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The coordination compounds of cobalt(II) {[Cs2Co(H2O)4(Me2Mal)2] · H2O}n (1) and {[Cs8Co36(H2O)34(OH)20(Me2Mal)30)] · 40H2O}n (2) (Me2Mal2– is the dimethylmalonic acid dianion) have been synthesized by varying the initial cobalt(II) salt (CoCl2 · 6H2O and Co(OAc)2 · 4H2O, respectively) in the reaction with cesium dimethylmalonate (reagent ratio, 1 : 2). X-ray diffraction shows that a crystal of complex 1 is built of cobalt(II) dimethylmalonate anionic layers spaced apart by aquated cesium cations, and a crystal of complex 2 is composed of 36-nuclear spherical anions with cobalt(II) atoms, cesium cations, and solvated and coordinated water molecules.

The reaction of Cd(NO3)2 · 4H2O and Eu(NO3)3 · 6H2O or Tb(NO3)3 · 6H2O with potassium 3,5-di-tert-butylbenzoate (Kbzo) and N-donor ligands (1,10-phenanthroline (phen), 2,4-lutidine (2,4-lut), 3,4-lutidine (3,4-lut), phenanthridine (phtd), 2,3-cyclododecenopyridine (cdpy), acridine (acr)) afforded heterometallic LnCd2 complexes: [EuCd2(bzo)7(EtOH)2(phen)] (2), [LnCd2(bzo)7(2,4-lut)4] (Ln = Eu (3), Tb (4)), [EuCd2(bzo)7(H2O)2(2,4-lut)2] · MeCN (5), [EuCd2(NO3)(bzo)6(EtOH)2(2,4-lut)2] (6), [EuCd2(bzo)7(H2O)(EtOH)(3,4-lut)2] · 5EtOH (7), 3[EuCd2(bzo)7(H2O)2(phtd)2] · 4phtd (8), [EuCd2(bzo)7(EtOH)3(cdpy)] (9), 2[EuCd2-(bzo)2(EtOH)4] · acr (10). The structures of complexes 2, 3, and 5–10 were determined by single-crystal X-ray diffraction. The isostructurality of complexes 3 and 4 was confirmed by powder X-ray diffraction. The structure of the trinuclear {Ln2Cd} metal core is stable and independent of the type of peripheral ligands coordinated to cadmium atoms. Photoluminescent properties of compounds 3 and 4 were studied.

The data on the synthesis and study of the crystal structure of compounds {[K2Mg2(VO)3(Bumal)6(H2O)15] · 2H2O}n (I) and {[Cd(VO)(Bumal)2(H2O)5] · H2O}n (II) are presented. According to X-ray diffraction, these compounds are formed by the anionic fragments [VO(Bumal)2(H2O)]2– with oxovanadium(IV) and two butylmalonate anions (H2Bumal is C5H10(COOH)2) coordinated via the chelate mode. In the crystals of compound I (CIF file CCDC no. 1911220), the [VO(Bumal)2(H2O)]2– anionic fragments are bound to each other by the K+ and Mg2+ cations into the 2D polymeic structure. In compound II (CIF file CCDC no. 1033008), these fragments are bound by the Cd2+ cations to form the 1D coordination polymer.

New trinuclear Cd–Ln molecular complexes [EuCd2(O2CC6F5)6(NO3)(Bipy)2] (I, Bipy is 2,2'-bipyridine) and [LnCd2(Bzo)6(NO3)(Phen)2] · 4MeCN (Ln = Tb (II), Eu (III), Bzo is anion of 3,5-di-tert-butylbenzoic acid, Phen is 1,10-phenanthroline) are studied. Their structures are determined by X-ray structure analysis (СIF files CCDC nos. 1938125 (I), 1938124 (II)) or by X-ray diffraction analysis (III), and the photoluminescence properties are studied. The reactions of complexes I and II with terephthalic acid (H2Bdc) are accompanied by the destruction of the heterometallic molecules to form 2D coordination polymers [Cd3(Bbdc)3(Bipy)2]3n · 4nMeCN · nH2O (IV) and [Cd2(Bdc)2(Phen)2]n · 2nDMF (V) (СIF files CCDC nos. 1938126 and 1937492, respectively).

The reaction of cobalt(II) chloride with potassium myrtenate (KMyr) followed by addition of 2,3-lutidine in ethanol gives the trinuclear compound [Co3(Myr)6(2,4-Lut)2] (I). The central cobalt(II) atom is linked to each of the two other metal atoms by three myrtenic acid anions. The reaction of a solution of compound I with lithium myrtenate (LiMyr) results in the formation of tetranuclear heterometallic complex [Li2-Co2(Myr)6(2,4-Lut)2] (II). Compound II is composed of two binuclear {LiCo(Myr)3(2,4-Lut)} moieties, in which the lithium(I) atoms are linked to cobalt(II) atoms by bridging myrtenate anions. The lithium atoms are connected by two oxygen atoms of acid anions. Compounds I and II were characterized by X-ray diffraction (CIF files CCDC nos. 1898096 (I), 1898097 (II)).

