CN1451712A - Organic electroluminescent calixarene material - Google Patents
Organic electroluminescent calixarene material Download PDFInfo
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- CN1451712A CN1451712A CN 03117828 CN03117828A CN1451712A CN 1451712 A CN1451712 A CN 1451712A CN 03117828 CN03117828 CN 03117828 CN 03117828 A CN03117828 A CN 03117828A CN 1451712 A CN1451712 A CN 1451712A
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- calixarene
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Abstract
An organic electroluminescent calixarene material is prepared from calixarene moleculae as platform through derivation. Its advantages are high-purity light (red, green or blue), easy dissolving in ordinary organic solvent, and good film-forming performance.
Description
One, technical field
The invention belongs to electroluminescent organic material, particularly the calixarene electroluminescent organic material.
Two, background technology
Application number for 02113399.9, publication number provides a kind of electroluminescent organic material for the Chinese patent application of CN 1369538A, this luminescent material is a part with calixarene west Buddhist alkali derivant, the complexing divalent-metal ion forms, structural formula is as follows:
In the said structure formula, R
1, R
2, R
3Be substituting group, M is a divalent-metal ion,
R
1Be H or t-Bu,
R
2Be CH
2Or CH
2CH
2Or CH
2CH
2CH
2,
R
3Be CH
3Or CH
2CH
3
Though this kind electroluminescent organic material has the rock steady structure conformation, can improve the work-ing life of electroluminescent device, and be soluble in ordinary organic solvents, spin coating legal system power backup electroluminescence device easy to use, reduce investment, reduce cost, but that weak point is the pure degree of light that sent is relatively poor.
Three, summary of the invention
The present invention aims to provide the calixarene electroluminescent organic material of novel texture, to increase the kind of electroluminescent organic material, satisfies needs of society.
Technical scheme of the present invention is: be the structural formula that elementary cell makes up luminescent material with the calixarene, this design has formed following calixarene electroluminescent organic material.
1, introduce calixarene neutral ligand and the formed rare earth compounding of beta diketone part complex rare-earth metal ion that calixarene forms by second part (neutral ligand)-phenanthroline, dipyridyl, its structural formula is as follows:
In the said structure formula, R
1, R
2Be substituting group, Ln is a rare earth ion.
R
1, R
2, Ln assembly four kinds of forms are arranged:
Or R
1Be Ph, R
2Be Ph, Ln is Eu
3+
Or R
1Be alkyl phenyl or alkoxyl phenyl, R
2Be alkyl phenyl or alkoxyl phenyl, wherein alkyl phenyl is tolyl, ethylbenzene base, and alkoxyl phenyl is p-methoxy-phenyl, ethoxyl phenenyl, and Ln is Eu
3+
Or R
1Be CF
3, R
2Be thiophene phenyl, Ln is Eu
3+
Or R
1Be CH
3, R
2Be CH
3, Ln is Tb
3+
The electroluminescent organic material of said structure can produce pure ruddiness and green glow, and the color of light is by the rare earth ion decision of institute's complexing, and for example: the metal ion of complexing is Eu
3+, then produce ruddiness, form red organic electrofluorescence material; The metal ion of complexing is Tb
3+, then produce green light, form green electroluminescent organic material.
The electroluminescent organic material of said structure, its preparation technology has two steps, and first step is the preparation of calixarene neutral ligand, and second step is the complexing of calixarene neutral ligand and beta diketone part and rare earth ion.Above-mentioned technology is all carried out under normal pressure, and concrete operations and processing condition are illustrated by embodiment.
2, articulate the formed calixarene pyrazoline derivative of pyrazoline derivative by calixarene, structural formula is as follows:
In the said structure formula, R is the pyrazoline substituting group.Can select in following three kinds of pyrazoline derivatives any to make the pyrazoline substituting group.
The light that the calixarene pyrazoline derivative electroluminescent material of said structure is produced is pure blue light.
