Electron Transfer in Coordination and Organometallic Chemistry, JPHC Information
Photoinduced electron transfer Information
Simple d1-d9 transition metal complexes
- Colour arises from d-d transitions
- Excited states very short lived
- Decay by internal conversion, a sequence of complicated steps that convert electronic energy into thermal energy
The [Ru(bpy)32+ chromophore
- Tris(bipyridine)ruthenium(II) chloride, [Ru(bpy)32+
- Ru2+ and three neutral 2,2'-bipyridine (bpy) bidentate ligands
- Absorbs a photon and undergoes metal-to-ligand charge transfer
- Excitation from [RuII(bpy)32+ to [RuIII(bpy)2(bpy−)]2+
The water splitting reaction
- Water splitting
- Photocatalytic water splitting
- Paraquat dication, AKA dimethylviologen, MV2+
Mixed-valence compounds Information
- Inner sphere electron transfer – electron(s) transferred from one metal atom to another via a bridging ligand
- Mixed valence compounds – contain the same element in two different oxidation states
Magnetite
- Magnetite, Fe3O4 is a mixed valence iron oxide, containing both Fe2+ and Fe3+
- Its electrical conductivity is a million times greater than isovalent Fe2O3, which contains only Fe3+
Prussian blue
- Prussian blue, , also contains both Fe2+ and Fe3+
- A three-dimensional coordination network of octahedral low-spin {FeII(CN)6} and high-spin {FeIII(NC)6} nodes
- Its intense blue colour is due to electron transfer from Fe2+ to Fe3+
The Robin-Day Classification
The Creutz-Taube ion
Electron Transfer in Coordination and Organometallic Chemistry, JPHC Information
Photoinduced electron transfer Information
Simple d1-d9 transition metal complexes
- Colour arises from d-d transitions
- Excited states very short lived
- Decay by internal conversion, a sequence of complicated steps that convert electronic energy into thermal energy
The [Ru(bpy)32+ chromophore
- Tris(bipyridine)ruthenium(II) chloride, [Ru(bpy)32+
- Ru2+ and three neutral 2,2'-bipyridine (bpy) bidentate ligands
- Absorbs a photon and undergoes metal-to-ligand charge transfer
- Excitation from [RuII(bpy)32+ to [RuIII(bpy)2(bpy−)]2+
The water splitting reaction
- Water splitting
- Photocatalytic water splitting
- Paraquat dication, AKA dimethylviologen, MV2+
Mixed-valence compounds Information
- Inner sphere electron transfer – electron(s) transferred from one metal atom to another via a bridging ligand
- Mixed valence compounds – contain the same element in two different oxidation states
Magnetite
- Magnetite, Fe3O4 is a mixed valence iron oxide, containing both Fe2+ and Fe3+
- Its electrical conductivity is a million times greater than isovalent Fe2O3, which contains only Fe3+
Prussian blue
- Prussian blue, , also contains both Fe2+ and Fe3+
- A three-dimensional coordination network of octahedral low-spin {FeII(CN)6} and high-spin {FeIII(NC)6} nodes
- Its intense blue colour is due to electron transfer from Fe2+ to Fe3+
The Robin-Day Classification
The Creutz-Taube ion