Electroluminescent material, containing organic luminescent substance

FIELD: physics.

SUBSTANCE: electroluminescent material is described, consisting of an electron injection layer, an active luminescent layer based on a metal chalate complex, a hole transport layer and a hole injection layer. The luminescent substance is in form of new zinc complexes based on sulphonylamino derivatives of 2-phenylbenzoxazole or 2-phenylbenzothiazole. The hole transport layer of the material is preferably a mixture of triphenylamine oligomers.

EFFECT: electroluminescent material with high moisture resistance, high resistance to crystallisation and high thermal stability.

9 cl, 5 ex

 

The invention relates to luminescent materials, namely, electroluminescent materials containing organic fluorescent substance.

Known electroluminescent material (ELM), consisting of electronic an injecting layer, an active luminescent layer-based fluorescent substance, a hole-transport layer and the hole-an injecting layer containing the luminescent layer evaporated layer of organic compounds - complexes of aluminum, zinc and some other metals derived from 8-hydroxyquinoline solution, 2-hydroxybenzimidazole, 2-hydroxyphenylacetate [U.Mitschke, .Bauerle. J.Mater. Chem., 2000, 10,1471-1507].

The closest to the technical nature of the present device is ELM, containing a luminescent layer of zinc complexes of 2-(2-hydroxyphenyl)benzoxazole (I) or 2-(2-hydroxyphenyl)benzothiazole (II) [Y.Hamada, T.Sano, H.Fujii, Y.Nishio, H.Takahashi, K.Shihata, Jpn. J.Appl.Phys. 1996, v.35, part 2, No. 10B, pp.L 1339 - L 1341] (see Fig.).

These compounds have good luminescent characteristics, for I quantum yield is 0.93 [Lioznova, Paviljonki, Ligurians, Mignani, Adherence, O.N. the vultures, J. General. chemistry, 1976, vol.46, issue 3, s-675], and compound II-generating broadband izlucheniya, considered one of the best fluorescent materials white light used in organic LEDs [T.Sano, Y.Nishio, Y.Hamada, H.Takahashi, T.Usuki, K.Shibata, J.Mater. Chemistry, 2000, 10, pp.157-161]. In addition, these materials have a much higher mobility of negative charges than widely used in organic light emitting diode Tris(8-hydroxyquinolinato) aluminum [T.Yasuda, Y.Yamaguchi, K.Fujita, T.Tsutsui, Chemistry Letters, 2003, v.32, N7, p.644-645].

At the same time as the hole - an injecting layer (anode) is applied transparent low-resistance layer based on a mixed oxide of indium and tin, In2O3-

SnO2(ITO), as the electron - an injecting layer (cathode) is aluminum or an alloy of magnesium and silver, and as the hole-transport layer is N,N'-diphenyl-N,N'-(3-were)-1,1'-biphenyl-4,4'-diamine (TPD).

However, the time resource devices using materials I and II are small. It may be associated with the coordination unsaturation of the zinc atom in the complex II [G.Yu, S.Yin, Y.Liu, Z.Shai, D.Zhu, JACS, 2003, v.125, pp.14816-14824; Adherence, Tasman, Bmikeandvicki, Oaasypow, Evolvence, Bambooteen, Lmebased, Nigenov, Vahlensieck, J. General. chemistry, 1976, vol.46, VIP, s-2710], easy oxidizability "phenolic" oxygen and hydrolysis due to the zinc - oxygen in I, II under the action with EDAW water and oxygen by insufficient sealing device. All this creates additional difficulties and prevents the practical use of these materials.

In addition, the time resource electroluminescent devices is limited to low temperature resistant materials, hole-transport layers, due to changes in the morphology of the layer with increasing temperature because of their low glass transition temperature (for TPD, the glass transition temperature is 60°C).

The present invention is the creation of ELM with increased temporary resource due to the increased stability of the active luminescent layer with respect to crystallization and hydrolysis, as well as high temperature resistance of the hole-transport layer.

The problem is solved by the fact that according to the invention the electroluminescent material consisting of e an injecting layer, an active luminescent layer-based fluorescent substance, a hole-transport layer and the hole-an injecting layer, as a fluorescent substance containing the metal complexes with ligands derived alkyl (aryl)sulfonylmethane 2-phenylbenzoxazole (III) or benzothiazole (IV) the General formula:

where M is an atom of zinc, n=2, X can be an oxygen atom, (III) or sulfur (IV).

The group R may be vibrans number:

is an alkyl group of 1-18 carbon atoms and having a normal or branched structure;

is a phenyl group;

- mono - or polyalkylene phenyl group in which the alkyl substituents consist of 1 to 18 carbon atoms and have a normal or branched structure;

- mono - or polyhalogen phenyl group in which the atoms of halogen is fluorine, chlorine, bromine, iodine;

- mono - or polyalkoxysiloxanes phenyl group in which the alkoxy substituents consist of 1 to 18 carbon atoms and have a normal or branched structure;

- 1 - or 2-naftalina group.

We expect that the presence of bulky alkyl (aryl)sulfonic group prevents the violation of the homogeneity of the layer due to the crystallization of the material. In addition, compounds of type III, IV should be less sensitive to oxidation and hydrolysis due to steric factors and the chemical nature of the substituent in comparison with complexes I, II. All this should have a positive impact on the operating characteristics of the electroluminescent device.

