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

Research output: Contribution to journalArticlepeer-review

36 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 languageEnglish
Pages (from-to)3060-3066
Number of pages7
JournalJournal of Physical Chemistry Letters
Volume7
Issue number15
DOIs
Publication statusPublished - 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).

All Science Journal Classification (ASJC) codes

  • Materials Science(all)
  • Physical and Theoretical Chemistry

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