CN102584870A - Rare-earth 2,4,6-tri(2-pyridyl) triazine complex containing aromatic carboxylic acid and preparation method for complex - Google Patents

Abstract

The invention discloses a rare earth organic light-emitting complex containing europium, terbium, samarium, 2,4,6-tripyridyl triazine, aromatic carboxylate ions and derivatives thereof and a preparation method thereof. It is characterized in that its chemical formula is RE _x (TPTZ) _x A _y B _z (C ₂ H ₅ OH) nH ₂ O, wherein RE is one of Sm ³⁺ , Eu ³⁺ , Tb ³⁺ , and A is Aromatic carboxylic acids and derivatives thereof, B is a negative monovalent inorganic anion, x=1 or 2, y>0, z≥0, n is a positive integer of 1-8; when A is a monocarboxylate, 3x= y+z; when A is a dibasic carboxylate, 3x=2y+z; TPTZ is 2,4,6-tripyridyltriazine. The rare earth organic light-emitting complex provided by the invention contains two organic ligands of TPTZ, aromatic carboxylate ions and derivatives thereof, and has good stability, excellent solubility, long service life and high luminous efficiency. The preparation method of the invention has the advantages of simple operation, mild conditions, strong controllability, short processing time and low energy consumption.

Description

A rare earth 2,4,6-tripyridyl triazine complex containing aromatic carboxylic acid and its preparation method

technical field

The present invention relates to a rare earth organic luminescent complex and a preparation method thereof, in particular to a complex containing europium, terbium, samarium, 2,4,6-tripyridyl triazine, aromatic carboxylate ions and derivatives thereof and its preparation method.

Background technique

Rare earth organic complexes are a kind of luminescent materials with good performance due to their excellent narrow-band luminescence properties and long fluorescence lifetime, and have been widely used in the field of optics. In addition, due to its high luminous intensity and good monochromaticity, it is also widely used in the fields of bioanalytical chemistry, laser materials, anti-counterfeiting trademarks, and color-changing inks.

Aromatic carboxylate ions are commonly used organic anion ligands, they can form stable complexes with rare earth ions, and can also act as "antennas" to transfer absorbed light energy to rare earth ions. Due to the electrostatic repulsion between inorganic anions, it is difficult for inorganic anions alone to saturate the coordination of rare earth ions, resulting in more solvent molecules participating in the coordination of rare earth ions, which reduces the luminous efficiency of rare earth ions.

Neutral organic ligands such as nitrogen-containing aromatic heterocyclic rings can absorb ultraviolet or visible light well, and can effectively transfer and transfer energy to the rare earth ions coordinated with them, thereby enhancing the luminescence intensity of rare earth complexes. Moreover, they can replace solvent molecules to coordinate with rare earth ions, thereby reducing the energy loss caused by solvent molecules. However, the complexes formed by neutral organic ligands and rare earth ions often contain more inorganic anions such as hydroxide, which quench the luminescence of rare earth ions. Therefore, it is of great significance to study the complexes composed of organic anionic ligands, neutral organic ligands and rare earth ions to obtain rare earth compounds with higher luminous efficiency.

2,4,6-tripyridyl-1,3,5-triazine (2,4,6-tri(2-pyridyl)-1,3,5-triazine, referred to as TPTZ) has multiple aromatic rings. It absorbs light well and transmits energy well. At the same time, the ligand has multiple nitrogen atom coordination points, and can form a five-membered ring with rare earth ions, which makes the complex have special stability. In 1969, Durham et al. synthesized the 2,4,6-tripyridyltriazine complex of lanthanide elements [Ln(TPTZ)(NO ₃ ) ₃ (H ₂ O)]·2H ₂ O for the first time in ethanol solution (Ln=La-Nd, Sm-Lu, Y; Journal of Inorganic Nuclear Chemistry, 1969, 31, 571). There are few reports about rare earth ions and TPTZ and organic anion ligands. In 2004, Zhiping Zheng et al. synthesized Eu(DBM) ₃ (TPTZ) ternary complexes and reported that the complexes had stronger luminescence intensity (Inorganica ChimicaActa , 2004, 357, 630), wherein DBM is the ligand of β-diketones.

Contents of the invention

The purpose of the present invention is to overcome the shortcomings and deficiencies of the prior art, and provide a rare earth organic light-emitting complex containing europium, terbium, samarium, TPTZ, aromatic carboxylate ions and derivatives thereof and a preparation method thereof. It is characterized in that it contains two organic ligands of TPTZ and aromatic carboxylate ions and its derivatives at the same time. Compared with the complex containing only TPTZ, a neutral organic ligand, this type of complex has stronger luminous intensity. The rare earth organic luminescent complex provided by the invention has good stability, excellent solubility, long service life and high luminous efficiency. The preparation method of the invention has the advantages of simple operation, mild conditions, strong controllability, short processing time and low energy consumption.

