ORGANIC ELECTROLUMINESCENT COMPOUND AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
20230255110 · 2023-08-10
Inventors
Cpc classification
H10K85/6572
ELECTRICITY
C09K2211/1059
CHEMISTRY; METALLURGY
C09K2211/1074
CHEMISTRY; METALLURGY
H10K85/6574
ELECTRICITY
H10K85/6576
ELECTRICITY
International classification
Abstract
The present disclosure relates to an organic electroluminescent compound, and an organic electroluminescent device comprising the same. By comprising the organic electroluminescent compound of the present disclosure, an organic electroluminescent device having improved driving voltage, luminous efficiency, lifespan characteristic, and/or power efficiency can be provided.
Claims
1. An organic electroluminescent compound represented by the following formula 1: ##STR00318## wherein X.sub.1 to X.sub.3 each independently represent N or CR; R and R.sub.11 each independently represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; L represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered)heteroarylene; ##STR00319## in formula 1 is represented by any one of the following formulas: ##STR00320## ##STR00321## ##STR00322## ##STR00323## ##STR00324## ##STR00325## ##STR00326## ##STR00327## ##STR00328## ##STR00329## ##STR00330## ##STR00331## ##STR00332## ##STR00333## ##STR00334## ##STR00335## ##STR00336## ##STR00337## ##STR00338## ##STR00339## wherein Y represents N—Ar.sub.2; Y′ represents N—Ar.sub.2, O, S, or CR.sub.aR.sub.b; Ar.sub.2, R.sub.a, R.sub.b, and B.sub.9 to B.sub.44 each independently represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di- (C1-C30)alkylamino, a substituted or unsubstituted mono- or di- (C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; R.sub.1 to R.sub.8 each independently represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di- (C1-C30)alkylamino, a substituted or unsubstituted mono- or di- (C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; or may be linked to an adjacent substituent to form a ring; and a represents an integer of 1 to 3, where a is an integer of 2 or more, each R.sub.11 may be the same or different.
2. The organic electroluminescent compound according to claim 1, wherein ##STR00340## is represented by any one of the following formulas: ##STR00341## wherein R, L, R.sub.11, and a are as defined in claim 1.
3. The organic electroluminescent compound according to claim 1, wherein the substituents of the substituted (C1-C30)alkyl, the substituted (C6-C30)aryl(ene), the substituted (3- to 30-membered)heteroaryl(ene), the substituted (C3-C30)cycloalkyl, the substituted (C1-C30)alkoxy, the substituted tri(C1-C30)alkylsilyl, the substituted di(C1-C30)alkyl(C6-C30)arylsilyl, the substituted (C1-C30)alkyldi(C6-C30)arylsilyl, the substituted tri(C6-C30)arylsilyl, the substituted mono- or di- (C1-C30)alkylamino, the substituted mono- or di- (C6-C30)arylamino, and the substituted (C1-C30)alkyl(C6-C30)arylamino in R, R.sub.1 to R.sub.8, R.sub.11, L, Ar.sub.2, R.sub.a, R.sub.b, and B, to B.sub.44 each independently are at least one selected from the group consisting of deuterium; a halogen; a cyano; a carboxyl; a nitro; a hydroxyl; a (C1-C30)alkyl; a halo(C1-C30)alkyl; a (C2-C30)alkenyl; a (C2-C30)alkynyl; a (C1-C30)alkoxy; a (C1-C30)alkylthio; a (C3-C30)cycloalkyl; a (C3-C30)cycloalkenyl; a (3- to 7-membered)heterocycloalkyl; a (C6-C30)aryloxy; a (C6-C30)arylthio; a (5- to 30-membered)heteroaryl unsubstituted or substituted with a (C6-C30)aryl(s); a (C6-C30)aryl unsubstituted or substituted with a (5- to 30-membered)heteroaryl(s); a tri(C1-C30)alkylsilyl; a tri(C6-C30)arylsilyl; a di(C1-C30)alkyl(C6-C30)arylsilyl; a (C1-C30)alkyldi(C6-C30)arylsilyl; an amino; a mono- or di- (C1-C30)alkylamino; a mono- or di- (C6-C30)arylamino unsubstituted or substituted with a (C1-C30)alkyl(s); a (C1-C30)alkyl(C6-C30)arylamino; a (C1-C30)alkylcarbonyl; a (C1-C30)alkoxycarbonyl; a (C6-C30)arylcarbonyl; a di(C6-C30)arylboronyl; a di(C1-C30)alkylboronyl; a (C1-C30)alkyl(C6-C30)arylboronyl; a (C6-C30)aryl(C1-C30)alkyl; and a (C1-C30)alkyl(C6-C30)aryl.
