Radical anions from some photochromic nitrocompounds. An electron paramagnetic resonance and electrochemical study

Five 6′-nitrospiro[indole-benzopyrans] have been reduced electrochemically in ACN to the corresponding radical anions. Their reduction potentials were in the range -1.32 to -1.40 V versus SCE, that is in the range expected for substituted nitrobenzenes. The EPR spectra of the species resulting from chemical reduction of the same compounds were also recorded, and suggested that the structure of the observed radicals varies with the reduction media: thus, while the spectra in DMSO could be attributed to the radical anions structurally similar to the starting compounds, those observed in THF under UV irradiation were assigned to the anions of the open merocyanines. It appears that also the species observed by reduction in DMF ought to be assigned the open structure.     

Electrochemical reduction and radical anions of benzo[b]thioxanthene-6,11,12-trione and thioxanthene-1,4,9-trione

The electrochemical reduction of benzo[b]thioxanthene-6,11,12-trione and thioxanthene-1,4,9-trione in DMSO, MeCN and HMPA is an EE process, which is characterized by two separate one electron reversible peaks on cyclic voltammograms, first peak retains reversibility in DMSO–H2O mixtures, corresponding radical anions were obtained by one electron reduction of the above compounds and characterized by EPR and DFT calculations at the (U)B3LYP/6-31+G* level of theory.     

Radical anions of flavonoids

Several representatives of natural flavonoids and their synthetic nitro‐derivatives have been investigated by polarography and electron paramagnetic resonance (EPR) spectroscopy under electrochemical reduction in acetonitrile, dimethylformamide (DMF), dimethylsulfoxide (DMSO) or 1,2‐dimethoxyethane. All the compounds studied are reduced in the first stage by one‐electron transfer, apart from flavanone, which accepts two electrons simultaneously. However, the primary radical anions were detected by EPR spectroscopy only for 4′‐nitroflavone. It was shown that radical anions of other flavonoids quickly dimerized. The analysis of the temperature dependence of the hyperfine interaction constants and broadening of lines in EPR spectra of 4′‐nitroflavone radical anions has shown that the distribution of spin density is due to both the change of polarity of the medium and rotation of the nitrophenyl moiety. The assignment of hyperfine structure constants for the 4′‐nitroflavone radical anion was confirmed by density functional theory (DFT) calculations. Copyright © 2011 John Wiley & Sons, Ltd.     

Isolation and characterization of four isomers of a C(60) bisadduct with a TTF derivative. Study of their radical ions.

A family of triads composed of C(60) attached by a rigid spacer to two identical TTF moieties has been synthesized, and some of the isomers have been isolated and characterized by UV-vis spectroscopy, LDI-TOF-MS, and HMBC NMR spectroscopy. AM1 semiempirical calculations of the dipolar moments and the heats of formation of the different isomers have been carried out in order to verify their assignments. Oxidation and reduction of the triads affords the derived radical ion systems, TTF(+*)-C(60)-TTF(+*) and TTF-C(60)(-*)-TTF, which were studied by EPR spectroscopy. Spin density distributions of these radical cations and radical anions show that the unpaired electron is located mainly on the TTF and fullerene moieties, respectively. However, while the EPR signals obtained from the radical cations are very similar for all the isomers, the structured signals observed for the radical anions arising from the coupling of the unpaired electron with the hydrogen atoms of the methylene bridges in the spacer show that there is a strong influence of the isomerism on the spin distribution. Importantly, the theoretical calculations of the spin density distributions of the radical anions fit well with the experimental EPR results.     

Synthesis,structure and bonding nature of heavy dipnictene radical anions

Cyclic voltammetry (CV) studies of two L(X)Ga-substituted dipnictenes [L(R₂N)GaE]₂ (E = Sb, R = Me 1; E = Bi; R = Et 2; L = HC[C(Me)NDipp]₂; Dipp = 2,6-i-Pr₂C₆H₃) showed reversible reduction events. Single electron reduction of 1 and 2 with KC₈ in DME in the presence of benzo-18-crown-6 (B-18-C-6) gave the corresponding dipnictenyl radical anions (DME)[K(B-18-C-6)][L(R₂N)GaE]₂ (E = Sb, R = Me 3; E = Bi, R = Et 4). Radical anions 3 and 4 were characterized by EPR, UV-vis and single crystal X-ray diffraction, while quantum chemical calculations gave deeper insight into the nature of the chemical bonding.

Dipnictene radical anions [K(DME)(B-18-C-6)][{L(R₂N)GaE}₂] (E = Sb, Bi) were characterized by single crystal X-ray diffraction, EPR spectroscopy and quantum chemical calculations.     