The electrochemical oxidation of a zero-valent metals (copper, cobalt, nickel, zinc, and cadmium) (1–5) in an acetonitrile-methanol solution containing the equimolar amounts of 1,10-phenanthroline (phen) and the 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) resulted in the formation of the mixed ligand complexes with a common formula [M(L)phen]. All compounds were characterized with C, H, N elemental analysis, FT-IR, 1H NMR, X-ray absorption spectroscopy and magnetic measurements. The structures of the complexes [Cu(L)phen] (1) and [Zn(L)phen] (4) were determined by X-ray single-crystal diffraction. In both complexes the metal centers are surrounded with imine and amide nitrogens, sulfur of thiol group of H2L and two nitrogens of phen used as co-ligand. The assignment and the nature of the bands in experimental UV–Vis spectra of adducts were analyzed using time-dependent (TD) DFT calculations.

The rare-earth metal(III) complexes [M2(piv)6(Hpiv)6] (monoclinic, P21/c, 1), [M2(piv)6(Hpiv)6]·Hpiv (monoclinic, C2/c, 2), [M(piv)3]n (trigonal, P63/m, 3), and [(Hpiv)2(iPrOH)2Sm2(piv)6]·2Hpiv (triclinic, P-1, 4), where piv is (CH3)3CCO2−, were synthesized, and their structures were determined by single-crystal X-ray diffraction (SC-XRD). The crystallization was shown to be controllable by varying the nature of the salting-out agent – the non-coordinating organic solvent in the M(OAc)3·4H2O–Hpiv system. The following bulky single-phase samples were obtained: dimers 1 or 2 with M = Pr, Nd, Sm, Eu, and Gd using hexane C6H14; dimer 1 or 1D polymer 3 with M = Y, Er, and Yb using EtOH; dimers 2 or 4 with M = Sm using iPrOH. A reversible phase transition to a commensurate modulated modification (P21/c) was observed for crystals of 1 (Pn). The magnetic properties of complexes 1a (Pr), 1b (Nd), 4 (Sm), 1d (Eu), 1f (Dy), 1 g (Ho), and 1 h (Er) were investigated.

1,10-Phenanthroline (Phen) adducts [M(L)Phen] in copper(II), cobalt(II), and zinc(II) chelates based on N,N,O-tridentate tosylamino-functionalized pyrazole-containing Schiff base (H2L), resulting from condensation of 2-tosylaminoaniline with 3-methyl-1-phenyl-4-formylpyrazol-5-ol, were obtained by electrosynthesis. The composition and structure of the mixed-ligand complexes were confirmed by elemental analysis, IR spectroscopy, and magnetochemical measurements. The structures of azomethine H2L and mixed-ligand copper(II) complex were determined by X-ray diffraction.

The recrystallization of complex [Ni9(OH)6(Piv)12(HPiv)4] (Piv– is anion of trimethylacetic acid) from a THF–MeCN (6 : 1) mixture gives a new hexanuclear compound of nickel(II): [Ni6(µ3-OH)2(Piv)10(THF)4]. Its structure (CIF file CCDC no. 1579976) exhibits rare examples of coordination of the µ2-THF and µ4-Piv ligands.

The exchange reaction of CdCl2 ⋅ 2H2O with KPiv affords cadmium(II) trimethyl acetate complexes (K[Cd6(Piv)12Cl] ⋅ 2MeCN (I), [K2Cd3(Piv)8(H2O)6] (II), and [Cd(Piv)2(Н2О)2] (III) as a mixture with complex II and [K3Cd2(Piv)7(MeCN)2]n (IV) (HPiv is trimethylacetic acid). The exchange reaction of CdSO4 ⋅ 8/3H2O with Ba(Piv)2 makes it possible to obtain complex III in a quantitative yield. Complex III can also be isolated by the recrystallization of {Cd(Piv)2} from water. The recrystallization of complex III or {Cd(Piv)2} from MeCN affords hexanuclear complex [Cd6(Piv)12(MeCN)2] (V), which transforms into complex III upon recrystallization from water. All new compounds are characterized by the data of single-crystal X-ray diffraction analysis (CIF files CCDC no. 1572202–1572206), IR spectroscopy, and C,H,N analysis.

