, and germanium-on-cadmium antisites are present in as-grown CdGeP2 crystals. These unintentional intrinsic point defects are best studied below room temperature with electron paramagnetic resonance (EPR) and optical absorption. Prior to exposure to light, the defects are in charge states that have no unpaired spins. Illuminating a CdGeP2 crystal with 700 or 850 nm light while being held below 120 K produces singly ionized acceptors (VCd−) and singly ionized donors (GeCd+), as electrons move from VCd2− vacancies to GeCd2+ antisites. These defects become thermally unstable and return to their doubly ionized charge states in the 150–190 K range. In contrast, neutral phosphorous vacancies (VP0) are only produced with near-band-edge light when the crystal is held near or below 18 K. The VP0 donors are unstable at these lower temperatures and return to the singly ionized VP+ charge state when the light is removed. Spin-Hamiltonian parameters for the VCd− acceptors and VP0 donors are extracted from the angular dependence of their EPR spectra. Exposure at low-temperature to near-band-edge light also introduces broad optical absorption bands peaking near 756 and 1050 nm. A consistent picture of intrinsic defects in II-IV-P2 chalcopyrites emerges when the present CdGeP2 results are combined with earlier results from ZnGeP2, ZnSiP2, and CdSiP2.

ATCUN-like Copper Site in βB2-Crystallin Plays a Protective Role in Cataract-Associated Aggregation.

Cataract is the leading cause of blindness worldwide, and it is caused by crystallin damage and aggregation. Senile cataractous lenses have relatively high levels of metals, while some metal ions can directly induce the aggregation of human γ-crystallins. Here, we evaluated the impact of divalent metal ions in the aggregation of human βB2-crystallin, one of the most abundant crystallins in the lens. Turbidity assays showed that Pb2+, Hg2+, Cu2+, and Zn2+ ions induce the aggregation of βB2-crystallin. Metal-induced aggregation is partially reverted by a chelating agent, indicating the formation of metal-bridged species. Our study focused on the mechanism of copper-induced aggregation of βB2-crystallin, finding that it involves metal-bridging, disulfide-bridging, and loss of protein stability. Circular dichroism and electron paramagnetic resonance (EPR) revealed the presence of at least three Cu2+ binding sites in βB2-crystallin, one of them with spectroscopic features typical for Cu2+ bound to an amino-terminal copper and nickel (ATCUN) binding motif, which is found in Cu transport proteins. The ATCUN-like Cu binding site is located at the unstructured N-terminus of βB2-crystallin, and it could be modeled by a peptide with the first six residues in the protein sequence (NH2-ASDHQF-). Isothermal titration calorimetry indicates a nanomolar Cu2+ binding affinity for the ATCUN-like site. An N-truncated form of βB2-crystallin is more susceptible to Cu-induced aggregation and is less thermally stable, indicating a protective role for the ATCUN-like site. EPR and X-ray absorption spectroscopy studies reveal the presence of a copper redox active site in βB2-crystallin that is associated with metal-induced aggregation and formation of disulfide-bridged oligomers. Our study demonstrates metal-induced aggregation of βB2-crystallin and the presence of putative copper binding sites in the protein. Whether the copper-transport ATCUN-like site in βB2-crystallin plays a functional/protective role or constitutes a vestige from its evolution as a lens structural protein remains to be elucidated.

