Understanding benzyl alcohol aggregation by chiral modification: the pairing step

Abstract

A combination of linear infrared and Raman spectroscopy in supersonic slit jet expansions is used to clarify the conformational preferences in the dimer of the transiently chiral benzyl alcohol (phenylmethanol)...

Rovibronic signatures of molecular aggregation in the gas phase: subtle homochirality trends in the dimer, trimer and tetramer of benzyl alcohol

“…16. The relative stability of the rotamers was examined in detail in previous publications, and it was demonstrated that only the gauche conformation is detected in a supersonic expansion, [13][14][15][16][17][18] just as in the gas phase at room temperature. 39 The four-fold degenerate minima are connected by reflection on the ring plane or through a plane perpendicular to the ring.…”

“…A full-range two-dimensional relaxed scan of the conformational space is available in the ESI of Ref. 16. The relative stability of the rotamers was examined in detail in previous publications, and it was demonstrated that only the gauche conformation is detected in a supersonic expansion, [13][14][15][16][17][18] just as in the gas phase at room temperature.…”

“…In this way, characterization of the OH•••O interaction has proceeded through systems of increasing complexity, mostly aliphatic [5][6][7][8][9][10][11] and aromatic alcohols. [12][13][14][15][16][17][18] This procedure enables investigating the intra-and intermolecular factors affecting intermolecular interactions, which also control large scale or macromolecular aggregation. One of the properties of the OH group that greatly complicates characterization of its intermolecular interactions is the existence of torsional isomerism.…”

“…In a previous work, Medel and Suhm explored how transient chirality modulates the aggregation of benzyl alcohol (BnOH) and 1-phenylethanol using a combination of FTIR and Raman spectroscopy. 16 The results were interpreted with the aid of density-functional theory (DFT) calculations. The authors concluded that homochiral aggregation was favored over the heterochiral counterparts.…”

Dynamic chiral self-recognition in aromatic dimers of styrene oxide revealed by rotational spectroscopy

“…With the recent insights brought by these experiments on increasingly larger chiral organic molecules, our understanding of chiral recognition has slowly departed from the more simplistic "three-point" interaction picture to pairing models where weak interactions play a decisive act. Moreover, the balance of dispersion and electrostatic interactions needs to be considered if one is to decode the nature of the contact points that mediate the molecular fit and hence chiral recognition [33][34][35][36] .…”