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Photochemical Tuning of Tris-Bidentate Acridine- and Phenazine-Based Ir(III) Complexes

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Abstract

Five new Ir(III) complexes of the type [Ir(ppy)2L]+ (where ppy = 2-phenylpyridine, L = bidentate N^N ligand) bearing linear and elbow-shaped acridine- and phenazine-based extended planar aromatic ligands have been successfully synthesized and characterized. The electrochemical and photochemical studies revealed that all complexes allow emission in the range 589–601 nm from excited states corresponding to a charge transfer between an Ir-ppy fragment and the extended planar ligand. Luminescence quenching occurs in water for [Ir(ppy)2dpac]+ (Ir-DPAC), [Ir(ppy)2dpacF2]+ (Ir-DPACF 2 ), [Ir(ppy)2dpacF4]+ (Ir-DPACF 4 ) and [Ir(ppy)2bdppz]+ (Ir-BDPPZ), while solely partial quenching is observed for [Ir(ppy)2npp]+ (Ir-NPP). This “light-switch” effect has been ascribed to the possible formation of a non-emissive mono-hydrogen-bonded excited state for the four complexes. The “elbow shaped” of Ir-NPP is believed to prevent the non-chelating nitrogen atom of the npp ligand to form H-bond with solvent molecules. The results emphasized the potential of small chemical modifications of the extended planar ligand on the properties of the corresponding Ir(III) complexes. Their tunable properties make them ideal candidates for applications such as DNA photoprobes.

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Acknowledgments

Q.D. and B.E. gratefully acknowledge the Université catholique de Louvain, the Fonds National pour la Recherche Scientifique (F.R.S.-F.N.R.S.), the Région Wallonne, and the Fondation Louvain (Prix Pierre et Colette Bauchau) for financial support. F.L. thanks the Labex Arcane, France (ANR-11-LABX-0003-01) and the chemistry platform NanoBio campus in Grenoble for luminescence lifetime measurement facilities. Q.D. also warmly thanks Alexandre Jacques, Cédric Lentz and Lionel Marcélis for their scientific help.

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Authors and Affiliations

  1. Institute of Condensed Matter and Nanosciences, Molecules, Solids and Reactivity (IMCN/MOST), Université catholique de Louvain, Place Louis Pasteur 1/L4.01.02, 1348, Louvain-la-Neuve, Belgium

    Quentin Deraedt & Benjamin Elias

  2. Département de Chimie Moléculaire, Université Grenoble-Alpes, CNRS UMR 5250, BP53, 38041, Grenoble, France

    Frédérique Loiseau

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  1. Quentin Deraedt
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  2. Frédérique Loiseau
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  3. Benjamin Elias
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Correspondence to Benjamin Elias.

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Deraedt, Q., Loiseau, F. & Elias, B. Photochemical Tuning of Tris-Bidentate Acridine- and Phenazine-Based Ir(III) Complexes. J Fluoresc 26, 2095–2103 (2016). https://doi.org/10.1007/s10895-016-1904-2

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  • DOI: https://doi.org/10.1007/s10895-016-1904-2

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