Experimental Observation of a Peculiar Effect in Saturated Electron Paramagnetic Resonance Spectra Undergoing Spin Exchange. Magnetic Polariton?

We report the experimental observation of a spectral manifestation of a magnetic polariton that was theoretically predicted last year. This unprecedented manifestation is demonstrated not only for N-enriched peroxylamine disulfonate, a radical that adheres strictly to the assumptions of the theory, but also for a radical, 4-oxo-2,2,6,6-tetramethylpiperidine-;1-15N-1-oxyl, that departs somewhat from the assumptions, as well as the Galvinoxyl radical that represents a severe departure. The magnetic polariton is likely to be of interest to physical chemists in other fields because of the intrinsic advantage of a finite basis set in developing theories.

New Ln-MOFs based on mixed organic ligands: synthesis, structure and efficient luminescence sensing of the Hg ions in aqueous solutions.

In view of Hg ion sensing by luminescence, a series of new, phenanthroline-decorated 3D lanthanide metal organic frameworks (Ln-MOFs) valorising an original combination of four different lanthanides and two organic ligands, thiobis(4-methylene-benzoic acid) (Htmba) and 1,10-phenanthroline (phen), have been successfully synthesized, namely {[Ln(tmba)(phen)]·(HO)(phen)} [Ln = Ce, = 3 (1); Pr, = 1 (2); Eu, = 3 (3); and Tb, = 3 (4)]. Compounds 1-4 were characterised by single-crystal X-ray diffraction, elemental and thermogravimetric analyses, and powder X-ray diffraction. The luminescence properties of complexes 3 and 4 were thoroughly investigated.

Designing 2D-2D g-CN/Ag:ZnInS nanocomposites for the high-performance conversion of sunlight energy into hydrogen fuel and the meaningful reduction of pollution.

The generation of hydrogen-based energy and environmental remediation using sunlight is an emerging topic of great significance for meeting the ever-growing global need. However, the actual photocatalytic performance is still far below expectations because of the relatively slack charge-carrier separation and migration as well as insufficient spectral absorption in semiconductors. Therefore, the rational construction of heterojunctions is considered as an effective approach to solving the above issues.

Combining enyne metathesis with long-established organic transformations: a powerful strategy for the sustainable synthesis of bioactive molecules.

This account surveys the current progress on the application of intra- and intermolecular enyne metathesis as main key steps in the synthesis of challenging structural motifs and stereochemistries found in bioactive compounds. Special emphasis is placed on ruthenium catalysts as promoters of enyne metathesis to build the desired 1,3-dienic units. The advantageous association of this approach with name reactions like Grignard, Wittig, Diels-Alder, Suzuki-Miyaura, Heck cross-coupling, etc.

Striking dual functionality of a novel Pd@Eu-MOF nanocatalyst in C(sp)-C(sp) bond-forming and CO fixation reactions.

Pd nanoparticles were immobilized on a highly porous, hydrothermally stable Eu-MOF via solution impregnation and H2 reduction to yield a novel Pd@Eu-MOF nanocatalyst. This composite was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), inductively coupled plasma optical emission spectroscopy (ICP-OES), powder X-ray diffraction (PXRD) and X-ray photoelectron spectroscopy (XPS). Unprecedentedly, the Pd@Eu-MOF nanocatalyst could be applied with excellent results in two strikingly different, mechanistically distinct, reactions i.

Efficient Suzuki⁻Miyaura C-C Cross-Couplings Induced by Novel Heterodinuclear Pd-bpydc-Ln Scaffolds.

An easy access to a series of previously unreported heterodinuclear Pd-Ln compounds, Pd-bpydc-La, Pd-bpydc-Ce and Pd-bpydc-Nd (bpydc = 2,2'-bipyridine-5,5'-dicarboxylate) has been developed. The Pd-Ln hybrid networks were effectively applied as catalysts in Suzuki⁻Miyaura C-C cross-coupling reactions of 4-bromoanisole and 4-bromobenzonitrile with phenylboronic acid, under mild conditions. A systematic investigation revealed Pd-bpydc-Nd as the most active catalyst.

