Self-Assembly of Goldberg Polyhedra from a Concave [WV₅O₁₁(RCO₂)₅(SO₄)]^3– Building Block with 5-Fold Symmetry

Abstract

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.

Equi–size nesting of Platonic and Archimedean metal–organic polyhedra into a twin capsid

“…4c, d). Thus, it can be concluded that an ion-exchange process occurred between the cationic dyes and [NH 2 Me 2 ] + cations 37 .…”

“…Given that the inner and outer cages in 1 are independent and assembled by supramolecular interactions, we try to obtain their discrete objects. On the basis of our research experience about polyoxovanadate-based MOPs 37,38 , the inner cage, (NH 2 Me 2 ) 12 [(V 5 O 9 Cl) 6 (TATB) 8 ]•(CH 3 OH) 4 (1a), was successfully isolated in high yield by reaction of VCl 4 , VOSO 4 , and H 3 TATB in DMF:CH 3 CN:CH 3 OH (4:1:1 v/v) at 130°C for 48 h (see the "Methods" section for a detailed synthesis procedure). Singe-crystal diffraction revealed that 1a crystallized in cubic system with space group Fm-3m (Supplementary Table 1).…”

A Giant Dy76 Cluster: A Fused Bi‐Nanopillar Structural Model for Lanthanide Clusters

“…We analyzed the peaks and did not find the molecular ion peak of the cluster.The difference between 3a-3c and 3a' '-3c' ',corresponding to Dy 76 in mixed solutions of CH 3 Thev ariable-temperature magnetic susceptibilities of Dy 76 and Dy 48 were measured from 2-300 K. As shown in Figure S4, the c m T values are 1032.3 cm 3 Kmol À1 for Dy 76 and 650.6 cm 3 Kmol À1 for Dy 48 at 300 K, which are close to the expected values of 1076.9 and 680.16 cm 3 Kmol À1 for 76 and 48 isolated Dy III ions with atotal angular momentum M J = 15/ 2a nd aL andØ g factor g = 4/3. [16] When the temperature was reduced from 300 to 100 K, the c m T values of Dy 76 and Dy 48 slightly decreased, and the values reached 1000.1 and 629.4 cm 3 Kmol À1 ,r espectively,a t1 00 K. Upon further lowering the temperature,t he c m T values abruptly decreased to minimum values of 592.5 and 363.6 cm 3 Kmol À1 for Dy 76 and Dy 48 ,respectively,at2K. These findings indicate the presence of weak antiferromagnetic interactions.…”

From Octahedral to Icosahedral Metal–Organic Polyhedra Assembled from Two Types of Polyoxovanadate Clusters

“…The4 -c metal SBU has been used earlier to construct MOPs by Zaworotkos, Schmittsand our group. [9] In addition, the double SBUs( 4-c and 5-c SBUs) are found in one MOP for the first time. [9] In addition, the double SBUs( 4-c and 5-c SBUs) are found in one MOP for the first time.…”