Tridentate Schiff base and 4,4′-bipyridine coordinated di/polynuclear Cu (II) complexes: Synthesis,crystal structure,DNA/protein binding and catecholase activity

4,4′-bipyridine bridged two Cu (II) complexes, [Cu₂L¹₂(4,4′-bipy)(H₂O)₂](ClO₄)₂ ( 1 ) and [Cu₂L²₂(4,4′-bipy)]_n·(2H₂O)_n ( 2 ) (where, HL¹ = 2-[(3-methylamino-propylimino)-methyl]-phenol, H₂L² = 3-[(2-hydroxy-3-methoxy-benzylidene)-amino]-propionic acid, and 4,4′-bipy = 4,4′-bipyridine) have been synthesized and characterized by single crystal structure determination, mass spectrometry, FT-IR, electronic absorption, and emission spectroscopy. Complex 1 is dinuclear cationic compound and counter balanced by perchlorate anion, whereas complex 2 possesses 1D poly-nuclear structure. Both the complexes crystallize in monoclinic system with P2₁/c space group and the copper centers possess square pyramidal geometry. H-bonding, C-H···π, π···π interactions results the formation of two dimentional supramolecular structure for both the complexes. Interactions of complexes with bovine serum albumins (BSA) and human serum albumins (HSA) have been studied by using electronic absorption and emission spectroscopic technique. The calculated values of binding constants (K_b) are (9.22 ± 0.26) × 10⁵ L mol⁻¹ ( 1 -BSA), (7.19 ± 0.16) × 10⁵ L mol⁻¹ ( 1 -HSA), (5.05 ± 0.20) × 10⁵ L mol⁻¹ ( 2 -BSA) and (3.56 ± 0.25) × 10⁵ L mol⁻¹ ( 2 -HSA). The mechanism of serum albumins-complex interactions have been investigated by fluorescence lifetime measurement. Fluorescence spectroscopic studies indicate that both the complexes interact with calf thymas-DNA. Catecholase activity of the complexes has been studied in methanol using 3,5-di-tert-butylcatechol (3,5-DTBC) as substrate and the result show that both the complexes are active for catalytic oxidation of 3,5-DTBC to 3,5-di-tert-butylquinone (3,5-DTBQ) in presence of molecular oxygen. Calculated values of turnover numbers are 71.81 ± 1.04 h⁻¹ and 69.45 ± 0.74 h⁻¹ for 1 and 2 , respectively.     

Facile amidation of esters with aromatic amines promoted by lanthanide tris (amide) complexes

The development of catalysts capable of catalyzing amidation of esters with amines to construct amides under mild conditions is of great importance. Compared to aliphatic amines, the direct catalytic amidation of esters with less nucleophilic aromatic amines is rather difficult. Employing simple lanthanide tris (amide) complexes Ln[N (SiMe₃)₂]₃(μ-Cl)Li (THF)₃ as the catalysts, it was found a broad range of aromatic amines and esters were efficiently converted into various amides in good yields under mild conditions. A plausible mechanism for this transformation was experimentally supported as starting from an amide exchange reaction between the lanthanide tris (amide) complex and the substrate amine.     

Heteroleptic [Cu(NN)P2]+-type cuprous complexes and their structural modulation on phosphorescent color: Synthesis,structural characterization,properties, and theoretical calculations

Four new heteroleptic [Cu(NN)P₂]⁺-type cuprous complexes— 1 -TPP, 2 -POP, 3 -Xantphos, and 4 -DPPF—were designed and synthesized using a diimine ligand 2-(2′-pyridyl)benzoxazole (2-PBO) and different phosphine ligands (TPP, triphenylphosphine; POP, bis[2-(diphenylphosphino)phenyl]ether; Xantphos, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; DPPF, 1,1′-bis(diphenylphosphino)-ferrocene). All complexes were characterized using single-crystal X-ray diffraction, spectroscopic analysis (infrared, UV–Vis.), elemental analysis, and photoluminescence (PL). Single-crystal X-ray diffraction revealed complexes 1 – 4 as isolated cation complex structures with a tetrahedral CuN₂P₂ coordination geometry and diverse P–Cu–P angles. Their UV–Vis. absorption spectra exhibited a blue-shift sequence in wavelength with an enlarged P–Cu–P angle from 4 to 2 then to 3 and then to 1 . The PL emission peaks of 1 – 3 also exhibited a similar blue-shift sequence ( 2 → 3 → 1 ). Their PL lifetime in microseconds (~7.5, 5.1, and 4.7 μs for 1 , 2 , and 3 , respectively) indicated that their PL behavior represents phosphorescence. Time-dependent density functional theory (TD-DFT) calculation and wavefunction analysis revealed that S₁ and T₁ states of 1 – 3 should be assigned as metal–ligand and ligand–ligand charge-transfer (ML + L'L)CT states. Their UV–Vis. absorption and phosphorescence should be attributed to the charge transfer from the P–Cu–P segment to the 2-PBO ligand. Therefore, as the P–Cu–P angle increased (lower HOMO), the energy of S₁ and T₁ states also increased, following the change of PL color.     

