Excimer Formation Inhibits the Intramolecular Singlet Fission Dynamics: Systematic Tilting of Pentacene Dimers by Linking Positions

Abstract

The role of excimer formation in inhibiting or enhancing the efficiency of the intramolecular singlet fission (iSF) process has been a subject of recent debate. Here, we investigated the effect of excimer formation on iSF dynamics by modifying its configuration by connecting pentacenes at various positions. Hence, pentacene dimers having slip-stacked (2,2′ BP, J-type), oblique (2,6′ BP), and facial (6,6′ BP, H-type) configurations were synthesized by covalently linking pentacenes at positions 2,2′, 2,6′, and 6,6′, respectively, with an ethynyl bridge, and their ultrafast excited-state relaxation dynamics were characterized. Femtosecond time-resolved transient absorption spectra revealed that the efficiency of iSF dynamics decreased from slip-stacked (182%) to oblique configuration (97%),whereas in the 6,6′ BP with facial configuration, strong electronic coupling led to the formation of excimers that decayed nonradiatively without formation of correlated triplet pairs. These studies reveal the formation of excimers by strong intrapentacene electronic coupling upon ultrafast excitation, preventing the efficient iSF process.