Self‐Assembly of a Phosphate‐Centered Polyoxo‐Titanium Cluster: Discovery of the Heteroatom Keggin Family

Over the past 200 years, the most famous and important heteroatom Keggin architecture in polyoxometalates has only been synthesized with Mo, W, V, or Nb. Now, the self‐assembly of two phosphate (PO₄^3?)‐centered polyoxo‐titanium clusters (PTCs) is presented, PTi₁₆ and PTi₁₂, which display classic heteroatom Keggin and its trivacant structures, respectively. Because Ti^IV has lower oxidate state and larger ionic radius than Mo^VI, W^VI, V^V, and Nb^V, additional Ti^IV centres in these PTCs are used to stabilize the resultant heteroatom Keggin structures, as demonstrated by the cooresponding theoretical calculation results. These photoactive PTCs can be utilized as efficient photocatalysts for highly selective CO₂‐to‐HCOOH conversion. This new discovery indicates that the classic heteroatom Keggin family can be assembled with Ti, thus opening a research avenue for the development of PTC chemistry.