Synthesis of a fluorescent gold(I) complex with a thiosemicarbazone, [Au2(3-NO2-Hbtsc)4]Cl2 · 2CH3CN

Direct reaction of gold(I) chloride with 3-nitrobenzaldehyde thiosemicarbazone (3-NO₂-Hbtsc) in the presence of triphenylphosphine in acetonitrile has yielded ionic complex, [Au₂(3-NO₂-Hbtsc)₄]Cl₂ · 2CH₃CN (1). It exhibited an intense fluorescence band (λ_em) at 383 nm (λ_ex = 300 nm), and two bands of medium intensity at 413 and 436 nm (λ_ex = 350 nm). Complex 1 represents first example of ionic gold(I) complex with a thiosemicarbazone.     

Synthesis, Structure and DNA Binding Properties of [Cu2(heae)(SCN)2]n?·?nH2O the First One-Dimensional Polymeric Copper(II) Complex Bridged Alternately by Oxamidate and Double End-to-End Thiocyanate Ligands

A new one-dimensional polymeric copper(II) complex, [Cu₂(heae)(SCN)₂] _n  · nH₂O [H₂heae is N,N′-bis(N-hydroxyethylaminoethyl)oxamide], has been synthesized and characterized by elemental analysis, molar conductivity measurement, IR and electronic spectra studies, and single-crystal X-ray diffraction. The structure of the complex exhibits a neutral one-dimensional polymeric copper(II) zigzag chain [Cu₂(heae)(SCN)₂] _n constructed by μ-trans-heae and double μ-1,3-thiocyanate ligands. The environment about copper can be described as a square-pyramid. The neighboring second building units (SBUs), [Cu(trans-heae)Cu]²⁺, are unequal with Cu···Cu separations of 5.287 and 5.273 ? for Cu1···Cu1ⁱ and Cu2···Cu2ⁱⁱ, respectively. The double thiocyanate ligands function as μ(1,3)-bridges to link these unequal SBUs thereby forming zigzag chains with a Cu1···Cu2 separation of 5.454 ?. The hydrogen bonds in the crystal structure self-assemble the one-dimensional chains into a three-dimensional supramolecular structure. The interaction of the polymeric copper(II) complex with herring sperm DNA (HS-DNA) has been investigated by using absorption and emission spectra, electrochemical techniques and viscometry. The results reveal that the polymeric copper(II) complex interacts with HS-DNA via a groove binding mode with the intrinsic binding constant of 1.38 × 10⁴ M⁻¹. To the best of our knowledge, this is the first example about the structure and DNA-bonding studies of a one-dimensional polymeric copper(II) complex that is bridged alternately by trans-oxamidate and double-thiocyanate ligands.     

Donor‐Stabilized Phosphenium Adducts as New Efficient and Immobilizing Ligands in Palladium‐Catalyzed Alkynylation and Platinum‐Catalyzed Hydrogenation in Ionic Liquids

The straightforward synthesis of a new donor‐stabilized phosphenium ligand 3d by addition of bromodifurylphosphine to 1,3‐dimethylimidazolium‐2‐carboxylate 1 is described. The obtained ligand exhibits a very strong π‐acceptor character, comparable to that of triphenyl phosphite [P(OPh)₃] or of tris‐halogenophosphines, with a ν_CO(A₁) at 2087 cm⁻¹ for its nickel tricarbonyl complex. This ligand, as well as the related 3a which was obtained from chlorodiphenylphosphine, were tested in palladium‐catalyzed aryl alkynylation and in the platinum‐catalyzed selective hydrogenation of chloronitrobenzenes, both in an ionic liquid phase. In C C bond cross‐coupling we observed that the increase of the π‐acceptor character in ligand 3d , due to the introduction of an additional electron‐withdrawing group, provides a very efficient catalyst in the alkynylation reaction of aryl bromides with phenylacetylene, including the deactivated 4‐bromoanisole or the sterically hindered 2‐bromonaphthalene. The catalytic activity decreases with recycling due to the sensitiveness of ligands to protonation in the ionic phase. Conversely, a multiple recycling of the metal/ligand system in non‐acidic media was achieved from platinum‐catalyzed hydrogenation of m‐chloronitrobenzene. The catalytic results obtained by employing the complex of platinum(II) chloride with 3a [trans‐PtCl₂( 3a )₂] in comparison with the non‐ionic related trans‐tris(triphenylphosphine)platinum dichloride [trans‐PtCl₂(PPh₃)₂] complex clearly indicate that the simultaneous existence of a strong π‐acceptor character and a positive charge within the ligand 3a significantly increases the life‐time of the platinum catalyst. The selectivity of the reaction is also improved by decreasing the undesirable formation of dehalogenation products. This cationic platinum complex trans‐PtCl₂( 3a )₂ is the first example of a highly selective catalyst for hydrogenation of chloronitroarenes immobilized in an ionic liquid phase. The system was recycled six times without noticeable metal leaching in the organic phase, and no loss of activity.     

