Controlled ring‐opening homo‐ and copolymerization of ɛ‐caprolactone and d,l‐lactide by iminophenolate aluminum complexes: An efficient approach toward well‐defined macromonomers

The aluminum complexes containing two iminophenolate ligands of the type (p‐XC₆H₄NCHC₆H₄O‐o)₂AlR' (R′=Me ( 3, 4 ) or R′=O(CH₂)₄OCH=CH₂ ( 5, 6 ), X=H ( 3, 5 ), F( 4, 6 )) were synthesized and characterized by ¹H, ¹³C NMR spectroscopy, and X‐ray crystallography. The reaction of AlMe₃ with two equivalents of substituted iminophenols gave five‐coordinated {ONR}₂AlMe ( 3, 4 ) complexes. Subsequent reaction of these methyl complexes with unsaturated alcohol, HO(CH₂)₄OCH=CH₂, resulted in target compounds 5 and 6 in a good yield. It was shown that the complexes ( 3 ‐ 6 ) are monomeric in solution (NMR) and in solid state (X‐ray analysis). The catalytic activity of the complexes 5 and 6 towards ring‐opening polymerization (ROP) of ?‐caprolactone and d,l ‐lactide was assessed. Complex 5 showed higher activity as compared with 6 , while both of these catalysts induced controlled homo‐ and copolymerization to afford the macromonomers with high content of vinyl ether end groups (F_n > 80%) in a broad range of molecular weights (M_n = 4000–30,000 g mol^?1) with relatively narrow MWD (M_w/M_n = 1.1–1.5). © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1237–1250     

In vitro biomolecular interaction studies and cytotoxic activities of copper(II) and zinc(II) complexes bearing ONS donor thiosemicarbazones

Among all the bio‐metals, zinc and copper derivatives of ONS donor thiosemicarbazone have aroused great interest because of their potential biological applications. Multisubstituted thiosemicarbazone ligand H₂dspt (3,5‐dichlorosalicylaldehyde‐N⁴‐phenylthiosemicarbazone) derived new ternary complexes like [Zn(dspt)(phen)]?DMF ( 1 ) and [Cu(dspt)(phen)]?DMF ( 2 ), and another thiosemicarbazone, H₂dsct (3,5‐dichlorosalicylaldehyde‐N⁴‐cyclohexylthiosemicarbazone), derived [Cu(dsct)(bipy)]?DMF ( 3 ). These complexes have been characterized by elemental analysis (CHNS), Fourier transform infrared (FT‐IR), ultraviolet–visible (UV–Vis) and proton nuclear magnetic resonance (¹H‐NMR) spectra. The structures of the complexes were obtained by single‐crystal X‐ray diffraction analysis. Compounds 1 and 2 got crystallized in the monoclinic P2₁/c space group. The complexes showed interesting supramolecular interaction, which in turn stabilizes the complexes. The ground state electronic configurations of the complexes were studied using the B3LYP/LANL2DZ basis set, and ESP plots of complexes were investigated. The interaction of the complexes with calf thymus DNA (CT‐DNA) was studied using absorption and fluorescence spectroscopic methods. A UV study of the interaction of the complexes with calf thymus DNA (CT‐DNA) has shown that the complexes can effectively bind to CT‐DNA, and [Cu(dspt)(phen)]·DMF ( 2 ) exhibited the highest binding constant to CT‐DNA (K_b = 3.7 × 10⁴). Fluorescence spectral studies also indicated that Complex 2 binds relatively stronger with CT DNA through intercalative mode, exhibiting higher binding constant (K_q = 4.7 × 10⁵). The DNA cleavage result showed that the complexes are capable of cleaving the DNA without the help of any external agent. Molecular docking studies were carried out to understand the binding of complexes with the molecular target DNA. Complex 2 exhibited the highest cytotoxicity against human breast cancer cell line MD‐MBA‐231 (IC₅₀ = 23.93 μg/mL) as compared to Complex 1 (IC₅₀ = 44.40 μg/mL) .     