Lithium dimethylaminomethanediphosphonate(1-) dihydrate (H 3 C) 2 HN+CH(PO 3 H)– 2 Li+·2H 2 O crystallizes from the aqueous solution at room temperature in the orthorhombic system (space group Pca2 1 , a = 9,861(2) A, b = 7,029(1) A, c = 14,946(3) A, z = 4). The crystal structure is determined by single-crystal X-ray diffraction analysis (R1 = 0,0737). The structure is constructed of zwitteranions (H 3 C) 2 HN+CH(PO 3 H)– 2 , cations Li+ and water molecules which are united together by interionic and hydrogen bonds. The zwitteranion is disordered: in the crystal there are two anions with occupancies of 0.5, which are linked together by pseudoplane, with common atom of phosphorus. The lithium cation occupying two positions with occupancies of ~ 0.5 is also disordered. The derivatography method has been used to study dehydration (t init. 110–115 °С, t min DTA 175 °С) and thermal stability (tinit. 240 °C) of the substance in the inert atmosphere. The list of wave numbers of absorption bands maxima in the IR spectrum is given. Solubility of the salt in water, in aqueous solutions of inorganic substances and in some particular organic solvents is evaluated.

A series of binuclear tetracarboxylate-linked Mn(II), Fe(II), Co(II), Ni(II), and Cu(II) complexes with 1,2-substituted pyridine, viz., 2,3-cyclododecenopyridine (L), were prepared. Study of the crystal structures of isolated compounds (CIF file CCDC nos. 1575855–1575859) revealed a distortion of the {Ni2(O2CR)4L2} binuclear moiety, manifested as a change in the NiNiN angle (151.67°), in the bridging function of two out of the four carboxylate groups (from μ2- to (κ2,μ2-)), and in the coordination environment of the metal ion (NiO5N). The results were analyzed in comparison with known data. The magnetic properties of copper(II) and nickel(II) complexes were studied. The copper(II) complex is diamagnetic as a result of strong exchange interactions between the unpaired electrons; in the nickel(II) complex antiferromagnetic exchange interactions were detected (JNi–Ni =–25 cm–1).

The heteromolecular insertion of carbon dioxide in combination with heterocumulenes, iso(thio)cyanates or N,N′-dicyclohexylcarbodiimide, into rhenium–alkoxy group bond was accomplished for the first time in relation to reactivity of rhenium oxoalkoxides. The ease of combined insertion of iso(thio)cyanate and carbon dioxide into Re–O(Me) bond is determined by the nature of the heterocumulene organic group. Indeed, if ethyl iso(thio)cyanate is used in the reaction, the insertion is reversible, whereas the reaction with PhNCS (unlike PhNCO) together with carbon dioxide leads to complete insertion into two Re–O(R) bonds to give the insertion product (OMe)10O6Re4[OC(O){N(Ph)C(S)}2-OMe]2. In similar reactions carried out with N,N′-dicyclohexylcarbodiimide, a dependence of the number of bonds participating in the inner-sphere condensation of the inserted moieties on the duration of the experiment was found for the first time. An increase in the time of synthesis from 3 to 5 h results in insertion involving six rather than three bonds, the heteromolecular insertion products being (OMe),O6Re4{OC(O)[(Hex)N=C=N(Hex)]2}3 and (OMe)6O6Re4{OC(O)[(Hex)N=C=N(Hex)]2}6, respectively.

A polymeric dinuclear copper(II) complex with a Schiff base based on 3-formyl-4-hydroxy-6-methylpyrone and 1,3-diaminopropanol-2 is synthesized. The crystal structure of the complex is determined by single crystal XRD (CCDC No. 1518681). The magnetic properties of the complex are studied. A ferromagnetic exchange interaction between copper(II) ions is demonstrated.

The N,N′-bis[chromen-2,4-dione]-3-{2′-hydroxypropylenediamine-N,N′,O,O′}copper(II) solvate complex with dimethylsulfoxide is synthesized. The crystal and molecular structure of the complex is determined by X-ray diffraction. The coordination polyhedron of the copper atom is a square pyramid with the base formed by two oxygen atoms and two nitrogen atoms of the ligand and a vertex consisting of the oxygen atom of the coordinated DMSO molecule.

The results on the synthesis and study of the crystal structures of compounds based on anionic fragments {VO(Cbdc)2}2– formed by oxovanadium(IV) (vanadyl, VO2+) and two chelate-bound anions of cyclobutane-1,1-dicarboxylic acid (H2Cbdc = C4H6(COOH)2) are presented. The use of ammonium cation NH4+ as a counterion in the synthesis leads to the formation of the mononuclear complex (NH4)2[VO(Сbdc)2(H2O)] · 2H2O (I). In the case of K+ cation, compound [K4(VO)2(Сbdc)4(H2O)4] n (II) with the 3D polymeric crystal structure is formed. The reaction of compound II with Mg(NO3)2 · 6H2O in an aqueous solution involves the partial substitution of K+ by Mg2+ cations to form 1D polymeric compound {[KMg0.5(VO)(Сbdc)2(H2O)6.5] · 3H2O} n (III), while a similar reaction of compound I does not afford the product of substitution of NH4+ by Mg2+ cations (CIF files CCDC 1551021–1551023 for compounds I–III, respectively).

