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Том 482, № 1 (2018)
- Год: 2018
- Статей: 7
- URL: https://journal-vniispk.ru/0012-5008/issue/view/9302
Chemistry
Quantum-Chemical Study of Spin Transitions in Bimetallic Fe–M Complexes (M = Co, Ni, Cu, Zn) with the 1,10-Phenanthroline Linker
Аннотация
The structure, energies, and magnetic properties of electromeric forms of binuclear Fe–M complexes (M = Co, Ni, Cu, Zn) with a 1,10-phenanthroline-based linker have been studied by the DFT UB3LYP*/6-311++G(d,p) method. Studying the spin-state switching mechanisms has demonstrated that all the compounds under consideration are capable of undergoing spin crossover at the iron ion. In solutions of complexes with cobalt and nickel bis-chelates, a competing process accompanied by the change in magnetic characteristics—configurational isomerism—is possible.
181-184
Triindolyl Macrocycle as a Molecular Platform in the Synthesis of Sumanene-Containing Polyphenols
Аннотация
A new strategy has been suggested for the synthesis of sumanene-containing polyphenols chemically bound to a molecular platform based on the triindolyl macrocycle. The initial assembly has been obtained by the Suzuki–Miyaura reaction of a bromo-containing indolyl macrocycle and boryl derivative of N,N'-disumanenylaniline. Subsequent benzylation with 3,5-dimethoxybenzyl bromide, exhaustive demethylation of the modified macrocycle, and partial blocking of the corresponding phenolic hydroxyls by two different acid-labile protective groups have led to the formation of the target polyphenol containing sumanene fragments. The obtained polyphenol has allowed us to develop on its basis a new positive resist for electronbeam nanolithography. This resist can realize topological structures with resolution of 9–12 nm.
185-188
Structure and Fluxional Behavior of Phenylmercury Derivatives of N,N'-Diarylform(benz)amidines
Аннотация
Activation barriers for fast 1,3-N,N' migrations of phenylmercury groups in the corresponding derivatives of N,N'-di(p-tolyl)form(benz)amidines have been calculated by density functional theory B3LYP/Gen, 6-311++G(d,p)/SDD to be ΔEZPE≠= 4.5 and 3.0 kcal/mol. The results correspond to the data of dynamic NMR, which have shown the upper limit of activation barriers of these rearrangements (ΔG≠) to be below 8 kcal/mol. The calculations have shown that the most stable is the E-syn form of N-phenylmercury-N,N'-di(p-tolyl)form(benz)amidines stabilized by supplementary intramolecular coordination of mercury atom with imine nitrogen atom of the amidine triad.
189-194
Chemical Technology
New Quinoxaline-Containing Monomers for Narrow-Bandgap Polymers
Аннотация
Two new fused quinoxaline-containing monomers—2,3-bis(9-(2-decyltetradecyl)-9H-carbazol-3-yl)dithieno[3,2-f:2'3'-h]quinoxaline (М1) and 2,5-di(nonadecan-3-yl)bis[1,3]thiazolo[4,5-a:5',4'-c]bisthieno[3,2-h:2',3'-j]phenazine (М2)—have been synthesized in high yields of 88 and 83% as promising building blocks of D-A polymers for photovoltaic applications. The optical bandgaps, found from the absorption edge, are 2.79 and 2.88 eV, respectively. The HOMO/LUMO energies of М1 and М2 are–5.83/–2.96 and–5.83/–2.98 eV, respectively. Both monomers have low-lying HOMO levels, which is favorable for a high open-circuit voltage and a high stability in air in the development of PSCs. The Egec values of monomers М1 and М2 are 2.87 and 2.85 eV and are consistent well with the optical bandgap (2.79 and 2.88 eV, respectively).
195-200
A New Method of Synthesis of Nanosized Metal Oxide Powders
Аннотация
A new method of synthesis of nanosized metal oxide powders (Al2O3, MgO, ZnO) has been suggested. The method involves successive heat treatment at 350°С and then at 800°С of saturated solutions of the corresponding metal salts and sucrose. Physicochemical and technological properties of the synthesized materials have been determined.
201-203
Biocompatibility of the Ti81Nb13Ta3Zr3 Alloy
Аннотация
Titanium-based alloy with low-toxic metals such as niobium, tantalum and zirconium (TiNbTaZr) was manufactured. The primary weight percentages of elements used for fusion were: titanium, 65%; niobium, 20%, tantalum, 10%; and zirconium, 5%. The TiNbTaZr alloy had a yield strength of about 550 MPa, a tensile strength of about 700 MPa, and a Young’s modulus of about 50 GPa, that is, it was comparable with Nitinol. A primary study of the biocompatibility of the TiNbTaZr alloy using the SH-SY5Y cells showed that the alloy did not have significant short-term toxicicity towards the cells incubated on the alloy surface. The number of non-viable cells was 2.5 times lower on the TiNbTaZr alloy than on Nitinol. The biocompatibility of TiNbTaZr was more pronounced than that of the Nitinol reference sample.
204-206
Bis[1,3]thiazolo[4,5-f:5',4'-h]thieno[3,4-b]quinoxaline Derivatives as New Building Blocks of Polymers for Organic Electronics
Аннотация
New derivatives of bis[1,3]thiazolo[4,5-f:5',4'-h]thieno[3,4-b]quinoxaline containing the fused thiadiazoloquinoxaline moiety have been prepared. Monomer M1 shows strong light absorption within 600–800 nm due to intramolecular charge transfer. The optical bandgap Egopt determined from the absorption edge in a film is 1.44 eV. The HOMO and LUMO levels are–5.44 and–3.12 eV, respectively. The new structural fragment has a rather low frontier molecular orbital energies and a small bandgap; therefore, it is a promising building block for the synthesis of polymers for organic electronics.
207-211