NDLI: Photophysical properties of a new series of water soluble iridium bisterpyridine complexes functionalised at the 4′ position

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Bhadbhade, Mohan Goldstein, Daniel C. Cheng, Yuen Yap Thordarson, Pall Schmidt, Timothy W.
Description	Author Affiliation: Goldstein DC ( School of Chemistry, University of New South Wales, Sydney, NSW 2052, Australia. d.goldstein@student.unsw.edu.au)
Abstract	Four new hetero- and homo-leptic iridium( III) bisterpyridine complexes have been prepared which incorporate aniline ( tpy-φ-NH $_{2}$ ), benzoic acid (tpy-φ-COOH), and benzyl alcohol ( tpy-φ-CH $_{2}OH$ ) substituents at the 4′ positions of the tpy ligands (tpy = 2,2′: 6′,2′′-terpyridine , φ = phenylene ). The electrochemical behaviour and ground and excited state spectroscopic properties of the complexes are reported, and the X-ray crystal structures of a homoleptic benzyl alcohol $[Ir(tpy-φ-CH_{2}OH)_{2}](PF_{6})_{3},$ homoleptic aniline $[Ir(tpy-φ-NH_{2})_{2}](PF_{6})_{3},$ and heteroleptic benzyl alcohol / aniline substituted complex [Ir(tpy-φ-CH $_{2}OH)(tpy-φ-NH$ $_{2})](PF$ $_{6})$ $_{3}$ have been solved. Complexes with aniline substituents were found to display absorption bands at around 430 nm corresponding to intraligand charge transfer (ILCT) that are sensitive to changes in solvent and pH. Strong emission in the visible region involving the ILCT state is observed in two of the complexes $(Φ_{e}$ = 0.7% and 2.6%) in acetonitrile . In the heteroleptic aniline / benzyl alcohol complex the Stokes shift is shown to be linearly related to solvent polarisability according to the Lippert equation, but only for solvents with weak hydrogen bonding interactions. Additionally, in water , emission from the ILCT state is quenched and only weak ligand centred ( LC ) emission is observed. The long lifetimes and quantum yields of these complexes make them interesting candidates for probes in sensing applications, especially [Ir(tpy-φ-CH $_{2}OH)(tpy-φ-NH$ $_{2})$ $_{2}](PF$ $_{6})$ $_{3}$ due to its unusual sensitivity to the solvent environment.
ISSN	14779226
Issue Number	9
Journal	Dalton Trans.
Volume Number	40
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2011-03-07
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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