Light-Controlled Switching of Perylene Bisimide Assemblies
Hee-Won Bahng1, Cathrin D Ertl1, Jennifer Yuan1
1Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC V6T 1Z1, Canada.
The Journal of Physical Chemistry Letters
|November 10, 2023
Summary
Light influences perylene bisimides (PBIs) assembly. Ground state interactions are sulfur-based, while excited states favor pi-pi stacking, influenced by solvent heteroatoms.
Area of Science:
- Supramolecular Chemistry
- Photochemistry
- Materials Science
Background:
- Perylene bisimides (PBIs) are functional dyes with tunable electronic properties.
- Supramolecular assembly is crucial for developing advanced materials.
- Controlling intermolecular interactions is key to directing self-assembly.
Purpose of the Study:
- To investigate light-driven changes in supramolecular interactions of PBIs.
- To elucidate the role of sulfur-containing groups in PBI assembly.
- To understand the influence of solvent heteroatoms on PBI aggregation.
Main Methods:
- Time-resolved fluorescence spectroscopy
- Transient absorption spectroscopy
- Steady-state spectroscopy
Main Results:
- Ground-state assembly is driven by S···X noncovalent interactions.
- Excited-state assembly is dominated by π-π stacking of PBI cores.
- Solvent heteroatoms accelerate π-stacking through PBI-solvent complex formation.
Conclusions:
- Light reversibly switches the dominant intermolecular forces in PBIs.
- Sulfur functionalization and solvent choice offer control over PBI supramolecular structure.
- These findings enable light-controlled design of PBI-based materials.
