Konstantin A Lyssenko

Lomonosov Moscow State University | MSU · Department of Physical Chemistry

New organometallic iridium compounds with phosphorus modified glucose ligands containing isopropylidene protection group or bearing uracil, thymine, and 5-fluorouracil (3,5,6-bicyclophosphite-1,2-O-isopropylidene-α-d-glucofuranoside, 3,5,6-bicyclophosphite-1-β-D-glucofuranosyluracil, 3,5,6-bicyclophosphite-1-β-D-glucofuranosylthymine, 3,5,6-bicyclo...

The search for new anticancer drugs based on biogenic metals, which have weaker side effects compared to platinum-based drugs, remains an urgent task in medicinal chemistry. Titanocene dichloride, a coordination compound of fully biocompatible titanium, has failed in pre-clinical trials but continues to attract the attention of researchers as a str...

We report crystal growth and characterization of 4 new ternary layered bismuthides with compositions KZn 2 Bi 2 ( I ), RbZn 2 Bi 2 ( II ), RbCd 2 Bi 2 ( III ), and CsCd 2 Bi 2 ( IV ) that belong to the vast 122 family of compounds. Single crystals were grown by self‐flux technique and characterized by a combination of powder X‐ray diffraction, scan...

Phenanthroline diamides (L) demonstrated a unique ability to extract uranium from nitric acid solutions into a polar organic solvent forming complexes of 1:2 stoichiometry as tight ion pairs {[UO2LNO3]+[UO2(NO3)3]-} by a novel extraction mechanism, which is a combination of two already well-known mechanisms: solvation and ion-pair anion exchange. A...

A new terbium(III) complex with a (3,4-diphenyl)(2-methylthienyl)cyclopentadienyl ligand was synthesized. Single-crystal X-ray analysis revealed a binuclear biscyclopentadienyl complex with a [TbCl2K]2 core. Luminescence properties of the terbium complex were analyzed.

A novel polydentate chelating antioxidant ligand and series of organotin complexes on its base were synthesized and characterized by NMR 1H, 13C, 119Sn, IR spectroscopy, X-ray, and elemental analysis. Their antioxidant activity was evaluated in DPPH and NBT-tests, and as lipoxygenase inhibitory activity. It was shown that ligand alone is a radical...

A series of potassium salts of di- and tri-arylsubstituted cyclopentadienes has been obtained by the metalation of the corresponding cyclopentadienes with benzylpotassium in THF media. Crystals of all compounds, afforded by recrystallization from THF/hexane, diglyme-THF/hexane and toluene/hexane mixtures, have been studied by X-ray diffraction. All...

PbCu(SeO4)(OH)2, the selenate sibling of the mineral linarite, was synthesized hydrothermally, investigated in measurements of magnetization M, specific heat Cp and dielectric permittivity ε, and analyzed within density functional theory formalism. This quasi-one-dimensional compound evidences formation of a short-range correlation regime at T* ~ 8...

Two bicyclic annulated isothiourea derivatives were synthesized using as a key stage either the reaction of isothiocyanate halide with sodium sulfide or cyclization of unsaturated thiourea in the presence of bromine. X-ray molecular structure of N-[(3aSR,7aRS,Z)-hexahydro-1,3-benzothiazol-2(3H)-ylidene]glycine was determined. The conjugate of colch...

The reaction of homopiperazine, C5N2H12, with BiBr3 in strong hydrobromic acid affords a new organic-inorganic hybrid (C5N2H14)2[BiBr6]Br·H2O. It crystallizes in the orthorhombic space group, Pbca, with unit cell dimensions of a = 15.0775 (2), b = 15.7569 (2), and c = 20.7881 (4) Å, and eight formula units per unit cell. The crystal structure featu...

A mixed-valence compound Pb2Cu10O4(SeO3)4Cl7 has a complex structure consisting of one nonmagnetic Cu+ (S = 0) ion and four nonequivalent magnetic Cu2+ (S = 1/2) ions. It exhibits antiferromagnetic ordering at TN = 10.2 K. At a temperature below TN, a sequence of spin-flop transition at Bspin-flop = 1.3 T and 1/3 plateau formation at Bspin-flip = 4...

