Charge transfer tuning by chemical substitution and uniaxial pressure in the organic complex tetramethoxypyrene-tetracyanoquinodimethane

Milan Rudloff, Kai Ackermann, Michael Huth, Harald Olaf Jeschke, Milan Tomic, Roser Valentí, Benedikt Wolfram, Martin Bröring, Michael Bolte, Dennis Chercka, Martin Baumgarten, Klaus Müllen

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

In the search for novel organic charge transfer salts with variable degrees of charge transfer we have studied the effects of two modifications of the recently synthesized donor-acceptor system [tetramethoxypyrene (TMP)]-[tetracyanoquinodimethane (TCNQ)]. One is of chemical nature by substituting the acceptor TCNQ molecules by F4TCNQ molecules. The second consists in simulating the application of uniaxial pressure along the stacking axis of the system. In order to test the chemical substitution, we have grown single crystals of the TMP-F4TCNQ complex and analyzed its electronic structure via electronic transport measurements, ab initio density functional theory (DFT) calculations and UV/VIS/IR absorption spectroscopy. This system shows an almost ideal geometrical overlap of nearly planar molecules stacked alternately (mixed stack) and this arrangement is echoed by a semiconductor-like transport behavior with an increased conductivity along the stacking direction. This is in contrast to TMP-TCNQ which shows a less pronounced anisotropy and a smaller conductivity response. Our band structure calculations confirm the one-dimensional behavior of TMP-F4TCNQ with pronounced dispersion only along the stacking axis. Infrared measurements illustrating the CN vibration frequency shift in F4TCNQ suggest however no improvement in the degree of charge transfer in TMP-F4TCNQ with respect to TMP-TCNQ. In both complexes about 0.1e is transferred from TMP to the acceptor. Concerning the pressure effect, our DFT calculations on the designed TMP-TCNQ and TMP-F4TCNQ structures under different pressure conditions show that application of uniaxial pressure along the stacking axis of TMP-TCNQ may be the route to follow in order to obtain a much more pronounced charge transfer.

Original languageEnglish
Pages (from-to)4118-4126
Number of pages9
JournalPhysical Chemistry Chemical Physics
Volume17
Issue number6
DOIs
Publication statusPublished - Feb 14 2015
Externally publishedYes

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Charge transfer
Substitution reactions
Tuning
tuning
charge transfer
substitutes
organic charge transfer salts
density functional theory
molecules
conductivity
pressure effects
frequency shift
Molecules
Density functional theory
absorption spectroscopy
routes
electronic structure
vibration
anisotropy
Pressure effects

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Charge transfer tuning by chemical substitution and uniaxial pressure in the organic complex tetramethoxypyrene-tetracyanoquinodimethane. / Rudloff, Milan; Ackermann, Kai; Huth, Michael; Jeschke, Harald Olaf; Tomic, Milan; Valentí, Roser; Wolfram, Benedikt; Bröring, Martin; Bolte, Michael; Chercka, Dennis; Baumgarten, Martin; Müllen, Klaus.

In: Physical Chemistry Chemical Physics, Vol. 17, No. 6, 14.02.2015, p. 4118-4126.

Research output: Contribution to journalArticle

Rudloff, M, Ackermann, K, Huth, M, Jeschke, HO, Tomic, M, Valentí, R, Wolfram, B, Bröring, M, Bolte, M, Chercka, D, Baumgarten, M & Müllen, K 2015, 'Charge transfer tuning by chemical substitution and uniaxial pressure in the organic complex tetramethoxypyrene-tetracyanoquinodimethane', Physical Chemistry Chemical Physics, vol. 17, no. 6, pp. 4118-4126. https://doi.org/10.1039/c4cp04461d
Rudloff, Milan ; Ackermann, Kai ; Huth, Michael ; Jeschke, Harald Olaf ; Tomic, Milan ; Valentí, Roser ; Wolfram, Benedikt ; Bröring, Martin ; Bolte, Michael ; Chercka, Dennis ; Baumgarten, Martin ; Müllen, Klaus. / Charge transfer tuning by chemical substitution and uniaxial pressure in the organic complex tetramethoxypyrene-tetracyanoquinodimethane. In: Physical Chemistry Chemical Physics. 2015 ; Vol. 17, No. 6. pp. 4118-4126.
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AU - Valentí, Roser

AU - Wolfram, Benedikt

AU - Bröring, Martin

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