Abstract
The π-π interactions between organic molecules are among the most important parameters for optimizing the transport and optical properties of organic transistors, light-emitting diodes, and (bio-) molecular devices. Despite substantial theoretical progress, direct experimental measurement of the π-π electronic coupling energy parameter t has remained an old challenge due to molecular structural variability and the large number of parameters that affect the charge transport. Here, we propose a study of π-π interactions from electrochemical and current measurements on a large array of ferrocene-thiolated gold nanocrystals. We confirm the theoretical prediction that t can be assessed from a statistical analysis of current histograms. The extracted value of t ≈35 meV is in the expected range based on our density functional theory analysis. Furthermore, the t distribution is not necessarily Gaussian and could be used as an ultrasensitive technique to assess intermolecular distance fluctuation at the subangström level. The present work establishes a direct bridge between quantum chemistry, electrochemistry, organic electronics, and mesoscopic physics, all of which were used to discuss results and perspectives in a quantitative manner.
Original language | English |
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Pages (from-to) | 3215-3224 |
Number of pages | 10 |
Journal | Nano Letters |
Volume | 17 |
Issue number | 5 |
DOIs | |
Publication status | Published - 10 May 2017 |
Externally published | Yes |
Keywords
- Cooperative effect
- coupled quantum dot
- molecular electronics
- nanoelectrochemistry
- transfer integral
- π−π interaction