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The Key Laboratory of Food Colloids and Biotechnology, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, China
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Dalton Trans., 2013,42, 4539-4543
28 Sep 2012,
13 Dec 2012
First published online
17 Dec 2012
In this paper, a C–F bond activation reaction of a chloro-bridged iridium(III) dimer (dfppy)2Ir(μ-Cl)2Ir(dfppy)2 (1) (dfppy denotes 2-(4,6-difluorophenyl)pyridyl) in the presence of sodium methoxide has been reported, leading to the formation of a heteroleptic cyclometalated iridium(III) fluorophenylpyridine complex 2. HPLC-mass analysis confirmed the release of formaldehyde in the product mixture. When sodium benzyloxide was used as the base, complex 2 was also generated with the release of a benzaldehyde derivative. Complex 2 has been fully characterized by 1H-NMR, 19F-NMR and X-ray crystallographic methods, confirming the partial loss of one of the fluorine atoms on one of the cyclometalated phenylpyridyl ligands. Photophysical studies of complex 2 show that it has a similar absorption spectrum to that of Ir(III)(dfppy)3. However, the emission spectrum shows a red shift maximum emission band at 478 nm due to the loss of a single fluorine atom, highlighting the critical effect of fluorine on the photoluminescence of these Ir(III) complexes. Finally, intensive mechanistic studies including HPLC-mass analysis, 1H-NMR, and 19F-NMR studies demonstrate that the formation of complex 2 should involve a critical β-hydride elimination of Ir(III)-alkoxide intermediate and the participation of Ir-hydride and/or Ir-fluoride intermediates.
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