Role of Nearby Charges on the Electronic Structure of pi-Conjugated Molecules: Symmetric versus Asymmetric Charge Distributions in Oligo(p-phenyleneethynylene)

Maj-Britt Suhr Kirketerp; Torben Ryhding; Kristian  Støchkel; Mogens Brøndsted Nielsen; Steen Brøndsted Nielsen

Role of Nearby Charges on the Electronic Structure of pi-Conjugated Molecules: Symmetric versus Asymmetric Charge Distributions in Oligo(p-phenyleneethynylene)

Maj-Britt Suhr Kirketerp, Torben Ryhding, Kristian Støchkel, Mogens Brøndsted Nielsen, Steen Brøndsted Nielsen

Department of Chemistry

1 Citation (Scopus)

Abstract

Oligo(p-phenyleneethynylene)s (OPEs) are conjugated oligomers of great interest within materials science and molecular electronics on account of their highly applicable electronic and optical properties. Here we use gas-phase action spectroscopy to elucidate how the intrinsic electronic properties of these chromophores are affected by nearby charges. An OPE3 chromophore with two nearby ammonium groups was synthesized. This molecule and a related OPE3 with only one amine protonation site were transferred to the gas phase by electrospray ionization and subjected to action spectroscopy. Ions were bunched in a 14-pole ion trap, accelerated to 50-keV kinetic energies, mass-to-charge selected by a magnet, and photoexcited in a crossed-beam configuration. Fragment ions were finally mass-analyzed by an electrostatic analyzer. The setup enables photodissociation mass spectrometry and action spectroscopy on the microsecond time scale. The gas-phase absorption of the mono- and dication was measured and compared to that of neutral chromophores in solution. Similar absorption was found for neutral chromophores (in solution) and the dication (in gas phase or solution), whereas the monocation absorbs at lower energies in the gas phase. Simple electrostatic considerations lead to an energy difference like the one found from the experiment. The work presented here addresses how the electronic properties of a π-conjugated system are affected by nearby charges, a question of fundamental interest in, for example, molecular electronics.

Original language	English
Journal	Journal of Physical Chemistry A
Volume	115
Pages (from-to)	1222-1227
ISSN	1089-5639
Publication status	Published - 24 Feb 2011

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Role of Nearby Charges on the Electronic Structure of pi-Conjugated Molecules: Symmetric versus Asymmetric Charge Distributions in Oligo(p-phenyleneethynylene). / Kirketerp, Maj-Britt Suhr; Ryhding, Torben; Støchkel, Kristian et al.

In: Journal of Physical Chemistry A, Vol. 115, 24.02.2011, p. 1222-1227.

Research output: Contribution to journal › Journal article › Research › peer-review

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title = "Role of Nearby Charges on the Electronic Structure of pi-Conjugated Molecules: Symmetric versus Asymmetric Charge Distributions in Oligo(p-phenyleneethynylene)",

abstract = "Oligo(p-phenyleneethynylene)s (OPEs) are conjugated oligomers of great interest within materials science and molecular electronics on account of their highly applicable electronic and optical properties. Here we use gas-phase action spectroscopy to elucidate how the intrinsic electronic properties of these chromophores are affected by nearby charges. An OPE3 chromophore with two nearby ammonium groups was synthesized. This molecule and a related OPE3 with only one amine protonation site were transferred to the gas phase by electrospray ionization and subjected to action spectroscopy. Ions were bunched in a 14-pole ion trap, accelerated to 50-keV kinetic energies, mass-to-charge selected by a magnet, and photoexcited in a crossed-beam configuration. Fragment ions were finally mass-analyzed by an electrostatic analyzer. The setup enables photodissociation mass spectrometry and action spectroscopy on the microsecond time scale. The gas-phase absorption of the mono- and dication was measured and compared to that of neutral chromophores in solution. Similar absorption was found for neutral chromophores (in solution) and the dication (in gas phase or solution), whereas the monocation absorbs at lower energies in the gas phase. Simple electrostatic considerations lead to an energy difference like the one found from the experiment. The work presented here addresses how the electronic properties of a π-conjugated system are affected by nearby charges, a question of fundamental interest in, for example, molecular electronics.",

author = "Kirketerp, {Maj-Britt Suhr} and Torben Ryhding and Kristian St{\o}chkel and Nielsen, {Mogens Br{\o}ndsted} and Nielsen, {Steen Br{\o}ndsted}",

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T1 - Role of Nearby Charges on the Electronic Structure of pi-Conjugated Molecules: Symmetric versus Asymmetric Charge Distributions in Oligo(p-phenyleneethynylene)

AU - Kirketerp, Maj-Britt Suhr

AU - Ryhding, Torben

AU - Støchkel, Kristian

AU - Nielsen, Mogens Brøndsted

AU - Nielsen, Steen Brøndsted

PY - 2011/2/24

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N2 - Oligo(p-phenyleneethynylene)s (OPEs) are conjugated oligomers of great interest within materials science and molecular electronics on account of their highly applicable electronic and optical properties. Here we use gas-phase action spectroscopy to elucidate how the intrinsic electronic properties of these chromophores are affected by nearby charges. An OPE3 chromophore with two nearby ammonium groups was synthesized. This molecule and a related OPE3 with only one amine protonation site were transferred to the gas phase by electrospray ionization and subjected to action spectroscopy. Ions were bunched in a 14-pole ion trap, accelerated to 50-keV kinetic energies, mass-to-charge selected by a magnet, and photoexcited in a crossed-beam configuration. Fragment ions were finally mass-analyzed by an electrostatic analyzer. The setup enables photodissociation mass spectrometry and action spectroscopy on the microsecond time scale. The gas-phase absorption of the mono- and dication was measured and compared to that of neutral chromophores in solution. Similar absorption was found for neutral chromophores (in solution) and the dication (in gas phase or solution), whereas the monocation absorbs at lower energies in the gas phase. Simple electrostatic considerations lead to an energy difference like the one found from the experiment. The work presented here addresses how the electronic properties of a π-conjugated system are affected by nearby charges, a question of fundamental interest in, for example, molecular electronics.

AB - Oligo(p-phenyleneethynylene)s (OPEs) are conjugated oligomers of great interest within materials science and molecular electronics on account of their highly applicable electronic and optical properties. Here we use gas-phase action spectroscopy to elucidate how the intrinsic electronic properties of these chromophores are affected by nearby charges. An OPE3 chromophore with two nearby ammonium groups was synthesized. This molecule and a related OPE3 with only one amine protonation site were transferred to the gas phase by electrospray ionization and subjected to action spectroscopy. Ions were bunched in a 14-pole ion trap, accelerated to 50-keV kinetic energies, mass-to-charge selected by a magnet, and photoexcited in a crossed-beam configuration. Fragment ions were finally mass-analyzed by an electrostatic analyzer. The setup enables photodissociation mass spectrometry and action spectroscopy on the microsecond time scale. The gas-phase absorption of the mono- and dication was measured and compared to that of neutral chromophores in solution. Similar absorption was found for neutral chromophores (in solution) and the dication (in gas phase or solution), whereas the monocation absorbs at lower energies in the gas phase. Simple electrostatic considerations lead to an energy difference like the one found from the experiment. The work presented here addresses how the electronic properties of a π-conjugated system are affected by nearby charges, a question of fundamental interest in, for example, molecular electronics.

M3 - Journal article

SN - 1089-5639

VL - 115

SP - 1222

EP - 1227

JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

ER -

Role of Nearby Charges on the Electronic Structure of pi-Conjugated Molecules: Symmetric versus Asymmetric Charge Distributions in Oligo(p-phenyleneethynylene)

Abstract

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