Seven new heterometallic 3,5-di- tert -butylbenzoate complexes with a {Co 2 Ln} metal core were synthesised and characterised by means of X-ray diffraction. Three of these complexes exhibit SMM behavior.

Five new heterometallic carboxylate complexes of the composition [Co2Li2(A)6(L)2] (L = 4-phenylpyridine, A = 2-furoate anion (1); L = 2,2'-bipyridine, A = 2-furoate anion (2), 3,5-di-tert-butylbenzoate anion (3); L = quinoline, A = 3-cyanobenzoate anion (4), 4-cyanobenzoate anion (5)) were synthesized. The structures of all compounds were determined by single-crystal X-ray diffraction. When monodentate N-donor ligands are replaced by chelating 2,2'-bipyridine, the coordination polyhedron of cobalt ions changes from a distorted tetrahedron to a distorted octahedron. Complexes 1-4 are field induced single-molecule magnets. Mechanisms of slow magnetic relaxation are discussed taking into account both experimental data and quantum chemical calculations.

A series of heterometallic carboxylate complexes [Co2Ln(NO3)(piv)6(bpy)2] (Ln = La (1), Eu (2), Gd (3); piv is pivalate-anion, bpy is 2,2′-bipyridine) was synthesized and characterized by means of single crystal as well as powder X-ray diffraction. Compounds 1 and 2 are field-induced single molecule magnets in which slow magnetic relaxation mainly attributed to the Raman and quantum tunneling of the magnetization (for 1) or Raman and direct (for 2) mechanisms which is typical for five-coordinated Co(II) ions. Compound 3 does not show single molecule magnet behavior.

The results of investigation of the heterometallic trinuclear Zn2Ln and Zn2Ca carboxylate coordination compounds are systematized in the review. The methods of the synthesis, structural peculiarities, and some physicochemical properties are discussed.

The interaction of preorganized iron(II) pivalate complexes with aromatic N-donor ligand (pyridine (py) or 2,2′-bipyridine (bpy)) and 1,4-diaminobutane (dab, putrescine) in anhydrous acetonitrile yielded a new 2D coordination polymer [Fe(piv)2(dab)2]n (1, piv = Me3CCO2–). The molecular structure of 1 in crystal was determined by single-crystal X-ray diffraction analysis and ATR-FTIR spectroscopy.

Reactions of anhydrous Zn(II) iodides with redox-active 1,4-diaza-1,3-butadiene (DAD) and its bis(imino)acenaphtene (BIAN) derivatives in absolute acetonitrile yielded a series of new complexes: [(Mes-DAD)ZnI2] (1), [(dpp-DAD)ZnI2] (2), and [(dpp-BIAN)ZnI2] (3). Single crystals of all compounds were obtained, and their molecular structures were unambiguously determined by X-ray diffraction analysis. Purity of bulk samples in solid state was confirmed by PXRD. Stability of the complexes in solution was investigated by means of UV-Vis and NMR spectroscopy. Cyclic voltammetry revealed two or three quasi-reversible reduction waves in the cathodic region for complexes 1–3. The ability of 3 to accept up to three electrons highlights the potential of these compounds as electrocatalysts for reductive transformations.

Получен моноядерный комплекс состава [Zn(phbz)2(phen)] (1, Hphbz. = 4-бифенилкарбоновая кислота, phen – 1,10-фенантролин), структура которого установлена методом рентгеноструктурного анализа. Комплекс дополнительно охарактеризован методами рентгенофазового анализа, ИК и ЯМР-спектроскопии. Теоретическое моделирование (DFT B3LYP/Def2-TZVP) процесса димеризации комплекса 1 показало, что невысокая энергия стабилизации гипотетического биядерного соединения [Zn2(phbz)4(phen)2] может являться одной из причин отсутствия экспериментальной фиксации димерных структур такого типа.

Heterometallic d-4f coordination complexes are of paramount interest in modern coordination chemistry because of their potential applications in organic light-emitting devices and spintronic materials. Here we report the synthesis and thorough investigation of Ln and M=Ln (M = Zn, Cd; Ln = Sm, Eu, Gd, Tb) molecular complexes based on 2-furancarboxylic acid anion (Hfur): [Ln(2)(NO3)(2)(fur)(4)(DME)(2)] (Ln = Eu, Gd, Tb; DME is dimethoxyethane) and [M(2)Ln(2)(NO3)(2)(fur)(8)(bpy)(2)] (M = Zn, Cd; Ln = Eu, Gd, Tb, Sm; bpy is 2,2 '-bipyridyl). The structure and isostructural nature of compounds were determined based on the single-crystal and powder X-ray diffraction data. The photophysical properties of the obtained compounds were studied in detail: The energies of the triplet levels of the furoate anion and d-blocks {M(fur)(2)(bpy)} (M = Zn, Cd), the relaxation times of the excited states, and the quantum yields were determined. Critical step from Ln complexes to Zn=Ln and Cd=Ln (Ln = Eu, Tb) is accompanied by an increase in quantum yields, which correlates with a change in the energy of the triplet level of the aromatic part of the complexes and with the results of quantum chemical calculations indicating different schemes for the origination of triplet levels in M=Ln compounds.