The binuclear copper(II) complex with bis-azomethine, viz., the product of condensation of 1,3-diaminopropanol-2 with 4-hydroxy-3-formylcoumarin (H3L), of the composition [Cu2L(μ2-CH3COO)] (I) is synthesized and studied. Complex I is characterized by the exchange interaction of the antiferromagnetic type (2J =–112 cm–1), which is switched to the ferromagnetic one (2J = +106 cm–1) after the recrystallization of the complex from dimethyl sulfoxide (DMSO) to form solvate [Cu2L(μ2-CH3COO)(μ2-DMSO)] · 0.5DMSO (II). The structure of solvate II is studied by X-ray diffraction analysis (CIF file CCDC no. 982198). The difference in the exchange character is explained by the stabilization by the μ2-coordinated DMSO molecule of a distorted (roof-shaped type) conformation of the polydentate ligand and the complex as a whole, unlike the symmetric conformation characteristic of the nonsolvated complex. The data obtained are compared with those on similar compounds synthesized earlier and with the quantum chemical modeling results for the exchange interaction in the framework of the DFT-BS approximation.

Tetranuclear copper(II) complex [Cu4L2(OOC(CH2)6COO)] (I) based on bis(azomethine), condensation product of 1-phenyl-3-methyl-4-formylpyrazolone-5 with 1,3-diaminopropanol-2, is synthesized. The structure of its DMSO-adduct (Ia) is determined by X-ray diffraction analysis (CIF file CCDC 1447891). The complexes contain two binuclear fragments bonded by the µ4-1,6-hexadicarboxylate linker. The magnetic exchange interaction in complex I is antiferromagnetic (2J =–155 cm–1), whereas that in complex Ia is ferromagnetic (2J = 129 cm–1), which is due to different conformations of the metallochelate cycles.

The synthesis of a series of adducts of 2-amino-1-ethylbenzimidazole (L1) in Cu(II), Co(II), Zn(II) and Ni(II) chelates of the N, N, S tridentate basic form of the tosylamino functionalized pyrazol containing Schiff base N-[2-[[3-methyl-1-phenyl-5-thioxo-pyrazole-4-ylidenemethyl]amino]phenyl]-4-methylbenzenesulfonamide (H2L) with common formula [M(L)L1] was performed. The compounds were characterized with C, H, N elemental analysis, FT-IR, 1H NMR, X-ray absorption spectroscopy and magnetic measurements. Crystal structure of nickel complex [Ni(L)L1] showed that the 2-amino-1-ethylbenzimidazole co-ligand is coordinated through the endocyclic nitrogen atom of pyridine type. The assignment and the nature of the electronic transitions observed in the UV–Vis spectra of chelates were analyzed using time-dependent (TD) DFT calculations.

The phase homogeneity of diphenylphosphinic acid (С6H5)2PO2H purified by benzol or aqueous solution recrystallization is proved by X-ray powder diffraction analysis. The thermal behavior of the compound is studied by method of derivatography. The solubility of the compound in the multiple inorganic and organic solvents media is estimated. The results of experimental study of diphenylphosphinic acid decomposition in the reactions with oxidants of different chemical nature (nitric acid, permanganate, dichromate, vanadate, bismuthate, cerium (+4), hexacyanoferrate (+3), hydrogen peroxide, peroxydisulfate, hypochlorite, sodium benzenesulfonemonochloramide, bromate, periodate, iodate, manganese dioxide, lead dioxide) in aqueous media are given. Large amount of strong oxidant is required for breaking of both C–P chemical bonds in the molecule of diphenylphosphinic acid.

2-Amino-1-ethylbenzimidazole (L1) adducts with copper(II), cobalt(II), and zinc(II) chelates of N,N,S tridentate tosylamino-functionalized mercaptopyrazole-containing Schiff base (H2L), resulting from condensation of 2-tosylaminoaniline with 1-phenyl-3-methyl-4-formylpyrazole-5-thiol, with the general formula [ML · L1] were obtained by electrochemical method. The structure and composition of the complexes were confirmed by the data of C, H, N elemental analysis, IR and 1H NMR spectroscopy, and magnetochemical and X-ray spectral measurements. The mononuclear structure of the copper(II) adduct with coordination bond located on the pyridine type endocyclic nitrogen atom of 2-amino-1-ethylbenzimidazole was proved by X-ray diffraction.

