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

• Published in: Chemical science (Cambridge) 2017-01, Vol.8 (1), p.423-429
• Main Authors: Hatanaka, Miho, Hirai, Yuichi, Kitagawa, Yuichi, Nakanishi, Takayuki, Hasegawa, Yasuchika, Morokuma, Keiji
• Format: Article
• Language: English
• Subjects: Barriers; Chemistry; Color; Emission; Excitation; Ligands; Phosphine oxide; Quenching; Thermometers
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/c6sc03006h

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 (Ln ), , [Tb Eu (hfa) (linker)] , where the Ln (hfa) complexes (hfa: hexafluoro acetylacetonato) are connected by a phosphine oxide "linker" molecule. First, the difference in the thermosensitivities of the emissions from Tb and Eu are discussed. With increasing temperature, the green-emission intensity from Tb decreases whereas the red-emission intensity from Eu does not change. This was found to originate from the different reaction barriers for the quenching of the Ln excited state the intersystem crossing (ISC) between the hfa-centered triplet state and the ground state. Next, the excitation energy transfer (EET) from Tb to Eu is discussed. Although the direct EET between Ln atoms is negligible because of the long distance between them, stepwise EET is found to occur 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 experimental measurements.