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.