Introducing Novel Redox-Active Bis(phenolate) N-Heterocyclic Carbene Proligands: Investigation of Their Coordination to Fe(II)/Fe(III) and Their Catalytic Activity in Transfer Hydrogenation of Carbonyl Compounds.

A simple and efficient procedure for synthesizing novel pincer-type tridentate N-heterocyclic carbene bisphenolate ligands is reported. The synthesis of pincer proligands with N,N'-disubstituted imidazoline core, 5 and 6, was carried out via triethylorthoformate-promoted cyclization of either N,N'-bis(2-hydroxy-3,5-di-tert-butylphenyl)cyclohexanediamine, 3, or N,N'-bis(2-hydroxyphenyl)cyclohexanediamine, 4, in the presence of concentrated hydrochloric acid. Cyclic voltammograms of the ligands revealed ligand-centered redox activity, indicating the noninnocent nature of the ligands. The voltammograms of the ligands exhibit two successive one-electron oxidations and two consecutive one-electron reductions. In contrast to previous reports, the redox-active ligands in this study exhibit one-electron oxidation and reduction processes. All products were thoroughly characterized by using 1H and 13C NMR spectroscopy. The base-promoted deprotonation of the proligands and subsequent reaction with iron(II) and iron(III) chlorides yielded compounds 7 and 8. These compounds are binuclear and tetranuclear iron(III) complexes that do not contain carbene functional groups. Complexes 7 and 8 were characterized by using elemental analysis and single-crystal X-ray crystallography. At low catalyst loadings, both 7 and 8 exhibited high catalytic activity in the transfer hydrogenation of selected aldehydes and ketones.

Reactivity of phenoxathiin-based thiacalixarenes towards C-nucleophiles.

A starting thiacalix[4]arene can be easily transformed into oxidized phenoxathiin-based macrocycles 9 and 9', representing an unusual structural motif in calixarene chemistry. The presence of electron-withdrawing groups (SO2, SO) and the considerable internal strain caused by the condensed heterocyclic moiety render these molecules susceptible to nucleophilic attack. The reaction with various organolithium reagents provides a number of different products resulting from the cleavage of either the calixarene skeleton or the phenoxathiin group or both ways simultaneously. This enables the preparation of thiacalixarene analogues with unusual structural features, including systems containing a biphenyl fragment as a part of the macrocyclic skeleton. The above-described transformations, unparalleled in classical calixarene chemistry, clearly demonstrate the synthetic potential of this thiacalixarene subgroup.

Novel rod-like [Cu(phen)2(OAc)]·PF6 complex for high-performance visible-light-driven photocatalytic degradation of hazardous organic dyes: DFT approach, Hirshfeld and fingerprint plot analysis.

A novel octahedral distorted coordination complex was formed from a copper transition metal with a bidentate ligand (1,10-Phenanthroline) and characterized by Ultraviolet-visible spectroscopy, Ultraviolet-visible diffuse reflectance spectroscopy, Fourier-transform infrared spectroscopy, Brunauer-Emmett-Teller, Field emission scanning electron microscopy, and Single-crystal X-ray diffraction. The Hirshfeld surface and fingerprint plot analyses were conducted to determine the interactions between atoms in the Cu(II) complex. DFT calculations showed that the central copper ion and its coordinated atoms have an octahedral geometry. The Molecular electrostatic potential (MEP) map indicated that the copper (II) complex is an electrophilic compound that can interact with negatively charged macromolecules. The HOMO-LUMO analysis demonstrated the π nature charge transfer from acetate to phenanthroline. The band gap of [Cu(phen)2(OAc)]·PF6 photocatalyst was estimated to be 2.88 eV, confirming that this complex is suitable for environmental remediation. The photocatalytic degradation of erythrosine, malachite green, methylene blue, and Eriochrome Black T as model organic pollutants using the prepared complex was investigated under visible light. The [Cu(phen)2(OAc)]·PF6 photocatalyst exhibited degradation 94.7, 90.1, 82.7, and 74.3 % of malachite green, methylene blue, erythrosine, and Eriochrome Black T, respectively, under visible illumination within 70 min. The results from the Langmuir-Hinshelwood kinetic analysis demonstrated that the Cu(II) complex has a higher efficiency for the degradation of cationic pollutants than the anionic ones. This was attributed to surface charge attraction between photocatalyst and cationic dyes promoting removal efficiency. The reusability test indicated that the photocatalyst could be utilized in seven consecutive photocatalytic degradation cycles with an insignificant decrease in efficiency.

