This work presents the synthesis and comprehensive study of a novel series of zinc(II) coordination compounds based on azomethine ligands derived from N-[2-(hydroxyalkyliminomethyl)phenyl]-4-methylbenzenesulfonamides. The ligands incorporate aliphatic spacers of varying length (CH2)n (n = 2–6), enabling a systematic investigation of the spacer’s influence on the structural, thermal, photophysical, and electroluminescent properties of the resulting complexes. The complexes were characterized by elemental analysis, and IR and NMR spectroscopy. Single-crystal X-ray diffraction analysis confirmed the formation of chelate complexes, where the Zn(II) ion adopts a distorted tetrahedral geometry, coordinated by two bidentate ligands via the nitrogen atoms of deprotonated sulfonamide and azomethine groups. Elongation of the methylene spacer does not significantly alter the core coordination geometry (Zn–N bond lengths, bond angles) or the dominant intermolecular interactions (hydrogen bonds, π–π stacking) governing crystal packing. These structural findings are strongly supported by density functional theory (DFT/B3LYP) calculations. In the solid state, the complexes exhibit intense blue photoluminescence with emission maxima ranging from 435 to 466 nm. The photoluminescence quantum yields (PLQY) vary from 7.4 to 21.5

New Zn(II) and Cd(II) complexes based on N-[2-[(E)-2-furylmethyliminomethyl]phenyl]-4-methyl-benzenesulfonamide were synthesized. The structures and physicochemical properties of the complexes were studied using single-crystal X-ray diffraction analysis, 1H nmR, IR, and UV-Vis spectroscopy and DFT calculations. It was shown that the two deprotonated ligands chelate the metal ions through the nitrogen atoms of the tosylamine and azomethine fragments. The coordination geometry around the Zn(II) and Cd(II) ions is highly distorted tetrahedron. Hirshfeld surface analysis was used to visualize and quantify intermolecular interactions, including hydrogen bonds, van der Waals forces, and pi-pi stacking in the crystal structures. The photoluminescent properties of the complexes were also investigated.

Single-crystal MOF with the initial M-3(2+)(BTC)(2)(3-) (H2Ow)(12)] (M = Co, Ni; BTC, benzene-1,3,5-tricarboxylate) and the refined framework compositions [Co-2.93(2+)(1)(BTC)(1.95)(3-)(H2Ow)(11.94(4))] and [Ni-2.94(2)(2+)(BTC)(1.96)(3-)(H2Ow)(11.96(4))] (M2+BTC; X-ray synchrotron single-crystal diffraction) and space group C2 (Z = 4) are synthesized by lowtemperature solvothermal method. The grinding of single crystals leads to a change in compositions (X-ray synchrotron powder diffraction), to a greater extent for Co2+BTC: [Co-2.71(2)(2+)(BTC)(1.81)(3-)(H2Ow)(11.14(4))] and [Ni-2.93(4)(2+)(BTC)(1.95)(3-)(H2Ow)(11.12(6))]. The crystal structure (unit cell parameters and structural characteristics, M site occupancy, water content; XRD) and local composition and coordination environment of M2+ ions (EXAFS/ XANES), surface composition (XPS, SEM), thermal (TGA, DSC), adsorption, catalytic, and antimicrobial properties as well as chemical and thermal stability (higher in CoBTC) and permanent porosity (absent in NiBTC) are different for phases with Co2+ and Ni2+, which is due to the high-spin state of Co2+ and a higher degree of covalence of the Co-O bond. Dehydration-rehydration process, firstly performed in in situ mode (EXAFS/ XANES), is accompanied by a change in the composition of M2+BTC and transformation of the coordination environment of M2+ ions with the creation of open and closed active centers. Higher adsorption of methane, hydrogen, and water vapor as well as greater antimicrobial activity against bacteria are found on powdered single crystals CoBTC, which is due to a higher dimensions of voids. NiBTC shows to be the most active and selective in the reaction of hydrogenation of phenylacetylene due to high Ni2+ ion content (active center). A pronounced dependence of the composition structure, and properties of M2+BTC on the conditions of synthesis and post-synthetic treatment is established.