4. The organic electroluminescent compound according to claim 1, wherein X.sub.1 to X.sub.3 each independently represent N or CR; R represents hydrogen, or a substituted or unsubstituted (C6-C20)aryl; R.sub.11 represents hydrogen, or a substituted or unsubstituted (C6-C15)aryl; L represents a single bond, a substituted or unsubstituted (C6-C15)arylene, or a substituted or unsubstituted (5- to 15-membered)heteroarylene; R.sub.1 to R.sub.8 each independently represent hydrogen, a substituted or unsubstituted (C6-C15)aryl, a substituted or unsubstituted (5- to 15-membered)heteroaryl, or a substituted or unsubstituted di(C6-C15)arylamino; or may be linked to an adjacent substituent to form a ring; and a represents 1 or 2.
5. The organic electroluminescent compound according to claim 1, wherein X.sub.1 to X.sub.3 each independently represent N or CR; R represents hydrogen, or a (C6-C20)aryl unsubstituted or substituted with a (C1-C6)alkyl(s); R.sub.11 represents hydrogen, or an unsubstituted (C6-C15)aryl; L represents a single bond, an unsubstituted (C6-C15)arylene, or an unsubstituted (5- to 15-membered)heteroarylene; R.sub.1 to R.sub.8 each independently represent hydrogen; an unsubstituted (C6-C15)aryl; a (5- to 15-membered)heteroaryl unsubstituted or substituted with a (C6-C12)aryl(s); or an unsubstituted di(C6-C15)arylamino; or may be linked to an adjacent substituent to form a ring; and a represents 1 or 2.
6. The organic electroluminescent compound according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of: ##STR00342## ##STR00343## ##STR00344## ##STR00345## ##STR00346## ##STR00347## ##STR00348## ##STR00349## ##STR00350## ##STR00351## ##STR00352## ##STR00353## ##STR00354## ##STR00355## ##STR00356## ##STR00357## ##STR00358## ##STR00359## ##STR00360## ##STR00361## ##STR00362## ##STR00363## ##STR00364## ##STR00365## ##STR00366## ##STR00367## ##STR00368## ##STR00369## ##STR00370## ##STR00371## ##STR00372## ##STR00373## ##STR00374## ##STR00375## ##STR00376## ##STR00377## ##STR00378## ##STR00379## ##STR00380## ##STR00381## ##STR00382## ##STR00383## ##STR00384## ##STR00385## ##STR00386## ##STR00387## ##STR00388## ##STR00389## ##STR00390## ##STR00391## ##STR00392## ##STR00393## ##STR00394## ##STR00395## ##STR00396## ##STR00397## ##STR00398## ##STR00399## ##STR00400## ##STR00401## ##STR00402## ##STR00403## ##STR00404## ##STR00405## ##STR00406## ##STR00407## ##STR00408## ##STR00409## ##STR00410## ##STR00411## ##STR00412## ##STR00413## ##STR00414## ##STR00415## ##STR00416## ##STR00417## ##STR00418## ##STR00419## ##STR00420## ##STR00421## ##STR00422## ##STR00423##
7. An organic electroluminescent material comprising the organic electroluminescent compound according to claim 1.
8. An organic electroluminescent device comprising the organic electroluminescent compound according to claim 1.
9. The organic electroluminescent device according to claim 8, wherein the organic electroluminescent compound is comprised in a light-emitting layer.
