N,N-dimethyl-p-anisidinium cation. Esr evidence for intermolecular spin-lone pair interaction

ESR characterisation of N,N-dimethyl-p-anisidinium dimer radical cation is reported.     

Charged states of α,ω-dicyano β,β'-dibutylquaterthiophene as studied by in situ ESR UV-vis NIR spectroelectrochemistry

The influence of the molecular structure on the stabilization of charged states was studied in detail by in situ ESR UV-vis NIR spectroelectrochemistry at a novel α,ω-dicyano substituted β,β'-dibutylquaterthiophene (DCNDBQT) and the electrochemically generated cation and anion radicals have been proved for the first time. The voltammetry of DCNDBQT results in two separate oxidation steps with the reversible first one. The experimental absorption maxima at 646 and 1052 nm together with the calculated ones (by DFT method) as well as an ESR signal at the first anodic step prove the presence of a radical cation. Three additional optical bands (554, 906, and 1294 nm for CT-transition) can be attributed to the formation of cation radical dimer. The dicationic structure formed in the second oxidation step is not stable. The stabilization proceeds via a dimer formation in two chemical follow-up reactions. The existence of the dimeric structures was proved by ex situ MALDI TOF mass spectrometry. As the substitution by cyano groups opens the route to cathodic reductions, DCNDBQT shows a single quasi-reversible reduction step. Here, the in situ ESR UV-vis NIR spectroelectrochemical measurements and theoretical calculations let us confirm the electrochemical generation of an anion radical. As we found a low number of anion radicals by quantitative ESR spectroelectrochemistry and an appearance of additional bands in the UV-vis NIR absorption spectra, the formation of dimeric structures must be considered and was corroborated by mass spectrometry. The role of dimerization in the reaction mechanism of the DCNDBQT oxidation and reduction are discussed in general. The experimental results were interpreted using the quantum chemical calculations based on density functional theory.     

六钨酸四丁基铵盐和异丙醇体系的催化氧化反应的ESR研究Ⅱ.

近年来,关于同多酸、杂多酸及其盐类的光催化研究报道较多^[1,2],而用电解方法研究它们的催化反应则很少见报道^[3]。本文采用恒电位电解条件,将六钨酸四丁基铵中的钨(Ⅵ)还原成钨(Ⅴ),再考察其催化异丙醇的氧化反应。结果表明,[W₆O₁₉]^2-非但具有光化学活性,也具有电化学活性^[4]。我们用电子自旋共振和自旋捕捉相结合的方法,检测到反应过程中产生的自由基中间体。用计算机模拟方     

六钨酸四丁基铵盐和异丙醇体系的催化氧化反应的ESR研究Ⅱ.

前言 近年来,关于同多酸、杂多酸及其盐类的光催化研究报道较多,而用电解方法研究它们的催化反应则很少见报道。本文采用恒电位电解条件,将六钨酸四丁基铵中的钨(Ⅵ)还原成钨(Ⅴ),再考察其催化异丙醇的氧化反应。结果表明,[W_6O_(19)]~(2-)非但具有光化学活性,也具有电化学活性。我们用电子自旋共振和自旋捕捉相结合的方法,检测到反应过程中产生的自由基中间体。用计算机模拟方法确定其结构,因而对机理的讨论更为清楚。     

Redox active surface films produced by electrooxidation of substituted indolysines

The electrochemical oxidation of substituted mono-and 3,3′-biindolysines is studied by methods of cyclic voltammetry and electron spin resonance (ESR) combined with in situ electrolysis. In acetonitrile, there occurs easy irreversible electrochemical oxidation and proceed processes of association of generated radical cations via unsubstituted positions of five-membered cycles. Polymeric products of oxidation of 2-arylindolysines, 3-indolysine-2-yl-quinoxalines, and 2,2′-diaryl-3,3′-biindolysines are obtained when cycling potential in the interval ?0.3 V → +0.8 V → ?1.3 V → ?0.3 V (Fc/Fc⁺). The products deposit on the electrode with the formation of redox-active films that are capable of undergoing reversible oxidation with the formation of stable paramagnetic states registered by the ESR method.     

