NDLI: Cyclometalated Ir(III) complexes of deprotonated N-methylbipyridinium ligands: effects of quaternised N centre position on luminescence

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Cyclometalated Ir(III) complexes of deprotonated N-methylbipyridinium ligands: effects of quaternised N centre position on luminescence

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Scrutton, Nigel S. Raftery, James Sánchez, Sergio Coe, Benjamin J. Peers, Martyn K. Helliwell, Madeleine
Description	Author Affiliation: Coe BJ ( School of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, UK. b.coe@manchester.ac.uk.)
Abstract	Six new tricationic $Ir^{III}$ complexes of cyclometalating ligands derived from 1-methyl-2-(2′-pyridyl)pyridinium or 1-methyl-4-(2′-pyridyl)pyridinium are described. These complexes of the form $[Ir^{III}(C\^N)_{2}(N\^N)]^{3+}$ (C^N = cyclometalating ligand; N^N = α-diimine) have been isolated and characterised as their $PF_{6}^{−}$ and $Cl^{−}$ salts. Four of the $PF_{6}^{−}$ salts have been studied by X-ray crystallography, and structures have been obtained also for two complex salts containing MeCN and $Cl^{−}$ or two $Cl^{−}$ ligands instead of N^N. The influence of the position of the quaternised N atom in C^N and the substituents on N^N on the electronic/optical properties are compared with those of the analogous complexes where C^N derives from 1-methyl-3-(2′-pyridyl)pyridinium (B. J. Coe, et al., Dalton Trans., 2015, 44, 15420). Voltammetric studies reveal one irreversible oxidation and multiple reduction processes which are mostly reversible. The new complexes show intramolecular charge-transfer absorptions between 350 and 450 nm, and exhibit bright green luminescence, with $λ_{max}$ values in the range 508–530 nm in both aqueous and acetonitrile solutions. In order to gain insights into the factors that govern the emission properties, density functional theory (DFT) and time-dependent DFT calculations have been carried out. The results confirm that the emission arises largely from triplet excited states of the C^N ligand $(^{3}LC),$ with some triplet metal-to-ligand charge-transfer $(^{3}MLCT)$ contributions.
ISSN	14779226
Issue Number	47
Volume Number	44
e-ISSN	13645447
Journal	Dalton Trans.
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2015-12-21
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Coordination Complexes Chemistry Iridium Pyridinium Compounds Crystallography, X-Ray Ligands Luminescence Molecular Structure Journal Article Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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