10. The organic electroluminescent device according to claim 9, wherein the light-emitting layer further comprises an organic electroluminescent compound besides the organic electroluminescent compound, and the further comprised organic electroluminescent compound is represented by the following formula 11: ##STR00424## wherein Ar.sub.3 to Ar.sub.6 each independently represent a substituted or unsubstituted (C6-C30)aryl; L.sub.1 represents a single bond, or a substituted or unsubstituted (C6-C30)aryl(ene); L.sub.2 represents a single bond, or a substituted or unsubstituted (C6-C30)arylene; R.sub.12 and R.sub.13 each independently represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di- (C1-C30)alkylamino, a substituted or unsubstituted mono- or di- (C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; or may be linked to an adjacent substituent to form a ring; m and n each independently represent an integer of 0 to 2, where at least one of m and n is 1 or more; and p and q each independently represent an integer of 1 to 4, where p and q are an integer of 2 or more, each R.sub.1 and each R.sub.2 may be the same or different.
Description
EXAMPLE 1: PREPARATION OF COMPOUND C-2
[0104] ##STR00281##
Synthesis of Compound 1-1
[0105] 17 g of 4-chlorobenzene-1,2-diamine (142 mmol) and 30 g of benzyl (119 mmol) were dissolved in 600 mL of ethanol in a flask, and the mixture was stirred at 110° C. for 4 hours. After completion of the reaction, the obtained solid was filtered, dried, and separated by column chromatography to obtain 20 g of compound 1-1 (yield: 53%).
Synthesis of Compound C-2
[0106] 6.95 g of compound 1-1 (21.0 mmol), 7 g of 7-phenyl-7,9-dihydrobenzo[g]indolo[2,3-b]carbazole (19.3 mmol), 833 mg of Pd.sub.2(dba).sub.3 (0.915 mmol), 751 mg of 2-dichlorohexylphosphino-2′,6′-dimethoxybiphenyl (s-Phos) (1.83 mmol), and 5.27 g of NaOtBu (54.9 mmol) were dissolved in 100 mL of o-xylene in a flask, and the mixture was refluxed at 180° C. for 2 hours. After completion of the reaction, the reactant was filtered with celite, dried, and separated by column chromatography to obtain 8.2 g of compound C-2 (yield: 67.7%).
[0107] .sup.1H NMR (600 MHz, DMSO, δ) 9.364 (s, 1H), 8.437-8.433 (d, J=24 Hz, 1H), 8.423-8.344 (m, 3H), 8.047-8.029 (m, 2H) 7.850-7.830 (m, 2H), 7.598-7.531 (m, 11H), 7.490 (s, 1H), 7.455-7.360 (m, 8H)
TABLE-US-00001 Compound MW M.P. C-2 662.80 303° C.
EXAMPLE 2: PREPARATION OF COMPOUND C-62
[0108] ##STR00282##
[0109] 6.9 g of compound 1-1 (25.3 mmol), 7 g of 14-phenyl-12,14-dihydrobenzo[a]indolo[3,2-h]carbazole (21.1 mmol), 960 mg of Pd.sub.2(dba).sub.3 (1.055 mmol), 866 mg of s-Phos (2.11 mmol), and 6 g of NaOtBu (63.3 mmol) were dissolved in 100 mL of o-xylene in a flask, and the mixture was refluxed at 180° C. for 2 hours. After completion of the reaction, the reactant was filtered with celite, dried, and separated by column chromatography to obtain 11 g of compound C-62 (yield: 85%).
[0110] .sup.1H NMR (600 MHz, DMSO, δ) 8.895 (s, 1H), 8.375-8.361 (m, 2H), 8.303-8.285 (m, 2H), 7.971-7.949 (m, 2H) 7.771-7.757 (d, J=84 Hz, 1H), 7.572-7.504 (m, 10H), 7.390-7.305 (m, 10H), 7.135-7.134 (d, J=6 Hz, 2H)
TABLE-US-00002 Compound MW M.P. C-62 662.80 245° C.
EXAMPLE 3: PREPARATION OF COMPOUND C-32
[0111] ##STR00283##
[0112] 8.9 g of compound 1-1 (25.3 mmol), 7 g of 5-phenyl-5,7-dihydroindolo[2,3-b]carbazole (21.1 mmol), 960 mg of Pd.sub.2(dba).sub.3 (1.055 mmol), 866 mg of s-Phos (2.11 mmol), and 6 g of NaOtBu (63.3 mmol) were dissolved in 100 mL of o-xylene in a flask, and the mixture was refluxed at 180° C. for 2 hours. After completion of the reaction, the reactant was filtered with celite, dried, and separated by column chromatography to obtain 11 g of compound C-32 (yield: 85%).
