tris(bipyridine)ruthenium(II) chloride

Tris(bipyridine)ruthenium(II) chloride is the chloride salt coordination complex with the formula u(bpy)₃l₂. This polypyridine complex is a red crystalline salt obtained as the hexahydrate, although all of the properties of interest are in the cation u(bpy)₃sup>2+, which has received much attention because of its distinctive optical properties. The chlorides can be replaced with other anions, such as PF₆⁻.

Synthesis and structure

left, 144px, Cis-Dichlorobis(bipyridine)ruthenium(II), ''cis''-Dichlorobis(bipyridine)ruthenium(II) is an intermediate in the synthesis of tris(bipyridine)ruthenium(II) chloride.
This salt is prepared by treating an aqueous solution of ruthenium trichloride with 2,2'-bipyridine. In this conversion, Ru(III) is reduced to Ru(II), and hypophosphorous acid is typically added as a reducing agent. u(bpy)₃sup>2+ is octahedral, containing a central low spin d⁶ Ru(II) ion and three bidentate bpy ligands. The Ru-N distances are 2.053(2), shorter than the Ru-N distances for u(bpy)₃sup>3+. The complex is chiral, with D₃ symmetry. It has been resolved into its enantiomers. In its lowest lying triplet excited state the molecule is thought to attain lower C₂ symmetry, as the excited electron is localized primarily on a single bipyridyl ligand.

Photochemistry of u(bpy)₃sup>2+

u(bpy)₃sup>2+ absorbs ultraviolet and visible light. Aqueous solutions of u(bpy)₃l₂ are orange due to a strong MLCT absorption at 452 ± 3 nm ( extinction coefficient of 14,600 M⁻¹cm⁻¹). Further absorption bands are found at 285 nm corresponding to ligand centered π^*← π transitions and a weak transition around 350 nm (d-d transition). Light absorption results in formation of an excited state have a relatively long lifetime of 890 ns in acetonitrile and 650 ns in water. The excited state relaxes to the ground state by emission of a photon or non-radiative relaxation. The quantum yield is 2.8% in air-saturated water at 298 K and the emission maximum wavelength is 620 nm. The long lifetime of the excited state is attributed to the fact that it is triplet, whereas the ground state is a singlet state and in part due to the fact that the structure of the molecule allows for charge separation. Singlet-triplet transitions are forbidden and therefore often slow.

Like all molecular excited states, the triplet excited state of u(bpy)₃sup>2+ has both stronger oxidizing and reducing properties than its ground state. This situation arises because the excited state can be described as an Ru³⁺ complex containing a bpy^•− radical anion as a ligand. Thus, the photochemical properties of u(bpy)₃sup>2+ are reminiscent of the photosynthetic assembly, which also involves separation of an electron and a hole.

u(bpy)₃sup>2+ has been examined as a photosensitizer for both the oxidation and reduction of water. Upon absorbing a photon, u(bpy)₃sup>2+ converts to the aforementioned triplet state, denoted u(bpy)₃sup>2+*. This species transfers an electron, located on one bpy ligand, to a sacrificial oxidant such as peroxodisulfate (S₂O₈²⁻). The resulting u(bpy)₃sup>3+ is a powerful oxidant and oxidizes water into O₂ and protons via a catalyst. Alternatively, the reducing power of u(bpy)₃sup>2+* can be harnessed to reduce methylviologen, a recyclable carrier of electrons, which in turn reduces protons at a platinum catalyst. For this process to be catalytic, a sacrificial reductant, such as EDTA⁴⁻ or triethanolamine is provided to return the Ru(III) back to Ru(II).

Derivatives of u(bpy)₃sup>2+ are numerous. Such complexes are widely discussed for applications in biodiagnostics, photovoltaics and organic light-emitting diode, but no derivative has been commercialized. Application of u(bpy)₃sup>2+ and its derivatives to fabrication of optical chemical sensors is arguably one of the most successful areas so far.

u(bpy)₃sup>2+ and photoredox catalysis

Photoredox catalysis exploits u(bpy)₃sup>2+ as a sensitizer as a strategy for organic synthesis. Many analogues of u(bpy)₃sup>2+ are employed as well. These transformations exploit the redox properties of u(bpy)₃sup>2+* and its reductively quenched derivative u(bpy)₃sup>+.

Safety

Metal bipyridine as well as related phenanthroline complexes are generally bioactive, as they can act as intercalating agents.

See also

* Primogenic Effect
* Tris(bipyridine)iron(II) chloride

References

{{DEFAULTSORT:Tris(Bipyridine)Ruthenium(Ii) Chloride
Ruthenium complexes
Photochemistry
Bipyridine complexes
Ruthenium(II) compounds
Chlorides
Pyridine complexes