Calixarene-Protected Titanium-Oxo Clusters and Their Photocurrent Responses and Photocatalytic Performances.

Three photosensitive tert-butylcalix[n]arene (TBC[n], n = 4, 6, 8)-protected titanium-oxo clusters (TOCs), formulated as [Ti4(μ3-O)2(TBC[4])2(OiPr)4(DEF)2]·DEF (1, TBC[4]-Ti4, DEF = N,N-diethylformamide), [Ti4(μ4-O)TBC[6](OCH3)9]·H2O (2, TBC[6]-Ti4), and [Ti4(μ3-O)2(OiPr)4TBC[8](DEF)2]·DEF (3, TBC[8]-Ti4), were successfully synthesized and characterized. Because of the generation of charge transfer from TBC[n] to the TiO core, the three TBC[n]-decorated TOCs show a broadened visible-light absorption and narrowed optical band gap based on the UV-visible spectra and density functional theory calculations. The corresponding photosensitive electrodes prepared using these three TOCs exhibit stable photocurrent responses. Furthermore, their photocatalytic performances for hydrogen evolution and methylene blue degradation were evaluated, and all of the materials display excellent photocatalytic activity and stability. The calixarene-Ti coordination is therefore an effective strategy to enlarge the visible-light absorption band of Ti-O materials and improve their photoelectric/photocatalytic performances.