New 1D polymers with general formula [Ln(4-phbz)3]n, where Ln = Sm, Eu, Gd, Tb, Dy, Ho, and 4-phbz is the 4-phenylbenzoate anion, were synthesized by the reaction of Ln(NO3)3∙xH2O, 4-phenylbenzoic acid and dry KOH. Thermal analysis shows that [Eu(4-phbz)3]n is thermally stable in an inert atmosphere up to 350 oC and melts at 297 oC. It was shown that the 4-phenylbenzoate anion (E(T1) ~ 22500 cm-1) in [Ln(4-phbz)3]n can play the role of an antenna and sensitize the luminescence of Eu3+ and Tb3+ ions. Analysis of magnetic data of the [Gd(4-phbz)3]n complex reveals weak antiferromagnetic coupling between Gd3+ ions (J = -0.053 cm-1). The [Dy(4-phbz)3]n compound shows noticeable frequency-dependent χ'' signals indicating slow magnetic relaxation and single-molecule magnet behavior with the energy barrier of ΔEeff/kB = 5 K.

Copper, nickel, and cobalt complexes of the N,N,S-tridentate tosylamino-functionalized mercaptopyrazole Schiff base were obtained by an electrochemical method. The structure and composition of the metal chelates were characterized by C, H, N elemental analysis data and IR and 1H NMR spectroscopy. More data on the structures of the complexes were obtained by magnetochemical and X-ray absorption spectroscopy measurements. The mononuclear structure of the copper(II) complex was confirmed by X-ray diffraction (CIF file CCDC no. 1473320).

The reaction of 4-formyl-5-mercaptopyrazole with thiosemicarbazides in methanol has afforded novel disulfide derivatives of thiosemicarbazones, and their structure has been studied by NMR and IR spectroscopy. X-ray diffraction analysis of [5,5'-dithiobis(4-formyl-3-methyl-1-phenylpyrazole)]-4-allylthio-semicarbazone has shown that it exists as a dimer with two molecules linked via the disulfide S–S bridge between the heterocycles in the crystal.

The structure of a samarium(III) complex with acylhydrazone of N-(2-hydroxyphenyl)iminodiacetic acid and 5-hydroxy-3-methyl-1-phenyl-4-formylpyrazole (Н5L) of the composition [Sm2(Н3L)3]·С2Н5ОН··10Н2О has been determined by single crystal X-ray diffraction. It has been found that in the dinuclear complex the coordination polyhedra have the geometry of a slightly distorted tri-capped trigonal prism and are linked with three iminodimethylene bridges arranged in a triple helix.

The chemical and electrochemical syntheses of the zinc (I) and cadmium (II) complexes are carried out on the basis of the tridentate Schiff base (H2L), the condensation product of (2-tosylaminoaniline) N-(2-aminophenyl)-4-methylbenzenesulfunamide with 1-phenyl-3-methyl-4-formylpyrazole-5-thiol. The structures and compositions of the synthesized metallochelates are proved by the data of C, H, and N elemental analyses, IR spectroscopy, and 1H NMR spectroscopy. X-ray absorption spectroscopy is used to determine the structure of the zinc complex. The binuclear structure of the cadmium complex is confirmed by the X-ray diffraction data (CIF file CCDC no. 1471159). The optical properties of H2L and the zinc and cadmium complexes in dimethyl sulfoxide (DMSO) solutions are studied.

3-{[Aryl(hetaryl)amino]methylene}chromane-2,4-diones (HL) were synthesized and used for chemical and electrochemical synthesis of Cu(II), Ni(II), and Co(II) complexes of the general formula ML2, as well as the ZnLOOCCH3 complex. The structure of the complexes was studied by IR, 1Н NMR, and X-ray absorption spectroscopy. Density functional theory (DFT) calculations showed that the energetically most favored form of compounds HL is an aminoketone tautomeric form. The crystal structure of the solvate of bis-{3-[(4-methylanilinato)methylene]chromane-2,4-dionato}copper(II) with two DMF molecules was determined by X-ray diffraction analysis.

Chemical and electrochemical syntheses of the zinc(II) and cadmium(II) complexes with the tetradentate Schiff base (H2L), the condensation product of 2-N-tosylaminobenzaldehyde with diaminodipropylamine, are carried out. The structures, compositions, and properties of the synthesized metal complexes are studied by elemental analyses, IR spectroscopy, 1H NMR, UV spectroscopy, X-ray absorption spectroscopy, and quantum-chemical calculations. The structure of the cadmium(II) complex is determined by X-ray diffraction analysis (CIF file CCDC no. 1446393). The cadmium(II) and zinc(II) complexes exhibit luminescence in a CH2Cl2 solution in the blue spectral range (λPL = 425–428 nm) with the photoluminescence quantum yields ϕ = 0.20 and 0.75, respectively.

