A5058373744- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Magnetism in coordination complexes
- Lanthanide and Transition Metal Complexes
- Metal complexes synthesis and properties
- Porphyrin and Phthalocyanine Chemistry
- Metal-Catalyzed Oxygenation Mechanisms
- Organometallic Complex Synthesis and Catalysis
- Photochromic and Fluorescence Chemistry
- Synthesis and Properties of Aromatic Compounds
- Electron Spin Resonance Studies
- Free Radicals and Antioxidants
- Synthesis and characterization of novel inorganic/organometallic compounds
- Molecular Junctions and Nanostructures
- Crystallography and molecular interactions
- Metal-Organic Frameworks: Synthesis and Applications
- Advanced Chemical Physics Studies
- Photochemistry and Electron Transfer Studies
- Photoreceptor and optogenetics research
- Organic and Molecular Conductors Research
- N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
- Catalytic Cross-Coupling Reactions
- Fullerene Chemistry and Applications
- Molecular Sensors and Ion Detection
- Inorganic Chemistry and Materials
Southern Federal University
2016-2025
Institute of Physical and Organic Chemistry
2014-2024
Astrakhan State Medical University
2023
Ministry of Health of the Russian Federation
2023
Astrakhan State University
2014
Southern Scientific Center
2011
Valence tautomerism (VT) involves a reversible stimulated intramolecular electron transfer between redox-active ligand and metal. Bis(dioxolene)-bridged dinuclear cobalt compounds provide an avenue toward controlled two-step VT interconversions of the form {CoIII-cat-cat-CoIII} ⇌ {CoIII-cat-SQ-CoII}⇌{CoII-SQ-SQ-CoII} (cat2- = catecholate, SQ•- semiquinonate). Design flexibility for complexes confers advantage over spin crossover future applications in devices or materials. The four this...
The bis‐chelate tin complex 1 , based on the 4,6‐di‐ tert ‐butyl‐ N ‐( ‐butyl)‐ ortho ‐aminophenol ligand and representing first example of a redox‐isomeric compound in main‐group chemistry, is synthesized characterized by X‐ray diffraction analysis. Complex exists two electromeric forms nonpolar solvents: diamagnetic pseudotetrahedral (AP) 2 Sn IV ( 1a ) paramagnetic tetragonal‐pyramidal structure low‐valence (imSQ) II 1b (where AP imSQ are dianionic radical‐anionic ligand, respectively)....
Compounds [Co(L-N4R2)(dbdiox)](BPh4) (L-N4R2 = N,N'-di-alkyl-2,11-diaza[3.3]-(2,6)pyridinophane, R iPr (1a), Et (2a); dbdiox 3,5-di-tert-butyldioxolene) and [M(L-N4iPr2)(dbdiox)](BPh4) (M Mn (3a), Fe (4a)) have been synthesized investigated with a view to possible valence tautomeric (VT) or spin crossover (SCO) interconversions. Single crystal X-ray diffraction data for all compounds at 100 130 K indicate trivalent metal cations di-tert-butylcatecholate (dbcat2-) dioxolene ligands. Variable...
The currently available literature data on the synthesis, molecular and electronic structure of mixed-ligand complexes (adducts) transition metals (chromium, manganese, iron, cobalt, ruthenium) with organic redox-active ligands are systematically considered for first time. possibility manifestation magnetic bistability by adducts tetracoordinate Co II Fe potential their application as switches studied in detail means quantum chemical modelling thermally initiated rearrangements controlled...
The switching phenomena of spin crossover (SCO) and valence tautomerism (VT) are respectively dominated by iron(ii) cobalt-dioxolene systems. To explore new possibilities for SCO or VT, the redox-active α-diimine ligand bis((phenyl)imino)acenaphthene (Ph-BIAN), which can adopt neutral (L0), monoanionic (L˙-), dianionic (L2-) states, was paired with zinc, cobalt, manganese iron to give [M(Ph-BIAN)3](BPh4)2 (M = Zn (1), Co (2), Mn (3), Fe (4)). Compounds 1, 2 3 a temperature invariant...
Magnetically bistable compounds attract considerable attention due to their possible applications in molecular electronics and spintronics devices. Of special interest are spin-crossover (SCO) systems that can interconvert between the low-spin...
The host-guest binding of Cucurbit[7]uril to a methylpyridinium-functionalized Co(II)-terpyridine complex shifts the spin equilibrium low-spin state (ΔT1/2 = 77 K) via secondary coordination sphere perturbation, providing new insights...
Abstract Various aspects related to the use of DFT method for study magnetic, geometry and energetic properties transition metal complexes with redox-active ligands are considered. Particular attention is given correct choice model compounds methodology calculations.
Novel O,N-heterocyclic germylenes were examined as catalysts for cyanosilylation and hydroboration of benzaldehyde.