The preparation technology of the electroluminescent organic material of said structure has only a step, and promptly pyrazoline derivative and calixarene articulates.Above-mentioned technology is carried out under normal pressure, and concrete operations and processing condition are illustrated by embodiment.
Calixarene electroluminescent organic material among the present invention is mainly used in the making electroluminescent device, its manufacture craft spin coating method.In view of the spin coating method is a kind of known, sophisticated technology, so be not described at this.
Calixarene electroluminescent organic material provided by the present invention has the following advantages and beneficial effect:
1, the fluorescence that has redness, green, blueness, and the color of light is pure, thereby enlarged Application Areas, and can simplify the preparation technology of some optical display.
2, owing to the introducing of calixarene, can strengthen the solubility property and the film forming properties of electroluminescent material, improve luminous efficiency, thereby can improve the work-ing life and the efficient of the electroluminescent device of making of this type of material.
3, be soluble in ordinary organic solvents, and good film-forming property, thereby the preparation electroluminescent device is to use the spin coating method, compares, can reduce investment, reduce cost with Vacuum Coating method.
4, rare earth calixarene complex compound adopts the high-high brightness of the prepared electroluminescent device of spin coating method to surpass other class rare-earth complex adopts the prepared electroluminescent device of same device manufacture method as electroluminescent material high-high brightness as electroluminescent material.
5, preparation technology is simple, and raw material easily obtains.
Four, embodiment
Embodiment 1:
Electroluminescent organic material in the present embodiment is a red illuminating material, introduces calixarene neutral ligand and the beta diketone part complex rare-earth metal ion Eu that calixarene forms by dipyridyl
3+Form, its structural formula is as follows:
In the said structure formula, substituent R
1, R
2Be Ph.
Preparation technology is:
1, the preparation of calixarene dipyridyl neutral ligand
(1) in the 50mL three-necked bottle that drying tube, device for absorbing tail gas, nitrogen protection and prolong have been installed, adds 1.93g (2mmol) 5; 11; 17; 23-tetra-tert-28-carboxymethoxyl-25; 26; 27-triethoxy carbonyl methoxyl group cup [4] aromatic hydrocarbons and 12.5mL thionyl chloride, back flow reaction 2.5 hours.Decompression steams unnecessary thionyl chloride and gets faint yellow solid 7,11,17,23-tetra-tert-28-chloroformyl methoxyl group-25,26,27-triethoxy carbonyl methoxyl group cup [4] aromatic hydrocarbons.
(2) in the 100mL three-necked bottle that drying tube, device for absorbing tail gas, nitrogen protection and prolong have been installed, add 0.51775mmol 4-methylol-4 '-methyl-2; 2 '-dipyridyl, the absolute anhydrous chloroform of 35mL and 0.2mL triethylamine; slowly drip 0.51775mmol 5 with dropping funnel; 11; 17,23-tetra-tert-28-chloroformyl methoxyl group-25,26; the absolute anhydrous chloroform solution of 18mL of 27-triethoxy carbonyl methoxyl group cup [4] aromatic hydrocarbons has white cigarette to produce in the reaction flask.After dropwising, stirring at room 24 hours.Add 40mL 1% hydrochloric acid in the reaction solution and stirred 0.5 hour, tell organic layer saturated common salt water washing 2 times, anhydrous sodium sulfate drying filters, and concentrates.Column chromatography for separation gets white solid 5,11,17,23-tetra-tert-28-dipyridyl methoxycarbonyl methoxyl group-25,26,27-triethoxy carbonyl methoxyl group cup [4] aromatic hydrocarbons, yield 88%, mp:67-68 ℃; ESI-MS:1147.4 (M
+); 1183 (M+35.5);
1HNMR (CDCl
3), δ (ppm): 6.767-6.65 (8H, Ph); 7.14 (3H, py); 7.27 (1H, py); 6.9 (1H, py); 6.56 (1H, py); 3.3 (4H, PhCH
2Ph); 4.1 (6H, OCH
2CH
3); 4.6 (2H, pyCH
2); 4.8-5 (12H, OCH
2CO﹠amp; PhCH
2Ph); 1.3-0.9 (48H, CH
3) IR (KBr compressing tablet), ν m
Ax(cm
-1): 2960 (s, CH
3); 1756 (C=O); 740 (Phen, C-H); Ultimate analysis C
70H
86N
2O
12Calculated value %:C, 73.27; H, 7.55; N, 2.44; Measured value %:C, 72.97; H, 7.85; N, 2.22.
