1H NMR isotope shifts arising from the substitution of 12C by 13C: application to polycyclic aromatic hydrocarbon anions

Isotope shifts are a well-established tool for structural analysis by NMR. The substitution of a protium with a deuterium is the most widely studied of these effects. However, such studies call for specific deuteration that requires complex synthetic techniques owing to the low natural abundance of deuterium. ¹³C occurs at a higher natural abundance and couples strongly with its attached proton. We have developed and refined a method to reliably observe these much smaller shifts without needing to resort to chemical synthesis. We show that carbon induced isotope shifts reflect structural features. Copyright © 2001 John Wiley & Sons, Ltd.     

Electromagnetic field theory solution of the infinite tapered-plane transmission line

Zusammenfassung Für den eingeschwungenen Zustand dertapered-plane transmission line wird eine neue Lösungsmethode beschrieben und gezeigt, dass die Impedanztransformation direkt vom Verhältnis der Abstände zwischen Anfang und Ende der leitenden Ebenen bestimmt wird. Die Phasendifferenz der Spannungen zwischen den Leitungsenden ist dem Öffnungswinkel der beiden Ebenen proportional. Kriterien für den Entwurf solcher Leitungen lassen sich angeben.

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This work was submitted byNoach Amitay in partial fulfillment of the Degree Doctor of Philosophy.     

Reductive Bergman-type cyclizations of cross-conjugated enediynes to fulvene and fulvalene anions: the role of the substituent

Various cross-conjugated enediynes undergo "Bergman-type" cycloaromatizations upon reduction with potassium metal, generating anions of fulvenes and fulvalene derivatives. This new anionic cyclization is considerably more facile than the classic Bergman cyclization with linear enediynes, creating highly reactive diradicals at -78 degrees C. Not all cross-conjugated enediynes yield cyclized dianions upon reduction; some give uncyclized, Y-shaped, cross-conjugated dianions, while others apparently yield radical-anions that either dimerize or persist as monomers. One system yields both a cyclized and an uncyclized dianion. The substituents are thus shown to be a critical factor in determining the outcome of the reduction. Cyclization occurs within a specific "window of opportunity" that is governed by the substituents.     

Wave-front control and aberration correction with a diffractive optical element

A method that permits aberration correction and wave-front reshaping with a diffractive optical element (DOE) is described. Two aligned DOE's made of two different dispersive materials are used. The different dispersions of the two materials in addition to freedom in choosing their thicknesses enables the chromatic aberration and the wave fronts to be manipulated. Design and simulation of such DOE's are described.     

Design of a diffractive optical element for wide spectral bandwidth

A new method for eliminating the chromatic aberration of a diffractive optical element (DOE) for wideband wavelengths is presented. The wideband-wavelength diffractive optical element (WBDOE) consists of two aligned DOE's. The use of different dispersive materials for the two DOE's eliminates chromatic aberration. The design and simulation of a WBDOE for the visible spectrum are presented.     

Antiaromaticity and reactivity of a planar cyclooctatetraene fully annelated with bicyclo[2.1.1]hexane units

A detailed investigation has been made into the antiaromaticity and chemical reactivity of a planar cyclooctatetraene (COT) molecule fully annelated with bicyclo[2.1.1]hexane units 2. In spite of its planar 8pi-electronic structure, theoretical calculations have indicated that the antiaromaticity of COT 2 is considerably decreased in comparison with a planar COT 16 with D 4h symmetry. This behavior appears to be related to the wider HOMO-LUMO gap of 2 relative to 16, which is caused by the raised LUMO level as a result of the effective sigma-pi* orbital interaction between the strained bicyclic framework and the COT pi system. The two-electron reduction of 2 required the use of potassium mirror or a combination of lithium/corannulene in highly dried [D8]THF at -78 degrees C under vacuum. In contrast, the [4+2] cycloaddition of 2 with tetracyanoethylene (TCNE) proceeded quite smoothly owing to the high-lying HOMO. Reaction of 2 with meta-chloroperbenzoic acid gave all-trans tetraepoxide 23 in the same way as the corresponding benzene derivative 3. While the Simons-Smith-type cyclopropanation of benzene 3 gave tricyclopropanated derivative 21, the reaction of 2 only afforded isomers of dicyclopropanated derivatives 25 and 26. Yet, the reactivity of 2 is higher than the parent COT, which does not show any reactivity under the same conditions. On the basis of homodesmic reactions, it was concluded that release of strain is also an important factor for such relatively high reactivity in the epoxidation and cyclopropanation of bicycloannelated COT 2 as well as benzene 3.