Fingerprints of Through-Bond and Through-Space Exciton and Charge π-Electron Delocalization in Linearly Extended [2.2]Paracyclophanes

José L. Zafra; Agustín Molina Ontoria; Paula Mayorga Burrezo; Miriam Peña-Alvarez; Marek Samoc; Janusz Szeremeta; Francisco J. Ramírez; Matthew D. Lovander; Christopher J. Droske; Ted M. Pappenfus; Luis Echegoyen; Juan T. López Navarrete; Nazario Martín; Juan Casado

doi:10.1021/jacs.6b12520

Fingerprints of Through-Bond and Through-Space Exciton and Charge π-Electron Delocalization in Linearly Extended [2.2]Paracyclophanes

José L. Zafra, Agustín Molina Ontoria, Paula Mayorga Burrezo, Miriam Peña-Alvarez, Marek Samoc, Janusz Szeremeta, Francisco J. Ramírez, Matthew D. Lovander, Christopher J. Droske, Ted M. Pappenfus, Luis Echegoyen, Juan T. López Navarrete, Nazario Martín, Juan Casado

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

22 Scopus citations

Abstract

New stilbenoid and thiophenic compounds terminally functionalized with donor-donor, acceptor-acceptor, or donor-acceptor moieties and possessing a central [2.2]paracyclophane unit have been prepared, and their properties interpreted in terms of through-bond and through space π-electron delocalization (i.e., π-conjugations). Based on photophysical data, their excited-state properties have been described with a focus on the participation of the central [2.2]paracyclophane in competition with through-bond conjugation in the side arms. To this end, two-photon and one-photon absorption and emission spectroscopy, as a function of temperature, solvent polarity, and pressure in the solid state have been recorded. Furthermore, charge delocalization through the [2.2]paracyclophane in the neutral state and in the oxidized species (radical cations, dications and radical trications) has been investigated, allowing the elucidation of the vibrational Raman fingerprint of through-space charge delocalization. Thus, a complementary approach to both “intermolecular” excitation and charge delocalizations in [2.2]paracyclophane molecules is shown which can serve as models of charge and exciton migration in organic semiconductors.

Original language	English (US)
Pages (from-to)	3095-3105
Number of pages	11
Journal	Journal of the American Chemical Society
Volume	139
Issue number	8
DOIs	https://doi.org/10.1021/jacs.6b12520
State	Published - Mar 1 2017

Bibliographical note

Funding Information:
The work at the University of Ma?laga was supported by MINECO through project reference CTQ2012-33733 and by the Junta de Andaluci?a through research project P09-FQM-4708. The work at the Complutense University of Madrid was supported by European Research Council ERC- 320441 (Chirallcarbon), MINECO of Spain (CTQ2014-52045-R), and Comunidad Auto?noma of Madrid (FOTOCARBON project S2013/MIT-2841). T.M.P. acknowledges University of Minnesota, Morris (UMM) Faculty Research Enhancement Funds supported by the University of Minnesota Office of the Vice President for Research. L.E. thanks the Robert A. Welch Foundation, grant AH-0033, and the U.S. National Science Foundation, grants DMR-1205302 and CHE-1408865, for generous financial support. M.S. acknowledges the National Science Centre DEC-2013/10/A/ST4/00114 grant.

Publisher Copyright:
© 2017 American Chemical Society.

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Zafra, J. L., Molina Ontoria, A., Mayorga Burrezo, P., Peña-Alvarez, M., Samoc, M., Szeremeta, J., Ramírez, F. J., Lovander, M. D., Droske, C. J., Pappenfus, T. M., Echegoyen, L., López Navarrete, J. T., Martín, N., & Casado, J. (2017). Fingerprints of Through-Bond and Through-Space Exciton and Charge π-Electron Delocalization in Linearly Extended [2.2]Paracyclophanes. Journal of the American Chemical Society, 139(8), 3095-3105. https://doi.org/10.1021/jacs.6b12520

Fingerprints of Through-Bond and Through-Space Exciton and Charge π-Electron Delocalization in Linearly Extended [2.2]Paracyclophanes. / Zafra, José L.; Molina Ontoria, Agustín; Mayorga Burrezo, Paula; Peña-Alvarez, Miriam; Samoc, Marek; Szeremeta, Janusz; Ramírez, Francisco J.; Lovander, Matthew D.; Droske, Christopher J.; Pappenfus, Ted M.; Echegoyen, Luis; López Navarrete, Juan T.; Martín, Nazario; Casado, Juan.