Three new anionic three-dimensional metal-organic frameworks based on heterocyclic polycarboxylate ligands have been synthesized: (H2NMe2)3[Zn2{NaZn2}(dabco)2(tdc)6]center dot 4.5DMF center dot H2O (1, CCDC 2527083), (H2NMe2) [NaZn(fdc)2] (2, CCDC 2527084), (H2NMe2)[CdLi(btdc)2] (3, CCDC 2527085), where tdc2-= 2,5-thiophenedi-carboxylate, dabco = 1,4-diazabicyclo[2.2.2]octane, DMF = N,N-dimethylformamide, fdc2-= 2,5-furanedicar-boxylate, btdc2-= 2,2 '-bithiophene-5,5 '-dicarboxylate. The structure of the compounds has been established by single crystal X-ray diffraction analysis; the chemical and phase purity of compounds 2 and 3 has been proved by elemental, thermogravimetric and powder X-ray diffraction analyses and IR spectroscopy. The luminescence excitation and emission spectra of the solid phases 2 and 3 have been recorded, and the quantum yields have been obtained. The influence of mono-, di-and trivalent metal cations on the luminescence intensity of the suspensions of the MOF 3 has been investigated, and the luminescence response of the MOF suspensions to the presence of Co(II) and Ni(II) has been revealed and studied quantitatively.

Based on salts Na+[Ln3+(C5HF6O2)4]- , where Ln3+= Er3+(1), Ho3+(2), Dy3+(3), and hexafluoroacetylacetone (C5HF6O2), and using metathesis reactions, salts with an organic dication 1,1 '-diethyl-4,4 '-dipyridinium (C14H18N22) of general composition C14H18N22 have been synthesized for the first time and characterized by X-ray analysis, IR spectroscopy and magnetometry. The effect of the nature of the rare earth metal (3+) and the dication size on the magnetic sublattice in salts 4-6 has been analyzed. It has been shown that an organic counterion can be used for tuning the coordination geometry and magnetic dynamics in the salts with [Ln3+(C5HF6O2)4]- anion.

Macroparts ( 0.24 x 0.19 x 0.06 mm3) of Czochralski-grown optical large-sized crystals, both pure (Ca1.8Sr1.2)(VO4)2 and (& Scy;a2.4Sr0.6)(VO4)2 doped with 0.5 and 1.0 wt% Tm2O3, are studied by X-ray diffraction using two diffractometers Xcalibur Eos S2 and XtaLAB Synergy-DW at T = 293 K and additionally at T = 30 K and structures were refined using Jana2020. The difference between the composition of melt and macro- or microparts ( 0.05 x 0.05 x 0.05 mm3; synchrotron; T =100 K; SHELXL) of crystals from different regions of the same single-crystal boule is established. Physicochemical and growth reasons for such discrepancy (lack of congruent melting, heterogeneity of composition along the crystal length and cross-section, block structure) and methodical features of the experiment (temperature, number of diffraction reflections both general and in refinement, size of the object under investigation, software and its capabilities, strategy and tactics for determining and refining crystal structures) are proposed. It is shown that reasons not fully or partially considered may lead to incorrect interpretation of refined compositions of crystals and erroneous conclusions. The combination of the obtained experimental results and their analysis allowed to reveal the "homeopathic" and relaxation effects as well as the effect of assistance in the formation of structure of multicomponent solid solutions of the general type (Ca,Sr, Tm)3(VO4)2. The essential difference in the compositions of complex solid solutions obtained by different methods from the charge with the same initial composition is discussed. The methodology is proposed and recommended for determining and/or refining the structures of bulk crystals of complex compositions with the presence of three cations in one crystallographic site using X-ray diffraction methods.

Doping-induced structural changes and spectroscopic parameters of Czochralski-grown RE3+-activated strontium molybdate SrMoO4 (SMO:RE; RE3+ = Pr, Nd, Eu, Yb) single crystals as well as specific local behavior of RE3+ ions depending on the type, concentration (0.2–3.0 wt.