The problem is solved also by the fact that as the hole-transport layer material preferably comprises a mixture of oligomers of triphenylamine (MOUTH) with the General formula

,

where n=8-9, when the molecular-mass distribution: Mn=332, Mw=3586 characterized by high glass transition temperature of 185°C, which ensures the preservation of the morphology of the hole-transport layer even at elevated temperatures [Yakushenko I.K., Kaplunov MG, Shamayev, S.N., Efimov O.N., Nikolaeva, GV, Belov, M., Marchenko, H.E., starlings A.G., Voronin, VA "a Method of obtaining a mixture of oligoadenylates, the method of obtaining 3-(4-biphenylyl)-4-(4-tertbutylphenyl)-5-(4-dimethylamino-phenyl)-1,2,4-triazole and the electroluminescent device", Patent of Russian Federation N 2131411 from 10.06.99].

The invention is illustrated by the following examples.

Example 1. Synthesis of 2-[2-(4-methylphenylsulfonyl)phenyl]-benzoxazole (VI)

The scheme for synthesis of:

Compound XIII was obtained by the method of [Mavashev, CHC, 1970, N 12, C.1597-1601], and polyphosphoric ester XV synthesized according to [G.Schramm, H.Grotsch, W.Pollmann. Angew. Chem. Intem. Ed., 1962, v.1, p.1].

a) In 75 ml of dry tetrahydrofuran was dissolved 2,73 g(25 mmol) of o-aminophenol and at 30-35°C for 50 min portions were added to 7.75 g (25 mmol) of acid chloride of 2-(4-toluensulfonate)benzoic acid (XIII). Then the mixture was heated to boiling under reflux for 1.5 hours, drove most of the solvent, and the residue after cooling to room temperature was treated with 100 ml of water. The precipitate was filtered, washed it successively with water, hexane, dried in the air. After the crystal is Itachi from methanol received 8.02 g of 2'-hydroxyanisole 2-(4-toluensulfonate)benzoic acid (compound XIV). The output 84% of theoretical.

b) of 7.64 g (20 mmol) of compound XIV suspended in 30 g of polyphosphoric ester XV. The mixture was heated to 100°C and kept at this temperature for 1 hour. Then cooled to room temperature, the mixture was poured into 200 ml of water, was established pH 6 with 2n sodium hydroxide and extracted the reaction mixture with chloroform. After removal of chloroform and crystallization of the residue from methanol received 4,63 g of compound VI. TPL 155-156°C. the Yield of 63% of theoretical. Elemental analysis. Found, %: C 66,49; N. Of 4.49; N 7,76; S 8,75. Gross formula C20H16N2O3S. Calculated, %: C 65,92; N 4,43; N 7,69; S 8,80.

Fluorescence spectrum (λvasb=370 nm): 508 nm

IR spectrum (cm-1): 3070, 3035, 2920, 2850, 1616, 1595, 1587, 1535, 1497, 1475, 1450, 1420, 1400, 1380, 1350,1340,1310, 1285, 1275, 1245, 123, 1187, 1170, 1155, 1130, 1120, 1110, 1090, 1055, 1045, 1020, 1000, 950, 915, 895, 865, 850, 815, 755, 740, 735, 715, 675, 630, 615, 570, 550, 540, 527, 465

PMR-spectrum (δ ppm) of 2.25 (3H, s), 7,28 (Shostakovich), 7,58 (Shostakovich), 7,63 (doctor), 7,72 (doctor), 7,83 (doctor), 7,95 (doctor), 8,12 (doctor), just N, 11,5 (NH, c.).

Mass spectrum: m/e (I/Imax, %): 364(M, 33), 300(35), 209(100), 182(22), 91(50), 65(45), 51(10), 39(27).

Example 2. Synthesis of 2-[2-(4-methylphenylsulfonyl)phenyl]-benzothiazole (VII) the Scheme for synthesis of:

To a solution of 1.13 g (9.0 mmol) of 2-aminothiophenol in 5 ml of anhydrous dimethylformamide under stirring was added in small portions throughout 5 min 2,94 g (9.5 mmol) of compound XIII. Then the mixture is heated under reflux to boiling and kept for 1 hour at this temperature. Upon cooling to the reaction mass was added 20 ml of water. The mixture was stirred and after 1 hour the precipitate was filtered, washed with water, methanol, dried in vacuum over phosphorus pentoxide, received of 3.07 g of compound VII. TPL KZT 166.5-167°C. Yield 90% of theoretical. Elemental analysis. Found, %: C 63,48; N. Of 3.94; N 7,74; S 16,73. Gross formula C20H16N2O2S2. Calculated, %: C 63,14; N 4,24; N Of 7.36; S16.85.

Fluorescence spectrum (λvasb=370 nm): 507 nm

IR spectrum (cm-1): 3040, 2950, 2925, 2850, 2825, 1775, 1605, 1600, 1580, 1490, 1460, 1440, 1430, 1415, 1380, 1330, 1310, 1305, 1290, 1250, 1240, 1200, 1150, 1120, 1100, 1050, 1015, 975, 940, 820, 760, 745, 730, 725, 700, 650, 635, 615, 575, 555, 540, 510, 450

PMR-spectrum (δ ppm) of 2.25 (3H, s), 7,05 (2H, d), 7,11 (1H, Shostakovich), 7,38 (1H, Shostakovich), was 7.45 (1H Shostakovich), 7,56 (1H Shostakovich), to 7.64 (2H, d), 7,72 (1H, d), to 7.77 (1H, d), 7,79 (1H, d), to 8.12 (1H, d), 12,25 (NH, s).

Mass spectrum: m/e (I/Imax, %): 380(M, 12), 316(13), 225(100), 198(14), 173(4), 109(7), 91(71), 65(50), 39(35).

Example 3. Synthesis of 2-(2-methylphenylsulfonyl)benzothiazole (VIII), 2-[2-(3,5-differentialformen)phenyl]benzothiazole (IX), 2-(2-phenylcarbonylamino)phenylbenzothiazole (X); 2-[2-(2-naftilan-phenylamino)phenyl]benzothiazole (XI); 2-[2-(4-pentadecylcatechol)phenyl]benzothiazole(XII).