Nano-sized Cu(II) and Zn(II) complexes and their use as a precursor for synthesis of CuO and ZnO nanoparticles: A study on their sonochemical synthesis,characterization, and DNA-binding/cleavage,anticancer, and antimicrobial activities

Two new divalent copper (C1) and zinc (C2) chelates having the formulae [M(PIMC)₂] (where M = Cu(II), Zn(II) and PIMC = Ligand [(E)-3-(((3-hydroxypyridin-2-yl)imino)methyl)-4H-chromen-4-one] were obtained and characterized by several techniques. Structures and geometries of the synthesized complexes were judged based on the results of alternative analytical and spectral tools supporting the proposed formulae. IR spectral data confirmed the coordination of the ligands to the copper and zinc centers as monobasic tridentate in the enol form. Thermal analysis, UV-Vis spectra and magnetic moment confirmed the geometry around the copper center to be tetrahedral, square pyramidal and octahedral. Study of the binding ability of the synthesized compounds with Circulating tumor DNA (CT-DNA) bas been evaluated applying UV-Vis spectral titration and viscosity measurements. The copper and zinc oxides were achieved from the copper and zinc nano-particles structures Schiff base complexes as the raw material after calcination for 5 hr at 600°C. On the other hand, synthesized of C1 and C2 NPs were used as suitable precursors to the preparation of CuO and ZnO NPs. Finally, the synthesized of the two complexes exhibited enhanced activity against the tested bacterial (Staphylococcus aureus and Escherichia Coli) and fungal strains (Candida albicans and Aspergillus fumigatus) as compared to HPIMC. Among all these synthesized compounds, C1 exhibits good cleaving ability compared to other newly synthesized C2.     

Architectural control of polystyrene physical properties using branched anionic polymerization initiated at ambient temperature

Ambient temperature-initiated anionic polymerization has generated branched polystyrenes of varying molecular weights and architectures by inclusion of a distyryl branching comonomer into a conventional sec-Butylithium-initiated polymerization of styrene. Primary chain length control within the branched polymers, and restriction of the branching points to varying segments of the primary chains, led to variations of glass transition temperature with no direct correlation to the branched polymer molecular weight but a strong relationship to the length of individual chains comprising the branched macromolecules.     

Samarium(II) Monoalkyl Complex Supported by a β-Diketiminato-Based Tetradentate Ligand: Synthesis,Structure, and Catalytic Hydrosilylation of Internal Alkynes

The synthesis and catalytic applications of trivalent rare-earth metal alkyl complexes have been well developed, but the chemistry of divalent rare-earth metal alkyl complexes lagged much behind. Herein, we report the synthesis, structure, and catalytic applications of a samarium(II) monoalkyl complex supported by a β-diketiminato-based tetradentate ligand, [LSmCH(SiMe₃)₂] (L=[MeC(NDipp)CHC(Me)NCH₂CH₂N(Me)CH₂CH₂NMe₂]⁻, Dipp=2,6-(iPr)₂C₆H₃). This complex is synthesized by the salt metathesis reaction of samarium iodide [LSm(μ-I)]₂ and KCH(SiMe₃)₂ in 63 % yield. Its structure is characterized by single-crystal X-ray diffraction, showing a distorted square-pyramid coordination geometry. This samarium(II) monoalkyl complex exhibits high catalytic activity in the hydrosilylation of aryl and methyl-substituted unsymmetrical internal alkynes with secondary hydrosilanes, selectively providing the α-(E) products in high yields.     

