RESUMEN
Carbene species play an integral role in high-energy chemistry, transition-metal-carbene chemistry, catalysis, photolytic formation of carbohydrates, and possibly even the formation of interstellar sugars. In 1921, "reactive formaldehyde"ânow known as hydroxymethylene (HCOH)âwas first implicated as an intermediate in photocatalytic processes. However, due to its transient nature, direct observation of HCOH has predominantly been attained using cryogenic isolation methods. As a result, HCOH gas-phase reactivity measurements have been limited. We directly observed HCOH using photoionization spectroscopy following UV photodissociation of methanol. Our measurements show it reacts slowly with O2 at room temperature. This work provides evidence for the formation mechanism of HCOH from CH3OH and its subsequent reactivity under gas-phase reaction conditions.
RESUMEN
Understanding the structural dynamics of covalent organic frameworks (COFs) in response to external temperature change is necessary for these materials' application at cryogenic temperatures. Herein, we report reversible structural dynamics observed in covalent organic frameworks as the temperature varies from 298 K to 30 K. A series of frameworks (COF-300, COF-300-amine, and COF-V) was studied in situ using a cryogenic infrared spectroscopy system. We observed peak shifts in the Fourier-transform infrared (FTIR) spectrum of COFs as temperature cooled to 30 K, and these peak shifts were reversed as temperature returned to 298 K. Comparison of these materials showed different degrees of temperature-dependent change, through the quantitative degree of the peak shift and a qualitative description of which peaks shifted. A general IR peak shift towards a higher frequency as temperature decreased was observed, with COF-300 exhibiting quantitatively larger blue shifts in key vibrational modes as compared with the other frameworks. The nature of the conformational changes giving rise to the IR shifts was studied using quantum-chemistry calculations on model systems. The results of the calculations indicate that key peak shifts arise from a pedal motion experienced by the frameworks during cooling. This understanding of temperature-dependent framework dynamics will enhance the development, selection, and application of covalent organic frameworks at extreme temperatures.
RESUMEN
Methyl nitrite has two stable conformational isomers resulting from rotation about the primary C-O-N-O dihedral angle: cis-CH3ONO and trans-CH3ONO, with cis being more stable by â¼5 kJ/mol. The barrier to rotational interconversion (â¼45 kJ/mol) is too large for isomerization to occur under ambient conditions. This paper presents evidence of a change in conformer abundance when dilute CH3ONO is deposited onto a cold substrate; the relative population of the freshly deposited cis conformer is seen to increase compared to its gas-phase abundance, measured by in situ infrared spectroscopy. We observe abundance changes depending on the identity of the bath gas (N2, Ar, and Xe) and deposition angle. The observations indicate that the surface properties of the growing matrix influence conformer abundance-contrary to the widely held assumption that conformer abundance in matrices reflects gas-phase abundance. We posit that differences in the angle-dependent host-gas deposition dynamics affect the growing surfaces, causing changes in conformer abundances. Quantum chemistry calculations of the binding energies between CH3ONO and a single bath-gas component reveal that significant energetic stabilization is not observed in 1:1 complexes of N2:CH3ONO, Ar:CH3ONO, or Xe:CH3ONO. From our results, we conclude that the growing surface plays a significant role in trapping cis-CH3ONO more effectively than trans-CH3ONO, likely because cis-CH3ONO is more compact. Taken together, the observations highlight the necessity for careful characterization of conformers in matrix-isolated systems, emphasizing a need for further study into the deposition dynamics and surface structure of chemically inert matrices.