One-electron Reduction Potentials Research Articles

Electron-deficient Indenofluorene-based Systems: Multicolor and Visible-to-near-infrared (NIR) Electrochromism and OFF-OFF-ON Electrofluorochromism.

Here, we report the synthesis and multi-functional electrochromic behaviour (multi-colour modulation, visible-to-near IR absorption switching, and electrofluorochromism) of electron-deficient indenofluorene-based systems. The compounds (IF1-IF5) have been obtained via Knoevenagel condensation of indenofluorenone (IFK) with various nucleophiles (malononitrile, benzylcyanide, dimethyl malonate, methyl cyanoacetate, benzothiazole-2-acetonitrile). IF1-IF5 possess strong colours and absorb in the visible region (λmax = 295-388 nm). These compounds are electroactive and exhibit two reversible reduction waves (-0.35 ̶ -0.88 V and -0.65 ̶ -1.30V vs Ag/AgCl), generating radical anion and dianion systems. For the electrochromic studies, upon applying the one-electron reduction potential (-0.35 V vs Ag/AgCl), the absorption maximum of IF1 redshift from 382 nm to 1240 nm (IF1-•), which subsequently blueshifts to 466 & 745 nm (IF12-•) upon increasing to two-electron reduction potential (-0.65 V vs Ag/AgCl). The color of the solution was switched from green to dark blue and further to light orange. The electrochromic behaviour is highly reversible and cycling. In addition, unlike the non-fluorescent (IF1 and IF1-•), the two-electron reduced system (IF12-•) is red-emissive (λem = 630 nm) due to the combination of radicals leading to the formation of antiaromatic quinoidal π-conjugated system (IF12-).

Probing the Molecular Interactions of Electrochemically Reduced Vitamin B2 with CO2.

The electrochemical reduction of riboflavin (vitamin B2) in a dimethyl sulfoxide solvent was examined under a CO2 atmosphere and compared with results under an argon atmosphere. Variable-scan-rate cyclic voltammetry combined with controlled potential electrolysis (CPE) and analysis by UV-vis and EPR spectroscopies provided insights into the nature of interactions of reduced flavins with dissolved CO2. Reductive exhaustive CPE experiments under CO2 indicated an overall two-electron stoichiometry, compared to one-electron reduction under an argon atmosphere, due to the lowering of the formal one-electron reduction potential of the flavin radical anion to form the dianion, which can be rationalized by riboflavin-CO2 molecular interactions. UV-vis spectroscopic measurements confirmed complete chemical reversibility of the redox transformations over extended time scales. Digital simulation modeling of the voltammetric data enabled extraction of thermodynamic and kinetic parameters for the proposed mechanism, comprising multiple proton-coupled electron transfer steps, diamagnetic anions, radical anions, and neutral radical intermediates enroute to the fully reduced state, as well as evidence of a long-lived solution phase complex of the reduced riboflavin with CO2.

First and Second Reductions in an Aprotic Solvent: Comparing Computational and Experimental One-Electron Reduction Potentials for 345 Quinones.