The decomposition of 1-phenyl-3-chloro-nortricyclene and 1-phenylnortricyclene on reduction in 1,2-dimethoxyethane. The EPR spectra of the radical ions

Radical anions of 1-phenyl-3-chloronortricyclene and 1-phenylnortricyclene were produced by reduction with potassium in 1,2-dimethoxyethane under a high vacuum. The initially formed radical anion of 1-phenyl-3-chloronortricyclene was very unstable, and decomposed finally to the anions of naphthalene and biphenyl. The only product of the reduction of 1-phenylnortricyclene was the biphenyl anion. The EPR spectra of the reaction mixtures were measured at temperatures from —80°C to room temperature.     

Anions from dihydro substituted ethyl benzoates and quinoline. New hydrogen donors for tin-free radical chemistry

The anions of substituted dihydro ethyl benzoates and quinoline are very good hydrogen donors to radicals in liquid ammonia and DMSO. With 4-substituted dihydro ethyl benzoates the rate of hydrogen transfer decreases and excellent yields of products are obtained by 6-exo ring closure reaction followed by reduction.     

Density functional calculations of electronic g-tensors for semiquinone radical anions. The role of hydrogen bonding and substituent effects

A recently developed density functional approach has been used to carry out a systematic computational study of electronic g-tensors for a series of 1,4-semiquinone radical anions. Good agreement with high-field EPR data in frozen 2-propanol is achieved only after taking into account the significant reduction of g-tensor anisotropy caused by hydrogen bonding to solvent molecules. The comparison of various model systems for the first solvation shell suggests two hydrogen bonds from 2-propanol molecules to each of the carbonyl groups of the radical anions, and one additional hydrogen bond to each of the methoxy groups in ubiquinone systems. 2-Propanol makes stronger hydrogen bonds than water and thus influences g-tensor anisotropy more strongly. Substituent effects at the semiquinone are reproduced quantitatively by the calculations. The g-tensor anisotropy is influenced significantly by the conformations of methyl and methoxy substituents, with opposite contributions. Analyses and interpretations of the interrelations between structure, bonding, and spectroscopic data are provided. The relevance of the computational results for the EPR spectroscopy of semiquinone radical anions in photosynthetic reaction centers is discussed.     

EPR spectra of free radicals formed during electrochemical reduction of 5-substituted 2-furaldehydes and 2-thiophenaldehydes

Using EPR we have found that during electrochemical reduction of 5-substituted 2-furaldehydes and 2-thiophenaldehydes, carbon-centered free radicals (products of protonation of radical anions) may form, along with radicals of a different structure, and also -type radical anions of different conjugated dimers. We have determined the hyperfine structure and measured the values of the constants for the EPR spectra of some of these radicals.Latvian Institute of Organic Synthesis, Riga LV-1006. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1051–1060, August, 1997.     

Comment on “Persistent Room-Temperature Radicals from Anionic Naphthalimides: Spin Pairing and Supramolecular Chemistry” and on “Persistent Radical Pairs between N-Substituted Naphthalimide and Carbanion Exhibit pKa-Dependent UV/Vis Absorption”

EPR spectroscopic evidence for intramolecular electron transfer in anionic N-substituted naphthalimides to yield persistent diradical anions and intermolecular electron transfer from a variety of carbanions to 6-bromo-N-phenyl-naphthalimide to yield persistent radical–radical anion pairs was recently claimed in two papers by Zhang et al. In this comment, it is shown that the EPR spectra published in both papers do not agree with the proposed triplet-state species. Rather, the spectra are due to various doublet-state radicals, deriving from minor side reactions. The misinterpretations invalidate the general conclusions of the papers.     

α-氰基苄基碳负离子钠盐与碳酸二乙酯的单电子转移反应动力学和机理

测定了α-氰基苄基碳负离子钠盐与碳酸二乙酯缩合反应产物的结构及其分布,反应中间体的EPR谱,反应过程中产物和溶剂的CIDNP效应和反应动力学,为这一缩合反应提出了单电子转移-负离子自由基分解-自由基偶合的非链式自由基机理     

Dynamics of intramolecular electron transfer in dinitrodibenzodioxin radical anions

