In this study, the dithiophosphonate precursor 2,4-bis(2,4-dimethoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4disulfide (SAV-A2) was used as the starting material. Its reaction with various alcohols produced a new series of dithiophosphonic acids, HLn [RRnP(S)SH], where R = 2,4-dimethoxyphenyl and Rn= Ln (L1= n-butyl-, L2 = 2pentyl-, L3 = 3-pentyl-, L4 = benzyl-). These crude acids were subsequently stabilized with ammonia gas to afford the corresponding ammonium salts ([NH4Ln]), which served as precursor ligands for Ni(II) complex formation ([Ni(Ln)2]). Furthermore, the reaction of these complexes with 1,10-phenanthroline (phen) yielded sixcoordinate Ni(II) complexes, [Ni(phen)3][(Ln)2]. The structures of the compounds so prepared were elucidated by spectroscopic techniques (1H-, 13C-, and 31P-NMR, FT-IR, and mass spectrometry) and magnetic susceptibility measurements (for [Ni(phen)3][(Ln)2]). The molecular structures of the [Ni(Ln)2] complexes were confirmed by single-crystal X-ray diffraction. The antiproliferative activities of the compounds, except for [Ni(Ln)2], were evaluated by MTT assay after 48 h of incubation. The compounds exhibited generally low cytotoxicity within the tested concentration range, with [Ni(phen)3][(L2)2] showing the highest activity against the DLD-1 cell line. The photophysical behaviour of all compounds was examined using UV-visible absorption and steady-state fluorescence spectroscopy.

Abstract 2,4-bis(3,4-dimethoxyphenyl)-1,3-dithia-2,4-diphosphetane 2,4-disulfide (SAV-A1) was treated with five different alcohols to obtain dithiophosphonic acids (HLn, HS2P((2,4-CH3O)2-C6H3)(ORn); n=1-5, R1=n-pentyl-; R2=2-pentyl-; R3=4-tert-but-benzyl-; R4=2-propyl-; R5=2-butyl-). HLn series were converted to their ammonium salts, ([NH4Ln]). [NH4Ln] were reacted with NiCl2.6H2O to obtain the corresponding Ni(II) coordination compounds ([Ni(Ln)2]) in ethanol medium. The structures of all the compounds were elucidated by spectroscopic techniques. Single-crystal X-ray diffraction analysis of [Ni(L1)2], [Ni(L2)2], [Ni(L4)2] and [Ni(L5)2] were also carried out. The ligands and their nickel complexes were tested on human liver and colon cancer cell lines using (MTT) assay method. The salts [NH4L2] and [NH4L5] demonstrated more antiproliferative effects than others in colon cancer cell line with IC50 values 82.73 and 74.87 µM, respectively. Density Functional Theory (DFT) calculations of [Ni(L1)2], [Ni(L2)2], [Ni(L4)2] and [Ni(L5)2] were done. The molecular docking studies of [Ni(L1)2], [Ni(L2)2], [Ni(L4)2] and [Ni(L5)2] with colon cancer antigen proteins, ID 2HQ6 and liver cancer protein, PDB ID: 3WZE were done to foresee the interactions of the complexes.

The first synthesis of 2,4-bis(3,4-dimethoxyphenyl)-1,3-dithia-2,4-diphosphetane 2,4-disulfide (SAV-A1 reagent) was achieved. Seven oxo-alkyl esters (HLn) were synthesized thereof. Ni(II) complexes ([Ni(Ln)(2)]) of these ligands were prepared in ethanol. The structures were identified by spectral studies. Ni(II) complexes were unambiguously determined by X-ray crystallography. In addition, the ligands and their Ni(II) complexes were tested on two different human cancer cell lines, including liver and colon. Moreover, density functional theory (DFT) calculations of the Ni(II) complexes were performed, and the molecular docking studies of these compounds with liver cancer protein, PDB ID: 3WZE and colon cancer antigen proteins, ID 2HQ6 were presented to investigate and predict potential interactions.

