Orbital views on electron-transport properties of cyclophanes: Insight into intermolecular transport

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Abstract

Electron-transport properties of cyclophanes are investigated with qualitative Hückel molecular orbital analysis for better understanding of the intermolecular interaction in molecular devices. Charge and electron transfers often take place via through-space interactions, which are observed both in large biological molecules and in organic molecular crystals. Since the intermolecular electronic coupling in π-stacked structures plays an important role in total device performance, in this work [2,2]paracyclophane is studied to investigate the effect of the intermolecular interactions in aromatic hydrocarbons on its electron-transport properties. According to the orbital symmetry rule, the symmetry-allowed and symmetry-forbidden connections for electron transport between the benzene rings are predicted just from the phase and amplitude of the frontier orbitals. The meta connection is symmetry allowed for electron transport while the para and ortho connections are symmetry forbidden. The qualitative predictions made with the Hückel approximation are found consistent with the calculation results obtained with density functional theory. The qualitative but essential understanding in the orbital views would extend the application of the rule from a single molecule to a crystal structure for the development of high-performance molecular devices.

Original languageEnglish
Pages (from-to)181-188
Number of pages8
JournalBulletin of the Chemical Society of Japan
Volume85
Issue number2
DOIs
Publication statusPublished - Mar 7 2012

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Electron transport properties
Molecular crystals
Aromatic Hydrocarbons
Molecules
Molecular orbitals
Benzene
Density functional theory
Crystal structure
Electrons
Electron Transport

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

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title = "Orbital views on electron-transport properties of cyclophanes: Insight into intermolecular transport",
abstract = "Electron-transport properties of cyclophanes are investigated with qualitative H{\"u}ckel molecular orbital analysis for better understanding of the intermolecular interaction in molecular devices. Charge and electron transfers often take place via through-space interactions, which are observed both in large biological molecules and in organic molecular crystals. Since the intermolecular electronic coupling in π-stacked structures plays an important role in total device performance, in this work [2,2]paracyclophane is studied to investigate the effect of the intermolecular interactions in aromatic hydrocarbons on its electron-transport properties. According to the orbital symmetry rule, the symmetry-allowed and symmetry-forbidden connections for electron transport between the benzene rings are predicted just from the phase and amplitude of the frontier orbitals. The meta connection is symmetry allowed for electron transport while the para and ortho connections are symmetry forbidden. The qualitative predictions made with the H{\"u}ckel approximation are found consistent with the calculation results obtained with density functional theory. The qualitative but essential understanding in the orbital views would extend the application of the rule from a single molecule to a crystal structure for the development of high-performance molecular devices.",
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T2 - Insight into intermolecular transport

AU - Li, Xinqian

AU - Staykov, Aleksandar

AU - Yoshizawa, Kazunari

PY - 2012/3/7

Y1 - 2012/3/7

N2 - Electron-transport properties of cyclophanes are investigated with qualitative Hückel molecular orbital analysis for better understanding of the intermolecular interaction in molecular devices. Charge and electron transfers often take place via through-space interactions, which are observed both in large biological molecules and in organic molecular crystals. Since the intermolecular electronic coupling in π-stacked structures plays an important role in total device performance, in this work [2,2]paracyclophane is studied to investigate the effect of the intermolecular interactions in aromatic hydrocarbons on its electron-transport properties. According to the orbital symmetry rule, the symmetry-allowed and symmetry-forbidden connections for electron transport between the benzene rings are predicted just from the phase and amplitude of the frontier orbitals. The meta connection is symmetry allowed for electron transport while the para and ortho connections are symmetry forbidden. The qualitative predictions made with the Hückel approximation are found consistent with the calculation results obtained with density functional theory. The qualitative but essential understanding in the orbital views would extend the application of the rule from a single molecule to a crystal structure for the development of high-performance molecular devices.

AB - Electron-transport properties of cyclophanes are investigated with qualitative Hückel molecular orbital analysis for better understanding of the intermolecular interaction in molecular devices. Charge and electron transfers often take place via through-space interactions, which are observed both in large biological molecules and in organic molecular crystals. Since the intermolecular electronic coupling in π-stacked structures plays an important role in total device performance, in this work [2,2]paracyclophane is studied to investigate the effect of the intermolecular interactions in aromatic hydrocarbons on its electron-transport properties. According to the orbital symmetry rule, the symmetry-allowed and symmetry-forbidden connections for electron transport between the benzene rings are predicted just from the phase and amplitude of the frontier orbitals. The meta connection is symmetry allowed for electron transport while the para and ortho connections are symmetry forbidden. The qualitative predictions made with the Hückel approximation are found consistent with the calculation results obtained with density functional theory. The qualitative but essential understanding in the orbital views would extend the application of the rule from a single molecule to a crystal structure for the development of high-performance molecular devices.

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