Synthesis and characterization of cobalt(II), nickel(II), copper(II), palladium(II) and dioxouranium(VI) complexes of the antipyrine Schiff base of 3-formylsalicylic acid

A new Schiff base has been synthesized from 4-aminoantipyrine and 3-formylsalicylic acid. The ligand has a dianionic tetradentate compartmental OONO donor system. The cobalt(II), nickel(II), copper(II) and dioxouranium(VI) complexes exist in phenolato-bridged dinuclear species, while palladium(II) gives a mononuclear complex with free –COOH groups. The complexes have been characterized by elemental analyses, i.r., u.v.-vis, thermal and magnetic measurements.     

Near‐IR Absorbing Ruthenium Complexes of Non‐Innocent 6,12‐Di(pyridin‐2‐yl)indolo[3,2‐b]carbazole: Variation as a Function of Co‐Ligands

This article deals with the hitherto unexplored metal complexes of deprotonated 6,12‐di(pyridin‐2‐yl)‐5,11‐dihydroindolo[3,2‐b]carbazole (H₂L). The synthesis and structural, optical, electrochemical characterization of dimeric [{Ru^III(acac)₂}₂(μ‐L^.?)]ClO₄ ([ 1 ]ClO₄, S=1/2), [{Ru^II(bpy)₂}₂(μ‐L^.?)](ClO₄)₃ ([ 2 ](ClO₄)₃, S=1/2), [{Ru^II(pap)₂}₂(μ‐L^2?)](ClO₄)₂ ([ 4 ](ClO₄)₂, S=0), and monomeric [(bpy)₂Ru^II(HL^?)]ClO₄ ([ 3 ]ClO₄, S=0), [(pap)₂Ru^II(HL^?)]ClO₄ ([ 5 ]ClO₄, S=0) (acac=σ‐donating acetylacetonate, bpy=moderately π‐accepting 2,2’‐bipyridine, pap=strongly π‐accepting 2‐phenylazopyridine) are reported. The radical and dianionic states of deprotonated L in isolated dimeric 1 ⁺/ 2 ³⁺ and 4 ²⁺, respectively, could be attributed to the varying electronic features of the ancillary (acac, bpy, and pap) ligands, as was reflected in their redox potentials. Perturbation of the energy level of the deprotonated L or HL upon coordination with {Ru(acac)₂}, {Ru(bpy)₂}, or {Ru(pap)₂} led to the smaller energy gap in the frontier molecular orbitals (FMO), resulting in bathochromically shifted NIR absorption bands (800–2000 nm) in the accessible redox states of the complexes, which varied to some extent as a function of the ancillary ligands. Spectroelectrochemical (UV/Vis/NIR, EPR) studies along with DFT/TD‐DFT calculations revealed (i) involvement of deprotonated L or HL in the oxidation processes owing to its redox non‐innocent potential and (ii) metal (Ru^III/Ru^II) or bpy/pap dominated reduction processes in 1 ⁺ or 2 ²⁺/ 3 ⁺/ 4 ²⁺/ 5 ⁺, respectively.     

Solvent‐Mediated Functionalization of Benzofuroxan on Electron‐Rich Ruthenium Complex Platform

An unprecedented reactivity profile of biochemically relevant R‐benzofuroxan (R=H, Me, Cl), with high structural diversity and molecular complexity on a selective {Ru(acac)₂} (acac=acetylacetonate) platform, in conjugation with EtOH solvent mediation, is revealed. This led to the development of monomeric [Ru^III(acac)₂(L^1R)] ( 1 a – 1 c ; L^1R=2‐nitrosoanilido derivatives) and dimeric [{Ru^II(acac)₂}₂(L^2R)] ( 2 a – 2 b ; L^2R=(1E,2E)‐N¹,N²‐bis(2‐nitrosophenyl)ethane‐1,2‐diimine derivatives) complexes in one pot with a change in the metal redox conditions. The functionalization of benzofuroxan in 1 and 2 implied in situ reduction of N=O to NH^? in the former and solvent‐assisted multiple N?C coupling in the latter. The aforesaid transformation processes were authenticated through structural elucidation of representative complexes, and evaluated by their spectroscopic/electrochemical features, along with C₂D₅OD labeling and monitoring of the impact of substituents (R) in the benzofuroxan framework on the product distribution process. The noninnocent potential of newly developed L¹ and L² in 1 and 2 , respectively, was also probed by spectroelectrochemistry in combination with DFT calculations.     

