Anion-encapsulating, discrete prism and extended frusta, from trimetallated triangular macrocycles and linkers.

Reaction of a trinuclear triangular macrocyclic complex PbL(CFSO) with bidentate linkers in a ratio of 3 equiv. of linker per 2 equiv. of complex, produces a prismatic structure with 4,4'-dipyridyl, and two unprecedented, extended 3D frustum-like structures with 1,2-di(4-pyridyl)ethylene and 1,4-di(4-pyridyl)benzene.

Electrophilic Si-H Activation by Acetonitrilo Benzo[h]quinoline Iridacycles: Influence of Electronic Effects in Catalysis.

The performance of six newly synthesized benzo[h]quinoline-derived acetonitrilo pentamethylcyclopentadienyl iridium(III) tetrakis(3,5-bis-trifluoromethylphenyl)borate salts bearing different substituents -X (-OMe, -H, -Cl, -Br, -NO and -(NO ) ) on the heterochelating ligand were evaluated in the dehydro-O-silylation of benzyl alcohol and the monohydrosilylation of 4-methoxybenzonitrile by Et SiH, two reactions involving the electrophilic activation of the Si-H bond. The benchmark shows a direct dependence of the catalytic efficiency with the electronic effect of -X, which is confirmed by theoretical assessment of the intrinsic silylicities Π of hydridoiridium(III)-silylium adducts and by the theoretical evaluation of the propensity of hydridospecies to transfer the hydrido ligand to the activated substrate. The revisited analysis of the Ir-Si-H interactions shows that the most cohesive bond in hydridoiridium(III)-silylium adducts is the Ir-H one, while the Ir-Si is a weak donor-acceptor dative bond.

(NHC-olefin)-nickel(0) nanoparticles as catalysts for the ()-selective semi-hydrogenation of alkynes and ynamides.

Nickel(0) nanoparticles coordinated to NHC ligands bearing N-coordinated cinnamyl moieties were readily prepared by reduction of a [NiCpBr(NHC-cinnamyl)] complex with methyl magnesium bromide. The combination of a strong σ-donor NHC ligand with a π-coordinating appended cinnamyl moiety likely prevents nickel(0) nanoparticle aggregation to larger inactive species, and allows the effective and ()-selective semi-hydrogenation of alkynes and ynamides

Synthesis of a helicene-fused porphyrin leading to a π-extended chiral chromophore.

The preparation of several covalently linked [6]-helicene-porphyrins is reported. A fused [6]-helicene-porphyrin π-extended aromatic system was isolated, the enantiomers separated and the chiroptical properties determined. The oxidative cyclodehydrogenation proved to be very effective for six-membered fused helical systems, but not suited for the formation of five-membered fused systems.

Rational engineering of an erythropoietin fusion protein to treat hypoxia.

Erythropoietin enhances oxygen delivery and reduces hypoxia-induced cell death, but its pro-thrombotic activity is problematic for use of erythropoietin in treating hypoxia. We constructed a fusion protein that stimulates red blood cell production and neuroprotection without triggering platelet production, a marker for thrombosis. The protein consists of an anti-glycophorin A nanobody and an erythropoietin mutant (L108A).

Towards a better understanding of magnetic interactions within m-phenylene alpha-nitronyl nitroxide and imino nitroxide based radicals, part III: Magnetic exchange in a series of triradicals and tetraradicals based on the phenyl acetylene and biphenyl coupling units.

The present work completes and extends our previous reports on the determination of the magnetic ground state and on the strength of the through bond exchange coupling within series of biradicals. This knowledge was subsequently exploited for the analysis of the magnetic interactions in their crystals. We report here the studies of series of triradicals incorporating alpha-nitronyl nitroxides (NN) or alpha-imino nitroxides (IN) as terminal radical fragments connected through a m-phenylene coupling unit in one case and a phenyl acetylene unit in other case.

Photochemical and thermal ligand exchange in a ruthenium(II) complex based on a scorpionate terpyridine ligand.

A ruthenium(II) complex containing a 1,10-phenanthroline unit and a terpyridine fragment covalently linked to a benzonitrile group has been synthesised; coordination and decoordination of the benzonitrile group can be induced thermally and photochemically respectively, in an acetone-water mixture.