Engineering carbon semi-tubes supported platinum catalyst for efficient oxygen reduction electrocatalysis

Innovation of catalyst structure is extremely important to develop the high-performance electrocatalysts for oxygen-reduction reaction (ORR). Herein, nitrogen-doped carbon semi-tube (N-CST) is used as a functional support for stabilizing the microwave-reduced Pt nanoparticles with an average size of ∼2.8nm to synthesize the semi-tubular Pt/N-CST catalyst. The contribution of interfacial Pt-N bond between N-CST support and Pt nanoparticles with electrons transfer from N-CST support to Pt nanoparticles is found by electron paramagnetic resonance (EPR) and X-ray absorption fine structure (XAFS) spectroscopy. This bridged Pt-N coordination can simultaneously help ORR electrocatalysis and promote electrochemical stability. As a result, the innovative Pt/N-CST catalyst exhibits excellent catalytic performance, realizing ORR activity and electrochemical stability superior to the commercial Pt/C catalyst. Furthermore, density functional theoretical (DFT) calculations suggest that the interfacial Pt-N-C site with unique affinity of O∗+ OH∗ can provide new active routes for the enhanced electrocatalytic ORR capacity.

Cataracts and copper: A spectroscopic perspective of copper-induced aggregation of betaB2-crystallin.

Cataracts disease is the principal cause of visual impairment worldwide. It is caused by damage, unfolding and subsequent non-amyloid aggregation of the highly soluble lens proteins: the crystallins. It has been demonstrated that essential metal ions, such as copper and zinc, can induce the aggregation of human gamma-crystallins. Here, we report the effect of metal ions one the aggregation of betaB2-crystallin: Pb(II), Hg(II), Cu(II) and Zn(II) ions can induce the non amyloid aggregation of this protein and the chelating agent EDTA can partially revert this effect. Furthermore, SDS-PAGE analysis of Cu(II)-induced protein aggregates reveal disulfide-bridged oligomerization. Spectroscopic studies of the Cu(II)-betaB2-crystallin interaction by electron paramagnetic resonance (EPR), circular dichroism (CD) and X-Ray absorption spectroscopy (XAS) show the presence of at least three metal binding sites. Surprisingly, one of them resembles that of Cu(II) bound to an amino-terminal copper and nickel binding motif (ATCUN), which is found in proteins and peptides that bind copper with high affinity and are involved in copper cellular trafficking. On the other hand, copper-induced formation of sulfur oxidized oligomers of betaB2-crystallin and a decreased EPR Cu(II) spin quantitation suggests the reduction of Cu(II) ions to Cu(I), as confirmed by XAS. Overall, these results suggests that copper-induced aggregation of betaB2-crystallin involves several mechanisms, including the formation of metal-bridged and disulfide-bridged species, and a very interesting copper-dependent redox process. This study expands the bioinorganic facet of cataract disease.

Identification of Alkoxy Radicals as Hydrogen Atom Transfer Agents in Ce-Catalyzed C-H Functionalization.

The intermediacy of alkoxy radicals in cerium-catalyzed C-H functionalization via H-atom abstraction has been unambiguously confirmed. Catalytically relevant Ce(IV)-alkoxide complexes have been synthesized and characterized by X-ray diffraction. Operando electron paramagnetic resonance and transient absorption spectroscopy experiments on isolated pentachloro Ce(IV) alkoxides identified alkoxy radicals as the sole heteroatom-centered radical species generated via ligand-to-metal charge transfer (LMCT) excitation. Alkoxy-radical-mediated hydrogen atom transfer (HAT) has been verified via kinetic analysis, density functional theory (DFT) calculations, and reactions under strictly chloride-free conditions. These experimental findings unambiguously establish the critical role of alkoxy radicals in Ce-LMCT catalysis and definitively preclude the involvement of chlorine radical. This study has also reinforced the necessity of a high relative ratio of alcohol vs Ce for the selective alkoxy-radical-mediated HAT, as seemingly trivial changes in the relative ratio of alcohol vs Ce can lead to drastically different mechanistic pathways. Importantly, the previously proposed chlorine radical-alcohol complex, postulated to explain alkoxy-radical-enabled selectivities in this system, has been examined under scrutiny and ruled out by regioselectivity studies, transient absorption experiments, and high-level calculations. Moreover, the peculiar selectivity of alkoxy radical generation in the LMCT homolysis of Ce(IV) heteroleptic complexes has been analyzed and back-electron transfer (BET) may have regulated the efficiency and selectivity for the formation of ligand-centered radicals.