The scheme of synthesis of ligands VIII-XII:

2-(2-AMINOPHENYL)benzothiazole (XVI) was synthesized from commercially available reagents according to method [WPIS, Gaidenko, CHC, 1970, N 12, s-1700]. Harangued the IDA alkyl - and arylsulfonic acids R=CH 3(VIII), a 3.5-F2With6H3(IX)6H5(X)2-C10H7(XI)6H4OS15H31(XII) are commercially available or obtainable according to known methods.

To a solution of 15 mmol of 2-(2-AMINOPHENYL)benzothiazole (compound XVI)in 15 ml dry pyridine was added dropwise at room temperature a solution of 15 mmol of the corresponding sulfochloride RSO2Cl [R=CH33.5 to F2-C6H3With6H5, 2-C10H7, 4-(C15H31O)6H4] in 10 ml of dry tetrahydrofuran. The mixture was stirred at the same temperature for 1 hour, then at boiling under reflux for another 1 hour. After removal of the principal amount of the mixture of solvents, the residue was treated with 100 ml of water. The precipitate was filtered off, washed with water, isopropanol, dried in the air. Then recrystallized from alcohol (methanol, ISO-propanol or 1-butanol).

2-(2-methylsulfonylamino)benzothiazole (VIII). Sopl. 171-172°C

Output 82,4% of theoretical. Elemental analysis. Found, %: C 55,79; N 4,39; N 8,95; S 21,31. Gross formula C14H12N2O2S2. Calculated, %: C 55,25; N. Of 3.97; N 9,20; S 21,07.

UV spectrum: 230, 360,490 nm

Fluorescence spectrum (λvasb=370 nm): 540 nm

PMR-spectrum (δ ppm) of 3.23 (3H, s), 7,34 (1H, Shostakovich), 7,54 (1H, Shostakovich), a 7.62 (2H, Shostakovich), of 7.70 (1H, d), of 8.06 (2H, d), by 8.22 (1H, d), 11,60 (NH, c.).

M is SS-spectrum: m/e (I/I max, %): 304(M, 100), 289(40), 225(98), 198(35), 173(13), 154(16), 109(20), 69(34), 63(29), 39(20).

2-[2-(3,5-differentialformen)phenyl]benzothiazole (IX). TPL172-173°C.

The output 94% of theoretical. Elemental analysis. Found, %: C 57,01; N 3,55; N 6,85; S 15,42. Gross formula C19H12F2N2O2S2. Calculated, %: C 56,71, N 3,01; N Of 6.96; S 15,93.

UV spectrum: 215,355 nm

Fluorescence spectrum (λvasb=370 nm): 505 nm

IR spectrum (cm-1): 3093, ~3000 (broad), 1606, 1584, 1508, 1441, 1428, 1342, 1316, 1298, 1285, 1252, 1240, 1213, 1161, 1128, 1082, 1033, 990, 978, 882, 862, 848, 772, 756, 726, 701, 671, 662, 629, 606, 586, 568, 548, 532, 515, 454

PMR-spectrum (δ ppm) of 7.35-7,66 (8H, m), 7,98 (1H, d), 8,14 (1H, d), 8,19 (1H, d), of 11.69 (NH, s).

Mass spectrum: m/e (I/Imax, %): 402(M, 8), 226(75), 198(15), 173(5), 154(10), 113(80), 82(28), 69(75), 63(100), 51(16), 39(40).

2-(2-phenylcarbonylamino)phenyl benzothiazole (X).TPL 187-188°C.

The output 94% of theoretical. Elemental analysis. Found, %: C 62,62; N. Of 3.75; N 8,07; S 17,03. Gross formula C19H14N2O2S2.

Calculated, %: C 62,28; N. Of 3.85; N Of 7.64; S 17,50.

Fluorescence spectrum (λvasb=370 nm): 517 nm

IR spectrum (cm-1): 3055, 2895, 2840, 1605, 1580, 1500, 1485, 1455, 1445, 1440, 1425, 1345, 1330, 1310, 1305, 1290, 1280, 1250, 1235, 1210, 1175, 1155, 1125, 1090, 1070, 1050, 1025, 1015, 990, 970, 920, 865, 840, 815, 760, 755, 748, 735, 715, 695, 682, 650, 625, 580, 550, 510, 445

PMR-spectrum (δ ppm) for 7.12 (1H, Shostakovich), 7,26 (2H, Shostakovich), 7,39 (2H, m), 7,45 (1H, Shostakovich), 7,56 (1H, Shostakovich), 7,72 (1H, Shostakovich), 7,76 (2H, d), 7,79 (1H, d), 7,89 (1H, d), 8,13 (1H, d), 12.3 (NH, c.).

Mass spectrum: m/e (I/Imax, %): 366(M, 80), 302(35), 28610), 225(100), 198(30), 173(10), 109(17), 82(7), 77(60), 69(21), 51(35), 39(12).

2-[2-(2-naphthylamine)phenyl]benzothiazole (XI).TPL 170-171°C.

Exit 95% of theoretical. Elemental analysis. Found, %: C 66,60; N To 3.92; N 6,88; S Of 14.76. Gross formula C23H16N2O2S2.

Calculated, %: C 66,33; N A 3.87; N, 6.73 X; S 15,39.

Fluorescence spectrum (λvasb=370 nm): 510 nm

IR spectrum (cm-1): 3060, 1620, 1600, 1575, 1500, 1485, 1455, 1430, 1420, 1330, 1295, 1245, 1230, 1200, 1155, 1130, 1125, 1170, 1050, 1015, 970, 950, 940, 920, 855, 810, 755, 750, 720, 700, 680, 660, 640, 610 570, 550, 545, 515, 495, 470, 455

PMR-spectrum (δ ppm) 7,26 (1H, Shostakovich), 7,45-7,69 (7H, m), 7,88-7,94 (4H, m), to 7.99 (1H, d), 8,13-8,18 (2H, Shostakovich), 8,98 (1H, s), 11,59 (NH, c.).

