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Issue 7, 2010
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Chirality influence on the aggregation of methyl mandelate

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The methyl ester of mandelic acid is investigated by a wide range of techniques to unravel its aggregation pattern and the influence of relative chirality of the aggregating monomers. Matrix isolation confirms that a single monomer conformation prevails. The electronic spectrum of the dimers is strongly affected by the relative monomer chirality. Vibrational effects are more subtle and can be explained in terms of the most stable homo- and heteroconfigurational dimer structures, when compared to results of MP2 and DFT-D computations. Selective IR/UV double resonance techniques and wide-band FTIR spectroscopy provide largely consistent spectroscopic fingerprints of the chirality discrimination phenomena. The dominant homochiral dimer has two intermolecular O–H⋯O[double bond, length as m-dash]C hydrogen bonds whereas the more strongly bound heterochiral dimer involves only one such hydrogen bond. This is a consequence of the competition between dispersion and intramolecular or intermolecular hydrogen bonding. Aromatic interactions also play a role in trimers and larger clusters, favoring homochiral ring arrangements. Analogies and differences to the well-investigated methyl lactate system are highlighted. Bulk phases show a competition between different hydrogen bond patterns. The enantiopure, racemic, and 3 : 1 crystals involve infinite hydrogen-bonded chains with different arrangements of the aromatic groups. They exhibit significantly different volatility, the enantiopure compound being more volatile than the racemic crystal. The accumulated experimental and quantum-chemical evidence turns methyl mandelate into a model system for the role of competition between dispersion forces and hydrogen bond interactions in chirality discrimination.

Graphical abstract: Chirality influence on the aggregation of methyl mandelate

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Publication details

The article was received on 22 Feb 2010, accepted on 19 Apr 2010 and first published on 11 Jun 2010

Article type: Paper
DOI: 10.1039/C0NJ00142B
Citation: New J. Chem., 2010,34, 1266-1285

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    Chirality influence on the aggregation of methyl mandelate

    M. Albrecht, A. Borba, K. Le Barbu-Debus, B. Dittrich, R. Fausto, S. Grimme, A. Mahjoub, M. Nedić, U. Schmitt, L. Schrader, M. A. Suhm, A. Zehnacker-Rentien and J. Zischang, New J. Chem., 2010, 34, 1266
    DOI: 10.1039/C0NJ00142B

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