CN101037390B

CN101037390B - Carbazole Bis-beta-diketonate ligand and preparation and usage thereof

Info

Publication number: CN101037390B
Application number: CN2007100214918A
Authority: CN
Inventors: 吴杰颖; 张胜义; 金葆康; 田玉鹏; 周虹屏; 杨家祥; 宋继梅; 杨林; 邓崇海
Original assignee: Anhui University
Current assignee: Anhui University
Priority date: 2007-04-11
Filing date: 2007-04-11
Publication date: 2010-06-23
Anticipated expiration: 2027-04-11
Also published as: CN101037390A

Abstract

A carbazo bis beta-diketone ligand which is produced by following steps: having the carbazole as initial material, producing intermediate (I) N-alkyl carbazole, (II) N-alkyl-3,6-diacylcarbazo by substitution reaction and acylation reaction in order, finally synthesizing target product by intermediate. The nitrate of the ligand and rare-earth element is to prepare the carbazo bis beta-diketone rare-earth complex. The complex is an excellent photoluminescence material.

Description

A kind of carbazole Bis-beta-diketonate ligand and its production and use

One, technical field

The present invention relates to a kind of electroluminescent material, especially red light material and preparation method thereof, particularly bi-beta-diketo class part and complex material thereof and preparation method, specifically a kind of carbazole Bis-beta-diketonate ligand preparation method and purposes.

Two, background technology

21 century is the epoch of an advanced IT application, can write down, stores, transmit fast and the optical material of processes and displays large vol information, will bring into play crucial effects.Therefore, start with from molecular designing, the synthesizing new luminescent material is one of focus of chemist and material scholar research.

The special molecular structure of beta-diketon makes it to become excellent chelating ligand, its easy and all rare earth ion generation coordination.The rare earth beta-diketone complex is that people study to such an extent that also be maximum rare earth compounding luminescence systems the earliest, owing to exist from beta-diketonate ligand with high uv-absorbing coefficient to Eu in this class title complex ³⁺, Tb ³⁺Deng the high efficiency energy transmission, thereby make them have very high fluorescence efficiency.But the synthetic first a kind of bi-beta-diketo H of the rarely seen so far report of bi-beta-diketo compound, 1958 (MartinD.F., Shamma M., Fernelius W.C.J.Am.Chem.Soc.1958,80,4891.) such as Martin D.F. ₂The BPOB compound just obtains H up to 2004 (Andrew P.B., Steven W.M.and et al.J.Am.Chem.Soc.2004,126,9413.) such as Andrew P.B. ₂The monocrystalline of BPOEB, and studied the light, electric work of its rare earth metal complex can character.

Rare earth compounding has plurality of advantages such as photoluminescence efficiency height, good, the stable height of light monochromaticity and Stock displacement are big, makes it very likely as electroluminescent material.The fluorescence of rare earth compounding mainly is that the part that is stimulated will be excited transmission ofenergy by radiationless intramolecular energy transfer and be given central ion, thereby make central ion send characteristic fluorescence, obviously the luminous power of rare earth compounding and the structure of rare earth ion and organic ligand have much relations.

Have big π-electron conjugated system and strong intramolecularly transfer transport in carbazole and the derivative molecular thereof.From (the Cotton F.A. of American I BM company in 1970, Donahue J.P., Murillo C.A.Inorg.Chem.2001,40,1234.) at first in duplicating machine, use the carbazoles derivative as organic light-guide material since, the scientist of countries in the world has produced keen interest to carbazole compound and character, and they have the potential application prospect at aspects such as electroluminescent, photoluminescence, nonlinear optical material, LB films.

Three, summary of the invention

The present invention is based on carbazole derivative and carry out molecular designing as parent, synthetic novel bi-beta-diketo part, with itself and rare earth element coordination, obtain rare earth compounding, aim to provide the good photoluminescence functional materials of a kind of good stability, luminous efficiency height and monochromaticity.Technical problem to be solved is the selection and the preparation of carbazole beta-diketonate ligand.

The present invention is alleged is that the structure of bi-beta-diketo class ligand molecular of substrate is as follows with the carbazole:

R wherein ₁, R ₂Be selected from phenyl, trifluoromethyl, R ₁With R ₂Can be identical, also can be different;

R is selected from ethyl, propyl group, butyl, amyl group, hexyl; But R1, R2 be all trifluoromethyl, R be ethyl except.

The preparation method of this ligand compound, be that parent (raw material) comprises substitution reaction, acylation reaction and synthetic and unit process such as separate with the carbazole, it is characterized in that: described substitution reaction is that carbazole and haloalkane refluxed in organic solvent 20～30 hours by the mol ratio by 1: 1～1.2, obtain white solid after the separation, i.e. intermediate N alkyl carbazole (9-alkyl carbazole) I; Described acylation reaction is that intermediate compound I and acyl chlorides reacted under the room temperature 10～15 hours in organic solvent by 1: 2～2.2 mol ratio, obtains faint yellow needle-like crystal after the separation, i.e. intermediate N alkyl-3,6-diacyl carbazole (II); Described synthesizing is that the intermediate II organic acid methyl ester was reacted under room temperature 2～7 hours by 1: 2～2.2 mol ratio, and obtaining the glassy yellow needle-like crystal after the separation is carbazole Bis-beta-diketonate ligand (carbazole diketone part).

Concrete synthetic route is as follows: (R is an ethyl, R ₁, R ₂Be all phenyl)

The alleged carbazole Bis-beta-diketonate rare earth compounding of the present invention is a carbazole diketone part and nitrate of rare earth element back flow reaction 3～5 hours in mixed organic solvents, obtains the carbazole Bis-beta-diketonate rare earth compounding after the separation.This title complex can be applicable to prepare the functional materials of photoluminescence.

