Specific MARY spectrum from radical anion of pentafluorobenzene

The paper presents the first resolved experimental magnetically affected reaction yield (MARY) spectrum for a system with nonequivalent nuclei, radical anion of pentafluorobenzene. This observation dispels the common apprehension that because of a rather involved energy level layout a system with not all nuclei magnetically equivalent cannot produce resolved MARY lines in nonzero fields, and greatly, increases the practical scope of level-crossing techniques for studies of spin-correlated radical pairs. The experimental finding is supported by schemes of energy levels calculated for this system.     

Kinetic Magnetic‐Field Effect Involving the Small Biologically Relevant Inorganic Radicals NO and O2.−

Oxidation of dihydrorhodamine 123 (DHR) to rhodamine 123 (RH) by oxoperoxonitrite (ONOO^?), formed through recombination of NO and O₂^.? radicals resulting from thermal decomposition of 3‐morpholinosydnonimine (SIN‐1) in buffered aerated aqueous solution at pH 7.6, represents a kinetic model system of the reactivity of NO and O₂^.? in biochemical systems. A magnetic‐field effect (MFE) on the yield of RH detected in this system is explored in the full range of fields between 0 and 18 T. It is found to increase in a nearly linear fashion up to a value of 5.5±1.6 % at 18 T and 23 °C (3.1±0.7 % at 40 °C). A theoretical framework to analyze the MFE in terms of the magnetic‐field‐enhanced recombination rate constant k_rec of NO and O₂^.? due to magnetic mixing of T₀ and S spin states of the radical pair by the Δg mechanism is developed, including estimation of magnetic properties (g tensor and spin relaxation times) of NO and O₂^.? in aqueous solution, and calculation of the MFE on k_rec using the theoretical formalism of Gorelik at al. The factor with which the MFE on k_rec is translated to the MFE on the yield of ONOO^? and RH is derived for various kinetic scenarios representing possible sink channels for NO and O₂^.?. With reasonable assumptions for the values of some unknown kinetic parameters, the theoretical predictions account well for the observed MFE.     

Mn site substitution of La0.67Ca0.33MnO3 with closed shell ions: Effect on magnetic transition temperature

Mn site is substituted with closed shell ions (Al, Ga, Ti, Zr and a certain combination of Zr and Al) and also with Fe and Ru ions carrying the magnetic moment (S=5/2 and 2 respectively) at a fixed concentration of 5 at %. Substitution did not change either the crystal symmetry or the oxygen stoichiometry. All substituents were found to suppress both the metal-insulator and ferromagnetic transition temperatures (T _p(ρ) and T _C, respectively) to varied extents. Two main contributions identified for the suppression are the lattice disorder arising due to difference in the ionic radii between the substituent (r _M) and the Mn³⁺ ion (r _Mn ³⁺) and in the case of the substituents carrying a magnetic moment, the type of magnetic coupling between the substituent and that of the neighboring Mn ion.     

Crucial role of paramagnetic ligands for magnetostructural anomalies in "breathing crystals"

Breathing crystals based on polymer-chain complexes of Cu(hfac)(2) with nitroxides exhibit thermally and light-induced magnetostructural anomalies in many aspects similar to a spin crossover. In the present work, we report the synthesis and investigation of a new family of Cu(hfac)(2) complexes with tert-butylpyrazolylnitroxides and their nonradical structural analogues. The complexes with paramagnetic ligands clearly exhibit structural rearrangements in the copper(II) coordination units and accompanying magnetic phenomena characteristic for breathing crystals. Contrary to that, their structural analogues with diamagnetic ligands do not undergo rearrangements in the copper(II) coordination environments. This confirms experimentally the crucial role of paramagnetic ligands and exchange interactions between them and copper(II) ions for the origin of magnetostructural anomalies in this family of molecular magnets.     

First acetylenic derivatives of stable 3-imidazoline nitroxides

The Stephens-Castro reaction of copper(I) salts of 1-aryl(hetaryl)alkynes with 2,2,5,5-tetramethyl-4-[2-(4-iodophenyl)-vinyl]imidazoline-3-oxide-1-ol proved to be a general method for the preparation of 2,2,5,5-tetramethyl-4-[2-(p-aryl(hetaryl)ethynylphenyl)]vinyl-3-imidazoline-3-oxide-1-oxyles.     

Theoretical Treatment of Degenerate Electron Exchange and Dimerization in Spin Dynamics of Radical Ion Pairs as Observed by Magnetic Field Effects

In this work we have compared manifestations of degenerate electron exchange (DEE) and dimerization reactions in MARY (magnetically affected reaction yield) spectroscopy and time-resolved magnetic field effects (TR-MFE) of radical ion pairs (RIPs). It is shown that dimerization results in phase and frequency changes of the quantum beats in TR-MFE traces, whereas DEE leads to relaxation-type changes in the spin dynamics of RIPs. Dimerization does not change the width of MARY lines considerably, but leads to new lines corresponding to dimer radical ions. In contrast, DEE substantially changes the MARY line widths. Our treatment provides ways to discriminate between both processes from experimental MARY spectra and TR-MFE kinetics. An experimental example dealing with concentration-dependent broadening of the MARY lines is also discussed.     

Biradical with the “non-linear” diacetylene fragment

The nitronyl nitroxide biradical, 2,2′-[1,1′-(hexa-2,4-diyne-1,6-diyl)bis(1H-pyrazole-4,1-diyl)]bis(4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole 3-oxide 1-oxyl), was synthesized. The structure and magnetic properties of the biradical were studied. In the solid state, this nitroxide contains the nonlinear C^S-C≡C-C≡C-C^S fragment. The C^S-C≡C and C≡C-C≡ angles are 172.4(5) and 171.1(3)°, respectively. Dedicated to Academician G. A. Tolstikov on the occasion of his 75th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 385–390, February, 2008. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 385–390, February, 2008.