Synthesis of an F-BODIPY [2]catenane using the chemistry of bis(dipyrrinato)metal complexes.

ML2 type complexes of an olefin terminated 5H-dipyrrin ligand can be subjected to twofold ring closing metathesis to give bis(dipyrrinato)copper(ii) and bis(dipyrrinato)zinc(ii) [2]catenates. Demetalation of the copper(ii) [2]catenate with KCN/N2H4·H2O gave the corresponding bis(dipyrrin) [2]catenand. The boron difluoride complex of this bis(dipyrrin) was obtained as the first fluorescent F-BODIPY [2]catenane.

Crystal structure of aqua-bis-(hepta-fluoro-butano-ato-κO)(1,10'-phenanthroline-κ(2) N,N')copper(II).

The title compound, [Cu(C4F7O2)2(C12H8N2)(H2O)], is mononuclear and contains a penta-coordinated Cu(II) ion. The geometry of Cu(II) ion can be described as distorted square-pyramidal with two O atoms of two butano-ate anions and two N atoms of the o-phenanthroline ligand occupying the basal plane, and a water O atom located at the axial position. In the crystal, C-H⋯(O,F) and O-H⋯(O,F) hydrogen bonds and π-π inter-actions [centroid-to-centroid distance 3.533 (2) Å] link the mol-ecules into a three-dimensional supra-molecular structure.

The Anticancer Activity of Complex [Cu2(µ-(C6H5)2CHCOO)3(bipy)2)] (ClO4) -Solid Lipid Nanoparticles on MCF-7 Cells.

Recent studies have focused on the potential use of metal-based complexes for the treatment of cancer. However, there are some limitations of metal-based ligands for the treatment of cancer due to their toxic effects. In the present study, a novel bimetallic Cu(II) complex, [Cu2(µ-(C6H5)2CHCOO)3 (bipy)2)](ClO4), has firstly been synthesized and characterized by FT-IR, and X-ray crystallography. Furthermore, Cu(II) complex-loaded solid lipid nanoparticles (SLNs) were initially prepared by hot homogenization method to overcome their toxic effects. After characterization, comparative cytotoxic and apoptotic activities of the complex and Cu(II) complex-SLNs on human breast cancer cells (MCF-7) and human umbilical vein endothelial cells (HUVEC) were determined. Cu(II) complex demonstrated considerable in vitro cytotoxic effects on MCF-7 (p<0.05) and induced apoptotic cell death (88.02 ± 3.95%) of MCF-7 cells. But, the complex has also toxic effects (69.5%) on HUVEC control cells. For this purpose, Cu(II) complex-loaded solid lipid nanoparticles (SLN) were firstly produced, with a distrubution range of 190±1.45 nm to 350±1.72 nm and zeta potentials of -27.4±1.98 mV and -18.2±1.07 mV, respectively. The scanning electron microscopy (SEM) images of SLNs were also obtained. In vitro studies have shown that Cu(II) complex-SLNs help in reducing the side effect of Cu(II) complex (29.9%) on HUVEC control cells. Therefore, metal based complex might potentially be used for cancer treatment through nanoparticle based drug delivery systems.

Crystal structure of bis-(µ-2-benzoyl-benzoato-κ(2) O:O')bis-[bis-(2,2'-bi-pyridine-κ(2) N,N')manganese(II)] bis-(perchlorate).

The title compound, [Mn2(C6H5COC6H4COO)2(C10H8N2)4](ClO4)2, comprises a centrosymmetric binuclear cation and two perchlorate anions. In the complex cation, two Mn(II) atoms are bridged by two O atoms of two different 2-benzoyl-benzoate ligands, each Mn(II) atom being further coordinated by two 2,2'-bi-pyridine (bipy) ligands in a distorted octa-hedral environment. Within the binuclear mol-ecule, the Mn⋯Mn separation is 4.513 (7) Å. Inter-molecular C-H⋯O and C-H⋯ π inter-actions link the mol-ecules into a three-dimensional network.

1-Pentamethylbenzyl-3-(n)buthylbenzimidazolesilver(I)bromide complex: synthesis, characterization and DFT calculations.

A novel NHC complex of silver(I) ion, 1-pentamethylbenzyl-3-(n)buthylbenzimidazolesilver(I)bromide, was prepared and fully characterized by single crystal X-ray structure determination. FT-IR, NMR and UV-vis spectroscopies were employed to investigate the electronic transition behaviors of the complex. Additionally, the molecular geometry, vibrational frequencies, gauge including atomic orbital (GIAO) (1)H and (13)C chemical shift and electronic transition values of silver(I) complex were calculated by using density functional theory levels (B3LYP and PBE1PBE) with LANL2DZ basis set. Also, the vibrational frequencies were supported on the basis of the potential energy distribution (PED) analysis calculated for PBE1PBE level. We were also investigated total static dipole moment (µ), the mean polarizability (〈α〉), the anisotropy of the polarizability (Δα), the mean first-order hyperpolarizability (〈ß〉) of the title complex. Natural bond orbital (NBO) analysis was performed to determine the presence of hyperconjugative interactions, and charge distributions.

Synthesis, spectroscopic and theoretical studies of ethyl (2E)-3-amino-2-({[(4-benzoyl-1,5-diphenyl-1H-pyrazol-3-yl)carbonyl]amino}carbonothioyl)but-2-enoate butanol solvate.