Mass spectrum: m/e (I/Imax, %): 416(M, 30), 352(35), 225(100), 198(30), 176(10), 127(83), 109(17), 69(22), 63(18), 39(15).

2-[2-(4-pentadecylcatechol)phenyl]benzothiazole (XII).

TPL 96-96,5°C. Yield 78.4% of theoretical. Elemental analysis. Found, %: C 69,23; N 7,21; N 4,54; S 10,35. Gross formula C34H44N2O3S2. Calculated, %: C 68,88; N. Of 7.48; N 4,73; S 10,22.

UV spectrum: 230, 300, 345 nm

Fluorescence spectrum (λvasb=370 nm): 517 nm

IR spectrum (cm-1): 3070, 3050, 2920, 2850, 1595, 1577, 1500, 1485, 1470, 1435, 1345, 1305, 1255, 1235, 1210, 1180, 1170, 1155, 1125, 1095, 1055, 1015, 975, 920, 855, 830, 760, 720, 700, 685, 625, 580, 550, 508

PMR-spectrum (δ ppm) of 0.85 (3H, T.), 1,20-1,42 (24, m), 3,85 (2H, Shostakovich), 6,69 (2H, d), 7,12 (1H, Shostakovich), 7,37 (1H, Shostakovich), was 7.45 (1H, Shostakovich), 7.55 (1H, Shostakovich), 7,66 (2H, d), 7,72 (1H, d), to 7.77 (1H, d), 7,89 (1H, d), to 8.12 (1H, d), 12,15 (NH, c.).

Mass spectrum: m/e (I/Imax, %): 593(M, 2, 395(7), 317(12), 225(95), 198(7), 109(12), 93(14), 69(25), 43(100).

Example 4. Synthesis of zinc-containing metal complexes XVII-XXIII.

The scheme for synthesis of:

where (VI, XVII) -X=O, R=-C6H4CH3(4-were);
(VII, XVIII) -X-S, R=-C6H4CH3(4-were);
(VIII, XIX) -X=S, R=-CH3(methyl);
(IX, XX) -X=S, R=3,5-F2With6H3- (3,5-differenl);
(X, XXI) -X=S, R=C6H5(phenyl);
(XI, XXII) -X-S, R=2-C10H7(2-naphthyl);
(XII, XXIII) -X=S, R=C6H4OC15H31(4-pentadecylcatechol).

0.01 M ligand (VI-XII) suspended in 15 ml dry methanol (XII - in 40 ml of methanol) and the mixture added 0.54 g (0.01 M) of sodium methylate, dissolved in 15 ml of methanol. Thus was formed a homogeneous solution (in the case of VI and XII partially precipitated sodium salt of the corresponding ligand), to which over 5 min with stirring was added dropwise a solution of 0,g (0.05 M) of anhydrous zinc chloride in 10 ml of methanol. The mixture was heated to 55-60°C and kept at this temperature for 1 hour. After cooling to room temperature the precipitate was filtered and then washed with methanol, water and again with methanol. After this was dried in vacuum over phosphorus pentoxide.

Zinc (II) bis 2-[2-(4-methylphenylsulfonyl)phenyl]benzoxazole (XVII)TPL 337,5-338,5°C. the Yield is 91% of theoretical. Elemental analysis. Found, %: C 61,13; N. Of 4.49; N 7,35; S 7,65; Zn 8,88. Gross formula C40H30N4O6S2Zn. Calculated, %: C 60,65; N 3,82; N 7,07 S 8,09; Zn 8,25.

UV spectrum: 230, 300, 313, 375 nm

Fluorescence spectrum (λvasb=370 nm): 415 nm

IR spectrum (cm-1): 3100, 3065, 2955, 2920, 2860, 1665, 1600, 1592, 1555, 1530, 1480, 1450, 1427, 1395, 1345, 1325, 1300, 1280, 1265, 1235, 1185, 1170, 1130, 1100, 1080, 1060, 1050, 1015, 1000, 970, 935, 890, 835, 805, 750, 740, 705,660,640, 577, 550, 530, 470

Zinc (II) bis 2-[2-(4-methylphenylsulfonyl)phenyl]benzothiazole (XVIII).TPL 357-358°C. the Yield of 94% of theoretical. Elemental analysis. Found, %: C 57,62; N 3,20; N 6,98; S 14,98; Zn Of 7.64. Gross formula C40H30N4O4S4Zn. Calculated, %: C 58,28; N To 3.67; N 6,80; S 15,56; Zn 7,93.

UV spectrum: 232, 260, 303, 390 nm

Fluorescence spectrum (λvasb=370 nm): 441 nm

IR spectrum (cm-1): 3065, 3035, 2950, 2925, 2860, 1597, 1550, 1480, 1455, 1445, 1425, 1320, 1295, 1280, 1265, 1240, 1205, 1180, 1160, 1135, 1080, 1060, 1015, 975, 930, 865, 833, 805, 700, 720, 705, 650, 545

Zinc (II) bis 2-(2-methylsulfonylamino)benzothiazole (XIX).TPL 341-342°C. the Yield 97% of the t of theoretical. Elemental analysis. Found, %: C 51,23; H 3,81; N 7,98; S 18,56; Zn 10,01. Gross formula C28H22N4O4S4Zn. Calculated, %: 50,04; H 3,30; N 8,33; S 19,08; Zn 9,73.