The object of the present invention is achieved through the following technical solutions:

A rare earth organic luminescent complex containing europium, terbium, samarium, TPTZ, aromatic carboxylate ions and derivatives thereof, characterized in that its chemical formula is RE _x (TPTZ) _x A _y B _z (C ₂ H ₅ OH) nH ₂ O, where RE is one of Sm ³⁺ , Eu ³⁺ , Tb ³⁺ , A is an aromatic carboxylate and its derivatives, B is a negative monovalent inorganic anion, x=1 or 2, y >0, z≥0, n is a positive integer of 1-8; when A is a monocarboxylate, 3x=y+z; when A is a dicarboxylate, 3x=2y+z; TPTZ is 2,4 , 6-tripyridyl triazine, its structural formula is:

Described aromatic carboxylate and derivatives thereof (A) are selected from benzoate, phenoxyacetate, o-hydroxybenzoate, m-hydroxybenzoate, p-hydroxybenzoate, p-nitrobenzoate, p- One of hydroxyphenoxyacetate, phthalate, isophthalate, terephthalate, and 1-naphthoate.

The negative monovalent inorganic anion (B) is selected from one or more of Cl ^- , Br ^- , I ^- , ClO ₄ ^- , NO ₃ ^- .

A method for preparing rare earth organic luminescent complex RE _x (TPTZ) _x A _y B _z (C ₂ H ₅ OH) nH ₂ O containing europium, terbium, samarium, TPTZ, aromatic carboxylate and derivatives thereof, comprising The following steps:

(1) Dissolve TPTZ in absolute ethanol, add a certain amount of ethanol solution of rare earth inorganic salt REB ₃ under stirring at 30°C to reflux temperature, and heat and stir for 0.5-24 hours at the reaction temperature from 30°C to reflux temperature , and then add a certain amount of ethanol and water mixed solution of aromatic carboxylic acid and its derivatives, adjust the pH value to 5-8, continue heating and stirring for 1-24 hours, and let stand overnight.

Wherein, the concentration of the ethanol solution of TPTZ is 0.001-1.0mol/L;

Wherein, the molar ratio of the rare earth inorganic salt REB ₃ to TPTZ is 1:1;

Wherein, the molar ratio of the aromatic carboxylic acid and its derivatives to TPTZ is 0.5-3:1;

Wherein, the volume ratio of ethanol and water in the mixed solution of ethanol and water is 20:1 to 1:20;

Wherein, the reaction temperature is further optimized as 50°C to reflux temperature, the pH range is further optimized as 6-7, the heating and stirring time is further optimized as 1-5 hours, and the heating and stirring time is further optimized Optimized for 1-5 hours;

(2) Filter the mixture obtained in step (1), wash the filter cake with absolute ethanol, and dry to obtain the rare earth organic complex.

Description of drawings

FIG. 1 is the fluorescence emission spectrum of Eu(TPTZ)(NO ₃ ) ₃ (C ₂ H ₅ OH)·H ₂ O prepared in Comparative Example 1.

Fig. 2 is the fluorescence emission spectrum of Eu(TPTZ)(C ₆ H ₅ COO) ₃ ·4H ₂ O prepared in Example 1 of the invention.

Fig. 3 is the fluorescence emission spectrum of Eu ₂ (TPTZ) ₂ (C ₈ H ₄ O ₄ )(NO ₃ ) ₄ (C ₂ H ₅ OH)·H ₂ O prepared in Example 2 of the invention.

4 is a fluorescence emission spectrum of Tb(TPTZ)(NO ₃ ) ₃ (C ₂ H ₅ OH)·H ₂ O prepared in Comparative Example 2. FIG.

Fig. 5 is a fluorescence emission spectrum of Tb(TPTZ)(C ₇ H ₅ O ₃ ) ₃ (C ₂ H ₅ OH)·2H ₂ O prepared in Example 3 of the invention.

Fig. 6 is a fluorescence emission spectrum of Tb ₂ (TPTZ) ₂ (C ₈ H ₄ O ₄ )(NO ₃ ) ₄ (C ₂ H ₅ OH)·H ₂ O prepared in Example 4 of the invention.

