Macrocyclic Inorganic Tin‐Containing Oxo Clusters: Heterometallic Strategy for Configuration and Catalytic Activity Modulation

Abstract

In this work, the first examples of inorganic macrocyclic tin-oxo clusters which are stabilized by sulfate ligands are reported. As determined by X-ray diffraction and photoelectron spectroscopy analyses, the prepared inorganic Sn₁₀ -oxo cluster displays interesting mixed valence behaviors, with 8 Sn⁴⁺ located at the cyclic skeleton and two Sn²⁺ encapsulated in the center. When further introducing Ti⁴⁺ and In³⁺ ions to the synthetic systems, heterometallic Sn₂ Ti₆ and SnIn₅ Ti₆ complexes with Ti₆ (SO₄ )₉ and SnIn₅ (SO₄ )₁₂ macrocyclic skeletons were prepared whose configuration and packing models were affected by the ionic radius of incorporated metals. Moreover, comparative CO₂ reduction experiments confirm that such heterometallic composition can significantly improve the catalytic activities of these inorganic macrocyclic oxo clusters. This work represents a milestone in constructing inorganic tin complexes and also macrocyclic metal oxo clusters with tunable configurations and properties.