Effect of sintering on the catalytic activity of a Pt based catalyst for CO oxidation: Experiments and modeling

The goal of this paper was to make the link between sintering of a 1.6% Pt/Al₂O₃ catalyst and its activity for CO oxidation reaction. Thermal aging of this catalyst for different durations ranging from 15 min to 16 h, at 600 and 700 °C, under 7% O₂, led to a shift of the platinum particle size distributions towards larger diameters, due to sintering. These distributions were studied by transmission electron microscopy. The number and the surface average diameters of platinum particles increase from 1.3 to 8.9 nm and 2.1 to 12.8 nm, respectively, after 16 h aging at 600 °C. The catalytic activity for CO oxidation under different CO and O₂ inlet concentrations decreases after aging the catalyst. The light-off temperature increased by 48 °C when the catalyst was aged for 16 h at 600 °C. The CO oxidation reaction is structure sensitive with a catalytic activity increasing with the platinum particle size. To account for this size effect, two intrinsic kinetic constants, related either to platinum atoms on planar faces or atoms on edges and corners were defined. A platinum site located on a planar face was found to be 2.5 more active than a platinum site on edges or corners, whatever the temperature. The global kinetic law {r (mol m⁻² s⁻¹) = 103 × exp(−64,500/RT)[O₂]^0.74[CO]^−0.5)} related to a reaction occurring on a platinum atom located on planar faces allows a simulation of the CO conversion curves during a temperature ramp. Modeling of the catalytic CO conversion during a temperature ramp, using the different aged catalysts, allows prediction of the CO conversion curves over a wide range of experimental conditions.     

Concomitant Crystallization of Copper(II) Sachharinato Complexes with 2-methylpyrazine as a Monomer and an One-dimensional Polymer: Syntheses,Crystal Structures,Spectroscopic and Thermal Properties

The reaction of [Cu(sac)₂(H₂O)₄] · 2H₂O with 2-methylpyrazine (mpyz) leads two complexes, concomitant crystallization of a mononuclear complex [Cu(sac)₂(mpyz)(H₂O)₂] (1) and a polymeric complex [Cu(sac)₂(μ-mpyz)]_n (2). Both complexes have been characterized by elemental analyses, magnetic measurements, FT-IR and ESR, TG-DTA and single-crystal X-ray diffraction analyses. Single-crystal X-ray analyses show that complex 1 consists of discrete molecules in which the copper(II) ions exhibits a square-pyramidal coordination geometry. The individual molecules of 1 are connected into a hydrogen-bonded chain structure, which is further assembled to form a three-dimensional network by π–π stacking interactions. Complex 2 is an 1D coordination polymer in which copper(II) centers are bridged by the mpyz ligand. The chains are further assembled to form two-dimensional frameworks by π–π and C–H···π stacking interactions.     

