Completing the triad: Synthesis and full characterization of homoleptic and heteroleptic carbonyl and nitrosyl complexes of the group VI metals

Oxidation of M(CO)$_{6}$ (M = Cr, Mo, W) with the synergistic oxidative system Ag[WCA]/0.5 I$_{2}$ yields the fully characterized metalloradical salts [M(CO)$_{6}$]+˙[WCA]− (weakly coordinating anion WCA = [F-{Al(OR$^{F}$)$_{3}$}$_{2}$]$^{-}$, R$^{F}$ = C(CF$_{3}$)$_{3}$). The new metalloradical cations with M = Mo and W showcase a similar structural fluxionality as the previously reported [Cr(CO)$_{6}$]$^{+}$˙. Their reactivity increases from M = Cr < Mo < W and their syntheses allow for in-depth insights into the properties of the group 6 carbonyl triad. Furthermore, the reaction of NO$^{+}$[WCA]$^{-}$ with neutral carbonyl complexes M(CO)$_{6}$ gives access to the heteroleptic carbonyl/nitrosyl cations [M(CO)$_{5}$(NO)]$^{+}$ as salts of the WCA [Al(ORF)$_{4}$]$^{-}$, the first complete transition metal triad of their kind

An Artificial SEI Layer Based on an Inorganic Coordination Polymer with Self-Healing Ability for Long-Lived Rechargeable Lithium-Metal Batteries

Upon immersion of a lithium (Li) anode into a diluted 0.05 to 0.20 M dimethoxyethane solution of the phosphoric-acid derivative (CF$_{3}$CH$_{2}$O)$_{2}$P(O)OH (HBFEP), an artificial solid-electrolyte interphase (SEI) is generated on the Li-metal surface. Hence, HBFEP reacts on the surface to the corresponding Li salt (LiBFEP), which is a Li-ion conducting inorganic coordination polymer. This film exhibits – due to the reversibly breaking ionic bonds – self-healing ability upon cycling-induced volume expansion of Li. The presence of LiBFEP as the major component in the artificial SEI is proven by ATR-IR and XPS measurements. SEM characterization of HBFEP-treated Li samples reveals porous layers on top of the Li surface with at least 3 μm thickness. Li−Li symmetrical cells with HBFEP-modified Li electrodes show a three- to almost fourfold cycle-lifetime increase at 0.1 mA cm$^{-2}$ in a demanding model electrolyte that facilitates fast battery failure (1 M LiOTf in TEGDME). Hence, the LiBFEP-enriched layer apparently acts as a Li-ion conducting protection barrier between Li and the electrolyte, enhancing the rechargeability of Li electrodes

Models of organometallic complexes for optoelectronic applications

Organometallic complexes have potential applications as the optically active components of organic light emitting diodes (OLEDs) and organic photovoltaics (OPV). Development of more effective complexes may be aided by understanding their excited state properties. Here we discuss two key theoretical approaches to investigate these complexes: first principles atomistic models and effective Hamiltonian models. We review applications of these methods, such as, determining the nature of the emitting state, predicting the fraction of injected charges that form triplet excitations, and explaining the sensitivity of device performance to small changes in the molecular structure of the organometallic complexes.Comment: To appear in themed issue of J. Mat. Chem. on the modelling of material

Chloride ion impact on materials for light-emitting electrochemical cells

Small quantities of Cl(-) ions result in dramatic reductions in the performance of ionic transition metal complexes in light-emitting electrochemical cells. Strong ion-pairing between aromatic protons and chloride has been established in both the solid state and solution. X-ray structural determination of 2{[Ir(ppy)2(bpy)][Cl]}·2CH2Cl2·[H3O]·Cl reveals the unusual nature of an impurity encountered in the preparation of [Ir(ppy)2(bpy)][PF6]

Hematology and Serum Chemistry of Free-ranging Jaguars (Panthera onca)

We collected and analyzed blood samples from 12 free-ranging jaguars (Panthera onca). Clinical examinations, hematolog, and serum chemistry indicate the jaguars were in good overall health. Results may help as values for free-ranging jaguars under the same handling conditions.FAPESP [Proc. 08/02573-0, 07/00976-7]FAPES

Linear Amine-Linked Oligo-BODIPYs: Convergent Access via Buchwald-Hartwig Coupling

A convergent route towards nitrogen-bridged BODIPY oligomers has been developed. The synthetic key step is a Buchwald-Hartwig cross-coupling reaction of an alpha-amino-BODIPY and the respective halide. Not only does the selective synthesis provide control of the oligomer size, but the facile preparative procedure also enables easy access to this type of dyes. Furthermore, functionalized examples were accessible via brominated derivatives