Triquinoline‐ versus Fullerene‐Based Cycloparaphenylene Ionic Complexes: Comparison of Photoinduced Charge‐Shift Reactions

Abstract

A triquinoline cationic moiety (TQ⋅H+) has recently been designed as a novel molecular unit for supramolecular chemistry. In addition to some useful features, TQ⋅H+ has strong electron‐acceptor properties, which renders the molecular cation a unique element in nanochemistry. TQ⋅H+ is found to form complexes with coronene (COR) and cycloparaphenylene (CPP). In this work, we report a computational study of photoinduced electron transfer in supramolecular complexes TQ⋅H+‐COR, TQ⋅H+⊂[12]CPP and (TQ⋅H+‐COR)⊂[12]CPP. The electron‐transfer rates are estimated by using the semi‐classical approach. The results are compared with the data previously obtained for a structurally similar inclusion complex Li+@C60⊂[10]CPP. In particular, we found a red solvatochromic shift for charge‐shift bands in the TQ⋅H+‐complexes unlike a blueshift showed by Li+@C60⊂[10]CPP. This distinction is explored in terms of electronic and structural features of the systems