Tailoring the structure, pH sensitivity and catalytic performance in Suzuki-Miyaura cross-couplings of Ln/Pd MOFs based on the 1,1'-di(p-carboxybenzyl)-2,2'-diimidazole linker.

An array of heterobimetallic Pd/Ln MOFs (1-4) with Sm, Eu, Tb, Dy as preferred metal nodes and 1,1'-di(p-carboxybenzyl)-2,2'-diimidazole (H2L) as a fairly suitable bifunctional organic linker have been synthesized, fully characterized and tested as catalysts in cross-coupling reactions. These robust MOFs, ensuring a uniform distribution of Pd, showed excellent stability in air and high catalytic activity in Suzuki-Miyaura reactions conducted in neat water, neat ethanol as well as water-ethanol mixture. Depending on the solvent, complex 1 could be effectively recycled 4-8 times without significant loss of catalytic activity.

Microwave-assisted Olefin Metathesis as Pivotal Step in the Synthesis of Bioactive Compounds.

Over the last two decades, olefin metathesis has emerged as a new avenue in the design of new routes for the synthesis of natural products and active pharmaceutical ingredients. In many cases, syntheses based on olefin metathesis strategies provide significant routes in terms of increasing the overall yields, improving the synthesis scope, and decreasing the number of steps. On the other hand, over the last decade, microwave-assisted chemistry has experienced an incredible development, which rapidly opened new areas in organic synthesis and in homogeneous catalysis.

Special Issue on Ruthenium Complexes.

The organic chemistry of ruthenium has been one of the most vigorously growing research areas over the past decades. Considerable effort has been extended towards the design and application of a broad series of ruthenium complexes, which culminated with the development by Ryoji Noyori (2001 Nobel Prize for Chemistry) of chiral ruthenium catalysts for stereoselective hydrogenation reactions [1], and the discovery by Robert H. Grubbs (2005 Nobel Prize for Chemistry) of well-defined ruthenium- benzylidene catalysts for olefin metathesis [2] [.

The synergistic effect of cobalt on a Pd/Co catalyzed Suzuki-Miyaura cross-coupling in water.

This work introduces the new trimetallic complex CoPd(HBPDC)Cl·(HO)(HBPDC = 2,2'-bipyridine-4,4'-dicarboxylic acid) as a highly efficient and more cost-effective catalyst for a Suzuki-Miyaura reaction proceeding in water, without additives and under aerobic conditions. Catalytic studies revealed a synergistic Co-Pd cooperativity, fostered by ligation through HBPDC, and accounting for the superior performance of the heterobimetallic complex vs. its Co-free counterpart.

Novel mononuclear Pt and Pd complexes containing (2,3-f)pyrazino(1,10)phenanthroline-2,3-dicarboxylic acid as a multi-donor ligand. Synthesis, structure, interaction with DNA, in vitro cytotoxicity, and apoptosis.

New cytotoxic, mononuclear Pt and Pd coordination complexes featuring the planar, multi-donor ligand (2,3-f)pyrazino(1,10)phenanthroline-2,3-dicarboxylic acid (HPPDA) have been synthesized under hydrothermal conditions (in water, at high temperature and pressure) and fully characterized. The complexes were proven to be isostructural by applying the single-crystal X-ray diffraction technique. UV-Vis and fluorescence spectroscopy investigations on their interaction with fish sperm DNA revealed a considerable binding capacity while gel electrophoresis provided evidence in favor of cleavage of pBR322 plasmid DNA.

Recent advances in metathesis-derived polymers containing transition metals in the side chain.

This account critically surveys the field of side-chain transition metal-containing polymers as prepared by controlled living ring-opening metathesis polymerization (ROMP) of the respective metal-incorporating monomers. Ferrocene- and other metallocene-modified polymers, macromolecules including metal-carbonyl complexes, polymers tethering early or late transition metal complexes, etc. are herein discussed.