2, calixarene dipyridyl neutral ligand and beta diketone part and Eu
3+The ionic complexing
In the 25mL round-bottomed flask, add 0.09632g (0.43mmol) two (benzoyl) methane, 0.165g (0.144mmol) calixarene dipyridyl neutral ligand and 6mL ethanol/acetone (1: 1); transfer about reacting liquid pH value to 10 with the 2M sodium hydroxide solution down at 50-60 ℃, drip 0.037g (0.144mmol) EuCl
3The aqueous solution, have yellow solid to separate out.After dropwising, transfer reacting liquid pH value to about the 5-6, a large amount of yellow mercury oxides occur with the 2M sodium hydroxide solution.The reactant temperature control was 50-60 ℃ of following restir 24 hours.Cooled and filtered gets yellow solid, and solid is used second alcohol and water repetitive scrubbing repeatedly, and vacuum-drying gets yellow solid powder 0.26g, yield 91%.Mp98-100 ℃; ESI-MS:1184.6 (calixarene dipyridyl neutral ligand+39) 1042.7 (dipyridyl, DBM and europium complexes); IR (KBr compressing tablet), ν
Max(cm
-1): 2960 (s, CH
3); 1756 (s, C=O); 724 (Phen, C-H); Ultimate analysis C
115H
119EuN
2O
18Calculated value: C, 70.14; H, 6.09; N, 1.42; Measured value: C, 70.47; H, 6.21; N, 1.35.
Red organic electrofluorescence material in the present embodiment is in the visible region, and its solution fluorescent emission wavelength is 615 nanometers, and peak width at half height is 10 nanometers; In being entrained in PVK, adopting the fluorescent emission wavelength of the film of spin coating method formation is 615 nanometers, and peak width at half height is 10 nanometers, is pure ruddiness.When adopting following electroluminescent device structure: ITO/PVK+12/Alq/Mg:Ag, under direct voltage drive, can obtain luminosity is 14.59cd/m
2-134.59cd/m
2The ruddiness electroluminescent device.
Embodiment 2:
Electroluminescent organic material in the present embodiment is a green luminescent material, introduces calixarene neutral ligand and the beta diketone part complex rare-earth metal ion Tb that calixarene forms by dipyridyl
3+Form, its structural formula is as follows:
In the said structure formula, R
1, R
2Be CH
3
Preparation technology is:
1, the preparation of calixarene dipyridyl neutral ligand
Technical process is seen embodiment 1 with that related parameter is arranged is identical with embodiment 1.
2, calixarene dipyridyl neutral ligand and beta diketone part and Tb
3+The ionic complexing
In the 25mL round-bottomed flask, add 0.04313g (0.43mmol) two (ethanoyl) methane, 0.165g (0.144mmol) calixarene dipyridyl neutral ligand and 6mL ethanol/acetone (1: 1); transfer about reacting liquid pH value to 10 with the 2M sodium hydroxide solution down at 50-60 ℃, drip 0.038g (0.144mmol) TbCl
3The aqueous solution, the adularescent solid is separated out.After dropwising, transfer reacting liquid pH value to about the 5-6, a large amount of white precipitates occur with the 2M sodium hydroxide solution.The reactant temperature control was 50-60 ℃ of following restir 24 hours.Cooled and filtered gets white solid, and with second alcohol and water repetitive scrubbing solid, vacuum-drying gets white solid powder terbium-two (ethanoyl) methane-calixarene dipyridyl title complex 0.187g, yield 90%.Mp:130-132 ℃; IR (KBr compressing tablet), ν
Max(cm
-1): 2960 (s, CH
3); 1755 (s, C=O); 1599 (C=O); Ultimate analysis C
85H
107N
2O
18Tb; Calculated value: C, 63.66; H, 6.73; N, 1.75; Measured value: C, 63.39; H, 6.62; N, 1.60.