Metal-organic single-molecule magnets (SMMs), especially single-ion magnets (SIMs), attract growing attention due to their unique magnetic behavior, which can be used for the development of computing technologies. Herein, we report the synthesis of a new mononuclear Dy(III) complex (2-Dy) using a calix[4]arene ligand (2), decorated with two lower rim-appended salicylideneamine groups, bearing azophenyl moieties. The structures of both the ligand and Dy(III) complex were thoroughly characterized in the crystalline phase. X-ray diffraction of ligand 2 revealed the formation of a racemic mixture of left-handed and right-handed conformers. Upon binding to the Dy(III) atom, the macrocycle 2 behaves as a highly coordinating ligand by totally capping the metal coordination sphere, leading to the formation of a distorted triangular dodecahedron coordination sphere (D2d symmetry). In the crystalline phase, for 2-Dy, two complex enantiomer counterparts were stacked into 1D homochiral chains due to weak CH/π interactions. Analysis of magnetic properties showed that the obtained complex exhibited slow magnetic relaxation behavior at a temperature up to 10 K in the absence of an external dc field.

The present work is devoted to studies on the interaction of copper(II)-chloride, bromide, and nitrate with (3-alanine ((3-Ala, 3-aminopropanoic acid, NH2(CH2)2COOH). The complex compounds [Cu2(mu 2-(3-Ala)4 x 2] X2 center dot nH2O X = Cl (n = 1) (1), Br (n = 2) (2), [Cu2(mu 2-(3-Ala)4(H2O)2](NO3)4 center dot 4H2O (3) have been prepared in aqueous solutions from the initial copper salts and (3-Ala taken in the molar ratio of CuX2:(3-Ala = 1:2. All the complexes have been characterized by the powder-, single crystal X-ray diffraction analysis, IR-, ESI-MSspectroscopy, elemental analysis. The cytotoxic activity (MTT assay) on the postnatal human dental pulp stem cells (DPSC) and the MCF-7 breast cancer cell line was found to be the dose-dependent one for both types of cells, [Cu2(mu 2-(3-Ala)4Br2]Br2 center dot 2H2O (2) demonstrating the highest difference in cytotoxicity for DPSC and MCF-7 at a concentration of 1 center dot 10-4 and 5 center dot 10-4 mol/L (survivability: 28.64 f 2.08 and 5.44 f 0.68 (MCF-7) and (61.57 f 4.49 and 22.01 f 1.74 % (DPSC)), in comparison with doxorubicin (Dox): 64.87 f 12.68 % (DPSC); 68.97 f 7.55 % (MCF-7)) at c = 1 center dot 10-4 mol/L. Quantum-chemical calculations (DFT method) allowed to predict the direction of complex formation and thermodynamic stability of the complexes obtained.

Осуществлён синтез двух новых комплексов никеля(II) бензоилгидразона 2-(N-тозиламино)бензальдегида (H2L) c дополнительными гетероциклическими донорными лигандами L1=2,2'-бипиридин и L2=1,10-фенантролин. Строение и состав полученных соединений установлены методом элементного анализа, 1Н ЯМР, ИК-спектроскопии. Кристаллическое и молекулярное строение комплексов Ni(II) определено с помощью РСА. Показано, что аддукты имеют димерное строение состава Ni2L2L1(CH3OH) и Ni2L2L2(CH3OH). В обоих аддуктах один из ионов никеля(II) находится в искаженном плоско-квадратном окружении, тогда как другой ион никеля(II) имеет октаэдрическое окружение за счет дополнительной координации 2,2'-бипиридина или 1,10-фенантролина и молекулы метанола. Исследована биологическая активность комплексов. Обнаружено, что оба аддукта проявляют протистоцидную активность в отношении Colpoda steinii, причем Ni2L2L1(CH3OH) в два раза менее активен, а Ni2L2L2(CH3OH) в два раза более активен по сравнению с препаратом сравнения хлорохином.