The crystal structure of TiF4[(Ph2P(O)CH2CH2C(O)NMe2)] chelate (I) was studied by X-ray crystallography, which revealed four crystallographically independent complex molecules of similar structure (1–4). It was found that the molecules are only slightly different in the bond lengths between the coordinated atoms and the central titanium ion and considerably different in the geometry of the seven-membered TiOPCCCO chelate ring. The geometry of the chelate rings was found to be almost identical in each pair of complexes 1, 2 (A) and 3, 4 (B), and a conclusion was drawn on the presence of two conformational isomers (A and B) of the chelate complex. Quantum chemical calculations of the relative thermodynamic stability of molecules 1–4 were performed, and their geometry optimization led to one theoretical structure. The comparison of the chelate ring geometry in the theoretical structure and in conformers A and B revealed that the conformation of the theoretical chelate ring coincides with that of conformer A.

A new radical cation salt of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) with iron(III) bis(1,2-dicarbollide) 8,8´-dichloro derivatives, that is (BEDT-TTF)2[8,8´-Cl2-3,3´-Fe-(1,2-C2B9H10)2], was synthesized. Its electroconducting and magnetic characteristics were studied, molecular and crystal structures were determined. The electroconductivity of crystals at room temperature was σ293 ~5 Ω–1 cm–1, which is close to the corresponding value for the salt of cobalt bis(1,2-dicarbollide) dichloro derivative and is considerably higher than the electroconductivity of a similar salt of unsubstituted iron bis(1,2-dicarbollide). The measurements of magnetic susceptibility at 2—300 K showed that this salt is paramagnetic.

The reaction of the freshly precipitated oxovanadium(IV) cyclo-hexamethylenedithiocarbamate complex with [AuCl4]– anions in a 2 M HCl solution is studied. The water-soluble heterovalent complex ([Au{S2CN(CH2)6}2]3[AuCl2]2Cl]) n (I) is formed due to the redox reaction. According to the X-ray diffraction data, structure I contains two species of complex cations [Au{S2CN(CH2)6}2]+ as conformers performing different structural functions: non-centrosymmetric cations and centrosymmetric cation B in a ratio of 2: 1. Cations A form centrosymmetric dimers [Au{2S2CN(CH2)6}4]2+ due to pairs of symmetrical secondary bonds Au…S. The aurophilic Au…Au and secondary Au…S interactions that occur between the complex cations and anions in crystal result in the formation of a polymer network.

The reaction products of [Cd(piv)2] (piv is–O2CBut) with isoquinoline (iqn), 2,4-lutidine (lut), phenanthridine (phend), 2,3-cyclododecenopyridine (cpy), and triethylamine (Et3N) were synthesized and their structures were determined. The steric factors were found to play a more important role in cadmium(ii) pivalate complexes compared to 3d metal carboxylates in the +2 oxidation state. The reaction of [Cd(piv)2] with isoquinoline produces only the mononuclear complex [Cd(piv)2(iqn)3] (1). The reaction of [Cd(piv)2] with pyridine derivatives bearing a bulky substituent at the α position is accompanied by the formation of symmetrical dinuclear complexes of the composition [Cd2(piv)4(L)2]. In the complexes with L = lut (2) or phend (3), the cadmium(ii) atoms are linked by two chelating-bridging carboxylate groups; in the complex with L = cpy (4), by four bidentate-bridging groups. The reaction of [Cd(piv)2] with Et3N in a solution of MeCN gives the centrosymmetric linear trinuclear complex [Cd3(piv)6(Et3N)2] (6); in a mixture of benzene and hexane, the ionic compound (HEt3N)[Cd2(piv)5(H2O)] (7). The crystal structures of all synthesized compounds were determined by X-ray diffraction.

Heterometallic malonate complexes [Ag2Ni(H2O)2(R2mal)2]n (R2mal2– is the dimethylmalonate dianion (Me2mal2–) (1) or the cyclobutane-1,1-dicarboxylate dianion (Cbdc2–) (2)) and [Ag2Cu(H2O)(Me2mal)2]n (3) were synthesized. The bis-chelate fragment {M(R2mal)2} (M = Ni, Cu) composed of two dianions of an acid and a 3d metal atom is the structure-forming unit of these complexes. The mononuclear fragments are linked by silver(I) atoms, which are involved in argentophilic interactions, to form 2D coordination polymers.

