Platinum complexes of diazo ligands. Studies of regioselective aromatic ring amination, oxidative halogen addition and reductive halogen elimination reactions

2-(Arylazo)pyridine ligands, L1a-1c react with the salt K2[PtCl4] to give the mononuclear complexes [PtCl2(L1)](1), which readily react with ArNH2 to yield the monochloro complexes of type [PtCl(L2)](HL2= 2-[(2-(arylamino)phenyl)azo]pyridine)(2) via regioselective ortho-amine fusion at the pendent aryl ring of coordinated L1. Oxidative addition of the electrophiles Y2(Y = Cl, Br, I) to the square-planar platinum(II) complex, has led to syntheses of the corresponding octahedral platinum(IV) complexes, [PtY3(L2)](3) in high yields. Ascorbate ion reductions of the platinum(IV) complexes, , resulted in reductive halogen elimination to revert to the platinum(II) complexes almost quantitatively. Isolation of products and X-ray structure determination of the representative complexes followed all these chemical reactions. In crystal packing, the compound [PtCl2(L1c)](1c) forms dimeric units with a Pt...Pt distance of 3.699(1) A. In contrast, the crystal packing of 2b revealed that the molecules are arranged in an antiparallel fashion to form a noncovalent 1D chain to accommodate pi(aryl)-pi(pyridyl) and Pt-pi(aryl) interactions. Notably, the oxidation of [Pt(II)Cl(L2a)](2a) by I2 produced a mixed halide complex [Pt(IV)ClI2(L2a)](5), which, in turn, is reduced by ascorbate ion to produce [Pt(II)I(L2a)] with the elimination of ClI. All the platinum(II) complexes are brown, the platinum(IV) complexes, on the other hand, are green. Low-energy visible range transitions in the complexes of the extended ligand [L2]- are ascribed to ligand basedpi-pi* transitions. Cyclic voltammetric behaviour of the complexes is reported.     

Nearly monodispersed ZnS nanospheres: Synthesis and optical properties

ZnS nanoparticles of diameters of 3–4 nm were self-assembled to form dense nanospheres of sizes 100 nm by a colloidal precipitation method using PVP as the stabilizing agent. Studies indicated that the ZnS nanoparticles maintained their individual properties inside the nanospheres. Optical absorption spectra of the samples demonstrated the effect of quantum confinement in the ZnS nanocrystals. Room temperature photoluminescence measurements showed a sharp UV emission at 370 nm, attributed to sulfur vacancies.     

Grafting Vinyl Monomers onto Silk Fibers. XI. Graft Copolymerization of Methyl Methacrylate onto Silk Using Fe3+-Thiourea Redox System

The results of some investigations into the synthesis and characterization of a new class of oligomers and polymers, the polyselenoacetals, are described.     

Effect of Fe addition on the crystallization behaviour and Curie temperature of CoCrSiB-based amorphous alloys

The crystallization behaviour and Curie temperature of melt-spun Co_{71? x} Fe _x Cr₇Si₈B₁₄ (x?=?0, 2, 3.2, 4, 6, 8 and 12?at.%) amorphous alloys have been studied. Differential scanning calorimetry (DSC) showed two stages of crystallization. The first stage of crystallization (T _X1) in the alloy with 6?at.%?Fe was the highest and it had the highest activation energy. X-ray diffraction studies revealed that the primary crystalline phase is hcp-(CoCr)₂Si for Fe-free alloy, whereas (CoFeCr)₂Si and (CoFeCr)₃Si phases were formed with the addition of Fe. hcp-Co was also formed along with these phases. The secondary crystalline phases were fcc-Co and various boron-rich phases. The Curie temperature of the alloys also changed with the addition of Fe to the system. Like the primary crystallization temperature, the Curie temperature of the alloys did not vary systematically with the Fe content. The addition of Fe to the Co-based system changes the nearest-neighbour interaction. This changes the exchange interaction between the transition metal elements. Due to the asymmetry in the Bethe–Slater curve, a systematic variation with Fe addition was not observed in the Curie temperature measurement.     

Evidence of a Proton Halo in <Superscript>23</Superscript>Al: A Mean Field Analysis

The structural properties of Al isotopes are analysed using the relativistic mean field formalism with NL3 parameter set. The Glauber model technique is implemented to study the reaction dynamics for ^23?28Al taking ¹²C as the target. The enhanced reaction cross section, high value of radius, narrow longitudinal momentum distribution and small proton separation energy of ²³Al favours a proton halo structure for this nucleus.     

Coumarinyl azoimidazolyl complexes of osmium(II) hydridocarbonyls: spectroscopic and structural characterization,oxidation catalysis,photovoltaic effect and density functional theory computation

Os(II) hydridocarbonyl complexes of coumarinyl azoimidazoles, [Osh(CO)(PPh₃)₂(CZ‐4R‐R′)]^0/+ ( 3 , 4 ) (CZ‐R‐H = 2‐(coumarinyl‐6‐azo)‐4‐substituted imidazole or 1‐alkyl‐2‐(coumarinyl‐6‐azo)‐4‐substituted imidazole), were characterized from spectroscopic data and the single‐crystal X‐ray data for one of the complexes, [Osh(CO)(PPh₃)₂(CZ‐4‐Ph)] ( 3c ) (CZ‐4‐Ph = 2‐(coumarinyl‐6‐azo)‐4‐phenylimidazolate), confirmed the structure. The complexes show higher emission (quantum yield ? = 0.0163–0.16) and longer lifetime (τ = 1.4–10.3 ns) than free ligands (? = 0.0012–0.0185 and τ = 0.685–1.306 ns). Cyclic voltammetry shows quasi‐reversible metal oxidation at 0.67–0.94 V for [Os(III)/Os(II)] and 1.21–1.36 V for [Os(IV)/Os(III)] and subsequent azo reductions (?0.68 to ?0.95 V for [? N?N? ]/[? N N? ]^? and irreversible < ?1.2 V for [? N N? ]^?/[? N? N? ]^2?) of the chelated coumarinyl azoimidazole. The complexes are photostable and show better photovoltaic power conversion efficiency than free ligands. Also, the complexes were used as catalysts for the oxidation of primary/secondary alcohols to aldehydes/ketones using oxidizing agents like N‐methylmorpholine N‐oxide, t‐BuOOH and H₂O₂. Density functional theory computation was carried out from the optimized structures and the data obtained were used to interpret the electronic and photovoltaic properties. Copyright © 2016 John Wiley & Sons, Ltd.     

Studies on Absorption and Emission Characteristics of Inclusion Complexes of Some 4-Arylidenamino-5-phenyl-4H-1, 2, 4-triazole-3-thiols

The inclusion complexes of a series of 4-arylidenamino-5-phenyl-4H-1, 2, 4-triazole-3-thiols have been prepared with β-cyclodextrin. The compounds and their inclusion complexes have been characterized by studying their physical and spectral properties. The thermodynamic stability constant and free energy of activation have been determined to know the stability of inclusion complexes and type of host-guest relation. Finally, absorption, excitation and emission spectra of the compounds (4-arylidenamino-5-phenyl-4H-1, 2, 4-triazole-3-thiols) and their inclusion complexes have been taken. It is found that inclusion complex formation brings about a drastic change in absorption and fluorescence characteristic (both excitation and emission spectra) of newly synthesized compounds.