Journal
ORGANOMETALLICS
Volume 36, Issue 14, Pages 2573-2580Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.organomet.7b00139
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Funding
- Basic Science Research Program [NRF-2014R1A1A2056364]
- National Research Foundation of Korea (NRF) [2009-0093818]
- NRF
- Ministry of Science, ICT and Future Planning [NRF-2015R1C1A1A01052947]
- National Research Foundation of Korea [22A20130000138, 2009-0093818] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
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Heteroleptic tris-cyclometalated Ir(III) complexes bearing an o-carborane at the 4- or 5-position in the phenyl ring of the ppy ligand (closo-1 and -2) were prepared and characterized. The X-ray crystal structure of closo-1 reveals the fac arrangement of the three C boolean AND N chelates around the Ir atom. Treatment of closo complexes with fluoride anions led to selective deboronation of the c/oso-carborane cage, producing the corresponding nido-carborane-substituted complexes (nido-1 and -2). Whereas, closo-1 and -2 Were almost nonemissive in THE, nido-1 and -2 were highly phosphorescent (Phi(PL) = 0.94-0.95). Theoretical studies suggested that, while the emission quenching in closo-1 can be ascribed to the substantial involvement of o-carborane in the (MLCT)-M-3 excited state, the intraligand charge transfer ((ILCT)-I-3) state from the nido-carborane to pyridyl moieties is responsible for the efficient phosphorescence in nido-1. The addition of fluoride to the buffered THF/H2O solution (1/1, v/v, pH 7) of closo-1 and -2-under mild heating led to strong emission intensity, allowing the turn-on phosphorescence detection of fluoride in aqueous medium at the ppb level.
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