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 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 C60 molecules in its interstitial cavities.

Design and synthesis of metal–organic polyhedra (MOPs) with targeted geometries from predetermined secondary building units (SBUs) is a long‐standing challenge in chemistry and material science. Theoretical prediction shows that there are 6 possible polyhedra from the 3‐coordinated, 4‐coordinated octahedron ((3,4)‐c octahedron) to (3,5)‐c icosahedron with minimal transitivity (simplest possible). Except for one missing polyhedron (mtr) due to the unfavorable angles, we report five MOPs based on these structures, including an octahedral (3,4)‐c VMOP‐21 (rdo), an icosahedral (3,5)‐c VMOP‐25 (trc), and three intermediate derived trinodal (3,4,5)‐c VMOP‐22–24 (ghm, hmg, xum). Remarkably, all these MOPs obey the minimal transitivity principle and are consistent with geometrical predictions.

Hybridm aterials have obtained well-deserved attention for energy storage devices, because they show high capacitances and high energy densitiesi nduced by the synergistic effect between complementary components. Polyoxometalate-based metal-organic frameworks( POMOFs) possess the abundantr edox-active sites and ordered structures of polyoxometalates (POMs) and metal-organic frameworks (MOFs), respectively.Here, an asymmetric supercapacitor (ASC) NENU-5/PPy/60//FeMo/Cw as fabricated in which both its electrodes are prepared from POMOFp recursors. A typical POMOF material, NENU-5, was first connected with polypyrrole (PPy) through electrodeposition to form the cathode materialN ENU-5/PPy. Another representative POMOFs material,P Mo 12 @MIL-100, was carbonizedt oo btain the anode material FeMo/C. Cathode NENU-5/PPye xhibited an extraordinary capacitance of 508.62 Fg À1 (areal capacitance:2 034.51 mF cm À2 ). In addition, anode FeMo/C shows excellent cyclic stabilitya ttributed to its unique structure. Finally,b enefiting from the outstanding capacitances and structuralm erits of the anode and cathode, assembled asymmetrics upercapacitor NENU-5/PPy/60//FeMo/C achieves an energy density of 1.12 mWh cm À3 at ap ower density output of 27.78 mW cm À3 ,a sw ell as an otable life of 10 000 cycles with an capacity retention of 80.62 %. Thus, the unique ASC is strongly competitive in high capacitance, long cycle life, and highe nergy-required energy storaged evices.Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Inspired by the structures of virus capsids, chemists have long pursued the synthesis of their artificial molecular counterparts through self-assembly. Building nanoscale hierarchical structures to simulate double-shell virus capsids is believed to be a daunting challenge in supramolecular chemistry. Here, we report a double-shell cage wherein two independent metal-organic polyhedra featuring Platonic and Archimedean solids are nested together. The inner (3.2 nm) and outer (3.3 nm) shells do not follow the traditional "small vs. large" pattern, but are basically of the same size. Furthermore, the assembly of the inner and outer shells is based on supramolecular recognition, a behavior analogous to the assembly principle found in double-shell viruses. These two unique nested characteristics provide a new model for Matryoshka-type assemblies. The inner cage can be isolated individually and proves to be a potential molecular receptor to selectively trap guest molecules.

A new supramolecular nanocage, VMOP‐31, based on polyoxovanadate as the molecular building block, has been designed and synthesized under solvothermal conditions. The structure of VMOP‐31 was determined by single‐crystal and powder X‐ray diffraction, FTIR spectroscopy, UV/Vis spectrophotometry, and thermogravimetric analysis. The nanocage exhibits octahedral geometry and is constructed of six {V5O9Cl(COO)4} at the vertices and eight TATB (H3TATB=4,4′,4′′‐(s‐triazine‐2,4,6‐triyl)tribenzoic acid) ligands on the faces. Impressively, VMOP‐31 exhibited high efficiency in the inhibition of cell growth of solid tumors, such as human liver cancer cells SMMC‐7721, and superior results in the treatment of liver tumors in mice compared with classic cisplatin. Detailed studies revealed that the potential mechanism of cell death induced by VMOP‐31 involves cell cycle arrests, DNA damage, and subsequent apoptosis. Moreover, VMOP‐31 exhibited negligible side effects in the mice compared with cisplatin. To the best of our knowledge, VMOP‐31 is the first supramolecular nanocage applied to hepatic tumors both in vitro and in vivo.

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Two polyoxovanadate-based metal-organic polyhedra with octahedral (oct) and rhombic dodecahedral (rdo) geometries have been constructed from a concave molecular building block and linear and triangular carboxylate ligands. VMOP-7 is constructed from {V5O9Cl} SBU and a linear anthracene-9,10-dicarboxylic acid ligand in which all the anthracene groups are perpendicular to the edge of the octahedron. Such an arrangement mode can effectively reduce the steric hindrance between ligands. VMOP-8 is constructed from {V5O9Cl} SBU and a triangular biphenyl 3,4,5-tricarboxylate ligand, which exhibits an elongated rhombic dodecahedral configuration due to the geometry of the ligand. Furthermore, VMOP-8 can serve as a heterogeneous catalyst and exhibits efficient and common catalytic activity for oxidative desulfurization.

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