Green electroluminescent organic material in the present embodiment is in the visible region, and its solution fluorescent emission wavelength is 545 nanometers, and peak width at half height is 10 nanometers; The fluorescent emission wavelength of its powder solid is 545 nanometers, and peak width at half height is 10 nanometers.When adopting following electroluminescent device structure: ITO/PVK+14/Alq/Mg:Ag, under direct voltage drive, can obtain luminosity is 20.89cd/m
2-163.03cd/m
2The green glow electroluminescent device.
Embodiment 3:
Electroluminescent organic material in the present embodiment is a red illuminating material, introduces calixarene neutral ligand and the beta diketone part complex rare-earth metal ion Eu that calixarene forms by phenanthroline
3+Form, its structural formula is as follows:
In the said structure formula, substituent R
1, R
2Be Ph.
Preparation technology is:
1, the preparation of calixarene phenanthroline neutral ligand
(1) in the 50mL three-necked bottle that drying tube, device for absorbing tail gas, nitrogen protection and prolong have been installed, adds 1.93g (2mmol) 5; 11; 17; 23-tetra-tert-28-carboxymethoxyl-25; 26; 27-triethoxy carbonyl methoxyl group cup [4] aromatic hydrocarbons and 12.5mL thionyl chloride, back flow reaction 2.5 hours.Decompression steams unnecessary thionyl chloride and gets faint yellow solid 7,11,17,23-tetra-tert-28-chloroformyl methoxyl group-25,26,27-triethoxy carbonyl methoxyl group cup [4] aromatic hydrocarbons.
(2) in the 100mL three-necked bottle that drying tube, device for absorbing tail gas, nitrogen protection and prolong have been installed, add 0.51775mmol 4-methylol-1; 10-phenanthroline, the absolute anhydrous chloroform of 35mL and 0.2mL triethylamine; slowly drip 0.51775mmol 5 with dropping funnel; 11; 17,23-tetra-tert-28-chloroformyl methoxyl group-25,26; the absolute anhydrous chloroform solution of 18mL of 27-triethoxy carbonyl methoxyl group cup [4] aromatic hydrocarbons has white cigarette to produce in the reaction flask.After dropwising, stirring at room 24 hours.Add 40mL 1% hydrochloric acid in the reaction solution and stirred 0.5 hour, tell organic layer, use anhydrous sodium sulfate drying, filter, concentrate with saturated common salt water washing 2 times.Column chromatography for separation gets yellow solid 5,11,17,23-tetra-tert-28-phenanthroline methoxycarbonyl methoxyl group-25,26,27-triethoxy carbonyl methoxyl group cup [4] aromatic hydrocarbons, yield 83%.Mp:61-62 ℃; ESI-MS:1159.4;
1HNMR (CDCl
3), δ (ppm): 0.84 (9H, t-Bu); 1.0-1.4 (36H, t-Bu ﹠amp; CH3); 3.2 (4H, PhCH2Ph); 4.0-5.0 (20H, PhCH2Ph ﹠amp; OCH
2CO ﹠amp; OCH
2CH
3); 6.2-7.8 (15H, ArH); IR (KBr compressing tablet), ν
Max(cm
-1): 2960 (s, CH
3); 1756 (s, C=O); 740 (Phen, C-H); Ultimate analysis C
71H
86N
2O
12Calculated value %:C, 73.55; H, 7.48; N, 2.42; Measured value: C, 72.89; H, 7.66; N, 2.32.
