Orthogonal Functionalization of Cyclopenta[<i>hi</i>]aceanthrylenes

A synthetic strategy to prepare 2,7- or 4,9-functionalized cyclopenta[<i>hi</i>]aceanthrylenes that are capable of Suzuki cross-coupling reactions is demonstrated. This method has been utilized to create a series of thiophene derivatized compounds that were subsequently used to investigate the role of substitution pattern on the photophysical and electronic properties of cyclopenta[<i>hi</i>]aceanthrylenes. The orthogonal functionalization provides access to unique substitution patterns (e.g., cruciform-like architectures) and materials with small optical band gaps (1.22–1.97 eV)