The search for new anticancer drugs is still a very important task for modern chemistry. Some of the most intensively studied objects are metal complexes, in particular complexes of platinum, ruthenium, iridium and osmium. To address this issue, novel organometallic ruthenium complexes with thiophene-based imines containing a Ru-C bond were synthesized and tested against cancer cell lines. The scaffold is designed to allow the generation of a broad library of cyclometallated compounds from commercially available substrates. Compounds were characterized using spectroscopic, electrochemical, and X-ray diffraction techniques. They were found to have a very good cytotoxicity among ruthenium complexes against A2780, A549 and MCF-7 cancer cells and against HEK cells.

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.

Two novel gold( iii ) complexes with doubly protonated forms of phenanthrolines, (neocH 2 )[AuCl 4 ]·Cl (1) and (1,7-phenH 2 )[AuCl 4 ]·NO 3 (2), were synthesized using the phenanthrolines.

Malonate ligands demonstrate versatility for intercalating metal complexes into layered rare-earth hydroxides (LREHs), enabling controlled tuning of coordination geometry and composition. As a proof of concept, a series of copper(II) malonate complexes with various substituents was synthesized and successfully intercalated into layered yttrium, europium, or terbium hydroxide at room temperature via anion-exchange reactions. The copper content in these hybrid materials increased in the order: butylmalonate < benzylmalonate < cyclopropanedicarboxylate < dimethylmalonate. To further expand the range of accessible metal malonate complexes, dimethyl- and benzylmalonate anions were intercalated into layered yttrium hydroxide for the first time and subsequently metalated in situ, yielding well-defined Cu2+ species within the interlayer space without disrupting the host lattice. Density functional theory (DFT) calculations provided insight into the structural arrangements of the copper complexes in the interlayer galleries. Comprehensive characterization of the resulting materials by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), IR, UV-vis, and electron paramagnetic resonance (EPR) spectroscopy confirmed both the successful formation of hybrid structures and elucidated the coordination environment of the intercalated copper species.

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.

The reaction of copper(II) chloride with azomethine ligand 4‐(pyridin‐2‐yl)methyleneamino‐1,2,4‐triazole (L) yielded crystals of a 1D coordination polymer [Cu(L)Cl 2 ] n ( 1 ), in whose structure metal atoms are bound by L molecules due to nitrogen atoms of imine, pyridyl, and triazole moieties. In contrast to this process, the reaction of zinc(II) chloride with L resulted in the formation of mononuclear complex [Zn(L) 2 Cl 2 ]·H 2 O ( 2 ), containing L molecules coordinated to the metal center in a monodentate mode due to triazole nitrogen atoms. The structures of the coordination compounds obtained were determined by single‐crystal X‐ray diffraction. The antimicrobial activity of 1 and 2 was assessed against the bacteria Escherichia coli , Staphylococcus aureus , Streptococcus spp., the fungi Candida albicans , Candida glabrata , Aspergillus fumigatus , Rhizopus oryzae , and the protozoa Colpoda steinii . Compound 1 showed high antiprotozoal activity, as well as significant antifungal activity against C. glabrata , and complex 2 demonstrated high bacteriostatic activity against Streptococcus spp. Thermal stability of 1 and 2 was studied by simultaneous thermal analysis under an argon atmosphere.

The interaction of Co(NO3)2 center dot 6H2O and MI2CO3 (MI = Rb or Cs) with dimethylmalonic acid (H2Me2mal) leads to the formation of 3D polymeric compounds: {[Co4Rb8(Me2mal)8(H2O)8]center dot 5H2O}n (1) and {[CoCs2(Me2mal)2 (H2O)4]center dot H2O}n (2), respectively. The structures of 1 and 2 were characterized using X-ray diffraction analysis and IR spectroscopy. Each complex contains CoII atoms arranged in four vertex polyhedra. Both compounds exhibit field-induced slow magnetic relaxation. The dc-magnetic measurements and ab initio calculation results show that 1 has "easy plane" type of magnetization, where the axial parameter D of both crystallographicaly independent Co2+ ions is positive. In contrast, parameter D of 2 is negative, which corresponds to "easy axis" type. For 2 the relaxation process includes the Orbach mechanism, which corresponds to the quantum chemical calculation.

