Metalloporphyrin hosts for supramolecular chemistry of fullerenes.
This paper is a tutorial review of the host-guest chemistry of fullerenes and metalloporphyrin. Among various host molecules for fullerenes, cyclic hosts composed of metalloporphyrin moieties possess one of the highest affinities toward fullerenes, which can be widely tuned simply by changing the central metal ions of the porphyrin moieties. Inclusion of fullerenes occurs not only by van der Waals interactions but also, in some cases, via pi-electronic charge-transfer from the host metalloporphyrin moieties to the guest fullerenes. Fullerenes such as C(120), upon inclusion with cyclic metalloporphyrin dimers, show an oscillatory motion within the host cavity, whose frequency reflects the solvation/desolvation dynamics of the fullerenes. A molecularly engineered metalloporphyrin host with a self-assembling capability allows a guest-directed formation of a supramolecular peapod, where included fullerenes, as peas, are aligned along the self-assembled metalloporphyrin nanotube, as a pod. Furthermore, certain metalloporphyrin hosts are applicable to the selective extraction of low-abundance higher fullerenes from an industrial production source and also allow spectroscopic discrimination of chiral fullerenes.
Tashiro
Kentaro
K
Department of Chemistry and Biotechnology, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan. tashiro@macro.t.u-tokyo.ac.jp
Aida
Takuzo
T