Ferrocenyldithiophosphonate type ligands in salt forms, ([NH4(FcLn)], FcLn = Fc(RO)P(S)S; n = 1, R = 3-phenyl-1-propyl-; n = 2, R = 1-phenyl-1-propyl-; n = 3, R = 3-methyl-1-butyl-; n = 4, R = 3-pentyl-) were prepared and reacting them with Ni(II) salts, complexes of the general formula [Ni(FcLn)2] were obtained. They were further treated with pyridine (Py) to yield [Ni(FcLn)2(Py)2]. X-ray structure of the complex, [Ni(FcL3)2] was elucidated. The density functional (DFT) and docking calculations on the same compound were also performed by using X-ray data. Docking studies showed a notable van der Waals interaction between the complex [Ni(FcL3)2] and human DNA. The cytotoxic activities of the compounds [Ni(FcLn)2] against three human cancer cell lines (HepG2, DLD-1, MDA-MB-231) were investigated for finding new drug candidates. The results indicate that [Ni(FcL1)2] and [Ni(FcL2)2] complexes have a mild degree of antiproliferative activity against liver, colon and breast cancerous cell lines. That the activity is mild indicate that the docking sites on DNA are not crucially active in malign reproduction.

A series of new ferrocenyldithiophosphonato complexes of Cd(II) and Hg(II) ions were synthesized and characterized by spectroscopic methods. The antiproliferative activities of the ligands and their Cd(II) complexes were screened against four human cell lines using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) method. While the ligands were inactive in the three cancer cell lines screened, their Cd(II) complexes showed a very toxic effect against all cell lines. The complexes especially demonstrated the highest efficacy in the breast cancer cell line among the others. They were found to have higher cytotoxic activity compared to positive controls used in all cell lines. Furthermore, the ligands and their Cd(II) complexes were tested for antimicrobial activity against some pathogen bacteria and yeast strains. The minimum inhibitory concentration (MIC) and minimal bactericidal concentration (MBC), values were found to be in the ranges of 39.06-612 mu M and 39.06-1250 mu M, respectively. Besides, interactions between the compounds and plasmid DNA were studied by agarose gel electrophoresis. All of these cleaved double-strand supercoiled plasmid DNA at the highest concentration indicating DNA cleavage activity. The restriction enzyme digestion of the compound-DNA mixtures showed that compounds bind to A/A and G/G nucleotides.

Three new metal complexes of ammonium n-butyl-(p-methoxyphenyl) dithiophosphinate (NH4L) were synthesized. NH4L was treated with NiCl2·6H2O and CoCl2·6H2O in ethanol to obtain a new trans-bis-[n-butyl-(p-methoxyphenyl) dithiophosphinato]nickel(II) and bis-{bis-[n-butyl-(p-methoxyphenyl) dithiophosphinato]cobalt(II)} complexes, ([Ni(L)2] and [Co2(μ-L)2(L)2], respectively). Square-planar nickel(II) complex was furthermore reacted with excess pyridine (Py) and the octahedral {bis-pyridine-bis-[n-butyl-(p-methoxyphenyl)]}nikel(II) complex, ([Ni(L)2(Py)2]), was obtained. The structures of the complexes were analyzed by elemental analysis, 1H-, 13C-, 31P- NMR; and also by MS-, FTIR- and Raman spectroscopies. The magnetic susceptibilities of the Co(II) and the pyridine-Ni(II) complexes were measured to throw further light on the hybridization patterns. The solid-state structures of the nickel complexes were also done by X-ray crystallography. The P–S bonds in the Ni(II) complexes are essentially of the same lengths; indicating an effective electron delocalization around the central PS2 moiety.

The high energy complexes [Ag (pp) (NO3)] (I), [Ag (dmpp) (NO3)] (II), [Ag (pp)ClO3)] (III), [Ag (dmpp) (ClO3)] (IV), [Ag (pp) (ClO4)] (V), [Ag (dmpp) (ClO4)] (VI) were synthesized from the ligands, Bis-2,6(Pyrazol-1-yl)Pyridine (pp) and Bis-2,6 (3,5-dimethylpyrazol-1-yl)Pyridine (dmpp). They were characterized via IR spectroscopy and elemental analysis. Suitable single crystals of complexes I, IV and VI have been obtained and their molecular structures were determined by X-Ray diffraction methods. The X-Ray study revealed that these complexes were di-nuclear. All complexes have been analyzed by TG-DTA. It was determined that they decompose exothermically in explosive reactions. Elevation in the thermal decomposition temperature, enthalpy of reaction and mass loss was observed with increasing number of oxygens within the anion in the complex structure. The HOMO and LUMO energy levels of the complexes, together with the theoretical formation enthalpies, were calculated by using Gaussian 09 software package whereas the enthalpies of thermal decomposition were measured by DSC. The products of decomposition were predicted from the theoretical formation enthalpy and the measured heat of reaction values according to Hess’ law. It was observed that the thermogravimetry plots of complexes I, II and VI were suitable for thermo-kinetics investigation. Thus, they were analyzed by means of isothermal (Coats-Redfern) and non-isothermal-isoconvertional (Flyn-Ozawa-Wall and Kissinger-Akahira-Sunose) methods and certain thermodynamic parameters were calculated. It was discovered that all complexes except complex II decomposed with rapid, single step reactions whereas complex II decomposed with a 2-step reaction.

