Self-Assembly of Goldberg Polyhedra from a Concave [WV ₅ O ₁₁ (RCO ₂ ) ₅ (SO ₄ )] ^3- Building Block with 5-Fold Symmetry

Nanoscale regular polyhedra with icosahedral symmetry exist naturally as exemplified by virus capsids and fullerenes. Nevertheless, their generation by supramolecular chemistry through the linking of 5-fold symmetry vertices remains unmet because of the absence of 5-fold symmetry building blocks with the requisite geometric features. This situation contrasts with that of tetrahedral and octahedral symmetry metal-organic polyhedra (MOPs), for which appropriate triangular and square molecular building blocks (MBBs) that can serve as vertices or faces are readily available. Herein, we report isolation of a pentagonal [WV ₅ O ₁₁ (SO ₄ ) ₆ ] ^8- cluster and reveal its utility to afford the first four examples of nanoscale Goldberg MOPs, based upon 5-fold MBBs. Two 32-faced G _v (1,1) MOPs and two 42-faced G _v (2,0) MOPs were formed using linear or triangular organic ligands, respectively. The largest Goldberg MOP-4, exhibits a diameter of 4.3 nm, can trap fullerene C ₆₀ molecules in its interstitial cavities.