Journal
GIANT
Volume 10, Issue -, Pages -Publisher
ELSEVIER
DOI: 10.1016/j.giant.2022.100098
Keywords
Self-organization; Supramolecular dendrimers; Conformational flexibility; Triphenylene; Diethylene glycol linker
Funding
- National Science Foundation [DMR-1807127, DMR-1720530, DMR-2104554]
- Humboldt Founda-tion
- P. Roy Vagelos Chair at Penn
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A library of triphenylene dendronized with self-assembling dendrons via a diethylene glycol linker was synthesized and showed different self-organizations, including hexagonal columnar, Frank-Kasper, and soft quasicrystal assemblies. The presence of the diethylene glycol linker affected phase transitions and isotropization temperatures, and induced strong pi-pi stacking in helical columns.
A library of triphenylene (Tp) dendronized with self-assembling dendrons via a diethylene glycol linker was synthesized and the corresponding self-organizations were analyzed. They self-organize via a crown conformation in helical columns and spherical helices that produce hexagonal columnar, Frank-Kasper and soft quasicrystal assemblies. The same self-organizations are produced in the absence of the diethylene glycol linker except that the phase transitions and isotropization temperatures occur at lower temperatures in the presence of the linker. The incorporation of the flexible diethylene glycol linker induces also strong pi-pi stacking in helical columns. Spherical helices are spherical distorted short fragments of helical columns and therefore the same principles determine the thermal stability of the hexagonal columnar and of Frank-Kasper and quasicrystal assemblies except that the length of the supramolecular backbone is much longer in helical columns. A comparison of these systems with side-chain liquid crystals indicates that supramolecular dendrimers are stabilized by extended supramolecular backbone conformations. This result suggests pathways to molecularly engineer phase transitions of supramolecular dendrimers self-organized from crown conformations.
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