RESUMEN
We have performed a study of several cesium oven designs. A comparison between recirculating (or sticking-wall) and collimating (or re-emitting-wall) ovens is made in order to extract the most efficient design in terms of beam brightness. Unfortunately, non-reproducible behaviors have been observed, and the most often observed output flux is similar to the sticking-wall case, which is the lowest theoretical value of the two cases, with a beam brightness close to 1018 at. sr-1 s-1 cm-2. The reason of this universally observed behavior is unclear despite having tested several materials for the collimating tube. Conclusion on possible improved design based on sticking of cesium on several (un)cleaned surfaces is given.
RESUMEN
Simple reactions of the most used functional groups allowing two molecular fragments to link under mild, sustainable conditions are among the crucial tools of molecular chemistry with multiple applications in materials science, nanomedicine, and organic synthesis as already exemplified by peptide synthesis and "click" chemistry. We are concerned with redox organometallic compounds that can potentially be used as biosensors and redox catalysts and report an uncatalyzed reaction between primary and secondary amines with organometallic electrophilic alkynes that is free of side products and fully "green". A strategy is first proposed to synthesize alkynyl organometallic precursors upon addition of electrophilic aromatic ligands of cationic complexes followed by endo hydride abstraction. Electrophilic alkynylated cyclopentadienyl or arene ligands of Fe, Ru, and Co complexes subsequently react with amines to yield trans-enamines that are conjugated with the organometallic group. The difference in reactivities of the various complexes is rationalized from the two-step reaction mechanism that was elucidated through DFT calculations. Applications are illustrated by the facile reaction of ethynylcobalticenium hexafluorophosphate with aminated silica nanoparticles. Spectroscopic, nonlinear-optical and electrochemical data, as well as DFT and TDDFT calculations, indicate a strong push-pull conjugation in these cobalticenium- and Fe- and Ru-arene-enamine complexes due to planarity or near-planarity between the organometallic and trans-enamine groups involving fulvalene iminium and cyclohexadienylidene iminium mesomeric forms.