Solid-state Electron Paramagnetic Resonance Research Articles

Unlocking Biradical Character in Diborepins.

Systems that possess open- and closed-shell behavior attract significant attention from researchers due to their inherent redox and charge transport properties. Herein, we report the synthesis of the first diborepin biradicals. They display tunable biradical character based on the steric and electronic profile of the stabilizing ligand and the resulting geometric deviation of the diborepin core from planarity. While there are numerous all-carbon-based biradical systems, boron-based biradical compounds are comparatively rare, particularly ones in which the radical sites are disjointed. Calculations using density functional theory (DFT) and multireference methods demonstrate that the fused diborepin scaffold exhibits high biradical character, up to 95%. Use of a nonsterically demanding diaminocarbene promotes the planarization of the pentacyclic framework, resulting in the synthetic realization of a diborepin containing a dibora-quinoidal core, which possesses a closed-shell ground state and thermally accessible triplet state. The biradicals were structurally authenticated and characterized by both solution and solid-state electron paramagnetic resonance (EPR) spectroscopy. Half-field transitions were observed at low temperatures (about 170 K), confirming the presence of the triplet state. Initial reactivity studies of the biradicals led to the isolation and structural characterization of bis(borepin hydride) and bis(borepin dianion).

Efficient Photothermal Energy Conversion Triggered by near-Infrared Light in a Dithiolene-Based Metal–Organic Framework

A Ni-dithiolene ligand, {Ni(pedt)2}− (pedt = 1-(pyridine-4-yl)ethylene-1,2-dithiolate), was used to prepare a novel interpenetrated redox-active Metal–Organic Framework (MOF), which exhibited an efficient photothermal conversion under low-power-density near-infrared (NIR) laser illumination. Solid-state UV–vis-NIR spectroscopy on bulk crystals indicated strong absorbance in the NIR region, attributed to the radical monoanion of the pedt ligands, which was also evident in the solid-state Electron Paramagnetic Resonance (EPR) spectrum. DFT computations on a model system provided new insights into the structural factors underpinning the photothermal properties. First, the NIR absorption corresponds to a high-energy excited state (D4), while the lowest-lying excited state (D1) is close in energy to the energies of the vibrational motions, facilitating the conversion of electronic to thermal energy. Second, close contacts between interpenetrated nets of the MOF may further enhance the propagation of thermal motion. The new photothermal MOF was then doped into a self-healing polymer, PDU (polydimethylsiloxane-urea), leading to composites which could recover from dynamic damage using the heat generated from the embedded MOF by photostimulus. This process led by the photothermal effect offers a highly efficient and energy-saving approach for self-healing materials design.

A Three-Dimensional Silicon-Diacetylene Porous Organic Radical Polymer

A Three-Dimensional Silicon-Diacetylene Porous Organic Radical Polymer

Interfacial charge transfer complex between TiO2 and non-aromatic ligand squaric acid

The attachment of squaric acid, a non-aromatic molecule, to the surface of TiO2 powder induced the optical absorption of the obtained hybrid material in the visible spectral range due to the interfacial charge transfer complex formation. The optical characterization of the hybrid is supported by the density functional theory calculations of the model cluster. The paramagnetic species generated upon excitation with ultraviolet or visible light, in both TiO2 powders, pristine and surface-modified, were identified conducting low-temperature solid-state and indirect electron paramagnetic resonance (EPR) spectroscopy experiments (spin trapping and spin scavenging). The solid-state EPR experiments indicated the promotion of electrons from the organic moiety to the titania conduction band under visible-light excitation of hybrid. Also, the spin scavenging experiments showed that the electrons generated in the hybrid upon the visible-light activation facilitate the reduction of the radical cations present in the dispersion, while these effects are not observed for pristine TiO2.