Synthesis, structure and magnetic properties of the first copper(II) complex with an (E)-4-aryl-4-oxo-2-butenoato ligand

A new binuclear Cu(II) complex with an (E)-4-(2,4-diisopropylphenyl)-4-oxo-2-butenoato ligand (L) was successfully synthesized and characterized by elemental analysis and IR-spectroscopy. The structures of (E)-4-(2,4-diisopropylphenyl)-4-oxo-2-butenoic acid (HL), and the corresponding (tetrakis)-μ-[(E)-4-(2,4-diisopropylphenyl)-4-oxo-2-butenoato]-bis(ethanol)-copper(II) complex, [Cu₂L₄(C₂H₅OH)₂], were determined by single crystal X-ray analyses and are preliminarily discussed. This is the first complex of a transition metal with ligand L, as well as the first determined crystal structure of a metal complex with this type of ligand. Analysis of the magnetic susceptibility measurements of the isolated [Cu₂L₄(C₂H₅OH)₂] · H₂O complex shows the existence of a strong anti-ferromagnetic intradimer coupling, with an exchange integral value 2J of −260 cm⁻¹.     

A New Nitrosyl-bridged Bimetallic Nitroprusside Complex: Synthesis,Crystal Structure,Supramolecular Self-assembly and Spectral Behavior of Interactions with DNA

A new nitrosyl-bridged bimetallic nitroprusside complex, [Ba(phen)₃(H₂O)][Fe(CN)₅NO]·1.5phen·2H₂O (phen = 1,10-phenanthroline) (1), has been synthesized and characterized by elemental analysis and single crystal X-ray diffraction. The crystal structure analysis reveals that complex 1 crystallizes in the triclinic space group Pī. The asymmetric structural unit is comprised of one [Ba(phen)₃(H₂O)]²⁺ complex cation, one [Fe(CN)₅NO]^2– complex anion, 1.5-uncoordinated phenanthroline molecules and two lattice water molecules. The complex ions are linked into a 1D chain-like arrangement by the trans CN and NO groups in nitroprusside. The six-coordinated Fe-atom forms a distorted octahedral coordination configuration, and the Ba-atom has a nine-coordinate monocapped antiprismatic geometry. Five types of π–π stacking interactions of phenanthroline and some intra- and intermolecular hydrogen bonds are observed in the 3D supramolecular self-assembly. Absorption spectroscopy, fluorescence titration and viscometry studies of the interaction between complex 1 and calf thymus DNA indicate that complex 1 is a moderate metallo-intercalator with the intrinsic binding constant of 3.70 × 10⁴ M⁻¹ and the linear Stern–Volmer quenching constant of 5.98 × 10⁴ M⁻¹.     

Synthesis, Characterization and Crystal Structure of a Novel Three-Dimensional Supramolecular Framework Containing Ni···π Interaction Heteronuclear Complex: {[Cu(4(5)-Meim)4][Ni(CN)4] · H2O}n

The heteronuclear complex, {[Cu(4(5)-Meim)₄][Ni(CN)₄] · H₂O}_n (1), (4(5)-Meim = 4(5)-methylimidazole) was synthesized and characterized by FT-IR spectroscopy, single crystal X-ray diffraction, thermal analysis and elemental analysis. The Cu(II) ion has a distorted square planar geometry, extended to (4 + 2) weak coordination by two nitrogen atoms of the cyano group. The coordination sphere around the Ni(II) ion should be described as a 4 + 2 geometry with the four cyano groups and the axial coordination site is located at the imidazole ring though a weak Ni···π interaction. The coordination bond is much stronger than the Ni···π interactions and it is expected that the formation of the coordination bond will affect more significantly the position of the absorption bands associated with the vibrations of the ligand. In addition, the out-of-plane modes of 4(5)-Meim are shifted to higher frequencies relative to free ligand. We propose that these shifts are indicative of the weak CH∙∙∙π and Ni∙∙∙π interactions, according to the crystallographic and spectroscopic data.     

Solvothermal Synthesis and Crystal Structure of a Novel 3D Triorganotin Polymer Containing Polyfunctional Ligand 5-mercapto-1(H)-tetrazoleacetic acid

A novel 3D tri-n-butyltin complex [(n-Bu₃Sn)₂(C₂H₂N₄SCO₂)]_n (1) has been solvothermally synthesized and structurally characterized by elemental analysis, FT-IR, NMR (¹H, ¹³C, and ¹¹⁹Sn) spectra and X-ray crystallography. X-ray data of complex 1 reveals that it is a 3D tri-n-butyltin coordination polymer with a metal-organic framework (MOF) structure , significant N → Sn interactions plays an important role in the construction of this structure.     

