The development of new, more effective, and selective anticancer agents is one of the most important tasks of modern medicinal chemistry. Recently, we have found that non-classical Pd(II) pincer complexes derived from thiophosphoryl-appended picolinamides exhibit promising cytotoxic properties. In this work, the potential of this class of metal-based derivatives was studied on an extended family of Pd(II) complexes with a deprotonated amide core featuring thiophosphoryl pendant arms, readily obtained by the direct cyclopalladation of new functionalized amide ligands upon interaction with PdCl2(NCPh)2 under mild conditions. The ligands, in turn, were obtained by conventional amide coupling methods using (aminobenzyl)- and (aminomethyl)diphenylphosphine sulfides as the key precursors and different N- and S-donor-substituted carboxylic acids. The effect of an acid component and carbon chirality in the ligand framework on the bioactivity of the resulting Pd(II) pincer complexes was elucidated by evaluating their cytotoxicity against different solid and blood cancer cell lines, apoptosis induction ability, and P-glycoprotein (P-gp) affinity, which revealed the high anticancer potential of some of them, and in particular, the potential to overcome drug resistance associated with P-gp overexpression. The representative palladocycle was also shown to possess moderate antibacterial activity.

We report a family of fullerene-based carboxylic acids with varied molecular structure affecting their ability to anchor to the surface of metal oxides, in particular SnO2, used as electron-transport materials in n-i-p perovskite solar cells. Compounds having the lowest solubility and/or increased number of carboxyl groups per fullerene core tend to form more robust passivation coatings over SnO2 and thus deliver the highest solar cell efficiencies and the best device operational stabilities. The results indicate the promise of further rational design of the fullerene-based acids with improved properties to achieve simultaneously a high solar light conversion efficiency and a long-term stability. Ag or Al V2O5-d PTA MAPbl3 PBCA or F1-F3 SnO2 TCO PCBA S O OH F1 F2 F3 OH O center dot Improved efficiency center dot Enhanced stability HO O O OH O OH

A new representative of hybrid pincer ligands has been synthesized by the thiocarbamoylation of a potassium salt of 3-(quinoxalin-2-yl)phenol with ClC(S)NMe2 to probe its cyclopalladation features in solution and under solvent-free conditions. The compound obtained is shown to readily undergo cyclometalation under the action of PdCl2(NCPh)2 upon heating in benzonitrile and, more importantly, in the absence of an added solvent, using the preliminary ground mixture of reactants as the starting material, which provides a powerful and green alternative to the conventional solution-based synthesis. The course and outcome of the solid-phase reaction were analyzed by IR spectroscopy, elemental and SEM/EDS analysis. The possibility to scale up the solid-phase synthesis using a simple thermoreactor was demonstrated for the first time. The resulting palladacycle exhibited high cytotoxic activity against several solid and hematopoietic cancer cell lines.

The tetrapyrrolic macrocycle as a scaffold for various chemical modifications provides broad opportunities for the preparation of complex multifunctional conjugates suitable for binary antitumor therapies. Typically, illumination with monochromatic light triggers the photochemical generation of reactive oxygen species (ROS) (photodynamic effect). However, more therapeutically valuable effects can be achieved upon photoactivation of tetrapyrrole derivatives. Herein we report the novel porphyrin-based complexes of transition metals with isocyanide and carbonyl ligands. Synthesis of complexes presumed the use of 5-(p-isocyanophenyl)-10,15,20-triphenylporphyrin as a ligand in reactions with metal carbonyl complexes, M(CO)6 (M = Cr, Mo, W), Re2(CO)10 and Re(CO)5Cl. Based on these complexes and isocyanocarborane, the heteroleptic carbonyl complexes with porphyrin and carborane isocyanide ligands were prepared. In cell-free systems, the new compounds retained photochemical characteristics of the parental porphyrin derivative, such as triplet state formation and ROS generation, upon light-induced activation. In the cell culture, the carborane-containing derivatives demonstrated a more pronounced intracellular accumulation than their nonboronated counterparts. As expected, illumination at the Soret band (405 nm) of cells loaded with the new complexes caused photodynamic cell damage. In contrast, illumination at 530 nm instead initiated the release of carbon oxide (CO) followed by cell death independently of the photodynamic effect. Light-induced CO release was analyzed using second derivatives of UV-Vis spectra and our originally developed Spectrophotometric elimiNAtion of Photoinduced Side reactions (SNAPS) method. The yield of CO release decreased in the raw depending on metals in the carbonyl moiety: Mo ≥ Cr > W > Re ≥ Re2. Overall, our novel metal carbonyl complexes with porphyrin and carborane isocyanide ligands emerge as potent bi-functional conjugates for combined photodynamic and photoinducible CO-releasing antitumor agents.

