Induced Supramolecular Chirality in Nanostructured Materials:  Ionic Self-Assembly of Perylene-Chiral Surfactant Complexes

Abstract

The synthesis and characterization of two liquid-crystalline ionically self-assembled (ISA) materials obtained by the complexation of an anionic perylene bisimide dye with cationic chiral surfactants is described for the first time. The influence of the chiral nature of the surfactants on the supramolecular organization of the resulting ISA materials is investigated. Circular dichroism (CD) spectroscopy shows that, upon complexation, the molecular chirality of the surfactants is expressed in the bisimide chromophore through the ionic linkage, clearly indicating that the surfactants act as structure-inducing moieties within the superstructures in both solution and the solid state. In solution, the complexes form left-handed helically stacked architectures. In the solid state, both systems are highly ordered and exhibit lamellar morphologies. The well-defined structures presented here are the first examples of ISA materials that show supramolecular chirality.

Stereochemical transfer to atmospheric aerosol particles accompanying the oxidation of biogenic volatile organic compounds

“…These CH 3 groups would be achiral if it were not for the induction of chirality -a common phenomenon found in supramolecular systems [Franke et al, 2006] -by a chiral environment. The data in Figure 2a then suggest that the organic material produced by a-pinene ozonolysis contains methyl groups that are present within a chiral superstructure (Figure 1b).…”

Morphology-controlled growth of perylene derivative induced by double-hydrophilic block copolymers

“…Such adsorption is very similar to the already wellknown formation of complexes by ISA. 6 However, the complex formation by binding of the polymer additive is highly localized and face selective and therefore allows for morphology tuning.…”

Self-assembly of chiral amphiphiles with π-conjugated tectons

“…Inspired by the unique features of fascinating biological superstructures, chemists have been able to design a variety aesthetically appealing helical supramolecular assemblies by elegantly utilizing cooperative noncovalent and covalent forces, such as  stacking, hydrogen bonding, solvophobic effects, van der Waals, metal-ligand and chirality [1][2][3][4][5][6][7][8][9]. In this context, the control of the supramolecular organization of -conjugated systems into helices of nanoscopic dimensions is of fundamental importance [10][11][12][13][14][15][16][17], as the resulting structures could find application in the emerging area of (supramolecular) electronics and photonics because of their unique electronic and optical properties [18,19].…”

“…Inspired by the unique features of fascinating biological superstructures, chemists have been able to design a variety aesthetically appealing helical supramolecular assemblies by elegantly utilizing cooperative noncovalent and covalent forces, such as  stacking, hydrogen bonding, solvophobic effects, van der Waals, metal-ligand and chirality [1][2][3][4][5][6][7][8][9]. In this context, the control of the supramolecular organization of -conjugated systems into helices of nanoscopic dimensions is of fundamental importance [10][11][12][13][14][15][16][17], as the resulting structures could find application in the emerging area of (supramolecular) electronics and photonics because of their unique electronic and optical properties [18,19].Among a variety of self-assembling building blocks, amphiphilic molecules with chiral substitutions, such as nucleic acids, proteins, polysaccharides, and phospholipids [20][21][22][23][24][25][26], and containing both hydrophilic and hydrophobic parts, forms one category of the most powerful building blocks. When amphiphiles are dispersed in solvent, the hydrophilic component of the amphiphile preferentially interacts with the aqueous or polar phase while the hydrophobic portion tends to reside in the air or in the nonpolar solvent.…”