The Effect of Coating TiO<Subscript>2</Subscript> on the CO Oxidation of the Pt/γ-Alumina Catalysts

Abstract  

The effect of coating TiO₂ on the CO oxidation of the Pt/γ-alumina catalysts was observed through activity tests and surface characterization spectroscopy by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) experiments. XPS results evidenced the occurrence of different Pt²⁺ species and metallic Pt⁰ at the surface which suggest electron transfer of titanium (cation) to the platinum atom and the reduction of titanium (Ti⁴⁺ → Ti³⁺). FTIR analyses suggested oxygen spillover mechanism at the interface between titanium dioxide and platinum that may explain the catalytic activity of the platinum titania-supported catalysts. The apparent activation energy for the CO oxidation was 52.5 kJ/mol and similar for all catalysts. However, the frequency factor changed significantly, indicating interfacial phenomena caused by CO and oxygen adsorptions over TiO _x species and Al₂O₃ support with similar dispersions.     

Solvothermal synthesis of 1D and 2D cobalt(II) and nickel(II) coordination polymers with 2,5-dihydroxy-p-benzenediacetic acid

1D cobalt(II) and nickel(II) coordination polymers {[Co(dba)(H₂O)₄] · H₂O}_n (1) and {[Ni(dba)(H₂O)₄] · H₂O}_n (2) (H₂dba = 2,5-dihydroxy-p-benzenediacetic acid) were synthesized under low temperature solvothermal condition. When 4,4′-bipyridine (bpy) was introduced to the synthetic systems of 1 and 2, respectively, two novel 2D coordination polymers {[Co(dba)(bpy)] · 0.5H₂O}_n (3) and [Ni(dba)(bpy)(H₂O)₂]_n (4) with different structures were obtained. All of the compounds were characterized by elemental analysis, FT-IR, UV–Vis spectra and single crystal X-ray diffraction.     

Low-temperature mild partial oxidation of ethanol over supported platinum catalysts

Supported platinum catalysts containing 1.2% Pt loaded on Al₂O₃ (1.2% Pt/Al₂O₃) and 1.9% Pt loaded on ZrO₂ (1.9% Pt/ZrO₂) were prepared by incipient wetness impregnation and sol–gel method, respectively. The activity of these catalysts in the partial oxidation of ethanol (POE) was examined in a fixed-bed reactor in a temperature range between 373 and 473 K. The results indicated that significant ethanol conversion (C_EtOH > 50%) was found at the low reaction temperature with a feed ratio of O₂/EtOH ratio >0.75. Oxygen molecules introduced in reactant were completely consumed in POE reactions performed. H₂, H₂O, CO and CO₂ were the major products detected. The selectivity of hydrogen (S_H2) and CO (S_CO) varied significantly with reaction conditions. High selectivity of hydrogen (S_H2 > 95%) and low selectivity of CO (S_CO  0%) were found from a mild oxidation at T_R = 373 K over Pt/ZrO₂. However, these two selectivities were drastically deteriorated through oxidation at high T_R, high O₂/EtOH ratio or over Pt/Al₂O₃ catalyst.     

Diplatinum(III) [Cl2(μ2-amidinate)4] compound derived from air oxidation of mononuclear cis-[Pt(NH3)2(amidine-κ)2] complex

The dinuclear platinum(III) complex [Pt₂Cl₂{μ₂-N(H)C(Et)N(H)}₄] (2) has been prepared by heating cis-[Pt(NH₃)₂{NHC(NH₂)Et}₂](Cl)₂ (cis-1) under aeration conditions in an EtOH/H₂O mixture at 70 °C for 2 d and it was characterized by elemental analyses (C, H, N), ESI⁺-MS, IR, ¹H and ¹³C NMR spectroscopies and also by X-ray diffraction. Complex 2 represents the second Pt^III dimer stabilized by the amidinate ligand ever known and it has a lantern-type structure with four amidinate ligands bridging two Pt^III centers with Pt–Pt distance of 2.4809(2) Å.     

