Molecular complexes of zinc and cadmium bis(1-phenyl-3-methyl-4-formyl-5-pyrazolonate) with amino-derivatives of nitric heterocycles, having luminescent activity

FIELD: chemistry.

SUBSTANCE: invention relates to molecular complexes of zinc and cadmium bis(1-phenyl-3-methyl-4-formyl-5-pyrazolonate) with amino-derivatives of nitric heterocycles of general formula (I) (NH2-Het)n, where NH2-Het is 1-aminoisoquinoline, 3-aminoquinoline, 6-aminoquinoline, 5-amino-4,6-dimethylquinoline, 2-aminopyridine, 2-amino-5-bromopyridine, 3-amino-5-methylisoxazole, 2-amino-1-ethylbenzimidazole, M is Zn, Cd, n=1, 2.

EFFECT: molecular complexes of formula (I) exhibit luminescent properties in the blue region of the spectrum and can be used as phosphors for making organic light-emitting diodes of white and visible light.

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The invention relates to new compounds in a series of bis(1-phenyl-3-methyl-4-formyl-5-pyrazolone)zinc and cadmium, namely the molecular complexes of bis(1-phenyl-3-methyl-4-formyl-5-pyrazolone)zinc and cadmium with amino derivatives of nitrogen heterocycles of General formula

where NH2-Het=1-aminoisoquinoline, 3-aminoquinoline, 6-aminoquinoline, 5-amino-4,6-dimethylphenol, 2-aminopyridine, 2-amino-5-bromopyridine, 3-amino-5-methylisoxazole, 2-amino-1-ethylbenzamide, M=Zn, Cd, n=1,2. The compounds I are luminescent properties in the blue region of the spectrum and can be used as phosphors to obtain organic light-emitting diodes and white visible light.

Known bis[1-methyl(phenyl)-3-methyl-4-methyl(phenyl)aminomethyl-5-pyrazoline)zinc General formula II

where R=CH3With6H5, R1=CH3C6H5. The compound (II) exhibit fluorescent properties. However, these properties are not sufficiently high. Quantum yields from 0,0018 to 0,0064 (Neartime, Avilov, Iyakkam, Lwill // AH, 198, t, No. 9, S-2085).

The most similar structure are molecular complexes of bis(1-phenyl-3-methyl-4-acetyl - (benzoyl)-5-pyrazolone) zinc and cadmium with nitrogen heterocycles of General formula III

where R=the H 3C6H6, NH2-Het=1-Mei, 1-benzylimidazole, M=Zn, Cd, n=2 (C.Pettinari, F.Marchetti, A.Cingolani, S.I.Troyanov, A.Drozdov // Polyhedron, 1998, Vol.17, No.10, p.1677-1691). Fluorescent activity of the compounds is not described.

Object of the invention is the extension of a series of phosphors emitting in the blue region of the spectrum.

The technical result of the invention are new compounds in a series of molecular complexes of bis(1-phenyl-3-methyl-4-formyl-5-pyrazolone)zinc and cadmium with amino derivatives of nitrogen heterocycles, exhibiting luminescent properties with high quantum yield.

The technical result is achieved by compounds of General formula I.

The invention satisfies the criterion of inventive step, since no known connections of a number of molecular complexes of bis(1-phenyl-3-methyl-4-formyl-5-pyrazolone)zinc and cadmium with aminoheterocycles exhibiting luminescent properties.

The method of obtaining the compounds of the first lies in the interaction of 1-phenyl-3-methyl-4-formyl-5-hydroxypyrazol with acetate dihydrate zinc or cadmium when heated with a subsequent effect on the obtained zinc or cadmium complex II aminoheterocycles.

Below are examples of making connections.

Example 1. Bis(1-phenyl-3-methyl-4-formyl-5-pyrazolone)zinc (IIa), M=Zn).

To the boiling solution of 2 mmole of 1-f the Nile-3-methyl-4-formyl-5-hydroxypyrazol in 10 ml of chloroform poured boiling solution of 1 mmole of two-water zinc acetate in 5 ml of methanol. The resulting solution is boiled for 1 hour. Then distilled off the solvent to volume of 5 ml, cool. The precipitation is filtered off, washed with methanol and dried in a drying Cabinet at 100°C. the white Crystals with TPL208-209°C. a Yield of 75%. Found, %: C, 56.40, H 3.97, N 12.06, Zn 13.82. For C22H18N4O4Zn calculated, %: C, 56.49, H 3.88, N 11.98, Zn 13.98.

IR spectrum (in the solid phase): 1628, 1598, 1538, 1497, 1457, 1404,1366, 1349, 1171, 1125, 1075, 1057, 1031, 1014, 902, 883, 835, 801, 752, 688, 594 cm-1.

1H NMR spectrum, CDCl3, δ, ppm: 2.22 (6N, s, 2CH3), 7.07 (2H, t, J=7.4 Hz, 4-H of phenyl), 7.21 (4H, t, J=8.4 Hz, 3-H and 5-H of phenyl), 7.68 (4H, d, J=7.8 Hz, 2-H and 6-H of phenyl), 8.82 (2H, s, 2CH=O).

Example 2. Bis(1-phenyl-3-methyl-4-formyl-5-pyrazolone)cadmium (IIb, M=Cd). Compound IIb is obtained analogously to example 1 using two-water acetate cadmium.

