Planarity and Length of the Bridge Control Rate and Efficiency of Intramolecular Singlet Fission in Pentacene Dimers.

Singlet fission (SF) improves the power conversion efficiency of optoelectronic devices by converting high-energy photons into two triplet excitons. SF dynamics and efficiency (Φ) are controlled by various factors. Here, the effect of planarity and length of the bridge in pentacene dimers on the intramolecular SF (iSF) process was investigated by synthesizing the dimers connected by bridges having fluorene (-, planar), methyl-substituted biphenyl (-, twisted), and diphenyl acetylene (-, longer) groups and characterizing their excited-state relaxation dynamics using nanosecond and femtosecond pump-probe spectroscopy. Transient absorption studies reveal that iSF dynamics of - having a planar bridge are ∼787 times faster (187 ps) and exhibit higher Φ (198%) by feasible electronic coupling, compared to - possessing a twisted bridge showing a low Φ of ∼16%. However compared to -, iSF dynamics of - with an increase of bridge length are slower by an order (1.09 ns) and show comparable Φ of 185% through extended conjugation. Thus, the planarity and length of the bridge in pentacene dimers control the rate and efficiency of the iSF process.