This paper presents an approach for the directed synthesis of new vinylcoppersiloxanes with 10-membered and bicyclic siloxanolate ligands from vinylcoppersodiumsiloxane with a globular structure in the presence of 2.2 '-bipyridine. The primary factor influencing the formation of a specific complex was the ratio of vinylcoppersodiumsiloxane to 2,2 '-bipyridine. The composition and structure of the resulting complexes were confirmed by elemental analysis and single crystal X-ray diffraction. Trimethylsiloxy-, vinyldimethylsiloxy-, and dimethylsiloxy-derivatives of stereoregular vinylsiloxanes with cis-bicyclic and cis-pentameric configurations, hitherto undescribed in the literature, were successfully synthesized using the obtained vinylcoppersiloxanes. Additionally, the possibility of generating amphiphilic Janus structures was demonstrated through hydrothiolation of the obtained vinylcyclosiloxanes with mercaptoacetic acid. The purity and structures of all cyclic compounds were confirmed by a complex of physico-chemical analytical techniques, including 1H, 13C and 29Si NMR, IR spectroscopy, mass spectrometry, GPC and elemental analysis.

Aromatic-substituted isoselenocyanates were reacted with sodium azide to yield novel sodium salts of phenyltetrazol-5-selenones, alongside analogous phenyltetrazol-5-thione derivatives for comparison. These compounds were fully characterized using single-crystal X-ray diffraction, NMR spectroscopy, IR/Raman spectroscopy, and high-resolution mass spectrometry. Surprisingly, X-ray crystallography revealed an unconventional coordination mode, with the sodium cation binding to the tetrazole nitrogen atoms rather than the selenium or sulfur centers, while preserving the C=Se/S double bonds. The electronic structure and delocalization effects were explored using DFT calculations, aromaticity criteria (EDDB and GIMIC), and vibrational spectroscopy in both solid and solution states. Hydrogen bonding studies demonstrated that nitrogen and chalcogen atoms in 2a and 5a interact with water, with S(Se)& sdot;& sdot;& sdot;HO bonds being significantly weaker than N & sdot;& sdot;& sdot;HO-consistent with the observed chalcogen-directed alkylation at Se/S centers. Additionally, the influence of deuterated solvents and temperature on (Herr, 2002)13 & Scy;-77Se bond NMR parameters was established. This comprehensive study offers novel insights into the coordination chemistry and reactivity of tetrazole-based chalcogen derivatives, while also elucidating their structural and electronic properties.

Herein, we describe a novel coupling between ambiphilic 2-pyridylselenyl reagents and nitriles featuring an active α-methylene group. Depending on the solvent employed, this reaction can yield two distinct types of cationic pyridinium-fused selenium-containing heterocycles, 1,3-selenazolium or 1,2,4-selenadiazolium salts, in high yields. This is in contrast to what we observed before for other nitriles. Notably, the formation of selenadiazolium is reversible, gradually converting into the more thermodynamically stable selenazolium product in solution. Our findings reveal, for the first time, the reversible nature of 1,3-dipolar cyclization between the CN triple bond and 2-pyridylselenyl reagents. Nitrile substitution experiments in the adducts confirmed the dynamic nature of this cyclization, indicating potential applications in dynamic covalent chemistry. DFT calculations revealed the mechanistic pathways for new cyclizations, suggesting a concerted [3 + 2] cycloaddition for the formation of selenadiazolium rings and a stepwise mechanism involving a ketenimine intermediate for the formation of selenazolium rings. Natural bond orbital analysis confirmed the involvement of σ-hole interactions and lone pair to σ* electron donation in these processes. Additionally, theoretical investigations of σ-hole interactions were performed, focusing on the selenium-centered contacts within the new compounds.

Bis(N-Alkyl-N-diphenylphosphinylmethyl)diglycolamides [Ph2P(O)CH2N(R)C(O)CH2]2O, where R = Et, i-Pr, n-Bu, i-Bu, n-Oct, were synthesized by reaction of diglycolyl chloride with N-alkyl-N-(diphenylphosphinylmethyl)amines Ph2P(O)CH2NHR obtained by the Kabachnik–Fields reaction of aminomethylation of diphenylphosphinous acid, and their hydrochlorides. The structure of the obtained compounds was studied by 1H, 13C and 31P NMR spectroscopy.

