Near-Infrared-Responsive Hydrocarbons Designed by p-Extension of Indeno[1,2,3,4-pgra]perylene at the 1,2,12-Positions

The relationship between the overall electronic structure of pi-conjugated molecules and the arrangement of their constituent elements is of fundamental importance. Establishing rational design guidelines for conjugated hydrocarbons with narrow HOMO-LUMO gaps is useful to develop near-infrared (NIR) responsive dyes and redox-active materials. This study describes the synthesis and properties of three conjugated hydrocarbons, i. e., an indenonaphthoperylene, an indenoterrylene, and a diindenoterrylene. These molecules exhibit NIR absorption despite the absence of significant antiaromaticity and diradical character. Notably, the indenonaphthoperylene exhibits red-to-NIR emission in the 620-850 nm region. The indenoterrylene and the diindenoterrylene exhibit NIR absorption tailing to 870 and 940 nm, respectively. Moreover, the effect of the pi-extension of indenoperylene is disclosed in order to propose guidelines for achieving a narrow HOMO-LUMO gap with negligible antiaromaticity and diradical character.