Using reference reduction potentials of quinones recently measured relative to the saturated calomel electrode (SCE) in N,N-dimethylformamide (DMF), we benchmark absolute one-electron reduction potentials computed for 345 Q/Q•- and 265 Q•-/Q2- half-reactions using adiabatic electron affinities computed with density functional theory and solvation energies computed with four continuum solvation models: IEF-PCM, C-PCM, COSMO, and SM12. Regression analyses indicate a strong linear correlation between experimental and absolute computed Q/Q•- reduction potentials with Pearson's correlation coefficient (r) between 0.95 and 0.96 and the mean absolute error (MAE) relative to the linear fit between 83.29 and 89.51 mV for different solvation methods when the slope of the regression is constrained to 1. The same analysis for Q•-/Q2- gave a linear regression with r between 0.74 and 0.90 and MAE between 95.87 and 144.53 mV, respectively. The y-intercept values obtained from the linear regressions are in good agreement with the range of absolute reduction potentials reported in the literature for the SCE but reveal several sources of systematic error. The y-intercepts from Q•-/Q2- calculations are lower than those from Q/Q•- by around 320-410 mV for IEF-PCM, C-PCM, and SM12 compared to 210 mV for COSMO. Systematic errors also arise between molecules having different ring sizes (benzoquinones, naphthoquinones, and anthraquinones) and different substituents (titratable vs nontitratable). SCF convergence issues were found to be a source of random error that was slightly reduced by directly optimizing the solute structure in the continuum solvent reaction field. While SM12 MAEs were lower than those of the other solvation models for Q/Q•-, SM12 had larger MAEs for Q•-/Q2- pointing to a larger error when describing multiply charged anions in DMF. Altogether, the results highlight the advantages of, and further need for, testing computational methods using a large experimental data set that is not skewed (e.g., having more titratable than nontitratable substituents on different parent groups or vice versa) to help further distinguish between sources of random and systematic errors in the calculations.

Adaptability of Heteropolytungstate Anions as Efficient Anode Redox Mediators in Redox Flow Polymer Electrolyte Fuel Cells.

Heteropolyanions (HPAs) are known as the candidate for an anode redox mediator for redox flow polymer electrolyte fuel cells (PEFCs). The electrochemical properties of HPAs differ depending on the transition elements and heteroatoms in HPAs. For example, heteropolytungstate anions (W-HPAs), in which the transition element is tungsten, have a lower one-electron reduction potential than other HPAs. Therefore, it has been reported that redox flow PEFCs adapted with W-HPAs exhibit high power generation performance. On the other hand, studies on the heteroatoms of HPAs are limited only to electrochemical properties, and statistical and comprehensive studies on the power generation performance of redox flow PEFCs are lacking. Thus, it is beneficial to clarify the optimal heteroatom in order to design anolytes suitable for redox flow PEFCs. In this study, heteropolytungstate anions with different heteroatoms were adapted as anodic redox mediators in a redox flow PEFC. In power generation tests, the redox flow PEFC with an anolyte of zinctungstate anion showed the highest performance. Zinctungstate anion exhibited the fastest reduction and oxidation rates among the W-HPAs investigated in this study.

Chemical Repair of Radical Damage to the GC Base Pair by DNA-Bound Bisbenzimidazoles.

The migration of an electron-loss center (hole) in calf thymus DNA to bisbenzimidazole ligands bound in the minor groove is followed by pulse radiolysis combined with time-resolved spectrophotometry. The initially observed absorption spectrum upon oxidation of DNA by the selenite radical is consistent with spin on cytosine (C), as the GC• pair neutral radical, followed by the spectra of oxidized ligands. The rate of oxidation of bound ligands increased with an increase in the ratio (r) ligands per base pair from 0.005 to 0.04. Both the rate of ligand oxidation and the estimated range of hole transfer (up to 30 DNA base pairs) decrease with the decrease in one-electron reduction potential between the GC• pair neutral radical of ca. 1.54 V and that of the ligand radicals (E0', 0.90-0.99 V). Linear plots of log of the rate of hole transfer versus r give a common intercept at r = 0 and a free energy change of 12.2 ± 0.3 kcal mol-1, ascribed to the GC• pair neutral radical undergoing a structural change, which is in competition to the observed hole transfer along DNA. The rate of hole transfer to the ligands at distance, R, from the GC• pair radical, k2, is described by the relationship k2 = k0 exp(constant/R), where k0 includes the rate constant for surmounting a small barrier.

Scandium Ion-Promoted Electron-Transfer Disproportionation of 2-Phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl 3-Oxide (PTIO•) in Acetonitrile and Its Regeneration Induced by Water.

