Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 16, Issue 40, Pages 12158-12167Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201000748
Keywords
chemodosimeters; host-guest systems; iridium; mercury; polymers
Categories
Funding
- National Basic Research Program of China (973 Program) [2009CB930601]
- National Natural Science Foundation of China [50803028, 20804019, 20774043]
- Natural Science Foundation of Jiangsu Province of China [BK2009427]
- Natural Science Fund for Colleges and Universities in Jiangsu Province [08KJD430017]
- Scientific and Technological Activities for Returned Personnel in Nanjing City [NJ209001]
- Nanjing University of Posts and Telecommunications [NY208045]
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For the development of excellent optical probes for mercury(II), a series of simple conjugated polymers that contain phosphorescent iridium(III) complexes as receptors for mercury(II) were designed and synthesized. These conjugated polymers showed energy transfer from the polymer host to iridium(III) complex guest in both solution and the solid state. Unexpectedly, they can work as excellent polymer chemodosimeters for mercury(II) by utilizing the mercury(II)-induced decomposition of iridium(III) complex. They exhibit a pronounced optical signal change with switchable phosphorescence and fluorescence, even when the concentration of a solution of mercury(II) in THF was as low as 0.5 ppb. With the addition of mercury(II), the phosphorescent emission intensity of iridium(III) complexes was quenched completely. As the emission from polymer backbones increased, the emission wavelength was redshifted simultaneously, thereby realizing ratiometric detection. Excellent selectivity toward mercury(II) over other potentially interfering cations was also realized. In addition, an obvious emission color change of polymer solution from red to yellow-green was observed, thus realizing a naked-eye detection of mercury(II). More importantly, the solid films of these polymer chemodosimeters also exhibited high sensitivity and rapid response to mercury(II), thereby demonstrating the possibility of the fabrication of sensing devices with fast and convenient detection of mercury(II). The sensing mechanism was also investigated in detail. This is the first report on chemodosimeters based on conjugated polymers with phosphorescent iridium(III) complexes.
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