NDLI: LMCT facilitated room temperature phosphorescence and energy transfer in substituted thiophenolates of Gd and Yb

Content Provider	Royal Society of Chemistry (RSC)
Author	Andreev, Boris A. Ilichev, Vasily A. Rozhkov, Anton V. Maltsev, Eugeny I. Rumyantcev, Roman V. Dmitriev, Artem V. Lypenko, Dmitry A. Fukin, Georgy K. Yablonskiy, Artem N. Bochkarev, Mikhail N. Grishin, Ivan D.
Copyright Year	2017
Abstract	To obtain luminescent lanthanide complexes with a low energy LMCT state the 2-(2′-mercaptophenyl)benzothiazolates, Ln(SSN)3, and 2-(2′-mercaptophenyl)benzoxazolates, Ln2(OSN)6 (Ln = Gd, Yb), were synthesized by the reaction of amides Ln[N(SiMe3)2]3 with respective thiophenols. Ytterbium complexes were structurally characterized by X-ray diffraction analysis. Cyclic voltammetry revealed that the deprotonated mercaptophenyl ligands have significantly lower oxidation potentials than their phenoxy analogues and some β-diketones. The photophysical properties of Gd and Yb compounds were studied both in solution and in the solid state. The fluorescence spectra of the compounds in solution display the bands of the keto and enol forms of the ligands. No energy transfer from the organic part to Yb3+ has been detected in solutions of both Yb complexes, whereas in solids an intense metal-centered emission in the near infrared region was observed. The solid Gd compounds exhibited room temperature phosphorescence caused by unusually efficient intersystem crossing facilitated by the essentially reducing properties of OSN and SSN ligands. To explain the sensitization process occurring in solids Yb2(OSN)6 and Yb(SSN)3 a specific non-resonant energy transfer mechanism via a ligand to metal charge transfer state has been proposed. Based on the Yb derivatives, NIR-emitting OLEDs with 860 μW cm−2 maximal irradiance were obtained. Their Gd counterparts showed bright electrophosphorescence (up to 1350 cd m−2) in the devices containing doped emission layers.
Starting Page	3041
Ending Page	3050
Page Count	10
File Format	HTM / HTML PDF
ISSN	14779226
Volume Number	46
Issue Number	9
Journal	Dalton Transactions
DOI	10.1039/c6dt04519g
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Lanthanide OSN Ytterbium X-ray crystallography Cyclic voltammetry Fluorescence Enol Infrared spectroscopy Phosphorescence Intersystem crossing Ligand Irradiance
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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