CN107698610B - Europium complex red luminescent material and synthetic method thereof - Google Patents

Europium complex red luminescent material and synthetic method thereof Download PDF

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CN107698610B
CN107698610B CN201710924725.3A CN201710924725A CN107698610B CN 107698610 B CN107698610 B CN 107698610B CN 201710924725 A CN201710924725 A CN 201710924725A CN 107698610 B CN107698610 B CN 107698610B
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唐群
张宁
李鹏飞
邹志明
张淑芬
梁福沛
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Yami Technology Guangzhou Co ltd
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Abstract

The invention discloses a europium complex red luminescent material and a synthesis method thereof. The europium complex red luminescent material has the chemical formula: [ Eu (C)10H8NO2)3(CH3OH)2]·CH3OH, molecular formula is: c33H36EuN3O9The molecular weight is: 770.62. the analytically pure methanol solution of europium chloride hexahydrate and the analytically pure methanol solution of 3-indoleacetic acid and potassium hydroxide are mixed uniformly. Naturally volatilizing at normal temperature, and obtaining colorless transparent needle crystals after one week. [ Eu (C)10H8NO2)3(CH3OH)2]·CH3OH produces red fluorescence with an intensity of 194365a.u. at 615nm wavelength with a luminescence lifetime of 0.956ms at an excitation wavelength of 365 nm. The method has the advantages of simple process, low cost, easy control of chemical components, good repeatability, high yield and the like.

