Barely fluorescent molecules. II. Twin-discharge jet laser-induced fluorescence spectroscopy of HSnBr and DSnBr.

HSnBr and DSnBr have been detected for the first time by a combination of laser-induced fluorescence (LIF), fluorescence hole-burning, and wavelength resolved emission spectroscopies. The transient molecules were produced in a twin-discharge jet using separate precursor streams of SnH4/SnD4 and HBr/DBr, both diluted in high pressure argon. The Ã1A″-X̃1A' spectrum of HSnBr only consists of the 00 0 and 20 1 cold bands that show clearly resolved subband structure with fluorescence lifetimes varying from 526 to 162 ns. The DSnBr LIF spectrum exhibits four bands (00 0, 20 1, 20 2, and 10 1) whose fluorescence lifetimes decrease from 525 ns (00) to 175 ns (11). Single vibronic level emission spectra have provided extensive information on the ground state vibrations, including all the anharmonicities and the harmonic frequencies. Fluorescence hole-burning experiments have shown that a few higher HSnBr nonfluorescent levels are very short-lived but still detectable. The ab initio studies of Tarroni and Clouthier [J. Chem. Phys. 156, 064304 (2022)] show that these molecules dissociate into SnBr + H on the excited state potential surface and this is the cause of the short fluorescence lifetimes and breaking off of the LIF spectra. HSnBr is a barely fluorescent molecule in the sense that only vibrational levels less than or equal to 317 cm-1 in the excited state emit detectable photons down to the ground state.

Data associated with a tellurium absorption atlas 19,000 - 24,000 cm-1.

Transmittance and absorbance data in the form of a spectral atlas have been obtained from Fourier transform spectra recorded on a commercial (Bomem DA3) instrument, operated with an external white light source injected through the instrument's `emission' port. The sample was a sealed, evacuated cell containing a small quantity of 130Te. This cell was placed in a ceramic furnace maintained close to 620 °C, with tellurium vapor pressures 8-11 Torr. The data are intended as an aid to spectral calibration in the blue-green to violet region. The data relate to work published in J. Mol. Spectrosc. 384 111,589 (2022).

Reconciliation of Differences in Apparent Diffusion Coefficients Measured for Self-Exchange Electron Transfer between Molecules Anchored to Mesoporous Titanium Dioxide Thin Films.

Redox-active sites present at large concentrations as part of a solid support or dissolved as molecules in fluid solutions undergo reversible self-exchange electron-transfer reactions. These processes can be monitored using a variety of techniques. Chronoamperometry and cyclic voltammetry are common techniques used to interrogate this behavior for molecules bound to mesoporous thin films of wide-bandgap semiconductors and insulators. In order to use these techniques to obtain accurate values for apparent diffusion coefficients, which are proxies for rate constants for self-exchange electron transfer, it is imperative to take into consideration nonidealities in redox titrations, parasitic currents, and ohmic resistances. Using spectroelectrochemical measurements taken concurrently with measurements of chronoamperometry data, we show that the spectroscopic data is not confounded from effects of parasitic currents or electroinactive dyes. However, we show that the thickness of the thin film over the region that is optically probed by the measurements must be known. When each of these considerations is included in data analyses, calculated apparent diffusion coefficients are, within error, independent of the method used to obtain the data. These considerations help reconcile variations in apparent diffusion coefficients measured using different techniques that have been reported over the past several decades and allow correct analyses to be performed in the future, independent of the method used to obtain the data.

Convergent Total Synthesis of Yaku'amide†A.

Total synthesis of the anticancer peptide natural product yaku'amide A is reported. Its ß-tert-hydroxy amino acids were prepared by regioselective aminohydroxylation involving a chiral mesyloxycarbamate reagent. Stereospecific construction of the E- and Z-ΔIle residues was accomplished through a one-pot reaction featuring anti dehydration, azide reduction, and O→N acyl transfer. Alkene isomerization was negligible during this process. These methods enabled a highly convergent and efficient synthetic route to the natural product.

Insights into base-free OsO4-catalyzed aminohydroxylations employing chiral ligands.

Attempts to perform the OsO4-catalyzed enantioselective base-free aminohydroxylation of ß,ß-disubstituted enoates are described. Low yields and racemic products were obtained in the presence of standard chiral ligands, suggesting the occurrence of a "Second Cycle" process due to slow hydrolysis of the amino alcohol product from the Os metal center. Support for this hypothesis was provided by the slightly improved enantioselectivity (60:40 er) obtained with an amino alcohol ligand. Based on density functional theory calculations, it is proposed that the lack of significant enantioselectivity is due to a low-energy (3 + 2) oxo/imido cycloaddition transition state without the chiral ligand in the Second Cycle that outcompetes protonolysis in the First Cycle.

Selective access to E- and Z-ΔIle-containing peptides via a stereospecific E2 dehydration and an O → N acyl transfer.

A concise synthesis of peptides that contain E- or Z-dehydroisoleucine (ΔIle) residues is reported. The key reaction is an unusual anti dehydration of ß-tert-hydroxy amino acid derivatives that is mediated by the Martin sulfurane. A subsequent tandem Staudinger reduction-O → N acyl transfer process forges an amide bond to the ΔIle residue with minimal E/Z alkene isomerization. Density functional calculations attribute the stereospecific dehydration to a highly asynchronous E2 anti process.