EPR and optical absorption of VO2+ doped tetramethylammonium tetrachloro-zincate

• EPR studies of VO 2+ ions in TMZ single crystals are done at room temperature. • EPR analysis indicates four magnetically equivalent VO 2+ sites. • The vanadyl ion is found to take up substitutional position. The principal g and A are determined. • The optical absorption study is also carried out. • By correlating EPR and optical data the nature of bonding in the crystal is discussed. Electron paramagnetic resonance (EPR) studies of VO 2+ ions in [N(CH 3 ) 4 ] 2 ZnCI 4 (TMZ) single crystals are done at room temperature. Four magnetically equivalent VO 2+ sites are observed from EPR analysis. VO 2+ ion substitutes at Zn 2+ site. The principal g and A tensors are determined from angular variation of the EPR spectra. The optical absorption study is also performed. Using EPR and optical data the nature of bonding in the crystal is discussed.

Temperature dependences of paramagnetic response in oxidized spark plasma sintered carbon nanotubes: The way of understanding the local electronic structure

Electron paramagnetic resonance (EPR) spectroscopy was used to study an electronic structure of carbon nanotubes (CNTs) consolidated by spark plasma sintering and additionally oxidized in vapor of boiling nitric acid. Two components were distinguished in the EPR absorption spectra: narrow and broad lines with different g-factors. This testified to the different surrounding of paramagnetic centers associated with the lines. Temperature dependence of spin numbers, associated with the narrow line, transfers from Curie-Weiss law to Curie law with increasing temperature. EPR susceptibility, associated with the broad line, can be attributed to a paramagnetic matrix with superparamagnetic inclusions.

Formation of Stilbene Azo-Dimer by Direct Irradiation of p-Azidostilbene†.

Triplet arylnitrenes may provide direct access to aryl azo-dimers, which have broad commercial applicability. Herein, the photolysis of p-azidostilbene (1) in argon-saturated methanol yielded stilbene azo-dimer (2) through the dimerization of triplet p-nitrenostilbene (3 1N). The formation of 3 1N was verified by electron paramagnetic resonance spectroscopy and absorption spectroscopy (λmax ~ 375 nm) in cryogenic 2-methyltetrahydrofuran matrices. At ambient temperature, laser flash photolysis of 1 in methanol formed 3 1N (λmax ~ 370 nm, 2.85 × 107 s-1 ). On shorter timescales, a transient absorption (λmax ~ 390 nm) that decayed with a similar rate constant (3.11 × 107 s-1 ) was assigned to a triplet excited state (T) of 1. Density functional theory calculations yielded three configurations for T of 1, with the unpaired electrons on the azido (TA ) or stilbene moiety (TTw , twisted and TFl , flat). The transient was assigned to TTw based on its calculated spectrum. CASPT2 calculations gave a singlet-triplet energy gap of 16.6 kcal mol-1 for 1 N; thus, intersystem crossing of 1 1N to 3 1N is unlikely at ambient temperature, supporting the formation of 3 1N from T of 1. Thus, sustainable synthetic methods for aryl azo-dimers can be developed using the visible-light irradiation of aryl azides to form triplet arylnitrenes.

Local electronic structure of carbon nanotubes consolidated by spark plasma sintering

Local electronic structure of carbon nanotubes (CNTs) consolidated by spark plasma sintering and further oxidized by nitric acid was studied by electron paramagnetic resonance (EPR), transmission electron microscopy, X-ray photoelectron and Raman spectroscopy. It was found that long time oxidation perforated and fragmented sintered CNTs and increased the oxygen content in the material causing an increase in the number of paramagnetic centers. Two components in the absorption EPR spectra were distinguished: A narrow and a broad line with different [Formula: see text]-factors, which testifies the different surrounding of paramagnetic centers associated with the lines. The results are of great importance for understanding the mechanism of nanotubes oxidation and development new types of catalysts, electromagnetic shielding materials and absorbents.

