


Volume 49, Nº 9 (2023)
Articles
Предисловие к тематическому выпуску, посвященному биологически активным координационным соединениям



Cytotoxic Copper(II) Complexes Based on 2,2'-Bipyridine/1,10- Phenanthroline and 5-(4-Chlorophenyl)-1H-tetrazole: Synthesis and Structures
Resumo
Five coordination compounds [Cu2(Bipy)2L4]·C2H5OH (Iа, Ib), [Cu2(Dmbipy)2L4] (II),
[Cu2(Phen)2L4]·H2O (IIIa), [Cu2(Dmphen)2L4] (IVa), and [Cu2(Phendione’)2L4]·2C2H5OH·2H2O (V) are
synthesized from 5-(4-chlorophenyl)-1H-tetrazole (HL), where Bipy is 2,2'-bipyridine, Dmbipy is 4,4'-
dimethyl-2,2'-bipyridine, Phen is 1,10-phenanthroline, Dmphen is 4,7-dimethyl-1,10-phenanthroline, and
Phendione’ is 6-ethoxy-6-hydroxy-1,10-phenanthrolin-5-one. The crystal structures of the complexes are
determined by X-ray diffraction (XRD) of single crystals (CIF files CCDC nos. 2225368 (Ia), 2225369 (Ib),
2225370 (II), 2225372 (IIIa), 2225373 (IVa), and 2225371 (V)). The compounds are binuclear due to the
bridging function of the tetrazolate anion, and the coordination number of copper is five in all synthesized
complexes. The cytotoxic activity of the complexes against the Hep2 and HepG2 cancer cell lines and noncancerous
human fibroblasts MRC-5 is studied. The complexes exhibit pronounced cytotoxic properties, and
compound V has the maximum selectivity index with respect to the cancer cells.



Synthesis, Structure, and Properties of the Iron Nitrosyl Complex with 2-Ethyl-4-pyridinecarbothioamide
Resumo
The synthesis and data on the physicochemical characteristics and biological activity of the new
iron nitrosyl complex (Q+)2[Fe2(S2O3)2(NO)4]2– (I), where Q+ is protonated 2-ethyl-4-pyridinecarbothioamide
(C8H11N2S), are presented. The structure and properties of the complex were studied by X-ray diffraction,
elemental analysis, IR and Mössbauer spectroscopy, and amperometry. The complex showed antibacterial
activity and efficiently inhibited cyclic guanosine monophosphate phosphodiesterase (cGMP PDE),
which may suggest its antihypertensive, anti-aggregation, and vasodilator activities.



Furancarboxylate Coordination Polymers of Gd3+ and Eu3+: Synthesis, Structural Variations, and Biological Properties
Resumo
A series of polymer complexes of Gd(III) and Eu(III) with 3-furancarboxylic (HFur) and 5-nitro-
2-furancarboxylic (HNfur) acids differed in the composition and coligands presented by solvent molecules
(CH3OH/C2H5OH/H2O) is synthesized: [Gd(Fur)3(CH3OH)(C2H5OH)]n (I), [Gd(Nfur)3(CH3OH)2]n·
CH3CN (II), [Eu(Fur)3(C2H5OH)]n (III), and [Eu(Nfur)3(H2O)2]n·3CH3CN (IV). According to the X-ray
diffraction (XRD) data, all complexes are 1D coordination polymers in which the lanthanide cation has the
coordination number 8 (LnO8) to form the environment as a doubly augmented triangular prism (I, II) or a
square antiprism (III, IV). The supramolecular levels of the polymers are stabilized due to intra- and intermolecular
hydrogen bonds between the coordinated solvent molecules and O atoms of the chelate-bound
anions of the acid and via two types of noncovalent C–H…O and N–O…π interactions that significantly contribute
to an additional stabilization of the crystal packings. The biological properties of complexes I, II, and
IV are studied with respect to the model nonpathogenic strain Mycolicibacterium smegmatis.