In: Journal of the American Chemical Society, Vol. 139, No. 8, 01.03.2017, p. 3095-3105.

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

Zafra, JL, Molina Ontoria, A, Mayorga Burrezo, P, Peña-Alvarez, M, Samoc, M, Szeremeta, J, Ramírez, FJ, Lovander, MD, Droske, CJ, Pappenfus, TM, Echegoyen, L, López Navarrete, JT, Martín, N & Casado, J 2017, 'Fingerprints of Through-Bond and Through-Space Exciton and Charge π-Electron Delocalization in Linearly Extended [2.2]Paracyclophanes', Journal of the American Chemical Society, vol. 139, no. 8, pp. 3095-3105. https://doi.org/10.1021/jacs.6b12520

Zafra, José L. ; Molina Ontoria, Agustín ; Mayorga Burrezo, Paula ; Peña-Alvarez, Miriam ; Samoc, Marek ; Szeremeta, Janusz ; Ramírez, Francisco J. ; Lovander, Matthew D. ; Droske, Christopher J. ; Pappenfus, Ted M. ; Echegoyen, Luis ; López Navarrete, Juan T. ; Martín, Nazario ; Casado, Juan. / Fingerprints of Through-Bond and Through-Space Exciton and Charge π-Electron Delocalization in Linearly Extended [2.2]Paracyclophanes. In: Journal of the American Chemical Society. 2017 ; Vol. 139, No. 8. pp. 3095-3105.

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title = "Fingerprints of Through-Bond and Through-Space Exciton and Charge π-Electron Delocalization in Linearly Extended [2.2]Paracyclophanes",

abstract = "New stilbenoid and thiophenic compounds terminally functionalized with donor-donor, acceptor-acceptor, or donor-acceptor moieties and possessing a central [2.2]paracyclophane unit have been prepared, and their properties interpreted in terms of through-bond and through space π-electron delocalization (i.e., π-conjugations). Based on photophysical data, their excited-state properties have been described with a focus on the participation of the central [2.2]paracyclophane in competition with through-bond conjugation in the side arms. To this end, two-photon and one-photon absorption and emission spectroscopy, as a function of temperature, solvent polarity, and pressure in the solid state have been recorded. Furthermore, charge delocalization through the [2.2]paracyclophane in the neutral state and in the oxidized species (radical cations, dications and radical trications) has been investigated, allowing the elucidation of the vibrational Raman fingerprint of through-space charge delocalization. Thus, a complementary approach to both “intermolecular” excitation and charge delocalizations in [2.2]paracyclophane molecules is shown which can serve as models of charge and exciton migration in organic semiconductors.",

author = "Zafra, {Jos{\'e} L.} and {Molina Ontoria}, Agust{\'i}n and {Mayorga Burrezo}, Paula and Miriam Pe{\~n}a-Alvarez and Marek Samoc and Janusz Szeremeta and Ram{\'i}rez, {Francisco J.} and Lovander, {Matthew D.} and Droske, {Christopher J.} and Pappenfus, {Ted M.} and Luis Echegoyen and {L{\'o}pez Navarrete}, {Juan T.} and Nazario Mart{\'i}n and Juan Casado",

note = "Funding Information: The work at the University of Ma?laga was supported by MINECO through project reference CTQ2012-33733 and by the Junta de Andaluci?a through research project P09-FQM-4708. The work at the Complutense University of Madrid was supported by European Research Council ERC- 320441 (Chirallcarbon), MINECO of Spain (CTQ2014-52045-R), and Comunidad Auto?noma of Madrid (FOTOCARBON project S2013/MIT-2841). T.M.P. acknowledges University of Minnesota, Morris (UMM) Faculty Research Enhancement Funds supported by the University of Minnesota Office of the Vice President for Research. L.E. thanks the Robert A. Welch Foundation, grant AH-0033, and the U.S. National Science Foundation, grants DMR-1205302 and CHE-1408865, for generous financial support. M.S. acknowledges the National Science Centre DEC-2013/10/A/ST4/00114 grant. Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

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doi = "10.1021/jacs.6b12520",

language = "English (US)",

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T1 - Fingerprints of Through-Bond and Through-Space Exciton and Charge π-Electron Delocalization in Linearly Extended [2.2]Paracyclophanes

AU - Zafra, José L.

