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Structure-Property Relationship of Perylene Bisimide Macrocycles Probed by Atomic Force Microscopy and Single-Molecule Fluorescence Spectroscopy

Lee, Ji-Eun ; Stepanenko, Vladimir ; Yang, Jaesung ; Yoo, Hyejin ; Schlosser, Felix ; Bellinger, Daniel ; Engels, Bernd ; Scheblykin, Ivan LU orcid ; Wuerthner, Frank and Kim, Dongho (2013) In ACS Nano 7(6). p.5064-5076
Abstract
Properties of a series of acetylene-linked perylene bisimide (PBI) macrocycles with different ring size composed of three to six PBI dyes were investigated by atomic force microscopy (AFM) and single-molecule fluorescence spectroscopy in a condensed phase. it was demonstrated that the structures of PBI cyclic arrays (CNs, N = 3, 4,5, and 6) become distorted with increasing the ring size through molecular dynamic (MD) simulations (PM6-DH2 method) and AFM height images of CNs on highly ordered pyrolytic graphite (HOPG) surface. The MD simulations showed that only C5 and C6 rings are highly flexible molecules whose planarization goes along with a significant energetic penalty. Accordingly, both molecules did not show ordered adlayers on a... (More)
Properties of a series of acetylene-linked perylene bisimide (PBI) macrocycles with different ring size composed of three to six PBI dyes were investigated by atomic force microscopy (AFM) and single-molecule fluorescence spectroscopy in a condensed phase. it was demonstrated that the structures of PBI cyclic arrays (CNs, N = 3, 4,5, and 6) become distorted with increasing the ring size through molecular dynamic (MD) simulations (PM6-DH2 method) and AFM height images of CNs on highly ordered pyrolytic graphite (HOPG) surface. The MD simulations showed that only C5 and C6 rings are highly flexible molecules whose planarization goes along with a significant energetic penalty. Accordingly, both molecules did not show ordered adlayers on a HOPG surface. In contrast, C3 and C4 are far more rigid molecules leading to well-ordered hexagonal (C3) and rectangular (C4) 20 lattices. At the single-molecule level, we showed that the fluorescence properties of single CNs are affected by the structural changes. The fluorescence lifetimes of CNs became shorter and their distributions became broader due to the structural distortions with increasing the ring size. Furthermore, the CNs of smaller ring size exhibit a higher photostability and an efficient excitation energy transfer (EET) due to the more well-defined and planar structures compared to the larger CNs. Consequently, these observations provide evidence that not only PBI macrocycles are promising candidates for artificial light-harvesting systems, but also the photophysical properties of CNs are strongly related to the structural rigidity of CNs. (Less)
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; ; ; ; ; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
macrocycles, light-harvesting system, excitation energy transfer, atomic, force microscopy, single-molecule spectroscopy, molecular dynamics, simulations
in
ACS Nano
volume
7
issue
6
pages
5064 - 5076
publisher
The American Chemical Society (ACS)
external identifiers
  • wos:000321093800040
  • scopus:84879643818
  • pmid:23656366
ISSN
1936-086X
DOI
10.1021/nn400616u
language
English
LU publication?
yes
additional info
The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Chemical Physics (S) (011001060)
id
2eea3120-0853-47d8-bae7-a23d21cd9624 (old id 3979118)
date added to LUP
2016-04-01 09:57:49
date last changed
2023-11-09 08:46:19
@article{2eea3120-0853-47d8-bae7-a23d21cd9624,
  abstract     = {{Properties of a series of acetylene-linked perylene bisimide (PBI) macrocycles with different ring size composed of three to six PBI dyes were investigated by atomic force microscopy (AFM) and single-molecule fluorescence spectroscopy in a condensed phase. it was demonstrated that the structures of PBI cyclic arrays (CNs, N = 3, 4,5, and 6) become distorted with increasing the ring size through molecular dynamic (MD) simulations (PM6-DH2 method) and AFM height images of CNs on highly ordered pyrolytic graphite (HOPG) surface. The MD simulations showed that only C5 and C6 rings are highly flexible molecules whose planarization goes along with a significant energetic penalty. Accordingly, both molecules did not show ordered adlayers on a HOPG surface. In contrast, C3 and C4 are far more rigid molecules leading to well-ordered hexagonal (C3) and rectangular (C4) 20 lattices. At the single-molecule level, we showed that the fluorescence properties of single CNs are affected by the structural changes. The fluorescence lifetimes of CNs became shorter and their distributions became broader due to the structural distortions with increasing the ring size. Furthermore, the CNs of smaller ring size exhibit a higher photostability and an efficient excitation energy transfer (EET) due to the more well-defined and planar structures compared to the larger CNs. Consequently, these observations provide evidence that not only PBI macrocycles are promising candidates for artificial light-harvesting systems, but also the photophysical properties of CNs are strongly related to the structural rigidity of CNs.}},
  author       = {{Lee, Ji-Eun and Stepanenko, Vladimir and Yang, Jaesung and Yoo, Hyejin and Schlosser, Felix and Bellinger, Daniel and Engels, Bernd and Scheblykin, Ivan and Wuerthner, Frank and Kim, Dongho}},
  issn         = {{1936-086X}},
  keywords     = {{macrocycles; light-harvesting system; excitation energy transfer; atomic; force microscopy; single-molecule spectroscopy; molecular dynamics; simulations}},
  language     = {{eng}},
  number       = {{6}},
  pages        = {{5064--5076}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{ACS Nano}},
  title        = {{Structure-Property Relationship of Perylene Bisimide Macrocycles Probed by Atomic Force Microscopy and Single-Molecule Fluorescence Spectroscopy}},
  url          = {{http://dx.doi.org/10.1021/nn400616u}},
  doi          = {{10.1021/nn400616u}},
  volume       = {{7}},
  year         = {{2013}},
}