Structural characterization of disperse black 9 based Cu (II) complex and investigation of its some properties

We obtained the azo‐imine ligand (2,2′‐[4‐(5‐methoxy salicylidene‐4‐iminophenylazo)phenylimino]diethanol) (HL) and its Cu (II) complex (CuL) from the ethanol solution. The complex Cu(L)₂ was obtained as single crystals from the CH₃OH solution and structurally characterized. The electronic and photoluminescence properties of the ligand and its Cu (II) complex were investigated both in DMF solution and solid state. The oxidation and reduction behaviours of the compounds were studied in the solution and found that the redox processes are irreversible. Thermal studies show that the ligand has higher thermal stability than the CuL complex. Single crystals of the complex were obtained from slow evaporation of a DMF solution of the complex. Crystals of the complex showed a diffraction pattern; however, the structure of the complex was able to be solved.     

Tributyltin(IV) Schiff base complexes with amino acid derivatives: synthesis,characterization and biological activity

The synthesis in one‐pot reactions and structural characterization of six new tri‐n‐butyltin(IV) derivatives of Schiff bases are reported. The compounds are derived from a condensation reaction between l ‐alanine, l ‐valine, l ‐isoleucine, l ‐methionine, l ‐phenylalanine or l ‐tryptophan and 3,5‐di‐tert‐butyl‐2‐hydroxybenzaldehyde. Characterization was completed using elemental analysis, infrared spectroscopy, mass spectrometry, one‐ and two‐dimensional solution NMR (¹H, ¹³C and ¹¹⁹Sn) as well as solid‐state ¹¹⁹Sn NMR. In addition, the crystal structures of three of the compounds were confirmed using single‐crystal X‐ray diffraction. Although five‐coordinated and polymeric in the solid state, the tin compounds are four‐coordinated and monomeric in solution. The coordination environment around the triorganotin units comprises three carbon atoms and two oxygen atoms from two ligands in a trigonal bipyramidal geometry. The anti‐proliferative effect of these compounds on the cervical carcinoma cell lines HeLa, CaSki and ViBo was screened in vitro, the compounds showing cytotoxic activity against all three strains and null or low cytotoxic activity (necrotic) as well. Copyright © 2016 John Wiley & Sons, Ltd.     

Structural distortion,charge modulation and local anisotropies in magnetite below the Verwey transition using resonant X‐ray scattering

The pattern of charge modulations and local anisotropies below the Verwey transition has been determined and quantified in high‐quality Fe₃O₄ single crystals and thin films grown on MgO by using resonant X‐ray scattering at the Fe K‐edge. The energy, polarization and azimuthal angle dependencies of an extensive set of reflections with potential sensitivity to charge or local anisotropy orderings have been analyzed to explore their origins. A charge disproportion on octahedral B sites of 0.20 ± 0.05 e^? with [0 0 1] and cubic periodicities has been confirmed, while no significant charge disproportion has been obtained with [0 0 1/2] cubic periodicity. Additional charge modulations in the monoclinic a–b plane are also present. In addition, the occurrence of new forbidden (1, 1, 0) and (0, 0, 2n + 1/2) cubic reflections that arise from the anisotropy of the local structure around different tetrahedral and octahedral Fe atoms is shown. This complex pattern of weak charge modulations and local anisotropies is fully compatible with the low‐temperature crystal structure refined in the non‐polar C2/c space group and disproves any bimodal charge disproportion of the octahedral Fe atoms.     