Reactions of vanadyl sulfate (VOSO4∙3H2O) with dimethylmalonic (H2Me2mal = = C3H6(CO2H)2), cyclobutane-1,1-dicarboxylic (H2cbdc = C4H6(CO2H)2), or butylmalonic acid (H2Bumal = C4H10(CO2H)2) and Li2CO3 in a ratio of 1: 2: 2 afforded novel coordination polymers of similar compositions ([Li2(VO)(Me2mal)2] n (1), [Li2(VO)(Me2mal)2(EtOH)-(H2O)] n (2), [Li4(VO)2(cbdc)4(H2O)7] n (3), and [Li2(VO)(Bumal)2(H2O)5.5] n (4)) but different structures. The crystal structures of the compounds containing the Me2mal2– and Bumal2– anions depend on the solvent nature.

Conditions for chemical assembly of new heterometallic trinuclear pivalates [Cd2M(piv)6L2] (M = Mg, Ca, or Sr; piv is pivalate) were found. Reactions with the nonchelating ligand 2,4-lutidine (lut) gave the crystals of heterometallic complexes [Cd2M(piv)6(lut)2] (M = Mg (1), Ca (2), and Sr (3)). With the chelating ligand 1,10-phenanthroline (phen), only the homometallic dimer [Cd2(piv)4(phen)2] (4) was obtained under these conditions. Yet heterometallic trinuclear complexes with 1,10-phenanthroline ([Cd2Mg(piv)6(H2O)(phen)2] (5), [CaCd2(piv)6(phen)2] (6), and [Cd2Sr(piv)6(phen)2]∙2MeCN (7)) were synthesized by reactions of phen with complexes 1—3. For all the complexes obtained, the molecular and crystal structures as well as the details of their molecular architecture were determined. The thermal behavior of aqua complex 5 was studied by TG and DSC. The complex eliminated the water molecule between 130 and 180 °C with a high endothermic effect (Q = 101 kJ mol–1) due to (1) intramolecular hydrogen bonds that stabilize its molecular architecture and (2) subsequent structural rearrangements.

The Dy(III) binuclear complex with N4O-donor 2,6-diformyl-4-tert-butylphenol bis-1′-phthalazinylhydrazone (H3L) of the composition [Dy2(H2L)3](NO3)3 · 3C2H5OH (CIF file CCDC 1048418) is synthesized and structurally characterized. In the complex cation [Dy2(H2L)3]3+, ligands H2L− form a three-blade helix around the Dy(III) ions. Both right-side (Δ configuration) and left-side (Λ) helicates are presented in crystal in an equimolar ratio. The magnetic properties of the complex are studied.

The synthesis and crystal structures of the polymeric compounds of vanadyl (VO2+) and alkaline-earth metal cations (Sr2+ and Ca2+) with the anions of substituted malonic acid analogs, R(COOH)2, were described. Reactions of vanadyl sulfate (VOSO4 · 3H2O) with calcium and strontium salts of cyclopropane-1,1-dicarboxylic (H2Cpdc, C3H4(COOH)2), cyclobutane-1,1-dicarboxylic (H2Cbdc, C4H6(COOH)2), and butylmalonic acids (H2BuMal, C4H10(COOH)2) gave polymeric structures with different (from 1D to 3D) dimensionality. The structure and dimensionality of the compound depends on the size of the substituent in the carboxylate dianion and the radius of the alkaline-earth metal ion.

Presented are the results of the construction of statistical models of the time series of air pollutants (particulate matter with the size of less than 10µm (PM10), CO, and NO2) for the network of automatic stations of air pollution control over Moscow megalopolis. The multiple nonlinear regression of pollutant concentration to external factors (meteorological and other) and values of concentration on previous days are taken as the statistical model of the time series of the average daily concentration of a certain pollutant. The nonlinear nature of the models of the time series can be caused with the dependence of pollutant concentration on wind speed and with other factors. Nonlinear regression based on the relatively short learning samples was used for simulating the series of average daily concentration of pollutants. The computations demonstrated that this gives much higher correlation between the computed and observed values of concentration and smaller standard deviation as compared with the model of inertial forecasting.

The copper(II) complexes [CuL1(NO3)] · CH3OH and [CuL2Cl] · CH3OH (L1 is 3,5-di-tert-butylsalicylal 1′-phthalazinyl hydrazone, and L2 is 2-N-tosylaminobenzal 2-imidazolinyl hydrazone) forming hydrogen-bonded dimers in a crystal were synthesized. A weak antiferromagnetic exchange interaction transmitted through extensive linkers incorporating the N–H···O hydrogen bond (2J is–3.0 and–2.6 cm–1, respectively) was recognized by EPR spectroscopy and low-temperature magnetochemistry.