A new octahedral pyridine-phosphonodithioato nickel(II) complex ([(RO)(R)PS2Ni(py)(2)], R = p-methoxyphenyl-; OR = 3-methyl-1-butoxy-; py = pyridine] was synthesized and elucidated by elemental analysis, MS, vibrational spectroscopies (FTIR and Raman). The single crystal of the compound has been prepared and characterized by single crystal X-ray diffraction. The empirical ground state electron density distribution of [(RO)(R)PS2Ni(py)(2)] obtained by X-ray crystallography was compared with the theoretical counterpart predicted by density functional theory (DFT) with B3LYP/LANL2DZ level. Moreover, the geometrical structures, atomic charges, frontier molecular orbitals, molecular electrostatic potential (MEP) surfaces and nonlinear optical (NLO) properties were studied by using DFT. (C) 2019 Elsevier B.V. All rights reserved.

The syntheses, spectroscopic properties, and antimicrobial activities of new pyranones and quinoline-based dihydrofurans accompanied by 3-alkenyl-substituted structures were investigated.

Five new dithiophosphonic acids ((p-MeO-C6H4)PS(SH)(OR), HLn, (n = 1-5); R = 3-pentyl-, HL1; R = 1-phenyl-1-propyl-, HL2; R = 4-tert-butyl benzyl-, HL3; R = diphenylmethyl-, HL4; R=4-tert-butylcyclohexyl-, HL5) were prepared by the reaction of Lawesson reagent with the corresponding alcohols. As the acids were viscous liquids and difficult to purify they were converted to their ammonium salts ([NH(4)Ln]) for purification through crystallization. Four coordinated Ni(II) complexes of the dithiophosphonates ([Ni(Ln)(2)]) were synthesized in methanol medium and purified. The reaction between these square planar complexes and pyridine was carried out to produce six coordinated pyridine derivatives ([Ni(Ln)(2)(py)(2)]). The structures of the fifteen compounds so prepared were elucidated by spectroscopy, elemental analysis methods and magnetic susceptibility measurement. The molecular and crystal structure of [Ni(L2)(2)(py)(2)] was determined by X-ray crystallography. DFT calculations were carried out using the B3LYP functional with the LANL2DZ basis set to the optimized geometrical structure and determine the energies, the orientations of the molecular orbitals (HOMOs and LUMOs) and the molecular electrostatic potential (MEP) surfaces of the octahedral complex [Ni(L2)(2)(py)(2)]. The results for [Ni(L2)(2)(py)(2)] revealed that these bonded to the active sites of A-DNA and B-DNA by weak non-covalent interactions, which was also supported by molecular docking investigations. (C) 2018 Elsevier B.V. All rights reserved.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

We report the synthesis and characterization, biological activity, DNA binding, colorimetric anion sensor properties, computational (HF) and molecular docking studies of a novel Schiff base (E)-4-[(4-ethoxyphenylimino)methyl]-2-methoxyphenol.The molecular structure of the title compound was experimentally determined using spectroscopic data and was compared to the structure predicted by theoretical calculations using density functional theory (DFT).In addition, atomic charges, molecular electrostatic potential (MEP), nonlinear optical (NLO) effects, the potential energy surface (PES) scans about two important torsion angles and thermodynamic properties of the title compound were predicted using DFT.The antimicrobial activity of the compound was investigated for minimum inhibitory concentration.UV-Vis spectroscopy studies of the interactions between the compound and calf thymus DNA (CT-DNA) showed that the compound interacts with CT-DNA via intercalative binding.The colorimetric response of the Schiff base receptors in DMSO was investigated.The most discernable color change in the Schiff base was caused by CN -, which demonstrated that the ligand can be used to selectively detect CN -.

In this study, the radical cyclization reactions of cyclic 1,3-dicarbonyl compounds (1a–c) and α,β-unsaturated alcohols (2a–d) through Mn(OAc)3 were performed. A series of biologically interesting dihydropyrans (3–5) and dihydrofurans (6–18) were synthesized as a result of these reactions. Spiro compounds (19–20) were obtained from the reactions of 1,3-dicarbonyl compounds and (E)-2,4-diphenyl-but-3-en-2-ol (2e). The unique structure of compound 19 was also confirmed by X-ray crystallography. In addition, the antibacterial activities of synthesized compounds were screened against some bacteria. Their zone diameters showed better results than some known antibiotics.