7 is a fluorescence emission spectrum of Sm(TPTZ)(NO ₃ ) ₃ (C ₂ H ₅ OH)·H ₂ O prepared in Comparative Example 3. FIG.

Fig. 8 is the fluorescence emission spectrum of Sm(TPTZ)(C ₇ H ₅ O ₃ ) ₃ (C ₂ H ₅ OH)·2H ₂ O prepared in Example 5 of the invention.

Detailed ways

The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments, but the present invention is not limited in any way.

The measurement method of the fluorescence spectrum and fluorescence quantum yield of the complex: at room temperature, the solid powder of the complex is measured with a FLS-920 fluorescence spectrometer for its fluorescence spectrum. The excitation and emission slits of the europium, terbium, and samarium complexes are respectively 3 nm, 1nm, 5nm, excitation wavelengths are 362nm, 355nm, 370nm respectively. The fluorescence quantum yield is calculated based on the fluorescence intensity and fluorescence lifetime of the complex (Journal of Fluorescence, 2009, 19, 641).

Comparative example 1

Weigh 0.936g (3.0mmol) of TPTZ, add 30mL of absolute ethanol to dissolve, stir at 50°C to dissolve completely, add 30mL of Eu(NO ₃ ) ₃ absolute ethanol solution with a concentration of 0.1mol/L, and use a mass concentration of 7 % ammonia water to adjust the pH value to 6.2, and a white precipitate appeared, and the stirring reaction was continued for 3 hours, and the mixture was allowed to stand overnight. After the white solid is filtered, washed with absolute ethanol and dried, the white powder obtained is the Eu(TPTZ)(NO ₃ ) ₃ (C ₂ H ₅ OH)·H ₂ O product. The element composition analysis results are: experimental value (theoretical value), C%, 33.28 (33.63); H%, 2.91 (2.82); N%, 17.52 (17.65); Eu%, 21.28 (21.27). The fluorescence emission spectrum (Fig. 1) shows that the complex exhibits pure red emission, the strongest emission wavelength is 615nm, and the intensity is 9.3×10 ³ au. The fluorescence quantum yield of the complex is 12.29%.

Example 1

Weigh 0.936g (3.0mmol) of TPTZ, add 30mL of absolute ethanol to dissolve, stir at 50°C to dissolve completely, add 30mL of EuCl ₃ absolute ethanol solution with a concentration of 0.1mol/L, stir and reflux for 1 hour, then add 30mL of Be the ethanol/aqueous solution of the benzoic acid of 0.3mol/L (the volume ratio of ethanol and water is 1: 1), be that the ammoniacal liquor of 7% is adjusted pH value to 6.5 with mass concentration, white precipitate appears, continue to stir reflux reaction 2 hours, Let stand overnight. After the white solid is filtered, washed with absolute ethanol and water and dried, the white powder obtained is the Eu(TPTZ)(C ₆ H ₅ COO) ₃ ·4H ₂ O product. The element composition analysis results are: experimental value (theoretical value), C%, 52.28 (52.06); H%, 3.76 (3.92); N%, 9.45 (9.34); Eu%, 16.47 (16.89). The fluorescence emission spectrum (Fig. 2) shows that the complex exhibits pure red emission, the strongest emission wavelength is 616nm, and the intensity is 2.8×10 ⁵ au. The fluorescence quantum yield of the complex is 15.23%.

Example 2

Weigh 0.936g (3.0mmol) of TPTZ, add 30mL of absolute ethanol to dissolve, stir at 50°C to dissolve completely, add 30mL of Eu(NO ₃ ) ₃ absolute ethanol solution with a concentration of 0.1mol/L, and stir at 70°C for 1 hour , then add 30mL concentration of 0.05mol/L ethanol/water solution of terephthalic acid (the volume ratio of ethanol to water is 10:1), adjust the pH value to 6.3 with mass concentration of 7% ammonia, and continue to stir for 2 hours, let stand overnight. After the white solid is filtered, washed with absolute ethanol and dried, the white powder obtained is Eu ₂ (TPTZ) ₂ (C ₈ H ₄ O ₄ )(NO ₃ ) ₄ (C ₂ H ₅ OH)·H ₂ O product . The analysis results of its element composition are: experimental value (theoretical value), C%, 39.12 (39.33); H%, 2.62 (2.58); N%, 15.82 (15.95); Eu%, 21.42 (21.63). The fluorescence emission spectrum (Fig. 3) shows that the complex exhibits pure red emission, the strongest emission wavelength is 616nm, and the intensity is 1.0×10 ⁶ au. The fluorescence quantum yield of the complex is 43.95%.