Three new manganese compounds on 5-(pyridin-2-yl)-3-phenyl-1,2,4-triazole (L) basis (HL)4[MnBr4]2H2O (1), (HL)2[MnCl4] (2) and [MnL2Cl2]H2O (3) have been synthesized and characterized in terms of their structure, photoluminescence (PL), and electroluminescence (EL) properties. Compounds 1 and 2 exhibit bright green luminescence (lambda em approximate to 550 nm) with high quantum yields of 75.1 and 71.2%, and 3 emits unusual blue emission at 438 nm with a quantum yield of 43.9%. Analysis of the spectral properties of complexes 1 and 2 indicates that luminescence is determined by the transfer of excitation energy from the triazole cation to the manganese cation. Electroluminescent devices based on complexes 1 and 3 show high brightness values of 3033 and 5230 Cd m-2, respectively.

пентафторбензоата кадмия {[Cd(H2O)4(pfb)](pfb)}n (Hpfb = пентафторбензойная кислота), пентафторбензоата европия [Eu2(H2O)8(pfb)6].2H2O и пиразино[2,3-f][1,10]фенантролина (pzphen) в MeCN привело к выделению кристаллов: координационного полимера - [Eu2(H2O)2Cd2(pzphen)2(pfb)10]n (1) при 25 оС и соединений [Eu2Cd4(pzphen)4(pfb)14]n.4nMeCN (2) и [Eu2Cd2(pzphen)4(pfb)10].10MeCN (3) при 75 оС. В случае использования в качестве N-донорных лигандов батофенантролина (bphen) и 2,9-диметилбатофенантролина (mbphen) температура кристаллизации не влияла на состав и строение образующихся соединений, и поэтому были получены комплексы [Eu2Cd2(bphen)2(pfb)10]n.2nMeCN (4) и [Eu2Cd2(mbphen)2(pfb)10].H2O (5). Синтезированные соединения охарактеризованы методами РСА, ИК-спектроскопии и CHN-анализа. Детально проанализирована структура и кристаллические упаковки полученных комплексов. Основной вклад в стабилизацию кристаллических упаковок вносят π··· π, C–H···F, C–F···π взаимодействия.

The reaction of 4-nitro-N'-(pyridin-2-ylmethylene)benzohydrazide (HL) with Ln (OAc)(3)4H(2)O in MeOH makes it possible to synthesize mononuclear complexes [Ln(L)(2)(OAc) (MeOH)]center dot 2H(2)O (Ln = Tb-III (1), Eu-III (2) and Gd-III (3)) with chelate acetate and L- anions. Compound 1 can be crystallized in reaction with molar ratio HL:Ln = 1:1, 2:1, 3:1, and we successfully synthesized complex with three chelate L anions [Tb(L)(3)](2)2MeOH center dot H2O (4) by interaction of TbCl3 center dot 6H(2)O with deprotonated HL (HL:Ln = 3:1). Terbium (III) compound 1 starts to decompose at similar to 323 K and becomes stable up to 552 K according to the STA. Compound 1 shows slow magnetic relaxation with parameters Delta(eff)/k(B) = (6.75 +/- 0.02) K, tau(0) = (1.71 x 10(-6)+/- 1 x 10(-8)) s. Complexes 1 and 2 exhibit only fluorescence and phosphorescence of the L-. Ion-centered luminescence of the Tb3+ or Eu3+ ion is not observed. Using the tangent method at the high-energy edge of the phosphorescence spectrum of Gd3+, complex 3 T-1 energy level of L- is estimated to be 19700 cm(-1). Reasons of luminescence quenching are discussed. Structures of 1 and 4 were determined by single crystal X-ray diffraction, and compounds 1-3 were characterized by powder X-ray diffraction (PXRD).

