Ligand-Protecting Strategy for the Controlled Construction of Multinuclear Copper Cores within a Ring-Shaped...

The ring-shaped polyoxometalate (POM) [P₈W₄₈O₁₈₄]^40- contains a large cavity and is an attractive inorganic multidentate ligand for accumulating metal cations. Until now, several multinuclear metal cores are constructed within the {P₈W₄₈} framework in aqueous solvents. However, it is still challenging to control the number and arrangement of introduced metal cations because of the numerous coordination sites inside the {P₈W₄₈} framework. In this study, we developed a novel approach for the selective synthesis of several multinuclear copper-containing ring-shaped POMs in organic solvents using methoxy groups as organic protecting ligands for the reactive coordination sites. Reacting a tetra-n-butylammonium (TBA) salt of [P₈W₄₈O₁₈₄]^40- (P8W48) with 4 and 8 equiv of copper(II) acetate in the presence of methanol (MeOH), tetra- and octacopper cores were incorporated into the cavity to form TBA₁₁H₁₃[Cu₄(H₂O)₄P₈W₄₈O₁₇₆(OCH₃)₈]·28H₂O·3CH₃NO₂ (Cu4) and TBA₁₄H₂[Cu₈(H₂O)₁₂P₈W₄₈O₁₇₆(OCH₃)₈]·24H₂O·CH₃CN (Cu8), respectively. For both structures, methoxy groups served as protecting ligands and temporarily inactivated vacant coordination sites. Without MeOH, dodeca- and hexadecacopper cores were constructed inside the cavity to form TBA₁₄H₂[Cu₁₂(H₂O)₁₆P₈W₄₈O₁₈₄]·4H₂O (Cu12) and TBA₁₆H₈[Cu₁₆(OH)₁₆(H₂O)₄P₈W₄₈O₁₈₄]·12H₂O·C₃H₆O (Cu16), respectively. The arrangement of copper ions on the same {P₂W₁₂} units could be controlled by the input number of copper ions. Moreover, all four POMs could be synthesized from P8W48 by the stepwise addition of 4 equiv of copper(II) acetate, clarifying the introduction process.