Self-assembly of supramolecular light-harvesting arrays from symmetric perylene-3,4-dicarboximide trefoils

Kelly M. Lefler, Chul Hoon Kim, Yi Lin Wu, Michael R Wasielewski

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

Unlike the widely studied perylene-3,4:9,10-bis(dicarboximide) (PDI) dyes, self-assembly of the corresponding perylene-3,4-dicarboximide (PMI) dyes into large arrays and studies of their excited state properties have received far less attention. Two symmetric PMI trefoils were synthesized by connecting the 9-position of the perylene core either directly (1) or through a phenylene linker (2) to the 1,3,5-positions of a central benzene ring. Synchrotron-based small-and wide-angle X-ray scattering measurements in methylcyclohexane show that trefoil 1 self-assembles into cofacial trimers (13) on average, while trefoil 2 forms much larger assemblies that are tridecamers (2 13) on average. Their photophysics were characterized using steady-state as well as transient absorption and emission spectroscopy. Time-resolved spectroscopy reveals that both 13 and 213 initially form excitonically coupled excited states that subsequently relax to excimer states having 20 and 8.4 ns lifetimes, respectively, which decay to ground-state primarily nonradiatively. The data are consistent with stronger electronic coupling between the PMI molecules in 213 relative to 13.

Original languageEnglish
Pages (from-to)1608-1615
Number of pages8
JournalJournal of Physical Chemistry Letters
Volume5
Issue number9
DOIs
Publication statusPublished - May 1 2014

Fingerprint

Perylene
Excited states
Self assembly
self assembly
Dyes
dyes
Emission spectroscopy
Coloring Agents
excimers
trimers
X ray scattering
Synchrotrons
Absorption spectroscopy
Ground state
assemblies
spectroscopy
excitation
Benzene
absorption spectroscopy
synchrotrons

Keywords

  • energy transfer
  • excimer
  • exciton coupling
  • ultrafast spectroscopy
  • X-ray scattering

ASJC Scopus subject areas

  • Materials Science(all)

Cite this

Self-assembly of supramolecular light-harvesting arrays from symmetric perylene-3,4-dicarboximide trefoils. / Lefler, Kelly M.; Kim, Chul Hoon; Wu, Yi Lin; Wasielewski, Michael R.

In: Journal of Physical Chemistry Letters, Vol. 5, No. 9, 01.05.2014, p. 1608-1615.

Research output: Contribution to journalArticle

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