Titanium(IV) Surface Complexes Bearing Chelating Catecholato Ligands for Enhanced Band-Gap Reduction

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Protonolysis reactions between dimethylamido titanium(IV) catecholate [Ti(CAT)(NMe 2 ) 2 ] 2 and neopentanol or tris( tert -butoxy)silanol gave catecholato-bridged dimers [(Ti(CAT)(OCH 2 t Bu) 2 )(HNMe 2 )] 2 and [Ti(CAT){OSi(O t Bu) 3 } 2 (HNMe 2 ) 2 ] 2, respectively. Analogous reactions using the dimeric dimethylamido titanium(IV) (3,6-di- tert -butyl)catecholate [Ti(CAT t Bu 2 -3,6)(NMe 2 ) 2 ] 2 yielded the monomeric Ti(CAT t Bu 2 -3,6)(OCH 2 t Bu) 2 (HNMe 2 ) 2 and Ti(CAT t Bu 2 -3,6)[OSi(O t Bu) 3 ] 2 (HNMe 2 ) 2 . The neopentoxide complex Ti(CAT t Bu 2 -3,6)(OCH 2 t Bu) 2 (HNMe 2 ) 2 engaged in further protonolysis reactions with Si–OH groups and was consequentially used for grafting onto mesoporous silica KIT-6. Upon immobilization, the surface complex [Ti(CAT t Bu 2 -3,6)(OCH 2 t Bu) 2 (HNMe 2 ) 2 ]@[KIT-6] retained the bidentate chelating geometry of the catecholato ligand. This convergent grafting strategy was compared with a sequential and an aqueous approach, which gave either a mixture of bidentate chelating species with a bipodally anchored Ti(IV) center along with other physisorbed surface species or not clearly identifiable surface species. Extension of the convergent and aqueous approaches to anatase mesoporous titania (m-TiO 2 ) enabled optical and electronic investigations of the corresponding surface species, revealing that the band-gap reduction is more pronounced for the bidentate chelating species (convergent approach) than for that obtained via the aqueous approach. The applied methods include X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and solid-state UV/vis spectroscopy. The energy-level alignment for the surface species from the aqueous approach, calculated from experimental data, accounts for the well-known type II excitation mechanism, whereas the findings indicate a distinct excitation mechanism for the bidentate chelating surface species of the material [Ti(CAT t Bu 2 -3,6)(OCH 2 t Bu) 2 (HNMe 2 ) 2 ]@[m-TiO 2 ].