2, calixarene phenanthroline neutral ligand and beta diketone part and Eu
3+The ionic complexing
In the 25mL round-bottomed flask, add 0.09632g (0.43mmol) two (benzoyl) methane, 0.1669g (0.144mmol) calixarene phenanthroline and 6mL ethanol/acetone (1: 1); transfer about reacting liquid pH value to 10 with the 2M sodium hydroxide solution down at 50-60 ℃, drip 0.037g (0.144mmol) EuCl
3The aqueous solution, have yellow solid to separate out.After dropwising, transfer reacting liquid pH value to about the 5-6, a large amount of yellow mercury oxides occur with the 2M sodium hydroxide solution.The reactant temperature control was 50-60 ℃ of following restir 24 hours.Cooled and filtered gets yellow solid, and solid is used second alcohol and water repetitive scrubbing repeatedly, and vacuum-drying gets yellow solid powder 0.275g, yield 95%.Mp:84-86 ℃; IR (KBr compressing tablet), ν
Max(cm
-1): 2960 (s, CH
3); 1748 (s, C=O); 1598 (C=O); 729 (Phen, C-H); Ultimate analysis C
116H
119EuN
2O
18Calculated value: C, 70.32; H, 6.05; N, 1.41; Measured value: C, 70.05; H, 6.28; N, 1.22.
Red organic electrofluorescence material in the present embodiment is in the visible region, and its solution fluorescent emission wavelength is 615 nanometers, and peak width at half height is 10 nanometers; In being entrained in PVK, adopting the fluorescent emission wavelength of the film of spin coating method formation is 615 nanometers, and peak width at half height is 10 nanometers, is pure ruddiness.
Embodiment 4:
Electroluminescent organic material in the present embodiment is a green luminescent material, introduces calixarene neutral ligand and the beta diketone part complex rare-earth metal ion Tb that calixarene forms by phenanthroline
3+Form, its structural formula is as follows:
In the said structure formula, R
1, R
2Be CH
3
Preparation technology is:
1, the preparation of calixarene phenanthroline neutral ligand
Technical process is seen embodiment 3 with that related parameter is arranged is identical with embodiment 3.
2, calixarene phenanthroline neutral ligand and beta diketone part and Tb
3+The ionic complexing
In the 25mL round-bottomed flask, add 0.04313g (0.43mmol) two (ethanoyl) methane, 0.1669g (0.144mmol) calixarene phenanthroline and 6mL ethanol/acetone (1: 1); transfer about reacting liquid pH value to 10 with the 2M sodium hydroxide solution down at 50-60 ℃, drip 0.038g (0.144mmol) TbCl
3The aqueous solution, the adularescent solid is separated out.After dropwising, transfer reacting liquid pH value to about the 5-6, a large amount of white precipitates occur with the 2M sodium hydroxide solution.The reactant temperature control was 50-60 ℃ of following restir 24 hours.Cooled and filtered gets white solid, and with second alcohol and water repetitive scrubbing solid, vacuum-drying gets white solid powder terbium-two (ethanoyl) methane-calixarene phenanthroline title complex 0.196g, yield 94%.Mp＞220 ℃; IR (KBr compressing tablet), ν
Max(cm
-1): 2960 (s, CH
3); 1792 (s, C=O); 1605 (s, C=O); Ultimate analysis: C
86H
107N
2O
18Tb; Calculated value: C, 63.93; H, 6.68; N, 1.73; Measured value: C, 63.85; H, 6.48; N, 1.89.
Green electroluminescent organic material in the present embodiment is in the visible region, and its solution fluorescent emission wavelength is 545 nanometers, and peak width at half height is 10 nanometers; The fluorescent emission wavelength of its powder solid is 545 nanometers, and peak width at half height is 10 nanometers.