UV spectrum: 207, 232, 258, 308, 385

Fluorescence spectrum (λvasb=370 nm): 463 nm

The infrared spectrum

Zinc (II) bis 2-[2-(3,5-differentialformen)phenyl]benzothiazole(XX). TPL 295-296°C. the Output is 92% of theoretical. Elemental analysis. Found, %: C 51,99; N 2,89; N 6,21; S 14,47. Gross formula C38H22F4N4O4S4Zn. Calculated, %: C 52,77; N To 2.55; N 6,45; S 14,77.

UV spectrum: 240, 315, 390 nm

Fluorescence spectrum (λvasb=370 nm): 429 nm

IR spectrum (cm-1): 3085, 3041, 1605, 1560, 1482, 1458, 1440, 1430, 1320, 1297, 1259, 1245, 1209, 1146, 1132, 1083, 1066, 988, 948, 884, 864, 831, 755, 721, 715, 689, 670, 646, 610, 591, 568, 524, 465

Zinc (II) bis 2-(2-phenylcarbonylamino)phenylbenzothiazole (XXI).TPL 302-303°C. the Yield of 94% of theoretical. Elemental analysis. Found, %: C 56,09; N 3,18; N 7,50; S 15,44. Gross formula C38H26N4O4S4Zn. Calculated, %: 56,89; N Is 3.27; N 6,98; S 15,98; Zn 8,15.

UV spectrum: 230, 265, 310, 390 nm

Fluorescence spectrum (λvasb=370 nm): 448 nm

IR spectrum (cm-1): 3065, 1685, 1670, 1600, 1550, 1487, 1460, 1450, 1430, 1385, 1320, 1302, 1285, 1270, 1260, 1247, 1206, 1180, 1160, 1142, 1090, 1065, 1020, 975, 940, 870, 840, 755, 720, 695, 645, 595, 580, 560, 520, 460

Zinc (II) bis 2-[2-(2-naphthylamine)phenyl]benzothiazole (XXII).The substance does not melt up to 370°C. the Yield of 93% of theoretical. Elemental analysis. Found, %: C 61,01; N 385; N 6,97; S 13,86; Zn 7,56. Gross formula C46H30N4O4S4Zn. Calculated, %: C 61,64; N 3,37 6,25 N; S 14,31; Zn 7,29.

UV spectrum: 235, 265, 305, 390 nm

Fluorescence spectrum (λvasb=370 nm): 445 nm

IR spectrum (cm-1): 3065, 1680, 1600, 1550, 1485, 1460, 1447, 1430, 1385, 1345, 1320, 1300, 1285, 1270, 1245, 1200, 1210, 1145, 1125, 1075, 1015, 980, 955, 935, 870, 830, 752, 727, 715, 680, 660, 615, 580, 560, 550,520,475

Zinc (II) bis 2-[2-(4-pentadecylcatechol)phenyl-benzothiazole (XXIII).The substance when heated to 167-175°C changes the shape of the crystals and melts at 185,5-187°C. the Yield of 95% of theoretical. Elemental analysis. Found, %: C 65,45; N 6,85; N 5,23; S 9,89; Zn 5,58. Gross formula C68H86N4O6S4Zn. Calculated, %: With 65.39; H 6,94; N 4,49; S 10,27; Zn 5,23.

UV spectrum: 205, 235, 310, 385 nm

Fluorescence spectrum (λvasb=370 nm): 450 nm

IR spectrum (cm-1): 3065, 2925, 2855, 1595, 1575, 1550, 1480, 1450, 1440, 1420, 1320, 1280, 1250, 1200, 1170, 1130, 1080, 1060, 975, 930, 860, 830, 750, 720, 710, 680, 640, 585, 575, 555, 520, 460

Example 5. The electroluminescent device.

For the manufacture of electroluminescent devices with the structure of the HIL/HTL/EML/EIL, where HIL - hole-an injecting layer, HTL - hole-transport layer, EML - active electroluminescent layer and EIL - cathode injects layer, use a glass substrate coated with a transparent layer of a mixed oxide of indium and tin (ITO) with resistance 20-25 Ohms/square. The substrate may be applied by the method of zentrifugenbau the aqueous solution of the polymer polyethyleneoxide, doped polystyrenesulfonate (PEDOT:PSS). The layer of ITO or ITO coated PEDOT:PSS serves as a hole-an injecting layer. On the surface of the hole-an injecting layer put a hole-transport layer composed of the MOUTH, by centrifuging from a solution in toluene. The thickness of the hole-transport layer 0.05-0.1 μm. Then by evaporation of one of the complexes XVII-XXIII in vacuum at the facility OPS-2K at a temperature of about 350°C and a base pressure of 5·10-6mm Hg is applied to the active electroluminescent layer thickness of 0.02-0.05 micron. The sample is placed in a vacuum installation VUP-4, pump out in a dynamic mode to vacuum 5·10-6mm Hg and sprayed metal electrode (cathode injects layer) by evaporation of aluminum. The thickness of the metal electrode is about 0.1 μm. The area of the illuminated surface of 4-5 mm2. Received the electroluminescent device emits blue light under the application of a direct voltage. The device structure ITO/PEDOT:PSS/PTA/(XX)/Al has the following parameters: brightness 100 CD/m2is achieved at a voltage of 8 V and a current density of 60 mA/cm2(the efficiency of 0.16 CD/A).

