Synthesis and Metal Complex Formation of a Bis(terpyridine) Derivative with a Phenylacetylene Framework

A new bis(terpyridine) derivative with a phenylacetylene framework was synthesized via a stepwise terpyridine construction strategy. The addition of ZnCl₂ to a solution of the bis(terpyridine) in chloroform resulted in UV/vis and ¹H NMR spectral changes because of complex formation.     

Ni Nanoparticles: Mild and Efficient Catalyst for the Chemoselective Synthesis of 2-Arylbenzimidazoles, 2-Arylbenzothiazoles,and Azomethines

A new and efficient method has been developed for the synthesis of biologically significant 2-arylbenzimidazoles, 2-arylbenzothiazoles, and azomethines using recyclable and inexpensive polyvinyl pyrrolidone (PVP)–stabilized Ni nanoparticles in ethylene glycol at room temperature in excellent yields.     

Investigation Micellar Catalysis of p-Nitrophenyl Acetate Hydrolysis with Mn(Niten)2H2O Complex

In this article, a mononuclear Mn(Niten)2H₂O complex was prepared to catalyze hydrolysis of p-nitrophenyl acetate (PNPA) in presence of Cetyltrimethylammonium bromide (CTAB) micellar system in different pH range from 6.5–10 at 25°C. These results obtained indicate that the complex exhibits good catalytic function. It also appears the complex accelerates the hydrolytic cleavage of PNPA in cationic CTAB micellar solution which may be due to coordinating ability of substrate to complex, electrostatic interaction between micelles and complex and due to electrostatic interaction between micelles with reactant.     

The asphericity of random 2‐dimensional complexes

We study random 2‐dimensional complexes in the Linial–Meshulam model and prove that for the probability parameter satisfying a random 2‐complex Y contains several pairwise disjoint tetrahedra such that the 2‐complex Z obtained by removing any face from each of these tetrahedra is aspherical. Moreover, we prove that the obtained complex Z satisfies the Whitehead conjecture, i.e. any subcomplex is aspherical. This implies that Y is homotopy equivalent to a wedge where Z is a 2‐dimensional aspherical simplicial complex. We also show that under the assumptions where c > 3 and , the complex Z is genuinely 2‐dimensional and in particular, it has sizable 2‐dimensional homology; it follows that in the indicated range of the probability parameter p the cohomological dimension of the fundamental group of a random 2‐complex equals 2. © 2013 Wiley Periodicals, Inc. Random Struct. Alg., 46, 261–273, 2015     

Asymptotic synchronization of continuous/discrete complex dynamical networks by optimal partitioning method

The synchronization problem for both continuous and discrete‐time complex dynamical networks with time‐varying delays is investigated. Using optimal partitioning method, time‐varying delays are partitioned into l subintervals and generalized results are derived in terms of linear matrix inequalities (LMIs). New delay‐dependent synchronization criteria in terms of LMIs are derived by constructing appropriate Lyapunov–Krasovskii functional, reciprocally convex combination technique and some inequality techniques. Numerical examples are given to illustrate the effectiveness and advantage of the proposed synchronization criteria. © 2014 Wiley Periodicals, Inc. Complexity 21: 193–210, 2015     

Optical properties of highly planar diketopyrrolopyrrole derivatives fixed by coordinate bonds

Diketopyrrolopyrrole (DPP) derivatives bearing 2-pyridyl groups were synthesized, which could serve as anionic N,N′-chelate ligands consisting of two nitrogen atoms of the lactam moieties and the pyridyl groups. Coordination of the DPP ligand to boron and platinum yielded the corresponding DPP complexes. Their crystal structures exhibited coplanar structures between the DPP core and the 2-pyridyl groups, which indicated extended π-conjugation. The maximum absorption wavelength of the DPP complexes was longer than that of the corresponding DPP ligands. The choice of the introduced element affects the optical properties of the DPP complexes; the platinum complex has a longer absorption wavelength than the boron complex. The theoretical calculation revealed that these absorptions can be attributed to the π–π* transition. The introduction of the coordinating elements predominantly lowers the band gap. In addition, the substituent on the 2-pyridyl group can also modulate the energy levels.     

