Acquiring Charge‐Transfer‐Featured Single‐Molecule Ultralong Organic Room Temperature Phosphorescence via Through‐Space Electronic Coupling

Although long-lived triplet charge-transfer (3 CT) state with high energy level has gained significant attention, the development of organic small molecules capable of achieving such states remains a major challenge. Herein, by using the through-space electronic coupling effect, we have developed a compound, namely NIC-DMAC, which has a long-lived 3 CT state at the single-molecule level with a lifetime of 210 ms and a high energy level of up to 2.50 eV. Through a combination of experimental and computational approaches, we have elucidated the photophysical processes of NIC-DMAC, which involve sequential transitions from the first singlet excited state (S1 ) that shows a 1 CT character to the first triplet excited state (T1 ) that exhibits a local excited state feature (3 LE), and then to the second triplet excited state (T2 ) that shows a 3 CT character (i.e., S1 (1 CT)→T1 (3 LE)→T2 (3 CT)). The long lifetime and high energy level of its 3 CT state have enabled NIC-DMAC as an initiator for photocuring in double patterning applications.