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Updated: Jun 16, 2026
Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization
Published on: November 29, 2018
Controlling Photophysical Properties in Bis-Cyclometalated Ir(III)-Terpyridine Complexes through Photoinduced
Joanna Palion-Gazda1, Aleksandra Kwiecień1, Mateusz Penkala1
1Institute of Chemistry, University of Silesia, 9 Szkolna Str., Katowice 40-006, Poland.
Abstract:
This work is the study of the role of a remote amine substituent on the terpyridine ligand in controlling the photophysical and electroluminescent behavior of complexes [Ir(Ph-btz)2(R-C6H4-terpy-κ2N)]PF6. Introduction of the amine group into the Ph-terpy framework induced perturbations in the absorption and luminescent characteristics of [Ir(Ph-btz)2(R-C6H4-terpy-κ2N)]PF6 relative to the parent chromophores [Ir(Ph-btz)2(terpy-κ2N)]PF6 and [Ir(Ph-btz)2(C6H5-terpy-κ2N)]PF6. Consistent with the presence of vibronic structure, negligible emission solvatochromism, weak rigidochromic behavior, and substantial overlap with the phosphorescence of 2-phenylbenzothiazole, the emissive triplet excited state of the model complexes was assigned to 3ILPh-btz with a minor 3MLCT contribution. The amine-substituted Ir(III) complexes were found to exhibit altered emission characteristics, manifested by a structureless emission band impacted by the amine group and solvent polarity. It was rationalized by a switch from the 3ILPh-btz/MLCT excited state in model chromophores to a configurationally mixed 3ILCT/IL/MLCTR-terpy in [Ir(Ph-btz)2(R-C6H4-terpy-κ2N)]PF6. With respect to the preliminary electroluminescence investigations, it was found that the introduction of the triphenylamine moiety enhances the stability of O/PEDOT/PSS/complex/Al devices. A deep insight into ground- and excited-state characters and photophysical properties of [Ir(Ph-btz)2(R-C6H4-terpy-κ2N)]PF6 was obtained by applying a wide range of experimental techniques, including cyclic voltammetry, UV-vis spectroscopy, photoluminescence spectroscopy, and transient absorption, complemented by DFT and TD-DFT calculations.
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