The crystals are white with TPL193-194°C. Yield 80%. Found, %: C, 51.41, H 3.65, N 11.01, Cd 21.72. For C22H18N4O4Cd calculated, %: C, 51.33; H 3.52, N 10.88, Cd 21.83.

IR spectrum (in the solid phase): 3016, 2915, 2825, 2720, 1629, 1595, 1524, 1511, 1499, 1458, 1438, 1390, 1367, 1313, 1265, 1183, 1165, 1077, 1061, 1038, 1014, 959, 898, 834, 803, 755, 745, 692, 679, 645, 628, 590, 570 cm-1.

1H NMR spectrum, DMSO-d6, δ, ppm: 2.21 (6N, s, 2CH3), 7.13 (2H, t, J=7.2 Hz, 4-H of phenyl), 7.36 (4H, t, J=7.8 Hz, 3-H and 5-H of phenyl),7.90 (4H, d, J=8.1 Hz, 2-H and 6-H of phenyl), 9.05 (2H, s, 2CH=O).

Example 3. The complex bis(1-phenyl-3-methyl-4-formyl-5-pyrazolone)zinc (II) with 1-amino what kinolina (Ia, NH2-Het=1-aminoisoquinoline, M=Zn, n=2).

To a solution of 2 mmole of bis(1-phenyl-3-methyl-4-formyl-5-pyrazolone)zinc (II) in 10 ml of tetrahydrofuran is poured a solution of 4 mmole of 1-aminoisoquinoline in 10 ml of tetrahydrofuran. The resulting solution is boiled for 1 hour, cooled, the precipitate filtered off, washed with tetrahydrofuran and dried. Recrystallized from ethanol, pale yellow crystals with TPL212-213°C. Yield 74%. Found, %: C at 63.47, H 4.67, N 14.96, Zn 8.80. For C40H34N8O4Zn calculated, %: C, 63.54; H 4.53, N 14.82, Zn 8.65

IR spectrum (in the solid phase): 3455, 3357, 3240, 3072, 2850, 1621, 1592, 1582, 1565, 1552, 1534, 1497, 1484, 1456, 1443, 1430, 1402,1384, 1347, 1323, 1290, 1263, 1179, 1164, 1110, 1097, 1071, 1053, 1029, 1006, 966, 944, 903, 867, 836, 797, 750, 688, 629, 591 cm-1.

1H NMR spectrum, CDCl3, δ, ppm: 2.28 (6N, s, 2CH3), 5.78 (4H, s, 2NH2), 7.00 (2H, d, J=6.0 Hz, H of isoquinoline), 7.22 (2H, t, J=7.5 Hz, 4-H of phenyl), 7.41 (4H, t, J=7.9 Hz, 3-H and 5-H of phenyl), 7.49 (2H, t, J=6.3 Hz, H of isoquinoline),7.64 (4H, d, J=7.5 Hz, 2-H and 6-H of phenyl), 7.74 (2H, d, J=8.1 Hz, H of isoquinoline), 7.90 (2H, d, J=6.3 Hz, 3-H of isoquinoline), 8.05 (4H, d, J=7.8 Hz, 8-H of isoquinoline), 9.07 (2H, s, 2CH=O).

Compounds I in examples 4-14 obtained analogously to example 2 using the appropriate aminoheterocycles.

Example 4. The complex bis(1-phenyl-3-methyl-4-formyl-5-pyrazolone)zinc (II) with 6-aminoquinoline (Ib, NH2-Het=6-aminoquinoline, M=Zn, n=2)

The dark green crystals with TPL159-160°C. Yield Of 95% was Found, %: C, 63.49, H 4.64, N 14.92, Zn 8.82. For C40H34N8O4Zn calculated, %: C, 63.54; H 4.53, N 14.82, Zn 8.65

IR spectrum (in the solid phase): 3417, 3340, 3279, 3062, 3031, 2993, 2919, 2833, 2586. 2520, 2395, 2264, 1632, 1595, 1527, 1499, 1458, 1437, 1400, 1367, 1350, 1298, 1246, 1223, 1181, 1152, 1126, 1099, 1074, 1058, 1029, 1004, 963, 939, 895, 860, 840, 760, 752, 690, 676, 665, 628, 590, 572, 557 cm-1.

1H NMR spectrum, DMSO-d6, δ, ppm: 2.25 (6N, s, 2CH3), 5.27 (4H, ush. s, 2NH2), 6.75 (2H, d, J=2.4 Hz, 5-H quinoline), 7.07 (2H, t, J=7.3 Hz, 4-H of phenyl), 7.11 - 7.20 (4H, m, 3-H and 4-H quinoline), 7.31 (4H, t, J=7.9 Hz, 3-H and 5-H of phenyl), 7.65 (2H, d, J=9.0 Hz, 7-H quinoline), 7.82 (2H, d, J=8.4 Hz, 8-H quinoline),), 7.99 (4H, d, J=8.4 Hz, 2-H and 6-H of phenyl), 8.40 (2H, t, J=2.1 Hz, 2-H quinoline), 8.97 (2H, s, 2CH=O).

Example 5. The complex bis(1-phenyl-3-methyl-4-formyl-5-pyrazolone)zinc (II) with 3-aminoquinoline (Ic, NH2-Het=3-aminoquinoline, M=Zn, n=1)

The crystals are pale yellow with TPL142-143°C. Yield 78%. Found, %: C 60.79, H 4.34, N 13.90, Zn 10.81. For C31H26N6O4Zn calculated, %: C, 60.84; H 4.28, N 13.73, Zn 10.68.