Multi-emissive 1D Cd(II) polymers with a biphenyl bridged bisazamacrocycle for ratiometric discrimination of nitroaromatics and selective visual detection of picric acid

Three one-dimensional ladder-like coordination polymers consisting of Cd₆ metalloring as the building unit, {[Cd₄LCl₄]·3H₂O}_n ( 1 ), {[Cd₃L(ClO₄)(H₂O)]ClO₄·3H₂O}_n ( 2 ), and {[Cd₆(L)₂(NO₃)₂(CH₃OH)(H₂O)](NO₃)₂·2CH₃OH·5H₂O}_n ( 3 ), were solvothermally constructed from a carboxylic functionalized bisazamacrocyclic ligand 4,4′-bis((4,7-bis(2-carboxyethyl)-1,4,7-triazacyclonon-1-yl)methyl)-1,1′-biphenyl (H₄L). These compounds dispersed in ethanol show the multiple emissions originating from the monomeric and intramolecularly overlapping biphenyl moieties which could be sensitively quenched by picric acid (PA) and 4-nitrophenol (4-NP) through the effective fluorescence resonance energy transfer process. The differential fluorescent responses of each compound on exposure to PA and 4-NP individually make the convenient ratiometric discrimination of two analytes based on the fluorescent intensity ratio (I₃₂₀/I₃₆₀) attainable, and 1 and 2 as ratiometric chemosensors for PA present a broad linear detection range from 4 to 300 μM with detection limits of 0.84 and 0.93 μM, respectively. Furthermore, the blue light emission of 1 under an ultraviolet lamp could be selectively quenched by PA even in the presence of all other interfering nitroaromatic pollutants, which empowers the fast visual detection of PA by naked eye.     

Nickel (II) tetrapyridyl complexes as electrocatalysts and precatalysts for water oxidation

Two nickel complexes, [Ni(tpen)](ClO₄)₂.0.5CH₃COCH₃ ( 1 ) and [Ni(tpbn)](ClO₄)₂ ( 2 ), of tetrapyridyl ligands N,N,N′,N′-tetrakis(2-pyridyl-methyl)-1,2-ethanediamine (tpen) and N,N,N′,N′-tetrakis(2-pyridyl-methyl)-1,4-butanediamine (tpbn) were prepared and their catalysis for water oxidation reaction (WOR) studied. In 0.1 M phosphate buffer solution (PBS) of pH 8.0, complex 1 is a homogeneous molecular catalyst with an overpotential of ~440 mV and a Faradaic efficiency of 89%. At pH ≥ 9.0, complex 1 degraded gradually during the catalytic process and formed NiO_x composite (nickel oxide with general formula Ni_xO_yH_z) active for WOR. In contrast, complex 2 deteriorated under measured conditions (pH 8.0–12.0) and formed NiO_x composite active for WOR. The NiO_x composite derived from 1 in 0.1 M PBS at pH 11.0 showed an activity with an overpotential of ~500 mV, a Tafel slope of ~90 mV/decade and a Faradaic efficiency of 97%. Mechanisms were proposed for water oxidation catalyzed by 1 and 2 . This work revealed that the catalytic activity of the nickel complexes was related to the flexibility of the tetrapyridyl ligands and the adaptability of the coordination sphere of the nickel(II) center.     

Minimizing Side Product Formation in Alkyne Functionalization of Ruthenium Complexes by Introduction of Protecting Groups

The synthesis of alkyne functionalized bipyridine ruthenium complexes are reported. The improved synthetic approach through application of stable protecting groups prevents formation of possible side products while facilitating purification. By applying copper-catalysed azide-alkyne cycloaddition reactions (CuAAC) pyrene units with flexible alkyl linkers are introduced at the periphery of the complex, opening up various applications including surface immobilization and DNA intercalation. All complexes are characterized structurally as well as photophysically, especially regarding the influence of the introduced alkyne and triazolyl substituents on their photophysical behavior.     

Thionylimido Complexes

An improved route to d-block and main group NSO complexes is presented including the synthesis of the first antimony(V) complexes, (Ar₃Sb(NSO)₂), and copper examples [CuBipy(PPh₃)NSO]. The structures of eight complexes are reported. The observed variation in M–N–S bond angles is due to the combination of orbital overlap (ligand-to-metal bonding) and the degree of ionicity of the bonding.