Supersonic jet studies of benzyl alcohols: minimum energy conformations and torsional motion

Conformational Landscape of Supersonically Expanded 1‐(Fluorophenyl)ethanols and Their Monohydrated Clusters

“…It shows two band progressions, the first starting at 37 140 cm À1 and the less intense second one at 37 211 cm . [32,33] Similar band progressions are observed in the 37 500-37 700 cm À1 region for asymmetric butterfly ring deformation (peaks [8][9][10][11][12][13][14][15][16] and in the 37 900-38 100 cm À1 ringbreathing region of the spectrum (peaks 17-21) ( Table 1). The 1cR2PI spectrum of pFE S is substantially different from that exhibited by the E R congener under similar experimental conditions, which is instead characterized by a single S 1 !…”

“…It is of some interest to compare the origin of the approximately 36 cm ÀC a torsion À1 progression observed in the mass-resolved excitation spectrum of supersonically expanded 2-fluorobenzyl alcohol (oFM). [32] The latter was attributed to a low-frequency librational motion of the OH group coupled with H-atom oscillation in the OH···F bond present in the most stable structure of oFM, similar to that of oB. The absence of a similar anharmonic progression in the oFE S spectrum confirms the large predominance of the oA conformer over the oB one in the supersonic expansion.…”

7‐Arylnorbornanes: Model Compounds for the Study of CH···π and OH···π Interactions

“…[21] Table 1 summarises the corresponding rotational barriers of ethers 5-10 and alcohols 11-16. In the case of alcohols 11-16, both 1 H and 13 C NMR spectra at 25°C show the presence of broad signals, and only four peaks corresponding to the norbornane structure are observed in the 13 C NMR spectra. This is an indication of a rapid exchange situation above the coalescence temperature.…”

“…[12][13][14][15][16][17][18][19][20] However, the role played by a OH···π interaction in the relative stability of rotamers remains controversial. Some of these studies provide no support for the existence of an intramolecular hydrogen bond [12] whereas ab initio calculations and spectroscopic data point to a very weak interaction, suggesting that the preferred gauche conformation cannot be fully explained by the presence of OH···π interactions.…”

Benzyl Alcohol-Water and -Ammonia Clusters: Ion Fragmentation and Chemistry.

“…The geometry of benzyl alcohol for S o and S 1 is determined to be such that tl(Corth o -Cipso -C a -OH) = 900 and 2 (Cipso -Ca -O-H) = 00. 6 Ionization threshold studies suggest that unlike molecular toluene, significant geometry changes occur for the benzyl alcohol molecule upon ionization. Most likely bothc 1 and t 2 change for the ion with --4 00 and 2 ---1800.…”