Self-assembly and induced circular dichroism in dendritic supramolecules with cholesteric pendant groups.
We report on the solid-state structural features of self-assembled chiral supramolecules based on ionic complexation of chiral cholesteric pendant groups with achiral dendritic macromolecules and show that their optical activity exhibits a systematic change in the ultraviolet/visible light (UV-vis) absorption and enhancement in the circular dichroism (CD) signal, indicating the occurrence of supramolecular chirality, also referred to as induced circular dichroism (ICD). We construct a homologous series of complexes by varying systematically from 1 to 3 the generation of dendritic units contained in dendrons, dendrimers, and dendronized polymers. The structural properties of the complexes are investigated by means of small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). Depending on the class of dendritic molecule and the generation, lamellar, columnar hexagonal, oblique columnar, and rectangular columnar phases can be found, with a direct correlation among the degrees of freedom of the dendritic macromolecules used and the level of order achieved in the self-assembled solid-state structures. The enhancement of the optical signals of these mesoscopic structures appears to be correlated with their order in the solid state. Complexes with the longest lattice correlation lengths also show the most enhanced CD signals. These results show the unique versatility of dendritic macromolecules as supramolecular templates capable of organizing low molecular weight chiral pendant units into a variety of solid-state structures with amplified optical properties.
Soininen
Antti J
AJ
Department of Applied Physics, Aalto University School of Science and Technology, 02150 Espoo, Finland.
Kasëmi
Edis
E
Schlüter
A Dieter
AD
Ikkala
Olli
O
Ruokolainen
Janne
J
Mezzenga
Raffaele
R
D002784:Cholesterol / Q000737:chemistry*; D002942:Circular Dichroism; D050091:Dendrimers / Q000138:chemical synthesis / Q000737:chemistry; D046911:Macromolecular Substances / Q000138:chemical synthesis / Q000737:chemistry; D015394:Molecular Structure; D010316:Particle Size; D011108:Polymers / Q000138:chemical synthesis* / Q000737:chemistry; D013499:Surface Properties
D050091:Dendrimers; D046911:Macromolecular Substances; D011108:Polymers; D002784:Cholesterol