Obtaining enhanced circular dichroism in [4]Heterohelicenium analogues

Jonas Elm; Jacob Lykkebo Jørgensen; Thomas Just Sørensen; Bo Wegge Laursen; Kurt Valentin Mikkelsen

doi:10.1021/jp304997b

Obtaining enhanced circular dichroism in [4]Heterohelicenium analogues

Jonas Elm, Jacob Lykkebo Jørgensen, Thomas Just Sørensen, Bo Wegge Laursen, Kurt Valentin Mikkelsen

Department of Chemistry

11 Citations (Scopus)

Abstract

Electronic circular dichroism in the three helicenium analogues dimethoxyquinacridinium (DMQA ⁺), dimethoxychromenoacridinium (DMCA ⁺), and dimethoxychromenoxanthenium (DMCX ⁺) were investigated in vacuum with time-dependent density functional theory methods using the CAM-B3LYP functional with the basis set 6-311++G**. The systems were thoroughly studied by designing derivatives with several different electron-donating and -withdrawing substituents while at the same time keeping the net charge of the molecule either positive, neutral, or negative. Fifty-six derivatives were examined, and we identify a superior substitution pattern that is found to be independent of the bridging atoms and gives a rotational strength close to 90 × 10 ^-40 esu ² cm ² for DMQA, DMCA, and DMCX. The optimal system shows promising applications as a chromophore because it has a highly allowed primary electronic transition with an angle between the electronic and magnetic transition dipole moments close to 50° and its chiroptical response is thereby limited only by the magnetic transition.

Original language	English
Journal	Journal of Physical Chemistry A
Volume	116
Issue number	34
Pages (from-to)	8744-8752
Number of pages	9
ISSN	1089-5639
DOIs	https://doi.org/10.1021/jp304997b
Publication status	Published - 30 Aug 2012

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title = "Obtaining enhanced circular dichroism in [4]Heterohelicenium analogues",

abstract = "Electronic circular dichroism in the three helicenium analogues dimethoxyquinacridinium (DMQA +), dimethoxychromenoacridinium (DMCA +), and dimethoxychromenoxanthenium (DMCX +) were investigated in vacuum with time-dependent density functional theory methods using the CAM-B3LYP functional with the basis set 6-311++G**. The systems were thoroughly studied by designing derivatives with several different electron-donating and -withdrawing substituents while at the same time keeping the net charge of the molecule either positive, neutral, or negative. Fifty-six derivatives were examined, and we identify a superior substitution pattern that is found to be independent of the bridging atoms and gives a rotational strength close to 90 × 10 -40 esu 2 cm 2 for DMQA, DMCA, and DMCX. The optimal system shows promising applications as a chromophore because it has a highly allowed primary electronic transition with an angle between the electronic and magnetic transition dipole moments close to 50° and its chiroptical response is thereby limited only by the magnetic transition.",

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year = "2012",

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doi = "10.1021/jp304997b",

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T1 - Obtaining enhanced circular dichroism in [4]Heterohelicenium analogues

AU - Elm, Jonas

AU - Jørgensen, Jacob Lykkebo

AU - Sørensen, Thomas Just

AU - Laursen, Bo Wegge

AU - Mikkelsen, Kurt Valentin

PY - 2012/8/30

Y1 - 2012/8/30

N2 - Electronic circular dichroism in the three helicenium analogues dimethoxyquinacridinium (DMQA +), dimethoxychromenoacridinium (DMCA +), and dimethoxychromenoxanthenium (DMCX +) were investigated in vacuum with time-dependent density functional theory methods using the CAM-B3LYP functional with the basis set 6-311++G**. The systems were thoroughly studied by designing derivatives with several different electron-donating and -withdrawing substituents while at the same time keeping the net charge of the molecule either positive, neutral, or negative. Fifty-six derivatives were examined, and we identify a superior substitution pattern that is found to be independent of the bridging atoms and gives a rotational strength close to 90 × 10 -40 esu 2 cm 2 for DMQA, DMCA, and DMCX. The optimal system shows promising applications as a chromophore because it has a highly allowed primary electronic transition with an angle between the electronic and magnetic transition dipole moments close to 50° and its chiroptical response is thereby limited only by the magnetic transition.

AB - Electronic circular dichroism in the three helicenium analogues dimethoxyquinacridinium (DMQA +), dimethoxychromenoacridinium (DMCA +), and dimethoxychromenoxanthenium (DMCX +) were investigated in vacuum with time-dependent density functional theory methods using the CAM-B3LYP functional with the basis set 6-311++G**. The systems were thoroughly studied by designing derivatives with several different electron-donating and -withdrawing substituents while at the same time keeping the net charge of the molecule either positive, neutral, or negative. Fifty-six derivatives were examined, and we identify a superior substitution pattern that is found to be independent of the bridging atoms and gives a rotational strength close to 90 × 10 -40 esu 2 cm 2 for DMQA, DMCA, and DMCX. The optimal system shows promising applications as a chromophore because it has a highly allowed primary electronic transition with an angle between the electronic and magnetic transition dipole moments close to 50° and its chiroptical response is thereby limited only by the magnetic transition.

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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

IS - 34

ER -

Obtaining enhanced circular dichroism in [4]Heterohelicenium analogues

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