Results of field corona poling experiments on thin film of polymethyl methacrylate (PMMA) polymer doped with molecules of substituted [2,2]paracyclophane are presented. Namely hydroxy/metoxy and formyl/ketone derivatives of [2,2]paracyclophane with different mutual orientation of the substituents were studied. The maximum value of second order NLO...

The photochemical 6π‐cyclization of diarylethenes (DAE), 2‐vinylbiaryls (VBA) and their derivatives is widely used in organic synthesis. Combination of these motifs in one molecule opens the issue of selectivity of the photochemical reaction. We have found that upon UV irradiation, 3‐(1,2‐diarylvinyl)‐2‐arylimidazo[1,2‐ a ]pyridines comprising both...

Novel 4-oxo-4H-furo[3,2-c]pyran-3-carboxylates and 4-oxo-4H-furo[3,2-c]chromene-3-carboxylates were prepared from available alkyl 3-bromo-3-nitroacrylates and 4-hydroxy-6- methyl-2H-pyran-2-one or 4-hydroxycoumarin, respectively. Their structures were confirmed by NMR and X-ray data.

A series of NHC-stabilized amido compounds (NHC)nM[N(SiMe3)2]2 (M = Yb(II), Sm(II), Ca(II); n = 1, 2) showed remarkable catalytic efficiency in addition of PhPH2 and PH3 to alkenes under mild conditions and low catalyst loading. The effect of σ-donor capacity of NHCs on catalytic activity in hydrophosphination of styrene with PhPH2 and PH3 was reve...

The reactions of sodium 2-(quinolyl-8-iminomethyl)phenolate with rare-earth element chlorides afford homoleptic mononuclear complexes [Ln{2-(8-quinolyl)N=CH–C6H4O}3] (Ln = La (I), Nd (II), Eu (III), and Tb (IV)) with the nonacoordinated rare-earth element ion. All synthesized complexes are similar in structure, and complexes II, III, and IV are iso...

The first examples of 1,10-phenanthroline-2,9-diamides bearing CF3-groups on the side amide substituents were synthesized. Due to stereoisomerism and amide rotation, such complexes have complicated behavior in solutions. Using advanced NMR techniques and X-ray analysis, their structures were completely elucidated. The possibility of the formation o...

New bicyclic unsymmetrical CNN palladium 5,6-membered pincer complex was synthesized from 3-ferrocenylmethyl-8-dimethylamino-3-azabicyclo[3.2.1]octane by its direct cyclo-palladation with Li2PdCl4 or Na2PdCl4 and sodium acetate in MeOH. The obtained complex exhibited high catalytic activity in the Suzuki cross-coupling between aryl bromides and phe...

We report the synthesis, structures, magnetic and luminescent properties of a series of three-blade propeller homoleptic lanthanide complexes [LnL3](ClO4)3·H2O·2MeCN (Ln = Eu (1), Tb (2), Dy (3), Er (4), Yb...

New ditopic ligands (L) consisting of 2-(2-pyridyl)benzothiazole and 5-pyridylmethylene-2-thioimidazol-4-one moieties linked with polymethylene chains of various lengths (compounds 4) or triazole-containing linker (compounds 9, 11) were synthesized and their coordination properties in the reactions with CuCl2 were investigated. All the obtained cop...

The oxidation reaction of 3,3′,5,5′-tetramethyl-1H,1′H-4,4′-bipyrazole in the HNO3–Fe3+ system unexpectedly resulted in the formation of 1Н-pyrazole-3,4,5-tricarboxylic acid (H3PTCA) isolated as acid sodium salt Na(H2O)2H2PTCA. The compound has a polymeric structure stabilized by rare seven-membered Н-bonded rings

Doping with transition metals is a promising way to expand the industrial applications of ionic liquids (ILs). This study reports the synthesis, structure and physicochemical properties of a novel butyl-dimethyl-(ferrocenylmethyl)ammonium bis(trifluoromethanesulfonyl)imide ([BDFA][NTf2]) IL. The thermo-gravimetric analysis combined with mass spectr...

New europium selenate tetrahydrate Eu2(SeO4)3∙4H2O was prepared by hydrothermal technique for the first time. Its crystal structure was determined by single crystal XRD. Title compound crystallize in triclinic system (Space group P 1¯, a = 6.9287(7)Å, b = 9.2547(10) Å, с = 10.8431(12) Å, α = 95.196(3) °, β = 106.825(3) °, γ = 99.240(3)°, Z = 2). Cr...

