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

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.

journal_name

Nat Commun

journal_title

Nature communications

authors

Batra A,Kladnik G,Vázquez H,Meisner JS,Floreano L,Nuckolls C,Cvetko D,Morgante A,Venkataraman L

doi

10.1038/ncomms2083

subject

Has Abstract

pub_date

2012-01-01 00:00:00

pages

1086

issn

2041-1723

pii

ncomms2083

journal_volume

3

pub_type

杂志文章

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