The activation energy for intramolecular electron transfer in radical anions of 2,7-dinitrodibenzodioxin and 2,8-dinitrodibenzodioxin, obtained by simulation of their temperature-dependent EPR spectra, are well predicted by the values calculated by the two-state Marcus-Hush model from the optical charge-transfer bands using quartic-adjusted energy surfaces. The electronic coupling is higher in the 2,8-dinitrodibenzodioxin (H(ab) = 485 cm(-1)) than in the 2,7-dinitrodibenzodioxin radical anion (H(ab) = 250 cm(-1)), but for each solvent the reorganization energy, taken as the maximum of the optical band, is only slightly higher in the latter. These values are consistent with the fact that the reaction is faster in the 2,8-dinitrodibenzodioxin radical anion isomer, as determined by EPR spectroscopy. The pre-exponential factors obtained combining the EPR-derived rate constants and the activation energies calculated from the optical bands fit well the theoretical (modified) nonadiabatic values in the less viscous solvents. However, for the more viscous solvents, the trend of the pre-exponential values with solvent can only be explained if dynamical solvent effects increasingly influence their value. The influence of solvent dynamics in the 2,8-dinitrodibenzodioxin radical anion starts in the less viscous solvents DMF and DMSO, but in the 2,7-dinitrodibenzodioxin isomer this is only fully evident for the more viscous PhCN and HMPA. The influence of solvent dynamics is higher in the radical with the lowest activation barrier.     

EPR-untersuchungen an carbonsäureestern—III: Thiooxalsäureester-radikalanionen

Polarographic and cyclovoltammetric investigation of the thiooxalates 1–6 shows that they are reversibly reduced to the corresponding radical anions. Accordingly, EPR spectra are obtained after in-situ electroreduction. Taking also the electronic spectra into consideration, conclusions about the spin density distribution can be drawn. It is shown thatp^π is higher at the oxygen atoms of oxoesters than at the sulfur atoms of the corresponding thiono esters.     

EPR Spectra and Spin Density Distribution of O,S-Dimethyl 4,4-Dithioterephthalate Radical Anions

Abstract

The preparation of O-methyl S-trideuteromethyl 4,4-dithioterephthalate and S-methyl O-trideuteromethyl 4,4-dithioterephthalate is described. The EPR spectra of the corresponding radical anions are measured. Comparison with the spectrum of O,S-dimethyl 4,4-dithioterephthalate radical anions allows the unequivocal assignment of the proton hyperfine structure (proton “hfs”) coupling constants in the above asymmetric species. Assignment of the arene proton hfs coupling constants is achieved by PM6 and density functional theory MO calculations of the spin density distribution and application of McConnell's relationship a^H _μ = ?2.4·ρ^π _μ. The spin density distribution in the asymmetric title compound is compared with those in the radical anions of dimethyl terephthalate and the corresponding symmetric sulfur analogs.     

Synthesis,Structures, and Properties of Crystalline Salts with Radical Anions of Metal‐Containing and Metal‐Free Phthalocyanines

Radical anion salts of metal‐containing and metal‐free phthalocyanines [MPc(3?)]^.?, where M=Cu^II, Ni^II, H₂, Sn^II, Pb^II, Ti^IVO, and V^IVO ( 1 – 10 ) with tetraalkylammonium cations have been obtained as single crystals by phthalocyanine reduction with sodium fluorenone ketyl. Their formation is accompanied by the Pc ligand reduction and affects the molecular structure of metal phthalocyanine radical anions as well as their optical and magnetic properties. Radical anions are characterized by the alternation of short and long C?N_imine bonds in the Pc ligand owing to the disruption of its aromaticity. Salts 1 – 10 show new bands at 833–1041 nm in the NIR range, whereas the Q‐ and Soret bands are blue‐shifted by 0.13–0.25 eV (38‐92 nm) and 0.04–0.07 eV (4–13 nm), respectively. Radical anions with Ni^II, Sn^II, Pb^II, and Ti^IVO have S=1/2 spin state, whereas [Cu^IIPc(3?)]^.? and [V^IVOPc(3?)]^.? containing paramagnetic Cu^II and V^IVO have two S=1/2 spins per radical anion. Central metal atoms strongly affect EPR spectra of phthalocyanine radical anions. Instead of narrow EPR signals characteristic of metal‐free phthalocyanine radical anions [H₂Pc(3?)]^.? (linewidth of 0.08–0.24 mT), broad EPR signals are manifested (linewidth of 2–70 mT) with g‐factors and linewidths that are strongly temperature‐dependent. Salt 11 containing the [Na^IPc(2?)]^? anions as well as previously studied [Fe^IPc(2?)]^? and [Co^IPc(2?)]^? anions that are formed without reduction of the Pc ligand do not show changes in molecular structure or optical and magnetic properties characteristic of [MPc(3?)]^.? in 1 – 10 .     

