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Geometry and electronic coupling in perylenediimide stacks: mapping structure-charge transport relationships
Josh Vura-Weis1, Mark A Ratner, Michael R Wasielewski
1Department of Chemistry and Argonne-Northwestern Solar Energy Research Center, Northwestern University, Evanston, Illinois 60208-3113, USA.
Journal of the American Chemical Society
|January 26, 2010
Summary
Researchers calculated electronic coupling in perylenediimide (PDI) dimers, finding it varies significantly with stacking geometry. This study identifies promising PDI derivatives for organic thin film transistors (OTFTs).
Area of Science:
- Materials Science
- Computational Chemistry
- Organic Electronics
Background:
- Perylenediimide (PDI) derivatives are crucial organic semiconductors.
- Understanding pi-stacked dimer electronic coupling is key for optimizing charge transport in organic thin film transistors (OTFTs).
Purpose of the Study:
- To investigate the relationship between stacking geometry and electronic coupling in PDI dimers.
- To identify promising PDI derivatives for high-performance OTFT applications.
Main Methods:
- Quantum chemical calculations using M06-2X/6-31++G** were employed.
- The binding energy and electronic coupling were systematically analyzed as a function of dimer stacking geometry.
- Electronic coupling was computed for 20 PDI derivatives with varied imide substitutions.
Main Results:
- Electronic coupling in PDI dimers exhibits significant (over an order of magnitude) variation due to shallow potential energy surface minima.
- Several PDI derivatives with specific imide substitutions demonstrated highly favorable electronic coupling values.
- The binding energy and electronic coupling analysis revealed promising candidates for OTFTs.
Conclusions:
- The stacking geometry critically influences electronic coupling in PDI dimers, impacting charge transport properties.
- The computational strategy of comparing binding energy and electronic coupling is effective for designing new OTFT materials.
- This approach can be extended to other pi-stacked organic semiconductors like pentacene and poly(thiophene) derivatives.
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