Whitlockite-type polycrystalline and single-crystal (Ca 3_ x Sr x )(VO 4 ) 2 solid solutions were successfully obtained by solid-state synthesis and Czochralski method, respectively. Synchrotron powder X-ray diffraction allowed to reveal actual compositions of polycrystalline (Ca 3_ x Sr x )(VO 4 ) 2 solid solutions with & khcy; = 0.3, 0.54, 0.9, 1.2, 1.35 refined by Rietveld method, which are slightly different from the initial ones. Synchrotron X-ray single-crystal diffraction analysis of Czochralski-grown undoped (Ca 1.8 Sr 1.2 )(VO 4 ) 2 (CSVO) revealed its actual composition (Ca 2.982(11) Sr 0.031 )(V & Ocy; 4 ) 2 . Difference between initial and refined compositions is analyzed and discussed. In the CSVO structure, Sr 2 + ions partially occupy monocapped Ca2 and two-capped Ca3 trigonal prismatic sites and Ca 2 + ions are in the Ca5 and Ca5 A sites, forming two independent strongly distorted tetrahedral Ca5O 4 and octahedral Ca5 A O 6 oxygen environments. Synchrotron X-ray single-crystal diffraction analysis together with Xray absorption spectroscopic study of ( & Scy; a 2.4 Sr 0.6 )(VO 4 ) 2 doped with 0.5 and 1.0 wt% Tm 2 O 3 ( & Scy; SVO:0.5Tm and CSVO:1.0Tm) allowed to establish the absence of cations in the Ca5 A site, the localization of Sr 2 + ions in the Ca2 and Ca3 sites and additionally in octahedral Ca4 site together with Tm 3 + ions, forming an individual eightcoordinated environment, in the refined compositions (Ca 2.776(7) Sr 0.210(4) Tm 3 + 0.008(1) )(VO 4 ) 2 and (Ca 2.855 (7) Sr 0.140(7) Tm 3 + 0.009(1) square 0.022(7) )(VO 4 ) 2 , respectively, with vacancies (marked by a square, square ) in the two-capped Ca1 trigonal prismatic site in the CSVO:1.0Tm structure. Additional interstitial oxygen, participating in the formation of the Tm 3 + environment, found in the residual electron density, together with vacancies in the Ca1 site provides electroneutrality to CSVO:0.5Tm and CSVO:1.0Tm crystals. Several structural models of the coordination environment of Tm 3 + ions were analyzed and the most correct one was proposed.

The present article is devoted to the consideration of the interconversions of copper(II) chloride complexes with caffeine (caf) ([CuII2(μ2-Cl)2(caf)2(H2O)2] (1),[CuII3(μ-Cl)6(caf)(H2O)]n (1a), [Cu4(μ2-Cl)6(μ4-O)(caf)4] (1b), 2[CuII(caf)Cl2].0·.25THF (1c), [CuII(caf)2Cl2] (2)), depending on the synthesis conditions, and to studies on the four-nuclear copper(II) bromide complex with acetamide (AcAm) ([Cu4(μ2-Br)6(μ4-O)(AcAm)4] (3)). The results obtained have been confirmed by different methods (powder XRD, single crystal XRD diffraction analysis, IR-, ESI-MS-, EPR-spectroscopy, and magnetic properties studies). Two bromide ions in (3) are non-equivalent to the other four and this fact may result in the modification of the exchange integral between bonded copper ions. Single crystal XRD data have been compared with the results of DFT calculations. It has been found that the thermodynamic stability of the complexes grows with an increase in the number of copper atoms and bridging chloride ions and a decrease in the number of water molecules in the formula unit of the compound. The calculation results for complexes with acetamide are in a good correlation with those of caffeine and experimental data.

Reaction of a series of 2,6-diacetylpyridine bis-hydrazones with copper(II) chloride and bromide yielded pentacoordinated complexes exhibiting high cytotoxic activity.

The YsxC protein from Staphylococcus aureus is a GTP-binding protein from the TRAFAC superfamily of the TrmE-Era-EngA-EngB-Septin-like GTPase class, EngB family of GTPases. Recent structural and biochemical studies of YsxC function show that it is an integral part of the pathogenic microorganism life cycle, as it is involved in the assembly of the large 50S ribosomal subunit. Structural studies of this protein with its specific functional features make it an attractive target for further development of new selective antimicrobials. In this study, we cloned the ysxC protein gene from S. aureus, overexpressed the protein in E. coli, and subsequently purified and crystallized it. Protein crystals were successfully grown using the vapor diffusion method, yielding diffraction data with a resolution of up to 2 Å. Comparative analysis of the structure of SaYsxC with known three-dimensional structures of homologs from other microorganisms showed the presence of structural differences for the apo form.