Characteristics of the present invention

1, from having the active carbazole of photoelectric functional, pass through molecular designing, the synthetic first novel bi-beta-diketo compound of a class, utilize its good chelating coordination, form stable title complex with rare earth ion, dexterously the mechanical stability of inorganics, thermostability are combined with the high optical activity of organic ligand, obtain comparatively ideal organic/inorganic composite optical function material.

2, utilize the synergy of outstanding luminous of rare earth ion and carbazole derivative bi-beta-diketo part, exist high efficiency energy transmission in the title complex from bi-beta-diketo part to rare earth ion with high uv-absorbing coefficient, improve the luminous efficiency of rare earth ion, obtained the good luminous molecular material of a class monochromaticity.By observing the solid fluorescence spectrogram of europium complex, find at the emission peak of ruddiness zone europium very by force and sharp-pointed, peak width at half height is very narrow, is several nanometers only, and in the title complex emission peak of part a little less than than the part of free state many.For shown in Figure 1.

3, by changing electron-donating group, can change the solubleness of compound in different solvents on the one hand, can optimize its character on the other hand, improve luminous efficiency.For shown in Figure 2.

4, the synthetic method of such compound is simple, and raw material is easy to get, and no matter the thermostability height is wiring solution-forming, still does film forming, all is the good molecular material that glows of monochromaticity with application prospect.

Four, description of drawings

Fig. 1: R ₁, R ₂For phenyl, R are the carbazole diketone europium complex photoluminescence collection of illustrative plates of ethylbenzene, europium has very strong red emission at the 611nm place, and peak width at half height is 3.5nm; Insertion figure is that the emission spectrum of 525～545nm wavelength region amplifies, and a weak part emission peak is arranged at the 533nm place, and its intensity falls sharply.

Fig. 2: R ₁, R ₂For trifluoromethyl, R are the carbazole diketone europium complex photoluminescence collection of illustrative plates of hexyl, europium has very strong red emission at the 612nm place, and peak width at half height only is 2nm; Insertion figure is that the emission spectrum of 400～510nm wavelength region amplifies, and a weak part emission peak is arranged at the 433nm place.

Five, embodiment

With the substrate is carbazole, R ₁, R ₂Be phenyl, R is that ethyl is described below for the example non-limiting examples:

1. the preparation of intermediate compound I (N-ethyl carbazole)

Carbazole is mixed with monobromethane, is added in the organic solvent (acetone), reflux to stir 20-30 hour, cool off white precipitate, be N-ethyl carbazole (9-ethyl carbazole).

2. the preparation of intermediate II (9-ethyl-3,6-diacetyl carbazole)

Intermediate compound I (N-ethyl carbazole) is dissolved in CH ₂Cl ₂, mix with acetyl chloride, stir, room temperature reaction 10-15 hour, faint yellow needle-like crystal, i.e. 9-ethyl-3,6-diacetyl carbazole.

3. part (9-ethyl-3,6-two (benzoyl ethanoyl) carbazole) is synthetic

With 9-ethyl-3,6-diacetyl carbazole mixes with methyl benzoate, stirs, and room temperature reaction 2～6 hours gets the glassy yellow needle-like crystal.

4. rare earth compounding is synthetic

(1) europium nitrate is dissolved in anhydrous methanol, the bi-beta-diketo part is dissolved in CHCl ₃, both mix, and stir, and reflux, and react 3～5 hours, obtain yellow mercury oxide, are the title complex of bi-beta-diketo europium.

(2) neodymium nitrate is dissolved in anhydrous methanol, the bi-beta-diketo part is dissolved in CHCl ₃, both mix, and stir, and reflux, and react 3～5 hours, obtain yellow mercury oxide, are the title complex of carbazole Bis-beta-diketonate neodymium.

(3) cerous nitrate is dissolved in anhydrous methanol, the bi-beta-diketo part is dissolved in CHCl ₃, both mix, and stir, and reflux, and react 3～5 hours, obtain yellow mercury oxide, are the title complex of carbazole Bis-beta-diketonate cerium.

Claims

1. 1 .A kind of carbazole Bis-beta-diketonate ligand is characterized in that by the compound shown in the following chemical formula

In the formula: R ₁, R ₂Be selected from phenyl, trifluoromethyl, R ₁With R ₂Can be identical, also can be inequality;

2. by the preparation method of the described carbazole diketone of claim 1 part, comprise substitution reaction, acylation reaction and synthetic and separate each unit process, it is characterized in that:

(1), described substitution reaction is carbazole and separate after haloalkane refluxed in organic solvent 20～30 hours by 1: 1～1.2 mol ratio, obtains intermediate N alkyl carbazole (I);

(2), to be intermediate (I) with acyl chlorides react under the room temperature in organic solvent by 1: 2～2.2 mol ratio described acylation reaction separates after 10～15 hours, obtains intermediate N alkyl-3,6-diacyl carbazole (II);

(3), described synthetic be that intermediate (II) separates after reacting 2～6 hours under the room temperature by 1: 2～2.2 mol ratio with organic acid methyl ester, obtain carbazole Bis-beta-diketonate ligand.

3. by the purposes of the described carbazole diketone of claim 1 part, it is characterized in that: this part is preparing the carbazole Bis-beta-diketonate rare earth compounding as the application in the embedded photoluminescent material with rare earth ion.

4. purposes according to claim 3 is characterized in that: this part and the application of europium in the conduct of preparation carbazole Bis-beta-diketonate europium complex glows material.