To design luminescent lanthanide complexes containing both p- and s-bonded antenna ligands in the coordination sphere, we synthesized 2,2'-bipyridine complexes of Nd, Tb and Gd with tri- and tetraphenyl substituted cyclopentadienyl ligands: [CpPh3LnCl2(bipy)(THF)] (CpPh3 = 1,2,4-triphenylcyclopenta- dienyl, bipy = 2,2'-bipyridine) and [CpPh4LnCl2(b...

A novel diarylpyrimidine derivative, 4-{[6-((2SR,4SR)-4-acetyl-4-methylpyrrolidin-2-yl)-2-(4-cyanophenoxy)pyrimidin-4-yl]oxy}- 3,5-dimethylbenzonitrile containing a pyrrolidine moiety at position 6 of the pyrimidine ring was obtained as a result of the tandem aza- Cope/Mannich reaction between 4-{[2-(4-cyanophenoxy)-6-formylpyrimidin-4-yl]oxy}-3,5-...

In this work, the solution conformations of seventeen 3,7-diacyl bispidines were studied by means of NMR spectroscopy including VT NMR experiments. The acyl groups included alkyl, alkenyl, aryl, hetaryl, and ferrocene moieties. The presence of syn/anti-isomers and their ratios were estimated, and some reasons explaining experimental facts were form...

The air- and moisture-sensitive title compound, [Tb(C 5 H 5 ) 2 (C 14 H 12 NO 2 )], was synthesized from tris(cyclopentadienyl)(tetrahydrofuran)terbium and 2-{[(2-methoxyphenyl)imino]methyl}phenol. Each Tb atom is coordinated by two cyclopentadienyl ligands in an η ⁵ -coordination mode and by one N and two O atoms of the organic ligand in a trident...

The new organometallic derivatives 1-N- and 2-N-ferrocenylmethylindazoles (1 and 2) were synthesized as ligand precursors. Direct cyclopalladation of 1 using different palladating agents (Li2PdCl4, Na2PdCl4, Pd(OAc)2/LiCl) followed by the addition of PPh3 led to the 6-membered palladacycle 3. The structures of new ferrocene ligand precursors 1 and...

Layered bismuthides of the family ATM2Bi2 are showing very interesting structural and physical properties. Here, we report crystal growth and characterization of new ternary layered bismuthides: RbCd2Bi2, RbZn2Bi2 and KZn2Bi2. Single crystals were grown by self-flux technique. As grown crystals were characterized by combination of powder X-ray diff...

A series of novel imidazole-containing ligands and their organotin complexes were synthesized and characterized by NMR, IR, MALDI and elemental analysis. Redox behavior was studied by cyclic voltammetry (CV). Antioxidant properties were estimated in model reactions of single-electron reduction (CUPRAC-test), scavenging of 2,2-diphenyl-1-picrylhydra...

Mono-3,4-diphenyl(9-anthracenyl)cyclopentadienyl dichloride complexes {[CpAntLn(thf)]2(µ2-Cl)2(µ3-Cl)3K(thf)}2 Ln= Nd, Gd, Tb, CpAnt = Ph2(C14H9)C5H2 were synthesized and structurally characterized. All the complexes were obtained in the form of tetranuclear ate complexes consisting of two [CpAntLn(thf)]2(µ2-Cl)2(µ3-Cl)3K(thf) units connected via t...

A series of europium and gadolinium complexes comprising a β-diketone moiety modified with a fluorinated side-group and thiophene ring have been designed and synthesized and a comparative study of their luminescence properties has been carried out. In this study, when the methyl side group was modified by sequential addition of fluorine substituent...

The N-arylation of N-Boc-bispidine with arylboronic acids was accomplished under the copper-catalyzed Chan—Lam—Evans reaction conditions. The reaction products were characterized by NMR spectroscopy and X-ray diffraction. The characteristic features of the transannular N⋯N interaction were investigated by X-ray diffraction.

