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Quantifying through-space charge transfer dynamics in π-coupled molecular systems

Author

Listed:
  • Arunabh Batra

    (Columbia University)

  • Gregor Kladnik

    (University of Ljubljana
    CNR-IOM Laboratorio Nazionale TASC)

  • Héctor Vázquez

    (Columbia University)

  • Jeffrey S. Meisner

    (Columbia University)

  • Luca Floreano

    (CNR-IOM Laboratorio Nazionale TASC)

  • Colin Nuckolls

    (Columbia University)

  • Dean Cvetko

    (University of Ljubljana
    CNR-IOM Laboratorio Nazionale TASC)

  • Alberto Morgante

    (CNR-IOM Laboratorio Nazionale TASC
    University of Trieste)

  • Latha Venkataraman

    (Columbia University)

Abstract

Understanding the role of intermolecular interaction on through-space charge transfer characteristics in π-stacked molecular systems is central to the rational design of electronic materials. However, a quantitative study of charge transfer in such systems is often difficult because of poor control over molecular morphology. Here we use the core-hole clock implementation of resonant photoemission spectroscopy to study the femtosecond charge-transfer dynamics in cyclophanes, which consist of two precisely stacked π-systems held together by aliphatic chains. We study two systems, [2,2]paracyclophane (22PCP) and [4,4]paracyclophane (44PCP), with inter-ring separations of 3.0 and 4.0 Å, respectively. We find that charge transfer across the π-coupled system of 44PCP is 20 times slower than in 22PCP. We attribute this difference to the decreased inter-ring electronic coupling in 44PCP. These measurements illustrate the use of core-hole clock spectroscopy as a general tool for quantifying through-space coupling in π-stacked systems.

Suggested Citation

  • Arunabh Batra & Gregor Kladnik & Héctor Vázquez & Jeffrey S. Meisner & Luca Floreano & Colin Nuckolls & Dean Cvetko & Alberto Morgante & Latha Venkataraman, 2012. "Quantifying through-space charge transfer dynamics in π-coupled molecular systems," Nature Communications, Nature, vol. 3(1), pages 1-7, January.
    • Handle: RePEc:nat:natcom:v:3:y:2012:i:1:d:10.1038_ncomms2083
    DOI: 10.1038/ncomms2083
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