Two-Photon Absorption in Pentacene Dimers: The Importance of the Spacer Using Upconversion as an Indirect Route to Singlet Fission

In this proof of concept study, we show that intramolecular singlet fission (iSF) can be initiated from a singlet excited state accessed by two-photon absorption, rather than through a traditional route of direct one-photon excitation (OPE). Thus, iSF in pentacene dimers 2 and 3 is enabled through NIR irradiation at 775 nm, a wavelength where neither dimer exhibits linear absorption of light. The adamantyl and meta-phenylene spacers 2 and 3, respectively, are designed to feature superimposable geometries, which establishes that the electronic coupling between the two pentacenes is the significant structural feature that dictates iSF efficiency.