A series of mono-, bis and tris(cyclopentadienyl) complexes of La, Nd and Tb with borohydride ligands were synthesized and structurally characterized. Various structural types of complex anions and cations containing cyclopentadienyl and borohydride ligands in the coordination sphere of Ln³⁺ have been studied by single-crystal X-ray diffraction. Fi...

A novel triiodide phase of the formamidinium cation, CH 5 N 2 ⁺ ·I 3 ⁻ , crystallizes in the triclinic space group P \overline{1} at a temperature of 110 K. The structure consists of two independent isolated triiodide ions located on inversion centers. The centrosymmetric character of I 3 ⁻ was additionally confirmed by the observed pronounced peak...

A new asymmetrical 1,1-dioxidothiomorpholinium- and morpholinium-based dicationic ionic liquid (4-ethyl-4-[3-(4-ethyl-1,1-dioxidothiomorpholin-4-ium-4-yl)propyl]morpholin-4-ium tetrafluoroborate (EtDTMC3EtM·2BF4)) was synthesized in four stages and characterized by ¹H, ¹³C, ¹H,¹H–COSY NMR, single X-ray diffraction, XPS spectroscopy and simultaneous...

It has been demonstrated that formamidinium–cesium polyiodides are facile reagents for converting metallic lead into perovskite at temperatures of 20–90 °C. For the first time, a tentative phase diagram of the [HC(NH2)2]I–I2 binary system was proposed, and sub- and supersolidus phase relations in the [HC(NH2)2]I–CsI–I2 ternary system were discussed...

The reactions of 1,3,5‐triazapentadiene 2,6‐iPr 2 C 6 H 3 NC(Ph)NC(Ph)NHC 6 H 3 iPr 2 ‐2,6 ( 1 ) with Ln(CH 2 SiMe 3 ) 3 (THF) 2 (Ln = Y, Lu) in hexane afford bis(alkyl) complexes [2,6‐iPr 2 C 6 H 3 NC(Ph)NC(Ph)NC 6 H 3 iPr 2 ‐2,6]Ln(CH 2 SiMe 3 ) 2 (THF) (Ln =Y ( 2 ), Lu ( 3 )) in 58 ( 2 ) and 62 ( 3 ) % yields. The X‐ray diffraction study reveale...

In this work, transformations of two cationic dinitrosyl iron complexes (DNICs), namely, mononuclear with N-ethylthiourea ligands [Fe(SC(NH2)(NHC2H5))2(NO)2]⁺Cl⁻∙[Fe(SC(NH2)(NHC2H5))Cl(NO)2]⁰ (complex 1) and binuclear with penicillamine ligands [Fe2(S(C(CH3)2CH(NH3)COOH))2(NO)4]SO4∙5H2O (complex 2) have been investigated in an aqueous solution in t...

A series of 2‐(hydroxyphenyl)‐1H‐benzo[d]imidazols bearing readily oxidizable 2,6‐di‐tert‐butyl‐phenol substituents and bis‐chelate Cu(II) complexes based on these ligands were synthesized. The structure of the compounds was characterized by NMR, IR, mass spectroscopy and X‐ray crystallographic analysis and redox behavior explored using ESR spectra...

A series of seven-coordinate pentagonal-bipyramidal (PBP) Cr(III) complexes with pentadentate pyridine-based ligands, 2,6-diacetylpyridine bis(4-methoxybenzoylhydrazone), H2DAPMBH (H2LOCH3) or 2,6-diacetylpyridine bis(benzoylhydrazone), H2DAPBH (H2L) and different axial ligands have been prepared. The reaction of the H2LOCH3 with CrCl2·4H2O in meth...

Recently, reactions of allylidenhydrazones with tetracyanoethylene were found to lead to cyclobutanes-products of usually unfavorable (2 + 2) cycloaddition. Herein we computationally demonstrate that the (4 + 2) product of this reaction is severely destabilized by incomplete C-N bond formation, arising from a complex interplay of substituent electr...

We report a new octahedral [Dy(OCPh3)2(THF)4][BPh4] luminescent SMM exhibiting a massive crystal-field splitting and an anisotropic barrier of 1385 cm-1. Magnetic measurements combined with ab initio analysis reveal a novel mechanism behind the high blocking barrier based on the quench of one-phonon transitions between the three low-lying crystal-f...