A novel strategy for site selective spin-labeling to investigate bioactive entities by DNP and EPR spectroscopy

A novel specific spin-labeling strategy for bioactive molecules is presented for eptifibatide (integrilin) an antiplatelet aggregation inhibitor, which derives from the venom of certain rattlesnakes. By specifically labeling the disulfide bridge this molecule becomes accessible for analytical techniques such as Electron Paramagnetic Resonance (EPR) and solid state Dynamic Nuclear Polarization (DNP). The necessary spin-label was synthesized and inserted into the disulfide bridge of eptifibatide via reductive followed by insertion by a double Michael addition under physiological conditions. This procedure is universally applicable for disulfide containing biomolecules and is expected to preserve their tertiary structure with minimal change due to the small size of the label and restoring of the previous disulfide connection. HPLC and MS analysis show the successful introduction of the spin label and EPR spectroscopy confirms its activity. DNP-enhanced solid state NMR experiments show signal enhancement factors of up to 19 in 13C CP MAS experiments which corresponds to time saving factors of up to 361. This clearly shows the high potential of our new spin labeling strategy for the introduction of site selective radical spin labels into biomolecules and biosolids without compromising its conformational integrity for structural investigations employing solid-state DNP or advanced EPR techniques.

Facile synthesis of chitosan-derived maillard reaction productions coated CuFeO2 with abundant oxygen vacancies for higher Fenton-like catalytic performance

The two shortcomings of the Fenton-like catalyst delafossite-type oxide (CuFeO2) lie in its spontaneous agglomeration and deactivation under neutral working pH. To remedy these drawbacks, novel Fenton-like catalyst chitosan-derived maillard reaction productions coated CuFeO2 with abundant oxygen vacancies (OV–CuFeO2@MRPs) was synthesized by hydrothermal method with no extra chemical reducing agent. The systemic characterization illustrated that richer oxygen vacancies and higher particles dispersion of OV-CuFeO2@MRPs contributed to better Rhodamine B (RhB) degradation under neutral pH compared to pure CuFeO2. Cooper antisite defects in OV-CuFeO2@MRPs were evidenced by X-ray powder diffraction (XRD), fourier transform infrared spectrometer (FTIR), Raman spectra and energy dispersive X-ray spectrometer (EDX) linescan. To keep the charge balance, OV-CuFeO2@MRPs should form rich oxygen vacancies, which was confirmed by X-ray photoelectron spectroscopy (XPS) and solid-state electron paramagnetic resonance spectrometer (solid-state EPR). Furthermore, the electrochemical impedance spectroscopy (EIS) analysis revealed that oxygen vacancies could improve the electron transfer. Scavenging experiments and electron spin resonance spectroscopy (ESR) analysis demonstrated that OH was main active radical during Fenton-like reaction, and the density functional theory (DFT) calculation verified that the oxygen vacancy could effectively adsorb H2O2 and elongate O–O bond of H2O2, thus promoting the activation of H2O2 into OH.

Investigation of lanthanum substitution effects in yttrium aluminium garnet: importance of solid state NMR and EPR methods

In this study, yttrium aluminium garnet (YAG) specimens in which yttrium was partially substituted by lanthanum Y3-xLaxAl5O12 (YLaAG) were prepared by an aqueous sol-gel method. YLaAG samples were analyzed by X-ray diffraction (XRD), solid state nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) methods. The presence of Ce3+ ions as an impurity originating from starting material was determined, therefore, luminescence measurements of YLaAG samples were also recorded. It was demonstrated that luminescent properties are strongly dependent on the phase composition of synthesized species. The XRD analysis results showed that only low substitution of yttrium by lanthanum is possible in Y3-xLaxAl5O12 without destroying garnet crystal structure. It was also demonstrated, that solid state NMR and EPR methods are indispensable tools for the explanation of processes and properties observed in the newly synthesized Y3-xLaxAl5O12 compounds.

Anionic redox reactions and structural degradation in a cation-disordered rock-salt Li1.2Ti0.4Mn0.4O2 cathode material revealed by solid-state NMR and EPR

The cation-disordered rock-salt Li1.2Ti0.4Mn0.4O2 is studied by solid-state NMR and electron paramagnetic resonance (EPR) spectroscopy during the first cycle. The anionic redox and structural degradation mechanism are discussed.