In the crystal of the title complex, [Cu(C7H6NO4S)2(C6H6N2O)2(H2O)], the CuII cation and the O atom of the coordinated water molecule reside on a twofold rotation axis. The CuII ion is coordinated by two carboxylate O atoms of the two symmetry-related 4-sulfamoylbenzoate (SB) anions and by two N atoms of the two symmetry-related nicotinamide (NA) molecules at distances of 1.978 (2) and 2.025 (3) Å, respectively, forming a slightly distorted square-planar arrangement. The distorted square-pyramidal coordination environment is completed by the water O atom in the axial position at a distance of 2.147 (4) Å. In the crystal, the molecules are linked via O—H...O and N—H...O hydrogen bonds with R22(8) and R22(18) ring motifs, forming a three-dimensional architecture. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H...O/O...H (42.2%), H...H (25.7%) and H...C/C...H (20.0%) interactions.

Density Functional Theory methods (BLYP, B3PW91, and B3LYP) with the 6-311G (d,p) basis set were used to calculate the molecular structure, vibrational frequencies and infrared intensities of the title compound. A comparison between the calculated geometric parameters and the corresponding single-crystal X-ray structure data of the title compound was performed. It was observed that the harmonic vibrations, calculated for this compound by the B3LYP/6-311G (d,p) method, are in good agreement with the experimental IR and Raman spectral data (RMSmol = 9.63). Also, the theoretical vibrational spectra of the title compound were evaluated by PEDs, using the SQM 2.0 program. Among the investigated methods, a general better performance of B3LYP was calculated by the aid of PAVF 1.0 program. (C) 2018 Elsevier B.V. All rights reserved.

New metalloporphyrazines (MgPz, ZnPz) containing peripheral tetrasubstitutions derived from 7,8-dihydro-6[Formula: see text],14[Formula: see text],19[Formula: see text]-dibenzo[bj][1,12,5,8]-dioxadithiacyclopentadecine-16,17-dicarbonitrile (6) have been synthesized by a multistep reaction sequence and characterized. Compound 6 has been prepared by the reaction of 1,3-di(2-bromomethyl phenoxy) propane (3) or 1,3-di(2-iodomethylphenoxy) propane (4) which were prepared via bromination or iodination of {2-[3-(2-hydroxymethylphenoxy)propoxy]-phenyl}methanol (2) and cis-1,2-dicyano-1,2-ethylenedithiolate (5). The novel magnesium porphyrazine was prepared by the cyclotetramerization reaction of 6 with magnesium butoxide. The one-step synthesis of porphyrazinato zinc complex has been achieved without a reaction sequence by using dicyano compound (6) and zinc butoxide. The prediction of the geometry optimization, normal mode frequencies, [Formula: see text]H, [Formula: see text]C NMR, UV absorption spectra, chemical shifts, electronic properties and NBO analysis of the compound were examined by using B3LYP method with a 6-31G([Formula: see text], [Formula: see text] basis set. These novel compounds were characterized by a combination of elemental analysis, [Formula: see text]H, [Formula: see text]C NMR, FT-IR, UV-vis and MS spectral data. An X-ray crystal structure of dicarbodinitrile compound (6) was also investigated.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

In this study, the manganese(III) acetate mediated radical addition-cyclization reactions of ferrocene substituted alkenes and active methylene compounds were carried out. The regio- and stereoselective radical cyclization reactions of (E)-styrylferrocene (1a) and active methylene compounds (2a-g) gave trans-5-ferrocenyl-4-phenyl-4,5-dihydrofuran compounds as the sole products. The reactions of 1-ferrocenyl-1-aryl(heteroaryl)ethenes (1b-e) and active methylene compounds (2a-f) via Mn(OAc)3 led to furan and benzofuran derivatives (10–33) in mid-good yields (up to 75%). Surprisingly, ferrocene substituted allylidene derivatives were obtained from the Mn(OAc)3 mediated reactions of 1-aryl-1-ferrocenylethene (1b-d) and 1,3-dimethylbarbituric acid (2g). The uses of ferrocene substituted alkenes in manganese(III) acetate mediated radical reactions is the first example in this field as far as we know.