Cyclometallated Iridium(III) Complexes with 2-Phenylbenzimidazole Derivatives – Spectroscopic, Electrochemical and Electrochemiluminescence Studies

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Abstract
Summary: Simple synthetic procedure (reactions between iridium trichloride hydrate with a series of fluorine substituted 2-phenyl-N-methyl-benzimidazole derivatives L) leads to the cyclometallated Ir(III) complexes IrL2(acac) and IrL2(pic) where acac = acetylacetonate and pic = α-picolinate anions, respectively. All the investigated complexes exhibit strong absorption in the UV region, due to the spin allowed intra-ligand (IL) transitions, and moderately intense bands in the visible region, due to the metal-to-ligand-charge-transfer (MLCT) transitions. The complexes exhibit also strong luminescence in the deoxygenated 1:1 acetonitrile/dioxane solutions at 298 K as well as in the butyronitrile glasses at 77 K. In both experimental conditions the structured emissions (with the 0–0 transition within the 480–510 nm range of UV-Vis radiation) have been observed. Cyclic voltammetry investigations point out to reversible character of the electrochemical reactions leading to stable IrL2(acac)+ or IrL2(pic)+ cations and IrL2(pic)− anions. The corresponding IrL2(acac)− species have been found to be unstable under the applied experimental conditions (1:1 acetonitrile/dioxane solutions containing 0.1 M (C4H9)4NPF6 as the supporting electrolyte) most probably due to the irreversible electrochemical reduction of the acac− ligand. Appropriate combination of the electrochemical and luminescence properties found for the investigated complexes allows for the electron transfer generation of the excited 3∗IrL2(pic) and 3∗IrL2(acac) species. Triple-potential-step technique was used to create electrochemiluminescence (ECL) emission by annihilation of the electrochemically generated IrL2(acac)+ or IrL2(pic)+ cations and 4,4’-dicyano-biphenyl radical anion. Very high ECL emission efficiencies (close to the excited 3∗IrL2(acac) and 3∗IrL2(pic) luminescence yields) have been found.

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