[0113] 1H NMR (600 MHz, DMSO, δ) 8.865 (s, 1H), 8.403 (s, 1H), 8.345-8.330 (d, J=90 Hz, 1H), 8.288-8.263 (m, 2H) 8.010-7.992 (m, 1H), 7.577-7.522 (m, 9H), 7.490 (s, 1H), 7.423-7.352 (m, 13H)
TABLE-US-00003 Compound MW M.P. C-32 612.74 224° C.
EXAMPLE 4: PREPARATION OF COMPOUND C-182
[0114] ##STR00284##
[0115] 6 g of compound 1-1 (18.9 mmol), 4.2 g of 7H-dibenzo[c,g]carbazole (15.8 mmol), 718 mg of Pd.sub.2(dba).sub.3 (0.789 mmol), 657 mg of s-Phos (1.6 mmol), and 4.5 g of NaOtBu (47.34 mmol) were dissolved in 100 mL of o-xylene in a flask, and the mixture was refluxed at 180° C. for 2 hours. After completion of the reaction, the reactant was filtered with celite, dried, and separated by column chromatography to obtain 4.5 g of compound C-182 (yield: 85%).
[0116] .sup.1H NMR (600 MHz, DMSO, δ) 9.279-9.260 (d, 2H), 8.467-8.441 (m, 2H), 8.061-8.049 (d, 2H), 8.009-8.005 (s, J=24 Hz, 1H) 7.994-7.991 (d, 2H), 7.884-7.710 (m, 4H), 7.600-7.542 (m, 6H), 7.417-7.347 (m, 6H)
TABLE-US-00004 Compound MW M.P. C-182 547.66 278° C.
EXAMPLE 5: PREPARATION OF COMPOUND C-152
[0117] ##STR00285##
Synthesis of Compound 5-1
[0118] 20 g of 5-bromo-7H-dibenzo[c,g]carbazole (57.76 mmol), 8.4 g of phenylboronic acid (69.32 mmol), 3.3 g of Pd(PPh.sub.3).sub.4 (2.88 mmol), 16 g of K.sub.2CO.sub.3 (115.5 mmol), 231 mL of toluene, 58 mL of ethanol, and 58 mL of purified water were introduced into a flask, and the mixture was stirred under reflux for a day. After completion of the reaction, the mixture was cooled to room temperature, and extracted with distilled water and ethyl acetate (EA). The obtained solid was dissolved in methylene chloride (MC) and separated by column chromatography to obtain 8 g of compound 5-1 (yield: 40%).
Synthesis of Compound C-152
[0119] 5.5 g of compound 1-1 (17.5 mmol), 5 g of compound 5-1 (14.6 mmol), 664 mg of Pd.sub.2(dba).sub.3 (0.73 mmol), 600 mg of s-Phos (1.46 mmol), and 4.2 g of NaOtBu (43.6 mmol) were dissolved in 100 mL of o-xylene in a flask, and the mixture was refluxed at 180° C. for 2 hours. After completion of the reaction, the reactant was filtered with celite, dried, and separated by column chromatography to obtain 3.1 g of compound C-152 (yield: 34%).
[0120] .sup.1H NMR (600 MHz, DMSO, δ) 9.311-9.274 (d, 2H), 8.451-8.405 (m, 2H), 8.050-8.038 (m, 2H), 7.991-7.973 (s, J=18 Hz, 1H)) 7.884-7.869 (s, J=90 Hz, 1H), 7.725-7.3321 (m, 4H)
TABLE-US-00005 Compound MW M.P. C-152 623.76 231° C.
EXAMPLE 6: PREPARATION OF COMPOUND C-13
[0121] ##STR00286##
Synthesis of Compound 6-1
[0122] 50 g of 3-bromobenzene-1,2-diamine (267 mmol) and 67.5 g of benzyl (321 mmol) were dissolved in 1.3 L of ethanol in a flask, and the mixture was stirred under reflux for 2.5 hours. After completion of the reaction, the mixture was cooled to 0° C., and the obtained solid was filtered, dried, and separated with silica filter to obtain 72 g of compound 6-1 (yield: 75%).