2-Phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl 3-oxide (PTIO•), a persistent nitronyl nitroxide radical, has been used for the detection and trapping of nitric oxide, as a redox mediator for batteries, for the activity estimation of antioxidants, and so on. However, there is no report on the reactivity of PTIO• in the presence of redox-inactive metal ions. In this study, it is demonstrated that the addition of scandium triflate, Sc(OTf)3 (OTf = OSO2CF3), to an acetonitrile (MeCN) solution of PTIO• resulted in an electron-transfer disproportionation to generate the corresponding cation (PTIO+) and anion (PTIO-), the latter of which is suggested to be stabilized by Sc3+ to form [(PTIO)Sc]2+. The decay of the absorption band at 361 nm due to PTIO•, monitored using a stopped-flow technique, obeyed second-order kinetics. The second-order rate constant for the disproportionation, thus determined, increased with increasing the Sc(OTf)3 concentration to reach a constant value. A drastic change in the cyclic voltammogram recorded for PTIO• in deaerated MeCN containing 0.10 M Bu4NClO4 was also observed upon addition of Sc(OTf)3, suggesting that the large positive shift of the one-electron reduction potential of PTIO• (equivalent to the one-electron oxidation potential of PTIO-) in the presence of Sc(OTf)3 may result in the disproportionation. When H2O was added to the PTIO•-Sc(OTf)3 system in deaerated MeCN, PTIO• was completely regenerated. It is suggested that the complex formation of Sc3+ with H2O may weaken the interaction between PTIO- and Sc3+, leading to electron-transfer comproportionation to regenerate PTIO•. The reversible disproportionation of PTIO• was also confirmed by electron paramagnetic resonance (EPR) spectroscopy.

Photoinduced One-Electron Chloride Oxidation in Water Using a Pentacationic Ir(III) Photosensitizer.

A novel iridium(III) photosensitizer containing pyridinium-decorated terpyridines has been used for the photo-oxidation of chloride in water. Despite its abundance, the very positive one-electron reduction potential (E° Cl•/- = 2.1-2.4 V vs NHE) restricted its use in energy conversion schemes and artificial photosynthesis. The kinetics of the photoinduced electron transfer process were investigated through Stern-Volmer quenching experiments and nanosecond transient absorption spectroscopy, which provided unambiguous evidence that photoinduced chloride oxidation occurred with a quenching rate constant kq = 5.0 × 1010 M-1 s-1. Complementary spectroelectrochemistry and photolysis experiments confirmed the formation of the reduced photosensitizer and showcased the redox and photostability of the Ir(III) photosensitizer that holds great promise for the HX splitting approach.

Insights into the contrasting effects of sulfidation on dechlorination of chlorinated aliphatic hydrocarbons by zero-valent iron

Contrasting effects of sulfidation on contaminants reduction by zero-valent iron (ZVI) has been reported in literature but the underlying mechanisms remain unclear. Here, under well-controlled conditions, we compared the performance of ZVI and sulfidated ZVI (S-ZVI) toward a series of chlorinated compounds. Results revealed that, although S-ZVI was more reactive than ZVI toward hexachloroethane, pentachloroethane, tetrachloroethylene, and trichloroethene, sulfidation hindered the dechlorination of the other ten tested chlorinated aliphatics by a factor of 1.5–125. Moreover, S-ZVI may lead to an accumulation of toxic partially-dechlorinated products. Analogous to its effects on ZVI reactivity, sulfidation also exerted positive, negligible, or negative effects on the electron efficiency of ZVI. Solvent kinetic isotope effect analysis suggested that direct electron transfer rather than reaction with atomic hydrogen was the dominant reduction mechanism in S-ZVI system. Hence, the sulfidation enhancing effects could be expected only when direct electron transfer is the preferred reduction route for target contaminants. Furthermore, linear free energy relationships analysis indicated one-electron reduction potential could be used to predict the transformation of chlorinated ethanes by S-ZVI, whereas for chlorinated ethenes, their adsorption properties on S-ZVI determined the dechlorination process. All these findings may offer guidance for the decision-making regarding the application of S-ZVI.

