Bright Circularly Polarized Electrochemiluminescence from Heterobinuclear Ir <sup>III</sup> –Au <sup>I</sup> Enantiomers
Abstract
Abstract The development of efficient circularly polarized electrochemiluminescence (CP‐ECL) probes is still at its infancy and examples are still very limited. Yet, their achievement would enable gathering a readout that carries privileged information on the probe's chiral environment by monitoring luminescence polarization bias with high signal‐to‐noise ratio. Notwithstanding, this is a highly challenging task and requires judicious chemical engineering of chiral ECL‐active emitters. Herein, we aim at expanding the palette of CP‐ECL luminophores by presenting a novel class of enantiopure heterobinuclear Ir(III)–Au(I) complexes, which are investigated thoroughly by means of chemical, structural, and (chiro‐)optical techniques. The ground and excited state properties are also elucidated by using density functional theory (DFT) approaches including spin‐orbital coupling (SOC) perturbation. The chiral‐at‐metal complexes display luminescence with a polarization bias of the emitted light that is function of the helical arrangement of the coordination sphere around the Ir(III) center. Overall, the photo‐ and electro‐active complexes unraveled in this work combine unparallelly high photoluminescence quantum yield in the orange region, excellent circularly polarized luminescence (CPL) brightness up to 4.5 M −1 cm −1 with a notable ECL activity. Finally, these features provide emitters with CP‐ECL efficiency that encompass remarkably by a factor 3.5 that of the well‐known benchmark tris ‐(2,2′‐bipyridyl)ruthenium(II).
Article Details
Authors (14)
Lavinia Ballerini
Université de Strasbourg, CNRS, Institut de Physique et Chimie des Matériaux de Strasbourg UMR 7504, 23 rue du Loess Strasbourg 67034 France
Miaoxia Liu
ISM, UMR CNRS 5255, University of Bordeaux, Bordeaux INP Pessac 33607 France
Lorenzo Arrico
Dipartimento di Chimica e Chimica Industriale Università di Pisa, Via Moruzzi 13 Pisa 56124 Italy
Silvia Voci
Institut Lavoisier de Versailles UVSQ CNRS UMR 8180, Université Paris‐Saclay 45, Avenue des États‐Unis Versailles 78035 France
Christophe Gourlaouen
Chimie de la Matière Complexe, CNRS UMR 7140, Université de Strasbourg, 4, Rue Blaise Pascal, Strasbourg 67000, France
Chantal Daniel
Laboratoire de Chimie Quantique Université de Strasbourg CNRS, UMR 7177 Institut Le Bel 4 rue Blaise Pascal Strasbourg 67000 France
Vincent César
LCC‐CNRS, Université de Toulouse CNRS, 205 Route de Narbonne, BP44099 Toulouse Cedex 4 31077 France
Stéphane Bellemin‐Laponnaz
Université de Strasbourg, CNRS, Institut de Physique et Chimie des Matériaux de Strasbourg UMR 7504, 23 rue du Loess Strasbourg 67034 France
Francesco Zinna
Dipartimento di Chimica e Chimica Industriale Università di Pisa, Via Moruzzi 13 Pisa 56124 Italy
Laurent Bouffier
ISM, UMR CNRS 5255, University of Bordeaux, Bordeaux INP Pessac 33607 France
Federico Polo
Department of Molecular Sciences and Nanosystems Ca’ Foscari University of Venice Via Torino 155 Venezia 30172 Italy
Lorenzo Di Bari
Dipartimento di Chimica e Chimica Industriale Università di Pisa, Via Moruzzi 13 Pisa 56124 Italy
Neso Sojic
University of Bordeaux, CNRS, Bordeaux INP, ISM, UMR, 5255
Matteo Mauro
Université de Strasbourg, CNRS, Institut de Physique et Chimie des Matériaux de Strasbourg UMR 7504, 23 rue du Loess Strasbourg 67034 France