Cyclophanes of perylene tetracarboxylic diimide with different substituents at bay positions

Junqian Feng, Yuexing Zhang, Chuntao Zhao, Renjie Li, Wei Xu, Xiyou Li*, Jianzhuang Jiang

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

57 Scopus citations

Abstract

Cyclophanes of perylene tetracarboxylic diimides (PDIs) with different substituents at the bay positions, namely four phenoxy groups at the Impositions (1), four piperidinyl groups at the 1,7-positions (2), and eight phenoxy groups at the 1,6,7,12-positions (3) of the two PDI rings, have been synthesized by the condensation of perylene dianhydride with amine in a dilute solution. These novel cyclophanes were characterized by 1H NMR spectroscopy, MALDI-TOF mass spectrometry, electronic absorption spectroscopy, and elemental analysis. The conformational isomers of cyclophanes substituted with four piperidinyl groups at the 1,7-positions (2 a and 2 b) were successfully separated by preparative TLC. The main absorption band of the cyclophanes shifts significantly to the higher energy side in comparison with their monomeric counterparts, which indicates significant π-π interaction between the PDI units in the cyclophanes. Nevertheless, both the electronic absorption and fluorescence spectra of the cyclophanes were found to change along with the number and nature of the side groups at the bay positions of the PDI ring. Time-dependent DFT calculations on the conformational isomers 2a and 2b reproduce well their experimental electronic absorption spectra. Electrochemical studies reveal that the first oxidation and reduction potentials of the PDI ring in the cyclophanes increase significantly compared with those of the corresponding monomeric counterparts, in line with the change in the energy of the HOMO and LUMO according to the theoretical calculations.

Original languageEnglish (US)
Pages (from-to)7000-7010
Number of pages11
JournalChemistry - A European Journal
Volume14
Issue number23
DOIs
StatePublished - Aug 8 2008

Keywords

  • Cyclophanes
  • Dimers
  • Perylenes
  • Photophysical properties
  • Supramolecular chemistry

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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