Stereo sensitivity of exchange interactions in Ni<Superscript>II</Superscript> and Cu<Superscript>II</Superscript> heterospin complexes with 5-formylpyrrolyl-substituted nitroxides

5-Formylpyrrolyl-substituted nitronyl and imino nitroxide radicals HL¹ and HL² were synthesized. Their solid phases are formed by packing pairs of the molecules. In the {HL¹...HL¹} pairs, the dominant interaction is the ferromagnetic exchange with J/kB = 8.8 K (Hamiltonian \(H = 2J\left( {\overrightarrow {{s_1}} \overrightarrow {{s_2}} } \right)\)). The ferromagnetic exchange occurs also in the heterospin molecules [Ni(L¹)₂], [Cu(L¹)₂], and [Ni(L²)₂(MeOH)₂]. In the complexes [Ni(L¹)₂] and [Cu(L¹)₂], a small change in the mutual orientation of the coordinated ligands has a considerable effect on the value and the sign of the energy of exchange interactions between the unpaired electrons of the metal ion and paramagnetic ligands.     

Precision Resonator Microwave Spectroscopy in Millimeter and Submillimeter Range

By the use of Fabry–Perot resonator with quality factor 600 000 and fast precision (down to one Hertz) frequency control of coherent millimeterwave radiation source the 20 Hz accuracy in measurements of the width of resonance curve is obtained. This accuracy corresponds to the detection of 1.8 × 10^–3 dB/km absorption in the sample filling the resonator and exceeds the before known sensitivity more than by an order of magnitude. The example of precise measurement of 60 GHz oxygen absorption band in the real atmosphere is presented. The new possibilities of application of precision resonator microwave spectroscopy to the atmospheric problems as well as to the ultra-low absorptions measurements in dielectrics and metal surfaces up to Terahertz frequencies are discussed.     

Evolution of fractal particles in systems with conserved order parameter

Computer simulations of the evolution of fractal aggregates in systems with conserved order parameter are described in this work. The aggregates are generated by diffusion-limited aggregation. This model describes such important processes as annealing of dendrite inclusions in solids, healing of cracks in ceramics, temperature-induced transformations in composites, relaxation of rough surfaces, aging of colloid particles, etc. It is shown that the evolution in fractal media differs significantly from that occurring in initially homogeneous systems and leads to different values of the scaling exponent. A relationship between the fractal dimension, mechanism of relaxation, and scaling exponent was also derived.     

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.     

Ferromagnetically Coupled S=1 Chains in Crystals of Verdazyl-Nitronyl Nitroxide Diradicals

Thermally stable organic diradicals with a triplet ground state along with large singlet-triplet energy gap have significant potential for advanced technological applications. A series of phenylene-bridged diradicals with oxoverdazyl and nitronyl nitroxide units were synthesized via a palladium-catalyzed cross-coupling reaction of iodoverdazyls with a nitronyl nitroxide-2-ide gold(I) complex with high yields. The diradicals exhibit high stability and do not decompose in an inert atmosphere up to 180 °C. For the diradicals, both substantial AF (ΔE_ST≈−64 cm⁻¹) and FM (ΔE_ST≥25 and 100 cm⁻¹) intramolecular exchange interactions were observed. The sign of the exchange interaction is determined both by the bridging moiety (para- or meta-phenylene) and by the type of oxoverdazyl block (C-linked or N-linked). Upon crystallization, diradicals with the triplet ground state form unique one-dimensional exchange-coupled chains with strong intra- and weak inter-diradical ferromagnetic coupling.     

Synthesis, structure, and magnetic properties of (6-9)-nuclear Ni(II) trimethylacetates and their heterospin complexes with nitroxides