We have synthesized ethyl (2E)-3-amino-2-({[(4-benzoyl-1,5-diphenyl-1H-pyrazol-3-yl)carbonyl]amino}carbonothioyl)but-2-enoate (2) by the reaction of 4-benzoyl-1,5-diphenyl-1H-pyrazole-3-carbonyl chloride (1), ammonium thiocyanate and ethyl 3-aminobut-2-enoate and then characterized by elemental analyses, IR, Raman, (1)H NMR, (13)C NMR and X-ray diffraction methods. The experimental and theoretical vibrational spectra of 2 were investigated. The experimental FT-IR (4000-400 cm(-1)) and Laser-Raman spectra (4000-100 cm(-1)) of the molecule in the solid phase were recorded. Theoretical vibrational frequencies and geometric parameters (bond lengths, bond angles) were calculated using Ab Initio Hartree Fock (HF), Density Functional Theory (B3LYP) methods with 6-311++G(d,p) basis set by Gaussian 09W program. The computed values of frequencies are scaled using a suitable scale factor to yield good coherence with the observed values. The assignments of the vibrational frequencies were performed by potential energy distribution (PED) analysis by using VEDA 4 program. The theoretical optimized geometric parameters and vibrational frequencies were compared with the corresponding experimental X-ray diffraction data, and they were seen to be in a good agreement with each other. Also, the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energies were calculated.

Synthesis, characterization, and luminescent properties of dinuclear gold(I) xanthate complexes: X-ray structure of [Au2(nBu-xanthate)2].

The synthesis and characterization of gold(I) complexes of butyl xanthate [Au(2)((n)()Bu-xanthate)(2)], 1, and ethyl xanthate [Au(2)(Et-xanthate)(2)], 2, are described. These complexes are readily prepared from the reaction between Au(THT)Cl (THT = tetrahydrothiophene) and the corresponding xanthate ligands as the potassium salts. The two xanthate complexes are characterized by (1)H NMR, IR, mass spectrometry, elemental analysis, and UV-vis techniques. Thermal gravimetric analysis (TGA) and differential thermal analysis (DTA) show that the gold xanthate complexes decompose to yield mainly gold metal at approximately 200 degrees C, confirmed by X-ray powder diffraction. Excitation of the complexes at 450 nm in the solid state at 77 K produces a strong red emission at ca. 690 nm with a broad asymmetric profile tailing to 850 nm. The dinuclear gold(I) xanthate complex, [Au(2)(nBu-xanthate)(2)], 1, is the first structurally characterized binary Au(I) xanthate. The Au...Au distance in the eight-membered ring is 2.8494(15) A while the shortest intermolecular Au...Au interaction between independent units is 3.64 A. The angle between the planes containing the molecules in the unit cell is approximately 69.56 degrees. The light green plates of [Au(mu-S(2)COBu(n))](2) crystallize in the orthorhombic space group P2(1)2(1)2 with a = 37.254(14) A, b = 7.287(3) A, c = 6.054(2) A, alpha = beta = gamma = 90 degrees, Z = 4, and V = 1643.4(11) A(3).

Syntheses and structures of dinuclear gold(I) dithiophosphonate complexes and the reaction of the dithiophosphonate complexes with phosphines: diverse coordination types.

The dinuclear gold(I) dithiophosphonate complex, [Au(2)(dtp)(2)] (1), where dtp = [S(2)P(R)(OR')](-) with R = p-C(6)H(4)OCH(3); R'= c-C(5)H(9), has been synthesized and its reaction studied with the phosphine ligands PPh(3) and Ph(2)P(CH(2))(n)PPh(2) (n = 1-4). Compound 1 contains two gold atoms homobridged by the anionic dithiophosphonate ligand, forming an eight-membered ring complex in a chair form. After the reaction of 1 with diphosphine ligands, the dinuclear open-ring complexes Au(2)(dppm)(dtp)(2) (2), Au(2)(dppe)(dtp)(2) (3), Au(2)(dppp)(dtp)(2) (4), Au(2)(dppb)(dtp)(2) (5) were formed (dppm = diphenylphosphinomethane; dppe = diphenylphosphinoethane; dppp = diphenylphosphinopropane; dppb = diphenylphosphinobutane). The reaction with dppm is stoichiometry-dependent. Thus, when 1 reacts with 2 equiv of dppm, the ionic complex [Au(2)(dppm)(2)(dtp)]dtp forms. This dtp counterion was exchanged with tetrafluoroborate to yield [Au(2)(dppm)(2)(dtp)]BF(4), the crystallization of which afforded two interconvertible isomers, 6-yellow and 7-white. Reaction of 1 with PPh(3) affords the tetracoordinate mononuclear complex [Au(dtp)(PPh(3))(2)] (8). The molecular structures of 1-8 were confirmed by X-ray crystallography and show multiple coordination modes and geometries. The crystal structures of 1 and its reaction products with dppm (2, 6, 7) show short intramolecular Au.Au aurophilic bonding interactions of 2.95-3.10 A while no intermolecular interactions were discernible. However, reaction products of 1 with longer-chain Ph(2)P(CH(2))(n)PPh(2) ligands, n = 2-4, exhibit structures that lack both intra- and intermolecular Au.Au interactions.