1,6- And 1,7-Regioisomers of Perylene Tetracarboxylic Dianhydride and Diimide: The Effects of Neutral Bay Substituents on the Electrochemical and Structural Properties

Abstract

The electrochemical and structural properties of a series of 1,6- and 1,7-regioisomers of different sized bay-appended perylene diimides (PDIs) and perylene tetracarboxylic dianhydrides (PTCDs) were assessed. Steric effects by large bay substituents triphenylsilylacetylene and tritylacetylene play a major role in the geometry of the solid and solution states. New triphenylsilylacetyene and 1-pentynyl derivatives were prepared and characterized. Suitable crystals for X-ray analysis of tritylacetylene and n-hexyl compounds illustrated the structural alterations in the bay region. The bulky tritylacetylene appended PDI assumed a nearly planar π-configuration, equivalent to an unsubstituted PDI. In contrast, a slender and less bulky hexyl chain incorporated PDI underwent a significant twisting of the central core of PDI. Neutral and conjugated groups at the bay region of PDI enhanced its reductive capability. In contrast, incorporation of neutral and nonconjugated groups at the bay region slightly diminished the reductive capability of resulting PDI derivative. PTCDs consisting of both bulky and slender groups were reduced significantly more readily in relation to the respective PDIs. Electrochemical reductive properties of selected PDIs and PTCDs were obtained along with optical properties of 1,6- and 1,7-PDIs.

GRAPHICAL ABSTRACT

Keywords:

• Regioisomers of perylene tetracarboxylic dianhydride and diimide
• synthesis
• electrochemical and structural properties
• bay substituents