We have prepared nickel complexes and freebases of cyclic porphyrin dimers linked by butadiyne or phenothiazine groups. The porphyrin dimers have self-assembling pyridyl groups at the opposite meso positions and include fullerenes such as C60, PCBM, C70, and Li+@C60 to give π-complexes. In particular, the phenothiazine-bridged cyclic porphyrin dimers exhibit notable high affinities toward C60 (K assoc > 106M−1) and C70 (K assoc > 107M−1). In the crystal structures, the π-complexes of C60 and PCBM within the butadiyne-bridged nickel dimer and the phenothiazine-bridged freebase dimer afford self-assembled porphyrin nanotubes containing the linear arrays of the fullerenes. These self-assemblies are formed by the C-H · · · N hydrogen bonds and π-π interactions of the meso pyridyl groups. On the other hand, the π-complexes of C60 and C70 within the butadiyne-bridged freebase dimer gave the zigzag chains of the fullerenes through van der Waals contacts with each fullerene. These well-ordered C60 arrays yield high electron mobilities (Σμ > 10−1 cm2V−1s−1). The π-complexes of C60 and Li+@C60 within the butadiyne-bridged dimers perform photoinduced electron transfer from the porphyrins to the fullerenes to give the CS states. The π-complexes of Li+@C60 with the butadiyne-bridged dimers afford the CS states of remarkably long lifetimes reaching submillisecond order.
!!!All Science Journal Classification (ASJC) codes
- 化学 (全般)