An Insight into Anion Extraction by Amphiphiles: Hydrophobic Microenvironments as a Requirement for the Extractant Selectivity.

Coupling of electron-deficient urea units with aliphatic chains gives rise to amphiphilic compounds that bind to phosphate and benzoate anions in the hydrogen bonding competitive solvent (DMSO) with KAss = 6 580 M-1 and KAss = 4 100 M-1, respectively. The anchoring of these receptor moieties to the dendritic support does not result in a loss of anion binding and enables new applications. Due to the formation of a microenvironment in the dendrimer, the high selectivity of the prepared compound toward benzoate is maintained even in the presence of aqueous media during extraction experiments. In the presence of binding sites at 5 mM concentration, the amount of benzoate corresponding to the full binding site occupancy is transferred into the chloroform phase from its 10 mM aqueous solution. A thorough investigation of the extraction behavior of the dendrimer reported here, supported by a series of molecular dynamics simulations, provides new insight into the fundamental principles of extraction of inorganic anions by amphiphiles.

Heteroleptic Silver(I) and Gold(I) N-Heterocyclic Carbene Complexes: Structural Characterization, Computational Analysis, Tyrosinase Inhibitory, and Biological Effects.

Derivatization of (NHC)M-Cl (M = Ag, Au) with selected sulfur donors from the family of dialkyldithiophosphates and bis(2-mercapto-1-methylimidazolyl)borate ligands gave a series of heteroleptic mononuclear complexes. In single-crystal X-ray diffraction analysis, Ag(I) complexes adopted a trigonal planar geometry, while Au(I) complexes are near-linear. TD-DFT and hole-electron analyses of the selected complexes gave insight into the electronic features of the metal complexes. In vitro cellular tests were conducted on the human cancerous breast cell line MCF-7 using 2 and 8. The antibacterial activities of complexes 1, 2, 3, 7, 8, and IPr-Ag-Cl were also screened against Gram-positive (Staphylococcus aureus PTCC 1112) and Gram-negative (Escherichia coli PTCC 1330) bacteria. Antityrosinase and hemolytic effects of the selected compounds were also determined.

Synthesis of Thiapillar[6]arenes Bearing Redox-Active (Hydro)quinone Groups. Electrochemical and XRD Study.

Pillar[n]arenes are among the newest members of the macrocyclic family. Nevertheless, their conformational behavior and binding properties as well as redox properties of dealkylated pillar[n]arenes are well-studied. At the same time, introducing a heteroatom into a cyclophane macrocycle is already known to alter all the above properties drastically. This study presents a simple synthetic approach based on thia-Michael addition cyclization that readily resulted into hexathiapillar[6]arene with four phenylene units alternated by two redox-active hydroquinone moieties. The straightforward synthesis of the macrocycle enabled a systematic study of its conformation and redox behavior. The modification of hexathiapillar[6]arene afforded five functionalized derivatives, which were studied structurally in detail. The findings revealed interesting redox and structural properties of the macrocycle and its derivatives including the formation of crystal lattices with continuous channels and empty voids.

Correction to "Homobimetallic Au(I)-Au(I) and Heterotrimetallic Au(I)-Fe(II)-Au(I) Complexes with Dialkyldithiophosphates and Phosphine Ligands: Structural Characterization, DFT Analysis, and Tyrosinase Inhibitory and Biological Effects".

[This corrects the article DOI: 10.1021/acsomega.3c00645.].

Homobimetallic Au(I)-Au(I) and Heterotrimetallic Au(I)-Fe(II)-Au(I) Complexes with Dialkyldithiophosphates and Phosphine Ligands: Structural Characterization, DFT Analysis, and Tyrosinase Inhibitory and Biological Effects.