Synthesis of Compound C-13
[0123] 8 g of compound 6-1 (22 mmol), 7 g of 7-phenyl-7,9-dihydrobenzo[g]indolo[2,3-b]carbazole (18 mmol), 0.83 g of Pd.sub.2(dba).sub.3 (0.92 mmol), 0.75 g of s-Phos (1.8 mmol), and 5.3 g of NaOtBu (55 mmol) were dissolved in 100 mL of o-xylene in a flask, and the mixture was stirred under reflux for a day. After completion of the reaction, the reactant was cooled to room temperature, filtered with celite, and distilled under reduced pressure, and the resulting solid was separated by column chromatography to obtain 1.1 g of compound C-13 (yield: 9%).
[0124] .sup.1H NMR (600 MHz, DMSO, δ) 9.66 (s, 1H), 9.26-9.25 (d, 1H), 8.68-8.67 (t, 1H), 8.34-8.32 (m, 1H) 8.23-8.22 (m, 1H), 8.13-8.09 (m, 2H), 7.95 (d, 1H), 7.88-7.86 (t, 1H), 7.59-7.56 (t, 3H), 7.51-7.38 (m, 10H), 7.25-7.24 (s, 1H), 7.17-7.14 (m, 1H), 7.07-7.02 (m, 4H), 7.00 (s, 1H)
TABLE-US-00006 Compound MW M.P. C-13 662.80 184° C.
EXAMPLE 7: PREPARATION OF COMPOUND C-193
[0125] ##STR00287##
[0126] 5 g of 7H-dibenzo[c,g]carbazole (18 mmol), 8.1 g of compound 6-1 (22 mmol), 0.6 g of Cu (9 mmol), 5.1 g of K.sub.2CO.sub.3 (37 mmol), and 94 mL of dichlorobenzene (DCB) were introduced into a flask, and the mixture was stirred under reflux for a day. After completion of the reaction, the mixture was cooled to room temperature, and the obtained solid was filtered under reduced pressure. The obtained solid was dissolved in methylene chloride (MC) and separated by column chromatography to obtain 9.8 g of compound C-193 (yield: 95%).
[0127] .sup.1H NMR (600 MHz, DMSO) 9.17-9.15 (d, 2H), 8.49-4.48 (d, 1H), 8.27-8.26 (d, 1H), 8.22-8.19 (t, 1H), 8.16-8.15 (d, 2H), 7.96-7.94 (d, 2H), 7.79-7.77 (t, 2H), 7.59-7.57 (t, 2H), 7.50-7.48 (m, 4H), 7.43-7.40 (m, 1H), 7.39-7.36 (m, 2H), 7.13-7.10 (m, 1H), 7.00-6.96 (m, 4H)
TABLE-US-00007 Compound MW M.P. C-193 547.65 278.3° C.
EXAMPLE 8: PREPARATION OF COMPOUND C-163
[0128] ##STR00288##
[0129] 5 g of compound 5-1 (14.55 mmol), 6.3 g of compound 6-1 (17.47 mmol), 0.4 g of Cu (7.27 mmol), 4 g of K.sub.2CO.sub.3 (29.11 mmol), and 73 mL of DCB were introduced into a flask, and the mixture was stirred under reflux for a day. After completion of the reaction, the mixture was cooled to room temperature, and the obtained solid was filtered under reduced pressure. The obtained solid was dissolved in MC and separated by column chromatography to obtain 3.4 g of compound C-163 (yield: 38%).
[0130] .sup.1H NMR (600 MHz, DMSO), 9.24-9.22 (d, 1H), 9.18-9.16 (d, 1H), 8.46-8.44 (d, 1H), 8.31-8.30 (d, 1H), 8.20-8.17 (t, 2H), 7.98-7.97 (d, 1H), 7.95-7.94 (d, 1H), 7.81-7.78 (m, 2H), 7.61-7.54 (t, 1H), 7.52-7.35 (m, 13H), 7.14-7.12 (m, 1H), 7.00-6.99 (d, 4H)
TABLE-US-00008 Compound MW M.P. C-163 623.7 255.8° C.
