Bis-cyclometalated iridium(iii) complexes with terpyridine analogues: syntheses, structures, spectroscopy and computational studies

Otaif, Haleema Y., Adams, Samuel J., Horton, Peter N., Coles, Simon J., Beames, Joseph M. ORCID: https://orcid.org/0000-0002-5508-8236 and Pope, Simon J. A. ORCID: https://orcid.org/0000-0001-9110-9711 2021. Bis-cyclometalated iridium(iii) complexes with terpyridine analogues: syntheses, structures, spectroscopy and computational studies. RSC Advances 11 (63) , 39718–39727. 10.1039/D1RA07213G

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Abstract

Two ligands based upon a 2,6-disubstituted pyridine bridge introduce bis-quinoxalinyl units in a fashion that yields analogues to the archetypal terdentate ligand, 2,2′:6′,2′′-terpyridine. The ligands were synthesised from the key intermediate 2,6-bis(bromoacetyl)pyridine: a new, high-yielding route is described for this reagent. Two ligand variants (differentiated by H/Me substituents on the quinoxaline ring) were explored as coordinating moieties for iridium(III) in the development of luminescent complexes. Computational studies (DFT approaches employing B3LYP, B3LYP/LANL2DZ, and M062X/LANL2DZ levels) were used to investigate the geometric and coordination mode preferences of the new ligands and two possibilities arose from theoretical investigations: [Ir(N^N^N)2]3+ and [Ir(N^N^C)2]+, with the former predicted to be more energetically favourable. Upon synthesis and isolation of the Ir(III) complexes, X-ray crystallographic studies revealed coordination spheres that were cyclometalated, the structures both showing a [Ir(N^N^C)2]PF6 arrangement. Further spectroscopic characterization via NMR confirmed the ligand arrangements in the complexes, and photophysical studies, supported by DFT, showed that a mixture of metal-to-ligand charge transfer (MLCT) and intra-ligand charge transfer (ILCT) character is likely to contribute to the emission features of the complexes, which phosphoresce orange-red (λem = 580–618 nm). The emission wavelength was influenced by the substituents on the quinoxaline ring (H vs. Me), thereby implying further tuneability is possible with future ligand iterations.

Item Type:	Article
Date Type:	Published Online
Status:	Published
Schools:	Advanced Research Computing @ Cardiff (ARCCA) Chemistry
Publisher:	Royal Society of Chemistry
ISSN:	2046-2069
Funders:	The Leverhulme Trust
Date of First Compliant Deposit:	16 December 2021
Date of Acceptance:	2 December 2021
Last Modified:	02 Aug 2024 13:53
URI:	https://orca.cardiff.ac.uk/id/eprint/146195

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