The role of bridging and terminal ligand electronic and steric properties on the structure and antiproliferative activity of two-coordinated gold(I) complexes was investigated on seven novel binuclear and trinuclear gold(I) complexes synthesized by the reaction of either Au2(dppm)Cl2, Au2(dppe)Cl2, or Au2(dppf)Cl2 with potassium diisopropyldithiophosphate, K[(S-OiPr)2], potassium dicyclohexyldithiophosphate, K[(S-OCy)2], or sodium bis(methimazolyl)borate, Na(S-Mt)2, which afforded air-stable gold(I) complexes. In 1-7, the gold(I) centers adopt a two-coordinated linear geometry and are structurally similar. However, their structural features and antiproliferative properties highly depend upon subtle ligand substituent changes. All complexes were validated by 1H, 13C{1H}, 31P NMR, and IR spectroscopy. The solid-state structures of 1, 2, 3, 6, and 7 were confirmed using single-crystal X-ray diffraction. A density functional theory geometry optimization calculation was used to extract further structural and electronic information. To investigate the possible cytotoxicities of 2, 3, and 7, in vitro cellular tests were carried out on the human cancerous breast cell line MCF-7. 2 and 7 show promising cytotoxicity.

Synthesis, identification, chiral separation and crystal structure of (3R,4R,7S,8S)-3,4,7,8-tetrachlorodecane and its stereoisomers.

Chlorinated paraffins (CPs) are a notoriously known class of compounds that stand amongst the most wide-spread persistent organic pollutants. Therefore, their reliable, repeatable, and reproducible quantitative analysis using well-defined reference standards is of utmost importance. In view of the increasing demand for constitutionally and stereochemically defined CP standards, we have synthesized a stereoisomeric mixture of 3,4,7,8-tetrachlorodecane. One stereoisomer - (3R,4R,7S,8S)-3,4,7,8-tetrachlorodecane was separated from the mixture, and enriched fractions of residual stereoisomers were achieved through crystallisation of the residual mother liquors. The molecular structure of the single isolated stereoisomer was confirmed through single-crystal X-ray crystallographic data. One fraction of 3,4,7,8-tetrachlorodecane stereoisomers was successfully separated on a chiral stationary phase using supercritical fluid chromatography hyphenated to mass spectrometry (column: Chiral ART Amylose-C; mobile phase: CO2/MeOH (96/4 v/v) with 0.1% diethylamine). The reported separation of stereoisomers is unprecedented in CP analysis so far.

The Unexpected Chemistry of Thiacalix[4]arene Monosulfoxide.

Thiacalix[4]arene monosulfoxide 4 possesses a very unusual chemistry, as demonstrated by several unprecedented derivatives in calixarene chemistry. Interestingly, compound 4 cannot be prepared by the dealkylation of its corresponding tetramethoxy derivative using BBr3. Instead, the borate complex is formed with a boron bound by the two neighboring phenolic oxygens and a sulfoxide group. A similar type of borate complex with a spirodienone fragment was then isolated as a by-product. The oxidation of monosulfoxide with Chloramine-T did not provide the expected spirodienone moiety, but rather a complex oxathiane-based spiroheterocyclic part containing a chlorine atom. X-ray analyses confirmed the structures of the unusual products and feasible formation mechanisms were proposed. These results provide further evidence of the distinction between thiacalixarene chemistry and the chemistry of classical CH2 analogues.

A novel Cu(II)-based DNA-intercalating agent: Structural and biological insights using biophysical and in silico techniques.

A new mixed-ligand Cu(II) complex formulated as [Cu(dipic)(amp)(H2O)].H2O (dipic: pyridine-2,6-dicarboxylic acid, amp: 2-amino-4-methylpyridine), was synthesized and structurally characterized by FTIR spectroscopy, CHN analysis, and the single-crystal X-ray crystallographic method. The complex crystallizes in an orthorhombic space group Pna21, and the coordination environment around the metal center was found to be a pentacoordinate CuN2O2OW distorted square-pyramidal geometry. In order to systematically explore a detailed in vitro and in silico study of the DNA binding of the title complex, various biophysical (UV-Vis absorption spectroscopy, fluorescence, competitive binding with ethidium bromide) and theoretical (DFT, molecular docking simulation, and QM/MM) methods were applied which revealed that the complex could intercalate with the insertion of the amp ligand between the DNA base pairs. The experimental thermodynamic parameters of the interaction revealed the spontaneity of the process and the domination of the hydrophobic interactions in the association and stabilization of the DNA-Cu(II) complex adduct, which was in line with the docking and QM/MM data. In vitro cytotoxic potential of the complex against the human breast adenocarcinoma (MCF-7) cells was examined using MTT assay, which indicated that cancerous cells showed inhibition in presence of the complex.

The Formation of Inherently Chiral Calix[4]quinolines by Doebner-Miller Reaction of Aldehydes and Aminocalixarenes.