Electron paramagnetic resonance study of quartz grains: Implications on uranium and thorium mineralization

Electron Paramagnetic Resonance (EPR) study of quartz grains of Athabasca basin of Wheeler river of Canada have been investigated at room temperature. EPR spectrum of WR 2522 quartz sample exhibits resonance signals at g˜ 4.24, 2.15760, 2.08503, 2.04243, 2.00933, 1.92389, and 1.87331. The resonance signal at g˜ 4.24 has been attributed to Fe3+ ions. The resonance signals at g˜ 2.15760, 2.08503, 2.04243, 2.00933, 1.92389, 1.87331have been attributed to radiation induced paramagnetic defects such as the centers C', 4,3, E1', E2' and E4'. EPR study of WR 2571 quartz sample exhibits resonance signals at g˜ 8.96, 4.25, 2.22, 2.05143, 2.03501, 2.01817, and 2.01884. The resonance signals at g˜ 8.96, 4.25, and 2.22 have been attributed to Fe3+ ions. The remaining resonance signals have been attributed to defect centers such as C', 4, 3, E1', respectively. The solid state EPR parameters have been evaluated for the two samples and implications of uranium and thorium mineralization have been explained.

Nuclear and Electron Magnetic Resonance Spectroscopies of Atomically Precise Gold Nanoclusters

Atomically precise gold nanoclusters display properties that are unseen in larger nanoparticles. When the number of gold atoms is sufficiently small, the clusters exhibit molecular properties. Their study requires extensive use of classic molecular physical chemistry and, thus, methods such as vibrational spectroscopies, electrochemistry, density functional theory and molecular dynamics calculations, and of course nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) spectroscopies. NMR and EPR studies have been mostly carried out on the benchmark, stable molecules Au25(SR)18, Au38(SR)24, Au102(SR)44, and Au144(SR)60 (where SR = thiolate). In this Account, we showcase examples primarily taken from our previous and ongoing NMR and EPR studies, which we hope will trigger further interest in the use of these sensitive, though often underutilized, techniques. Indeed, 1D and 2D NMR spectra of pure, atomically precise clusters can be very detailed and informative. Molecular clusters are molecules and, thus, have discrete energy levels and undergo stepwise oxidation or reduction. The effect of the charge state on the chemical shifts and line shapes is a function of the ligand type (ligands differ due to specific bonds with different Au atom types) and the position of the chemical group along the ligand backbone: for groups near the Au core, they can be very dramatic. Ligand-protected gold clusters are hard-soft molecules where a hard metal core is surrounded by a dynamic molecular layer. The latter provides a nanoenvironment that interfaces the cluster core with the surrounding environment and can be permeated by molecules and ions. NMR spectroscopy is especially useful to assess its structure. For example, the data show that whereas long alkanethiolates form bundles, shorter chains exhibit more conformational freedom and are quite folded. NMR spectroscopy allows studying diastereotopic effects and provides information on possible hydrogen bonds of ligands with sulfur or surface gold atoms. EPR spectroscopy is a very precise technique to check and characterize the magnetic state of gold clusters or clusters doped with foreign-metal atoms. Electron nuclear double resonance (ENDOR) provides a powerful tool to assess the interaction of an unpaired electron with nuclei, as we showed for 197Au and 1H. It can be used as a sensitive probe of the spin-density distribution in nanoclusters: for example, it showed that the singly occupied molecular orbital may span outside the Au core by nearly 6 Å. Solid-state EPR spectroscopy has provided compelling evidence that the specific ligands and the crystallinity degree are very important factors in determining the interactions between clusters in the solid state. Depending on the condition, paramagnetic, superparamagnetic, ferromagnetic, or antiferromagnetic behavior can be observed. Time-resolved EPR was successfully tested to determine the efficiency of singlet-oxygen generation via sensitization of Au25 clusters. This Account thus demonstrates some of the remarkable insights that can be gained into the properties of atomically precise clusters through detailed NMR and EPR studies.

