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Cyclophanes of Perylene Tetracarboxylic Diimide with Different Substituents at Bay Positions
Author(s) -
Feng Junqian,
Zhang Yuexing,
Zhao Chuntao,
Li Renjie,
Xu Wei,
Li Xiyou,
Jiang Jianzhuang
Publication year - 2008
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200800136
Subject(s) - perylene , chemistry , diimide , monomer , absorption spectroscopy , ring (chemistry) , crystallography , cyclophane , homo/lumo , absorption (acoustics) , photochemistry , stereochemistry , molecule , crystal structure , organic chemistry , materials science , polymer , physics , quantum mechanics , composite material
Cyclophanes of perylene tetracarboxylic diimides (PDIs) with different substituents at the bay positions, namely four phenoxy groups at the 1,7‐positions ( 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 1 H 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 2 a and 2 b 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.