Structures and photophysical performances of (fluoro)salicylate stabilized polyoxo-titanium clusters

We herein report the synthesis and structures of two salicylate-stabilized polyoxo-titanium clusters (PTCs) with and without fluorine, namely, H2[Ti13(μ3-O)7(μ2-O)4(Sal-F)9(OiPr)14] (PTC-95, H2Sal-F = 5-fluorosalicylic acid) and H2[Ti14(μ3-O)8(μ2-O)4(Sal)8(OiPr)18]·HOiPr (PTC-96, H2Sal = salicylic acid). Structural analyses indicated that PTC-95 is a fairly compact structure made up of a quadrangular prism with an appended linear Ti3 cluster and two additional Ti atoms. PTC-96 possesses an arch bridge-shaped structure linked by two Ti4(μ3-O)2 and two Ti3(μ3-O) clusters. Apart from the intrinsic structural features, their diverse photocurrent response properties and photocatalytic activities towards dye degradation were also demonstrated.