Chiral Perylene Diimides: Building Blocks for Ionic Self-Assembly

• Published in: Chemistry : a European journal Vol. 21; no. 13; pp. 5118 - 5128
• Main Authors: Echue, Geraldine, Lloyd-Jones, Guy C., Faul, Charl F. J.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 23.03.2015; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc
• Subjects: Amino acids; Aqueous solutions; Chemistry; Chemistry, Multidisciplinary; Chirality; chiro-optical devices; Dichroism; Diimide; helical superstructures; Mathematical models; perylene diimide; Physical Sciences; Science & Technology; Self assembly; Surface layer; Texture; SURFACTANT COMPLEXES; SOLDIERS PRINCIPLE; chirality; perylene diimide; OPTICAL-PROPERTIES; BOLA-AMPHIPHILES; SUPRAMOLECULAR CHIRALITY; self-assembly; LIQUID-CRYSTALLINE PHASES; helical superstructures; BISIMIDE-MELAMINE ASSEMBLIES; chiro-optical devices; MULTIVALENT GLYCOCLUSTERS; MOLECULAR ASSEMBLIES; NANOSTRUCTURED MATERIALS
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201406094

A chiral perylene diimide building block has been prepared based on an amine derivative of the amino acid L‐phenylalanine. Detailed studies were carried out into the self‐assembly behaviour of the material in solution and the solid state using UV/Vis, circular dichroism (CD) and fluorescence spectroscopy. For the charged building block BTPPP, the molecular chirality of the side chains is translated into the chiral supramolecular structure in the form of right‐handed helical aggregates in aqueous solution. Temperature‐dependent UV/Vis studies of BTPPP in aqueous solution showed that the self‐assembly behaviour of this dye can be well described by an isodesmic model in which aggregation occurs to generate short stacks in a reversible manner. Wide‐angle X‐ray diffraction studies (WXRD) revealed that this material self‐organises into aggregates with π–π stacking distances typical for π‐conjugated materials. TEM investigations revealed the formation of self‐assembled structures of low order and with no expression of chirality evident. Differential scanning calorimetry (DSC) and polarised optical microscopy (POM) were used to investigate the mesophase properties. Optical textures representative of columnar liquid–crystalline phases were observed for solvent‐annealed samples of BTPPP. The high solubility, tunable self‐assembly and chiral ordering of these materials demonstrate their potential as new molecular building blocks for use in the construction of chiro‐optical structures and devices. Chirality for construction! A chiral perylene diimide building block has been prepared based on an amine derivative of the amino acid L‐phenylalanine. Detailed studies were carried out into the self‐assembly behaviour of the material in solution and the solid state using UV/Vis, circular dichroism (CD) and fluorescence spectroscopy, as well as polarised light microscopy (see figure).