Ionic rare-earth complex luminescent material and preparation method and application therefor

A technology of rare earth complexes and ions, applied in luminescent materials, chemical instruments and methods, organic chemistry, etc., can solve the problems of poor photostability, poor stability, and easy dissociation of neutral ligands, etc., and achieve stable complex structures, Excludes quenching, strong interaction effects

Active Publication Date: 2015-08-19
PEKING UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] In order to solve the technical problem of poor stability of traditional rare earth complexes and obtain a rare earth luminescent material with high luminous efficiency, good thermal stability and strong ultraviolet light resistance, the present invention focuses on the selection of ligand types and the design of complex structures. From this point of view, a new type of rare earth complexes is provided
In this structure, a stable bidentate chelated five-membered ring is formed between the ND ligand and the rare earth ion. The effect is strong, the coordination is relatively tight, and the dissociation of the ligand is not easy to occur, thus solving the problems of easy dissociation of the neutral ligand and poor thermal stability and light stability of the complex, and obtaining an efficient and stable luminescent material

Method used

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  • Ionic rare-earth complex luminescent material and preparation method and application therefor
  • Ionic rare-earth complex luminescent material and preparation method and application therefor
  • Ionic rare-earth complex luminescent material and preparation method and application therefor

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] Embodiment 1. the rare earth complex compound shown in synthetic formula II-1 (being R in the formula II 1 =CN,R 3 =CH 3 , R 2 = R 4 = R 5 =H, Ln=Eu, M=Na)

[0040]

[0041] With 4mmol of 8mCND (i.e. R in formula I 1 =CN,R 3 =CH 3 , R 2 = R 4 = R 5 =H) and 4 mmol of NaOH in a mixed solution of ethanol and water 1:1 (volume ratio) were heated to reflux for 30 minutes. Then, 1 mmol of an aqueous solution of europium trichloride hexahydrate was added dropwise to the above solution or suspension, and refluxed for 2 hours. Filtered, washed with water, washed with a small amount of ethanol, and dried in vacuum. After recrystallization from ethanol / chlorobenzene, 0.81 g of the white target europium complex was obtained.

[0042] Mass spectrometry (ESI-MS) analysis, measured molecular ion peak M / Z=889.1, [M-Na] - . Elemental analysis (mass percentage): C, 52.70 (52.88); H, 2.65 (2.67); N, 18.44 (18.51), the theoretical values ​​in brackets. Dissolving the com...

Embodiment 2

[0043] Embodiment 2. the rare earth complex shown in synthetic formula II-2 (being R in the formula II 1 = R 3 =CH 3 , R 2 = R 4 = R 5 =H, Ln=Eu, M=Na)

[0044]

[0045] The synthesis steps are the same as in Example 1, except that the ligand is changed to 2m8mND (i.e. R in formula I 1 = R 3 =CH 3 , R 2 = R 4 = R 5 = H). 0.69 g of the light yellow target europium complex was obtained. Mass spectrometry (ESI-MS) analysis, recorded molecular ion peak M / Z=845.2, [M-Na] - . Dissolving the complex represented by formula II-2 in acetone solution, or in the form of solid powder, can obtain bright red emission under the excitation of ultraviolet lamp.

Embodiment 3

[0046] Embodiment 3. the rare earth complex shown in synthetic formula II-3 (being R in the formula II 1 = CF 3 , R 3 =CH 3 , R 2 = R 4 = R 5 =H, Ln=Eu, M=Na)

[0047]

[0048] The synthesis steps are the same as in Example 1, except that the ligand is changed to 3CF 3 8mND (that is, R in formula I 1 = CF 3 , R 3 =CH 3 , R 2 = R 4 = R 5 = H). 0.88 g of white powder of the target europium complex was obtained. Mass spectrometry (ESI-MS) analysis, recorded molecular ion peak M / Z=1061.1, [M-Na] - . Dissolving the complex represented by formula II-3 in acetone solution, or in the form of solid powder, can obtain bright red emission under the excitation of ultraviolet lamp.

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Abstract

The invention discloses an ionic rare-earth complex luminescent material, a preparation method therefor and application therefor. The structural formula of the rare-earth complex is [Ln(ND)4]M, wherein ND is a 4-hydroxyl-1,5-naphthyridine anionic ligand; Ln represents rare earth ions comprising yttrium, lanthanum, europium, gadolinium, terbium, ytterbium ions; M is counter cations comprising alkali metal ions, alkyl substituted quaternary ammonium ions, alkyl substituted quaternary phosphonium ions, l,3-dialkyl substituted imidazolium ions and N-alkyl substituted pyridinium ions. According to the europium complex provided by the invention, the ligand is hardly dissociated and the complex is high in thermal decomposition temperature; furthermore, the europium complex further has a high-efficiency photoluminescent quantum yield and good resistance to ultraviolet light, and can be used as photoluminescent and electroluminescent materials.

Description

technical field [0001] The invention relates to a rare earth complex luminescent material and its preparation method and application. Background technique [0002] Rare earth ions have unique luminescent properties such as narrow-band emission, large Stokes shift, and long luminescence lifetime, so they have broad application prospects in the fields of lighting, display, marking, light conversion film, and biological imaging. However, the light absorption coefficient of rare earth ions is relatively small and the luminous intensity is poor, so a certain sensitizing matrix is ​​usually required to transfer energy to them. Organic molecules have a large molar absorptivity coefficient, and the use of organic ligands to coordinate with rare earth ions can effectively transfer the energy absorbed by the ligands to rare earth ions, greatly increasing the luminous intensity. Therefore, the rare earth complex is a kind of luminescent material with superior performance, which has be...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D471/04C09K11/06
CPCC07D471/04C09K11/06C09K2211/182
Inventor 卞祖强卫慧波刘志伟黄春辉
Owner PEKING UNIV
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