Embodiment 5:
Electroluminescent organic material in the present embodiment is a blue emitting material, articulates pyrazoline derivative by calixarene and forms, and its structural formula is as follows:
Preparation technology is:
In the 25mL three-necked bottle that drying tube, device for absorbing tail gas, nitrogen protection and prolong have been installed, add 0.065g (0.21mmol) 5-(4 '-hydroxy phenyl)-1; 3-phenylbenzene-4; 5-dihydro-1-H-pyrazoles, the absolute anhydrous chloroform of 5mL and 0.2mL triethylamine; slowly drip 0.21mmol 5 with dropping funnel; 11; 17; 23-tetra-tert-28-chloroformyl methoxyl group-25; 26; the absolute anhydrous chloroform solution of 10mL of 27-triethoxy carbonyl methoxyl group cup [4] aromatic hydrocarbons has white cigarette to produce in the reaction flask.After dropwising, stirring at room 24 hours.Add 40mL1% hydrochloric acid in the reaction solution and stirred 0.5 hour, separatory, saturated common salt water washing 2 times, anhydrous sodium sulfate drying filters, and concentrates.Column chromatography for separation gets 0.13g yellow solid calixarene pyrazoline derivative, yield 49%.Mp:66-68 ℃; ESI-MS:1283.6 (M
++ 23);
1HNMR (CDCl
3), δ (ppm): 0.87 (9H, CH
3); 1.4-1.2 (36H, CH
3); 3.2 (4H, PhCH
2Ph); 3.4 (2H, CH
2); 3.8 (1H, CH); 4.2 (6H, OCH
2); 4.5 (4H, PhCH
2Ph); 5.0 (2H, OCH
2CO); 5.3 (6H, OCH
2CO); 6.8-7.6 (22H, Ph); IR (KBr compressing tablet), ν
Max(cm
-1): 2960 (s, CH
3); 1755 (s, C=O); 1596 (C=N); Ultimate analysis C
79H
92N
2O
12Calculated value %:C, 75.21; H, 7.35; N, 2.22; Measured value: C, 75.06; H, 7.44; N, 2.28.
Blue organic electroluminescent material in the present embodiment is in the visible region, and its solution fluorescent emission wavelength is 465 nanometers, and peak width at half height is 70 nanometers; The fluorescent emission wavelength of film is 455 nanometers, and peak width at half height is 80 nanometers, is pure blue light.When adopting following electroluminescent device structure: ITO/PVK+13/Alq/Mg:Ag, under direct voltage drive, can obtain luminosity is 13.68cd/m
2-122.42cd/m
2The blue light electroluminescent device.
Embodiment 6:
Electroluminescent organic material in the present embodiment is a blue emitting material, articulates pyrazoline derivative by calixarene and forms, and its structural formula is as follows:
Preparation technology is:
In the 25mL three-necked bottle that drying tube, device for absorbing tail gas, nitrogen protection and prolong have been installed, add 0.065g (0.21mmol) 3-(2 '-hydroxy phenyl)-1; 5-phenylbenzene-4; 5-dihydro-1-H-pyrazoles (4), the absolute anhydrous chloroform of 5mL and 0.2mL triethylamine; slowly drip 0.21mmol 5 with dropping funnel; 11; 17; 23-tetra-tert-28-chloroformyl methoxyl group-25; 26; the absolute anhydrous chloroform solution of the 10mL of 27-triethoxy carbonyl methoxyl group cup [4] aromatic hydrocarbons (10) has white cigarette to produce in the reaction flask.After dropwising, stirring at room 24 hours.Add 40mL 1% hydrochloric acid in the reaction solution and stirred 0.5 hour, separatory, saturated common salt water washing 2 times, anhydrous sodium sulfate drying filters, and concentrates.Column chromatography for separation gets 0.095g orange solids calixarene pyrazoline derivative, yield 35.8%.Mp:82-84 ℃; ESI-MS:1283.6 (M
++ 23);
1HNMR (CDCl
3), δ (ppm): IR (KBr compressing tablet), ν
Max(cm
-1): 2960 (s, CH
3); 1758 (s, C=O); 1622 (C=N); Ultimate analysis C
79H
92N
2O
12Calculated value %:C, 75.21; H, 7.35; N, 2.22; Measured value: C, 74.96; H, 7.52; N, 2.01.