New polynuclear nickel trimethylacetates [Ni6(OH)4(C5H9O2)8(C5H10O2)4] (6), [Ni7(OH)7(C5H9O2)7(C5H10O2)6(H2O)] x 0.5 C6H14 x 0.5 H2O (7), [Ni8(OH)4(H2O)2(C5H9O2)12] (8), and [Ni9(OH)6(C5H9O2)12(C5H10O2)4] x C5H10O2 x 3 H2O (9), where C5H9O2 is trimethylacetate and C5H10O2 is trimethylacetic acid, have been found. Their structures were determined by X-ray crystallography. Because of their high solubility in low-polarity organic solvents, compounds 6-9 reacted with stable organic radicals to form the first heterospin compounds based on polynuclear Ni(II) trimethylacetate and nitronyl nitroxides containing pyrazole (L(1)-L(3)), methyl (L(4)), or imidazole (L(5)) substituent groups, respectively, in side chain [Ni7(OH)5(C5H9O2)9(C5H10O2)2(L(1))2(H2O)] x 0.5 C6H14 x H2O (6+1a), [Ni7(OH)5(C5H9O2)9(C5H10O2)2(L2)2(H2O)] x H2O (6+1b), [Ni7(OH)5(C5H9O2)9(C5H10O2)2(L(3))2(H2O)] x H2O (6+1c), [Ni6(OH)3(C5H9O2)9(C5H10O2)4(L(4))] x 1.5 C6H14 (6'), and [Ni4OH)3(C5H9O2)5(C5H10O2)4(L(5))] x 1.5 C7H8 (4). Their structures were also determined by X-ray crystallography. Although Ni(II) trimethylacetates may have varying nuclearity and can change their nuclearity during recrystallization or interactions with nitroxides, this family of compounds is easy to study because of its topological relationship. For any of these complexes, the polynuclear framework may be derived from the [Ni6] polynuclear fragment {Ni6(mu4-OH)2(mu3-OH)2(mu2-C5H9O2-O,O')6(mu2-C5H9O2-O,O)(mu4-C5H9O2-O,O,O',O')(C5H10O2)4}, which is shaped like an open book. On the basis of this fragment, the structure of 7-nuclear compounds (7 and 6+1a-c) is conveniently represented as the result of symmetric addition of other mononuclear fragments to the four Ni(II) ions lying at the vertexes of the [Ni6] open book. The 9-nuclear complex is formed by the addition of trinuclear fragments to two Ni(II) ions lying on one of the lateral edges of the [Ni6] open book. This wing of the 9-nuclear complex preserves its structure in another type of 6-nuclear complex (6') with the boat configuration. If, however, two edge-sharing Ni(II) ions are removed from [Ni6] (one of these lies at a vertex of the open book and the other, on the book-cover line), we obtain a 4-nuclear fragment recorded in the molecular structure of 4. Twinning of this 4-nuclear fragment forms highly symmetric molecule 8, which is a new chemical version of cubane.     

Bis(1,1,1,3,5,5,5-heptafluoro-4-iminopent-2-ene-2-aminato)copper(<Emphasis Type="SmallCaps">ii</Emphasis>) — a new metal-containing matrix in the design of heterospin systems

The first heterospin compounds based on bis(1,1,1,3,5,5,5-heptafluoro-4-iminopent-2-ene-2-aminato)copper(ii) (CuL₂) and nitronyl nitroxide radicals, 2-R-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyls (NIT-R, where R = H, Me, Ph, and 1-methylpyrazol-4-yl), were synthesized and structurally characterized. An important peculiarity of the structure of synthesized solid phases is the formation of a supramolecular structure due to hydrogen bonds between the oxygen atoms of the nitronyl nitroxide fragments of NIT-R and the hydrogen atoms of the NH groups of CuL₂.     

Copper(II) bis(hexafluoroacetylacetonate) complexes with 2-(2-methyltetrazolyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole 1-oxides

An efficient procedure was developed for the synthesis of alkyltetrazolyl-substituted nitronyl nitroxides (L ¹ and L ²). These compounds were used to prepare the first alkyltetrazolyl-substituted imino nitroxides (L ³ and L ⁴). The molecular structures of L ³ and L ⁴ were confirmed by X-ray diffraction. Investigation of the products prepared by the reaction of copper(II) bis(hexafluoroacetylacetonate), Cu(hfac)₂, with nitroxides made it possible to divide ligands L ¹—L ⁴ into two groups. The reactions of spin-labeled tetrazoles L ¹—L ³ with Cu(hfac)₂ afford the heterospin complexes Cu(hfac)₂L₂, whereas L ⁴ serves as a bidentate ligand in the Cu(hfac)₂ L ⁴ complex. In the solid Cu(hfac)₂L₂ complexes, antiferromagnetic exchange interactions between the unpaired electrons of the nitroxide fragments of the adjacent molecules prevail, due to which μ_eff decreases with decreasing temperature, and the spins of nitroxides are completely compensated at 5–10 K. The Cu(hfac)₂ L ⁴ complex displays strong intramolecular ferromagnetic coupling, due to which μ_eff at room temperature is close to 2.9 μ_B. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 64–70, January, 2006.     

1,3-Dipolar cycloaddition in the synthesis of pyrazolyl-substituted nitronyl nitroxides

A new approach to the synthesis of polyfunctional pyrazolyl-substituted nitronyl nitroxides was developed based on the presynthesized pyrazole derivatives prepared by 1,3-dipolar cycloaddition. The structures of the resulting mono-and biradicals were confirmed by X-ray diffraction. Dedicated to Academician A. L. Buchachenko on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2105–2116, September, 2005.     

Hydrothermal synthesis of one-dimensional (1D) Na<Subscript>x</Subscript>TiO<Subscript>2</Subscript> nanostructures

Nanorods of sodium titanium dioxide bronze Na_xTiO₂ were synthesized by the hydrothermal treatment of the amorphous TiO₂·nH₂O gel with 10 M NaOH followed by ultrasonication in 0.1 M HCl and thermal treatment (500°C, 10 h). The thermal treatment of the nanorods does not change the morphology of the particles. According to the electron diffraction data, the Na_xTiO₂ nanorods grow along the c axis.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 71–73, January, 2005.