How Do Defects in Carbon Nanostructures Regulate the Photoinduced Electron Transfer Processes? The Case of Phenine Nanotubes

Photoinduced electron transfer is studied in a series of inclusion complexes of structurally modified phenine nanotubes (pNT) with C(70) using the TD‐DFT method. Analysis of electronic properties of the complexes shows that the electron transfer is infeasible in pNT_4d⊃C(70) built on the tetrameric array of [6]cyclo‐meta‐phenylene ([6]CMP) units. However, replacing one or more [6]CMP units with a coronene moiety enables electron transfer from pNT to C(70). The generation of the charge separated states from the lowest locally excited states occurs on a sub‐nanosecond time scale. Depending on the number of the [6]CMP units, the charge recombination rate varies from 1.8 ⋅ 10(7) to 3.1 ⋅ 10(2) s(−1), i. e., five orders of magnitude.