Hybrid inorganic–organic poly(carborane‐siloxane‐arylacetylene) structural isomers with in‐chain aromatics: Synthesis and properties

Structural isomers of thermo‐oxidatively stable poly(carborane‐siloxane‐arylacetylene) (PCSAA), namely, m‐PCSAA and p‐PCSAA, were synthesized by the reaction of the dimagnesium salts of m‐diethynylbenzene or p‐diethynylbenzene with 1,7‐bis(chlorotetramethyldisiloxyl)‐m‐carborane. The developed polymers have exceptional thermo‐oxidative properties similar to their diacetylene counterpart poly(carborane‐siloxane‐acetylene), PCSA. Thermal treatment of either of the PCSAAs results in a fully crosslinked thermoset by 500 °C resulting from the cycloaddition reactions involving the acetylene and aryl functionalities and subsequent formation of bridging disilylmethylene entities as discerned from Fourier transform infrared, ¹³C and ²⁹Si solid‐state NMR, and XPS studies. X‐ray diffraction analysis revealed that the thermosets obtained from p‐PCSAA possess enhanced crystallinity when compared to that obtained from m‐PCSAA possibly due to more efficient packing interactions of the p‐diethynylbenzene groups during thermoset formation. The presence of the aryl groups in the backbone of the PCSAAs' chains appeared to have enhanced the storage and bulk moduli of their thermosets when compared to the thermoset of PCSA. Dielectric studies of m‐PCSAA and p‐PCSAA revealed segmental relaxation peaks, α, above their glass transition temperatures with p‐PCSAA exhibiting a broader peak with a slower relaxation rate than m‐PCSAA. © 2013 Wiley Periodicals, Inc.^? J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2638–2650     

Crystal structures of functional building blocks derived from bis(benzo[b]thiophen‐2‐yl)methane

The syntheses of three bis(benzo[b]thiophen‐2‐yl)methane derivatives, namely bis(benzo[b]thiophen‐2‐yl)methanone, C₁₇H₁₀OS₂, (I), 1,1‐bis(benzo[b]thiophen‐2‐yl)‐3‐(trimethylsilyl)prop‐2‐yn‐1‐ol, C₂₂H₂₀OS₂Si, (II), and 1,1‐bis(benzo[b]thiophen‐2‐yl)prop‐2‐yn‐1‐ol, C₁₉H₁₂OS₂, (III), are described and their crystal structures discussed comparatively. The conformation of ketone (I) and the respective analogues are rather similar for most of the compounds compared. This is true for the interplanar angles, the C_aryl—C_bridge—C_aryl angles and the dihedral angles. The best resemblance is found for a bioisotere of (I), viz. 2,2′‐dinaphthyl ketone, (VII). By way of interest, the crystal packings also reveal similarities between (I) and (VII). In (I), the edge‐to‐face interactions seen between two napthyl residues in (VII) are substituted by S…π contacts between the benzo[b]thiophen‐2‐yl units in (I). In the structures of the bis(benzo[b]thiophen‐2‐yl)methanols, i.e. (II) and (III), the interplanar angles are also quite similar compared with analogues and related active pharmaceutical ingredients (APIs) containing the dithiophen‐2‐ylmethane scaffold, though the dihedral angles show a larger variability and produce unsymmetrical molecules.     

Coumarin‐tethered (benz)imidazolium salts and their silver(I) N‐heterocyclic carbene complexes: Synthesis,characterization, crystal structure and antibacterial studies

A series of new sterically modulated chlorocoumarin‐substituted (benz)imidazolium salts and their bis‐N‐heterocyclic carbene silver(I) complexes were prepared and characterized. The complexes were prepared in good yields following the in situ deprotonation method by treating azolium salts with silver(I) oxide in the dark. All the compounds were characterized using various spectroscopic and analytical methods. Additionally, one of the benzimidazolium salts was characterized using single‐crystal X‐ray diffraction technique. In this salt, intermolecular π–π stacking interactions operate between benzimidazole as well as coumarin heterocyclic systems with adjacent molecules. In the preliminary antibacterial studies, the silver complexes were found more active than the corresponding salts against a panel of bacterial strains. Interestingly, the complexes displayed improved antibacterial efficacy against Escherichia coli strain, comparable with that of the standard drug ampicillin.