ROMP Synthesis of Iron-Containing Organometallic Polymers.

The paper overviews iron-containing polymers prepared by controlled "living" ring-opening metathesis polymerization (ROMP). Developments in the design and synthesis of this class of organometallic polymers are highlighted, pinpointing methodologies and newest trends in advanced applications of hybrid materials based on polymers functionalized with iron motifs.

Editorial of Special Issue Ruthenium Complex: The Expanding Chemistry of the Ruthenium Complexes.

Recent trends in Ru complex chemistry are surveyed with emphasis on the development of anticancer drugs and applications in catalysis, polymers, materials science and nanotechnology.

Synthesis, characterization, interaction with DNA and cytotoxicity of Pd(II) and Pt(II) complexes containing pyridine carboxylic acid ligands.

Four metal complexes [Pd(L(1))Cl(2)·2H(2)O] (1), [Pt(L(1))Cl(2)·2H(2)O] (2), [Pd(L(2))Cl(2)·H(2)O] (3) and [Pt(L(2))Cl(2)·H(2)O] (4) (L(1) = 2,2'-bipyridyl-5,5'-dicarboxylic acid, L(2) = 2,2'-bipyridyl-4,4'-dicarboxylic acid) have been synthesized under hydrothermal conditions and fully characterized by IR and (1)H-NMR spectra, elemental analysis, and X-ray single crystal diffraction analysis. Interactions of these complexes with fish sperm DNA (FS-DNA) were investigated using UV-Vis absorption and fluorescence spectroscopic methods. Further insight was brought by quantum chemistry calculations by means of G03 package and taking B3LYP functional Lanl2dz Gen basis set.

Metathesis access to monocyclic iminocyclitol-based therapeutic agents.

By focusing on recent developments on natural and non-natural azasugars (iminocyclitols), this review bolsters the case for the role of olefin metathesis reactions (RCM, CM) as key transformations in the multistep syntheses of pyrrolidine-, piperidine- and azepane-based iminocyclitols, as important therapeutic agents against a range of common diseases and as tools for studying metabolic disorders. Considerable improvements brought about by introduction of one or more metathesis steps are outlined, with emphasis on the exquisite steric control and atom-economical outcome of the overall process. The comparative performance of several established metathesis catalysts is also highlighted.

FT Raman--a valuable tool for surveying kinetics in RCM of functionalized dienes.

In this article the suitability of FT Raman spectroscopy for monitoring kinetics of ring-closing metathesis promoted by the Grubbs' 1st generation precatalyst was demonstrated for the first time. Reactions at room temperature and under low catalyst loadings were carried out on a series of representative diene substrates. The time evolution of the characteristic Raman stretching vibrations unequivocally described the reaction progress allowing for precise calculation of the substrate conversion and of the yield in the expected cyclic product, based on the corresponding peak heights.

ESR study of aqueous micellar solutions of perfluoropolyether surfactants with the use of fluorinated spin probes.

Fluoroalkyl esters of 3-carboxy pyrroline nitroxide, FPn (n=8 and 12), containing (n-2) CF(2) groups in the side-chain, were used as novel ESR spin probes of fluorinated micellar systems. The method was applied to study aqueous solutions of perfluoropolyether surfactants of the general formula Cl(C(3)F(6)O)(2)CF(2)COOX, consisting of two perfluoroisopropoxy units and the counterion X = Na(+) or NH(+)(4). By measuring the change of (14)N hyperfine splitting with surfactant concentration the critical micellar concentration of the ammonium salt was determined at temperatures of 297, 313 and 333 K.

Modulation of oxidative damage by nitroxide free radicals.

Piperidine nitroxides like 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) are persistent free radicals in non-acidic aqueous solutions and organic solvents that may have value as therapeutic agents in medicine. In biological environments, they undergo mostly reduction to stable hydroxylamines but can also undergo oxidation to reactive oxoammonium compounds. Reactions of the oxoammonium derivatives could have adverse consequences including chemical modification of vital macromolecules and deleterious effects on cell signaling.