Towards chiral distributions of dopants in microporous frameworks: helicoidal supramolecular arrangement of (1R,2S)-ephedrine and transfer of chiralityElectronic supplementary information (ESI) available: Additional RDFs, energy diagrams, angle distributions and pictures. See DOI: 10.1039/c4cp03957b

• Main Authors: Gómez-Hortigüela, Luis, Álvaro-Muñoz, Teresa, Bernardo-Maestro, Beatriz, Pérez-Pariente, Joaquín
• Format: Journal Article
• Language: English
• Published: 03.12.2014
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/c4cp03957b

A molecular-mechanics computational study is performed in order to analyze the arrangement of (1 R ,2 S )-(-)-ephedrine molecules within the 12-MR channels of the AFI aluminophosphate microporous framework and the influence on the spatial distribution of dopants embedded in the tetrahedral network. Results showed that ephedrine molecules arrange exclusively as dimers by π-π stacking of the aromatic rings within the AFI channels. Interestingly, the asymmetric nature of ephedrine and the presence of H-bond-forming groups (NH 2 and OH) involve a preferential orientation where consecutive dimers within the channels are rotated by an angle of +30°; this is driven by the establishment of inter-dimer H-bonds. This preferential orientation leads to the development of a supramolecular enantiomerically-pure helicoidal (chiral) arrangement of ephedrine dimers. In addition, the computational results demonstrate that the particular molecular structure of ephedrine imparts a strong trend to attract negative charges to the vicinity of the NH 2 + positively-charged groups. Hence divalent dopants such as Mg, whose replacement by trivalent Al in the aluminophosphate network involves the generation of a negative charge, will tend to locate close to the NH 2 + molecular groups, suggesting that an imprinting of the organic arrangement to the spatial distribution of dopants would be feasible. Combined with the trend of ephedrine to arrange in a helicoidal fashion, an enantiomerically-pure helicoidal distribution of dopants would be expected, thus inducing a new type of chirality in microporous materials. (1 R ,2 S )-Ephedrine develops a supramolecular helicoidal arrangement that can be imprinted onto the microporous framework through a helicoidal distribution of dopants.