Blue organic electroluminescent material in the present embodiment is in the visible region, and its solution fluorescent emission wavelength is 455 nanometers, and peak width at half height is 70 nanometers; The fluorescent emission wavelength of film is 445 nanometers, and peak width at half height is 80 nanometers, is pure blue light.
Embodiment 7:
Electroluminescent organic material in the present embodiment is a blue emitting material, articulates pyrazoline derivative by calixarene and forms, and its structural formula is as follows:
Preparation technology is:
In the 25mL three-necked bottle that drying tube, device for absorbing tail gas, nitrogen protection and prolong have been installed, add 0.065g (0.21mmol) 3-(4 '-hydroxy phenyl)-1; 5-phenylbenzene-4; 5-dihydro-1-H-pyrazoles, the absolute anhydrous chloroform of 5mL and 0.2mL triethylamine; slowly drip 0.21mmol 5 with dropping funnel; 11; 17; 23-tetra-tert-28-chloroformyl methoxyl group-25; 26; the absolute anhydrous chloroform solution of 10mL of 27-triethoxy carbonyl methoxyl group cup [4] aromatic hydrocarbons has white cigarette to produce in the reaction flask.After dropwising, stirring at room 24 hours.Add 40mL1% hydrochloric acid in the reaction solution and stirred 0.5 hour, separatory, saturated common salt water washing 2 times, anhydrous sodium sulfate drying filters, and concentrates.Column chromatography for separation gets yellow solid 0.11g calixarene pyrazoline derivative, yield 41.5%.Mp:100-104 ℃; ESI-MS:1283.6 (M
++ 23);
1HNMR (CDCl
3), δ (ppm): 7.8-6.6 (22H, Ph); 5.2 (2H, OCH
2CO); 4.9 (6H, OCH
2CO); 4.63 (4H, PhCH
2Ph); 4.3 (2H, CH
2); 4.2 (6H, OCH
2CH
3); 3.8 (1H, CH); 3.2 (4H, PhCH
2Ph); 1.3-1.0 (36H, t-Bu); 0.9 (9H, CH
3); IR (KBr compressing tablet), ν
Max(cm
-1): 2960 (s, CH
3); 1755 (s, C=O); 1596 (C=N); Ultimate analysis C
79H
92N
2O
12Calculated value %:C, 75.21; H, 7.35; N, 2.22; Measured value: C, 75.66; H, 7.22; N, 2.12.
Blue organic electroluminescent material in the present embodiment is in the visible region, and its solution fluorescent emission wavelength is 455 nanometers, and peak width at half height is 70 nanometers; The fluorescent emission wavelength of film is 450 nanometers, and peak width at half height is 80 nanometers, is pure blue light.
