The Role of Linkers in the Excited-State Dynamic Planarization Processes of Macrocyclic Oligothiophene 12-Mers

Woojae Kim, Jooyoung Sung, Kyu Hyung Park, Hideyuki Shimizu, Mika Imamura, Minwoo Han, Eunji Sim, Masahiko Iyoda, Dongho Kim

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

Linkers adjoining chromophores play an important role in modulating the structure of conjugated systems, which is bound up with their photophysical properties. However, to date, the focus of works dealing with linker effects was limited only to linear π-conjugated materials, and there have been no detailed studies on cyclic counterparts. Herein we report the linker effects on the dynamic planarization processes of π-conjugated macrocyclic oligothiophene 12-mers, where the different ratio between ethynylene and vinylene linkers was chosen to control the backbone rigidity. By analyzing transient fluorescence spectra, we demonstrate that the connecting linkers play a crucial role in the excited-state dynamics of cyclic conjugated systems. Faster dynamic planarization, longer exciton delocalization length, and higher degree of planarity were observed in vinylene inserted cyclic oligothiophenes. Molecular dynamics simulations and density functional theory calculations also stress the importance of the role of linkers in modulating the structure of cyclic oligothiophenes.

Original languageEnglish
Pages (from-to)4444-4450
Number of pages7
JournalJournal of Physical Chemistry Letters
Volume6
Issue number21
DOIs
Publication statusPublished - 2015 Oct 23

All Science Journal Classification (ASJC) codes

  • Materials Science(all)
  • Physical and Theoretical Chemistry

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