NC-(CF2)4-CNSSN radical containing 1,2,3,5-dithiadiazolyl radical dimer exhibiting triplet excited states at low temperature and thermal hysteresis on melting-solidification: structural, spectroscopic, and magnetic characterization

A high yield, one-pot synthesis of the 1,2,3,5-dithiadiazolyl radical NC-(CF2)4-CNSSN radical by reduction of the corresponding 1,3,2,4-dithiadiazolium salt is reported. In the solid state, the title compound is dimerized in trans-cofacial fashion with intra-dimeric Sdelta+...N(delta-) interactions of ca. 3.2 angstroms, and the dimeric units are linked by electrostatic -C triple bond N(delta-)...Sdelta+ interactions forming an infinite chain. Magnetic susceptibility measurements performed on the solid state sample indicate a magnetic moment of 1.8 microB per dimer (1.3 microB per monomer) at 300 K and a good fit to the Bleaney-Bowers model in the temperature range 2-300 K with 2J = -1500 +/- 50 cm(-1), g = 2.02(5), rho = 0.90(3)%, and TIP = 1.25(4) x 10(-3) emu mol(-1). The [NC-(CF2)4-CNSSN radical]2 dimer is the second example of a 1,2,3,5-dithiadiazolyl radical dimer with an experimentally detected triplet excited state as probed by solid-state EPR [2J = -1730 +/- 100 cm(-1), |D| = 0.0278(5) cm(-1), |E| = 0.0047(5) cm(-1)]. The value of the singlet-triplet gap has enabled us to estimate the "in situ" dimerization energy of the radical dimer as ca. -10 kJ mol(-1). The diradical character of the dimer was calculated [CASSCF(6,6)/6-31G*] as 35%. The title radical shows magnetic bistability in the temperature range of 305-335 K as probed by the solid-state EPR presumably arising from the presence of a metastable paramagnetic supercooled phase. Bistability is accompanied by thermochromic behavior with a color change from dark green (dimeric solid) to dark brown (paramagnetic liquid).     

A microfluidic channel flow cell for electrochemical ESR

The design, fabrication, and characterization of microfluidic channel flow devices for in situ simultaneous hydrodynamic electrochemical ESR is reported. The microelectrochemical reactors consist of gold film electrodes situated within rectangular ducts of height 350 microm and widths in the range 500-2000 microm. The small dimensions of the channels result in minimal dielectric loss when centralized within a cylindrical TE011 resonant cavity, leading to a high level of sensitivity. This is demonstrated by using the one-electron oxidation of N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) in acetonitrile as a model system, wherein the ESR spectra obtained for the corresponding stable radical cation are of a high signal-to-noise ratio. Signal intensity is measured as a function of flow rate for this system, and the behavior is validated by means of 3-dimensional numerical modeling of the hydrodynamic flow profile.     

Radical Cation of Pyrazine-di-N-oxide as a Mediator in Electrocatalytic Oxidation of Organic Compounds

The mechanism of oxidation of cyclohexanol, methanol, diethyl ether, triethyl orthoformate, and cyclohexane in the presence of a mediator—electrochemically generated radical cation of pyrazine-di-N-oxide (PyrDNO)—is studied on glassy carbon and platinum in a 0.1 M LiClO₄ solution in acetonitrile employing cyclic voltammetry, ESR electrolysis, and gas chromatography. Effect of temperature, additives of acid and water, oxygen, and the nature of the substrate and solvent on the shape of cyclic voltammograms and intensity of ESR signal of PyrDNO is examined. ESR spectra for radical cations and anions of PyrDNO with g factors equal to, respectively, 2.0090 and 2.0031 are recorded. A mechanism for the overall two-electron catalytic oxidation of an organic substance, which involves a stage in which it complexes with the radical cation of PyrDNO, is suggested.     

An endor and ESR study of the radical cation of N,N′-bis-(4-fluorophenyl)-4,4′-bipyridylium dichloride

The ESR and ENDOR spectra of the radical cation of N,N′-bis-(4-fluoro-phenyl)-4-4′-bipyridylium dichloride (fluorophenylquat FPQ) in methanol was studied over a temperature range from +_40° to ?90°. The ENDOR technique was used to obtain accurately the splitting constans for a highly complicated ESR spectrum and computer simulation showed excellent agreement. Fluorine ENDOR resonance was clearly observed with a line width similar to that of the protons. On decreasing the temperature the concentration of the radical cation decreases until at ?90° the ESR intensity was very small. This process is reversible and concentration studies indicate that the radical cation is in equilibrium with a diamagnetic dimer species. The thermodynamic parameters ΔH°, ΔG° and ΔS° for the process are reported.     

