Issue 15, 2014

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 = EOXERED) 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.

Graphical abstract: Structure–property relationships based on Hammett constants in cyclometalated iridium(iii) complexes: their application to the design of a fluorine-free FIrPic-like emitter

Supplementary files

Article information

Article type
Paper
Submitted
01 Oct 2013
Accepted
29 Nov 2013
First published
02 Dec 2013

Dalton Trans., 2014,43, 5667-5679

Structure–property relationships based on Hammett constants in cyclometalated iridium(III) complexes: their application to the design of a fluorine-free FIrPic-like emitter

J. Frey, B. F. E. Curchod, R. Scopelliti, I. Tavernelli, U. Rothlisberger, M. K. Nazeeruddin and E. Baranoff, Dalton Trans., 2014, 43, 5667 DOI: 10.1039/C3DT52739E

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