In Quest of the Alanine R3 Radical: Multivariate EPR Spectral Analyses of X-Irradiated Alanine in the Solid State.

The amino acid l-α-alanine is the most commonly used material for solid-state electron paramagnetic resonance (EPR) dosimetry, due to the formation of highly stable radicals upon irradiation, with yields proportional to the radiation dose. Two major alanine radical components designated R1 and R2 have previously been uniquely characterized from EPR and electron-nuclear double resonance (ENDOR) studies as well as from quantum chemical calculations. There is also convincing experimental evidence of a third minor radical component R3, and a tentative radical structure has been suggested, even though no well-defined spectral signature has been observed experimentally. In the present study, temperature dependent EPR spectra of X-ray irradiated polycrystalline alanine were analyzed using five multivariate methods in further attempts to understand the composite nature of the alanine dosimeter EPR spectrum. Principal component analysis (PCA), maximum likelihood common factor analysis (MLCFA), independent component analysis (ICA), self-modeling mixture analysis (SMA), and multivariate curve resolution (MCR) were used to extract pure radical spectra and their fractional contributions from the experimental EPR spectra. All methods yielded spectral estimates resembling the established R1 spectrum. Furthermore, SMA and MCR consistently predicted both the established R2 spectrum and the shape of the R3 spectrum. The predicted shape of the R3 spectrum corresponded well with the proposed tentative spectrum derived from spectrum simulations. Thus, results from two independent multivariate data analysis techniques strongly support the previous evidence that three radicals are indeed present in irradiated alanine samples.

Bulk Quantum Computation with Pulsed Electron Paramagnetic Resonance: Simulations of Single-Qubit Error Correction Schemes

We investigate the possibility to restore transient nutations of electron spin centers embedded in the solid using specific composite pulse sequences developed previously for the application in nuclear magnetic resonance spectroscopy. We treat two types of systematic errors simultaneously: (i) rotation angle errors related to the spatial distribution of microwave field amplitude in the sample volume, and (ii) off-resonance errors related to the spectral distribution of Larmor precession frequencies of the electron spin centers. Our direct simulations of the transient signal in erbium- and chromium-doped CaWO\(_{4}\) crystal samples with and without error corrections show that the application of the selected composite pulse sequences can substantially increase the lifetime of Rabi oscillations. Finally, we discuss the applicability limitations of the studied pulse sequences for the use in solid-state electron paramagnetic resonance spectroscopy.

Heavy Water as a Probe of the Free Radical Nature and Electrical Conductivity of Melanin.

Melanins are pigmentary macromolecules found in many locations throughout nature including plants and vertebrate animals. It was recently proposed that the predominant brown-black pigment eumelanin is a mixed ionic-electronic conductor which has led to renewed interest in its basic properties as a model bioelectronic material. This exotic hybrid electrical behavior is strongly dependent upon hydration and is closely related to the free radical content of melanin which is believed to be a mixed population of two species: the semiquinone (SQ) and a carbon-centered radical (CCR). The predominant charge carrier is the proton that is released during the formation of the SQ radical and controlled by a comproportionation equilibrium reaction. In this paper we present a combined solid-state electron paramagnetic resonance (EPR), adsorption, and hydrated conductivity study using D2O as a probe. We make specific predictions as to how the heavy isotope effect, in contrast to H2O, should perturb the comproportionation equilibrium and the related outcome as far as the electrical conductivity is concerned. Our EPR results confirm the proposed two-spin mechanism and clearly demonstrate the power of combining macroscopic measurements with observations from mesoscopic probes for the study of bioelectronic materials.

