Synthesis and Spectroelectrochemistry of Ir(bpy)(phen)(phi)3+, a Tris(heteroleptic)
Metallointercalator
Posted on 2001-08-30 - 00:00
A tris(heteroleptic) phenanthrenequinone diimine (phi) complex of Ir(III), Ir(bpy)(phen)(phi)3+, was synthesized
through the stepwise introduction of three different bidentate ligands, and the Λ- and Δ-enantiomers were resolved
and characterized by CD spectroscopy. Like other phi complexes, this tris(heteroleptic) iridium complex binds
avidly to DNA by intercalation. Electrochemical studies show that Ir(bpy)(phen)(phi)3+ undergoes a reversible
one-electron reduction at E0 = −0.025 V in 0.1 M TBAH/DMF (versus Ag/AgCl), and spectroelectrochemical
studies indicate that this reduction is centered on the phi ligand. The EPR spectrum of electrochemically generated
Ir(bpy)(phen)(phi)2+ is consistent with a phi-based radical. The electrochemistry of Ir(bpy)(phen)(phi)3+ was also
probed at a DNA-modified electrode, where a DNA binding affinity of K = 1.1 × 106 M-1 was measured. In
contrast to Ir(bpy)(phen)(phi)3+ free in solution, the complex bound to DNA undergoes a concerted two-electron
reduction, to form a diradical species. On the basis of UV−visible and EPR spectroscopies, it is found that
disproportionation of electrochemically generated Ir(bpy)(phen)(phi)2+ occurs upon DNA binding. These results
underscore the rich redox chemistry associated with metallointercalators bound to DNA.
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Stinner, Christine; Wightman, Matthew D.; Kelley, Shana O.; Hill, Michael G.; Barton, Jacqueline K. (2016). Synthesis and Spectroelectrochemistry of Ir(bpy)(phen)(phi)3+, a Tris(heteroleptic)
Metallointercalator. ACS Publications. Collection. https://doi.org/10.1021/ic010376t
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AUTHORS (5)
CS
Christine Stinner
MW
Matthew D. Wightman
SK
Shana O. Kelley
MH
Michael G. Hill
JB
Jacqueline K. Barton