IR spectrum (in the solid phase): 3417, 3340, 3279, 3062, 3031, 2993, 2919, 2833, 2586, 2520, 2395, 2264, 1632, 1595, 1527, 1499, 1458, 1437, 1400, 1367, 1350, 1298, 1246, 1223, 1181, 1152, 1126, 1099, 1074, 1058, 1029, 1004, 963, 939, 895, 860, 840, 760, 752, 688, 665, 628, 615, 592, 568 cm-1.

1H NMR spectrum, CDC13, δ, ppm: 2.27 (6N, s, 2CH3), 3.99 (2H, USS, NH2), 7.15 (2H, t, J=7.4 Hz, 4-H of phenyl), 7.33-7.38 (4H, m, 3-H and 5-H of phenyl), 7.44-7.48 (2H, m, H quinoline), 7.58-7.61 (2H, m, H quinoline), 7.97 (4H, d, J=7.8 Hz, 2-H and 6-H of phenyl), 8.34 (1H, t, J=5.0 Hz, 4-H ginoli is a),), 8.53 (1H, s, 2-H quinoline), 9.00 (2H, s, 2CH=O).

Example 6. The complex bis(1-phenyl-3-methyl-4-formyl-5-pyrazolone)zinc (II) with 5-amino-4,6-dimethylindoline (Id, NH2-Het=5-amino-4,6-dimethylphenol, M=Zn, n=2)

The crystals are yellow-green with TPL182-183°C. the Yield was 73%. Found, %: C, 61.79; H 4.79, N 13.21, Zn 10.30. For C33H30N6O4Zn calculated, %: C, 61.93; H 4.72, N 13.13, Zn 10.21.

IR spectrum (in the solid phase): 3427, 3332, 3214, 2989, 2847, 1628, 1590, 1579, 1535, 1513, 1497, 1484, 1455, 1401, 1369, 1345, 1390, 1252, 1242, 1177, 1154, 1130, 1098, 1071, 1054, 1028, 1006, 979, 960, 902, 846, 828, 793, 753, 690, 677, 628, 594, 565, 552 cm-1.

1H NMR spectrum, DMSO-d6, δ, ppm: 2.21 (6N, s, 2CH3quinoline), 2.23 (6N, s, 2CH3quinoline), 2.95 (6N, s, 2CH3of pyrazole), 5.09 (4H, s, 2NH2), 7.05 (2H, d, J=3.9 Hz, 3-H quinoline), 7.08-7.21 (4H, m, 4-N-phenyl and N quinoline), 7.32-7.37 (6N, m, 3-H and 5-H phenyl and N quinoline), 7.95 (4H, d, J=7.8 Hz, 2-H and 6-H of phenyl); 8.47 (2H, d, J=4.2 Hz, 2-H quinoline), 9.02 (2H, , 2CH=O).

Example 7. The complex bis(1-phenyl-3-methyl-4-formyl-5-pyrazolone)zinc (II) with 2-aminopyridine (Ie, NH2-Het=2-aminopyridine, M=Zn, n=2)

The crystals are white with TPL172-173°C (decomp.). Yield 78%. Found, %: C, 58.43; H 4.67, N 17.15, Zn 10.04. For C32H30N8O4Zn calculated, %: C, 58.59, H 4.61, N 17.08, Zn 9.96

IR spectrum (in the solid phase): 3445, 3341, 3227, 3041, 2852, 1622, 1591, 1582, 1566, 1551, 1530, 1493, 1482, 1456, 1402, 1367, 1348, 1324, 1263, 1181, 1155, 1129, 1097, 1072, 1052, 1029, 1005, 955, 903, 851, 836, 792, 768, 752, 690, 676, 630, 590 cm-1.

1H NMR spectrum, CDCl 3, δ, ppm: 2.28 (6N, s, 2CH3), 5.00 (4H, s, 2NH2), 6.47 (2H, d, J=8.4 Hz, 3-H of pyridine), 6.62 (2H, t, J=6.3 Hz, 4-H of pyridine), 7.18 (2H, t, J=7.5 Hz, 4-H of phenyl), 7.36-7.46 (6N, m, 3-H and 5-H phenyl and 5-H of pyridine), 8.01-8.06 (6N, m, 2-H and 6-H phenyl and 6-H of pyridine), 9.05 (2H, s, 2CH=O).

Example 8. The complex bis(1-phenyl-3-methyl-4-formyl-5-pyrazolone)zinc (II) with 2-amino-5-bromopyridine (If, NH2-Het=2-amino-5-bromopyridin, M=Zn, n=2)

The crystals are white with TPL179-180°C. Yield 80%. Found, %: C 47.13, H 3.58, N 13.85, Zn 8.14. For C32H28Br2N8O4Zn calculated, %: C, 47.23; H 3.47, N 13.77, Zn 8.03.

IR spectrum (in the solid phase): 3445, 3328, 3288, 3243, 3215, 3098, 3060, 2841, 1625, 1603, 1596, 1584, 1553, 1528, 1488, 1457, 1392, 1363, 1350, 1318, 1262, 1182, 1170, 1156, 1141, 1114, 1095, 1072, 1055, 1031, 1012, 920, 899, 832, 819, 800, 754, 687, 653, 634, 595, 563 cm-1.