Preparation and characterization of cetyltrimethylammonium bromide (CTAB)-stabilized Fe3O4 nanoparticles for electrochemistry detection of citric acid

Sensing systems containing iron oxide nanoparticles have shown high potential for improving the catalytic activity of diverse analytes. However, the role of magnetic systems in these processes is not fully understood. In addition, colloidal stability of iron oxide nanoparticles is another obstacle for their application in sensing platforms. In this study, we report the synthesis of cetyltrimethylammonium bromide (CTAB) stabilized Fe3O4 magnetic nanoparticles (MNPs), characterization and their electrochemistry applications for citric acid detection, which is an important addictive in industrial products. The stability of these particles was monitored and compared by zeta potential, dynamic light scattering (DLS) measurements and nanoparticle tracking analysis (NTA). X-ray diffraction (XRD) pattern confirmed the presence of the single crystalline phase. Electron paramagnetic resonance (EPR) measurements were taken at some selected temperatures showing that the main feature of the X-band solid state EPR spectrum has a strong transition at geff=2 at room temperature (RT). This absorption band is correlated to the symmetry of the cubic inverse spinel structure of magnetite which reinforced the results obtained by XRD powder pattern. Thermal evolution dependence of Landé g-factor, resonance field and line width has been evaluated. The size of the superparamagnetic nanocrystallites can be easily controlled with diameter less than 5nm (4.2±0.3nm) according to Transmission Electron Microscopy (TEM) measurement. Electrochemical measurements have been employed to investigate how the catalytic properties of Fe3O4 nanoparticles stabilized with CTAB immobilized by Layer-by-Layer (LbL) technique influence on the reduction of citric acid. Chronoamperometry gives a sensitivity of 3.0nAμM−1 for the citric acid in the linear range (R2: 0.997) between 50μM and 2.5mM with a limit of detection (LOD, s/n=3) of 40μM, which agreed with the dynamic chronoamperometry results. Dynamic chronoamperometry signals also demonstrate that the sensor response is not affected for some interferents such as: Ca2+, Na+, Mg2+, K+, Cl, uric acid, glucose, catechol and dopamine. In summary, we demonstrate that CTAB-stabilized magnetic nanoparticles improve the catalytic reduction of citric acid and present high potential for sensor applications.

Bis(toluene)chromium(I) [1,2,5]Thiadiazolo[3,4-c][1,2,5]thiadiazolidyl and [1,2,5]Thiadiazolo[3,4-b]pyrazinidyl: New Heterospin (S1 = S2 = 1/2) Radical-Ion Salts

Bis(toluene)chromium(0), Cr(0)(η(6)-C7H8)2 (3), readily reduced [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazole (1) and [1,2,5]thiadiazolo[3,4-b]pyrazine (2) in a tetrahydrofuran solvent with the formation of heterospin, S1 = S2 = ½, radical-ion salts [3](+)[1](-) (4) and [3](+)[2](-) (5) isolated in high yields. The salts 4 and 5 were characterized by single-crystal X-ray diffraction (XRD), solution and solid-state electron paramagnetic resonance, and magnetic susceptibility measurements in the temperature range 2-300 K. Despite the formal similarity of the salts, their crystal structures were very different and, in contrast to 4, in 5 anions were disordered. For the XRD structures of the salts, parameters of the Heisenberg spin Hamiltonian were calculated using the CASSCF/NEVPT2 and broken-symmetry density functional theory approaches, and the complex magnetic motifs featuring the dominance of antiferromagnetic (AF) interactions were revealed. The experimental χT temperature dependences of the salts were simulated using the Van Vleck formula and a diagonalization of the matrix of the Heisenberg spin Hamiltonian for the clusters of 12 paramagnetic species with periodic boundary conditions. According to the calculations and χT temperature dependence simulation, a simplified magnetic model can be suggested for the salt 4 with AF interactions between the anions ([1](-)···[1](-), J1 = -5.77 cm(-1)) and anions and cations ([1](-)···[3](+), J2 = -0.84 cm(-1)). The magnetic structure of the salt 5 is much more complex and can be characterized by AF interactions between the anions, [2](-)···[2](-), and by both AF and ferromagnetic (FM) interactions between the anions and cations, [2](-)···[3](+). The contribution from FM interactions to the magnetic properties of the salt 5 is in qualitative agreement with the positive value of the Weiss constant Θ (0.4 K), whereas for salt 4, the constant is negative (-7.1 K).