AU - Molina Ontoria, Agustín

AU - Mayorga Burrezo, Paula

AU - Peña-Alvarez, Miriam

AU - Samoc, Marek

AU - Szeremeta, Janusz

AU - Ramírez, Francisco J.

AU - Lovander, Matthew D.

AU - Droske, Christopher J.

AU - Pappenfus, Ted M.

AU - Echegoyen, Luis

AU - López Navarrete, Juan T.

AU - Martín, Nazario

AU - Casado, Juan

N1 - Funding Information: The work at the University of Ma?laga was supported by MINECO through project reference CTQ2012-33733 and by the Junta de Andaluci?a through research project P09-FQM-4708. The work at the Complutense University of Madrid was supported by European Research Council ERC- 320441 (Chirallcarbon), MINECO of Spain (CTQ2014-52045-R), and Comunidad Auto?noma of Madrid (FOTOCARBON project S2013/MIT-2841). T.M.P. acknowledges University of Minnesota, Morris (UMM) Faculty Research Enhancement Funds supported by the University of Minnesota Office of the Vice President for Research. L.E. thanks the Robert A. Welch Foundation, grant AH-0033, and the U.S. National Science Foundation, grants DMR-1205302 and CHE-1408865, for generous financial support. M.S. acknowledges the National Science Centre DEC-2013/10/A/ST4/00114 grant. Publisher Copyright: © 2017 American Chemical Society.

PY - 2017/3/1

Y1 - 2017/3/1

N2 - New stilbenoid and thiophenic compounds terminally functionalized with donor-donor, acceptor-acceptor, or donor-acceptor moieties and possessing a central [2.2]paracyclophane unit have been prepared, and their properties interpreted in terms of through-bond and through space π-electron delocalization (i.e., π-conjugations). Based on photophysical data, their excited-state properties have been described with a focus on the participation of the central [2.2]paracyclophane in competition with through-bond conjugation in the side arms. To this end, two-photon and one-photon absorption and emission spectroscopy, as a function of temperature, solvent polarity, and pressure in the solid state have been recorded. Furthermore, charge delocalization through the [2.2]paracyclophane in the neutral state and in the oxidized species (radical cations, dications and radical trications) has been investigated, allowing the elucidation of the vibrational Raman fingerprint of through-space charge delocalization. Thus, a complementary approach to both “intermolecular” excitation and charge delocalizations in [2.2]paracyclophane molecules is shown which can serve as models of charge and exciton migration in organic semiconductors.

AB - New stilbenoid and thiophenic compounds terminally functionalized with donor-donor, acceptor-acceptor, or donor-acceptor moieties and possessing a central [2.2]paracyclophane unit have been prepared, and their properties interpreted in terms of through-bond and through space π-electron delocalization (i.e., π-conjugations). Based on photophysical data, their excited-state properties have been described with a focus on the participation of the central [2.2]paracyclophane in competition with through-bond conjugation in the side arms. To this end, two-photon and one-photon absorption and emission spectroscopy, as a function of temperature, solvent polarity, and pressure in the solid state have been recorded. Furthermore, charge delocalization through the [2.2]paracyclophane in the neutral state and in the oxidized species (radical cations, dications and radical trications) has been investigated, allowing the elucidation of the vibrational Raman fingerprint of through-space charge delocalization. Thus, a complementary approach to both “intermolecular” excitation and charge delocalizations in [2.2]paracyclophane molecules is shown which can serve as models of charge and exciton migration in organic semiconductors.

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Fingerprints of Through-Bond and Through-Space Exciton and Charge π-Electron Delocalization in Linearly Extended [2.2]Paracyclophanes

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