Coordination Chemistry Laboratory, Department of Chemistry, Graduate School of Science, The University of Osaka

Creation of Metalloaggregates Based on Metalloligand

The design and creation of homometallic and heterometallic molecular aggregates that possess unique structures and properties have attracted increasing attention. While the most common approach to creating metalloaggregates is the use of functional organic ligands that can bridge two or more metal centers, our efforts have concentrated on the use of thiolato metal complexes as an S-donating metalloligand.

We have shown that [Au(D-Hpen-S)₂]^- (D-H₂pen = D-penicillamine) reacts with Ag^I to produce a photoluminescent Au^I₂Ag^I₂ complex, which further reacts with Cu^II in the presence of Cl^- to produce a metallo-supramolecular compound containing all three coinage metals. Remarkably, this product was found to be composed of monocationic 20-nuclear Au^I₆Ag^I₈Cu^II₆ and monoanionic 21-nuclear Au^I₆Ag^I₉Cu^II₆ supramolecular cages, which are coupled to each other to form an unprecedented 1:1 supramolecular salt with a 'rock-salt'-like lattice structure.

In addition, we have shown that red Au^I₂Ni^II₂, purple Au^I₃Ni^II₂, light blue Au^I₂Ni^II₂, and green Au^I₃Ni^II₂ complexes are created only from [Au(D-pen-S)₂]^3? in combination with Ni^II. It was found that the red complex is triply reversible with the purple, light blue, and green complexes in response to Ni^II:[Au(D-pen-S)₂]^3- stoichiometry and solution pH, accompanied not only by the readily detectable color change, but also by drastic switches in magnetism and chirality.

For detailed information, please see our account:
A. Igashira-Kamiyama & T. Konno, Dalton Trans., 2011, 40, 7249-7263 (Perspective) [link]

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