Nitro-Substituted Pyridinimine Complexes of Pd(II): Synthesis and Inhibition of MAO-B ex vivo
Resumo
The first ever synthesis of complexes [PdLCl2] (I) and [PdLBr2] (II) was successfully achieved,
where L = 2,6-dimethyl-4-nitro-N-(pyridin-2-ylmethylildene)aniline, a ligand with a purported ability to
inhibit monoamine oxidase B (MAO-B). To gain insight into the molecular structure of complexes I
and II, as well as the ligand precursor 2,6-dimethyl-4-nitroaniline L4 (CIF files CCDC nos. 2255106 (I),
2255105 (II), 2255103 (L), 2255104 (L4)), X-ray diffraction analysis was utilized. Complex I underwent further
characterization to determine its stability, solubility, and lipophilicity. Cytotoxicity studies of substances
L, I, and II on human embryonic kidney cell line HEK-293 showed no evidence of cytotoxic activity. To evaluate
the inhibitory activity of new substances L, I, and II as well as established substances III−IX, selegiline,
and rasagiline, ex vivo studies were conducted, establishing a structure/activity relationship.



Triphenylphosphine Thiolate Gold(I) Complexes with Redox-Active Schiff Bases: Synthesis, Electrochemical Properties, and Biological Activity
Resumo
New gold(I) phosphine thiolate complexes [(Ph3P)Au(SLn)] I–V with Schiff bases LnSH containing
redox-active catechol, phenol, or quinone methide moieties were synthesized and characterized. The
molecular structure of compound I in the crystalline state was established by X-ray diffraction (CCDC
no. 2237815). The electrochemical behavior of compounds I–V was studieв by cyclic voltammetry. The proposed
electrooxidation mechanism of the complexes involves the Au–S bond cleavage, the disulfide formation,
as well as the oxidation of the redox active group of the ligand. In the cathode region, complexes I–III
tend to form relatively stable monoanionic species. The radical scavenging activity of complexes decreases in
comparison to free ligands in the reactions with synthetic radicals and the CUPRAC test. Compounds I, II,
IV, and V have no clear-cut effect on the promoted DNA damage; however, they show antioxidant action
in the non-enzymatic lipid peroxidation of rat liver homogenate. Compounds I–V demonstrate a weak antibacterial
activity against Staphylococcus aureus strains. The gold(I) complexes cytotoxicity was studied against
A-549, MCF-7, and HTC-116 cancer cell lines using MTT assay. The test compounds are characterized by
higher selectivity to certain types of cells than the sulfur-containing Schiff bases. The presence of quinone
methide moiety in the ligand in case of V significantly increases the cytotoxicity against all of the cell lines.



Synthesis, Structure, and Study of the Cytotoxic Activity of Zinc(II) Complex with 5-Benzyltetrazole and 1,10-Phenanthroline
Resumo
The complex [Zn(Phen)(H2O)L2] (I), where HL is 5-benzyltetrazole, Phen is 1,10-phenanthroline,
was synthesized. The compound was characterized by standard physicochemical methods (elemental
analysis, powder X-ray diffraction, IR spectroscopy). According to X-ray diffraction data (CCDC no.
2220597), zinc coordination environment in the crystal structure of I corresponds to a distorted trigonal
bipyramid. The ligand HL is monodentate and is coordinated via tetrazolate ring nitrogen. The stability of
complex I was studied by NMR spectroscopy in DMSO. The cytotoxic properties of the compound were
assessed against HepG-2 (hepatocellular carcinoma) and MRC-5 (noncancerous human fibroblasts) cells.
Complex I exhibits weak cytotoxic properties in the studied concentration range (1–100 μM).



Specific Features of Binding Bioactive Organic Molecules with the Metallic Matrix of Heteronuclear 3d-4f Structures Containing Soft and Hard Metallocenters Using the Nd(III)–Cu(II) Complex as an Example
Resumo
The polynuclear alanine hydroximate metallamacrocyclic complex Nd(C8H7NO4)(H2O)[15-
MCCu(II)Alaha-5](CH3COO) with the axial 3-hydroxy-4-pyridinone ligand is synthesized for the first time
from the (3-hydroxy-2-methyl-4-oxo-4H-pyridin-1-yl) acetate ligand. The X-ray diffraction (XRD) (CIF
file CCDC no. 2242224) and quantum chemical methods show that the interaction of ligand L with the Nd3+
ion retained due to ionic bonds with the oxygen atoms in the copper-containing metallamacrocyclic matrix
results in the formation of axial bonds (having a covalent contribution) between Nd3+ and the dioxolene fragment
of the pyridinone ligand. In topological and energy characteristics, these axial bond approach the bonds
of Cu2+ with the amine nitrogen atoms of the alanine hydroximate metallamacrocycle.


