Inorganic–Organic Hybrid Polyoxoniobates: Polyoxoniobate Metal Complex Cage and Cage Framework

Abstract

The combination of polyoxoniobates (PONbs) with 3d metal ions, azoles, and organoamines is a general synthetic procedure for making unprecedented PONb metal complex cage materials, including discrete molecular cages and extended cage frameworks. By this method, the first two PONb metal complex cages K₄ @{[Cu₂₉ (OH)₇ (H₂ O)₂ (en)₈ (trz)₂₁ ][Nb₂₄ O₆₇ (OH)₂ (H₂ O)₃ ]₄ } and [Cu(en)₂ ]@{[Cu₂ (en)₂ (trz)₂ ]₆ (Nb₆₈ O₁₈₈ )} have been made. The former exhibits a huge tetrahedral cage with more than 120 metal centers, which is the largest inorganic-organic hybrid PONb known to date. The later shows a large cubic cage, which can act as building blocks for cage-based extended assembly to form a 3D cage framework {[Cu(en)₂ ]@{[Cu₂ (trz)₂ (en)₂ ]₆ [H₁₀ Nb₆₈ O₁₈₈ ]}}. These materials exhibit visible-light-driven photocatalytic H₂ evolution activity and high vapor adsorption capacity. The results hold promise for developing both novel cage materials and largely unexplored inorganic-organic hybrid PONb chemistry.