Free radicals in vicarious C-amination reactions of 1-methyl-4-nitropyrazole

The primary radical anions of substrate in the reactions of vicarious nucleophilic substitution of hydrogen in 1-methyl-4-nitropyrazole with 1,1,1-trimethylhydrazinium iodide and 4-amino-1,2,4-triazole in t-BuOK-DMSO were observed and identified by EPR monitoring. The probable mechanism of the substrate radical anions formation is discussed.     

Radical nucleophilic substitution of 2-(4-halophenyl)-2-methyl-1-chloropropane with enolate ions of ketones

The photoinitiated reaction of 2-(4-halophenyl)-2-methyl-1-chloropropane 2a,b (halogen=Br, I, respectively) with the anions of pinacolone (3a) and acetophenone (3b) either in DMSO or in liquid ammonia are reported. In DMSO, the main reaction is the SRN1 nucleophilic substitution at the aromatic (Csp2-halogen) center with substitution or reduction at the aliphatic (Csp3-Cl) one. In liquid ammonia, the main reaction is substitution at the aromatic C-halogen site. This difference in product distribution is ascribed to modifications in the rate constant of Csp3-Cl dissociation of the radical anions proposed as intermediates in going from DMSO (rt) to liquid NH3 (-33 degrees C).     

Model Calculations of Radiation-Induced Damage in 1-Methyluracil:9-Ethyladenine

Detailed EPR and ENDOR experiments on the cocrystalline complex of 1-methyluracil:9-Ethyladenine (MUEA) have revealed that the major radiation-induced products observed at 10 K on MU are: MUEA1, a radical formed by net hydrogen abstraction from the N1-CH₃ methyl group, MUEA2, the MU radical anion, and MUEA3, the C5 H-addition radical. The following four products were observed on the adenine moiety at 10 K, MUEA4, the N3 protonated adenine anion, MUEA5, the native adenine cation, MUEA6, the amino deprotonated adenine cation, and MUEA7, the C8 H-addition radical formed by net H-addition to C8 of the adenine base. The geometries, energetics, and hyperfine properties of all possible radicals of MU and EA, the native anions and cations, as well as radicals formed via net hydrogen atom abstraction (deprotonated cations) or addition (protonated anions) were investigated theoretically. All systems were optimized using the hybrid Hartree–Fock–density functional theory functional B3LYP, in conjunction with the 6-31G(d,p) basis set of Pople and co-workers. Calculations of the anisotropic hyperfine couplings for all the radicals observed in MUEA are presented and are shown to compare favorably with the experimentally measured hyperfine couplings. The calculated ionizations potentials indicate that EA would be the preferred oxidation site. In MUEA, both the adenine cation and its N4-deprotonated derivative were observed. The calculated electron affinities indicate that MU would be the preferred reduction site. In MUEA radical, MUEA2 is a uracil reduction product, however the protonation state of this radical could not be determined experimentally. Calculations suggest that MUEA2 is actually the C4=O protonated anion.     

Reductive polymerization of Para-cyanobenzaldehyde in dimethyl sulfoxide solutions using the rotating ring-disk electrode technique

The rotating ring-disk electrode (RRDE) technique has been employed to study the reductive polymerization mechanism of para-cyanobenzaldehyde (CBA) in dimethyl sulfoxide (DMSO) solutions. The radical anion of CBA underwent polymerization through two different reaction routes. They were found to be the successive parent molecule addition to the radical anion reactions and the dimerization of the radical anion followed by parent molecule additions. Digital simulation methods were employed to simulate the mechanism and to obtain the second-order reaction rate constants of the radical anions from collection efficiency measurements. The reaction rate constants were found to be 1.45 M^?1 s^?1 for reactions of the radical anion with the parent molecules, and 28.6 M^?1 s^?1 for dimerization of the radical anion followed by trapping a parent molecule immediately after the dimeric dianion is generated.     

Reversible Self-Assembling of Boryl Radical Anions to Their Diradicals with Tunable Singlet Ground States

Two novel boron-centered diradicals based on dimesitylpyridine borane ( 1 ) were synthesized by the self-assembling of the corresponding radical sodium and potassium salts, respectively. The sodium diradical was obtained by re-dissolving the crystals of the radical salt 1Na in toluene, while the potassium diradical was directly obtained by the reduction of 1 with potassium in THF. The diradicals could be converted back to their radical anions in THF solution, forming a reversible process. EPR spectroscopy and SQUID measurements, together with theoretical calculations, show that the diradicals have singlet ground states with excited triplet states. Their singlet–triplet energy gaps are tunable with metals.