Self-assembly of Goldberg polyhedra from a concave [WV5O11(RCO2)5(SO4)]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 [WV5O11(SO4)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 Gv(1,1) MOPs and two 42-faced Gv(2,0) MOPs were formed using linear or triangular organic ligands, respectively. The largest Goldberg MOP-4, ex-hibits a diameter of 4.3 nm, can trap fullerene C60 molecules in its interstitial cavities.