Description

Europium complex red luminescent material and synthetic method thereof
Technical Field
The invention belongs to the technical field of complex preparation, and particularly relates to a europium complex red luminescent material [ Eu (C)10H8NO2)3(CH3OH)2]·CH3OH and a synthetic method.
Background
Modern luminescent materials have been supporting materials in the fields of information display, lighting sources, photoelectric devices and the like after decades of development, and are increasingly important for social development and technical progress. Especially at the present time of energy shortage, the development of luminescent materials with high conversion efficiency is one of the methods for solving the problem of energy shortage. MOFs materials have structural diversity, which also has great potential in light emitting properties. In the field of luminescent materials, fromRare earth metal and d10Transition metals in electronic configuration have received a great deal of attention. At present, the research on luminescent materials mainly focuses on three aspects of white light emitting materials, near infrared light emitting materials and luminescent thermometers. In addition, 3-indoleacetic acid has a highly conjugated benzopyrrole ring, indicating that it is an excellent chromophore. The complex formed by the rare earth metal europium and the 3-indoleacetic acid has various structures, and has great research significance for designing and synthesizing the complex with a target structure.
Disclosure of Invention
The invention aims to provide a europium complex red luminescent material [ Eu (C)10H8NO2)3(CH3OH)2]·CH3OH and a synthetic method.
The idea of the invention is as follows: the europium complex is obtained by utilizing 3-indoleacetic acid and europium chloride hexahydrate through a normal-temperature volatilization method.
The europium complex has the chemical formula as follows: [ Eu (C)10H8NO2)3(CH3OH)2]·CH3OH, molecular formula is: c33H36EuN3O9The molecular weight is: 770.62 belonging to the monoclinic system, P21The/c space group. The central ion is Eu3+. In the complex, Eu in the center3+Is nine-coordinate, Eu3+The nine coordinating oxygen atoms are from four different 3-indoleacetic acid ligands and two methanol molecules, respectively. Eu (Eu)3+The clusters are further stacked to form a three-dimensional network structure by utilizing the pi-pi interaction of a benzopyrrole ring on a 3-indoleacetic acid ligand. The crystal structure data are shown in the table I, and the bond angles of part of the bond lengths are shown in the table II.
TABLE 1 [ L a (C)10H8NO2)3CH3OH]·CH3Crystal parameter of OH
Figure BDA0001427386830000011
Figure BDA0001427386830000021
aR1＝Σ||Fo|–|Fc||/Σ|Fo|.bwR2＝[Σw(|Fo 2|–|Fc 2|)2/Σw(|Fo 2|)2]1/2
TABLE II [ L a (C)10H8NO2)3CH3OH]·CH3Bond length of OH
Figure BDA0001427386830000023
Angle of harmony key (°)
Figure BDA0001427386830000022
Figure BDA0001427386830000031
Symmetry codes:(i)-x,-y+2,-z.
The [ Eu (C)10H8NO2)3(CH3OH)2]·CH3Specific steps of OH synthesis:
(1) 0.1832g of analytically pure europium chloride hexahydrate are weighed out and placed in 20m L analytically pure anhydrous methanol and stirred for half an hour.
(2) 0.2625g of analytically pure 3-indoleacetic acid and 0.084g of analytically pure potassium hydroxide are weighed out and dissolved in 20-30 m L analytically pure anhydrous methanol, and stirred for half an hour.
(3) 0.1832g of analytically pure europium chloride hexahydrate, 0.2625g of analytically pure 3-indoleacetic acid and 0.084g of analytically pure potassium hydroxide are dissolved in 40-50 m L analytically pure anhydrous methanol, stirred at room temperature for half an hour and then filtered to obtain colorless clear filtrate.
(4) And (3) uniformly mixing the solutions obtained in the steps (1) and (2), stirring for half an hour to obtain a colorless clear liquid, and filtering.
(5) Putting the filtrate obtained in the step (3) or the step (4) into a 100m L beaker, and sealing by a preservative film;after one week, colorless transparent needle-like crystals are generated at the bottom of the beaker [ Eu (C)10H8NO2)3(CH3OH)2]·CH3OH。
The method has the advantages of simple process, low cost, easy control of chemical components, good repeatability, high yield and the like.
At room temperature, compound [ Eu (C)10H8NO2)3(CH3OH)2]·CH3The luminescence properties of the OH crystallite samples were determined. [ Eu (C)10H8NO2)3(CH3OH)2]·CH3The emission spectrum of OH, measured at an excitation wavelength of 365nm, gives a red fluorescence with an intensity of 194365a.u. at a wavelength of 615nm, with a luminescence lifetime of 0.956 ms.
Drawings
FIG. 1 shows [ Eu (C) of the present invention10H8NO2)3(CH3OH)2]·CH3OH molecular structure diagram.
FIG. 2 shows [ Eu (C) according to the present invention10H8NO2)3(CH3OH)2]·CH3Structure stacking diagram of OH complex.
FIG. 3 shows [ Eu (C) according to the present invention10H8NO2)3(CH3OH)2]·CH3Emission spectrum of OH at 365nm excitation wavelength.
FIG. 4 shows [ Eu (C) according to the present invention10H8NO2)3(CH3OH)2]·CH3And the luminous life spectrum of OH at the excitation wavelength of 365 nm.
FIG. 5 shows [ Eu (C) according to the present invention10H8NO2)3(CH3OH)2]·CH3And (3) a luminous photo of OH under a 365nm ultraviolet lamp.
Detailed Description
Example 1:
(1) 0.1832g of analytically pure europium chloride hexahydrate is weighed, placed in 20m L analytically pure anhydrous methanol and stirred for half an hour;
(2) weighing 0.2625g of analytically pure 3-indoleacetic acid and 0.084g of analytically pure potassium hydroxide, dissolving in 20m L analytically pure anhydrous methanol, and stirring for half an hour;
(3) uniformly mixing the solutions obtained in the steps (1) and (2), stirring for half an hour to obtain a colorless clear solution, filtering, placing the filtrate into a 100m L beaker, sealing a preservative film, generating colorless and transparent needle crystals at the bottom of the beaker after one week, wherein the yield is 0.139g, and the yield is 75.87%, and measuring [ Eu (C) by a single crystal diffractometer10H8NO2)3(CH3OH)2]·CH3The OH structure, crystal structure data are shown in Table I, and bond length and bond angle data are shown in Table II.
Example 2:
(1) 0.1832g of analytically pure europium chloride hexahydrate, 0.2625g of analytically pure 3-indoleacetic acid and 0.084g of analytically pure potassium hydroxide are dissolved in 50m L analytically pure anhydrous methanol, the mixture is stirred at room temperature for half an hour and then filtered to obtain colorless clear filtrate, the filtrate is placed in a 100m L beaker, a preservative film is sealed, after one week, colorless transparent needle crystals are generated at the bottom of the beaker, the yield is 0.143g, the yield is 81.02%, and [ Eu (C) is measured by a single crystal diffractometer10H8NO2)3(CH3OH)2]·CH3The OH structure, crystal structure data are shown in Table I, and bond length and bond angle data are shown in Table II.
(2) Taking [ Eu (C) obtained in the step (1)10H8NO2)3(CH3OH)2]·CH3A crystal sample of OH was subjected to fluorescence measurement and under 365nm incident light illumination, red fluorescence with an intensity of 194365a.u. was generated at 615nm wavelength and its emission lifetime reached 0.965 ms.

Claims (2)

