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Multiple Intermolecular Exciplexes in Highly Polar Solvents.

Joseph P Dinnocenzo1, Elizabeth C. Feinberg1, Samir Farid1

  • 1Department of Chemistry, University of Rochester , Rochester, New York 14627, United States.

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Summary

Exciplexes formed by tetracyanoanthracene (TCA) and alkylbenzenes exhibit ionic character. Solvent polarity influences reorganization energy and emission spectra, suggesting composite exciplex structures in polar environments.

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Area of Science:

  • Photochemistry
  • Supramolecular Chemistry
  • Organic Electronics

Background:

  • Exciplexes are crucial in photophysical processes and organic electronic devices.
  • Understanding exciplex behavior in different solvent polarities is key to tuning their properties.

Purpose of the Study:

  • To investigate the photophysical properties of tetracyanoanthracene (TCA) exciplexes with alkylbenzenes across a range of solvents.
  • To analyze the relationship between solvent polarity, redox potentials, and emission characteristics of these exciplexes.

Main Methods:

  • Spectroscopic analysis of exciplex emission in various solvents from cyclohexane to acetonitrile.
  • Correlation of reduced emission maxima (hνav) and redox potential differences (Eredox).
  • Analysis of spectral parameters including energy gap (ΔG), energy difference (δEx), and total reorganization energy (Σλ).

Main Results:

  • A linear correlation (slope ≈ 1) between hνav and Eredox indicates highly ionic exciplex character.
  • Deviation from linearity in polar solvents suggests increased total reorganization energy (Σλ).
  • Full width at half-maximum (fwhm) deviations in polar solvents point to composite emissions from distinct exciplex structures.

Conclusions:

  • Solvent polarity significantly impacts the photophysics of TCA-alkylbenzene exciplexes, primarily through alterations in reorganization energy.
  • Observed deviations in polar solvents are attributed to a larger Σλ and potentially composite emission from multiple exciplex configurations.
  • The study provides insights into designing exciplex-based materials for optoelectronic applications by controlling solvent interactions.