Functional Model of Compound II of Cytochrome P450: Spectroscopic Characterization and Reactivity Studies of a FeIV-OH Complex.

Herein, we show that the reaction of a mononuclear FeIII(OH) complex (1) with N-tosyliminobenzyliodinane (PhINTs) resulted in the formation of a FeIV(OH) species (3). The obtained complex 3 was characterized by an array of spectroscopic techniques and represented a rare example of a synthetic FeIV(OH) complex. The reaction of 1 with the one-electron oxidizing agent was reported to form a ligand-oxidized FeIII(OH) complex (2). 3 revealed a one-electron reduction potential of -0.22 V vs Fc+/Fc at -15 °C, which was 150 mV anodically shifted than 2 (Ered = -0.37 V vs Fc+/Fc at -15 °C), inferring 3 to be more oxidizing than 2. 3 reacted spontaneously with (4-OMe-C6H4)3C• to form (4-OMe-C6H4)3C(OH) through rebound of the OH group and displayed significantly faster reactivity than 2. Further, activation of the hydrocarbon C-H and the phenolic O-H bond by 2 and 3 was compared and showed that 3 is a stronger oxidant than 2. A detailed kinetic study established the occurrence of a concerted proton-electron transfer/hydrogen atom transfer reaction of 3. Studying one-electron reduction of 2 and 3 using decamethylferrocene (Fc*) revealed a higher ket of 3 than 2. The study established that the primary coordination sphere around Fe and the redox state of the metal center is very crucial in controlling the reactivity of high-valent Fe-OH complexes. Further, a FeIII(OMe) complex (4) was synthesized and thoroughly characterized, including X-ray structure determination. The reaction of 4 with PhINTs resulted in the formation of a FeIV(OMe) species (5), revealing the presence of two FeIV species with isomer shifts of -0.11 mm/s and = 0.17 mm/s in the Mössbauer spectrum and showed FeIV/FeIII potential at -0.36 V vs Fc+/Fc couple in acetonitrile at -15 °C. The reactivity studies of 5 were investigated and compared with the FeIV(OH) complex (3).

Mitochondria Play Essential Roles in Intracellular Protection against Oxidative Stress-Which Molecules among the ROS Generated in the Mitochondria Can Escape the Mitochondria and Contribute to Signal Activation in Cytosol?

Questions about which reactive oxygen species (ROS) or reactive nitrogen species (RNS) can escape from the mitochondria and activate signals must be addressed. In this study, two parameters, the calculated dipole moment (debye, D) and permeability coefficient (Pm) (cm s-1), are listed for hydrogen peroxide (H2O2), hydroxyl radical (•OH), superoxide (O2•-), hydroperoxyl radical (HO2•), nitric oxide (•NO), nitrogen dioxide (•NO2), peroxynitrite (ONOO-), and peroxynitrous acid (ONOOH) in comparison to those for water (H2O). O2•- is generated from the mitochondrial electron transport chain (ETC), and several other ROS and RNS can be generated subsequently. The candidates which pass through the mitochondrial membrane include ROS with a small number of dipoles, i.e., H2O2, HO2•, ONOOH, •OH, and •NO. The results show that the dipole moment of •NO2 is 0.35 D, indicating permeability; however, •NO2 can be eliminated quickly. The dipole moments of •OH (1.67 D) and ONOOH (1.77 D) indicate that they might be permeable. This study also suggests that the mitochondria play a central role in protecting against further oxidative stress in cells. The amounts, the long half-life, the diffusion distance, the Pm, the one-electron reduction potential, the pKa, and the rate constants for the reaction with ascorbate and glutathione are listed for various ROS/RNS, •OH, singlet oxygen (1O2), H2O2, O2•-, HO2•, •NO, •NO2, ONOO-, and ONOOH, and compared with those for H2O and oxygen (O2). Molecules with negative electrical charges cannot directly diffuse through the phospholipid bilayer of the mitochondrial membranes. Short-lived molecules, such as •OH, would be difficult to contribute to intracellular signaling. Finally, HO2• and ONOOH were selected as candidates for the ROS/RNS that pass through the mitochondrial membrane.

