Higher fullerenes (≥C76) were selectively extracted from a fullerene mixture obtained from a combustion-based industrial production source by cyclic dimers of β-unsubstituted porphyrin zinc complexes 2C5−2C7 with C5−C7 alkylene spacers as host molecules. Results of single extraction of the fullerene mixture with 2C5−2C7 together with a β-substituted analogue of 2C6 (1C6) and spectroscopic titration of 2C6 and 1C6 with C60, C70, and C96 indicated that the host selectivity toward higher fullerenes is much dependent on the structure of the porphyrin units and the size of the host cavity. Sequential three-stage extraction of the fullerene mixture with the best-behaved 2C6 resulted in considerable enrichment in very rare fullerenes C102−C110 (<0.1 abs %) up to 82 abs % (C76−C114, 99 abs %) (356 nm) of total fullerenes.
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