Dysprosium(iii) and neodymium(iii) complexes with aliphatic dicarboxylic acid bispicolyl-amidrazones were synthesized and studied. X-ray diffraction data showed that the compounds under study have a binuclear structure, in which the coordination polyhedra are bound by two aliphatic bridges. When excited with UV radiation, neodymium complexes exhibit weak ionic photoluminescence, while no luminescent activity was shown by dysprosium complexes. The temperature dependence of magnetic susceptibility of dysprosium complexes was studied.

Three novel dinuclear copper(II) complex with spacer-armed bispicolylamidrazone ligands were synthesized and characterized by elemental analysis, UV–Vis and IR-spectroscopy and X-ray crystal analysis. Structural analysis demonstrated quite long distances (6–8 A) between copper(II) ions. Despite these long distances, antiferromagnetic interaction between paramagnetic centers was found. Temperature dependences of magnetic susceptibility and EPR studies are in agreement with an antiferromagnetic dinuclear behavior in solid state yielding exchange parameters of −2 J of 1.47–5.9 cm −1 .

The results on the synthesis and study of the crystal structures of molecular complexes of transition metals with anions of α- and β-naphthoic acids and monodentate N-donor ligands (MeCN, 2,3-lutidine) are presented. The compositions and structures of the isolated complexes are determined by the following factors: steric hindrances, intermolecular interactions of the aromatic fragments, and the electronic structure of the metal center.

The binuclear copper(II) complex [Cu2(L)(Mp)(H2O)((CH3)2SO)] (Mp is 6-methoxypurinate anion) with the heterocyclic azomethine ligand, which is the condensation product of 1,3-diaminopropan-2-ol and 4-hydroxy-3-formylcoumarin (H3L), is synthesized and structurally characterized (CIF file CCDC no. 982199). The temperature dependence of the magnetic susceptibility is measured and shows a significant exchange interaction of the antiferromagnetic type (2J = −348 cm−1) in the compound. This sharply distinguishes the new complex from the earlier studied compounds with a similar exchange fragment characteristic of the ferromagnetic exchange. The antiferromagnetic exchange parameter is calculated by the quantum-chemical DFT method in the broken symmetry approximation.

Antiferromagnetic interactions between the Co2+ or Ni2+ ions were found in complexes [(μ3 ‐ L)2Co 5 II (μ ‐ OH)2(Piv)7(NO3)] and [(μ3 ‐ L)2(HPiv)Ni 4 II (μ3 ‐ OH)2(Piv)4(NO3)2] (Piv– = pivalic acid anion, L = 1,1′-dipyridazinylferrocene) possessing a metal core with distorted rhombic topology M4(μ3-OH)2. In contrast to the case of symmetrical analogs, the signs of all the exchange interaction parameters J were determined unambiguously.

2-N-Tosylaminobenzaldehyde ferrocenoylhydrazone was synthesized. The crystal structure of the hydrazone was shown to include two independent molecules differing in mutual orientation of the tosyl and ferrocene fragments. Quantum-chemical simulation of the hydrazone tautomerism was performed. Its complexes with Cu(II), Ni(II), Zn(II), and Cd(II) were synthesized and investigated.

The structures of iron(III) and nickel(II) complexes with the composition [FeL2]Cl·H2O (1) and [Ni(HL′2)]·DMSO·0.5H2O (2), where L and HL′ are monodeprotonated residues of 1′-phthalazinylhydrazones of 2-acetyl benzimidazole and 1-phenyl-3-methyl-4-formyl-5-hydroxypyrazole respectively, are determined using single crystal X-ray diffraction analysis. Both compounds crystallize in the monoclinic symmetry. The Fe(III) and Ni(II) ions in the complexes have octahedral N6 and N4O2 donor environments respectively. Due to intermolecular hydrogen bonds, the molecules of the complexes form corrugated (complex 1) and linear (complex 2) molecular chains in the crystal.

Reactions of coordinated ligands in uranyl hydroxylaminate complexes with benzaldehyde were studied. Methods of the synthesis of uranyl complexes containing E and Z isomers of benzaldehydoxime were developed. The structures of [UO2((E)-C7H6NO)2{(CH3)2SO}2] and [UO2((Z)-C7H6NO)2{(CH3)2SO}2] were determined by X-ray diffraction.

2-N-Tosylaminobenzaldehyde ferrocenoylhydrazone (H2L) and the octahedral nickel(II) complex [Ni(HL)2] · 2CH3OH (I) are synthesized and structurally characterized (CIF files CCDC 981876 (H2L) and 981877 (I)). The crystal structures of both compounds include two independent molecules with different mutual orientations of the tosyl and ferrocene fragments. In a single crystal of H2L, the independent molecules are joined by intermolecular hydrogen bonds into infinite linear chains extended along the crystallographic axis x. The π-stacking interaction between the cyclopentadienyl rings is observed along with hydrogen bonds in a single crystal of complex I.