Mechanistic and Kinetic Consideration of the Photochemically Generated Oxidative Organic Radicals in Dissolved Black Carbon Solutions under Simulated Solar Irradiation.

The photochemically generated oxidative organic radicals (POORs) in dissolved black carbon (DBC) was investigated and compared with that in dissolved organic matter (DOM). POORs generated in DBC solutions exhibited higher one-electron reduction potential values (1.38-1.56 V) than those in DOM solutions (1.22-1.38 V). We found that the photogeneration of POORs from DBC is enhanced with dissolved oxygen (DO) increasing, while the inhibition of POORs is observed in reference to DOM solution. The behavior of the one-electron reducing species (DBC•-/DOM•-) was employed to explain this phenomenon. The experimental results revealed that the DO concentration had a greater effect on DBC•- than on DOM•-. Low DO levels led to a substantial increase in the steady-state concentration of DBC•-, which quenched the POORs via back-electron reactions. Moreover, the contribution of POORs to the degradation of 19 emerging organic contaminants (EOCs) in sunlight-exposed DBC and DOM solutions was estimated. The findings indicate that POORs play an important role in the photodegradation of EOCs previously known to react with triplets, especially in DBC solutions. Compared to DOM solutions, POOR exhibits a lower but considerable contribution to EOC attenuation. This study enhances the understanding of pollutant fate in aquatic environments by highlighting the role of DBC in photochemical pollutant degradation and providing insights into pollutant transformation mechanisms involving POORs.

Predicting Redox Potentials of Flow Battery-Relevant Model Electrolytes

Redox flow batteries (RFBs) are rapidly gaining traction among large-scale storage solutions for intermittent renewable energy. Given the anticipated global scale of this technology, there is an intensive ongoing search for active electrolyte species containing all earth-abundant elements. Potential RFB actives must satisfy several criteria to maximize battery performance, namely, high solubility in the RFB solvent, optimum reduction potential, and chemical stability in all redox states. Given the near infinite possible molecular combinations of the primary atoms C, H, N, O, S, and Fe, computational chemistry is an invaluable tool to accelerate the discovery of promising new RFB active compounds.Towards that end, we performed DFT calculations on two major systems: iron(III/II) tris-2,2’-bipyridine, [Fe(bpy)3]3+/2+, as a model organometallic species, and azoles as a class of small, aromatic organic compounds. For [Fe(bpy)3]3+/2+, after extensive benchmarking of various functionals, basis sets, and other parameters, we accurately predict this complex’s one-electron reduction potential. The computational protocols employed on this system serve to open up the entire class or organometallics to predictive DFT calculations for future high-throughput screening. We also performed frequency calculations in the construction of a potential energy surface of [Fe(bpy)3]3+/2+’s degradation products, with consideration of all possible spin states, during this species’ hydrolysis-initiated dimerization to µ-O-[Fe(III)(bpy)2(H2O)]2 4+. The PES is discussed in light of literature-reported mechanisms for this system.Our study on functionalized azole compounds is motivated by recent demonstrations of azo compounds for RFBs in both aqueous and non-aqueous configurations. The azo group and its related nitro to amino group-containing monomeric species offers a plethora of potentially reversible redox transformations. Here, we investigate the redox potential and solvation energies of six azole-based compounds via DFT. Amino/nitro-functionalized azoles are small, aromatic compounds with the possibility to store up to six electrons per core, which would afford unprecedented energy densities in RFBs. The findings identify several species along the nitro-azo-amino pathway that have favorable redox potentials as anolyte or catholyte species (Fig. 1), as well as potentially high water solubility. Such coupling of anolyte-catholyte species from the same class of compounds would afford a crossover-proof RFB configuration analogous to vanadium systems that has not been demonstrated for aqueous organic flow batteries. Moreover, redox potentials between cis and trans isomers of the azo species were quantified, implicating further utility of these compounds in photo-mediated cells. These results will guide experimental investigations into the feasibility of implementing azole compounds for RFBs.Figure 1. Calculated redox potentials (Latimer diagram) for various azoles, including monomeric (nitro-nitroso-hydroxylamine-amino) and dimeric (azo-type) electron transfer events. Species falling outside the -0.5 to 0.5 V range (dotted lines) implicate their potential viability as RFB anolyte (V<-0.5) or catholyte (V>0.5) redox couples. Potentials were derived from DFT-level frequency calculations (free energies) utilizing the TPSS functional, def2-TZVPP basis set, and implicit solvation (CPCM H2O, vacuum- and solvent-optimized geometries). Figure 1

