Synthesis of Geometrically Well-Defined Covalent Acene Dimers for Mechanistic Exploration of Singlet Fission

We report the first synthesis of norbornyl-bridged acene dimers (2 and 3) with well-defined and controlled spatial relationships between the acene chromophore subunits. We employ a modular 2-D strategy wherein the central module, common to all our compounds, is a norbornyl moiety. The acenes are attached to this module using the Diels–Alder reaction, which also forms one of the acene rings. Manipulation of the Diels–Alder adducts provides the desired geometrically defined bis-acenes. The modular nature of this synthesis affords flexibility and allows for the preparation of a variety of acene dimers, including functionalized tetracene dimers.