NDLI: Dipyridylketone as a versatile ligand precursor for new cationic heteroleptic cyclometalated iridium complexes

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Volpi, Giorgio Gobetto, Roberto Nervi, Carlo Breuza, Emanuele Garino, Claudio
Description	Author Affiliation: Volpi G ( Department of Chemistry IFM, University of Turin, Via P. Giuria 7, 10125, Turin, Italy.)
Abstract	Three new bis-cyclometalated iridium(III) complexes, of general formula $[Ir(2-phenylpyridine)_{2}(L)]^{+},$ are reported. The compounds contain a dipyridine-type ligand (L) derived from di-2-pyridylketone ( dipyridin-2-ylmethanol , 2,2′-(hydrazonomethylene)dipyridine and 3-hydroxy-3,3-di(pyridine-2-yl)propanenitrile ) and were synthesized through two different reaction pathways. The alternative synthetic pathway herein proposed, namely the direct reactions on the complex $[Ir(2-phenylpyridine)_{2}(2,2′-dipyridylketone)]^{+},$ overcame the inconveniences encountered with the standard reaction between the dimeric precursor $[Ir(2-phenylpyridine)_{2}(μ-Cl)]_{2}$ and the ancillary ligands (L). The photophysical characterization of the iridium complexes reveals that modifications on the ancillary ligand introduce large changes in the photophysical behaviour of the complexes. High emission quantum yield is associated with the presence of a saturated carbon between the two pyridyl moieties: $[Ir(2-phenylpyridine)_{2}(2,2′-dipyridylketone)]^{+}$ and $[Ir(2-phenylpyridine)_{2}(2,2′-(hydrazonomethylene)dipyridine)]^{+}$ are extremely low emissive, while $[Ir(2-phenylpyridine)_{2}(dipyridin-2-ylmethanol)]^{+}$ and $[Ir(2-phenylpyridine)_{2}(3-hydroxy-3,3-di(pyridine-2-yl)propanenitrile)]^{+}$ are good photoemitters. DFT and TD-DFT calculations confirmed the mixed LC/MLCT character of the excited states involved in the absorption and emission processes and highlighted the role of the π-conjugation between the two subunits of the ancillary ligand in determining the nature of the LUMO.
ISSN	14779226
Issue Number	3
Journal	Dalton Trans.
Volume Number	41
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2012-01-21
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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