1. The electroluminescent material consisting of electron-an injecting layer, an active luminescent layer-based fluorescent substance, a hole-transport layer and the hole-an injecting layer, great for the decomposing those as the fluorescent substance containing the metal complexes with ligands based on derivatives of 2-(2-AMINOPHENYL)benzoxazole or 2-(2-AMINOPHENYL)benzothiazole General formula

where M is an atom of zinc; n=2; X can be an oxygen atom or sulfur; R can be selected from a number:
an alkyl group of 1-18 carbon atoms and having a normal or branched structure;
phenyl group;
mono - or polyalkylene phenyl group in which the alkyl substituents consist of 1 to 18 carbon atoms and have a normal or branched structure;
mono - or polyhalogen phenyl group in which the atoms of halogen is fluorine, chlorine, bromine, iodine;
mono - or polyalkoxysiloxanes phenyl group in which the alkoxy substituents consist of 1 to 18 carbon atoms and have a normal or branched structure;
1 - or 2-naftalina group.

2. The electroluminescent material according to claim 1, characterized in that the luminescent substances it contains zinc(II) bis 2-[2-(4-methylphenylsulfonyl)phenyl]benzoxazole:

3. The electroluminescent material according to claim 1, characterized in that the luminescent substances it contains zinc(II) bis 2-(2-methylsulfonylamino)benzothiazolin:

4. E is chronometrically material according to claim 1, characterized in that the luminescent substances it contains zinc(II) bis 2-(2-phenylcarbonylamino)benzothiazolin:

5. The electroluminescent material according to claim 1, characterized in that the luminescent substances it contains zinc(II) bis 2-[2-(4-methylphenylsulfonyl)phenyl]benzothiazole:

6. The electroluminescent material according to claim 1, characterized in that the luminescent substances it contains zinc (II) bis 2-[2-(3,5-differentialformen)phenyl]benzothiazole:

7. The electroluminescent material according to claim 1, characterized in that the luminescent substances it contains zinc (II) bis 2-[2-(4-pentadecylcatechol)sulfonylamino]phenylbenzothiazole:

8. The electroluminescent material according to claim 1, characterized in that the luminescent substances it contains zinc(II) bis 2-[2-(2-naphthyl)sulfonylamino]phenylbenzothiazole:

9. The electroluminescent material according to claim 1, characterized in that substances hole-transport layer contains a mixture of oligomers of triphenylamine General formula:

where n=8-9 at the molecular-mass distribution: Mm=2332, Mw=3586.



 

Same patents:

FIELD: polymer materials.

SUBSTANCE: invention provides luminescent material showing semiconductor properties and being product of complex polymerization in glow discharge, which is formed as a supported polymer layer located either between electrodes or on any of electrodes. Starting pyrromethene complex is difluoroborate complex of 1,3,5,7,8-pentamethyl-2,6-diethylpyrromethene (Pyrromethene 567). Method of preparing luminescent semiconductor polymer material comprises glow-discharge polymerization for 2 to 120 min of Pyrromethene 567 vapors at temperature preferably 250-350°C, pressure 10-1 to 10-2 Pa, and discharge power 0.5-3 W. Resulting luminescent polymer is characterized by thickness preferably 0.001-10 μm, conductivity 1·10-10 to 5·10-10 Ohm-1cm-1 (20°C), luminescence emission maximum in the region of 540-585 nm at band halfwidth 55-75 nm. Polymer is obtained with quantum yield 0.6-0.8 and is designed for creation of film light-emitting devices.

EFFECT: improved performance characteristics of material.

13 cl, 3 ex

FIELD: microelectronics; production of light-emitting diodes.

SUBSTANCE: the invention is pertinent to microelectronics and may be used in production of light-emitting diodes. Electroluminescent polymeric nanocomposite material contains 50-99.5 mass % of polymer - water-soluble polyphenylamine with electron-hole conductance, and 50-0.5 mass % of an electroluminescing organic ingredient in the form of J- component units - a cyanine dye, a squaryl dye or a porphyrin. For production of the electroluminescent material first solve polyphenylamine in water, then introduce a powder of the indicated dye. Formation of J- component units fix according to a change of the solution color. Produced nanocomposite material is applied on the current-conducting substrate, dried. Then apply a layer of a metal-cathode. The invention allows to produce electroluminescent layers with a band of electroluminescence from 400 up to 1600 nm having high characteristics, for instance, luminance and efficiency.

EFFECT: the invention ensures production of electroluminescent layers with a band of electroluminescence from 400 up to 1600 nm having high luminance and efficiency.

6 ex

The invention relates to the field of lighting, element base of microelectronics, electronic materials science

The invention relates to an electroluminescent indicator panels, in particular, to an electroluminescent indicator panels with a high degree of specularity and high contrast

The invention relates to the field of electronic equipment, particularly, to electroluminescent devices for light-emitting diodes, electroluminescent screens and t

FIELD: chemistry.

SUBSTANCE: invention concerns fluorescent bleach containing a mix of two asymmetrically substituted and one symmetrically substituted triazinylaminostilbene disulfone acid, a new symmetrically substituted derivative, method of their obtaining, and application of the mix in synthetic or natural organic material (especially paper) bleaching and in fluorescent bleaching and sun resistance boost of textile.

EFFECT: high substantivity and light resistance of the claimed fluorescent bleaches and their mixes, and better water solubility of the claimed mixes in comparison to the solubility of each individual bleach.

15 cl, 2 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: polynucleotide is obtained, coding chromo- or fluorescen mutant wild type DsRed (SEQ ID N0:2), where chromo- or fluorescent mutant contains a substitute in the amino acid position 42 SEQ ID N0:2, and optionally one or more substitutes in the amino acid positions, chosen from a group, consisting of 4, 2, 5, 6, 21, 41, 44, 117, 217, 145. Using the polynucleotide in the vector, the host cells which express chromo- or fluorescent mutant DsRed are transformed. The invention allows for obtaining chromo- or fluorescent polypeptide DsRed, which matures faster than wild type DsRed.

EFFECT: increased effectiveness.

26 cl, 10 dwg, 2 tbl, 4 ex

FIELD: print engineering.