1. A europium complex red luminescent material is characterized in that the chemical formula of the europium complex red luminescent material is as follows: [ Eu (C)10H8NO2)3(CH3OH)2]·CH3OH, molecular formula is: c33H36EuN3O9The molecular weight is: 770.62, C10H8NO2Is 3-indoleacetate; crystal structure data are shown in a table I, and partial bond length and bond angle are shown in a table II; the compound belongs to a monoclinic system, P21A/c space group with Eu as central ion3+；[Eu(C10H8NO2)3(CH3OH)2]·CH3OH produces red fluorescence with intensity 194365a.u. at 615nm wavelength with a luminescence lifetime of 0.956ms at 365nm excitation wavelength;
table one: [ Eu (C)10H8NO2)3(CH3OH)2]·CH3Crystal parameter of OH
Figure FDA0001427386820000011
aR1＝Σ||Fo|–|Fc||/Σ|Fo|.bwR2＝[Σw(|Fo 2|–|Fc 2|)2/Σw(|Fo 2|)2]1/2
Table two: [ Eu (C)10H8NO2)3(CH3OH)2]·CH3Bond length of OH
Figure FDA0001427386820000021
Angle of harmony key (°)
Eu1—O3i 2.335(2) Eu1—O6 2.384(2) Eu1—O7 2.394(2) Eu1—O8 2.405(2) Eu1—O1 2.434(2) Eu1—O4 2.449(2) Eu1—O5 2.456(2) Eu1—O2 2.469(2) Eu1—O3 2.5524(18) O3—Eu1i 2.335(2) O3i—Eu1—O6 84.89(7) O3i—Eu1—O7 154.49(7) O6—Eu1—O7 75.05(8) O3i—Eu1—O8 79.15(7) O6—Eu1—O8 77.32(7) O7—Eu1—O8 81.16(8) O3i—Eu1—O1 76.87(7) O6—Eu1—O1 125.71(8) O7—Eu1—O1 127.78(7) O8—Eu1—O1 144.38(7) O3i—Eu1—O4 118.60(7) O6—Eu1—O4 145.09(8) O7—Eu1—O4 74.15(7) O8—Eu1—O4 82.10(8) O1—Eu1—O4 86.67(8) O3i—Eu1—O5 86.64(8) O6—Eu1—O5 53.23(7) O7—Eu1—O5 93.58(8) O8—Eu1—O5 129.59(7) O1—Eu1—O5 74.78(7) O4—Eu1—O5 144.60(8) O3i—Eu1—O2 128.36(7) O6—Eu1—O2 113.90(8) O7—Eu1—O2 75.22(8) O8—Eu1—O2 149.53(8) O1—Eu1—O2 52.67(7) O4—Eu1—O2 73.19(8) O5—Eu1—O2 71.58(8) O3i—Eu1—O3 67.19(7) O6—Eu1—O3 141.56(7) O7—Eu1—O3 121.19(7) O8—Eu1—O3 72.04(6) O1—Eu1—O3 74.54(6) O4—Eu1—O3 51.41(6) O5—Eu1—O3 143.33(7) O2—Eu1—O3 104.24(7)
Symmetry codes:(i)-x,-y+2,-z。
2. The europium complex red emitter [ Eu (C) of claim 110H8NO2)3(CH3OH)2]·CH3The OH synthesis method is characterized by comprising the following specific steps:
(1) 0.1832g of analytically pure europium chloride hexahydrate is weighed, placed in 20m L analytically pure anhydrous methanol and stirred for half an hour;
(2) weighing 0.2625g of analytically pure 3-indoleacetic acid and 0.084g of analytically pure potassium hydroxide, dissolving the 3-indoleacetic acid and the 0.084g of analytically pure potassium hydroxide into 20-30 m L analytically pure anhydrous methanol, and stirring for half an hour;
(3) 0.1832g of analytically pure europium chloride hexahydrate, 0.2625g of analytically pure 3-indoleacetic acid and 0.084g of analytically pure potassium hydroxide are dissolved in 40-50 m L analytically pure anhydrous methanol, stirred at room temperature for half an hour and then filtered to obtain colorless clear filtrate;
(4) uniformly mixing the solutions obtained in the steps (1) and (2), stirring for half an hour to obtain a colorless clear liquid, and filtering;
(5) putting the filtrate obtained in the step (3) or the step (4) into a 100m L beakerSealing with a preservative film; after one week, colorless transparent needle-shaped crystals are generated at the bottom of the beaker, namely europium complex red luminescent material [ Eu (C)10H8NO2)3(CH3OH)2]·CH3OH。
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104194772A (en) * 2014-08-25 2014-12-10 桂林理工大学 Fluorescent material [CuNa(ehbd)2(dca)(CH3OH)] and synthesis method thereof
CN104230967A (en) * 2014-09-09 2014-12-24 桂林理工大学 Fluorescent material Zn2(hfoac)4(phen)2 and synthetic method
CN104263352A (en) * 2014-09-09 2015-01-07 桂林理工大学 Fluorescent material Zn(hfoac)2(phen)H2O and synthesis method thereof
CN105694867A (en) * 2016-04-08 2016-06-22 桂林理工大学 Fluorescent material [Cu2Na2(mtyp)2(CH3COO)2(H2O)3]n and synthesis method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104194772A (en) * 2014-08-25 2014-12-10 桂林理工大学 Fluorescent material [CuNa(ehbd)2(dca)(CH3OH)] and synthesis method thereof
CN104230967A (en) * 2014-09-09 2014-12-24 桂林理工大学 Fluorescent material Zn2(hfoac)4(phen)2 and synthetic method
CN104263352A (en) * 2014-09-09 2015-01-07 桂林理工大学 Fluorescent material Zn(hfoac)2(phen)H2O and synthesis method thereof
CN105694867A (en) * 2016-04-08 2016-06-22 桂林理工大学 Fluorescent material [Cu2Na2(mtyp)2(CH3COO)2(H2O)3]n and synthesis method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Synthesis, Crystal Structure, and DNA Interaction and Cleavage Studies of a Novel Dinuclear Cu(II) Complex with 3-Indolylacetic Acid;Y.H.Fan 等;《Russian Journal of Coordination Chemistry》;20121231;第38卷;第519-525页 *
稀土（Pr,Eu）-吲哚-3-乙酸配合物的合成及其荧光性质的研究;李 君 等;《新疆农业大学学报》;20121231;第35卷;第484-488页 *

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