Synthesis,spectroscopy, electrochemistry,and methylation reaction of the dithiolate-based cobalt(II) complex derived from tert-butyl N-(2-mercaptoethyl)carbamate

A dithiolate-containing a carbamate mononuclear cobalt(II) complex namely, [Co(Boc-S)₂] (1), was obtained by the reaction of a methanolic solution of cobalt(II) nitrate hexahydrate with two equimolar amounts of the deprotonated form of tert-butyl N-(2-mercaptoethyl)carbamate (Boc-SH). The cobalt(II) complex (1) was characterized in the solid state and in solution by using FT–IR, Raman, UV–visible, and EI–mass spectroscopies, as well as thermal and X-ray diffraction studies. Spectral data showed that the carbamate (Boc-SH) acts as a mono-anionic bidentate ligand coordinating the cobalt(II) ion through two imine nitrogen and two deprotonated thiolate sulfur donor atoms in a distorted tetrahedral geometry. The thermoanalytical data evidence that the complex is stable up to 165 °C and undergoes complete decomposition, resulting in CoO. TEM imaging of the oxide residue shows its nano size clusters, suggesting that the complex (1) may be used as a precursor for nano-oxides. X-ray powder diffraction patterns evidence an isomorphism among the complex. The redox behavior of the cobalt(II) complex was also investigated by cyclic voltammetry. The reaction of the dithiolate cobalt(II) complex (1) with methyl iodide appears to occur intramolecularly with the cobalt-bound dithiolate, forming the cobalt(II)-bound dithioether complex [Co(Boc–SCH₃)₂]I₂ (2), as a dication complex with a clean second-order reaction of 13.24 × 10⁻² M⁻¹·s⁻¹.     

Imidazolidinium ferrate complexes: Synthesis and catalytic properties

The new well-defined and air stable anionic iron complexes bearing an imidazolidinium ligand (2a–d) have been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction studies. Starting from FeBr₂, [imidazolidinium][FeBr₄] complexes 2a and 2b were prepared. The reaction of imidazolidinium chlorides with Fe(OAc)₂, followed by a recrystallization in the air led to bis(imidazolidinium) μ-oxido-bis[trichloroferrate(III)] complexes 2c and 2d. The catalytic activity of these novel complexes has been evaluated in the cross-coupling reactions of alkyl halides with Grignard reagents.     

A paradigm shift in rate determining step from single electron transfer between phenylsulfinylacetic acids and iron(III) polypyridyl complexes to nucleophilic attack of water to the produced sulfoxide radical cation: a non‐linear Hammett

Mechanism of oxidative decarboxylation of phenylsulfinylacetic acids (PSAAs) by iron(III) polypyridyl complexes in aqueous acetonitrile medium has been investigated spectrophotometrically. An initial intermediate formation between PSAA and [Fe(NN)₃]³⁺ is confirmed from the observed Michaelis–Menten kinetics and fractional order dependence on PSAA. Significant rate retardation with concentration of [Fe(NN)₃]³⁺ is rationalized on the basis of coordination of a water molecule at the carbon atom adjacent to the ring nitrogen of the metal polypyridyl complexes by nucleophilic attack at higher concentrations. Electron‐withdrawing and electron‐releasing substituents in PSAA facilitate the reaction and Hammett correlation gives an upward ‘V’ shaped curve. The apparent upward curvature is rationalized based on the change in the rate determining step from electron transfer to nucleophilic attack, by changing the substituents from electron‐releasing to electron‐withdrawing groups. Electron‐releasing substituents in PSAA accelerate the electron transfer from PSAA to the complex and also stabilize the intermediate through resonance interaction leading to negative reaction constants (ρ). Conversely, electron‐withdrawing groups, while retarding the electron transfer exert an accelerating effect on the nucleophilic attack of H₂O which leading to low magnitude of ρ⁺ compared to high ρ^? values of electron‐releasing groups. Marcus theory is applied, and a fair agreement is seen with the experimental values. Copyright © 2016 John Wiley & Sons, Ltd.     

Grain size effects on microstructural stability and creep behaviour of nanotwinned Ni free-standing foils at room temperature

Creep tests were performed on the high stacking fault energy (SFE) nanotwinned (NT) Ni free-standing foils with nearly the same twin thickness at room temperature (RT) to investigate the effects of grain size and loading rate on their microstructural stability and creep behaviour. The grain growth mediated by the twinning/detwinning mechanism at low applied stresses (<800 MPa) and grain refinement via the detwinning mechanism at high applied stresses (>800 MPa) were uncovered in the present NT-Ni foils during RT creep, both of which are attributed to the interactions between dislocations and boundaries. It appears that a higher initial dislocation density leads to a faster primary creep strain rate and a slower steady-state creep strain rate. Unlike the non-twinned metals in which grain growth often enhances the creep strain rate, the twinning/detwinning-mediated grain growth process unexpectedly lowers the steady-state creep strain rate, whereas the detwinning-mediated grain refinement process accelerates the creep strain rate in the studied NT-Ni foils. A modified phase-mixture model combined with Arrhenius laws is put forward to predict the scaling behaviour between the creep strain rate and the applied stress, which also predicts the transition from grain growth-reduced to grain refinement-enhanced steady-state creep strain rate at a critical applied stress. Our findings not only provide deeper insights into the grain size effect on the mechanical behaviour of nanostructured metals with high SFE, but also benefit the microstructure sensitive design of NT metallic materials.