SUBSTANCE: invention provides ink containing first fluorescent color material emitting fluorescence at specified emission wavelength used for measurement or determination of excitement at specified excitement wavelength; and second fluorescent color material emitting fluorescence when excited at specified excitement wavelength, said second color material being contained in larger amount than said first color material. To obtain fluorescence at desired emission wavelength, excitement spectrum of the first color material in ink should have peak wavelength range adjoining specified fluorescent wavelength, and emission fluorescence spectrum of the second color material has emission wavelength range that includes at least above-mentioned peak wavelength range.

EFFECT: enhanced fluorescence intensity due to presence of several fluorescent coloring substances.

9 cl, 26 dwg, 3 tbl, 6 ex

FIELD: organic chemistry.

SUBSTANCE: invention relates to novel derivatives of some N,N'-bis-(9-anthrylmethyl)-substituted alkanediamines, namely, to N,N'-bis-(9-anthrylmethyl)cyclohexane-1,2-diamine of the formula (I): . This compounds possesses properties of highly selective fluorescent hemosensor for cations Zn2+ in neutral medium. Proposed N,N'-bis-(9-anthrylmethyl)cyclohexane-1,2-diamine as compared with its analog by structure and using, i. e. N,N'-bis-(9-anthrylmethyl)ethane-1,2-diamine, elicits more effective and selective hemosensor properties with respect to ions Zn2+.

EFFECT: improved and valuable chemical properties of compound.

1 dwg, 2 ex

FIELD: luminescent substances, organic chemistry.

SUBSTANCE: invention relates to electroluminescent materials containing organic luminescent substance. Invention describes novel electroluminescent material consisting of injection layer, active luminescent layer based on chelate metal complex, hole-transporting layer and hole-injecting layer. Material comprises metal complexes based on sulfanyl derivatives of 8-aminoquinoline as a luminescent substance, in particular, zinc complexes of 8-(methylsulfanylamino)-quinoline and 8-(3,5-difluorophenylsulfanylamino)-quinoline. Material comprises a mixture of triphenylamine oligomers as a hole-transporting layer. Invention provides creature of electroluminescent material showing the enhanced moisture resistance, enhanced resistance to crystallization and enhanced thermal stability.

EFFECT: improved and valuable properties of material.

4 cl, 5 ex

FIELD: polymer items possessing fluorescent properties and property of reflection in opposite direction; information and signaling appliances.

SUBSTANCE: proposed sheet item has sublayer of film coated with fluorescent paint at concentration of from 0.001 to 1.5 wt-% relative to polymer matrix of sublayer, film of overlayer coated with fluorescent paint at concentration of from 0.001 to 1.5 wt-% relative to polymer matrix of overlayer. Fluorescent film of overlayer coated with paint possesses higher resistance to light as compared with sublayer film. Sheet of painted fluorescent film of overlayer lies over sheet of sublayer fluorescent film. Sheet item has selected fluorescent color different from color of overlayer fluorescent film and from color of sublayer fluorescent film. Specification gives description of production of such items.

EFFECT: enhanced resistance to action of atmospheric conditions; enhanced durability of color; wide range of color.

53 cl, 17 dwg, 8 tbl, 15 ex

FIELD: polymer material.

SUBSTANCE: invention relates to polymeric multilayer fluorescently stained particles widely applicable for distribution of visible information and provides sheet-shaped fluorescence-emitting articles. These have at least two film layers, each of which contains fluorescent dye in polymer matrix. Stained film of the upper layer is characterized by higher resistance to UV emission than stained sublayer film, and article itself has specified fluorescent coloration differing both from coloration of said stained fluorescent sublayer film and from coloration of said stained fluorescent upper layer. Manufacturing process for such articles is also described. Articles may optionally contain light-returning elements suitable as warning signs such as pedestrian crossing signs and signs indicating school zones, which emit fluorescent yellow color.

EFFECT: ensured resistance to weather conditions, increased color durability, and improved coloration characteristics regulated by industrial standards for particular conditions.

37 cl, 14 dwg, 3 tbl, 11 ex

FIELD: capillary luminescent flaw detection, possible use in aviation, automobile, shipbuilding and other branches of mechanical engineering, and also power engineering, chemical and nuclear industries for detection of surface defects, cracks, pores, foliating, abscesses, inter-crystallite corrosion and other defects of material discontinuity flaw type, primarily with small dimensions, in case of especially precise control of products.

SUBSTANCE: penetration agent includes organic phosphor, non-ionic surfactant and solvent, while as organic phosphor a mixture of phosphors from the class of coumarin colorants is used - mixture of donor-coumarin and acceptor-coumarin, as nonionic surfactant a specially defined substance is used, and as solvent a mixture of dibutyl phthalate and propylene carbonate is used with mass ratio ranging from 1:1,5 to 1:0,8. As donor-coumarin, 4-methyl-7-dethyl amine coumarin (K-47) may be used, and as coumarin-acceptor, at least one coumarin of yellow-green luminescence, with mass ratio ranging from 1,1:1 to 1,8:1.

EFFECT: increased sensitivity and reliability of flaw detection, while simultaneously reducing fire hazard and toxicity of used composition.

1 ex, 1 tbl

FIELD: organic chemistry.

SUBSTANCE: invention relates to novel compounds, namely zinc bis-[2-(tosylamino)benzylidene-N-alkyl(aryl, hetaryl)aminates] of the general formula (I): wherein Ts means tosyl; R means (C1-C6)-alkyl with exception isopropyl, (C1-C6)-alkyl-substituted phenyl, (C1-C6)-alkoxy-substituted phenyl with exception para- and ortho-methoxyphenyl, pyridyl, (C1-C6)-alkylpyridyl, or R + R form in common disulfidodialkyl group -(CH2)n-S-S-(CH2)n- wherein n = 1-3, but preferably to zinc bis-[2-(tosylamino)benzylidene-N-alkylidenemercaptoaminates] of the general formula (Ia): Compounds can be used for synthesis of light-radiating organic diode of white and visible light. Fluorescence can be observed in blue region of spectrum with fluorescence bands maximum at 428-496 nm. Quantum yields are 0.2-0.25.

