Reduction of LPhSnCl with 0.66 eq. of LiBsBu3H affords the mixed-valent homocatenated tri-tin complex (LPhSn)3Cl whose HOMO primarily comprises σ-bonding along the Sn–Sn–Sn framework.
Wavenumber and intensity calibration of a Raman spectrometer is performed with the use of pure rotational Raman bands (Δν = 0, ΔJ = ± 2) of H 2 , HD, D 2 , and vibration-rotation Raman bands (Δν = 1, ΔJ = ± 2) of O 2 as primary standards. Wavenumber calibration is based on reference transition wavenumbers available from accurate theoretical and experimental results. Intensity calibration is based on ratios of accurate theoretical Raman intensities for transitions from common rotational states to eliminate temperature effects. Polarization dependence is corrected to ensure that all of these bands have the correct depolarization ratio, ρ = 0.75. The calibrated Raman spectrometer is used to measure standard Raman spectra of carbon tetrachloride, benzene, cyclohexane, toluene, and benzonitrile, for which the relative Raman intensities and depolarization ratios are determined with carefully estimated uncertainties. Vibrational frequencies of indene used for routine wavenumber calibration are updated.
Inspired by the induced-fit mechanism in nature, we developed the process of water-induced self-assembly (WISA) to make water an active substrate that regulates the self-assembly and function of amphiphilic discotic molecules (ADMs). The ADM is an isotropic liquid that self-assembles only when in contact with water. Characterization results indicate that water fits into the hydrophilic core of the ADMs and induces the formation of a hexagonal columnar phase (Col h ), where each column contains a hydrated artificial water channel (AWC). The hydrated AWCs are adaptive rather than static; the dynamic incorporation/removal of water results in the reversible assembly/disassembly of the adaptive AWCs (aAWCs). Furthermore, its dynamic characteristics can enable water to act as an orientation−directional guest molecule that controls the growth direction of the aAWCs. Well-aligned aAWC arrays that showed the ability of water transport were obtained via a "directional WISA" method. In WISA, water thus governs the supramolecular chemistry and function of synthetic molecules as it does with natural materials. By making water an active component in adaptive chemistry and enabling host molecules to dynamically interact with water, this adaptive aquatic material may motivate the development of synthetic molecules further toward biomaterials.
We report an exhaustive compilation of wavelength-dependent matrix elements over the mean polarizability (α¯) and polarizability anisotropy (γ) operators for the rovibrational states of the H, HD, and D molecules together with an accompanying computer program for their evaluation. The matrix elements can be readily evaluated using the provided codes for rovibrational states with J = 0-15 and v = 0-4 and for any laser wavelengths in the interval 182.25-1320.6 nm corresponding to popular, commercially available lasers. The presented results substantially extend the scope of the data available in the literature, both in respect of the rovibrational transitions analyzed and the range of covered laser frequencies. The presented detailed tabulation of accurate polarizability tensor invariants is essential for successful realization of our main long-term goal: developing a universal standard for determining absolute Raman cross sections and absolute Raman intensities in experimental Rayleigh and Raman scattering studies of molecules.
Vibrational assignments are proposed for solid NaNH2SO3 on the basis of room temperature polarized Raman spectra of single crystals. Infrared data for the region 4000–50 cm−1 of the polycrystalline sample are also presented. The results indicate that (1) there is no water of crystallization, (2) the hydrogen bonding is extremely weak, and (3) the strength of N—S bond is stronger than in sulphamic acid.
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