Effects of Spiro-Cyclohexane Substitution of Nitroxyl Biradicals on Dynamic Nuclear Polarization

Spiro-substituted nitroxyl biradicals are widely used as reagents for dynamic nuclear polarization (DNP), which is especially important for biopolymer research. The main criterion for their applicability as polarizing agents is the value of the spin–spin exchange interaction parameter (J), which can vary considerably when different couplers are employed that link the radical moieties. This paper describes a study on biradicals, with a ferrocene-1,1′-diyl-substituted 1,3-diazetidine-2,4-diimine coupler, that have never been used before as DNP agents. We observed a substantial difference in the temperature dependence between Electron Paramagnetic Resonance (EPR) spectra of biradicals carrying either methyl or spirocyclohexane substituents and explain the difference using Density Functional Theory (DFT) calculation results. It was shown that the replacement of methyl groups by spirocycles near the N-O group leads to an increase in the contribution of conformers having J ≈ 0. The DNP gain observed for the biradicals with methyl substituents is three times higher than that for the spiro-substituted nitroxyl biradicals and is inversely proportional to the contribution of biradicals manifesting the negligible exchange interaction. The effects of nucleophiles and substituents in the nitroxide biradicals on the ring-opening reaction of 1,3-diazetidine and the influence of the ring opening on the exchange interaction were also investigated. It was found that in contrast to the methyl-substituted nitroxide biradical (where we observed the ring-opening reaction upon the addition of amines), the ring opening does not occur in the spiro-substituted biradical owing to a steric barrier created by the bulky cyclohexyl substituents

One-pot synthesis of 4′-alkyl-4-cyanobiaryls on the basis of the terephthalonitrile dianion and neutral aromatic nitrile cross-coupling

A convenient one-pot approach to alkylcyanobiaryls is described. The method is based on biaryl cross-coupling between the sodium salt of the terephthalonitrile dianion and a neutral aromatic nitrile in liquid ammonia, and successive alkylation of the long-lived anionic intermediate with alkyl bromides. The reaction is compatible with benzonitriles that contain methyl, methoxy and phenyl groups, fluorine atoms, and a 1-cyanonaphthalene residue. The variety of ω-substituted alkyl bromides, including an extra bromine atom, a double bond, cyano and ester groups, as well as a 1,3-dioxane fragment are suitable as alkylation reagents

Light-Induced Spin State Switching in Copper(II)-Nitroxide-Based Molecular Magnet at Room Temperature

International audienceMolecular magnets Cu(hfac)(2)L-R exhibit an unusual type of photoinduced magnetostructural switching in exchange-coupled copper(II)-nitroxide clusters. Such photoswitching from strongly coupled to weakly coupled spin state (SS -> WS) was recently found to be ultrafast, thus enhancing the interest in these systems and the scope of their potential applications. However, to date such SS -> WS photoswitching was demonstrated only at cryogenic temperatures, being limited by the absence of suitable SS states and short relaxation times at T > 100 K. In this work we selected model compound Cu(hfac)(2)Liso-Pr residing in the mixed SS/WS state at room temperature and investigated it using femtosecond optical spectroscopy. Photoinduced spin dynamics was detected, and an ultrafast SS -> WS photoswitching was for the first time demonstrated at room temperature, constituting an important milestone in the development of copper(II)-nitroxide molecular magnets for practical purposes

Fluorinated Organic Paramagnetic Building Blocks for Cross-Coupling Reactions

New stable polyfluorinated nitroxide radicals for use in cross-coupling reactions, namely, N-tert-butyl-N-oxyamino-2,3,5,6-tetrafluoro-4-iodobenzene and N-tert-butyl-N-oxyamino-2,3,5,6-tetrafluoro-4-ethynylbenzene, were prepared from perfluoroiodobenzene. The reaction of the polyfluoro derivative with tert-butylamine under autoclaving conditions leading to the formation of N-tert-butyl-2,3,5,6-tetrafluoro-4-iodoaniline proved to be the key stage of the whole process. The fluorinated tert-butyl iodophenyl nitroxide was found to form in a solid state via N–O···I halogen bonds, a one-dimensional assembly of the radicals. The acceptor role of the nitroxide group in the halogen bonding changes to a donor role when the nitroxide reacts with Cu(hfac)2. In the last case, zero-dimensional assembly prevails, giving a three-spin complex with axial coordinated nitroxide groups and, as a consequence, causing ferromagnetic intramolecular exchange interactions between Cu(II) and radical spins

