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Conformational switching modulates excited-state pathways in a cofacial perylene dimer
Giovanni Bressan1, Denis Hartmann2, Jonathan Brouwer1
1School of Chemistry, University of East Anglia Norwich NR4 7TJ UK g.bressan@uea.ac.uk.
Chemical Science
|January 30, 2026
Summary
Flexible perylene diimide (PDI) dimers switch between conformations, controlling excited-state pathways. This supramolecular switching strategy tunes excimer and multiexciton dynamics for advanced optoelectronic materials.
Area of Science:
- Supramolecular chemistry
- Photophysics
- Materials science
Background:
- Controlling excited-state pathways in chromophore assemblies is crucial for next-generation optoelectronic and photonic materials.
- Flexible organic chromophores offer potential for dynamic control over material properties.
Purpose of the Study:
- To elucidate the conformation-dependent photophysics of a flexible perylene diimide (PDI) dimer, valPDI2.
- To investigate the solvent-driven switching between distinct dimer geometries and its effect on excited-state dynamics.
Main Methods:
- Exciton-coupling calculations
- Ultrafast spectroscopy
- Half-broadband 2D electronic spectroscopy
Main Results:
- The valPDI2 dimer switches between open (chloroform) and cofacial stacked (DMSO/water) conformations.
- The open conformer exhibits slow excimer formation, while the stacked conformer shows rapid, barrierless excimer and multiexciton formation.
- Conformation-dependent vibrational coherences were observed, influencing excimer formation.
Conclusions:
- Environmentally driven conformational control is a powerful non-covalent strategy to modulate excimer and multiexciton dynamics in PDI assemblies.
- Supramolecular switching in flexible chromophore arrays is a general principle for tuning excited-state behavior.
- This approach has implications for developing responsive optoelectronic and energy-conversion materials.
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