The reaction of methyl anthranilate with 2-methylphenyl- iso -selenocyanate in boiling absolute ethanol affords a new compound: 3-(2-methylphenyl)-2-selenoxo-2,3-dihydroquinazolin-4(1 Н )-one (HL). Free ligand HL, which is selone, is preliminarily transformed into the corresponding sodium selenolate [C 15 H 11 N 2 OSeNa] ( I) , which is then used without isolation in the reaction with cadmium chloride. This reaction leads to the formation of complex [Cd 2 (μ-L) 2 (L) 2 (C 2 H 5 OH) 2 ] ( II ). The structures of the compounds are determined by X-ray diffraction (XRD) (CIF files CCDC nos. 2142342 (НL) and 2246014 ( II )) and NMR spectroscopy ( 1 Н, 13 С, 15 N, and 77 Se). In the crystal, the molecules of HL form one-dimensional chains due to H…O and H…Se contacts and alternate in the syndiotactic order. Compound II is the centrosymmetric binuclear complex [C 64 H 56 Cd 2 N 8 O 6 Se 4 ]. The cadmium atoms in complex II are hexacoordinated by two chelate anionic ligands L – . According to the NMR data, in a DMSO-d 6 solution free ligand HL has the selone structure, whereas in cadmium complex II this ligand exists in the selenolate form, which is consistent with the XRD data on the crystal structures of the compounds.

The synthesis of novel stereoregular carborane-containing phenylcyclosiloxanes (4, 5, 6, 8, and 12 –SiO– units in the ring) has been developed.

A series of novel hybride ferrocene carborane derivatives containing allyl functionalities at the carborane carbon atoms were firstly synthesized in a good yield providing their potential applications in various fields of material science. Synthesized compounds were characterized using various spectroscopic techniques like IR, ESI-MS, 1H and 11B NMR data. Some compounds were investigated by cyclic voltammetry. The total charge density around each atom was calculated for 1-allyl-9-ferrocenylmethyl-m-carborane. Particular attention has been focused on the analysis of 1H NMR spectra of diallyl-substituted ferrocene carboranes which made it possible to discover the migration of the double bond in allyl substituent and the formation along with diallyl derivative of the corresponding allylpropenyl isomer compounds.

Herein, we present the first experimental study of individual water-soluble fullerene derivatives proving their ability to inhibit SARS-CoV-2 in vitro. The initial screening allowed us to identify a few new compounds that have demonstrated pronounced antiviral activity with IC50 values as low as 390 nM and selectivity indexes reaching 214. Time-of-addition analysis and molecular docking results suggested that the viral protease and/or the spike protein are the most probable targets inhibited by the fullerene derivatives. Further rational design of fullerene derivatives might lead to the development of compounds with further enhanced antiviral activity and decreased toxicity.

Here we report the synthesis of novel fullerene derivatives with attached aliphatic residues based on the previously unknown reactions of chlorofullerene C60Cl6 with CH-acids and silyl enol ether.

Perovskite solar cells (PSCs) with p-i-n architecture attracted particular attention from the research community due to their simple and scalable fabrication at low temperatures. However, the operational stability of p-i-n PSCs has to be improved, which requires the development of advanced charge transport interlayers. Fullerene derivatives such as phenyl-C-61-butyric acid methyl ester (PC61BM) are commonly used as electron transport layer (ETL) materials in PSCs, though they strongly compromise the device stability. Indeed, it has been shown that PC61BM films actively absorb volatile products resulting from photodegradation of lead halide perovskites and transport them towards top metal electrode. Thus, there is an urgent need for development of new fullerene-based electron transport materials with improved properties, in particular the ability to heal defects on the perovskite films surface and block the diffusion of volatile perovskite photodegradation products. To address this challenge, a systematic variation of organic addends structure should be performed in order to tailor the properties of fullerene derivatives. Herein, we rationally designed a series of fullerene derivatives with different side chains and explored their performance as ETL materials in perovskite solar cells. It has been shown that among all studied compounds, a methanofullerene with thiophene pendant group enables both high efficiency and improved device operational stability. The obtained results suggest that further engineering of fullerene-based materials could pave a way for the development of advanced ETL materials enabling long lifetimes of p-i-n perovskite solar cells.

