Supramolecular Assemblies Based on Organometallic Quinonoid Linkers: A New Class of Coordination Networks

Self-assembly of coordination frameworks exhibiting original architectures is an active area of research. Generally, such assemblies are constructed from organic spacers and transition metals of different geometrical structures. Herein, we report a novel class of supramolecular coordination assemblies with organometallic linkers based on metalated quinonoid and thioquinonoid complexes that serve as spacers. The organometallic ligands are stable and have the general formula [Cp*M(η⁴-benzoquinone)] (o- and p-benzoquinone, Cp*=C₅Me₅, M=Rh, Ir) and [Cp*Ir(η⁴-thiobenzoquinone)] (o- and p-thiobenzoquinone). These units bind through both oxygen or sulfur atoms to metal ions of different coordination geometry, such as CuI, AgI, and PtII, to generate supramolecular coordination networks, with the metalated quinonoid or thioquinonoid linkers acting as backbones and the metal centers as nodes. This novel family of supramolecular assemblies exhibits short π-π and M···M interactions. These results illustrate successfully the role of the organometallic linkers to produce an impressive range of novel supramolecular architectures that hold promise for the development of functional materials.