Guiding Suprastructure Chirality of an Oligothiophene by a Single Amino Acid

Abstract

Within the present work, synthesis and properties of three stereoisomeric hybrid materials consisting of a πconjugated oligothiophene backbone and a single amino acid (proline), which is attached by click chemistry, are described. The hybrids were in particular investigated regarding their self-assembling behavior in solution. From optical investigations, including circular dichroism spectroscopy, the formation of chiral suprastructures could be deduced and correlated with the stereochemistry of the proline residue. In addition, an elaborate theoretical model of the compounds' self-assembly into suprastructures was developed on the basis of the experimental findings.

Redox‐Active Peptide‐Functionalized Quinquethiophene‐Based Electrochromic π‐Gel

“…π‐Gel 1 shows the oxidation potential at 1.21 V and the corresponding reduction peak at 0.58 V. This significant CV Scheme implies the successive formation of a cation radical as well as a dication adduct by compound 1 during oxidation. The oxidation potentials exhibited by π‐gel are comparable to those reported potentials of oligothiophene derivatives . This redox responsive colorimetric alterations could be reproducible by repetitive scanning schemes (Figure b), since the extended π‐conjugated oligothiophene core can stabilize the formed oxidized‐species.…”

“…Theo xidation potentials exhibitedb y p-gel arec omparablet ot hose reported potentials of oligothiophened erivatives. [72][73][74] This redoxr esponsivecolorimetrica lterationsc ouldb er eproducibleb yr epetitives cannings chemes (Figure3b),s ince thee xtended p-conjugatedo ligothiophene core cans tabilize thef ormedo xidized-species. Thee lectrochromicr esponse cana lsob eo bservedf romt he p-gel film of compound 1 coated on an ITOg lasse lectrode ( Figure 3c, Scheme 1).Electrochromic device fabricationprocessisdepicted in Scheme 1.…”

Supramolecular Chirality in Self-Assembled Systems

“…In this context, the π−π interactions between the aromatic rings play very important roles for forming chiral assemblies. Aida and co-workers studied dendritic zinc porphyrins with two carboxylic acid groups (136). These porphyrins could form J aggregates in CHCl 3 through π−π interactions from the porphyrin rings and also from the aromatic rings within their dendritic substituents.…”

“…Interestingly, the handedness of the supramolecular chirality of the films can be controlled by changing the direction of the spin coating ( Figure 99). 248 Aside from spin coating, the stirring of benzene solutions of achiral dendritic zinc porphyrins with two carboxylic acid groups (136) can also produce supramolecular chirality. Strong CD signals can be detected from the porphyrin solution upon stirring.…”

Electroactive Amphiphiles for Addressable Supramolecular Nanostructures

“…The self‐assembly of these EAAs allows for the preparation of well‐defined structures, with properties that are often enhanced owing to the macroscopic order of the material. A wide range of such EAAs have been investigated, from small molecules such as anthraquinone and POMs,, to oligomers and polymers ,…”