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Issue 23, 2016
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Blue-shifted emission and enhanced quantum efficiency via π-bridge elongation in carbazole–carborane dyads

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Abstract

Carbazole–carborane linear dyads and di(carbazole)–carborane V-shaped dyads with phenyleneethynylene-based bridges have been synthesized. The V-shaped dyads display the expected red-shifts in the location of their UV-Vis absorption maxima on bridge-lengthening, but show unusual blue-shifts in charge-transfer (CT) emission on the same π-system lengthening. These blue-shifts can be attributed to the 2n + 3 electron count within the carborane cluster in the excited state. The linear dyads luminesce via a combination of local excited (LE) and CT emission, with a red-shift in LE emission and a blue-shift in CT emission accompanying π-bridge elongation. A quantum efficiency as high as 86% in the solution state is achieved from the hybrid LE/CT emission. Time-dependent density functional theory (TD-DFT) calculations at the excited state of these compounds have clarified the photoluminescence blue-shift and suggested a typical cluster C–C bond elongation in the V-shaped dyads. Calculations on the elongated linear dyads have suggested that the electron density is localized at the phenyleneethynylene-containing bridge.

Graphical abstract: Blue-shifted emission and enhanced quantum efficiency via π-bridge elongation in carbazole–carborane dyads

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Publication details

The article was received on 29 Apr 2016, accepted on 20 May 2016 and first published on 20 May 2016


Article type: Paper
DOI: 10.1039/C6CP02870E
Citation: Phys. Chem. Chem. Phys., 2016,18, 15719-15726
  • Open access: Creative Commons BY-NC license
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    Blue-shifted emission and enhanced quantum efficiency via π-bridge elongation in carbazole–carborane dyads

    Z. Wang, P. Jiang, T. Wang, G. J. Moxey, M. P. Cifuentes, C. Zhang and M. G. Humphrey, Phys. Chem. Chem. Phys., 2016, 18, 15719
    DOI: 10.1039/C6CP02870E

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