title: Structure-property relationships based on Hammett constants in cyclometalated iridium(III) complexes: their application to the design of a fluorine-free FIrPic-like emitter.
abstract: While phosphorescent cyclometalated iridium(iii) complexes have been widely studied, only correlations between oxidation potential EOX and Hammett constant σ, and between the redox gap (ΔEREDOX = EOX-ERED) and emission or absorption wavelength (λabs, λem) have been reported. We present now a quantitative model based on Hammett parameters that rationalizes the effect of the substituents on the properties of cyclometalated iridium(iii) complexes. This simple model allows predicting the apparent redox potentials as well as the electrochemical gap of homoleptic complexes based on phenylpyridine ligands with good accuracy. In particular, the model accounts for the unequal effect of the substituents on both the HOMO and the LUMO energy levels. Consequently, the model is used to anticipate the emission maxima of the corresponding complexes with improved reliability. We demonstrate in a series of phenylpyridine emitters that electron-donating groups can effectively replace electron-withdrawing substituents on the orthometallated phenyl to induce a blue shift of the emission. This result is in contrast with the common approach that uses fluorine to blue shift the emission maximum. Finally, as a proof of concept, we used electron-donating substituents to design a new fluorine-free complex, referred to as EB343, matching the various properties, namely oxidation and reduction potentials, electrochemical gap and emission profile, of the standard sky-blue emitter FIrPic.
authors.affiliation: Laboratory of Photonics and Interfaces, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland.
authors.forename: Julien
authors.initials: J
authors.lastname: Frey
authors.forename: Basile F E
authors.initials: BF
authors.lastname: Curchod
authors.forename: Rosario
authors.initials: R
authors.lastname: Scopelliti
authors.forename: Ivano
authors.initials: I
authors.lastname: Tavernelli
authors.forename: Ursula
authors.initials: U
authors.lastname: Rothlisberger
authors.forename: Mohammad K
authors.initials: MK
authors.lastname: Nazeeruddin
authors.forename: Etienne
authors.initials: E
authors.lastname: Baranoff