EFFECT: valuable physical properties of compounds.

5 cl, 8 ex

FIELD: organic chemistry, luminophores.

SUBSTANCE: invention relates to colorless at daylight organic luminophores, in particular, to novel, water-soluble, colorless luminophores A of the formula:

wherein X means oxygen (O) or sulfur (S) atom; Q means compounds of the formulas and wherein R1 and R2 taken separately or in common mean compounds of the formulas: -NHCH2COOM, -N(CH2COOM)2, Cl wherein M means Na, K, NH4. As comparing with the known colorless organic luminophores - optical whitening agents possessing with blue-sky blue fluorescence only, novel luminophores show fluorescence in the range from blue to yellow-orange color and can be used as components of fluorescent, colorless at daylight, inks for jet printers or stamp dyes.

EFFECT: improved and valuable properties of luminophores.

14 ex

FIELD: chemistry.

SUBSTANCE: invention concerns novel compound of zinc mezzo-triphenyltetra-[-(п-triphenylmethylphenoxybenzo)]monoazaporphyrinate.

EFFECT: possible application as fat-soluble green colourant for polymers, as material for thin film microelectronics, as catalyst, and in other scientific and technical fields.

1 cl, 1 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to obtaining etyheleneammonium bis(1-hydroxyethane-1,1-diphosphonato(2-))cuprate (+2), etyheleneammonium bis(1-hydroxyethane-1,1-diphosphonato(2-)) zincate(+2) and etyheleneammonium bis(1-hydroxyethane-1,1-diphosphonato(2-)) nickelate(+2) and can be used for processing toxic wastes of obtaining metal coatings - waste electrolytes of galvanic copper, zinc and nickel plating, waste solutions of chemical nickel plating and copper plating. Products, obtained by said method, can be used for preparation of electrolytes, metal corrosion inhibitors, for obtaining various copper, zinc and nickel compounds, including catalysts of organic and inorganic substance synthesis. Claimed method includes using liquid industrial wastes, containing metal(+2), ethyleneammonium and/or anion of 1-hydroxyethane-1,1-diphosphonic acid as reagents. Target products are obtained by crystallisation from reaction water solution with separation of sediment from solution, process is carried out at temperature from (-5) to 105°C and atmospheric pressure. Method allows to obtain pure crystalline products with yield up to 98%, to reduce expenditures on environment protection.

EFFECT: method simplification and increase of its manufacturability.

7 cl, 9 ex

FIELD: chemistry.

SUBSTANCE: as photosensibilizers emulsions of alkylthiosubstituted phalocyanides of general formula , where R1=R4=Cl, R2=R3=n-C10H21S, M=Zn or R1=t-C4H9S, R2=R3=R4=H, M=HH or R1=t-C4H9S, R2=R4=H, R3=t-C4H9, M=HH or R1=R3=t-C4H9S, R2=R4=H, M=HH or R1=R2=R3=R4=t-C4H9S, M=HH or R1=R4=Cl, R2=R3=t-C4H9S, M=Zn, in water solution of Proxanol 268 are suggested.

EFFECT: elaboration of highly selective and efficient photosensibilizers for application in photodynamic therapy of tumours.

3 cl, 18 ex, 4 tbl, 9 dwg

FIELD: chemistry.

SUBSTANCE: invention concerns a new compound, zinc meso-trans-dihexadecyltetrabenzoporphyrinate .

EFFECT: compound can be applied as a fat-soluble green colorant for solution dyeing of paraffin and polyethylene.

1 cl, 2 ex, 2 dwg

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention proposes an improved method for synthesis of bis-(1-vinylimidazole)-zinc diacetate representing a complex compound of zinc diacetate with 1-vinylimidazole and known as medicinal preparation acizol. Acizol is an effective antidote and antihypoxic agent of the broad spectrum of effect. Method for synthesis of 1-vinylimidazole metal with zinc diacetate of the composition 2:1 involves carrying reaction in the absence of solvent and using available commercial zinc diacetate of the formula Zn(OCOCH3)2 x 2 H2O in the stoichiometric mole ratio 1-vinylimidazole : salt in the range from 2.9:1 to 2:1, and synthesized pure product is isolated by water distilling off or its azeotropic mixture with 1-vinylimidazole. Method provides excluding the dehydration step of parent zinc salt from technological process and to decrease consumption of used reagent 1-vinylimidazole significantly, Invention provides significant reducing energetic and industrial consumptions, simplifying and decreasing cost of process and retaining the quantitative yield of highly pure pharmacopoeia acizol preparation.

EFFECT: improved method of synthesis.

4 ex

FIELD: luminescent substances, organic chemistry.

SUBSTANCE: invention relates to electroluminescent materials containing organic luminescent substance. Invention describes novel electroluminescent material consisting of injection layer, active luminescent layer based on chelate metal complex, hole-transporting layer and hole-injecting layer. Material comprises metal complexes based on sulfanyl derivatives of 8-aminoquinoline as a luminescent substance, in particular, zinc complexes of 8-(methylsulfanylamino)-quinoline and 8-(3,5-difluorophenylsulfanylamino)-quinoline. Material comprises a mixture of triphenylamine oligomers as a hole-transporting layer. Invention provides creature of electroluminescent material showing the enhanced moisture resistance, enhanced resistance to crystallization and enhanced thermal stability.

EFFECT: improved and valuable properties of material.

4 cl, 5 ex

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