Interfacial Dynamics within an Organic Chromophore-Based Water Oxidation Molecular Assembly.
Zachary A MorsethToan V PhoMatthew V SheridanThomas J MeyerKirk S SchanzeJohn R ReynoldsJohn M PapanikolasPublished in: ACS applied materials & interfaces (2017)
Photoinduced electron injection, intra-assembly electron transfer, and back-electron transfer are investigated in a single-site molecular assembly formed by covalently linking a phosphonated terthiophene (T3) chromophore to a Ru(terpyridine)(bipyridine)(L)2+ (L = MeCN or H2O) water oxidation catalyst adsorbed onto a mesoporous metal-oxide (MOx) film. Density functional theory calculations of the T3-trpy-Ru-L assembly indicate that the molecular components are strongly coupled with enhanced low-energy absorptions owing to the presence of an intraligand charge transfer (ILCT) transition between the T3 and trpy moieties. Ultrafast spectroscopy of the MOx//T3-trpy-Ru-L assemblies reveals that excitation of the surface-bound T3 chromophore results in ps-ns electron injection into the metal-oxide conduction band. Electron injection is followed by rapid (<35 ps) intra-assembly electron transfer from the RuII catalyst to regenerate the T3 chromophore with subsequent back-electron transfer on the microsecond time scale.
Keyphrases
- electron transfer
- density functional theory
- molecular dynamics
- room temperature
- energy transfer
- reduced graphene oxide
- highly efficient
- ultrasound guided
- ionic liquid
- molecular dynamics simulations
- high resolution
- metal organic framework
- mass spectrometry
- loop mediated isothermal amplification
- oxide nanoparticles