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Nanoscale "Chessboard" Pattern Lamellae in a Supramolecular Perylene-Diimide Polydiacetylene System
Ian J Martin1, Francis Kiranka Masese1, Kuo-Chih Shih2,3
1Department of Chemistry, University of Connecticut, Storrs, CT 06269, USA.
Molecules (Basel, Switzerland)
|March 27, 2025
Summary
Altering the composition of imidazole-appended perylene diimide and docosadiynedioic acid to a 2:1 ratio enhances supramolecular assembly and ionic conductivity. This advancement is crucial for developing next-generation semiconducting polymers for energy applications.
Area of Science:
- Materials Science
- Polymer Chemistry
- Supramolecular Chemistry
Background:
- Ordered chromogenic supramolecular polymeric systems are vital for advanced stimuli-responsive, optical, and semiconducting materials.
- Previous work established a 1:1 ratio platform using imidazole-appended perylene diimide and 10, 12 docosadiynedioic acid for stimuli-responsive self-assembly.
Purpose of the Study:
- To investigate the impact of a 2:1 composition of imidazole-appended perylene diimide and 10, 12 docosadiynedioic acid on supramolecular assembly, morphology, and properties.
- To explore the potential of these materials in energy applications through enhanced ionic conductivity.
Main Methods:
- Fabrication of drop-cast films with varying imidazole-appended perylene diimide methylene spacer lengths (n=3, 4, 6) and 10, 12 docosadiynedioic acid in a 2:1 ratio.
- Topochemical polymerization via UV radiation and subsequent thermal treatment to induce phase transformations.
- Characterization using Differential Scanning Calorimetry (DSC), Small-Angle X-ray Scattering (SAXS), and Wide-Angle X-ray Scattering (WAXS).
- Ionic conductivity measurements after doping with an ionic liquid.
Main Results:
- UV radiation induced blue-phase polydiacetylene formation, with thermal treatment causing a thermoresponsive blue-to-red phase transformation.
- DSC revealed a dual dependence of thermal transitions on methylene spacer length and stimuli treatment.
- SAXS and WAXS demonstrated well-defined hierarchical semiconducting nanostructures with interconnected "chessboard"-patterned lamellar stacking.
- The 2:1 platform exhibited higher ionic conductivity compared to the 1:1 platform upon ionic liquid doping.
Conclusions:
- The composition and architecture of the supramolecular system significantly influence ionic domain connectivity and ionic conductivity.
- The 2:1 platform demonstrates promise for developing advanced semiconducting polymers for energy applications.
- Findings provide critical insights for the rational design of materials for fuel cells, batteries, ion-exchange membranes, and mixed ionic conductors.
