Mechanism of Ultrafast Triplet Exciton Formation in Single Cocrystals of π-Stacked Electron Donors and Acceptors

Ultrafast triplet formation in donor-acceptor (D-A) systems typically occurs by spin-orbit charge-transfer intersystem crossing (SOCT-ISC), which requires a significant orbital angular momentum change and is thus usually observed when the adjacent πsystems of D and A are orthogonal; however, the results presented here show that subnanosecond triplet formation occurs in a series of D-A cocrystals that form one-dimensional cofacial πstacks. Using ultrafast transient absorption microscopy, photoexcitation of D-A single cocrystals, where D is coronene (Cor) or pyrene (Pyr) and A is N,N-bis(3′-pentyl)-perylene-3,4:9,10-bis(dicarboximide) (C₅PDI) or naphthalene-1,4:5,8-tetracarboxydianhydride (NDA), results in formation of the charge transfer (CT) excitons Cor^•+-C₅PDI^•-, Pyr^•+-C₅PDI^•-, Cor^•+-NDA^•-, and Pyr^•+-NDA^•-in <300 fs, while triplet exciton formation occurs in τ = 125, 106, 484, and 958 ps, respectively. TDDFT calculations show that the SOCT-ISC rates correlate with charge delocalization in the CT exciton state. In addition, time-resolved EPR spectroscopy shows that Cor^•+-C₅PDI^•-and Pyr^•+-C₅PDI^•-recombine to form localized ^3*C₅PDI excitons with zero-field splittings of |D| = 1170 and 1250 MHz, respectively. In contrast, Cor^•+-NDA^•-and Pyr^•+-NDA^•-give triplet excitons in which |D| is only 1240 and 690 MHz, respectively, compared to that of NDA (2091 MHz), which is the lowest energy localized triplet exciton, indicating that the Cor-NDA and Pyr-NDA triplet excitons have significant CT character. These results show that charge delocalization in CT excitons impacts both ultrafast triplet formation as well as the CT character of the resultant triplet states.