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

• Published in: Chemistry : a European journal Vol. 27; no. 65; pp. 16117 - 16120
• Main Authors: Wang, Di, Chen, Guang‐Hui, Yuan, Lv‐Bing, Feng, Cheng‐Cheng, Zhang, Jian, Zhang, Lei
• Format: Journal Article
• Language: English
• Published: 22.11.2021
• Subjects: cluster compounds; heterometallic complexes; macrocycles; structure-activity relationships; tin
• DOI: 10.1002/chem.202103226
• ISSN: 0947-6539; 1521-3765

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 Sn2Ti6 and SnIn5Ti6 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. Unprecedented macrocyclic inorganic tin‐containing oxo clusters have been successfully constructed, whose configuration, host‐guest behaviors, supramolecular packing and catalytic activities are significantly modulated by the introduction of heterometals with different ionic radius.