Electron paramagnetic resonance in positively charged Au25 molecular nanoclusters

In this study, we investigated the unpaired electrons and singly occupied molecular orbitals (SOMO) of positively charged Au(25) molecular clusters using solid-state electron paramagnetic resonance (EPR). The EPR powder spectra of the positively charged (Au(25) (+)) and neutral (Au(25) (0)) species of Au(25) are discussed and compared. Our study demonstrates that Au(25) (+) is paramagnetic with a SOMO that is mostly localized about the central gold atom in the core of the molecule and possesses a strong p-type atomic character. The unpaired electron spin is demonstrated to strongly interact with the nuclear spins from other (197)Au nuclei in the core of Au(25) (+) molecules and the hyperfine tensor describing such interaction was extracted from the comparison of the EPR spectra with quantum mechanical simulations assuming an anisotropic structure of the core. Our simulations suggest that the core of Au(25) (+) molecular clusters is more distorted than in the corresponding neutral counterpart. They also confirm previous hypotheses suggesting that the icosahedral core of Au(25) (+) experiences contraction with decreasing temperature.

Molecular Structures of Amyloid and Prion Fibrils: Consensus versus Controversy

Many peptides and proteins self-assemble into amyloid fibrils. Examples include mammalian and fungal prion proteins, polypeptides associated with human amyloid diseases, and proteins that may have biologically functional amyloid states. To understand the propensity for polypeptides to form amyloid fibrils and to facilitate rational design of amyloid inhibitors and imaging agents, it is necessary to elucidate the molecular structures of these fibrils. Although fibril structures were largely mysterious 15 years ago, a considerable body of reliable structural information about amyloid fibril structures now exists, with essential contributions from solid state nuclear magnetic resonance (NMR) measurements. This Account reviews results from our laboratories and discusses several structural issues that have been controversial. In many cases, the amino acid sequences of amyloid fibrils do not uniquely determine their molecular structures. Self-propagating, molecular-level polymorphism complicates the structure determination problem and can lead to apparent disagreements between results from different laboratories, particularly when different laboratories study different polymorphs. For 40-residue β-amyloid (Aβ₁₋₄₀) fibrils associated with Alzheimer's disease, we have developed detailed structural models from solid state NMR and electron microscopy data for two polymorphs. These polymorphs have similar peptide conformations, identical in-register parallel β-sheet organizations, but different overall symmetry. Other polymorphs have also been partially characterized by solid state NMR and appear to have similar structures. In contrast, cryo-electron microscopy studies that use significantly different fibril growth conditions have identified structures that appear (at low resolution) to be different from those examined by solid state NMR. Based on solid state NMR and electron paramagnetic resonance (EPR) measurements, the in-register parallel β-sheet organization found in β-amyloid fibrils also occurs in many other fibril-forming systems. We attribute this common structural motif to the stabilization of amyloid structures by intermolecular interactions among like amino acids, including hydrophobic interactions and polar zippers. Surprisingly, we have recently identified and characterized antiparallel β-sheets in certain fibrils that are formed by the D23N mutant of Aβ₁₋₄₀, a mutant that is associated with early-onset, familial neurodegenerative disease. Antiparallel D23N-Aβ₁₋₄₀ fibrils are metastable with respect to parallel structures and, therefore, represent an off-pathway intermediate in the amyloid fibril formation process. Other methods have recently produced additional evidence for antiparallel β-sheets in other amyloid-formation intermediates. As an alternative to simple parallel and antiparallel β-sheet structures, researchers have proposed β-helical structural models for some fibrils, especially those formed by mammalian and fungal prion proteins. Solid state NMR and EPR data show that fibrils formed in vitro by recombinant PrP have in-register parallel β-sheet structures. However, the structure of infectious PrP aggregates is not yet known. The fungal HET-s prion protein has been shown to contain a β-helical structure. However, all yeast prions studied by solid state NMR (Sup35p, Ure2p, and Rnq1p) have in-register parallel β-sheet structures, with their Gln- and Asn-rich N-terminal segments forming the fibril core.