The novel octahedral complexes of the bidentate 4,6-di-tert-butyl-1,2-benzoquinone-2-monooxime (HL) ligand have been synthesized by reaction with the perchlorate salts of divalent Fe, Co, Ni and Zn ions - (HNEt3)[FeL3]0.5H(2)O (1), mer-[(CoL3)-L-III] (2), [Ni2L4(H2O)(2)] (3), (HNEt3)[NiL3] (4) and [Zn3L6] (5). Conclusions about the structures of the complexes and the influence of the nature of the complexing metal on the electronic structure of the coordinated ligand have been drawn from IR, M & ouml;ssbauer, H-1 NMR spectroscopy, single crystal X-Ray diffraction, and magnetochemistry data. Coordination compounds, containing fac-[ML3](-) anionic unit have been obtained for M = Fe(II) (1), and M = Ni(II) (4). In both anions facial isomer is stabilized by electrostatic and hydrogen bonding interaction of triethylammonium countercation and uncoordinated oxygen atoms of nitroso-groups of the L ligand. For Ni(II) also the binuclear complex with composition [Ni2L4(H2O)(2)] (3) has been obtained, which can be readily converted to (4) by reflux with excess of HL. In case of reaction of Co(II) salt neutral mer-[(CoL3)-L-III] compound has been isolated (2) due to oxidation of metal ion to + 3 state. In case of Zn(II) trinuclear compound with composition [Zn3L6] has been separated (5) with linear arrangement of Zn(II) cations due to central Zn cation coordination of two mononuclear fac-[ZnL3](-) units. Fe(II) (1) and Co(III) (2) complexes are diamagnetic due to strong ligand field and d(6) electronic configuration. For Ni binuclear compound (3) DC magnetic field (5000 Oe) measurements of the temperature dependence of magnetic susceptibility reveal antiferromagnetic exchange interaction between paramagnetic centers with J = -35.71(11) cm(-1). For mononuclear complex (4) medium easy plane-type magnetic anisotropy (D = +4.63(6) cm(-1)) has been observed. Experimental magnetic properties and relative stability of the spin states of paramagnetic compounds are rationalized with quantum chemical modelling.

The photochemical and photophysical properties of the new ligand N-[2-(5,6-dihydrobenzimidazo[1,2-c]quinazoline-6-yl)phenyl]-4-methylbenzolsulfamide (1) and its zinc complexes, namely [2-[(E)-[2-(1H-benzimidazol-2-yl)phenyl]iminomethyl]-N-(p-tolylsulfonyl)anilino]chloro-zinc (3) and acetoxy-[2-[(E)-[2-(1H-benzimidazol-2-yl)phenyl]iminomethyl]-N-(p-tolylsulfonyl)anilino]zinc (4) were studied using UV spectroscopy, time-resolved luminescence and stationary photolysis. Compound 1 combines the properties of Schiff bases and benzimidazole derivatives, both known as good luminophores. The structures of compounds in the crystalline state were determined by means of XRD. Ligand 1 demonstrates high photoluminescence quantum yields (PLQY) in solutions, while for the soluble zinc complex 3 it drops in an order of magnitude. PLQY in the solid state for all the compounds are moderate (0.2–0.3). For complex 3 the PLQY in the solid state is ca. 3 times higher than in solutions, demonstrating the effect of aggregation-induced enhancement of luminescence. The approach based on combining properties of the two classes of luminophores seems prospective for further development of luminescent materials.