1H NMR spectrum, CDCl3, δ, ppm: 2.21 (6N, s, 2CH3), 6.15 (4H, s, 2NH2), 6.41 (2H, d, J=8.7 Hz, 4-H of pyridine), 7.12 (2H, t, J=7.1 Hz, 4-H of phenyl), 7.36 (4H, t, J=7.5 Hz, 3-H and 5-H of phenyl), 7.49 (2H, DD, J=8.9 Hz, J=2.6 Hz, 4-H of pyridine), 7.93-7.95 (6N, m, 2-H and 6-H phenyl and 6-H of pyridine), 9.01 (2H, s, 2CH=O).

Example 9. The complex bis(1-phenyl-3-methyl-4-formyl-5-pyrazolone)zinc (II) with 2-amino-1-ethylbenzothiazolium (Ig, NH2-Het=2-amino-1-ethylbenzamide, M=Zn, n=2)

The white crystals from ethanol with TPL204-205°C. Yield 63%. Found, %: C, 60.77; H 5.23, N 17.86, Zn 8.15. For C40H40N10O4Zn calculated, %: C, 60.80; H 5.10, N 17.73, Zn 8.27.

IR spectrum (in solid phase): 3377, 3318, 213, 3050, 2986, 2921, 2883, 2813, 2509, 1629, 1594, 1559, 1526, 1493, 1463, 1445, 1397, 1361, 1321, 1295, 1242, 1191, 1149, 1130, 1109, 1097, 1072, 1058, 1018, 1002, 982, 912, 901, 838, 803, 781, 753, 732, 716, 696, 681, 642, 625, 594, 570, 554 cm-1.

1H NMR spectrum, CDCl3, δ, ppm: 1.27 (6N, t, J=7.1 Hz, 2CH2CH3), 2.22 (6N, s, 2CH3), 4.02 (4H, K, J=7.2 Hz, 2CH2CH3), 6.49 (4H, s, 2NH2), 6.86-6.89 (4H, m, H-benzimidazole), 7.03-7.09 (4H, m, H-benzimidazole), 7.31 (6N, t, J=8.0 Hz, 3-H and 5-H of phenyl), 8.01 (4H, d, J=8.1 Hz, 2-H and 6-H of phenyl), 9.01 (2H, s, 2CH=O).

Example 10. The complex bis(1-phenyl-3-methyl-4-formyl-5-pyrazolone)zinc (II) with 3-amino-5-methylisoxazole (Ih, NH2-Het=3-amino-5-methylisoxazol, M=Zn, n=1). The crystals are white with TPL173-174°C (decomp.). Yield 85%. Found, %: C, 60.77; H 5.23, N 17.86, Zn 8.15. For C40H40N0O4Zn calculated, %: C, 60.80; H 5.10, N 17.73, Zn 8.27.

IR spectrum (in the solid phase): 3408, 3275, 3168, 3134, 2922, 2838, 1627, 1593, 1532, 1514, 1488, 1455, 1438, 1397, 1366, 1341, 1285, 1165, 1114, 1072, 1057, 1022, 1007, 936, 903, 845, 802, 762, 749, 695, 676, 661, 631, 592, 562 cm-1.

1H NMR spectrum, DMSO-d6, δ, ppm: 2.23 (3H, s, CH3the isoxazol), 2.25 (6N, s, 2CH3pyrazol ring), 5.12 (2H, s, NH2), 5.50 (1H, s, 4-N isoxazol), 7.07 (2H, t, J=7.4 Hz, 4-H of phenyl), 7.31 (4H, t, J=7.9 Hz, 3-H and 5-H of phenyl), 7.99 (4H, d, J=7.8 Hz, 2-H and 6-H of phenyl), 8.97 (2H, s, 2CH=O).

Example 11. The complex bis(1-phenyl-3-methyl-4-formyl-5-pyrazolone)cadmium (II) with 1-aminoisoquinoline (Ii, NH2-Het=1-aminoisoquinoline, M=Cd, n=2).

White crystals with TPL213214°C. Yield 74%. Found, %: C, 59.77; H 4.37, N 14.04, Cd 13.88. For C40H34N8O4Cd calculated, %: C 59.82, H 4.27, N 13.95, Cd 13.99.

IR spectrum (in the solid phase): 3016, 2915, 2825, 2720, 1629, 1595, 1524, 1511, 1499, 1458, 1438, 1390, 1367, 1313, 1265, 1183, 1165, 1077, 1061, 1038, 1014, 959, 898, 834, 803, 755, 745, 692, 679, 645, 628, 590, 570 cm-1.

1H NMR spectrum, DMSO-d6, δ, ppm: 2.21 (6N, s, 2CH3), 6.81 (4H, c, 2NH2), 6.89 (2H, d, J=6.0 Hz, H of isoquinoline), 7.13 (2H, t, J=7.2 Hz, 4-H of phenyl), 7.36 (4H, t, J=7.8 Hz, 3-H and 5-H of phenyl), 7.42-7.48 (2H, m, H of isoquinoline), 7.57-7.63 (2H, m, H of isoquinoline), 7.68 (2H, d, J=8.1 Hz, H of isoquinoline), 7.77 (2H, d, J=5.7 Hz, H of isoquinoline), 7.90 (4H, d, J=7.8 Hz, 2-H and 6-H of phenyl), 8.17 (2H, d, J=8.4 Hz, 8-H of isoquinoline), 9.06 (2H, s, 2CH=O).