Voltammetric and electrochemical ESR studies of oxidation reactions mediated by tris(4-bromophenyl)amine in acetonitrile

The electrochemical oxidation of tris(4-bromophenyl)amine in the presence of 2,6-lutidine is examined in acetonitrile. Voltammetric and spectroscopic investigations suggest that the electrogenerated triaryl aminium radical cation oxidizes 2,6-lutidine in an EC' mechanism, and an equilibrium constant for this homogeneous electron transfer is estimated. The mediated oxidation of a protected phenyl selenoglycoside by this reaction mixture is studied by the use of electrochemical ESR, employing a tubular flow cell, and signal intensity data is found to be consistent with the proposed mechanism, allowing the determination of kinetic parameters by computational simulation. Products of the mediated glycoside oxidation are determined by proton NMR and mass spectrometry.     

A combination of in situ ESR and in situ NMR spectroelectrochemistry for mechanistic studies of electrode reactions: the case of p-benzoquinone

A combined in situ NMR and in situ ESR spectroelectrochemical study of a reaction mechanism is presented detecting and describing the whole number of paramagnetic and diamagnetic intermediates and final products in an electrode reaction. While in situ NMR spectroelectrochemistry provides a powerful method for the study of structural or electronic changes of diamagnetic molecules in any electrochemical reaction mechanism, in situ ESR spectroelectrochemistry is the method of choice to detect paramagnetic structures and to characterise their electronic state via the g-value and hyperfine splitting in redox reactions. To demonstrate the power of this combination of magnetic spectroscopies in electrochemistry, the reduction of p-benzoquinone to hydroquinone is followed by both these spectroelectrochemical methods at selected pH values, thus considering the influence of the proton on the reaction mechanism. The results of both in situ spectroelectrochemical methods at the same redox system are used to get the complete reaction mechanism of p-benzoquinone at electrodes in aqueous solutions.     

Study on polymerization and structure of polydiphenylamine

The electrochemical oxidation of diphenylamine in acetonitrile produces an adherent uniform polymer film which exhibits mutiple colour variation(yellow-green-blue) in a wide range of potential scan. The polymerization mechanism and the structure of the polymer were studied by cyclic voltammetry, FT-IR and in situ ESR. The results indicate that the electrochemical polymerization of diphenylamine belongs to a cationic radical polymerization process. During electrolysis, only oligomers were initialy produced, then polymer film was formed on the electrode surface. The electropolymerization performs via the 4,4' C-C phenyl-phenyl coupling mechanism.     

Synthetic Diversity from a Versatile and Radical Nitrating Reagent

We leverage the slow liberation of nitrogen dioxide from a newly discovered, inexpensive succinimide-derived reagent to allow for the C−H diversification of alkenes and alkynes. Beyond furnishing a library of aryl β-nitroalkenes, this reagent provides unparalleled access to β-nitrohydrins and β-nitroethers. Detailed mechanistic studies strongly suggest that a mesolytic N−N bond fragmentation liberates a nitryl radical. Using in situ photo-sensitized, electron paramagnetic resonance spectroscopy, we observed direct evidence of a nitryl radical in solution by nitrone spin-trapping. To further exhibit versatility of N-nitrosuccinimide under photoredox conditions, the late-stage diversification of an extensive number of C−H partners to prepare isoxazolines and isoxazoles is presented. This approach allows for the formation of an in situ nitrile oxide from a ketone partner, the presence of which is detected by the formation of the corresponding furoxan when conducted in the absence of a dipolarophile. This 1,3-dipolar cycloaddition with nitrile oxides and alkenes or alkynes proceeds in a single-operational step using a mild, regioselective, and general protocol with broad chemoselectivity.     

Cathodic reduction of bisulfite and sulfur dioxide in aqueous solutions on copper electrodes: an electrochemical ESR study

The electrochemical reduction of aqueous solutions of sulfite under acidic conditions on copper electrodes is reported, and a mechanism is proposed. Cyclic voltammetry at a copper disk suggests the operation of two reduction processes, the dominant process depending on solution pH. At very low pH (0-2), sulfur dioxide is reduced in a two-electron, two-proton reaction, but at higher pH (2-5), bisulfite is the electroactive species, being reduced by a single electron to ultimately yield the SO2*- radical anion. Simultaneous electrochemical electron spin resonance (ESR) measurements using a tubular flow cell support this proposal, and suggest that the radical anion is in equilibrium with dithionite, which is found to decay at low pH. Digisim modeling of the system is shown to be consistent with this mechanism over the experimental pH range.     