Comparative example 2

Weigh 0.936g (3.0mmol) of TPTZ, add 30mL of absolute ethanol to dissolve, stir at 60°C to dissolve completely, add 30mL of Tb(NO ₃ ) ₃ absolute ethanol solution with a concentration of 0.1mol/L, and use a mass concentration of 7 % ammonia water to adjust the pH value to 6.2, and a white precipitate appeared, and the stirring reaction was continued for 3 hours, and the mixture was allowed to stand overnight. After the white solid is filtered, washed with absolute ethanol and dried, the white powder obtained is Tb(TPTZ)(NO ₃ ) ₃ (C ₂ H ₅ OH)·H ₂ O product. The element composition analysis results are: experimental value (theoretical value), C%, 33.32 (33.30); H%, 2.63 (2.79); N%, 17.42 (17.48); Tb%, 22.12 (22.03). The fluorescence emission spectrum (Fig. 4) shows that the complex emits pure green light, the strongest emission wavelength is 542nm, and the intensity is 2.4×10 ⁴ au.

Example 3

Weigh 0.936g (3.0mmol) of TPTZ, add 30mL of absolute ethanol to dissolve, stir at 60°C to dissolve completely, add 30mL of Tb(NO ₃ ) ₃ absolute ethanol solution with a concentration of 0.1mol/L, and stir at 70°C for 1 hour , then add 30 mL of ethanol/water solution (the volume ratio of ethanol to water is 10:1) of 0.3 mol/L p-hydroxybenzoic acid, adjust the pH value to 6.4 with mass concentration of 7% ammonia, and continue stirring for 2 hours, let stand overnight. After the white solid is filtered, washed with absolute ethanol and dried, the white powder obtained is Tb(TPTZ)(C ₇ H ₅ O ₃ ) ₃ (C ₂ H ₅ OH)·2H ₂ O product. Its element composition analysis results are: experimental value (theoretical value), C%, 50.14 (51.05); H%, 4.17 (3.87); N%, 8.59 (8.71); Tb%, 16.52 (16.47). The fluorescence emission spectrum (Fig. 5) shows that the complex emits pure green light, the strongest emission wavelength is 542nm, and the intensity is 2.6×10 ⁴ au.

Example 4

Weigh 0.936g (3.0mmol) of TPTZ, add 30mL of absolute ethanol to dissolve, stir at 55°C to dissolve completely, add 30mL of Tb(NO ₃ ) ₃ absolute ethanol solution with a concentration of 0.1mol/L, and stir at 70°C for 1 hour , then add 30mL concentration of 0.05mol/L ethanol/water solution of terephthalic acid (the volume ratio of ethanol to water is 10:1), adjust the pH value to 6.6 with mass concentration of 7% ammonia, and continue stirring for 2 hours, let stand overnight. After the white solid is filtered, washed with absolute ethanol and dried, the white powder obtained is Tb ₂ (TPTZ) ₂ (C ₈ H ₄ O ₄ )(NO ₃ ) ₄ (C ₂ H ₅ OH)·H ₂ O product . The element composition analysis results are: experimental value (theoretical value), C%, 38.52 (38.94); H%, 2.67 (2.56); N%, 15.54 (15.80); Tb%, 22.27 (22.40). The fluorescence emission spectrum (Fig. 6) shows that the complex exhibits pure green emission, the strongest emission wavelength is 542nm, and the intensity is 9.3×10 ⁴ au.

Comparative example 3

Weigh 0.936g (3.0mmol) of TPTZ, add 30mL of absolute ethanol to dissolve, stir at 60°C to dissolve completely, add 30mL of Sm(NO ₃ ) ₃ absolute ethanol solution with a concentration of 0.1mol/L, and use a mass concentration of 7 % ammonia water to adjust the pH value to 6.2, and a white precipitate appeared, and the stirring reaction was continued for 3 hours, and the mixture was allowed to stand overnight. After the white solid is filtered, washed with absolute ethanol and dried, the white powder obtained is the Sm(TPTZ)(NO ₃ ) ₃ (C ₂ H ₅ OH)·H ₂ O product. The element composition analysis results are: experimental value (theoretical value), C%, 33.63 (33.70); H%, 2.55 (2.83); N%, 17.65 (17.69); Sm%, 21.00 (21.09). The fluorescence emission spectrum shows that the strongest emission wavelength of the complex is 595nm, and the intensity is 1.2×10 ⁴ au.

