A gas-phase electron diffraction study of the molecular structure of tetravinylsilane

The molecular structure of tetravinylsilane has been studied by gas-phase electron diffraction. The radial distribution curve suggests the absence of conformers having vinyl double bonds staggered with respect to the SiC₄ skeleton. Of the eclipsed or approximately-eclipsed conformers, the one with S₄ symmetry gives the best fit with experiment, although a small admixture of a C₁ conformation cannot be ruled out. Least-squares refinement gave the following values for the independent structural parameters (lengths, r_a basis; angles, r_α basis): C-H = 1.118 ± 0.003 Å, CC = 1.355 ± 0.002 Å, Si-C = 1.855 ±0.002 Å, ∠SiCC = 124.0 ± 0.3°, ∠SiCH = 118.4 ± 1.0°, torsion angles CSiCC are 17.5 ± 0.6° from the eclipsed conformation. During the refinement the vibrational amplitudes u and perpendicular amplitude corrections K were held constant at calculated values. The CC bond length provides evidence of interaction between the vinyl π-bonds and the vacant d-orbitals of silicon.     

Chemical studies on the anobiidae: Sex pheromone of the drugstore beetle, stegobium paniceum (L.) (coleoptera)

Chemical an spectroscopic evidence is presented to show that 2,3-dihydro-2,3,5-trimethyl-6-(1-methyl-2-oxobutyl)-4H-pyran-4-one (10) is the sex pheromone produced by the female drugstore beetle, Stegobium paniceum L.     

Isocyanide addition to MN2(CO)5(Ph2PCH2PPh2)2 and the formation of a four-electron doubly-bridging isocyanide

The reactions of Fe(CO)₅, Fe(CO)₄P(C₆H₅)₃, M(CO)₆ (M  W, Mo, Cr), and (CH₃C₅H₄Mn(CO)₃ with KH and several boron and aluminium hydrides were investigated. Iron pentacarbonyl was converted quantitatively to K⁺Fe(CO)₄-(CHO) by hydride transfer from KBH(OCH₃)₃ allowing isolation of [P(C₆H₅)₃]₂-Nⁿ⁺Fe(CO)₄(CHO)^? in 50% yield. Lower yields were obtained with LiBH(C₂H₅)₃, and other hydride sources gave little or no formyl product. The stability of Fe(CO)₄(CHO)^? in THP was found to depend on the cation, decreasing in the order [P(C₆H₅)₃]₂N⁺ > K⁺ > Na⁺ > Li⁺. No formyl complexes were isolated and no spectroscopic evidence for formyl formation was observed in the reactions of the other transition metal carbonyls with several hydride sources. Fe(CO)₄-P(C₆H₅)₃ gave K₂Fe(CO)₄ when treated with KHB(OCH₃)₃. When treated with LiBH(C₂H₅)₃, W(CO)₆ gave a mixture of HW₂(CO)₁₀^?and (OC)₅W(COC₂H₅)^?; the latter was methylated to give the carbene complex (OC)₅WC(OCH₃)C₂H₅.     

Vibrational studies in aqueous solutions: Part II. The acid oxalate ion and oxalic acid

Assignments for oxalic acid in solution are re-examined. A detailed assignment of the IR and Raman spectra of the acid oxalate ion is presented for the first time. Raman spectroscopy is used to study the first ionization of oxalic acid.     

Br2 in an ar matrix: an example of complete damping of the resonance raman scattering amplitude in the discrete resonance limit

Raman scattering and relaxed fluorescence is observed upon cw laser excitation resonant with the lower vibrational manifold of the X(¹Σ_o+u) → B(³Π_o+u) transition of matrix isolated Br₂ at liquid He temperatures. The excitation profile of the relaxed fluorescence maps out the resonances, but neither detectable enhancement of Raman scattering nor resonance fluorescence is observed.     

Trends in the CNDO/2 molecular orbital study of electronic structure in some neurotransmitter drugs

An investigation of electronic structure in some neurotransmitter drugs has been made using the CNDO/2 semi-empirical molecular orbital method.The electronic structure has been conveniently characterized by the electronic parameters nett atomic population (NAP) and bond index (BI). A variation of these electronic parameters with respect to conformation has been studied and has been found unlikely to exceed 0.1 e in most. cases. Further, the useful extent to which the electronic parameters of some commonly occurring functional groups may be regarded as conformationally invariant has been demonstrated. Also presented are (i) a discussion on the intramolecular close-approach of functional groups — the interaction between terminal —COO^? and ?NH₃⁺ groups of α-ω anaino acids is explicitly considered; (ii) an enquiry into the extension of ‘standard’ (idealized) geometry models in the elucidation of electronic structure.The implication of the results and observations presented here are briefly discussed with reference to classical and quantum structure-activity studies of drug molecules.     

π-CONJUGATED OLIGOMERS IN SUPRAMOLECULAR CRYSTALS AND THEIR OPTOELECTRONIC FUNCTIONS

Functional organic molecular materials and conjugated oligomers or polymers now allow the low-cost fabrication of thin films for insertion into new generations of electronic and optoelectronic devices. The performance of these devices relies on the understanding and optimization of several complementary processes. Our goal is to discuss the relationship between the molecular stacking structures and their optoelectronic properties that are of importance in all these areas. The concept of intermolecular interaction should be taken here in the special sense that is inter-dipole coupling. Specifically, we will address the impact of inter-dipole interaction between adjacent molecules in aggregate state on the solid-state emission properties.     

Medium effects on fluorescence quantum yields and lifetimes for coumarin laser dyes

Fluorescence quantum yields and lifetimes of coumarin dyes are sharply reduced in polar solvents if amine substituent groups are free to rotate. The polar solvent effect is interpreted in terms of relaxation of excited dye from an initial planar conformation to a twisted zwitterionic state.     

Microwave spectrum of N2D4, 14N quadrupole coupling constants,and the barrier to inversion of the amino group

The microwave spectrum of N₂D₄ has been observed and analyzed. Based on five low-J rotational transitions the effective rotational constants are: A = 74712.9 ± 1.9 MHz, B = 18500.42 ± 0.46 MHz, and C = 18439.91 ± 0.46 MHz. The quadrupole coupling constants of the ¹⁴N nuclei are X_aa = 4.23 ± 0.04 MHz, X_bb = 1.98 ± 0.05 MHz, and X_cc = ?2.25 ± 0.05 MHz. Using the observed ground state inversion splittings for N₂D₄ and N₂H₄ the barrier to inversion of a single amino group is computed to be 5.00 kcal mol^?1.     

A comparison of phototautomerism in different sites of free-base porphin (H2P) in n-alkane crystals

Selective laser-induced phototautomerism of free-base porphin in different n-alkanes (n-hexane, n-heptane, n-octane, nnonane, n-decane, n-undecane and n-dodecane) has been used to identify tautomer splittings in a number of sites in polycrystalline samples at 2 K. Pairs or lines arising from the two molecular orientations in each site can be reversibly transformed into each other. In the odd n-alkanes the occupation of different sites was not dependent on the rate at which the samples were frozen, but in the even n-alkanes metastable sites were only occupied following rapid quenching.