Divalent Heterometal Doped Titanium-Oxide Cluster Polymers: Structures, Photoresponse, and Photocatalysis

Five cluster polymers based on heterometal-doped titanium-oxide cluster (TOC) monomers are reported. The monomers feature Ti₁₀-oxide cluster cores and are connected to the divalent closed-shell heterometal anchors by salicylate ligands. The Sr²⁺, Ba²⁺, and Pb²⁺ dopants cause the monomers to bind head-to-head and generate linear chains, while the Ca²⁺ and Cd²⁺ lead to head-to-tail connections and zigzag chains. The cluster polymers are responsive to visible-light up to 565 nm and photo-catalytically active in both H₂ evolution and CO₂/epoxide cycloaddition reactions. The photo-absorption, photo-charge separation, and photocatalytic properties of the cluster polymers are dependent on the heterometal dopants in order Cd > Pb > Ba > Sr > Ca. Heterometals serve as the catalytic sites in the cluster polymers, which depending on the contribution of the pCB bottom, facilitate photo-charge separation and interfacial charge transfer, further enhancing catalytic activity. The tunable compositions and topologies of the cluster polymers shown herein may inspire the design and synthesis of more multidimensional functional metal-oxide cluster materials for a variety of applications in the future.