An efficient approach to the preparation of functional organosilicon compounds by sequential hydrothiolation (Ht) and hydrosilylation (Hs) reactions using commercially available catalysts and activators is presented.

A series of three closely related unsymmetrical pincer ligands featuring thione sulfur donors have been derived from m-thiophosphorylated phenyl isothiocyanate to probe the effect of a spectator heteroatom in the flanking ring on their direct cyclopalladation. The reaction efficiency is shown to drastically increase on passing from a thionated thiazolidinone derivative to its oxazolidinone analog, and further to an imidazolidinone ligand. The investigations by IR and NMR spectroscopy as well as X-ray diffraction confirmed the realization of S,C,S'-type pincer coordination but did not reveal considerable differences in the molecular structures of the Pd(II) com-plexes obtained; however, the results of DFT calculations provided some valuable insights into the peculiarities of their formation. In addition, the possibility of solid-phase synthesis of the target pincer complexes upon ther-mally induced CH activation has been demonstrated. This methodology does not afford a significant yield enhancement over the conventional solution-based technique but appears to be highly advantageous in terms of the absence of a solvent at the synthesis step and reaction time.

The reaction of aromatic ring-substituted isoselenocyanates with 2-thiopheacetic and 4-pyridinecarboxylic acid hydrazides yielded selenosemicarbazides which were further converted into previously unknown 1,2,4-triazole-3-selones and 3,3'-di(4H-1, 2,4-triazolyl)diselenides. The structures of the obtained compounds were studied by NMR spectroscopy, IR spectroscopy, and high-resolution mass spectroscopy (HR-MS). The bactericidal and fungicidal activity of some obtained compounds was evaluated in molecular modeling studies such as docking and simulation studies. The compound 3ba was reported as the most promising compound to show robust binding energy with different antibacterial and antifungal compounds. The compounds were observed in strong hydrophilic and hydrophobic interactions and remained in stable binding conformation with the receptor enzymes. Furthermore, the interatomic interaction energies were dominated by Van der Waals and electrostatic energies indicating the formation of stable complexes.

Amino-functionalized phosphoryl compounds are among the most useful molecular scaffolds in medicinal chemistry, while the potential of their thiophosphorylated analogs, especially those having an alkylamino moiety, is still uncovered. This is mainly due to the lack of convenient synthetic routes to these organophosphorus derivatives. To address this issue, we have suggested the facile approaches to α-(aminomethyl)- and substituted/unsubstituted α-(aminobenzyl)diphenylphosphine sulfides based on either the sequential transformations of (hydroxymethyl)diphenylphosphine sulfide, with the Staudinger reaction of an azide derivative as the key stage, or the addition of Ph2P(S)H to hydrobenzamides followed by the acid hydrolysis. The compounds obtained were reacted with picolinyl chloride to yield functionalized amides which readily underwent direct cyclopalladation, resulting in new representatives of non-classical N-metalated Pd(II) pincer complexes. The latter exhibit promising cytotoxic activity against several human cancer cell lines and apoptosis inducing ability along with the remarkable cytotoxic effects on doxorubicin-resistant cell sublines.

Thesynthesis of a storage-stable organosilicon modifierwith adioxaborolane-protecting group is described. Its high reactivity andselective anti-Markovnikov addition in hydrosilylation reactions toafford siloxanes of various structures are shown. The possibilityof deprotection of both the initial modifier and its siloxane derivativesunder mild conditions using water in yields up to 96% is demonstrated.The existence of an equilibrium between the organosilicon derivativesof phenylboronic acids and their cyclic six-membered boroxines wasconfirmed by H-1 NMR spectroscopy and X-ray diffractionanalysis data. The use of siloxane derivatives of phenylboronic acidsin Suzuki-Miyaura and Chan-Lam cross-coupling reactionswas studied. All synthesized compounds were characterized by NMR (H-1, B-11, C-13, and Si-29), IRspectroscopy, and high-resolution mass spectrometry.

We report a novel reaction of the recently discovered family of fullerene derivatives C1-C60Ar5Th' with thiophene derivatives Th''H yielding a previously unknown family of C1-C60Ar5Th'Th''H compounds with three different types of functional aromatic addends attached to the carbon cage. The discovered reaction paves a way to the synthesis of novel C60 fullerene derivatives with promising antioxidant and antiviral properties.