A geometric constraint, the head-to-tail exclusion rule, may be the basis for the isolated-pentagon rule in fullerenes with more than 60 vertices.

Abstract

Carbon atoms self-assemble into the famous soccer-ball shaped Buckminsterfullerene (C(60)), the smallest fullerene cage that obeys the isolated-pentagon rule (IPR). Carbon atoms self-assemble into larger (n > 60 vertices) empty cages as well-but only the few that obey the IPR-and at least 1 small fullerene (n <or= 60) with adjacent pentagons. Clathrin protein also self-assembles into small fullerene cages with adjacent pentagons, but just a few of those. We asked why carbon atoms and clathrin proteins self-assembled into just those IPR and small cage isomers. In answer, we described a geometric constraint-the head-to-tail exclusion rule-that permits self-assembly of just the following fullerene cages: among the 5,769 possible small cages (n <or= 60 vertices) with adjacent pentagons, only 15; the soccer ball (n = 60); and among the 216,739 large cages with 60 < n <or= 84 vertices, only the 50 IPR ones. The last finding was a complete surprise. Here, by showing that the largest permitted fullerene with adjacent pentagons is one with 60 vertices and a ring of interleaved hexagons and pentagon pairs, we prove that for all n > 60, the head-to-tail exclusion rule permits only (and all) fullerene cages and nanotubes that obey the IPR. We therefore suggest that self-assembly that obeys the IPR may be explained by the head-to-tail exclusion rule, a geometric constraint.