Methanol is the simplest stable organic molecule with H-bonding capability. There is a wide interest in the structural and dynamical properties of liquid methanol as a prototype of the large category of alcohols and for its widespread applications as a medium in organic synthesis, biochemistry, and biotechnology. As is the case of water, liquid methanol forms H-bond networks and supports anomalously high mobility of protons, promoting itself to a carrier for proton diffusion in the operation of methanol fuel cells. Compared to water the amphiphilicity of a methanol molecule makes it unique with a hydrophobic, chemically inert methyl group and a polarizable, chemically active hydroxyl group. The presence of the methyl group leaves a methanol molecule two H-bonding sites, one of which for H-bond donation and the other for H-bond acceptance. This leads to the formation of H-bond networks in (quasi) one-dimensional linear fashion while more complex three-dimensional networks are dominant in water.  The H-bonded networks of alcohol clusters have been found to be reactive in electron transfer and in tautomerization as catalysts.1,2 In this work, we identify the formation of alcohol clusters and their subsequent role as Br�nsted bases in non-aqueous intermolecular acid-base reactions for the first time. The molecular-level mechanism is revealed in the combined study of organic synthesis, steady-state/time-resolved electronic spectroscopy, and quantum mechanical calculation. 1. Mohammed, O. F.; Kwon, O.-H.; Othon, C. M.; Zewail, A. H. Angew. Chem., Int. Ed. 2009 , 48, 6251.2. Park, S.-Y.; Jang, D.-J. J. Am. Chem. Soc. 2010 , 132, 297.

Elucidation of the dynamic role of alcohol molecular clusters in non-aqueous acid-base reactions

248th National Meeting (2014)

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