EXAMPLE 9: PREPARATION OF COMPOUND C-20
[0131] ##STR00289##
Synthesis of Compound 9-1
[0132] 24 g of (2-amino-5-chlorophenyl)(phenyl)methaneone (104 mmol), 12.1 g of benzaldehyde (114 mmol), 24 g of NH.sub.4OAc (311 mmol), and 27.9 g of CuCl.sub.2 (207 mmol) were dissolved in 1 L of ethanol in a flask, and the mixture was stirred under reflux for 3 hours. After completion of the reaction, the mixture was cooled to 0° C., and the solid obtained by adding water was filtered, dried, and separated with silica filter to obtain 28.0 g of compound 9-1 (yield: 85%).
Synthesis of Compound C-20
[0133] 5 g of compound 9-1 (16 mmol), 5 g of 7-phenyl-7,9-dihydrobenzo[g]indolo[2,3-b]carbazole (13 mmol), 0.60 g of Pd.sub.2(dba).sub.3 (0.65 mmol), 0.54 g of s-Phos (1 mmol), and 3.8 g of NaOtBu (39 mmol) were dissolved in 70 mL of o-xylene in a flask, and the mixture was stirred under reflux for 1 hour. After completion of the reaction, the reactant was cooled to room temperature, filtered with celite, and distilled under reduced pressure, and the resulting solid was separated by column chromatography to obtain 2.4 g of compound C-20 (yield: 28%).
[0134] .sup.1H NMR (600 MHz, DMSO, δ) 9.67 (s, 1H), 9.25-9.24 (d, 1H), 8.67-8.66 (m, 3H), 8.42 (s, 2H) 8.22 (s, 1H), 8.14-8.13 (d, 1H), 7.98-7.96 (d, 1H), 7.87-7.85 (t, 1H), 7.83-7.82 (d, 2H), 7.70-7.68 (m, 4H), 7.63-7.62 (m, 3H), 7.59-7.53 (m, 7H), 7.48-7.46 (t, 2H), 7.42-7.40 (m, 1H)
TABLE-US-00009 Compound MW M.P. C-20 662.80 190° C.
EXAMPLE 10: PREPARATION OF COMPOUND C-170
[0135] ##STR00290##
[0136] 5 g of compound 5-1 (14.55 mmol), 5.5 g of compound 9-1 (17.47 mmol), 0.66 g of Pd.sub.2(dba).sub.3 (0.72 mmol), 0.6 g of s-Phos (1.49 mmol), and 4.2 g of NaOtBu (43.67 mmol) were dissolved in 73 mL of o-xylene in a flask, and the mixture was stirred under reflux for a day. After completion of the reaction, the mixture was cooled to room temperature, and the obtained solid was filtered under reduced pressure. The obtained solid was dissolved in MC and separated by column chromatography to obtain 4.4 g of compound C-170 (yield: 49%).
[0137] .sup.1H NMR (600 MHz, DMSO), 9.21-9.19 (d, 1H), 9.14-9.13 (d, 1H), 8.69-8.67 (m, 2H), 8.49-8.48 (d, 1H), 8.43-8.41 (m, 1H), 8.31-8.30 (d, 1H), 8.18-8.17 (d, 1H), 8.04-8.03 (d, 1H), 8.02-7.98 (m, 3H), 7.81-7.78 (m, 3H), 7.68 (s, 1H), 7.66-7.58 (m, 4H), 7.57-7.54 (m, 8H), 7.49-7.47 (m, 1H)
TABLE-US-00010 Compound MW M.P. C-170 623.7 241.9° C.
EXAMPLE 11: PREPARATION OF COMPOUND C-200
[0138] ##STR00291##
[0139] 4 g of 7H-dibenzo[c,g]carbazole (14.96 mmol), 5.6 g of compound 9-1 (17.95 mmol), 0.68 g of Pd.sub.2(dba).sub.3 (0.74 mmol), 0.6 g of s-Phos (1.49 mmol), and 4.31 g of NaOtBu (44.88 mmol) were dissolved in 75 mL of o-xylene in a flask, and the mixture was stirred under reflux for a day. After completion of the reaction, the mixture was cooled to room temperature, and the obtained solid was filtered under reduced pressure. The obtained solid was dissolved in MC and separated by column chromatography to obtain 4.2 g of compound C-200 (yield: 51%).