A series of five neutral mononuclear lanthanide complexes [Ln(HL)(L)] (Ln = Dy 3+ , Ho 3+ Er 3+ and Tb 3+) with rigid pentadentate N3O2-type Schiff base ligands, H2L H (1-Dy, 3-Ho, 4-Er and 6-Tb complexes) or H2L OCH3 , (2-Dy complex) has been synthesized by reaction of two equivalents of 1,1′-(pyridine-2,6-diyl)bis(ethan-1-yl-1-ylidene))dibenzohyd...

The interaction of the pivalate complexes of iron(iii), [Fe3O(Piv)6(H2O)3]·HPiv, and cadmium(ii), [Cd(Piv)2], in Et2O resulted in one more type of "ferric wheel" family complex, namely [Fe8(Piv)16{Cd(Piv)2}(μ-OH)8]·Et2O (1). The complex is an octanuclear iron(iii) wheel with a {Cd(Piv)2} moiety asymmetrically incorporated into the ring.

Molecular [Li2Cd2(L)2(Piv)6]·Solv (Piv = trimethylacetate anion, L = 2,4-lutidine (1), 2,2′-bipyrdine (2), 2,2’:6′,2″-terpyridine (3),·Solv = 4MeCN (2)), chain [Li3Cd(MeCN)(THF)(Piv)5]n (4) and three-dimensional polymer [Li4Cd5(H2O)4(Piv)14]n.4H2O (5) complexes were synthesized and structurally characterized. All the new molecules contain the basic...

Alkyl 2,3-dibromo-3-nitroacrylates react with arylthiols and phenols to give earlier unknown representatives of β-functionalized gem-bromonitroethenes, namely, 2-arylsulfanyl- and 2-aryloxy-3-bromo-3-nitroacrylates; their structure was characterized by IR, UV, and NMR (1H, 13C{1H}, HMQC, HMBC) spectroscopy. X-ray diffraction analysis showed that me...

New PIM-1 copolymers with 2,3,6,7-anthracenetetrayl moiety have been synthesized as fine powders from 2,3,6,7-tetrahydroxy-9,10-di(p-fluorophenyl)anthracene monomer in DMSO, with crystal structure of the monomer as well as its precursors and the product of its model side crosslinking reaction being determined using X-ray diffraction. The microporos...

A series of nine novel indigo derivatives, including diiodoindigo, octahalogenated indigoids and compounds with extended π-conjugated system, were synthesized, characterized and investigated as semiconductor materials in organic field-effect transistors (OFETs). Among them, 6,6′-diiodoindigo demonstrated the ambipolar behavior with balanced p-type...

In the cocrystalline salts [(Me5C5)2Fe]⁺I3⁻/(4-XC6H4OH) (X = Cl, I), the directionality of X⋯I−I2 halogen bonds is a significant packing factor notwithstanding their relatively low energies (∼10 kcal mol⁻¹), as compared to the fivefold stronger ionic bonding between [(Me5C5)2Fe⁺] and [I3]⁻ (∼50 kcal mol⁻¹). This adds significant details to the stru...

Organophosphate-chloride complexes [{(2,6- i Pr2C6H3-O)2POO}2LnCl(CH3OH)4]·2CH3OH, Ln = Nd (1), Eu (2), Gd (3), and Tb (4) have been obtained and structurally characterized. Their reaction with 2,2':6',2″-terpyridine leads to the formation of 1:1 adducts ([{(2,6- i Pr2C6H3-O)2POO}2LnCl(terpy)(H2O)2(CH3OH)], Ln = Eu (5), Gd (6), Tb (7) with exceptio...

A new synthetic pathway to four substituted imidazoles from readily available 2-((4-aryl(thienyl)-5H-1,2,3-dithiazol-5-ylidene)amino)phenols has been developed. Benzo[d]oxazol-2-yl(aryl(thienyl))methanimines were proved as key intermediates in their synthesis. The formation of an imidazole ring from two methanimine derivatives likely includes the o...

We report the synthesis, structure and magnetic properties’ investigations of a series of new dysprosium heteroleptic mono- and dinuclear complexes based on the association of chloride and different diazabutadiene (DAD2R = [2,6-iPr2C6H3N–CRCR–NC6H3iPr2-2,6]; R = H, Me) ligands showing different redox states. While using dianionic DAD2R ligands aff...

