Direct observation of nuclear spin diffusion in real space

Images directly visualizing the spatial spin-diffusion process are reported. The measurements were performed using a magnetic resonance force microscope. The field gradient associated with the force-detection experiment is large enough to affect the spin dynamics and a modified kinetics of the spin-diffusion process is observed. The effects of the gradient were compensated for by a pulse scheme and a pure Zeeman diffusion rate constant of D=(6.2+/-0.7)x10{-12} cm{2}/s in CaF2 was observed.     

Kinetische Untersuchungen über die Silicium—Aryl-Spaltung mit Bromwasserstoff

Rate constants of the cleavage reaction of silicon aryl linkages with HBr were estimated for various aryl derivatives by means of NMR. A row of substituents was obtained, dependent on the cleavage rates. Correlation with theHammett function shows the electrophilic character of the reaction. The different cleavage rates give the possibility for specific cleavages of aryl groups from silanes.

     

Enantioselective [6pi]-photocyclization reaction of an acrylanilide mediated by a chiral host. Interplay between enantioselective ring closure and enantioselective protonation

The [6pi]-photocyclization of the anilides 1a and 5 was studied in the absence and in the presence of the enantiomerically pure chiral lactam 4. The relative configuration of the products was unambiguously established by single-crystal X-ray crystallography and by NMR spectroscopy. A significant enantiomeric excess was observed upon reaction of compound 1a to its photocyclization products at -55 degrees C employing lactam 4 as a chiral complexing agent in toluene as the solvent (66% yield). The trans product ent-3a was obtained in 57% ee, and the minor diastereoisomer (trans/cis = 73/27), cis product ent-2a, was obtained in 30% ee. DFT calculations were conducted modeling the complexation of intermediates 8 and ent-8 to host 4. In agreement with steric arguments concerning the conrotatory ring closure of 1a, the formation of ent-8 is favored leading to the more stable complex 4.ent-8 as compared to 4.8. Whereas the enantioselectivity in the photocyclization to trans compound ent-3a increased upon reduction in the reaction temperature, the enantiomeric excess in the formation of cis compound ent-2a went through a maximum at -15 degrees C (45% ee) and decreased at lower temperatures. Deuteration experiments conducted with the pentadeuterated analogue of 1a, d(5)-1a, revealed that the protonation of the intermediates 8 and ent-8 is influenced by chiral amide 4. In the formation of ent-3a/3a, both the enantioselective ring closure and the enantioselective protonation by amide 4 favor the observed (6aS,10aS)-configuration of the major enantiomer ent-3a. In the formation of ent-2a/2a, the enantioselective ring closure (and the subsequent diastereoselective protonation) favors the (6aR,10aS)-configuration that is found in compound 2a. Contrary to that, the enantioselective protonation by amide 4 shows a preference for ent-2a with the (6aS,10aR)-configuration.     

One-dimensional spin-polarized quantum-wire states in Au on Ni(110)

Au chain structures have been prepared on Ni(110). Au6 s,p-derived features in photoemission spectra are identified as quantum-wire states due to their strong dispersion along the chains and absence of dispersion perpendicular to the chains in agreement with our ab initio calculation of the electronic structure. Spin analysis reveals that the states have minority-spin character showing that the confinement of electrons in the chain structure depends on the electron spin.