Modulation of Symmetry-Breaking Intramolecular Charge-Transfer Dynamics Assisted by Pendant Side Chains in π-Linkers in Quadrupolar Diketopyrrolopyrrole Derivatives

Woojae Kim; Jooyoung Sung; Marek Grzybowski; Daniel T. Gryko; Dongho Kim

doi:10.1021/acs.jpclett.6b01248

Modulation of Symmetry-Breaking Intramolecular Charge-Transfer Dynamics Assisted by Pendant Side Chains in π-Linkers in Quadrupolar Diketopyrrolopyrrole Derivatives

Woojae Kim, Jooyoung Sung, Marek Grzybowski, Daniel T. Gryko, Dongho Kim

Department of Chemistry

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

50 Citations (Scopus)

Abstract

The effect of the length of pendant side chains in centrosymmetric quadrupolar molecules on dynamics of their most perplexing photophysical phenomenon, i.e., symmetry-breaking intramolecular charge transfer, has been discovered. Unexpectedly, considerable influence of length of these pendant side chains in π-linkers arose as a structural factor enabling the control of the degree of fluorescence solvatochromism. The symmetry-breaking intramolecular charge-transfer dynamics has been described on quadrupolar diketopyrrolopyrrole derivatives possessing fluorene moieties as π-linkers and diarylamino groups as electron donors. On the basis of the evolution of transient fluorescence spectra obtained by a femtosecond broadband fluorescence up-conversion spectroscopy, it was found that the relative contribution of diffusive solvation and torsional relaxation in overall spectral relaxation can be modulated by the length of pendant side chain in π-linkers. Consequently, we demonstrated that this modulation plays a significant role in determining the photophysical properties of diketopyrrolopyrroles in a polar medium.

Original language	English
Pages (from-to)	3060-3066
Number of pages	7
Journal	Journal of Physical Chemistry Letters
Volume	7
Issue number	15
DOIs	https://doi.org/10.1021/acs.jpclett.6b01248
Publication status	Published - 2016 Aug 4

Bibliographical note

Funding Information:
The work at Yonsei University was supported by the Global Research Laboratory Program (2013K1A1A2A02050183) funded by the Ministry of Science, ICT & Future, Korea. The quantum calculations were supported by the National Institute of Supercomputing and Network (NISN)/Korea Institute of Science and Technology Information (KISTI) with supercomputing resources including technical support. D.T.G. thanks the National Science Center of the Republic of Poland (MAESTRO-2012/06/A/ST5/00216).

Publisher Copyright:
© 2016 American Chemical Society.

All Science Journal Classification (ASJC) codes

Materials Science(all)
Physical and Theoretical Chemistry

Access to Document

10.1021/acs.jpclett.6b01248

Cite this

@article{cbe3407327d540bbb2191dbe31f33eec,

title = "Modulation of Symmetry-Breaking Intramolecular Charge-Transfer Dynamics Assisted by Pendant Side Chains in π-Linkers in Quadrupolar Diketopyrrolopyrrole Derivatives",

abstract = "The effect of the length of pendant side chains in centrosymmetric quadrupolar molecules on dynamics of their most perplexing photophysical phenomenon, i.e., symmetry-breaking intramolecular charge transfer, has been discovered. Unexpectedly, considerable influence of length of these pendant side chains in π-linkers arose as a structural factor enabling the control of the degree of fluorescence solvatochromism. The symmetry-breaking intramolecular charge-transfer dynamics has been described on quadrupolar diketopyrrolopyrrole derivatives possessing fluorene moieties as π-linkers and diarylamino groups as electron donors. On the basis of the evolution of transient fluorescence spectra obtained by a femtosecond broadband fluorescence up-conversion spectroscopy, it was found that the relative contribution of diffusive solvation and torsional relaxation in overall spectral relaxation can be modulated by the length of pendant side chain in π-linkers. Consequently, we demonstrated that this modulation plays a significant role in determining the photophysical properties of diketopyrrolopyrroles in a polar medium.",

author = "Woojae Kim and Jooyoung Sung and Marek Grzybowski and Gryko, {Daniel T.} and Dongho Kim",

note = "Funding Information: The work at Yonsei University was supported by the Global Research Laboratory Program (2013K1A1A2A02050183) funded by the Ministry of Science, ICT & Future, Korea. The quantum calculations were supported by the National Institute of Supercomputing and Network (NISN)/Korea Institute of Science and Technology Information (KISTI) with supercomputing resources including technical support. D.T.G. thanks the National Science Center of the Republic of Poland (MAESTRO-2012/06/A/ST5/00216). Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