How MoS2 assisted sulfur vacancies featured Cu2S in hollow Cu2S@MoS2 nanoboxes to activate H2O2 for efficient sulfadiazine degradation?

This work synthesized a series of hollow Cu2S@MoS2-x nanoboxes by using Cu2O nanocubes as precursor. Electron paramagnetic resonance (EPR) and X-ray absorption spectroscopy (XAS) analysis identified the existence of Sv in Cu2S@MoS2-x. Sulfadiazine (SDZ), a typical antibiotic, was selected as the target contaminant to evaluate the catalytic activity of Cu2S@MoS2-x via H2O2 activation. With adding 0.2 g/L Cu2S@MoS2-2 and 5 mM H2O2, 95.9% of SDZ (20 μM) was removed in 60 min and the reaction rate constant obtained by Cu2S@MoS2-2 (0.239 min−1) was improved by 4 times and 10 times in contrast with Cu2S (0.0622 min−1) and MoS2 (0.0219 min−1). EPR analysis and radical scavenger tests confirmed •OH and 1O2 as the dominated reactive oxygen species (ROS). In Cu2S@MoS2-2 activated H2O2 system, the yield of 1O2 was 6.12 × 10-14 mol/L, more than 8 times that in Cu2S/H2O2 system (0.73 × 10-14 mol/L). Density functional theory (DFT) calculation revealed that the Cu atoms exposed by the formation of Sv on Cu2S@MoS2-2 were the preferred adsorption sites for O2, which further achieved the conversion of O2 to •O2−. In the activation process, Cu2S mainly produced •OH through sulfur-enhanced Fenton process, while MoS2 shell accounted for the O2 production. Thereafter, the obtained O2 acquired electrons from the Cu atoms exposed by Sv to produce •O2−, followed by the generation of 1O2. The cooperation between MoS2 and Cu2S resulted in the superior catalytic activity. The excellent recyclability, stability, and adaptability demonstrated Cu2S@MoS2-2 as a reliable candidate for activating H2O2 toward refractory organics degradation.

Promoting the water dissociation of nickel sulfide electrocatalyst through introducing cationic vacancies for accelerated hydrogen evolution kinetics in alkaline media

Developing cost-effective non-precious electrocatalysts with excellent HER performance in alkaline media is of significance for industrial hydrogen production. Herein, we successfully endow Ni3S2 with unprecedentedly enhanced alkaline HER activities by introducing nickel vacancies. The Ni3S2 catalyst with nickel vacancies exhibits an ultralow overpotential of 35 mV at 10 mA cm−2 in 1 M KOH electrolyte, outperforming commercial Pt/C (56 mV) and most reported non-precious electrocatalysts. The electron paramagnetic resonance and X-ray absorption fine structure etc. validates the formation of Ni vacancies and the change of the geometric/electronic structure of Ni3S2. Additionally, the theoretical calculations reveal that the Ni sites with higher valence state neighbouring the Ni vacancies can promote the water dissociation, playing a vital role in accelerating HER kinetics in alkaline media. This work may provide a universal strategy to enhance the HER activity of transition-metal compound catalysts in alkaline media by means of cationic defect engineering.

Electron Paramagnetic Resonance and Synchrotron X-ray Absorption Spectroscopy for Highly Sensitive Characterization of Calcium Arsenates.