Example 12. The complex bis(1-phenyl-3-methyl-4-formyl-5-pyrazolone)cadmium (II) with 6-aminoquinoline (Ij, NH2-Het=6-aminoquinoline, M=Cd, n=2)

The dark green crystals with TPL117-118°C. a Yield of 75%. Found, %: C 59.72, H 4.39, N 14.01, Cd 13.89. For C40H34N8O4Cd calculated, %: C 59.82, H 4.27, N, 13.95. Cd 13.99.

IR spectrum (in the solid phase): 3016, 2915, 2825, 2720, 1629, 1595, 1524, 1511, 1499, 1458, 1438,1390,1367, 1313, 1265,1183,1165, 1077, 1061,1038, 1014, 959, 898, 834, 803, 755, 745, 692, 679, 645, 628, 590, 570 cm-1.

1H NMR spectrum, DMSO-d6, δ, ppm: 2.20 (6N, s, 2CH3), 5.58 (4H, s, 2NH2), 6.77 (2H, d, J=2.4 Hz, 5-H quinoline), 7.14 (4H, DD, J=9.0 Hz, J=2.2 Hz, H quinoline), 7.23-7.28 (2H, m, 4-H of phenyl), 7.36 (4H, t, J=7.5 Hz, 3-H and 5-H of phenyl), 7.68 (2H, d, J=8.7 Hz, 7-H quinoline), 7.90 (4H, d, J=8.1 Hz, 2-H and 6-H of phenyl), 8.03 (2H, d, J=7.5 Hz, N is inoline), 8.45 (2H, d, J=3.6 Hz, H quinoline), 9.05 (2H, s, 2CH=O).

Example 13. The complex bis(1-phenyl-3-methyl-4-formyl-5-pyrazolone)cadmium (II) with 3-aminoquinoline (Ik, NH2-Het=3-aminoquinoline, M=Cd, n=2)

The crystals are white with TPL216-217°C. Yield 79%. Found, %: C 59.74, H 4.32, N 13.99, Cd 13.91. For C40H34N8O4Cd calculated, %: C 59.82, H 4.27, N13.95, Cd 13.99.

IR spectrum (in the solid phase): 3016, 2915, 2825, 2720, 1629, 1595, 1524, 1511, 1499, 1458,1438,1390, 1367,1313, 1265,1183, 1165, 1077, 1061, 1038, 1014, 959, 898, 834, 803, 755, 745, 692, 679, 645, 628, 590, 570 cm1.

1H NMR spectrum, DMSO-d6, δ, ppm: 2.20 (6N, s, 2CH3), 5.65 (4H, c, 2NH2), 7.11-7.15 (4H, m, 4-N-phenyl and N quinoline), 7.23-7.30 (4H, m, H quinoline), 7.36 (4H, t, J=7.8 Hz, 3-H and 5-H of phenyl), 7.58 (2H, d, J=7.8 Hz, H quinoline), 7.75 (2H, d, J=8.1 Hz, H quinoline), 7.90 (4H, d, J=7.8 Hz, 2-H and 6-H phenyl), 8.42 (2H, d, J=2.7 Hz, H quinoline), 9.05 (2H, s, 2CH=O).

Example 14. The complex bis(1-phenyl-3-methyl-4-formyl-5-pyrazolone)cadmium (II) with 5-amino-4,6-dimethylindoline (I1, NH2-Het=5-amino-4,6-dimethylphenol, M=Cd, n=2)

Recrystallized from benzene crystals yellow with TPL111-112°C. Yield 78%. Found, %: C 61.42, H 5.01, N 13.12, Cd 13.02. For C44H42N8O4Cd calculated, %: C 61.50, H 4.93, N 13.04, Cd 13.08.

IR spectrum (in the solid phase): 3016, 2915, 2825, 2720, 1629, 1595, 1524, 1511, 1499, 1458, 1438, 1390, 1367, 1313, 1265, 1183, 1165, 1077, 1061, 1038, 1014, 959, 898, 834, 803, 755, 745, 692, 679, 645, 628, 590, 570 cm-1.

1H NMR spectrum, DMSO-d6, δ, ppm: 2.20 (6N, s, 2CH3hee is oline), 2.23 (6N, s, 2CH3quinoline), 2.94 (6N, s, 2CH3of pyrazole), 5.07 (4H, s, 2NH2), 7.04 (2H, d, J=3.9 Hz, H quinoline), 7.10-7.23 (6N, m, 4-H phenyl H quinoline), 7.35 (4H, t, J=7.8 Hz, 3-H and 5-H of phenyl), 7.90 (4H, d, J=7.8 Hz, 2-H and 6-H of phenyl), 8.46 (2H, d, J=4.2 Hz, H quinoline), 9.05 (2H, s, 2CH=O).

The obtained compounds were investigated by standard methods, spectral-absorption and spectral-luminescent properties in solution of dimethyl sulfoxide or dimethylformamide at T=293K. The maxima of the long-wave absorption bands are in the area 288-365 nm.