year = "2016",

month = aug,

day = "4",

doi = "10.1021/acs.jpclett.6b01248",

language = "English",

volume = "7",

pages = "3060--3066",

journal = "Journal of Physical Chemistry Letters",

issn = "1948-7185",

publisher = "American Chemical Society",

number = "15",

}

Modulation of Symmetry-Breaking Intramolecular Charge-Transfer Dynamics Assisted by Pendant Side Chains in π-Linkers in Quadrupolar Diketopyrrolopyrrole Derivatives. / Kim, Woojae; Sung, Jooyoung; Grzybowski, Marek et al.
In: Journal of Physical Chemistry Letters, Vol. 7, No. 15, 04.08.2016, p. 3060-3066.

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

TY - JOUR

T1 - Modulation of Symmetry-Breaking Intramolecular Charge-Transfer Dynamics Assisted by Pendant Side Chains in π-Linkers in Quadrupolar Diketopyrrolopyrrole Derivatives

AU - Kim, Woojae

AU - Sung, Jooyoung

AU - Grzybowski, Marek

AU - Gryko, Daniel T.

AU - Kim, Dongho

N1 - Funding Information: The work at Yonsei University was supported by the Global Research Laboratory Program (2013K1A1A2A02050183) funded by the Ministry of Science, ICT & Future, Korea. The quantum calculations were supported by the National Institute of Supercomputing and Network (NISN)/Korea Institute of Science and Technology Information (KISTI) with supercomputing resources including technical support. D.T.G. thanks the National Science Center of the Republic of Poland (MAESTRO-2012/06/A/ST5/00216). Publisher Copyright: © 2016 American Chemical Society.

PY - 2016/8/4

Y1 - 2016/8/4

N2 - The effect of the length of pendant side chains in centrosymmetric quadrupolar molecules on dynamics of their most perplexing photophysical phenomenon, i.e., symmetry-breaking intramolecular charge transfer, has been discovered. Unexpectedly, considerable influence of length of these pendant side chains in π-linkers arose as a structural factor enabling the control of the degree of fluorescence solvatochromism. The symmetry-breaking intramolecular charge-transfer dynamics has been described on quadrupolar diketopyrrolopyrrole derivatives possessing fluorene moieties as π-linkers and diarylamino groups as electron donors. On the basis of the evolution of transient fluorescence spectra obtained by a femtosecond broadband fluorescence up-conversion spectroscopy, it was found that the relative contribution of diffusive solvation and torsional relaxation in overall spectral relaxation can be modulated by the length of pendant side chain in π-linkers. Consequently, we demonstrated that this modulation plays a significant role in determining the photophysical properties of diketopyrrolopyrroles in a polar medium.

AB - The effect of the length of pendant side chains in centrosymmetric quadrupolar molecules on dynamics of their most perplexing photophysical phenomenon, i.e., symmetry-breaking intramolecular charge transfer, has been discovered. Unexpectedly, considerable influence of length of these pendant side chains in π-linkers arose as a structural factor enabling the control of the degree of fluorescence solvatochromism. The symmetry-breaking intramolecular charge-transfer dynamics has been described on quadrupolar diketopyrrolopyrrole derivatives possessing fluorene moieties as π-linkers and diarylamino groups as electron donors. On the basis of the evolution of transient fluorescence spectra obtained by a femtosecond broadband fluorescence up-conversion spectroscopy, it was found that the relative contribution of diffusive solvation and torsional relaxation in overall spectral relaxation can be modulated by the length of pendant side chain in π-linkers. Consequently, we demonstrated that this modulation plays a significant role in determining the photophysical properties of diketopyrrolopyrroles in a polar medium.

UR - http://www.scopus.com/inward/record.url?scp=84982795851&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84982795851&partnerID=8YFLogxK

U2 - 10.1021/acs.jpclett.6b01248

DO - 10.1021/acs.jpclett.6b01248

M3 - Article

AN - SCOPUS:84982795851

SN - 1948-7185

VL - 7

SP - 3060

EP - 3066

JO - Journal of Physical Chemistry Letters

JF - Journal of Physical Chemistry Letters

IS - 15

ER -

Modulation of Symmetry-Breaking Intramolecular Charge-Transfer Dynamics Assisted by Pendant Side Chains in π-Linkers in Quadrupolar Diketopyrrolopyrrole Derivatives

Abstract

Bibliographical note

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this