High throughput selection of organic cathode materials.

Efficient and affordable batteries require the design of novel organic electrode materials to overcome the drawbacks of the traditionally used inorganic materials, and the computational screening of potential candidates is a very efficient way to identify prospective solutions and minimize experimental testing. Here we present a DFT high-throughput computational screening where 86 million molecules contained in the PUBCHEM database have been analyzed and classified according to their estimated electrochemical features. The 5445 top-performing candidates were identified, and among them, 2306 are expected to have a one-electron reduction potential higher than 4 V versus (Li/Li+ ). Analogously, one-electron energy densities higher than 800 Whkg-1 have been predicted for 626 molecules. Explicit calculations performed for certain materials show that at least 69 candidates with a two-electron energy density higher than 1300 Whkg-1 . Successful molecules were sorted into several families, some of them already commonly used electrode materials, and others still experimentally untested. Most of them are small systems containing conjugated CO, NN, or NC functional groups. Our selected molecules form a valuable starting point for experimentalists exploring new materials for organic electrodes.

Linear Free Energy Relationship for Predicting the Rate Constants of Munition Compound Reduction by the Fe(II)-Hematite and Fe(II)-Goethite Redox Couples.

Abiotic reduction by iron minerals is arguably the most important fate process for munition compounds (MCs) in subsurface environments. No model currently exists that can predict the abiotic reduction rates of structurally diverse MCs by iron (oxyhydr)oxides. We performed batch experiments to measure the rate constants for the reduction of three classes of MCs (poly-nitroaromatics, nitramines, and azoles) by hematite or goethite in the presence of aqueous Fe2+. The surface area-normalized reduction rate constant (kSA) depended on the aqueous-phase one-electron reduction potential (EH1) of the MC and the thermodynamic state (i.e., pe and pH) of the iron oxide-Feaq2+ system. A linear free energy relationship (LFER), similar to that reported previously for nitrobenzene, successfully captures all MC reduction rate constants that span 6 orders of magnitude: . The finding that the rate constants of all the different classes of MCs can be described by a single LFER suggests that these structurally diverse nitro compounds are reduced by iron oxide-Feaq2+ couples through a common mechanism up to the rate-limiting step. Multiple mechanistic implications of the results are discussed. This study expands the applicability of the LFER model for predicting the reduction rates of legacy and emerging MCs and potentially other nitro compounds.

N-Alkylated Pyridoxal Derivatives as Negative Electrolyte Materials for Aqueous Organic Flow Batteries: Computational Screening.

N-functionalized pyridinium frameworks derived from the three major vitamers of vitamin B6, pyridoxal, pyridoxamine and pyridoxine, have been screened computationally for consideration as negative electrode materials in aqueous organic flow batteries. A molecular database including the structure and the one-electron standard reduction potential of related pyridinium derivatives has been generated using a computational protocol that combines semiempirical and DFT quantum chemical methods. The predicted reduction potentials span a broad range for the investigated pyridinium frameworks, but pyridoxal derivatives, particularly those involving electron withdrawing substituents, have potentials compatible with the electrochemical stability window of aqueous electrolytes. The stability of radicals formed upon one-electron reduction has been analyzed by a new computational tool proposed recently for large-scale computational screening.