The formation of inherently chiral calix[4]arenes by the intramolecular cyclization approach suffers from a limited number of suitable substrates for these reactions. Here, we report an easy way to prepare one class of such compounds: calixquinolines, which can be obtained by the reaction of aldehydes with easily accessible aminocalix[4]arenes in acidic conditions (Doebner-Miller reaction). The synthetic procedure represents a very straightforward approach to the inherently chiral macrocyclic systems. The complexation studies revealed the ability of these compounds to complex quaternary ammonium salts with different stoichiometries depending on the guest molecules. At the same time, the ability of enantioselective complexation of chiral N-methylammonium salts was demonstrated.

Therapeutic potential of phospho-thiadiazole derivatives as anti-glioblastoma agents: synthesis, biological assessment and computational study.

In this study, three new phospho thiadiazole compounds (A, F and W) were investigated as possible cytotoxic agents. The compounds were synthesised and characterised by using spectroscopy methods. The crystal structure of compound A was investigated using X-ray crystallography, since the title compounds can exist as different tautomeric forms, their conformational and geometrical aspects were investigated computationally by the DFT method. NBO analysis suggested that these compounds can function as appropriate ligands for the reaction with the nitrogen bases of DNA. All the synthesised compounds were evaluated in vitro for their cytotoxic activities against cancer in the human glioblastoma cell lines (U-251) using the MTT assay. According to the annexin V-FITC/PI results, a combination of synthesised compounds with ReoT3D showed a synergistic effect to increase the percentage of apoptotic cells. Molecular docking study for A (the most toxic compound) showed how it interacts with DNA. Both in vitro and in silico results showed that A has promising inhibitory potential (IC50: 48.1 ± 0.3 µM) and binding energy (-6.67 kcal/mol).

Regioselective Lithiation of Tetrabromocalix[4]arenes: A Simple Way for the Desymmetrization of the Macrocyclic Skeleton.

Desymmetrization of persubstituted calix[4]arenes represents an interesting way to yield distally disubstituted derivatives. The reaction of tetrabrominated calixarenes in three different conformations (cone, partial cone, and 1,3-alternate) with an excess of n-BuLi surprisingly leads with high selectivity to distally dilithiated derivatives that, by reaction with electrophiles, give substitution patterns which are difficult to obtain by other ways. Using a combination of synthetic and theoretical approaches (DFT), we tried to demonstrate the usefulness of this method and provide a possible explanation for this unexpected selectivity.

Template synthesis, DNA binding, antimicrobial activity, Hirshfeld surface analysis, and 1D helical supramolecular structure of a novel binuclear copper(ii) Schiff base complex.

A new binuclear copper(ii) Schiff base complex [Cu2 L2 - (NO3)2]·2CH3OH (1) [L = 2,6-bis((E)-(p-tolylimino)methyl)-4-methoxyphenol] was synthesized using a template method in which the tridentate N2O Schiff base ligand was derived from [1 + 2] condensation of 2,6-diformyl-4-methoxyphenol and p-methyl aniline in the presence of copper(ii) ions as the template agent. The X-ray diffraction analyses revealed that this complex crystallizes in the monoclinic system with space group P21/n. The most remarkable structural feature of 1 is that it contains two types of 1D right-handed helical chains. The molecules are linked by intermolecular hydrogen bonds and π⋯π interactions, then a 3D supramolecular network was constructed. Moreover, the intermolecular interactions on the crystal packing of 1 have been further studied using Hirshfeld surface analysis and corresponding 2D fingerprint plots. Binding interaction of this complex with calf thymus DNA (CT-DNA) has been investigated using absorption and emission studies, viscosity experiments and circular dichroism studies. Complex 1 shows significant binding to the DNA. The results of fluorescence spectroscopy and UV absorption spectroscopy, CD spectroscopy and viscosity indicated that this complex interacted with CT-DNA in a groove binding mode where the binding constant was 1.3 ± 0.2 × 104 L mol-1. Our fluorimeteric study showed that the reaction between 1 and CT-DNA was exothermic (ΔH = 59.6 kJ mol-1; ΔS = 268.79 J mol-1 K-1). Antibacterial activities of the complex were screened by the disc diffusion method against three Gram-positive bacteria (Staphylococcus aureus ATCC 25923, Enterococcus faecalis ATCC 23212 and S. epidermidis ATCC 34384), and three Gram-negative bacteria (Escherichia coli ATCC 25922, Pseudomonas aeruginosa ATCC 27853 and Klebsiella pneumonia ATCC 70063). The results indicated that this complex demonstrated acceptable antibacterial activities.

