Ultralong 20 Milliseconds Charge Separation Lifetime for Photoilluminated Oligophenylenevinylene–Azafullerene Systems

Abstract

AbstractThe synthesis and characterization of oligophenylenevinylene (OPV)–azafullerene (C59N) systems in the form of OPV–C59N donor–acceptor dyad 1 and C59N–OPV–C59N acceptor–donor–acceptor triad 2 is accomplished. Photoinduced electronic interactions between OPV and C59N within 1 and 2 are assessed by UV–vis and photoluminescence. The redox properties of 1 and 2 are investigated, revealing a set of one‐electron oxidation and three one‐electron reduction processes owed to OPV and C59N, respectively. The electrochemical bandgap for 1 and 2 is calculated as 1.44 and 1.53 eV, respectively, and the free energy for the formation of the charge‐separated state for 1 and 2 via the singlet‐excited state of OPV is found negative, proving a thermodynamically favorable the process. Photoexcitation assays are performed in toluene and o‐dichlorobenzene (oDCB) and the reactions are monitored with time‐resolved absorption and emission spectroscopies. Competitive photoinduced energy and electron transfer are identified to occur in both systems, with the former being dominant in 2. Markedly, the charge‐separated state in oDCB exhibits a much longer lifetime compared to that in toluene, reaching 20 ms for 1, the highest ever reported value for fullerene‐based materials. These unprecedented results are rationalized by considering conformational phenomena affecting the charge‐separated state.