对二嗪N,N’-二氧化物光还原的电子自旋共振研究

报道了利用原位电子自旋共振(ESR)技术研究对二嗪N,N′-二氧化物光解的结果。研究结果表明,化合物5,6,7和8通过光还原过程从溶剂分子夺取氢原子分别生成稳定的自由基,记录出它们分辨良好的ESR谱。文中还讨论了对二嗪N,N′-二氧化物的光化学反应的自由基机理。     

氧化锌纳米微晶的顺磁共振特性

半导体纳米微粒是制备新一代电子器件的理想材料［1，2］．电子自旋共振谱（ESR）是研究纳米微晶表面电子自旋构象和表面结构的一种有效方法．体相ZnO是一种抗磁性物质，通常观察不到顺磁共振信号（ESR）．有关ZnO纳米微晶电子顺磁共振特性研究还未见文献报导．本文ZnO纳米微晶是用微乳法制备的：这样就制成了纳米尺度的具有表面包覆的ZnO微粒有机溶胶．这里表面活性剂起着“空间位阻”作用，一方面防止成胶过程中粒子间的聚合，使胶粒均匀细小；另一方面，包覆能减少微粒表面缺陷，使粒子性质变得十分稳定．将上述制得的ZnO纳米微粒…     

In situ ESR and UV/vis spectroelectrochemical study of eosin Y upon reduction with and without Zn(II) ions.

The electroreduction of eosin Y on a platinum electrode in deaerated slightly acidic aqueous 0.1 mol L(-1) potassium chloride medium is followed in situ by electron spin resonance (ESR) spectroscopy and UV/Vis spectroscopy. The electrochemical formation of a semiquinone radical is proved by both the appearance of an absorbing band at 408 nm, and a strong ESR signal observed during a negative-going scan. The system is also studied in the presence of Zn(II) ions due to its importance for understanding the growth mechanism of nanostructured ZnO/Eosin Y hybrid films by electrodeposition; under such conditions the ESR and UV/Vis response of the semiquinone radical is not observed. Zinc (II) ions form a complex with the dye, which is reduced by a fast two-electron process.     

光诱导反应机理研究 ⅩⅦ.ESR波谱法研究多氯甲烷对降冰片二烯的光敏化加成反应机理

在以前的研究工作中^[1]我们已经证明芳胺可以有效地光敏化多氯甲烷对双环[2,2,1]-2,5-庚二烯的加成反应。该反应具有百分之百的区域选择性,在我们所选择的实验体系中只得到了3.5-加成物,而没有2.3-加成物。这一结果不同于典型的热诱导自由基加成反应^[2]。     

Experimental and theoretical evidence of a persistent radical-cation dimer generated during the electrooxidation of an N-glucosamine-pyrrole derivative

The results of the electrochemical characterization by cyclic voltammetry of 1,3,4,6-tetra-O-acetyl-2-amino-2-deoxy-2-(pyrro-1-yl)-β-d-glucopyranose (Py-GSATA) are presented. This compound was analyzed in acetonitrile containing 0.1 M tetrabutylammonium perchlorate, using a platinum disk electrode as the working electrode. Py-GSATA showed two irreversible oxidation signals, the first at 1.24 and the second at 1.54 V vs Fc(+)/Fc. After successive cyclic voltammetry, under different experimental conditions, it was shown that it is not possible to electropolymerize this pyrrole derivative. Surprisingly, the bulk anodic electrolysis of Py-GSATA generated a single electroactive soluble product with an electrochemical cathodic signal located at -0.35 V vs Fc(+)/Fc. Mass spectrometry of the solution showed the presence of a dimeric species of the parent compound. ESR spectroscopy of the electrolysis solution showed a persistent radical species stable at least for 6 months (4 °C). UV-vis spectroscopy was consistent with low chain cation-radical oligomers. In order to propose an explanation to the dimer cation stability in solution, molecular modeling using a B3LYP/6-31+G** level of theory was used to analyze the stability and feasibility of the electrogenerated species.     

甲苯异构体在石墨电极上的直接电氧化

通过循环伏安法、电化学原位红外光谱和恒电位电解法研究了甲苯异构体在0.05 mol/L硫酸体系中的直接电氧化行为. 结果表明, 对甲氧基甲苯、对甲基甲苯、对氯甲苯和对叔丁基甲苯4种含不同取代基的甲苯异构体具有相似的电氧化行为, 均在1710 cm^-1左右出现向下的羰基伸缩振动峰(υ_C=O), 在1130 cm^-1左右出现向上的甲基消耗峰. 通过气相色谱-质谱法(GC-MS)对恒电位电解产物进行检测, 进一步证实了在石墨电极、硫酸水溶液体系中甲苯异构体直接电氧化主要产物为相应的芳香醛, 40 ℃时, 对甲氧基苯甲醛的产率为70.9%.