Direct, Mediated, and Delayed Intramolecular Singlet Fission Mechanism in Donor–Acceptor Copolymers

Donor-acceptor (D-A) extended copolymers have shown great potential to be exploited for intramolecular singlet fission (iSF) because of their modular tunability and intrinsic ability to incorporate low-lying charge-transfer (CT) and a triplet-pair ( 1 TT) states. While the SF mechanism has been widely debated in homo- and heterodimers, little is known about the singlet splitting process in A-D-A copolymer trimers. Unlike traditional two-site SF, the process of iSF in D-A copolymers involves three molecular units consisting of two A's and one D following an A-D-A polymeric chain. This scenario is, therefore, different from that of the homodimer analogues in terms of which states (if any) may drive the SF process. In this work, we identify how singlet splitting occurs in prototypical iSF D-A copolymer poly(benzodithiophene- al -thiophene-1,1-dioxide) by means of wave packet propagations on the basis of the linear vibronic coupling model Hamiltonian. Our results reveal that three different mechanisms drive the S 1 → 1 TT population transfer via antisymmetric and symmetric vibrational motion, including two favorable mechanisms of direct and mediated interactions, as well as a parasitic decay pathway that potentially delays the process. Remarkably, we uncover the interplay between an upper state of marked multiexcitonic character and a low-lying CT state in balancing the splitting efficiency, which anticipates their major role in defining future guidelines for the molecular design of D-A copolymers for iSF.