A new crystal modification of the N-heterocyclic carbene 1,3-bis(2,6-di-isopropylphenyl)-4,5-dichloroimidazol-2-ylidene (IPrCl, 1 ) is obtained and structurally characterized. The hydrolysis of this compound leads to the formation of the (IPrClH) + Cl – ( 2 ) hydrochloride. The [Co 3 (Piv) 4 Cl 2 (IPrCl) 2 ]·2C 7 H 8 ( 3 ·2C 7 H 8 ) mixed-ligand complex is synthesized by the interaction of the [Co(Piv) 2 ] n cobalt pivalate with IPrCl and is characterized by XRD.

Методом теории функционала плотности (DFT B3LYP/Def2-TZVP) исследованы геометрические характеристики и термодинамическая устойчивость производных пивалата цинка(II) с функционализированными N-гетероциклическими карбенами R-NHC-X (R= Dipp, tBu, Mes, iPr; X = OMe, H, Br, CN). Показано, что ключевую роль в образовании координационных соединений различного состава ([Zn(Piv)2(R-NHC-X)] или [Zn(Piv)2(R-NHC-X)2]) играют стерические препятствия, создаваемые объемными группами R при атомах азота в карбенах. Введение электроноактивных групп X в положения 4 и 5 карбенов оказывает незначительное дестабилизирующее влияние на устойчивость образуемых аддуктов.

Imidazolium salts with complex anions [Co2Li2(Piv)8]2– are formed as undesirable products of the reactions of heterometallic compound [Co2Li2(Piv)6(Py)2] with N-heterocyclic carbenes ItBu and IPr. The study of the magnetic properties of complex (HItBu)2[Co2Li2(µ2-Piv)6(κ1-Piv)2] shows that this compound is a single molecule magnet. Slow magnetic relaxation in the complex occurs due to a combination of the direct and Raman mechanisms.

The reactions of calcium hydroxide with pivalic, 1-naphthoic, and 2-furancarboxylic acids afford the corresponding polymeric calcium carboxylates. Depending on the crystallization conditions, calcium pivalate is isolated as two different coordination polymers: [Ca3(Piv)6(DMF)2]n · 0.635nC6H6 · 0.365nDMF (I) and [Ca(Рiv)(H2O)2.333(DMF)0.666]n · nРiv·0.333H2O (II). The synthesized calcium 1-naphthoate contains coordinated water molecules [Сa(Naph)2(H2O)2]n (III), and calcium furoate [Ca(Fur)2]n (IV) contains no ancillary ligands. The structures of compounds I–IV are determined by X-ray diffraction (XRD) (CIF files CCDC nos. 2342790–2342793, respectively). The structures of compounds I–III are characterized by the 1D polymeric structure, and compound IV is the 3D polymer.

The reaction of potassium hydride with 2,3,4,5,6-pentafluorobenzamide (FBAm) in dimethoxyethane results in activation of the C–F bond in the para-position to the C(O)NH2 group followed by dimerization of FBAm to form a potassium salt with one free amide group. The structure of the binuclear reaction product (DME)2K+[C6F5–C(O)N–C6F4–C(O)NH2]–2 (I) was determined by X-ray diffraction (CCDC 2311402), the purity of the product was confirmed by NMR spectroscopy.

A mononuclear complex [Zn(phbz) 2 (phen)] ( 1 , Hphbz = 4-biphenylcarboxylic acid, phen is 1,10-phenanthroline) is obtained, and its structure is determined by single crystal X-ray diffraction (XRD). It is additionally characterized by powder XRD, IR and NMR spectroscopy. The theoretic simulation (DFT B3LYP/Def2-TZVP) of the dimerization process of the complex shows that one of the reasons for the lack of experimental detection of dimeric structures of this type may be a low stabilization energy of the hypothetical binuclear compound [Zn 2 (phbz) 4 (phen) 2 ].

