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

Content Provider	Royal Society of Chemistry (RSC)
Author	Hirai, Yuichi Kitagawa, Yuichi Hatanaka, Miho Nakanishi, Takayuki Hasegawa, Yasuchika Morokuma, Keiji
Copyright Year	2017
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.
Starting Page	423
Ending Page	429
Page Count	7
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	8
Issue Number	1
Journal	Chemical Science
DOI	10.1039/c6sc03006h
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Subscribed
Subject Keyword	Ligand Phosphine ISC Intersystem crossing Epoxyeicosatrienoic acid Correlation and dependence Chameleon Phosphine oxide
Content Type	Text
Resource Type	Article
Subject	Chemistry

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