Bmim ionic liquids as media for the electrochemical oxidation of 2,6-di-<Emphasis Type="Italic">t</Emphasis>-butylphenol

The electrochemical oxidation of the substituted phenol 2,6-di-t-butylphenol is studied at platinum electrodes using a number of 1-butyl-3-methylimidazolium (bmim) ionic liquids (BF₄, PF₆ and N(CF₃SO₂)₂), and compared with the oxidation obtained using a traditional solvent/electrolyte system (CH₃OH/CH₂Cl₂ and LiClO₄). The electrolysis leads to anodic coupling, resulting in the corresponding diphenoquinone, which upon reduction produces the biphenol. Best results were obtained for the conventional solvent and electrolyte, where the oxidation was found to take place via an indirect method. It was found that the ionic liquids performed better upon dilution with a suitable solvent such as acetonitrile, yielding higher conductivities due to ion separation. Dilution studies were performed with acetonitrile, methanol, dichloromethane and acetone and the resulting increase in conductivity of the ionic liquid was in the order: acetonitrile > methanol > acetone > dichloromethane. This trend is in line with the dielectric constant and the dipole moment of the solvent used. It was found that the electrolysis proceeded best in the following order: conventional solvent/electrolyte > ionic liquid suitably diluted > ionic liquid. Among the ionic liquids, best results were obtained for [bmim][BF₄]. Cyclic voltammetry data was used to further explain the electrolysis as a function of dilution.     

Differential pulse voltammetric determination of chlorphenoxamine hydrochloride and its pharmaceutical preparations using platinum and glassy carbon electrodes

Voltammetric methods have been used for the determination of chlorphenoxamine hydrochloride (Ch-HCl) in raw material and in its pharmaceutical preparations (Allergex and Allergex caffeine tablet). It was found that Ch-HCl gives a characteristic cyclic voltammetric (CV) and differential pulse voltammetric (DPV) peak in acetonitrile using platinum and glassy carbon working electrodes. The I _p of the DPV peak increases linearly within the concentration range from 4.5 × 10⁻⁴ to 1.0 × 10⁻² mol L⁻¹ of the investigated drug. The concentration of Ch-HCl in raw drug material and in its pharmaceutical preparations was determined using the standard addition method, Randles–Sevcik equation and indirectly via its complexation with sodium tetraphenylborate (NaTPB). The obtained over all average recoveries were 101.44 and 100.49% with SD 0.45 and 0.38 (n = 4) for platinum and glassy carbon electrodes, respectively. The effect of scan rate, sample concentration, and supporting electrolyte on the I _p and E _p was also investigated.     

Inactivation of Bacteria E. coli and photodegradation of humic acids using natural sunlight

In this work, the disinfection of bacteria Escherichia coli and degradation of humic acids, using sunlight, sunlight + TiO₂ (Degussa P25) in suspension or TiO₂ supported on Ahlstrom paper (NW10) fixed around concentric tubes inside the photoreactor, were investigated in a pilot plant. The inactivation of bacteria E. coli proved to be more efficient (only 1 kJ_UV/L for 5-log decrease in concentration) when using sunlight and TiO₂ in suspension. However, true disinfection was not achieved under the conditions reported in this work. A first-order model was able to fit the photocatalytic deactivation of E. coli ([TiO₂] = 50 mg/L) with an inactivation rate constant of 8.21 L/kJ. A Langmuir–Hinshelwood-like model was successfully applied for modelling photolysis and supported-TiO₂ photocatalysis of bacteria E. coli, considering an initial latency period, a classical log-linear behaviour and a tail region. The effect of the flow rate between 5 and 15 L/min was negligible in the inactivation of E. coli in the presence of sunlight and supported TiO₂. The inactivation rate constant increased with the initial concentration of E. coli. Almost no bacterial regrowth was observed in dark conditions during 24 h after illumination of E. coli suspension until complete deactivation. The humic acids (HA) degradation was also investigated by solar photocatalysis with suspended and supported TiO₂ and exposure to sunlight-only, in a CPC photoreactor. Supported-TiO₂ photocatalysis of HA originated 70% concentration reduction after Q_UV ≈ 14 kJ/L, whereas only 20% reduction was obtained by photolysis and slurry photocatalysis. First-order kinetic constants of 0.088 and 0.010 L/kJ were obtained, respectively, for suspended and supported TiO₂.     

