Effects of metal–ligand coordination on the self-assembly behaviour of a crown ether functionalised perylenetetracarboxylic diimide

Abstract

A novel perylenetetracarboxylic diimide (PDI) derivative, N,N′-di(4′-benzo-15-crown-5-ether)-1,7-di(4-tert-butyl-phenoxy)perylene-3,4;9,10-tetracarboxylic diimide (CRPDI), has been synthesised and characterised. Dimerisation of CRPDI is induced by the presence of K⁺ in CHCl₃ or spontaneously occurs in methanol, as revealed by absorption and emission spectroscopy. In particular, the formation of co-facial dimer in the presence of K⁺ proceeds in a three-stage process, as indicated by absorption spectroscopy. The belt- and rope-like nanostructures of CRPDI fabricated from methanol and CHCl₃ solution in the presence of K⁺ are obtained by scanning electron microscopy. Furthermore, the conductivity of the rope-like nanostructures from the cation-induced dimeric species is more than ca. 1 order of magnitude higher than the belt-like nanostructures from the solvent-induced dimeric species. The present result represents the further effort towards realisation of controlling and tuning the morphology of self-assembled nanostructures of PDI derivatives through molecular design and synthesis. It will be valuable for the design and preparation of PDI-based nano-(opto)electronic devices with good performance due to the close relationship between the molecular ordering and dimensions of nanostructures and the performance of nanodevices.

Keywords:

• perylenetetracarboxylic diimide
• crown ether
• self-assembly
• nanostructure
• semiconductor

Acknowledgements

Financial support from the Natural Science Foundation of China (20871055), Natural Science Foundation of Shandong Province (ZR2011BZ005) and University of Jinan in China is gratefully acknowledged.