This study explores the effects of minor chemical structure modifications on the thermometric performance of a novel mixed-metal complex [Tb0.94Eu0.06L3(TPPO)2] (HL - 4,4,4-trifluoro-1-(furan-2-yl)butan-1,3-dione, TPPO - triphenylphosphine oxide). By replacing NO3- with an HL- anion, we observed a significant enhancement in the complex's luminescent properties, including a shift in the high-sensitivity temperature range from 250 K to 150 K and a 3.3-fold increase in the relative thermal sensitivity (Sr). The modified behavior of the charge transfer (CT) state improved the energy transfer efficiency between Eu3+ and Tb3+ ions. Additionally, a convolutional neural network (CNN) was employed to analyze temperature-dependent luminescence data under real-world conditions, yielding superior accuracy and precision to conventional methods. This combination of structure variation and machine learning advances the potential of luminescent thermometers in real-world applications.

New series of seven zinc complexes with general formulae ZnL2 where HL-(4-(alkylaminomethylene)-5-methyl-2-phenyl-pyrazol-3-ones, have been prepared and characterized by NMR, IR, ESI-MS and UV-vis spectroscopies, elemental and thermal analysis, and single-crystal X-ray diffraction. Photophysical properties of title complexes were studied both in solutions and solid state. Complexes displayed strong blue luminescent emissions (QY = 4.8-22.9 %) in the solid state and weak emissions in solution. Moreover, an excitation-dependent emission due to retarded rotation around the C=N bond is observed for the complex with benzyl azomethine derivative. For complexes with propyl, butyl and benzyl substituents thin-film electroluminescent devices producing blue emission with brightness up to 4700 Cd/m2 have been obtained.

The reactions of [Zn(Piv)2]n and [Gd(Piv)3]n or Gd(NO3)3∙6H2O with 2-hydroxypyridine (Hhp) or its 6-methyl derivative (Hmhp) afford heterometallic complexes [ZnGd(Рiv)5(Hhp)2]·0.5H2O (I), [Zn2Gd(Рiv)6(Hhp)2NO3]∙2C6H6 (II), [Zn3GdO(Рiv)7(Hmhp)2]∙MeCN (III), and [Zn2Gd(Рiv)6-(Hmhp)2NO3]∙0.5MeCN (IV), respectively. In the carboxylate metal cage of the synthesized complexes, the Hhp and Hmhp molecules in the form of 2-pyridone are coordinated by the metal atoms via the monodentate mode through the oxygen atoms. The introduction of Et3N into the reaction with [Zn(Рiv)2]n, Gd(NO3)3∙6H2O, and Hhp is found to result in the formation of compound [Zn4Gd2(OH)2-(Рiv)6(hp)6(Hhp)2] (V) in which the 2-hydroxypyridine anions perform the bridging function. The molecular structures of complexes I‒V are determined by XRD (CIF files CCDC nos. 2365419–2365423).

We synthesized and investigated a new series of Sm3+ 1,3-diketonate complexes with CnF2n+1-homologous thiophene-containing ligands. A clear correlation was found between the number of fluorine atoms in the 1,3-diketone's carbon chain and the luminescent properties of the samarium(iii) complexes. The ligand modification method employed facilitates targeted and significant enhancements in the photoluminescence quantum yield (PLQY). Notably, the PLQY value peaked at 5.2% for the complex with n = 4 before decreasing with longer chains, a trend contrasting with that observed for Eu and Nd complexes. Temperature-dependent shifts in the CIE coordinates were observed, making these compounds suitable as luminescent thermometers with a sensitivity of 2.2% K-1 and resolution of 0.2 K at 120 K.

