Reversible Solution π-Dimerization and Long Multicenter Bonding in a Stable Phenoxyl Radical

Nico M. Bonanno; Prashanth K. Poddutoori; Kazunobu Sato; Kenji Sugisaki; Takeji Takui; Alan J. Lough; Martin T. Lemaire

doi:10.1002/chem.201802204

Reversible Solution π-Dimerization and Long Multicenter Bonding in a Stable Phenoxyl Radical

Nico M. Bonanno, Prashanth K. Poddutoori, Kazunobu Sato, Kenji Sugisaki, Takeji Takui, Alan J. Lough, Martin T. Lemaire

Chemistry & Biochemistry

Research output: Contribution to journal › Article › peer-review

11 Scopus citations

Abstract

Reversible solution π-dimerization is observed in the stable neutral phenoxyl radical 2,6-bis-(8-quinolylamino)-4-(tert-butyl)phenoxyl baqp and is spectroscopically characterized. This behavior, not previously observed for π-extended phenoxyl radicals, is relevant to the formation of long multicenter bonding in the π-dimer at low temperature akin to previously reported phenalenyl radicals. Our experimental data are supported in a quantitative manner by results from density functional theory (DFT) and ab initio molecular orbital theory calculations. Our theoretical results indicate that the solution dimer features strong bonding interactions between the two phenoxyl rings but that the stability of the dimer is also related to dispersion interactions between the flanking nearly parallel quinolyl rings.

Original language	English (US)
Pages (from-to)	14906-14910
Number of pages	5
Journal	Chemistry - A European Journal
Volume	24
Issue number	56
DOIs	https://doi.org/10.1002/chem.201802204
State	Published - Oct 9 2018

Bibliographical note

Funding Information:
M.T.L. acknowledges NSERC (RGPIN-2017-05230) and Brock University for support of this work. N.M.B. thanks NSERC for a graduate fellowship (CGS M). We thank Prof. Art van der Est (Brock) for preliminary EPR experiments. Part of this work was made possible by the facilities of the Shared Hierarchical Academic Research Computing Network (SHARCNET: www.sharc-net.ca) and Compute/Calcul Canada. The Osaka City University (OCU) group acknowledges the support by JSPS KAKENHI Grant Numbers JP17H03012 and JP18K03465 from Ministry of Education, Culture, Sports, Science and Technology, Japan (MEXT, Japan) and by Open Advanced Research Facilities Initiative Program from MEXT, Japan. The OCU group also acknowledges AOARD for support by AOARD Scientific Project on “Quantum Properties of Molecular Nanomagnets” (Award No. FA2386-13-1-4029, 4030, 4031) and AOARD Project on “Molecular Spins for Quantum Technologies” (Award No. FA2386-17-1-4040), The work has been partially supported by Grants-in-Aid for Scientific Research on Innovative Areas (Quantum Cybernetics) from MEXT, Japan and by FIRST Quantum Information Processing Project, the Cabinet Office, Japan.

Funding Information:
M.T.L. acknowledges NSERC (RGPIN-2017-05230) and Brock University for support of this work. N.M.B. thanks NSERC for a graduate fellowship (CGS M). We thank Prof. Art van der Est (Brock) for preliminary EPR experiments. Part of this work was made possible by the facilities of the Shared Hierarchical Academic Research Computing Network (SHARCNET: www.sharcnet.ca) and Compute/Calcul Canada. The Osaka City University (OCU) group acknowledges the support by JSPS KAKENHI Grant Numbers JP17H03012 and JP18K03465 from Ministry of Education, Culture, Sports, Science and Technology, Japan (MEXT, Japan) and by Open Advanced Research Facilities Initiative Program from MEXT, Japan. The OCU group also acknowledges AOARD for support by AOARD Scientific Project on “Quantum Properties of Molecular Nanomagnets” (Award No. FA2386-13-1-4029, 4030, 4031) and AOARD Project on “Molecular Spins for Quantum Technologies” (Award No. FA2386-17-1-4040), The work has been partially supported by Grants-in-Aid for Scientific Research on Innovative Areas (Quantum Cybernetics) from MEXT, Japan and by FIRST Quantum Information Processing Project, the Cabinet Office, Japan.