Ruthenium(II)‐Catalyzed Synthesis of Spirobenzofuranones by a Decarbonylative Annulation Reaction

The first decarbonylative insertion of an alkyne through C?H/C?C activation of six‐membered compounds is reported. The Ru‐catalyzed reaction of 3‐hydroxy‐2‐phenyl‐chromones with alkynes works most efficiently in the presence of the ligand PPh₃ to provide spiro‐indenebenzofuranones. Unlike previously reported metal‐catalyzed decarbonylative annulation reactions, in the present decarbonylative annulation reaction, the annulation occurs before extrusion of carbon monoxide.     

Complexification of three potential models — II

A new kind of $ \mathcal{P}\mathcal{T} $ \mathcal{P}\mathcal{T} and non-$ \mathcal{P}\mathcal{T} $ \mathcal{P}\mathcal{T} -symmetric complex potentials are constructed from a group theoretical viewpoint of the sl(2,C) potential algebras. The real eigenvalues and the corresponding regular eigenfunctions are also obtained. The results are compared with the ones obtained before.     

Performance limitations of flat-histogram methods

We determine the optimal scaling of local-update flat-histogram methods with system size by using a perfect flat-histogram scheme based upon the exact density of states of 2D Ising models. The typical tunneling time needed to sample the entire bandwidth does not scale with the number of spins N as the minimal N2 of an unbiased random walk in energy space. While the scaling is power law for the ferromagnetic and fully frustrated Ising model, for the +/-J nearest-neighbor spin glass the distribution of tunneling times is governed by a fat-tailed Fréchet extremal value distribution that obeys exponential scaling. Furthermore, the shape parameters of these distributions indicate that statistical sample means become ill defined already for moderate system sizes within these complex energy landscapes.     

A facile synthesis of steroidal D-ring fused pyrazolo[1,5-a]pyrimidines

A facile method for the synthesis of steroidal D-ring fused pyrazolo[1,5-a]pyrimidines through a microwave mediated reaction between steroidal β-bromovinyl aldehydes and pyrazoloamines using palladium(II) catalyst has been described.     

Experimental observation of dust circulation in unmagnetized cogenerated dusty plasma

The vortex motion of a dust cloud was experimentally observed in unmagnetized cogenerated dusty plasma in different experimental parameters. Particle image velocimetry analysis demonstrated that several vortex zones exist in the dust cloud at relatively low pressures (0.06 mbar (or 6 Pa)–0.08 mbar (or 8 Pa)) and low discharge voltages (peak‐to‐peak voltage 540–560 V), whereas in relatively high pressure (0.4 mbar (or 40 Pa)–0.7 mbar (or 70 Pa)) and high discharge voltage (peak‐to‐peak voltage 690–740 V), dust vortices formed in dense dust cloud with background plasma fluctuation.     

Peptide‐poly(ε‐caprolactone) biohybrids by grafting‐from ring‐opening polymerization: Synthesis,aggregation, and crystalline properties

Well‐defined peptide‐poly(ε‐caprolactone) (Pep‐PCL) biohybrids were successfully synthesized by grafting‐from ring‐opening polymerization (ROP) of ε‐caprolactone (CL) using designed amine‐terminated sequence‐defined peptides as macroinitiators. MALDI‐TOF‐MS and ¹H NMR analyses confirmed the successful attachment of peptide to the PCL chain. The gel permeation chromatography (GPC) measurement showed that the Pep‐PCL biohybrids with controllable molecular weights and low polydispersities (PDI <1.5) were obtained by this approach. The aggregation of Pep‐PCL hybrid molecules in THF solution resulted in the formation of micro/nanospheres as confirmed through FESEM, TEM, and DLS analyses. The circular dichroism study revealed that the secondary structure of peptide moiety was changed in the peptide‐PCL biohybrids. The crystallization and melting behavior of Pep‐PCL hybrids were somewhat changed compared with that of neat PCL of comparable molecular weight as revealed by DSC and XRD measurements. In Pep‐PCL biohybrids, extinction rings were observed in the PCL spherulites, in contrast with the normal spherulite morphology of the neat PCL. There was a substantial decrease (4–5 folds) in the spherulitic growth rate after the incorporation of peptide moiety at the end of PCL chain as measured by polarizing optical microscopy. Pseudomonas lipase catalyzed enzymatic degradation was studied for Pep‐PCL hybrids and neat PCL. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

A facile synthesis of benzo[b][1,4]thiazepine derivatives by palladium acetate catalyzed reaction

The preparation of steroid/nonsteroid fused benzo[b][1,4]thiazepines and 2-arylsubstituted benzo[b][1,4]thiazepines is described from Pd(OAc)₂ catalyzed reaction of steroidal/nonsteroidal β-halovinyl aldehydes and 2-aminothiophenols in DMF under heating condition.