Increasing Fuel Loads, Fire Hazard, and Carbon Emissions from Fires in Central Siberia

The vast Angara region, with an area of 13.8 million ha, is located in the southern taiga of central Siberia, Russia. This is one of the most disturbed regions by both fire and logging in northern Asia. We have developed surface and ground fuel-load maps by integrating satellite and ground-based data with respect to the forest-growing conditions and the disturbance of the territory by anthropogenic and natural factors (fires and logging). We found that from 2001 to 2020, fuel loads increased by 8% in the study region, mainly due to a large amount of down woody debris at clearcuts and burned sites. The expansion of the disturbed areas in the Angara region resulted in an increase in natural fire hazards in spring and summer. Annual carbon emissions from fires varied from 0.06 to 6.18 Mt, with summer emissions accounting for more than 95% in extreme fire years and 31–68% in the years of low fire activity. While the trend in the increase in annual carbon emissions from fires is not statistically significant due to its high interannual variability and a large disturbance of the study area, there are significantly increasing trends in mean carbon emissions from fires per unit area (p p p p p < 0.025) forests. This indicates deeper burning and loss of legacy carbon that impacts on the carbon cycle resulting in climate feedback

A Crystallographic Study of a Novel Tetrazolyl-Substituted Nitronyl Nitroxide Radical

Spin-labelled compounds are widely used in chemistry, physics, biology, and material sciences, but the directed synthesis of some functionalized organic radicals is still a challenge. We succeeded in the preparation of a tetrazolyl-substituted nitronyl nitroxide radical in pure crystalline form. According to the single-crystal X-ray data, intra- (NH&hellip;O, 2.43 &Aring;) and inter-molecular hydrogen bonds (NH&hellip;O, 1.91 &Aring;) are formed between NH groups of the tetrazole cycles and O atoms of the paramagnetic moieties. The intermolecular H-bonds connect the molecules forming chains along the a-axis. Moreover, there are short intermolecular contacts between the O atoms (3.096 &Aring;) and between the O and C atoms (3.096 &Aring;) of the nitronyl nitroxide moieties within the chain. The spin-unrestricted broken-symmetry calculations performed at the BS-UB3LYP/def2-TZVP level of theory predicted a sufficient ferromagnetic interaction (J &asymp; 20 cm&ndash;1) between the adjacent radicals inside the chain, but a weak antiferromagnetic interaction (&minus;J &le;0.2 cm&minus;1) between the nearest radicals belonging to the different chains. Thus, a rare case when stable radicals, the tetrazolyl-substituted nitronyl nitroxides, are ordered into ferromagnetic chains was revealed; an investigation of the magneto-structural correlations inherent in the nitroxide radical will demand a special experiment in the sub-Kelvin regime

Trityl-based alkoxyamines as NMP controllers and spin-labels

International audienceRecently, new applications of trityl-nitroxide biradicals were proposed. In the present study, attachment of a trityl radical to alkoxyamines was performed for the first time. The rate constants k(d) of C-ON bond homolysis in these alkoxyamines were measured and found to be similar to those for alkoxyamines without a trityl moiety. The electron paramagnetic resonance (EPR) spectra of the products of alkoxyamine homolysis (trityl-TEMPO and trityl-SG1 biradicals) were recorded, and the corresponding exchange interactions were estimated. The decomposition of trityl-alkoxyamines showed more than an 80% yield of biradicals, meaning that the C-ON bond homolysis is the main reaction. The suitability of these labelled initiators/controllers for polymerisation was exemplified by means of a successful nitroxide-mediated polymerisation (NMP) of styrene. Thus, this is the first report of a spin-labelled alkoxyamine suitable for NMP

The effect of the oxophilic Tb(III) cation on C-ON bond homolysis in alkoxyamines

WOS:000430904400002Recently, we reported on the activation of the C-ON bond homolysis in alkoxyamines R1R2NOR3 using the coordination of the alkyl fragment R-3 with metal cations Cu(II) and Zn(II). Here, we report the selective coordination of the diethylphosphoryl group carried by the nitroxyl fragment by the oxophilic metal cation Tb(III). Coordination on the nitroxyl fragment afford a slight 2-fold decrease in the C-ON bond homolysis rate constant kd. (C) 2018 Elsevier B.V. All rights reserved