Syntheses, Structures, and Luminescent Properties of Two Novel Coordination Polymers with Mixed Ligands

Two novel metal–organic coordination polymers {[Pb₂(MIP)₂(BDC)₂]·H₂O} _n 1 and [Cd(MIP)(NDC)] _n 2 [MIP = 2-(3-methoxyphenyl)-1H-imidazo [4,5-f] [1, 10] phenanthroline, BDC = terephthalic acid, NDC = naphthalene-1,4-dicarboxylic acid] were obtained from hydrothermal reaction and characterized by elemental analysis, thermogravimetric (TG) analysis, infrared spectrum (IR) and single-crystal X-ray diffraction. The coordination polymers crystallize in triclinic, space group P-1 with a = 1.0335(2), b = 1.4224(3), c = 1.8156(4) nm, β = 106.088(3)° for complex 1 and the complex 2 crystallizes in monoclinic, space group P2(1)/n with a = 1.2562(8), b = 1.4800(9), c = 1.3723(8) nm, β = 97.257(1)°, respectively. The metal ions Pb(II) are located in [:PbN2O4] pentagonal bipyramidal geometry in complex 1. The metal ions Cd(II) in complex 2 act as distorted octahedral geometry, being surrounded by four carboxylate oxygen atoms from three NDC ligands and two donor nitrogen atoms from one MIP molecule. Moreover, there are hydrogen bonds in the two complexes, and it is noteworthy that the existence of hydrogen bonds and π–π interactions reinforce the structural stability of the title complexes, which have been proved by TG analysis. The luminescent properties for the ligand MIP, NDC and complex 2 are also discussed in detail.     

Water soluble luminescent cyclometalated platinum(II) complex — A suitable probe for bio-imaging applications

A highly water soluble platinum(II) complex, [Pt(ppy)(en)]Cl, (where ppy = 2-phenylpyridine and en = ethane-1, 2-diamine) with a strong green luminescence in solution was synthesized in two steps. Initially, an intermediate complex, [Pt(ppy)(ppyH)(Cl)], 1 was isolated which was transformed into the light-emitting mononuclear platinum(II) complex, [Pt(ppy)(en)]Cl, 2. The green emission of 2 was changed into yellow in their solid state. The strong π^…π intermolecular interactions that interplays between the phenyl rings lying into the two consecutive molecules which led to the solid state emission. The low cytotoxicity of 2 ensures the feasibility for using these in bioimaging probe. The testing bioimaging results demonstrate that the compound penetrates the cell membrane in both cancer (HeLa, U87MG and Nuro2a) and normal cells (CHO-K1 and 3T3-L1). The cellular uptake was observed to much higher in cancerous cells only. Co-localization study confirmed the localization of it into the cell nucleus.     

The first polypseudo-rotaxane structure based on the Wells–Dawson polyoxometalate

A polyoxometalate-based compound, (bix)[Cu(bix)][Cu₂(bix)₂(P₂W₁₈O₆₂)]·2H₂O (1) (bix = 1,4-bis(imidazol-1-ylmethyl)benzene), was hydrothermally synthesized, and characterized by elemental analyses, IR spectroscopy, thermogravimetric analysis, and single X-ray diffraction. Compound 1 exhibits the 1D + 1D polypseudo-rotaxane structure consists of two parts: the P₂W₁₈–Cu₂–(bix)₂ chain which contains 26-membered Cu₂(bix)₂ macrocycles and the 1D Cu-bix line. Remarkably, it represents the first polypseudo-rotaxane structure based on the Wells–Dawson polyoxometalate.