Взаимодействием ацетата кобальта(II), бензойной кислоты (Hbz) и N,N'-бис(2,4,6-триметилфенил)-1,4-диаза-1,3-бутадиена (Mes-DAD) в абсолютированном ацетонитриле получен молекулярный трехъядерный комплекс кобальта(II) [Co3(bz)6(Mes-DAD)2]∙2MeCN (I). Кристаллическое строение I установлено методом РСА (CCDC № 2423405): бензоат-анионы проявляют функцию мостиков, формируя линейный металлоостов, 1,4-диаза-1,3-бутадиеновые лиганды хелатно связаны с концевыми атомами кобальта. Фазовая чистота I подтверждена методом рентгенофазового анализа.

In this work, new NiII coordination compounds with cyclopropane-1,1-dicarboxylic acid (H2cpdc) dianions were synthesized: {[Na2Ni(cpdc)2(H2O)6]4H2O}n (1), {[K6Ni3(cpdc)6(H2O)10]8H2O}n (2), {[Rb6Ni3(cpdc)6(H2O)12]5.5H2O}n (3), and [Cs2Ni(cpdc)2(H2O)8]n (4). All complexes contained mononuclear bischelate fragments {NiII(cpdc)2(H2O)2}2- bound by alkali atoms in a 1D coordination polymer for 1, 2D for 2 and 4, and 3D for 3. In the topological representation of coordination bonds and ionic interactions, the Ni center represents the 4-c node of underlying (simplified) nets for all the four compounds. Na+, K+, Rb+, and Cs+ provide coordination numbers 4, 5&7&8, 6&7&8, and 6 in the underlying nets. The periodicity is higher for compounds with higher coordination numbers of large cations and a less amount of terminal aqua ligands. In the topological representation of ionic interactions, the fragment {Ni(cpdc)2(H2O)2}2- plays the role of 4-c (1-3) or 2-c (4) node of the underlying nets. H-bonds produce highly connected 3D supramolecular networks. The compounds were characterized by single-crystal X-ray diffraction. The DC magnetic data and ab initio calculations revealed that Ni2+ ions in 2 and 3 possess a positive D value and an "easy-plane" anisotropy type.

An approach to the synthesis of derivatives of unsymmetric 1,1′-disubstituted azinylferrocenes containing phenol fragments was proposed. It was found that the introduction of the quinoline or 2,2′-bipyridine moiety increases the E/Z selectivity of the reaction. The monosubstituted acetylferrocene produces the products of the pinacoline rearrangement due to the McMurry coupling, whereas only 1-azinyl-1′-1-[(4-hydroxyphenyl)-phenylmethylene]ethylferrocenes were formed in the reaction with 1-azinyl-1′-acetyl-ferrocenes. The high antioxidant activity of the synthesized compounds in the ABTS and FRAP assays and high inhibitory activity against self-aggregation of β-amyloid (1–42) was shown. Cytotoxic activity of these compounds was studied on human breast cancer cells (MCF7), non-small-cell lung cancer cells (A549), colorectal cancer cells (DLD-1), and normal dermal fibroblasts (DF-2).

The exchange interaction of lanthanum and some lanthanides salts (neodymium, samarium, europium, gadolinium, terbium and dysprosium) with sodium salt of 2,4-dichlorophenoxyacetic acid (HL) in dimethylformamide medium produced lanthanum and lanthanide carboxylates. The compounds were studied by elemental and thermal analysis, infrared spectroscopy and X-ray structure analysis. It was found that the complexes form two isostructural series: [Ln2L6(DMF)3]center dot Solv (Ln = La, Nd, Sm, Eu) and [LnL3(H2O)2]center dot 2DMF center dot Solv (Ln = Gd, Tb, Dy). Both series have a one-dimensional polymer structure in which the central atoms are connected by bridging carboxylate anions. The crystal structures of the complexes have a branched network of noncovalent D-H...A and Cl...Cl interactions. An analysis of the photophysical properties of all compounds revealed a bright luminescence with a quantum yield up to 39.5 % and an excited state lifetime of 1330 mu s for the europium polymer enhanced by 2,4-dichlorophenoxyacetate ligands.

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.

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.