Synthesis and Disassembly/Reassembly of Giant Ring‐Shaped Polyoxotungstate Oligomers

Abstract

The disassembly and reassembly of giant molecules are essential processes in controlling the structure and function of biological and artificial systems. In this work, the disassembly and reassembly of a giant ring-shaped polyoxometalate (POM) without isomerization of the monomeric units is reported. The reaction of a hexavacant lacunary POM that is soluble in organic solvents, [P2 W12 O48 ](14-) , with manganese cations gave the giant ring-shaped POM [{γ-P2 W12 O48 Mn4 (C5 H7 O2 )2 (CH3 CO2 )}6 ](42-) . This POM is a hexamer of manganese-substituted {P2 W12 O48 Mn4 } units, and its inner cavity was larger than any of those previously reported for ring-shaped polyoxotungstates. It was disassembled into monomeric units in acetonitrile, and the removal of the capping organic ligands on the manganese cations led to reassembly into a tetrameric ring-shaped POM, [{γ-P2 W12 O48 Mn4 (H2 O)6 }4 (H2 O)4 ](24-) .

FeIII48‐Containing 96‐Tungsto‐16‐Phosphate: Synthesis, Structure, Magnetism and Electrochemistry

“…In 2014 our group reported the 4‐oxalato‐6‐titanium‐containing [Ti 6 (C 2 O 4 ) 4 P 4 W 32 O 124 ] 20− [6c] . In 2016 Mizuno's group reported the 24‐manganese(III)‐containing species [{P 2 W 12 O 48 Mn III 4 (C 5 H 7 O 2 ) 2 (CH 3 CO 2 )} 6 ] 42− (using Mn III (acac) 3 as precursor) [6d] …”

Microporous Cyclic Titanium‐Oxo Clusters with Labile Surface Ligands

“…Self‐assembly is a versatile approach to organize building blocks of specific functionalities into complex supramolecules in a prescribed manner . The stacking of macrocyclic molecules often results in porous tubular structures, creating both intrinsic and extrinsic porosity, which has however not been achieved in the system of cyclic TOCs .…”

Calix[n]arene-based polyradicals: enhancing ferromagnetism by avoiding edge effects

“…It is obvious that the most straightforward manner to remove edge effects in finite systems is by generating a ring-like structure. Inorganic chemistry has provided extraordinary relevant examples, [23][24][25][26][27][28][29][30][31][32][33] but the localized nature of the magnetic centres and the presence of necessary bridging ligands often result in low-spin ground states and weak to moderate antiferromagnetic interactions. In organic chemistry, on the other hand, remarkable examples of ring-like molecules [34][35][36][37][38][39][40][41][42][43][44] in the field of host-guest and supramolecular chemistry have been achieved.…”