Tuning of the stability and energy levels of singlet exciton fission relevant excited states of pentacenes by site-specific substitution

• The stability of pentacene derivatives is discussed based on the frontier orbital energies.
• Electron-withdrawing groups can stabilized pentacene derivatives efficiently.
• Sulfur containing groups are efficient on stabilizing pentacene compounds.
• Singlet fission of pentacenes are exothermic, no mater what kind of substituent is connected.

Pentacene crystals or oligomers undergo efficient singlet exciton fission (SF) after photo-excitation, which is expected to be useful in overcoming the Shockley-Queisser theoretical limit of solar cells. However, pentacenes are extremely unstable in air due to oxidation by oxygen. In this work, we designed a group of pentacene compounds with different substituents at different positions. The energy levels of HOMO and LUMO, which are believed to be closely related to the stability of pentacene, were calculated. The relationship between the molecular structure and the stability was discussed. The driving force for SF was estimated from the difference between the energy of first singlet excited state (E(S1)) and the energy of two triplet excited state (2 × E(T1)) following equation E(S1) − 2E(T1). Strong electron-withdrawing groups can stabilize pentacene compounds significantly, but induce a decrease on the driving force of SF slightly. Electron-donating groups destabilize the pentacene compounds dramatically and hence the introduction of electron donating groups to pentacene is not recommended. TIPS is an ideal group to improve the stability of pentacene compounds. TIPS does not change the driving force of SF significantly. Sulfur containing groups are also efficient on stabilizing pentacene compounds. These groups increase the driving force of SF at ɑ position, and recued the driving force of SF at other positions. The results of this work provide a theoretical ground for rational design of new SF molecules based on pentacenes.

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