Controlled Anchoring of (Phenylureido)sulfonamide-Based Receptor Moieties: An Impact of Binding Site Multiplication on Complexation Properties.

The repetition of urea-based binding units within the receptor structure does not only lead to monomer properties multiplication. As confirmed by spectroscopic studies, UV-Vis and 1H-NMR in classical or competitive titration mode, the attachment to a carrier allocates the active moieties to mutual positions predetermining the function of the whole receptor molecule. Bivalent receptors form self-aggregates. Dendritic receptors with low dihydrogen phosphate loadings offer a cooperative complexation mode associated with a positive dendritic effect. In higher dihydrogen phosphate concentrations, the dendritic branches act independently and the binding mode changes to 1:1 anion: complexation site. Despite the anchoring, the dendritic receptors retain the superior efficiency and selectivity of a monomer, paving the way to recyclable receptors, desirable for economic and ecological reasons.

Nucleophile-induced transformation of phenoxathiin-based thiacalixarenes.

Oxidized phenoxathiin-based macrocycles, easily accessible thiacalix[4]arene derivatives, consist of a unique set of structural elements representing a key prerequisite for the unexpected reactivity described in this paper. As proposed, the internal strain, imposed by the presence of a heterocyclic moiety, together with a number of electron-withdrawing groups (SO2) opens the way to the cleavage of the macrocyclic skeleton through a cascade of three SNAr reactions triggered by the nucleophilic attack of an SH- anion. The whole transformation, which is unparalleled in classical calixarene chemistry, leads to unique linear sulfinic acid derivatives with a rearranged phenoxathiin moiety that can serve as building blocks for macrocyclic systems of a new type.

Hydrogen-bond directionality and symmetry in [C(O)NH](N)2P(O)-based structures: a comparison between X-ray crystallography data and neutron-normalized values, and evaluation of reliability.

For [C(O)NH](N)2P(O)-based structures, the magnitude of the differences in the N-H...O, H...O=P and H...O=C angles has been evaluated when the N-H bond lengths, determined by X-ray diffraction, were compared to the neutron normalized values and the maximum percentage difference was obtained, i.e. about 3% for the angle even if the N-H bond lengths have a difference of about 30% (0.7 Šfor the X-ray and 1.03 Šfor the neutron-normalized value). The symmetries of the crystals are discussed with respect to the symmetry of the molecules, as well as to the symmetry of hydrogen-bonded motifs, and the role of the most directional hydrogen bond in raising the probability of obtaining centrosymmetric crystal structures is investigated. The work was performed by considering nine new X-ray crystal structures and 204 analogous structures retrieved from the Cambridge Structural Database.

Substrate-Controlled Regioselective Bromination of 1,2-Disubstituted Cyclobutenes: An Application in the Synthesis of 2,3-Disubstituted Cyclobutenones.

Easily available disubstituted cyclobutenes were regioselectively halogenated at the allylic position by means of a reaction with bromine. The regioselectivity of bromination is controlled by the presence of a carbocation-stabilizing group. The prepared disubstituted 3-bromocyclobutenes were converted into the corresponding disubstituted cyclobutenones. On the basis of the performed experiments, the mechanism behind the bromination reaction was also proposed.

Breaking thiacalix[4]arene into pieces - a novel synthetic approach to higher calixarenes bearing mixed (-S-, -CH2-) bridges.

A novel approach to calix[5-7]arenes possessing mixed (S and CH2) bridges within the skeleton is based on the reaction of thiacalix[4]arene monosulfoxide with BuLi leading to a linear phenolic tetramer in essentially quantitative yield. This key intermediate is then cyclized with suitable building blocks to give macrocyclic calixarene analogues. Compared to the traditional stepwise construction of similar systems, this procedure based on thiacalixarene cleavage represents a scalable, robust, and straightforward synthesis and enables the preparation of larger calixarenes on a gram scale. As shown by 1H NMR and UV-vis titration experiments, the mixed-bridge calix[7]arene is able to recognize fullerenes C60 and C70, thus showing possible applications of such systems. The structures of the mixed bridge systems were confirmed by single crystal X-ray analysis, and the behavior of novel macrocyclic skeletons in solution was studied using dynamic NMR techniques.