The separation of light alkanes is one of the most important tasks for modern industry due to the widespread use of ethane and propane as chemical feedstocks. Their extraction from natural gas is a challenging task and is now carried out by cryogenic distillation at a limited number of plants around the world. The development of new materials for adsorption separation is therefore important. Among the different types of adsorbents, metal-organic frameworks (MOFs) are one of the most interesting due to their infinite design possibilities. Here we present a highly porous perfluorinated MOF [Sc(OH)(1,3-tFbdc)] (1,1,3-tFbdc2--1,3-C6F4(COO)2 2- tetrafluoroisophthalate linker) with a BET surface area greater than 1000 m center dot g-1 and its ability to separate light alkanes was investigated. The ability of 1 to separate light hydrocarbons at 0 and 25 degrees C is demonstrated by IAST calculation of selectivity factors as well as by dynamic breakthrough experiments. The role of fluorine substituents within the organic linker of MOF 1 in gas adsorption is revealed by quantum chemical calculations.

A number of new copper(II) complexes of 2-(N-tosylamino)benzaldehyde benzoylhydrazone (H2L) CuLLn (n = 1–6) with heterocyclic donor ligands (L1 = 1-propyl-2-aminobenzimidazole, L2 = 1‑hexyl-2-aminobenzimidazole, L3 = 1-octyl-2-aminobenzimidazole, L4 = 2,2'-bipyridine, L5 = 1,10-phenanthroline, and L6 = 2-aminopyridine) is synthesized. The structures and compositions of the synthesized compounds are determined by elemental analysis, 1Н NMR spectroscopy, IR spectroscopy, and magnetochemistry. The molecular structures of complexes CuLL1,2,4−6 are determined by XRD (CIF files CCDC nos. 2341480 (CuLL1), 2341468 (CuLL2), 2341478 (CuLL4), 2341477 (CuLL5), and 2341479 (CuLL6)). The biological activity of the complexes is studied. The adducts with L1, L2, and L6 exhibit a significantly higher anti-protist activity than chloroquine used as the reference compound.

We report a first example of field-induced (H-DC = 2500 Oe) slow magnetization relaxation in the homotrinuclear linear heterospin manganese coordination compound with S = 7/2 ground state, based on the bidentate 3,5-di-tert-butyl-1,2-benzoquinone-1-monooxime (HL) ligand with composition {[MnL3]Mn[MnL3]}.

Whitlockite-type polycrystalline and single-crystal (Ca3−xSrx)(VO4)2 solid solutions were successfully obtained by solid-state synthesis and Czochralski method, respectively. Synchrotron powder X-ray diffraction allowed to reveal actual compositions of polycrystalline (Ca3−xSrx)(VO4)2 solid solutions with х = 0.3, 0.54, 0.9, 1.2, 1.35 refined by Rietveld method, which are slightly different from the initial ones. Synchrotron X-ray single-crystal diffraction analysis of Czochralski-grown undoped (Ca1.8Sr1.2)(VO4)2 (CSVO) revealed its actual composition (Ca2.982(11)Sr0.031)(VО4)2. Difference between initial and refined compositions is analyzed and discussed. In the CSVO structure, Sr2+ ions partially occupy monocapped Ca2 and two-capped Ca3 trigonal prismatic sites and Ca2+ ions are in the Ca5 and Ca5A sites, forming two independent strongly distorted tetrahedral Ca5O4 and octahedral Ca5AO6 oxygen environments. Synchrotron X-ray single-crystal diffraction analysis together with X-ray absorption spectroscopic study of (Сa2.4Sr0.6)(VO4)2 doped with 0.5 and 1.0 wt% Tm2O3 (СSVO:0.5Tm and CSVO:1.0Tm) allowed to establish the absence of cations in the Ca5A site, the localization of Sr2+ ions in the Ca2 and Ca3 sites and additionally in octahedral Ca4 site together with Tm3+ ions, forming an individual eight-coordinated environment, in the refined compositions (Ca2.776(7)Sr0.210(4)Tm3+0.008(1))(VO4)2 and (Ca2.855(7)Sr0.140(7)Tm3+0.009(1)□0.022(7))(VO4)2, respectively, with vacancies (marked by a square,□) in the two-capped Ca1 trigonal prismatic site in the CSVO:1.0Tm structure. Additional interstitial oxygen, participating in the formation of the Tm3+ environment, found in the residual electron density, together with vacancies in the Ca1 site provides electroneutrality to CSVO:0.5Tm and CSVO:1.0Tm crystals. Several structural models of the coordination environment of Tm3+ ions were analyzed and the most correct one was proposed.