The fluorescence of the complexes is observed in the blue region of the spectrum with maxima of the fluorescence bands at 355-482 nm. The efficiency of the fluorescence of some of them is also high, their quantum yields reach values of 0.06-0.76 to. For example, compounds 1A, where NH2-Het=1-aminoisoquinoline, M=Zn, n=2, Ib, where NH2-Het=6-aminoquinoline, M=Zn, n=2, 1, where NH2-Het=3-aminoquinoline, M=Zn, n=1, Id, where NH2-Het=5-amino-4,6-dimethylphenol, M=Zn, n=2, Ie, where NH2-Het=2-aminopyridine, M=Zn, n=2, Ii, where NH2-Het=1-aminoisoquinoline, M=Cd, n=2, Ij, where NH2-Het=6-aminoquinoline, M=Cd, n=2, Ik, where NH2-Het=3-aminoquinoline, M= Cd, n=2, Il, where NH2-Het=5-amino-4,6-dimethylphenol, M=Cd, n=2, have the following meanings:

absorption characteristics: the maximum of the absorption band λ(Ia)=345 nm, λ(Ib)=292, 365 nm, λ(Ic)=288 and 358 nm, λ(Id)=331 nm, λ(Ie)=307 nm, λ(Ii)=333 nm, λ(Ij)=355 nm, λ(Ik)=34 nm, λ(Il)=339 nm;

characteristics of fluorescence: the band maximum fluorescence λ(Ia)=402 nm, λ(Ib)=440 nm, λ(Ic)=416 nm, λ(Id)=482 nm, λ(Ie)=355 nm, λ(Ii)=382 nm, λ(Ij)=431 nm, λ(Ik)=408 nm, λ(Il)=482 nm; band maximum fluorescence excitation λ(Ia)=335 nm, λ(Ib)=354 nm, λ(1C)=364 nm, λ(Id)=320 nm, λ(Ie)=303 nm, λ(Ii)=320 nm, λ(Ij)=320 nm, λ(Ik)=320 nm, λ(I1)=320 nm; quantum yield fluorescence φ(Ia)=0,37, φ(Ib)=0,76, φ(Ic)=0,16, φ(Id)=0,10φ, (Ie)=0,15, φ(Ii)=0,37, φ(Ij)=0,12, φ(Ik)=0,06, φ(Il)=0,094.

Molecular complexes of bis(1-phenyl-3-methyl-4-formyl-5-pyrazolone)zinc and cadmium with amino derivatives of nitrogen heterocycles of General formula

where NH2-Het=1-aminoisoquinoline, 3-aminoquinoline, 6-aminoquinoline, 5-amino-4,6-dimethylphenol, 2-aminopyridine, 2-amino-5-bromopyridine, 3-amino-5-methylisoxazole, 2-amino-1-ethylbenzamide, M=Zn, Cd, n=1, 2.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: disclosed are novel 4-biphenyl carboxylic acid derivatives of formula 1 as an organic mechanoluminescent material. Also disclosed is a mechanoluminescent composition which contains an effective amount of the mechanoluminescent substance of formula 1 and a luminescent substance.

EFFECT: novel efficient mechanoluminescent materials based on cheap and nontoxic organic substances.

3 cl, 2 dwg, 1 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: aqueous solution of quantum dots based on cadmium selenide coated with mercapto acids is stabilised by adding sodium sulphite until achieving its concentration of 0.02-0.2 mol/l in the solution.

EFFECT: high stability of aqueous solution of quantum dots while preserving luminescence brightness, hydrodynamic diameter and active groups of the quantum dots.

2 dwg

FIELD: chemistry.

SUBSTANCE: method involves breaking down said lamps and devices, grinding, heating, evacuating the scrap lamps in a chamber and subsequent condensation of mercury vapour in cooled traps with successive sealing of all processes, wherein a batch of lamps and devices is broken down right away; grinding is carried out to particle size of not more than 20 mm, destruction and extraction of mercury is carried out at temperature of 150-200°C and a vacuum of up to 10 Pa and holding for 30 minutes; a second step for cleaning the scrap with a washing liquid (1 N sulphuric acid or hydrochloric acid solution) is carried out, followed by separation of sockets and scrap glass. When filling the chamber with scrap lamps with washing liquid, circulation mixing is carried out for at least 5 minutes. After separating from the scrap, the washing liquid is subjected to filtration and thermal decomposition to metallic mercury at temperature higher than 500°C. Separation of cleaned sockets and scrap glass is carried out by sieving through a sieve with different cell size under vibration action.

EFFECT: high efficiency and environmental friendliness of the process, efficiency of extracting mercury while reducing power consumption.

5 cl, 6 ex

FIELD: chemistry.

SUBSTANCE: polymer nanoparticles contain a medium for photon up-conversion and a stabilising agent. Said medium contains a polymer matrix having two organic components distributed therein. The first component is capable of absorbing light at a first wavelength in the range w≤λ1≤x and acts as a sensitiser in said medium. The second component is capable of emitting light at a second wavelength in the range y≤λ2≤z, where λ2≤λ1, and acts as an emitting component in said medium. The stabilising agent is selected from hydrophilic or amphiphilic polymers.

EFFECT: polymer nanoparticles have versatility with respect to the radiation wavelengths, both incident and emitted, the size and surface properties of said nanoparticles can be controlled, thereby enabling photon up-conversion for opto-electronic devices.

15 cl, 13 dwg, 4 ex

FIELD: chemistry.

SUBSTANCE: polymer nanoparticles contain a medium for photon up-conversion and a stabilising agent. Said medium contains a polymer matrix having two organic components distributed therein. The first component is capable of absorbing light at a first wavelength in the range w≤λ1≤x and acts as a sensitiser in said medium. The second component is capable of emitting light at a second wavelength in the range y≤λ2≤z, where λ2≤λ1, and acts as an emitting component in said medium. The stabilising agent is selected from hydrophilic or amphiphilic polymers.

