The microwave spectrum and skeletal torsion of 2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane

The microwave spectrum of 2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane was measured in the region from 12.4 to 26.5 GHz. Vibrational satellites for eleven states of the skeletal torsion were observed and measured. Vibrational transition frequencies were obtained from the solid-phase laser Raman spectrum and also by microwave intensity measurements. From these data the quantitative form of the potential function for the skeletal vibration was determined to be V(X) = 7.47(−0.702X² + X⁴) cm⁻¹. The barrier height is calculated to be 0.920 ± 0.20 cm⁻¹. As this is well below the energy of the v = 0 state, the molecule exists in the untwisted (C_3v) configuration.     

REFLECTIVE INFRARED ELLIPSOMETRY OF PLASTIC FILMS

High resolution reflective ellipsometry is used to study freely suspended plastic films. We determine room temperature optical constants in the infrared for a variety of plastics using ellipsometry. The films are typically 6 to 100 μm thick and measurements are performed from near infrared to long wave-IR. The setup includes modeling software to fit the ellipsometric data to a generalized oscillator model. The films studied include acrylics, fluoropolymers, and variations of polyethylene, polystyrene, and polyvinyl chloride (PVC) among others. We are able to determine in-plane and out-of-plane optical constants. Transmission spectra from FTIR measurements are plotted and compared with ellipsometry results.     

Energy transfer and excimer formation in a flowing afterglow of Mg metastables

Mg atoms were vaporized into a fast flowing Ar carrier stream and then excited by an ac discharge. Downstream of the discharge in the afterglow region metastable Mg (³P) atoms were reacted with vaporized metals. The resultant chemiluminescence consisted of metal atom resonance lines and continuous emission bands of the molecule KMg.     

A formal [3 + 3] cycloaddition reaction. 5. An enantioselective intramolecular formal aza-[3 + 3] cycloaddition reaction promoted by chiral amine salts

A detailed account on chiral secondary amine salt promoted enantioselective intramolecular formal aza-[3 + 3] cycloadditions is described here for the first time. The dependence of enantioselectivity on the structural feature of these chiral amines is thoroughly investigated. This study also reveals a very interesting reversal of the stereochemistry in the respective cycloadducts obtained using C(1)- and C(2)-symmetric amine salts. In addition, the influence of solvents, counteranions, and temperatures on the enantioselectivity is described, and a unified mechanistic model based on experimental results as well as semiempirical calculations is proposed.     

Total synthesis of lepadiformine alkaloids using N-Boc α-amino nitriles as trianion synthons

Lepadiformine A, B, and C were synthesized in an enantiomerically pure form using a reductive cyclization strategy. N-Boc α-amino nitriles were deprotonated and alkylated with enantiomerically pure dibromides to afford the first ring. The products were manipulated to introduce phosphate leaving groups, and subsequent reductive lithiation followed by intramolecular alkylation formed the second ring with high stereoselectivity. The third ring was formed by intramolecular displacement of a mesylate by the deprotected amine. Lepadiformine A and B contain a hydroxymethyl group adjacent to the amine. This appendage was introduced in a sequence using a Polonovski-Potier reaction as the key step. The synthetic strategy is stereoselective and convergent and demonstrates the utility of N-Boc α-amino nitriles as linchpins for alkaloid synthesis.     

Comparison of optical properties of periodic photonic–plasmonic and randomly textured back reflectors for nc-Si solar cells

Light trapping is essential to harvest long-wavelength red and near-infrared photons in thin film silicon solar cells. Light trapping in p-i-n thin film cells is commonly achieved with back-reflectors, and in n-i-p cells with textured front transparent conductors. We systematically compare the optical properties and performance of randomly roughened back reflectors with periodic plasmonic-photonic back-reflectors in p-i-n solar cells. The randomly textured back reflectors were prepared to have very high diffuse reflectance comparable to the state of the art. The periodic back reflectors of tapered nano-pillars/bumps show enhanced quantum efficiency and optical absorption over randomly structured back reflectors using the same solar cell architecture in nc-Si solar cells. The strong diffraction and light concentration in periodic back reflectors may be more beneficial than the light scattering offered by randomly textured back reflectors.     

The microwave spectrum of trioxaadamantane

The microwave spectrum of 2,8,9-trioxaadamantane has been investigated in the region from 12.4 to 26.5 GHz. The observed spectrum exhibited the expected symmetric top pattern, with the rotational constant B₀ = 1848.64 MHz. Numerous weaker lines were observed and were attributed to vibrational satellites of the main rotational transition. The transitions from J = 3 → 4 through J = 6 → 7 were studied and no centrifugal distortion effects were observed.A structure is derived that is consistent with the observed rotational constants of the normal and one isotopic species by use of the method of diagnostic-least-squares.The second order stark effect for the K = 0 state yielded a dipole moment of 3.01 ± 0.03 D.