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Dalton Trans. 2013 Sep 14;42(34):12093-100. doi: 10.1039/c3dt50807b. Epub 2013 May 17.

A highly selective and sensitive ratiometric chemodosimeter for Hg2+ ions based on an iridium(III) complex via thioacetal deprotection reaction.

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1
Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan.

Abstract

A novel luminescent biscyclometalated iridium(III) complex [Ir(C^N)2bpy]PF6 (Ir-S, bpy = 2,2'-bipyridine) containing two 2-phenylpyridine (ppy) cyclometalating ligands (C^N) functionalized with 1,3-dithiane for the detection of Hg(2+) ions has been synthesized and characterized by spectroscopic and photophysical measurements. The luminescence of Ir-S exhibits a ratiometric response upon the addition of Hg(2+) ions. The absorption, emission, (1)H NMR and ESI mass spectral changes of Ir-S in the absence and presence of Hg(2+) ions have all demonstrated the Hg(2+)-promoted thioacetal deprotection reaction of Ir-S and the generation of a complex [Ir(pba)2bpy]PF6 (Ir-CHO, Hpba = 4-(pyridin-2-yl)benzaldehyde). DFT calculation studies suggest that the dominant participation of the 1,3-dithiane group in the HOMO of Ir-S leads to different excited states and distinct excited energies of Ir-S and Ir-CHO and consequently results in their different emission properties. The titration and competition experiments significantly reveal the highly sensitive and selective properties of Ir-S as a promising indicator for Hg(2+) ions over other metal cations.

PMID:
23685636
DOI:
10.1039/c3dt50807b
[Indexed for MEDLINE]
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