EFFECT: polymer nanoparticles have versatility with respect to the radiation wavelengths, both incident and emitted, the size and surface properties of said nanoparticles can be controlled, thereby enabling photon up-conversion for opto-electronic devices.

15 cl, 13 dwg, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to complexes of lanthanides and organic ligands which are luminescent in the visible spectrum and are used in electroluminescent devices, means of protecting security paper and documents from falsification etc. Disclosed are novel luminescent coordination compounds of lanthanides of formula: where Ln is Eu3+, Tb3+, Dy3+, Sm3+, Gd3+.

EFFECT: said compounds have high luminescence intensity and considerable thermal tolerance of up to 400°C, which enables use thereof in modern production of light-emitting diodes.

4 dwg, 2 tbl

FIELD: physics.

SUBSTANCE: invention relates to optical information recording materials, particularly archival information recording based on photo-induced fluorescence, with possibility of use in optical memory devices, including three-dimensional optical memory systems for Read Only Memory (ROM). The disclosed light-sensitive polymer material with fluorescent information reading contains a precursor of an organic fluorescent compound (OFC) in form of a solution in an optically transparent copolymer of methyl methacrylate (MMA) and 2,2,2-trichloroethyl methacrylate (TCEMA) or 2,2,2-tribromoethyl methacrylate (TBEMA). Content of OFC in the solution is equal to 0.1-2 wt %. A coloured fluorescent form of OFC is formed under the action of radiation in the range of 250-330 nm. To expand the spectral range of radiation to 500 nm, the material can additionally contain pyrazolines, e.g., 1,3,5-triphenyl pyrazoline.

EFFECT: disclosed light-sensitive material has low colour intensity and fluorescence before exposure, low diffusion mobility of components which sensitise OFC fluorescence, and also widen the radiation band suitable for turning the OFC into a coloured fluorescent form in the long-wave region to 500 nm.

4 cl, 6 dwg, 2 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an compound of general formula

(1). In general formula (1), each of R1-R14 is independently selected from a hydrogen atom, an alkyl group with 1-4 carbon atoms, a diphenylamino, a phenyl group, a biphenyl group, a terphenyl group, a fluoranthenyl group, a naphthyl group and a pyridinyl group; wherein the diphenylamino group can have an alkyl group as a substitute; and wherein the phenyl group, the biphenyl group, the terphenyl group, the fluoranthenyl group and the naphthyl group can have an alkyl and an aryl group as a substitute. The invention also relates to an organic light-emitting device, a display device, an image-forming device and an illumination device using said organic compound.

EFFECT: compounds are suitable for emitting blue light and enable to obtain light-emitting devices with good radiation characteristics.

8 cl, 6 tbl, 33 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: colourless phosphorescing red glowing phosphor Eu(L2)3 is a product of reacting a europium (III) compound with [2-(aminocarbonyl)phenoxy]acetic acid (HL2) and subsequent vacuum drying in a furnace at residual pressure of 20 Pa. Said phosphor has phosphorescence maximum at 18636, 14360, 16180, 16860 cm-1 and provides considerable intensity of red luminescence which is 40.43 times higher than quantum efficiency of luminescence compared to existing colourless phosphorescing red glowing phosphor - a compound of europium (III) with salicylic acid.

EFFECT: improved properties.

1 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a chrysene compound of general formula [1]: , where each of R1-R9 denotes a hydrogen atom, and Ar1 Ar2 and Ar3 are each independently selected from a group represented by general formulae [2]:

where X1-X26 are each independently selected from a group consisting of a hydrogen atom, an alkyl group consisting of only carbon and hydrogen, containing 1-4 carbon atoms, a phenyl group which can be substituted with an alkyl group consisting of only carbon and hydrogen, containing 1-4 carbon atoms, a naphthyl group which can be substituted with an alkyl group consisting of only carbon and hydrogen, containing 1-4 carbon atoms, a phenanthryl group which can be substituted with an alkyl group consisting of only carbon and hydrogen, containing 1-4 carbon atoms, and a fluorenyl group which can be substituted with an alkyl group consisting of only carbon and hydrogen, containing 1-4 carbon atoms, under the condition that one of X1-X8, one of X9-X16 and one or X17-X26 each independently denotes a chrysene ring represented by general formula [1]; and Y1 and Y2 are each independently selected from an alkyl group consisting of only carbon and hydrogen, containing 1-4 carbon atoms. The invention also relates to an organic light-emitting device and a display using said compound.

EFFECT: use of the disclosed compound sufficiently increases emission efficiency and service life.

8 cl, 50 ex, 9 tbl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to electroluminescent substances and specifically to zinc (II) bis{3-methyl-1-phenyl-4-[(quinoline-3-imino)-methyl]1-H-pyrazol-5-onato} of general formula I . Also disclosed is an electroluminescent device which contains zinc (II) bis{3-methyl-1-phenyl-4-[(quinoline-3-imino)-methyl]1-H-pyrazol-5-onato} of general formula I.

EFFECT: compound exhibits electroluminscent properties in the yellow spectral region with high brightness.

2 cl, 4 ex

FIELD: chemistry.

SUBSTANCE: method involves reaction of a zinc halide with trialkylaluminium containing a hydride and trialkylaluminium with one or more polymerised alkyl groups. Content of hydride in trialkylaluminium ranges from 0.01 wt % to 0.10 wt %. After reaction, dialkylzinc containing not more than 10 ppmw aluminium is separated from the reaction products and dialkylaluminium monohalide containing not more than 10 ppmw zinc is then separated.

