The Role of Intraligand Charge Transfer Processes in Iridium(III) Complexes with Morpholine-Decorated 4′-Phenyl-2,2′:6′,2″-terpyridine

Abstract

To investigate the impact of the electron-donating morpholinyl (morph) group on the ground- and excited-state properties of two different types of Ir(III) complexes, [IrCl3(R-C6H4-terpy-κ3N)] and [Ir(R-C6H4-terpy-κ3N)2](PF6)3, the compounds [IrCl3(morph-C6H4-terpy-κ3N)] (1A), 4[Ir(morph-C6H4-terpy-κ3N)2](PF6)3 (2A), [IrCl3(Ph-terpy-κ3N)] (1B) and [Ir(Ph-terpy-κ3N)2](PF6)3 (2B) were obtained. Their photophysical properties were comprehensively investigated with the aid of static and time-resolved spectroscopic methods accompanied by theoretical DFT/TD-DFT calculations. In the case of bis-terpyridyl iridium(III) complexes, the attachment of the morpholinyl group induced dramatic changes in the absorption and emission characteristics, manifested by the appearance of a new, very strong visible absorption tailing up to 600 nm, and a significant bathochromic shift in the emission of 2A relative to the model chromophore. The emission features of 2A and 2B were found to originate from the triplet excited states of different natures: intraligand charge transfer (3ILCT) for 2A and intraligand with a small admixture of metal-to-ligand charge transfer (3IL–3MLCT) for 2B. The optical properties of the mono-terpyridyl iridium(III) complexes were less significantly impacted by the morpholinyl substituent. Based on UV–Vis absorption spectra, emission wavelengths and lifetimes in different environments, transient absorption studies, and theoretical calculations, it was demonstrated that the visible absorption and emission features of 1A are governed by singlet and triplet excited states of a mixed MLLCT-ILCT nature, with a dominant contribution of the first component, that is, metal-ligand-to-ligand charge transfer (MLLCT). The involvement of ILCT transitions was reflected by an enhancement of the molar extinction coefficients of the absorption bands of 1A in the range of 350–550 nm, and a small red shift in its emission relative to the model chromophore.