Calcium arsenates such as pharmacolite (CaHAsO4·2H2O), haidingerite (CaHAsO4·H2O), and weilite (CaHAsO4) are important sinks for arsenic in mine tailings as well as other natural and contaminated sites and are useful for reducing the mobility and bioavailability of this toxic metalloid in the environment. However, calcium arsenates usually occur in trace amounts dominated by other phases, making their detection, identification, and quantification challenging. In this contribution, pharmacolite, haidingerite, and weilite are shown to exhibit subtle but distinct postedge differences in As K-edge X-ray absorption near-edge structure (XANES) spectra and feature characteristic [AsO3]2-, [AsO4]2-, and [AsO4]4- radicals, all derived from the diamagnetic [HAsO4]2- precursor during γ-ray irradiation, in electron paramagnetic resonance (EPR) spectra. In particular, the 75As (nuclear spin I = 3/2 and natural isotope abundance = 100%) hyperfine coupling constants of the [AsO3]2- radicals in pharmacolite and haidingerite as well as other minerals (e.g., calcite and gypsum) are clearly distinct, allowing the unambiguous identification of calcium arsenates by the EPR technique readily at ∼0.1 wt %. Similarly, linear combination fittings of As K-edge XANES spectra demonstrate that pharmacolite and haidingerite at ∼0.1 wt % each in gypsum-rich mixtures can be detected and quantified as well. Therefore, a combination of the EPR and XANES techniques is a powerful approach for the highly sensitive characterization of calcium arsenates in the quest for the safe management and remediation of arsenic contamination. This work demonstrates the highly sensitive characterization of calcium arsenates by integrated electron paramagnetic resonance and synchrotron X-ray absorption spectroscopy.

Cu2+ and Cu3+ acceptors in β-Ga2O3 crystals: A magnetic resonance and optical absorption study

Electron paramagnetic resonance (EPR) and optical absorption are used to characterize Cu2+ (3d9) and Cu3+ (3d8) ions in Cu-doped β-Ga2O3. These Cu ions are singly ionized acceptors and neutral acceptors, respectively (in semiconductor notation, they are Cu− and Cu0 acceptors). Two distinct Cu2+ EPR spectra are observed in the as-grown crystals. We refer to them as Cu2+(A) and Cu2+(B). Spin-Hamiltonian parameters (a g matrix and a 63,65Cu hyperfine matrix) are obtained from the angular dependence of each spectrum. Additional electron-nuclear double resonance (ENDOR) experiments on Cu2+(A) ions give refined 63Cu and 65Cu hyperfine matrices and provide information about the nuclear electric quadrupole interactions. Our EPR results show that the Cu2+(A) ions occupy octahedral Ga sites with no nearby defect. The Cu2+(B) ions, also at octahedral Ga sites, have an adjacent defect, possibly an OH− ion, an oxygen vacancy, or an H− ion trapped within an oxygen vacancy. Exposing the crystals at room temperature to 275 nm light produces Cu3+ ions and reduces the number of Cu2+(A) and Cu2+(B) ions. The Cu3+ ions have an S = 1 EPR spectrum and are responsible for broad optical absorption bands peaking near 365, 422, 486, 599, and 696 nm. An analysis of loops observed in the Cu3+ EPR angular dependence gives 2.086 for the g value and 22.18, 3.31, and −25.49 GHz for the principal values of D (the fine-structure matrix). Thermal anneal studies above room temperature show that the Cu3+ ions decay and the Cu2+ ions recover between 75 and 375 °C.

XAS and EPR in Situ Observation of Ru(V) Oxo Intermediate in a Ru Water Oxidation Complex.

In this study, we combine in situ spectroelectrochemistry coupled with electron paramagnetic resonance (EPR) and X‐ray absorption spectroscopies (XAS) to investigate a molecular Ru‐based water oxidation catalyst bearing a polypyridinic backbone [RuII(OH2)(Py2Metacn)]2+ . Although high valent key intermediate species arising in catalytic cycles of this family of compounds have remain elusive due to the lack of additional anionic ligands that could potentially stabilize them, mechanistic studies performed on this system proposed a water nucleophilic attack (WNA) mechanism for the O−O bond formation. Employing in situ experimental conditions and complementary spectroscopic techniques allowed to observe intermediates that provide support for a WNA mechanism, including for the first time a Ru(V) oxo intermediate based on the Py2Metacn ligand, in agreement with the previously proposed mechanism.