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Issue 1, 2017
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Organic linkers control the thermosensitivity of the emission intensities from Tb(III) and Eu(III) in a chameleon polymer

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Abstract

Thermometers whose emission color gradually changes with temperature are called chameleon emitters. In this study, we discuss the mechanism of the thermosensitivity of the emission color of polymers that contain two lanthanides (Ln3+), e.g., [Tb0.99Eu0.01(hfa)3(linker)]n, where the Ln3+(hfa)3 complexes (hfa: hexafluoro acetylacetonato) are connected by a phosphine oxide “linker” molecule. First, the difference in the thermosensitivities of the emissions from Tb3+ and Eu3+ are discussed. With increasing temperature, the green-emission intensity from Tb3+ decreases whereas the red-emission intensity from Eu3+ does not change. This was found to originate from the different reaction barriers for the quenching of the Ln3+ excited state via the intersystem crossing (ISC) between the hfa-centered triplet state and the ground state. Next, the excitation energy transfer (EET) from Tb3+ to Eu3+ is discussed. Although the direct EET between Ln3+ atoms is negligible because of the long distance between them, stepwise EET is found to occur via the linker-centered triplet state with a reasonable barrier. Thus, we propose a new idea—thermosensitivity can be controlled by the linker as well as by the ligand (hfa). To confirm the role of the linker, four phosphine oxides were examined. The thermosensitivity dependence on the linker is validated via experimental measurements.

Graphical abstract: Organic linkers control the thermosensitivity of the emission intensities from Tb(iii) and Eu(iii) in a chameleon polymer

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Publication details

The article was received on 08 Jul 2016, accepted on 23 Aug 2016 and first published on 25 Aug 2016


Article type: Edge Article
DOI: 10.1039/C6SC03006H
Citation: Chem. Sci., 2017,8, 423-429
  • Open access: Creative Commons BY license
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    Organic linkers control the thermosensitivity of the emission intensities from Tb(III) and Eu(III) in a chameleon polymer

    M. Hatanaka, Y. Hirai, Y. Kitagawa, T. Nakanishi, Y. Hasegawa and K. Morokuma, Chem. Sci., 2017, 8, 423
    DOI: 10.1039/C6SC03006H

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