Publisher Copyright:
© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords

density functional calculations
molecular devices
multicenter bonding
stable radicals
π-dimerization

Publisher link

10.1002/chem.201802204

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title = "Reversible Solution π-Dimerization and Long Multicenter Bonding in a Stable Phenoxyl Radical",

abstract = "Reversible solution π-dimerization is observed in the stable neutral phenoxyl radical 2,6-bis-(8-quinolylamino)-4-(tert-butyl)phenoxyl baqp and is spectroscopically characterized. This behavior, not previously observed for π-extended phenoxyl radicals, is relevant to the formation of long multicenter bonding in the π-dimer at low temperature akin to previously reported phenalenyl radicals. Our experimental data are supported in a quantitative manner by results from density functional theory (DFT) and ab initio molecular orbital theory calculations. Our theoretical results indicate that the solution dimer features strong bonding interactions between the two phenoxyl rings but that the stability of the dimer is also related to dispersion interactions between the flanking nearly parallel quinolyl rings.",

keywords = "density functional calculations, molecular devices, multicenter bonding, stable radicals, π-dimerization",

author = "Bonanno, {Nico M.} and Poddutoori, {Prashanth K.} and Kazunobu Sato and Kenji Sugisaki and Takeji Takui and Lough, {Alan J.} and Lemaire, {Martin T.}",

note = "Funding Information: M.T.L. acknowledges NSERC (RGPIN-2017-05230) and Brock University for support of this work. N.M.B. thanks NSERC for a graduate fellowship (CGS M). We thank Prof. Art van der Est (Brock) for preliminary EPR experiments. Part of this work was made possible by the facilities of the Shared Hierarchical Academic Research Computing Network (SHARCNET: www.sharc-net.ca) and Compute/Calcul Canada. The Osaka City University (OCU) group acknowledges the support by JSPS KAKENHI Grant Numbers JP17H03012 and JP18K03465 from Ministry of Education, Culture, Sports, Science and Technology, Japan (MEXT, Japan) and by Open Advanced Research Facilities Initiative Program from MEXT, Japan. The OCU group also acknowledges AOARD for support by AOARD Scientific Project on “Quantum Properties of Molecular Nanomagnets” (Award No. FA2386-13-1-4029, 4030, 4031) and AOARD Project on “Molecular Spins for Quantum Technologies” (Award No. FA2386-17-1-4040), The work has been partially supported by Grants-in-Aid for Scientific Research on Innovative Areas (Quantum Cybernetics) from MEXT, Japan and by FIRST Quantum Information Processing Project, the Cabinet Office, Japan. Funding Information: M.T.L. acknowledges NSERC (RGPIN-2017-05230) and Brock University for support of this work. N.M.B. thanks NSERC for a graduate fellowship (CGS M). We thank Prof. Art van der Est (Brock) for preliminary EPR experiments. Part of this work was made possible by the facilities of the Shared Hierarchical Academic Research Computing Network (SHARCNET: www.sharcnet.ca) and Compute/Calcul Canada. The Osaka City University (OCU) group acknowledges the support by JSPS KAKENHI Grant Numbers JP17H03012 and JP18K03465 from Ministry of Education, Culture, Sports, Science and Technology, Japan (MEXT, Japan) and by Open Advanced Research Facilities Initiative Program from MEXT, Japan. The OCU group also acknowledges AOARD for support by AOARD Scientific Project on “Quantum Properties of Molecular Nanomagnets” (Award No. FA2386-13-1-4029, 4030, 4031) and AOARD Project on “Molecular Spins for Quantum Technologies” (Award No. FA2386-17-1-4040), The work has been partially supported by Grants-in-Aid for Scientific Research on Innovative Areas (Quantum Cybernetics) from MEXT, Japan and by FIRST Quantum Information Processing Project, the Cabinet Office, Japan. Publisher Copyright: {\textcopyright} 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

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AU - Bonanno, Nico M.

AU - Poddutoori, Prashanth K.

AU - Sato, Kazunobu

AU - Sugisaki, Kenji

AU - Takui, Takeji

AU - Lough, Alan J.

AU - Lemaire, Martin T.