A series of non-porous zinc-containing coordination compounds with mono- and polydentate ligands has been used to produce carbon materials with a hierarchical porous structure. Adjustment of the carbonization mode enables to increase the target product yield by an average of three times. The obtained carbons have a combination of micro- and mesopores with a pronounced maximum at 3.5 nm. The gas-sorption behavior of the obtained carbons has been studied over a wide range of temperatures and pressures. It has been established that the amount of excess adsorption for hydrogen and methane reaches 2.7 and 15 wt%, respectively. The extension of the proposed approach to the use of simple bimetallic complexes as precursors may be promising for obtaining effective catalysts based on a carbon matrix with controlled porosity and encapsulated nanoscale particles of a catalytically active metal.

The interaction of the binuclear complex [Zn2(Рiv)4(Рhen)2] with water in toluene or acetonitrile results in its monomerization with the formation of compound [Zn(Рiv)2(H2O)(Рhen)], the crystal structure of which is determined by XRD (CIF file CСDC no. 2374361). The individual character of the formed crystalline phase is confirmed by powder XRD. Nanoparticles of zinc peroxide/hydroxide are proposed to be used as a water source for the obtaining of single crystals of [Zn(Рiv)2(H2O)(Рhen)] suitable for XRD.

A new azomethine compound 4-methyl-N-[2-pentafluorophenyliminomethyl)phenyl]methylbenzenesulfamide and a Cu(II) complex based on it are obtained and characterized by 1H NMR, IR spectroscopy and the elemental analysis. Crystal structures of azomethine and its complex are analyzed by single crystal X-ray diffraction (XRD). From the single crystal XRD data it is found that the Cu(II) complex crystallizes in the triclinic space group P1̅ . The unit cell contains two crystallographically independent mononuclear molecules with similar geometries. In the complex, copper ions have a distorted tetrahedral environment of four nitrogen atoms, which is formed by two bidentate coordinated azomethine ligands. From magnetic measurements it is found that the Cu(II) complex is paramagnetic.

Geometric characteristics and the thermodynamic stability of zinc(II) pivalate derivatives with functionalized N-heterocyclic carbenes R–NHC–X (R= Dipp, t-Bu, Mes, i-Pr; X = OMe, H, Br, CN) are studied using the density functional theory (DFT B3LYP/Def2-TZVP). It is shown that formation of coordination compounds ([Zn(Piv)2(R–NHC–X)] or [Zn(Piv)2(R–NHC–X)2]) of various compositions is mainly determined by steric hindrances created by the bulky groups R at the nitrogen atoms in carbenes. The introduction of electron-active groups X into carbene positions 4 and 5 slightly diminishes the stability of the resulting adducts.

The reaction of the heterometallic complex [Zn2Ca(piv)6(py)2] (piv is pivalate anion, py is pyridine) with isophthalic acid (1,3-H2bdc) under the solvothermal conditions afforded a series of new ZnCa coordination polymers [Zn2Ca(DMF)2(1,3-bdc)3]n • •n(DMF) (1), [Zn3Ca3(H2O)5(DMF)(1,3-bdc)6]n • 3n(C6H6) • 3n(DMF) (2), and [Zn4Ca3(H2O)4(NMP)(1,3-bdc)8]n (3, NMP is N-methylpyrrolidone). The structures of the new compounds were determined by single-crystal X-ray diffraction. Depending on the conditions of the synthesis and crystallization, porous coordination polymers with different structures and composition were obtained. The use of poorly soluble zinc iso-phthalate as one of the starting compounds in the reaction with calcium nitrate enabled the preparation of single-phase complex 1 in amounts required for further investigations. The synthesized compounds were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, IR spectroscopy, and elemental analysis.

The reaction of the heterometallic complex [Zn2Ca(piv)6(py)2] (piv is pivalate anion, py is pyridine) with isophthalic acid (1,3-H2bdc) under the solvothermal conditions afforded a series of new {ZnCa} coordination polymers [Zn2Ca(DMF)2(1,3-bdc)3]n center dot center dot n(DMF) (1), [Zn3Ca3(H2O)5(DMF)(1,3-bdc)6]n center dot 3n(C6H6) center dot 3n(DMF) (2), and [Zn4Ca3(H2O)4(NMP)(1,3-bdc)8]n (3, NMP is N-methylpyrrolidone). The structures of the new compounds were determined by single-crystal X-ray diffraction. Depending on the conditions of the synthesis and crystallization, porous coordination polymers with different structures and composition were obtained. The use of poorly soluble zinc iso-phthalate as one of the starting compounds in the reaction with calcium nitrate enabled the preparation of single-phase complex 1 in amounts required for further investigations. The synthesized compounds were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, IR spectroscopy, and elemental analysis.