Photochemical electron transfer though the interface of hybrid films of titania nano-sheets and mono-dispersed spherical mesoporous silica particles

Photochemical Electron Transfer (ET) between an organic dye, the porphyrin derivative TMPyP, and an electron acceptor, methyl viologen MV2+, have been investigated at the interface of two different inorganic films, i.e., layered titania nano-sheets (TNS) and a monolayer film of spherical and mono-dispersed mesoporous silica (sMPS) particles (ca. 0.5 μm). TMPyP ions were intercalated within the sMPS nano-cavities to form (TMPyP–sMPS) while MV2+ ions were intercalated into the TNS interlayers to form (MV2+–TNS). The (TMPyP–sMPS) and (MV2+–TNS) films were then stacked on a silica substrate in this order to form a (MV2+–TNS)/(TMPyP–sMPS) film and, upon UV light irradiation, ET could be induced. However, when this film was stacked inversely, i.e., for the (TMPyP–sMPS)/(MV2+–TNS) films on a silica substrate, no photoinduced ET were observed. Interestingly, however, even for this photo-inactive inversely stacked film, ET could be generated by inserting a gold vapor-deposited layer between the (MV2+–TNS) and (TMPyP–sMPS) films. The conjugation conditions at the interface of the inversely stacked (TMPyP–sMPS)/(MV2+–TNS) hybrid film were, thus, confirmed to strongly affect the photoinduced electron transfers and their efficiencies.