Abstract A stable O , N ‐heterocyclic stannylene 1 bearing novel tetradentate 2,4‐di‐tert‐butyl‐6‐((2‐(1‐((pyridin‐2‐ylmethyl)imino)ethyl)phenyl)amino)phenolate ligand ( R APH 2 ) was synthesized and characterized. Complex is monomeric in crystal solution due to two additional intramolecular → Sn donor–acceptor interactions. The diverse reactivity of compound towards various iron carbonyl compounds studied. Oxidative addition [Fe (μ‐S )(CO) 6 ] the tin center resulted a new six‐coordinate...
A new concept for the structural design of valence tautomeric (VT) metal complexes involving formation stable adducts a tetracoordinate transition complex with suitable bidentate redox-active ligand has been computationally studied using DFT B3LYP*/6-311++G(d,p) method. The calculations, performed on series Co(II) diketonates o-benzoquinone and its mono- diimines, showed that mixed-ligand bis-(hexafluoroacetylacetonate) o-benzoquinone, imine diimine satisfy whole set necessary conditions to...
Spin crossover (SCO) complexes can reversibly switch between low spin (LS) and high (HS) states, affording possible applications in sensing, displays, molecular electronics. Dinuclear SCO with access to [LS-LS], [LS-HS], [HS-HS] states may offer increased levels of functionality. The nature the interconversion dinuclear is influenced by local electronic environment. We report synthesis characterization [{FeIII(tpa)}2spiro](PF6)2 (1), [{FeIII(tpa)}2Br4spiro](PF6)2 (2),...
Judicious pairing of ancillary and redox-active ligands affords thermally-induced two-step valence tautomerism for a dinuclear cobalt complex bridged by conjugated bis(dioxolene) ligand.
The possibility of employing the mechanism intramolecular electron transfer between metal and ligand centers in valence tautomeric complexes formed as electrically neutral 2 : 1 adducts Co(II) diketonates redox-active tetradentate di-o-quinones, for quantum information processing, has been computationally studied using DFT B3LYP*/6-311++G(d,p) method. It shown that by proper choice a linker group bridging quinone rings substituents diketonate fragments, with properties required 2-qubit gates...
3,5-di-tert-Butylcatecholate (DTBC) germanium complexes (DTBC)2Ge[Py(CN)n]2 (n = 0…2) have been synthesized from GeO2, 3,5-di-tert-butylcatechol and cyano-substituted pyridines Py(CN)n characterized by elemental analysis, NMR, IR UV-VIS spectroscopy. The structure of 1 (with 4-cyanopyridine) has determined X-ray single crystal analysis. spectra shown that these are stable in CH3CN, toluene CH2Cl2 solutions; contrast, they rapidly decomposed dimethylformamide tetrahydrofuran. Complexes 2...
A series of neutral triangular polycyclic aromatic hydrocarbons functionalized with various radical groups (dithiadiazolyl, verdazyl, nitronylnitroxyl, tert-butyl-nitroxyl and also (2,2,6,6-tetramethylpiperidin-1-yl)oxyl) has been computationally studied by the DFT UB3LYP/6-311++G(d,p) quantum-chemical modelling their electronic structure magnetic properties. The dependence nature strength exchange interactions between paramagnetic centers on size core, presence heteroatoms in moiety, type...
Abstract New adducts with the composition [Co 2 Gd(NO 3 )(Piv) 6 L ] (L=2,4‐lutidine (lut) ( 1 ), 2‐phenylpyridine (PhPy) 4 2‐ethynylpyridine (EtPy) 5 )) and Eu(NO ) were synthesized. According to X‐ray diffraction data, molecular complexes comprise two atoms of cobalt(II) one central atom gadolinium(III) bridged by carboxylate ligands. The donor base molecules are coordinated cobalt atoms. Magnetic measurements new previously synthesized quinoline pyridine ligands showed ferromagnetic...
It has been shown that the computationally designed bimetallic complexes formed as adducts of Co(II) diketonates and salicylaldiminates with Fe(II) chelates 1,10-phenanthroline-5,6-dione are susceptible to synchronized thermally induced intramolecular rearrangements between their electromeric forms LSCo(III)-SQ-LSFe(II), LSCo(III)-SQ-HSFe(II), HSCo(II)-BQ-LSFe(II), HSCo(II)-BQ-HSFe(II) also HSCo(II)-SQ-LSFe(III), which governed by spin-crossover (SCO), valence tautomerism (VT)...
Abstract The potential valence tautomeric (VT) properties of bischelate complexes group 14 elements with 2,6‐di‐ tert ‐butyl‐4‐[(3,5‐di‐ ‐butyl‐2‐hydroxyphenyl)imino]cyclohexa‐2,5‐dienone ( I ) and 4,6‐di‐ ‐butyl‐ N ‐(R)‐ o ‐aminophenol II , R = Ph t Bu) were studied computationally. According to DFT B3LYP/6‐311++G(d,p)/SDD calculations, the silicon will be present as Si IV isomers pseudotetrahedral coordination sites. Geometry optimizations both lead bischelates result in...