Claims (4)
1, a kind of calixarene electroluminescent organic material is characterized in that this luminescent material is formed by calixarene neutral ligand and the beta diketone part complex rare-earth metal ion that phenanthroline introducing calixarene forms, and structural formula is as follows:
In the said structure formula, R
1, R
2Be substituting group, Ln is a rare earth ion,
Or R
1Be Ph, R
2Be Ph, Ln is Eu
3+,
Or R
1Be alkyl phenyl or alkoxyl phenyl, R
2Be alkyl phenyl or alkoxyl phenyl, Ln is Eu
3+,
Or R
1Be CF
3, R
2Be thiophene phenyl, Ln is Eu
3+,
Or R
1Be CH
3, R
2Be CH
3, Ln is Tb
3+
2, a kind of calixarene electroluminescent organic material is characterized in that this luminescent material is formed by calixarene neutral ligand and the beta diketone part complex rare-earth metal ion that dipyridyl introducing calixarene forms, and structural formula is as follows:
In the said structure formula, R
1, R
2Be substituting group, Ln is a rare earth ion,
Or R
1Be Ph, R
2Be Ph, Ln is Eu
3+,
Or R
1Be alkyl phenyl or alkoxyl phenyl, R
2Be alkyl phenyl or alkoxyl phenyl, Ln is Eu
3+,
Or R
1Be CF
3, R
2Be thiophene phenyl, Ln is Eu
3+,
Or R
1Be CH
3, R
2Be CH
3, Ln is Tb
3+
3, calixarene electroluminescent organic material according to claim 1 and 2 is characterized in that alkyl phenyl is tolyl, ethylbenzene base, and alkoxyl phenyl is p-methoxy-phenyl, ethoxyl phenenyl.
4, a kind of calixarene electroluminescent organic material is characterized in that this luminescent material articulates pyrazoline derivative by calixarene and forms, and structural formula is as follows:
In the said structure formula, R is the pyrazoline substituting group, can select in following three kinds of pyrazoline derivatives any to make the pyrazoline substituting group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031178286A CN1195042C (en) | 2003-05-08 | 2003-05-08 | Organic electroluminescent calixarene material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031178286A CN1195042C (en) | 2003-05-08 | 2003-05-08 | Organic electroluminescent calixarene material |
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| Publication Number | Publication Date |
|---|---|
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| CN1195042C CN1195042C (en) | 2005-03-30 |
Family
ID=29222822
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|---|---|---|---|
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| CN (1) | CN1195042C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792664A (en) * | 2010-03-11 | 2010-08-04 | 同济大学 | Method for preparing hybrid mesoporous luminescent material of calixarene and functionalized rare earth |
| CN102618066A (en) * | 2012-02-28 | 2012-08-01 | 中山大学 | Organic dye containing calixarene derivative and preparation method and application thereof |
| CN104311546A (en) * | 2014-09-12 | 2015-01-28 | 三峡大学 | Calixarene-rare earth complex and its preparation method and use |
| CN109438430A (en) * | 2018-10-10 | 2019-03-08 | 郑州大学 | A kind of resorcinol calixarene compound and preparation method and application |
| CN113527207A (en) * | 2020-04-22 | 2021-10-22 | 常州强力电子新材料股份有限公司 | Ethoxy/propoxy modified pyrazoline organic matter, application thereof, photocuring composition and photoresist |
-
2003
- 2003-05-08 CN CNB031178286A patent/CN1195042C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792664A (en) * | 2010-03-11 | 2010-08-04 | 同济大学 | Method for preparing hybrid mesoporous luminescent material of calixarene and functionalized rare earth |
| CN102618066A (en) * | 2012-02-28 | 2012-08-01 | 中山大学 | Organic dye containing calixarene derivative and preparation method and application thereof |
| CN104311546A (en) * | 2014-09-12 | 2015-01-28 | 三峡大学 | Calixarene-rare earth complex and its preparation method and use |
| CN109438430A (en) * | 2018-10-10 | 2019-03-08 | 郑州大学 | A kind of resorcinol calixarene compound and preparation method and application |
| CN109438430B (en) * | 2018-10-10 | 2021-11-12 | 郑州大学 | Calixarene compound and preparation method and application thereof |
| CN113527207A (en) * | 2020-04-22 | 2021-10-22 | 常州强力电子新材料股份有限公司 | Ethoxy/propoxy modified pyrazoline organic matter, application thereof, photocuring composition and photoresist |
| CN113527207B (en) * | 2020-04-22 | 2023-06-06 | 常州强力电子新材料股份有限公司 | Ethoxy/propoxy modified pyrazoline organic matter, application thereof, photo-curing composition and photoresist |
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| Publication number | Publication date |
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| CN1195042C (en) | 2005-03-30 |
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