High-Lying 3¹A_g Dark-State-Mediated Singlet Fission

Singlet fission (SF), the conversion of one high-energy singlet to two low-energy triplets, provides the potential to increase the efficiency of photovoltaic devices. In the SF chromophores with C₂ symmetry, exemplified by polyenes, singlet-to-triplet conversion generally involves a low-lying 2¹A_g dark state, which serves as either a multiexciton (ME) intermediate to promote the SF process or a parasitic trap state to shunt excited-state populations via internal conversion. This controversial behavior calls for a deep understanding of dark-state-related photophysics involving the higher-lying singlet state. However, the optical "dark" and "transient" nature of these dark states and strong correlation feature of double exciton species make their characterization and interpretation challenging from both experimental and computational perspectives. In the present work combining transient spectroscopy and multireference electronic structure calculations (XDW-CASPT2), we addressed a new photophysical model, i.e., a high-lying 3¹A_g dark-state-mediated ultrafast SF process in the benzodipyrrolidone (BDPP) skeleton. Such a 3¹A_g dark state with distinctive double excitation character, described as the ME state, could be populated from the initial 1¹B_u bright state on an ultrafast time scale given the quasi-degeneracy and intersection of the two electronic states. Furthermore, the suitable optical band gap and triplet energy, high triplet yield, and excellent photostability render BDPP a promising SF candidate for photovoltaic devices. These results not only enrich the arsenal of SF materials but also shed new insights into the understanding of dark-state-related photophysics, which could promote the development of new SF-active materials.