N1 - Funding Information: M.T.L. acknowledges NSERC (RGPIN-2017-05230) and Brock University for support of this work. N.M.B. thanks NSERC for a graduate fellowship (CGS M). We thank Prof. Art van der Est (Brock) for preliminary EPR experiments. Part of this work was made possible by the facilities of the Shared Hierarchical Academic Research Computing Network (SHARCNET: www.sharc-net.ca) and Compute/Calcul Canada. The Osaka City University (OCU) group acknowledges the support by JSPS KAKENHI Grant Numbers JP17H03012 and JP18K03465 from Ministry of Education, Culture, Sports, Science and Technology, Japan (MEXT, Japan) and by Open Advanced Research Facilities Initiative Program from MEXT, Japan. The OCU group also acknowledges AOARD for support by AOARD Scientific Project on “Quantum Properties of Molecular Nanomagnets” (Award No. FA2386-13-1-4029, 4030, 4031) and AOARD Project on “Molecular Spins for Quantum Technologies” (Award No. FA2386-17-1-4040), The work has been partially supported by Grants-in-Aid for Scientific Research on Innovative Areas (Quantum Cybernetics) from MEXT, Japan and by FIRST Quantum Information Processing Project, the Cabinet Office, Japan. Funding Information: M.T.L. acknowledges NSERC (RGPIN-2017-05230) and Brock University for support of this work. N.M.B. thanks NSERC for a graduate fellowship (CGS M). We thank Prof. Art van der Est (Brock) for preliminary EPR experiments. Part of this work was made possible by the facilities of the Shared Hierarchical Academic Research Computing Network (SHARCNET: www.sharcnet.ca) and Compute/Calcul Canada. The Osaka City University (OCU) group acknowledges the support by JSPS KAKENHI Grant Numbers JP17H03012 and JP18K03465 from Ministry of Education, Culture, Sports, Science and Technology, Japan (MEXT, Japan) and by Open Advanced Research Facilities Initiative Program from MEXT, Japan. The OCU group also acknowledges AOARD for support by AOARD Scientific Project on “Quantum Properties of Molecular Nanomagnets” (Award No. FA2386-13-1-4029, 4030, 4031) and AOARD Project on “Molecular Spins for Quantum Technologies” (Award No. FA2386-17-1-4040), The work has been partially supported by Grants-in-Aid for Scientific Research on Innovative Areas (Quantum Cybernetics) from MEXT, Japan and by FIRST Quantum Information Processing Project, the Cabinet Office, Japan. Publisher Copyright: © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2018/10/9

Y1 - 2018/10/9

N2 - Reversible solution π-dimerization is observed in the stable neutral phenoxyl radical 2,6-bis-(8-quinolylamino)-4-(tert-butyl)phenoxyl baqp and is spectroscopically characterized. This behavior, not previously observed for π-extended phenoxyl radicals, is relevant to the formation of long multicenter bonding in the π-dimer at low temperature akin to previously reported phenalenyl radicals. Our experimental data are supported in a quantitative manner by results from density functional theory (DFT) and ab initio molecular orbital theory calculations. Our theoretical results indicate that the solution dimer features strong bonding interactions between the two phenoxyl rings but that the stability of the dimer is also related to dispersion interactions between the flanking nearly parallel quinolyl rings.

AB - Reversible solution π-dimerization is observed in the stable neutral phenoxyl radical 2,6-bis-(8-quinolylamino)-4-(tert-butyl)phenoxyl baqp and is spectroscopically characterized. This behavior, not previously observed for π-extended phenoxyl radicals, is relevant to the formation of long multicenter bonding in the π-dimer at low temperature akin to previously reported phenalenyl radicals. Our experimental data are supported in a quantitative manner by results from density functional theory (DFT) and ab initio molecular orbital theory calculations. Our theoretical results indicate that the solution dimer features strong bonding interactions between the two phenoxyl rings but that the stability of the dimer is also related to dispersion interactions between the flanking nearly parallel quinolyl rings.

KW - density functional calculations

KW - molecular devices

KW - multicenter bonding

KW - stable radicals

KW - π-dimerization

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Reversible Solution π-Dimerization and Long Multicenter Bonding in a Stable Phenoxyl Radical

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