Accessing the Triplet State in Heavy‐Atom‐Free Perylene Diimides

Previous studies of perylenediimides (PDIs) mostly utilized the lowest singlet excited state S1 . Generation of a triplet excited state (T1 ) in PDIs is important for applications ranging from photodynamic therapy to photovoltaics; however, it remains a formidable task. Herein, we developed a heavy-atom-free strategy to prompt the T1 ←S1 intersystem crossing (ISC) by introducing electron-donating aryl (Ar) groups at the head positions of an electron-deficient perylenediimide (PDI) core. We found that the ISC efficiency increases from 8 to 54 % and then to 86 % by increasing the electron-donating ability of head-substituted aryl groups from phenyl (p-PDI) to methoxyphenyl (MeO-PDI) and then to methylthioxyphenyl (MeS-PDI). By enhancing the intramolecular charge-transfer (ICT) interaction from p-PDI to MeO-PDI, and then to MeS-PDI, singlet oxygen generation via energy-transfer reactions from T1 of PDIs to (3)O2 was demonstrated with the highest yield of up to 80 %. These results provide guidelines for developing new triplet-generating PDIs and related rylene diimides for optoelectronic applications.