Extended Open-Chain Polyenides as Versatile Delocalized Anion Ligands for Metal Chain Clusters

Although small cyclic- and open-chain unsaturated hydrocarbon anions such as cyclopentadienide and open-chain pentadienide are used as the strongly electron-donating auxiliary ligands for metal complexes, more extended π-conjugated unsaturated hydrocarbon anions have rarely been used in coordination chemistry, despite their potential ability to serve as the multiply bridging π-ligands for metal clusters. This work reports isolation of metal chain clusters bearing the multi-dentate, open-chain extended unsaturated hydrocarbon anion ligands. The extended open-chain π-conjugated polyenyl ligands could effectively stabilize oxidized palladium chains, including an unprecedented [Pd₄]⁴⁺ chain.     

o-Trityl phenoxy-imino vanadium (III) complexes: synthesis,characterization, and catalysis on ethylene (co)polymerization

Several phenoxy-imine ligands bearing o-trityl group in phenoxy moiety RN=CHArOH (Ar = C₆H₂(CPh₃)^tBu, R = 2,6-Me₂C₆H₃ ( L ₁ H ); 2,6-ⁱPr₂C₆H₃ ( L ₂ H ); 3,5-(CF₃)₂C₆H₃ ( L ₃ H ); 3,5-(OMe)₂C₆H₃ ( L ₄ H ); CHPh₂ ( L ₅ H ); CPh₃ ( L ₆ H )) were synthesized and characterized by¹H NMR and ¹³C NMR spectroscopy. The vanadium complexes based on these ligands LVCl₂(THF)₂ ( 1–6 ) were synthesized via conventional transmetalation reaction in moderate to high yields. Complexes 1–6 were fully characterized by FT-IR, elemental analyses and the molecular structures of 1 , 2 ·H₂O, (2 ·H₂O ) ₂ (μ-Cl) ₂ , 4 , and 5 were confirmed by X-ray crystallographic analysis in which the six-coordinated vanadium centers are in a typical octahedral geometry. Upon activation with Et₂AlCl in toluene, complexes 1–6 showed high activities in ethylene polymerization affording polymers with moderate molecular weight (5.9–11.8 × 10⁴ Da). Moreover, in hexane or CH₂Cl₂, 1–6 /Et₂AlCl exhibited enhanced activities. When activated with MAO or MMAO in toluene, these complexes showed relatively low activities but afforded polymers with ultra-high molecular weight (up to 3.30 × 10⁶ Da). 1–6 /Et₂AlCl also showed high activities in ethylene/1-hexene copolymerization at room temperature giving moderate molecular-weight polymers (6.5–11.4 × 10⁴ Da) with co-monomer incorporation being of 6.0 ~ 7.8%.     

New organoruthenium metallates containing ferrocenecarboxalidine thiosemicarbazones and their nucleic acid/albumin binding and in vitro cytotoxicity

A string of four new hetero binuclear Ru(III) complexes of ferrocenecarboxaldehyde-4(N)-substituted thiosemicarbazones were synthesized and characterized by various spectral (infrared, ultraviolet–visible, Electron Paramagnetic Resonance (EPR) and High Resolution Mass Spectrometry (HR-MS) techniques. The binding abilities of the ligands/complexes with nucleic acid (calf thymus DNA, CT-DNA) and bovine serum albumin (BSA) were analyzed by absorption and emission titration methods. The complexes exhibited better DNA binding affinity than their parent ligands. The interaction with CT-DNA was found to be intercalative and with BSA static quenching mechanism was observed. All the synthesized Ru(III) complexes were subjected to study their in vitro cytotoxicity against MCF-7 (human breast cancer) and HT-29 (human colon cancer) cell lines. Among the four complexes, complex 3 [RuCp (FF-etsc)PPh₃]Cl exhibited the highest cytotoxicity in MCF-7 cells and complex 4 [RuCp (FF-ptsc)PPh₃]Cl was the most active on HT-29 cells.     

Donor-acceptor copolymers from cyclopentannulation polymerizations with dicyclopenta[cd,jk]pyrene and dicyclopenta[cd,lm] perylene acceptors

A series of donor-acceptor copolymers with dicyclopenta[cd,jk]pyrene and dicyclopenta[cd,lm]perylene acceptor units was prepared via palladium catalyzed cyclopenta-annulation reactions. The acceptor units were paired with diethynyl containing donor groups based on benzo[1,2-b:4,5-b’]dithiophene, thieno[3,2-b]thiophene, and 4-octyl-4H-dithieno[3,2-b:2′,3′-d]pyrrole to create six polymer variants. The cyclopentannulation polymerization resulted in copolymers with molecular weights (Mn) of 6–14 kDa and broad light absorption in the visible region with band gaps of 1.38–1.85 eV. The synthetic methodology, as well as optoelectronic properties, including thin-film absorption and cyclic voltammetry, of the donor-acceptor copolymers are presented.     

Hydrothermal Synthesis and Structure of a Novel Coordination Polymer Co_3(tma)(pda)_2(H_2O)_3]n·nH_2O

1INTRODUCTION Recently,the design and preparation of coordina-tion polymers with new porous frameworks are of great interest due to their potential functionalities such as catalysis,gas absorption,separation and molecu-lar recognition.In designing1-D,2-D and3-D porous coordination polymers,the selection of appropriate ligands is crucial for determining the structure.The mixed-linker systems of both carboxylates and pyri-dyls have proved to be effective for the preparation of novel coordi…     

Spectrophotometric analysis, thermal analysis and gravimetric determination of some metal ions with oxime and Schiff's base derivatives of N-furoylphenylhydroxylamine

The oxime and Schiff's base of N-furoylphenylhydroxylamine form complexes with Co²⁺, Cu²⁺, Zn²⁺ and Fe³⁺. These complexes were studied by means of the UV — Vis. spectra of nujol mulls, electron spin resonance (ESR) spectra and magnetic susceptibility to determine their stereochemistry. The complexes were characterized via elemental analyses, molar conductivities and thermogravimetric analyses. Organic reagents were used for the gravimetric determination of Co²⁺, Cu²⁺ and Fe³⁺ through the precipitation of their complexes. The compounds were also used for separation of a binary mixture of Cu²⁺ and Cu²⁺. Interferences were studied.     

Studies on basicity of alkali metal catron exchanged β and X zeolites by pyrrole-IR spectroscopy

The strength of basic sites has been measured by pyrrole-IR on alkali metal cation exchanged β and X zeolites, as well as NaOH loaded Naβ. The influence of cation type and the structure of zeolites on their basicity has been studied. The acidic and basic properties of the samples were investigated by NH3-TPD and isopropanol reaction. It was shown that the strength of basic sites on samples could be characterized by the shift of vNH band in the pyrrole-IR spectra. The framework oxygen charges were calculated from the Sanderson electronegativity. The changes in basic properties with various alkali metal cation are consistent with the changes of local oxygen charges of the zeolite framework.     

Halomethanes in tri-n-octylamine and squalane mixtures at infinite dilution

The retention behavior of eight halomethanes and four saturated hydrocarbons was measured in gas chromatographic stationary phases consisting in tri-n-octylamine (TOA), squalane (SQ) and six TOA+SQ mixtures, at 55.0, 58.5, 62.5 and 65.0°C. Equlibrium constants for complex formation were extracted from experimental data by using a lattice model developed by Martire. The results may be interpreted in terms of the formation of weak hydrogen-bonded complexes, with sociation constants of about 0.13 L-mol^–1 for haloforms and 0.07 L-mol^–1 for dihalomethanes at 60°C.