Structure-property relationship of perylene bisimide macrocycles probed by atomic force microscopy and single-molecule fluorescence spectroscopy

Ji Eun Lee, Vladimir Stepanenko, Jaesung Yang, Hyejin Yoo, Felix Schlosser, Daniel Bellinger, Bernd Engels, Ivan G. Scheblykin, Frank Würthner, Dongho Kim

Research output: Contribution to journalArticle

25 Citations (Scopus)

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 dynamics (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) 2D 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.

Original languageEnglish
Pages (from-to)5064-5076
Number of pages13
JournalACS Nano
Volume7
Issue number6
DOIs
Publication statusPublished - 2013 Jun 25

Fingerprint

Fluorescence spectroscopy
Atomic force microscopy
atomic force microscopy
fluorescence
Molecules
rings
Graphite
spectroscopy
pyrolytic graphite
molecules
Molecular dynamics
Fluorescence
molecular dynamics
Acetylene
Excitation energy
planar structures
Computer simulation
structural stability
penalties
acetylene

All Science Journal Classification (ASJC) codes

  • Materials Science(all)
  • Engineering(all)
  • Physics and Astronomy(all)

Cite this

Lee, Ji Eun ; Stepanenko, Vladimir ; Yang, Jaesung ; Yoo, Hyejin ; Schlosser, Felix ; Bellinger, Daniel ; Engels, Bernd ; Scheblykin, Ivan G. ; Würthner, Frank ; Kim, Dongho. / Structure-property relationship of perylene bisimide macrocycles probed by atomic force microscopy and single-molecule fluorescence spectroscopy. In: ACS Nano. 2013 ; Vol. 7, No. 6. pp. 5064-5076.
@article{3e821018ff6f4c9a8d11f4ed31f7df3c,
title = "Structure-property relationship of perylene bisimide macrocycles probed by atomic force microscopy and single-molecule fluorescence spectroscopy",
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 dynamics (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) 2D 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 Vladimir Stepanenko and Jaesung Yang and Hyejin Yoo and Felix Schlosser and Daniel Bellinger and Bernd Engels and Scheblykin, {Ivan G.} and Frank W{\"u}rthner and Dongho Kim",
year = "2013",
month = "6",
day = "25",
doi = "10.1021/nn400616u",
language = "English",
volume = "7",
pages = "5064--5076",
journal = "ACS Nano",
issn = "1936-0851",
publisher = "American Chemical Society",
number = "6",

}

Lee, JE, Stepanenko, V, Yang, J, Yoo, H, Schlosser, F, Bellinger, D, Engels, B, Scheblykin, IG, Würthner, F & Kim, D 2013, 'Structure-property relationship of perylene bisimide macrocycles probed by atomic force microscopy and single-molecule fluorescence spectroscopy', ACS Nano, vol. 7, no. 6, pp. 5064-5076. https://doi.org/10.1021/nn400616u

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 G.; Würthner, Frank; Kim, Dongho.

In: ACS Nano, Vol. 7, No. 6, 25.06.2013, p. 5064-5076.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Structure-property relationship of perylene bisimide macrocycles probed by atomic force microscopy and single-molecule fluorescence spectroscopy

AU - Lee, Ji Eun

AU - Stepanenko, Vladimir

AU - Yang, Jaesung

AU - Yoo, Hyejin

AU - Schlosser, Felix

AU - Bellinger, Daniel

AU - Engels, Bernd

AU - Scheblykin, Ivan G.

AU - Würthner, Frank

AU - Kim, Dongho

PY - 2013/6/25

Y1 - 2013/6/25

N2 - 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 dynamics (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) 2D 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.

AB - 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 dynamics (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) 2D 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.

UR - http://www.scopus.com/inward/record.url?scp=84879643818&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84879643818&partnerID=8YFLogxK

U2 - 10.1021/nn400616u

DO - 10.1021/nn400616u

M3 - Article

VL - 7

SP - 5064

EP - 5076

JO - ACS Nano

JF - ACS Nano

SN - 1936-0851

IS - 6

ER -