Features of EPR Application to Systems Containing Paramagnetic Centers and Ferromagnetic Nanoparticles

The scope of the electron paramagnetic resonance (EPR) technique in catalysis is often limited because of the presence of the ferromagnetic nanoparticles in many catalytic systems. The present work gives an effective method to discriminate solid-state EPR spectra in the microwave resonance absorption while investigating such systems. The approach is based on the different features of the EPR spectra and ferromagnetic resonance absorption that are simultaneously observed in the system.

Solid-state NMR and EPR analysis of carbon-doped titanium dioxide photocatalysts (TiO 2−xC x)

Carbon-doped TiO 2 have received attention recently because of their potential for environmental photocatalysis and solar hydrogen conversion applications. Three different carbon-doped TiO 2 nanoparticle materials were synthesized via sol–gel and hydrothermal procedures, and analyzed by 13C solid-state nuclear magnetic resonance (SSNMR) and other methods to characterize the environment of the doping species. UV/vis spectra and powder X-ray diffraction (XRD) patterns showed that the synthesized materials absorbed visible light and their crystal structures corresponded to anatase. 13C SSNMR analyses of TiO 2− x C x displayed signals corresponding to carbonate-type or sp 2-type carbon species. Variable contact CP-MAS and dipolar dephasing analyses gave evidence for the presence and proximity of H atoms near these carbonate species. Electron paramagnetic resonance (EPR) spectroscopy showed that the thermally oxidized TiO 2− x C x displayed a complex mixture of point defects, electron and hole trapping centers, all attributable to the incorporation of carbon, while the XPS data ruled out the presence of carbide species.

Stable and Highly Persistent Quinoxaline-Centered Metalloorganic Radical Anions: Preparation, Structural, Spectroscopic, and Computational Investigations

Coordination of diazines such as quinoxaline to transition metals stabilizes radical anions generated by chemical or electrochemical cathodic reduction. However, even though various sorts of radical anionic diazines have been subjected to spectroscopic investigations in the recent past, reports combining structural, solid-state electron paramagnetic resonance (EPR) and computational investigations of kinetically stable species are still missing. In this study, four radical anions derived from tricarbonylmanganese- and tricarbonylrhenium-bound quinoxaline chelates, embedded within a triple-decker architecture, have been prepared from neutral substrates by chemical reduction over alkaline metals (K, Rb); the electronic structure of the latter metalloorganic paramagnetic salts was investigated by the means of structural X-ray diffraction analysis, electrochemistry, solution and crystal EPR spectroscopy, and density functional theory (DFT). Unprecedented structures of three manganese-bound and one rhenium-bound quinoxaline-derived paramagnetic salts were obtained from solutions of the corresponding radical anions crystallized in the presence of cryptand 222. It is inferred from a comparative study of the structures of anionic and neutral quinoxaline complexes that reduction does not have any significant impact over the coordination mode of the metal centers and over the overall geometry of the triple-decker architecture. The most notable changes in the radical-anionic metalloorganic species, as compared to the neutral parent molecules, comprise a slight hapticity shift of the metal-bound benzyl moiety and a weak intraannular distortion of the quinoxalyl core. Single-crystal EPR experiments carried out with the rhenium and manganese compounds produced the respective anisotropic g tensor, which was found in each case to be essentially located at the quinoxalyl fragment. Computations, carried out using DFT methods (B3LYP-LANL2DZ and Becke-Perdew-TZP), corroborated the features suggested by structural analysis. Single-point calculation using the B3LYP functional and various basis sets [LANL2DZ, 6-31G(d), 6-311+G(d), and 6-311+G(2d,p)] provided us with values of anisotropic g tensors and hyperfine coupling constants consistent with those determined experimentally. It is inferred from this study that the two metal centers bound to the nitrogen atoms of the quinoxalyl core contribute in the lowering of the HOMO-LUMO gap in the neutral species. The triple-decker arrangement, which combines chelation of the metal, steric protection, and encapsulation of the central quinoxalyl core, is a stabilizing factor that provides a long-lived character to the radical-anionic species.