Example 5

Weigh 0.936g (3.0mmol) of TPTZ, add 30mL of absolute ethanol to dissolve, stir to dissolve completely, add 60mL of Sm(NO ₃ ) ₃ absolute ethanol solution with a concentration of 0.1mol/L, stir at 70°C for 1 hour, then add 30 mL of 0.3 mol/L ethanol/water solution of p-hydroxybenzoic acid (the volume ratio of ethanol to water is 10:1), adjust the pH value to 6.4 with 7% ammonia water, continue stirring for 2 hours, and wait Leave overnight. After the white solid is filtered, washed with absolute ethanol and dried, the white powder obtained is the Sm(TPTZ)(C ₇ H ₅ O ₃ ) ₃ (C ₂ H ₅ OH)·2H ₂ O product. Its element composition analysis results are: experimental value (theoretical value), C%, 51.14 (51.50); H%, 4.10 (3.90); N%, 8.76 (8.79); Sm%, 15.41 (15.73). The fluorescence emission spectrum shows that the emission wavelength of the complex is 595nm and the intensity is 1.6×10 ⁴ au.

It can be seen from the comparative examples and examples that, compared with the binary rare earth organic luminescent complexes formed by europium, terbium, samarium and 2,4,6-tripyridyl triazine, the complexes formed after the introduction of aromatic carboxylate ligands Ternary rare earth ions have stronger luminous intensity and higher fluorescence quantum yield.

Claims (10)

1. one kind contains europium, terbium, samarium and 2,4, the organic light-emitting rare earth complexe of 6-TPTZ and aromatic carboxylic acid radical ion and verivate thereof, and the chemical formula that it is characterized in that it is RE _x(TPTZ) _xA _yB _z(C ₂H ₅OH) nH ₂O, wherein RE is Sm ³⁺, Eu ³⁺, Tb ³⁺In a kind of, A is aromatic carboxylic acid root and verivate thereof, B is negative univalent inorganic anion, x=1 or 2, y＞0, z>=0, n is the positive integer of 1-8; When A is the monocarboxylic acid root, 3x=y+z; When A is the di-carboxylic acid root, 3x=2y+z; TPTZ is 2,4, the 6-TPTZ, and its structural formula is:

2. one kind prepares the organic light-emitting rare earth complexe RE that contains europium, terbium, samarium and TPTZ and aromatic carboxylic acid root and verivate thereof _x(TPTZ) _xA _yB _z(C ₂H ₅OH) nH ₂The method of O may further comprise the steps:

(1) TPTZ is used anhydrous alcohol solution, is made into the solution that concentration is 0.001-1.0mol/L, 30 ℃ to reflux temperature, stir and to add a certain amount of inorganic salt of rare earth REB down ₃Ethanolic soln, 30 ℃ to the temperature of reaction of reflux temperature heated and stirred 0.5-24 hour, add the ethanol and the water mixed solution of a certain amount of aromatic carboxylic acid and verivate thereof then, regulate the pH value to 5-8, continued heated and stirred 1-24 hour, hold over night.

(2) mixture with step (1) gained filters, and filter cake is used absolute ethanol washing, and oven dry gets rare earth organic complex.

3. title complex as claimed in claim 1; It is characterized in that described aromatic carboxylic acid root and verivate (A) thereof are selected from a kind of in benzoate anion, phenoxy acetic acid root, salicylic acid root, m-Salicylic acid root, PHB root, p-Nitrobenzenecarboxylic acid root, para hydroxybenzene fluoroacetic acid root, phthalate, m-phthalic acid root, terephthaldehyde's acid group, the 1-naphthoic acid root.

4. title complex as claimed in claim 1 is characterized in that, described aromatic carboxylic acid root and verivate (A) thereof are selected from a kind of in benzoate anion, PHB root, the terephthaldehyde's acid group.

5. title complex as claimed in claim 1 is characterized in that, described negative univalent inorganic anion (B) is selected from Cl ^-, Br ^-, I ^-, ClO ₄ ^-, NO ₃ ^-In one or more.

6. method as claimed in claim 2 is characterized in that, described inorganic salt of rare earth REB ₃With the mol ratio of TPTZ be 1: 1.

7. method as claimed in claim 2 is characterized in that, the mol ratio of aromatic carboxylic acid and verivate thereof and TPTZ is 0.5-3: 1.

8. method as claimed in claim 2 is characterized in that, the volume ratio of second alcohol and water is 20: 1 to 1: 20 in described ethanol and the water mixed solution.

9. method as claimed in claim 2 is characterized in that, said temperature of reaction can further be optimized for 50 ℃ to reflux temperature.

10. method as claimed in claim 2 is characterized in that, said pH value scope can further be optimized for 6-7.

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