Refluxing of equimolar amounts of 2,2'-bipyridine (bipy) and N, N, S-tridentate basic form of the Schiff base N-[2-[[3-methyl-1-phenyl-5-thioxo-pyrazole-4-ylidenemethyl]amino]phenyl]-4-methylbenzenesulfonamide (H2L) with corresponding metal acetate hydrate (Cu, Ni, Zn, Cd) in acetonitrile-methanol solution (1:1) give rise to the formation of mononu...

The aminophosphinite pincer complex (POCNH)NiBr was found to effectively catalyze transfer hydrogenation of aldehydes and ketones with 2-propanol and KOtBu as a base, presenting a rare example of bifunctional nickel transfer hydrogenation catalysts. Transfer hydrogenation of aldehydes and ketones was found to be selective tolerating a wide range of...

We report the synthesis, structure, and magnetic investigations of the new Dy3+ heteroleptic complex [Dy(tBu4Carb)(o-Me2NC6H4CH2)2]·C7H8 (1; tBu4Carb = 1,3,6,8-tetra-tert-butyl-9H-carbazole, o-Me2NC6H4CH2)2 = o-N,N-dimethylaminobenzyl). The carbazolyl ligand exhibits an unprecedented η5 πinteraction with the magnetically anisotropic dysprosium(III)...

We report here the synthesis, structure, magnetic and photoluminescence properties of three new bifunctional Schiff‐base complexes [Dy(L1)2(py)2][B(Ph)4]·py (1), [Dy(L1)2Cl(DME)]·0.5DME (2) and [Dy(L2)2Cl]·2.5(C7H8) (3) (HL1 = Phenol, 2, 4‐ bis(1, 1‐ dimethylethyl) ‐ 6‐ [[(2‐ methoxy‐ 5‐ methylphenyl) imino] methyl]; HL2 = Phenol, 2, 4‐ bis(1, 1‐ d...

The reactions of lithium derivatives of sydnones with 1,3-dichloro-1,1,3,3-tetramethyldisiloxane have been studied. The first representatives of sydnon-4-yl substituted disiloxanes and silicon macrocyclic derivatives of sydnones were obtained and their molecular structures were studied by X-Ray and 1H, 13C, 29Si, and 15 N NMR spectroscopy.

We report the synthesis, structures, magnetic and luminescent properties of a series of heteroleptic lanthanide complexes based on a tripodal tetradentate ligand [Ln(Tpma)(NO3)3]•nMeCN (Ln = Eu (1), Tb (2), Dy (3), Er (4), n = 0.5; Yb (5), n = 0; Tpma = tris((1H-pyrazol-1-yl)methyl)amine). The europium, terbium and dysprosium analogues exhibit a la...

A facile and straightforward synthesis of unsymmetrically substituted N-aryl oxalamides from 2,2'-biphenyldiamines, 2-chloroacetic acid derivatives, elemental sulfur, and water has been developed. This protocol is distinguished by efficiency in water under metal-free conditions for N-aryl oxalamides bearing a side-chain NH2-group; it can be adapted...

We report the synthesis, structure and magnetic investigations of two new Dy3+ homoleptic ate-complexes based on different ene-diamido ligands [K(THF)2][Dy(DAD2R)2] (R = H (1), Me (2) DAD2R = [2,6-iPr2C6H3N–CR=CR–NC6H3iPr2-2,6 showing...

Aseries of cyclobutane-1,1,2,2-tetracarbonitriles contained a compound with significant activity against various cancer cell lines. The compound featured a thiosemicarbazide and the α,β-unsaturated aldehyde myrtenal in its structure and showed the highest activity against leukemia cells, the average growth inhibition against which was 88%. The prop...

The aminomethylene derivatives of pyrazole-5-one (6) and pyrazole-5-thione (7) were synthesized in the reaction of 2-aminophenol (4) with corresponding 1-phenyl-3-methyl-5-X-pyrazole-4-carbaldehyde (1, X = hydroxy) or (2, X= sulfanyl). Reaction of 2-aminobenzenethiol (5) with 1-R-3-methyl-5-sulfanyl-pyrazole-4-carbaldehydes (2, R = phenyl and 3, R...