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Structural Rules for the Chiral Supramolecular Organization of OPE-based Discotics: Induction of Helicity and Amplification of Chirality

Author:
García, Fátima, Sánchez, Luis
Source:
Journal of the American Chemical Society 2012 v.134 no.1 pp. 734-742
ISSN:
1520-5126
Subject:
chemical structure, gelation, organic compounds, stereoisomerism
Abstract:
A systematic study on the structural rules that regulate the chiral supramolecular organization of oligo(phenylene ethynylene) (OPE)-based discotics is presented. This study is based on the chirooptical properties of two different series of triangular shape OPEs. The first of them is composed by OPE-based trisamides with a variable number of chiral side chains (compounds 1) that self-assemble following a cooperative mechanism. The CD experiments carried out with these desymmetrized trisamides demonstrate that only one stereogenic center is sufficient to achieve a helical organization with a preferred handedness. However, the ability to amplify the chirality decreases upon decreasing the number of stereocenters at the peripheral side chains. The second series is constituted by triangular shape OPEs with a variable number of ether and amide functional groups and constant absolute configuration of the stereogenic centers at all of the peripheral chains (compounds 2). These compounds do not self-assemble into helical aggregates as demonstrated by the corresponding CD studies. The amplification of chirality observed in the mixtures of some of the components of both series has been investigated. The combination of chiral trisamide 1d with chiral but nonhelical 2b or 2c does not produce an amplification of chirality most probably due to the mismatch between the stereogenic centers of both components. However, the combination of achiral trisamide 1a with chiral but nonhelical bisamide 2c generates, in a cooperative manner, helical structures with a preferred handedness in a process involving the transfer of helicity from 1a to 2c and the transfer of chirality from 2c to 1a. The structural features of the OPE discotics also exert a strong influence on the columnar aggregates. Thus, while achiral 1a bundles into thick filaments to form an organogel, the gelation ability of these triangular OPEs decreases upon increasing the number of stereogenic centers, being totally canceled for compounds 2 in which the amide functionalities are replaced by ether linkages. Finally, we have also registered AFM images of the helical aggregates obtained from the mixture of 1a+2c, which implies an efficient transfer of the chiral objects from solution to surfaces. The study presented herein increases the understanding of the structural rules that regulate the chiral supramolecular organization of discrete molecules in general and, more specifically, those based on π-conjugated oligomers.
Agid:
5384785