Electron Transfer Energy and Hydrogen Atom Transfer Energy-Based Linear Free Energy Relationships for Predicting the Rate Constants of Munition Constituent Reduction by Hydroquinones.

No single linear free energy relationship (LFER) exists that can predict reduction rate constants of all munition constituents (MCs). To address this knowledge gap, we measured the reduction rates of MCs and their surrogates including nitroaromatics [NACs; 2,4,6-trinitrotoluene (TNT), 2,4-dinitroanisole (DNAN), 2-amino-4,6-dinitrotoluene (2-A-DNT), 4-amino-2,6-dinitrotoluene (4-A-DNT), and 2,4-dinitrotoluene (DNT)], nitramines [hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and nitroguanidine (NQ)], and azoles [3-nitro-1,2,4-triazol-5-one (NTO) and 3,4-dinitropyrazole (DNP)] by three dithionite-reduced quinones (lawsone, AQDS, and AQS). All MCs/NACs were reduced by the hydroquinones except NQ. Hydroquinone and MC speciations were varied by controlling pH, permitting the application of a speciation model to determine second-order rate constants (k) from observed pseudo-first-order rate constants. The intrinsic reactivity of MCs (oxidants) decreased upon deprotonation, while the opposite was true for hydroquinones (reductants). The rate constants spanned ∼6 orders of magnitude in the order NTO ≈ TNT > DNP > DNT ≈ DNAN ≈ 2-A-DNT > DNP- > 4-A-DNT > NTO- > RDX. LFERs developed using density functional theory-calculated electron transfer and hydrogen atom transfer energies and reported one-electron reduction potentials successfully predicted k, suggesting that these structurally diverse MCs/NACs are all reduced by hydroquinones through the same mechanism and rate-limiting step. These results increase the applicability of LFER models for predicting the fate and half-lives of MCs and related nitro compounds in reducing environments.

An Efficient Multilayer Approach to Model DNA-Based Nanobiosensors.

In this work, we present a full computational protocol to successfully obtain the one-electron reduction potential of nanobiosensors based on a self-assembled monolayer of DNA nucleobases linked to a gold substrate. The model is able to account for conformational sampling and environmental effects at a quantum mechanical (QM) level efficiently, by combining molecular mechanics (MM) molecular dynamics and multilayer QM/MM/continuum calculations within the framework of Marcus theory. The theoretical model shows that a guanine-based biosensor is more prone to be oxidized than the isolated nucleobase in water due to the electrostatic interactions between the assembled guanine molecules. In addition, the redox properties of the biosensor can be tuned by modifying the nature of the linker that anchor the nucleobases to the metal support.

Ferrocene/ferrocenium, cobaltocene/cobaltocenium and nickelocene/nickelocenium: from gas phase ionization energy to one-electron reduction potential in solvated medium.

We propose a theoretical procedure for accurate determination of reduction potentials for three metallocene couples, Cp2M+/Cp2M, where M = Fe, Co and Ni. This procedure first computes the gas phase ionization energy (IE) using the explicitly correlated CCSD(T)-F12 method and includes the zero-point energy correction, core-valence electronic correlation, and relativistic and spin-orbit coupling effects. By means of Born-Haber thermochemical cycle, the one-electron reduction potential is obtained as the sum of the gas phase IE and the corresponding Gibbs free energies of solvation (ΔGsolv) for both the neutral and cationic species. Among the three solvent models (PCM, SMD and uESE) investigated here, it turns out that only the SMD model (computed at the DFT level) gives the best estimation of the value for "ΔGsolv(cation) - ΔGsolv(neutral)" and thus, combining with the accurate IE values, the theoretical protocol is capable of yielding reliable values (in V) for , and . These predictions compare favorably with the available experimental data (in V): , , and . We show that our theoretical procedure is reliable for accurate reduction potential predictions of Cp2Fe+/Cp2Fe, Cp2Co+/Cp2Co and Cp2Ni+/Cp2Ni redox couples in aqueous and non-aqueous media; the maximum absolute deviation is as small as ≈120 mV, which outperforms those of the existing theoretical methods.

