Chiral phase transition in two-dimensional supramolecular assemblies of prochiral molecules

The self-assembly of the rodlike two-dimensional chiral molecule 4-[trans-2-(pyrid-4-yl-vinyl)] benzoic acid on the Cu(100) surface has been investigated by scanning tunneling microscopy. Upon adsorption at T>or=300 K, the molecules are deprotonated and assemble in parquet patterns when the coverage remains below a critical value. Corresponding high-resolution data reveal that the ordering implies mesoscopic chiral resolution as a result of chiroselective interactions (i.e., two domains comprise exclusively one enantiomer). When the critical coverage is exceeded, an abrupt transition to a single racemic phase is observed with a different lateral molecular coupling scheme. The shifting of the subtle balance between the weak lateral coupling, substrate bonding, and the packing requirements encountered with the increased molecular coverage is suggested to be the driving force for this homochiral-to-heterochiral phase transition.     

Oxygen isotope effect in the ab-plane reflectance of underdoped YBa(2)Cu(3)O(7-delta)

We have measured the effect of oxygen isotope substitution on the ab-plane reflectance of underdoped YBa(2)Cu(3)O(7-delta). The frequency shift of the transverse optic phonons due to the substitution of 16O by 18O yields an isotope effect of the expected magnitude for copper-oxygen stretching modes with alpha=0.5+/-0.1. The reflectance shoulder at 400-500 cm(-1) shows a much smaller exponent of alpha=0.1+/-0.1 in the normal state and alpha=0.23+/-0.1 in the superconducting state. These observations suggest that the shoulder is of electronic origin and not due to a phonon mode as has been suggested recently.     

Two chain gallium fluorodiphosphates: synthesis,structure solution,and their transient presence during the hydrothermal crystallisation of a microporous gallium fluorophosphate

Two novel gallium fluorodiphosphates have been isolated and their structures solved ab initio from powder X-ray diffraction data; the materials readily interconvert under hydrothermal conditions, and are metastable with respect to an open-framework zeolitic gallium fluorophosphate, during the synthesis of which they are present as transient intermediates.     

Novel approach to the synthesis of enantioenriched sulfoxides. Highly diastereoselective alkylation of sulfenate anions with 1,4-asymmetric induction

[reaction: see text] Efficient 1,4-asymmetric induction with an enantiopure aminoalkyl group as the chiral auxiliary has been achieved in the first example of diastereoselective alkylation (up to 98:2) of a sulfenate anion, readily prepared by oxidation of the corresponding thiolate. The stereochemistry of the sulfoxide produced is the opposite of that obtained by the conventional route based on oxidation of the sulfide precursor.     

Two successive one-pot reactions leading to the expeditious synthesis of (−)-centrolobine

A very short and efficient synthesis of (−)-centrolobine has been achieved by using two successive one-pot reactions. The first sequence involves a cross-metathesis reaction/hydrogenation/lactonization and the second sequence is a Grignard addition/reduction.     

The role of the hydration configuration in electronic processes involving ions in aqueous solution

The nature of small ions in electrolytic (e.g., aqueous) solutions is discussed in terms of the configuration of the adjoining polarized medium, and the role of this configuration in electronic transitions involving one or a pair of ions is treated in a general way. Light absorption by a single ion is shown to depend critically on this configuration; a theory developed previously by the authors is reviewed, and future possibilities of exploring the nature of the configuration by investigation of such spectra are explained. Electronic transitions, such as an “electron transfer” process, during binary collisions of ions are treated, and a general method is developed, based uponDebye's “diffusion” theory for ion collision rates and a nonadiabatic type of potential curve. Rates of chemical processes are found to depend decisively on the interaction of two ions at separations where the simple coulomb law is not valid.     

Double deprotonation of acetylenic oxiranes: synthesis of allenic ketones through Dilithio Ynenolates

[reaction: see text] The double deprotonation of acetylenic oxiranes gives allenic ketones through the 1,2-H or 1,2-Ar shift on the transient oxiranyl dianion intermediates. The resulting dilithium ynenolates give allenic ketones upon hydrolysis or can be quenched with various electrophiles.