Heterometallic Ce^IV/ V^V Oxo Clusters with Adjustable Catalytic Reactivities

Heterometallic Ce^IV/M oxo clusters are underexplored yet and can benefit from synergistic properties from combining cerium and other metal cations to produce efficient redox catalysts. Herein, we designed and synthesized a series of new Ce₁₂V₆ oxo clusters with different capping ligands: Ce₁₂V₆-SO₄, Ce₁₂V₆-OTs (OTs: toluenesulfonic acid), and Ce₁₂V₆-NBSA (NBSA: nitrobenzenesulfonic acid). Single crystal X-ray diffraction (SCXRD) for all three structures reveals a Ce₁₂V₆ cubane core formulated [Ce₁₂(VO)₆O₂₄]¹⁸⁺ with cerium on the edges of the cube, vanadyl capping the faces, and sulfate on the corners. While infrared spectroscopy (IR), ultraviolet–visible spectroscopy (UV–vis), electrospray ionization mass spectrometry (ESI-MS), and proton nuclear magnetic resonance (¹H NMR) proved the successful coordination of the organic ligands to the Ce₁₂V₆ core, liquid phase ⁵¹V NMR and small-angle X-ray scattering (SAXS) confirmed the integrity of the clusters in the organic solutions. Furthermore, functionalization of the Ce₁₂V₆ core with organic ligands both provides increased solubility in term of homogeneous application and introduces porosity to the assemblies of Ce₁₂V₆-OTs and Ce₁₂V₆-NBSA in term of heterogeneous application, thus allowing more catalytic sites to be accessible and improving reactivity as compared to the nonporous and less soluble Ce₁₂V₆-SO₄. Meanwhile, the coordinated ligands also influenced the electronic environment of the catalytic sites, in turn affecting the reactivity of the cluster, which we probed by the selective oxidation of 2-chloroethyl ethyl sulfide (CEES). This work provides a strategy to make full use of the catalytic sites within a class of inorganic sulfate capped clusters via organic ligand introduction.