A Contrasting Effect of Acid in Electron Transfer, Oxygen Atom Transfer, and Hydrogen Atom Transfer Reactions of a Nickel(III) Complex.

There have been many examples of the accelerating effects of acids in electron transfer (ET), oxygen atom transfer (OAT), and hydrogen atom transfer (HAT) reactions. Herein, we report a contrasting effect of acids in the ET, OAT, and HAT reactions of a nickel(III) complex, [NiIII(PaPy3*)]2+ (1) in acetone/CH3CN (v/v 19:1). 1 was synthesized by reacting [NiII(PaPy3*)]+ (2) with magic blue or iodosylbenzene in the absence or presence of triflic acid (HOTf), respectively. Sulfoxidation of thioanisole by 1 and H2O occurred in the presence of HOTf, and the reaction rate increased proportionally with increasing concentration of HOTf ([HOTf]). The rate of ET from diacetylferrocene to 1 also increased linearly with increasing [HOTf]. In contrast, HAT from 9,10-dihydroanthracene (DHA) to 1 slowed down with increasing [HOTf], exhibiting an inversely proportional relation to [HOTf]. The accelerating effect of HOTf in the ET and OAT reactions was ascribed to the binding of H+ to the PaPy3* ligand of 2; the one-electron reduction potential (Ered) of 1 was positively shifted with increasing [HOTf]. Such a positive shift in the Ered value resulted in accelerating the ET and OAT reactions that proceeded via the rate-determining ET step. On the other hand, the decelerating effect of HOTf on HAT from DHA to 1 resulted from the inhibition of proton transfer from DHA•+ to 2 due to the binding of H+ to the PaPy3* ligand of 2. The ET reactions of 1 in the absence and presence of HOTf were well analyzed in light of the Marcus theory of ET in comparison with the HAT reactions.

Aliphatic and Aromatic C–H Bond Oxidation by High-Valent Manganese(IV)-Hydroxo Species

The strong C-H bond activation of hydrocarbons is a difficult reaction in environmental and biological chemistry. Herein, a high-valent manganese(IV)-hydroxo complex, [MnIV(CHDAP-O)(OH)]2+ (2), was synthesized and characterized by various physicochemical measurements, such as ultraviolet-visible (UV-vis), electrospray ionization-mass spectrometry (ESI-MS), electron paramagnetic resonance (EPR), and helium-tagging infrared photodissociation (IRPD) methods. The one-electron reduction potential (Ered) of 2 was determined to be 0.93 V vs SCE by redox titration. 2 is formed via a transient green species assigned to a manganese(IV)-bis(hydroxo) complex, [MnIV(CHDAP)(OH)2]2+ (2'), which performs intramolecular aliphatic C-H bond activation. The kinetic isotope effect (KIE) value of 4.8 in the intramolecular oxidation was observed, which indicates that the C-H bond activation occurs via rate-determining hydrogen atom abstraction. Further, complex 2 can activate the C-H bonds of aromatic compounds, anthracene and its derivatives, under mild conditions. The KIE value of 1.0 was obtained in the oxidation of anthracene. The rate constant (ket) of electron transfer (ET) from N,N'-dimethylaniline derivatives to 2 is fitted by Marcus theory of electron transfer to afford the reorganization energy of ET (λ = 1.59 eV). The driving force dependence of log ket for oxidation of anthracene derivatives by 2 is well evaluated by Marcus theory of electron transfer. Detailed kinetic studies, including the KIE value and Marcus theory of outer-sphere electron transfer, imply that the mechanism of aromatic C-H bond hydroxylation by 2 proceeds via the rate-determining electron-transfer pathway.