EFFECT: invention enables to obtain dialkylzinc and dialkylaluminium monohalide of high purity and with high output.

7 cl, 2 dwg, 1 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to novel substituted metal phthalocyanines, which can be used as direct and acid dyes for dyeing cotton and protein fibre. Disclosed are tetra-4-[(4'-carboxy)phenylamino]phthalocyanine metal complexes of formula, where M=Cu, Ni, Zn.

EFFECT: metal phthalocyanines expand the colour gamma of the current light-blue copper tetra-4-carboxyphthalocyanine, which is the closest on structure and application, to a blue-green and green colour.

6 dwg, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing zinc meso-tetra-aminotetrabenzoporphyrinate. The method involves reaction of a phthalic anhydride with aminoacetic acid to obtain N-carboxymethylphthalimide, from which while heating with zinc oxide, a zinc salt of N-carboxymethylphthalimide is obtained. The obtained salt reacts with phthalimide at high temperature from 240°C to 320°C for 2-2.5 hours, followed by treatment of the reaction mass with hydrazine hydrate in pyridine solution at boiling point thereof for 1.5-2 hours.

EFFECT: high safety of the process owing to prevention of formation of dangerous and toxic acetic and nitric acids, high cost-effectiveness of the process and obtaining an end product of high purity.

3 dwg

FIELD: chemistry.

SUBSTANCE: disclosed are novel phthalocyanines, which are quaternised derivates of zinc and aluminium tetra(3-thiophenyl)phthalocyanines of formula MPc(SPh)4Rn, where: MPc(SPh)4Rn is zinc or aluminium tetra(3-thiopheny)phthalocyanine, M=Zn, AlX; X=Cl, HO, , , n=4-9. The disclosed phthalocyanines are sensitising agents for formation of singlet oxygen under the effect of visible light. Also disclosed is a method of treating water using said phthalocyanines or mixture thereof with acridine, rhodamine or phenothiazine dyes and visible light in the presence of oxygen.

EFFECT: efficient treatment of water from bacterial contamination.

2 cl, 1 dwg, 3 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: disclosed is a method for synthesis of compounds of general formula R1-M1-AdzLix (I) by reacting compound R1 - A (III) with element M1, where M1 denotes Mn, Cu, Zn, Li, Bi, in the presence of lithium salts. Also disclosed is a method for synthesis of a compound of general formula R1m - M3 - TnzLix (II) by reacting compound R1 - A (III) with an M3-containing compound in the presence of lithium salts and in the presence of an elementary metal M2 - Li, Na, Mg. Metal M3 can be selected from Al, Mg, B.

EFFECT: improved method.

14 cl, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to novel derivatives of 1-allylimidazole with metal salts , where R denotes allyl, E denotes a metal, e.g. Zn (II) or Co (II), An denotes chlorine or acetate, n equals 2.

EFFECT: novel 1-allylimidazole derivatives having antihypoxic activity are obtained.

1 cl, 7 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: in the compound of formula I, M denotes identical or different metal atoms selected from a group comprising: Pd, Fe, Mn, Co, Ni, Cu, Zn or Mo, R1 and R2 independently denote hydrogen, amino, hydroxyl, carboxy, cyano, C1-12alkyl, C2-12alkenyl, C2-12alkynyl, C1-12alkoxy, C1-12alkylamino, C1-12alkoxycarbonyl, C1-12alkylamido,arylamido. Alkyl groups in the said substitutes may in turn be substituted with one or more of the following groups: hydroxyl, oxo, carboxy, amino or amido, R3-R10 independently denote hydrogen, or NHR3R4 and NHR5R6, taken together, and(or) NHR7R8 and NHR9R10, taken together, denote a ligand (or ligands) containing one or more donor aliphatic or aromatic nitrogen atoms and which occupy the cis-position near metal (M) atoms. The invention also discloses a pharmaceutical composition, use of the compound to prepare a medicinal drug and a therapeutic treatment method.

EFFECT: obtaining compounds capable of boosting efficiency of medicinal drugs.

25 cl, 17 ex, 23 tbl

FIELD: chemistry.

SUBSTANCE: electroluminescent device has a hole injection layer, a hole transport layer, an active luminescent layer based on electroluminescent substance of formula I , a hole blocking layer, an electron transport layer and an electron injection layer.

EFFECT: high luminance of devices emitting in the green spectral region.

1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to 1-alkenylimidazole derivatives of general formula 1 , where R is vinyl, allenyl or isopropenyl, R1 is hydrogen or methyl, E is Zn (II) or Fe(III), An is chlorine or acetate, n equals 1, 2 or 4, except compounds where R is vinyl, R1 is hydrogen, E is Zn(II), An is chlorine or acetate and n equals 2.

EFFECT: compounds have antihypoxic properties for different types of hypoxia.

5 ex, 8 tbl

FIELD: chemistry of organometallic compounds, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing the chelate compound bis-(1-vinylimidazole)zinc diacetate (I) representing the medicinal preparation of acizol that is the effective antidote and antioxidant. Method for preparing the compound (I) is carried out in the absence of organic solvents at temperature 20-35°C in the mole ratio 1-vinylimidazole : zinc diacetate in the range from 10:1 to 3:1. Method provides exclusion fire hazard and explosion hazard solvent from the technological process and enhancement of the yield of highly pure acizol satisfied for Pharmacopoeia requirements.

EFFECT: improved method for preparing.

2 cl, 4 ex

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