[0140] .sup.1H NMR (600 MHz, DMSO), 9.13-9.12 (d, 2H), 8.72-8.70 (m, 2H), 8.52-8.50 (d, 1H), 8.38-8.36 (m, 1H), 8.29-8.28 (d, 1H), 8.17-8.15 (d, 2H), 8.04-8.01 (m, 4H), 7.79-7.75 (m, 4H), 7.67-7.62 (m, 3H), 7.61-7.56 (m, 5H)
TABLE-US-00011 Compound MW M.P. C-200 547.65 266.6° C.
EXAMPLE 12: PREPARATION OF COMPOUND C-43
[0141] ##STR00292##
[0142] 9.1 g of compound 6-1 (25 mmol), 7.0 g of 5-phenyl-5,7-dihydroindolo[2,3-b]carbazole (21 mmol), 0.96 g of Pd.sub.2(dba).sub.3 (1 mmol), 0.86 g of s-Phos (2 mmol), and 6.1 g of NaOtBu (63 mmol) were dissolved in 100 mL of o-xylene in a flask, and the mixture was stirred under reflux for a day. After completion of the reaction, the mixture was cooled to room temperature, filtered with celite, and distilled under reduced pressure, and the resulting solid was separated by column chromatography to obtain 1.2 g of compound C-43 (yield: 9%).
[0143] .sup.1H NMR (600 MHz, CDCl.sub.3, δ) 9.13 (s, 1H), 8.38-8.35 (t, 2H), 8.34-8.32 (dd, 1H), 8.11-8.08 (t, 1H), 7.53-7.46 (m, 6H), 7.43-7.31 (m, 8H), 7.29-7.28 (d, 1H), 7.22-7.20 (d, 1H), 7.18-7.16 (t, 1H), 7.08-7.02 (m, 4H), 6.91 (s, 1H)
TABLE-US-00012 Compound MW M.P. C-43 612.74 239° C.
EXAMPLE 13: PREPARATION OF COMPOUND C-50
[0144] ##STR00293##
[0145] 5.7 g of compound 9-1 (15 mmol), 5.0 g of 5-phenyl-5,7-dihydroindolo[2,3-b]carbazole (18 mmol), 0.69 g of Pd.sub.2(dba).sub.3 (0.75 mmol), 0.62 g of s-Phos (2 mmol), and 4.3 g of NaOtBu (45 mmol) were dissolved in 70 mL of o-xylene in a flask, and the mixture was stirred under reflux for 2 hours. After completion of the reaction, the mixture was cooled to room temperature, filtered with celite, and distilled under reduced pressure, and the resulting solid was separated by column chromatography to obtain 3.8 g of compound C-50 (yield: 41%).
[0146] .sup.1H NMR (600 MHz, CDCl.sub.3, δ) 9.15 (d, 1H), 8.67-8.65 (m, 2H), 8.42-8.39 (m, 2H), 8.37-8.35 (m, 2H), 8.19 (m, 1H), 7.83-7.81 (m, 2H), 7.66-7.61 (m, 7H), 7.58-7.51 (m, 4H), 7.49-7.46 (m, 1H), 7.45-7.41 (m, 2H), 7.38-7.33 (m, 4H)
TABLE-US-00013 Compound MW M.P. C-50 612.74 180° C.
EXAMPLE 14: PREPARATION OF COMPOUND C-1
[0147] ##STR00294##
[0148] 5 g of 6-chloroquinoxaline (30.04 mmol), 10 g of 14-phenyl-12,14-dihydrobenzo[a]indolo[3,2-h]carbazole (25.3 mmol), 1.2 g of Pd.sub.2(dba).sub.3 (1.27 mmol), 1 g of s-Phos (2.53 mmol), and 7.3 g of NaOtBu (75.9 mmol) were dissolved in 130 mL of o-xylene in a flask, and the mixture was stirred at 180° C. for 2 hours. After completion of the reaction, the reactant was filtered with celite, dried, and separated by column chromatography to obtain 3.1 g of compound C-1 (yield: 24%).
[0149] 1H NMR (600 MHz, CDCl.sub.3, δ): 9.34 (s, 1H), 9.08 (d, J=8.3 Hz, 1H), 8.38 (dd, J=7.7, 1.1 Hz, 1H), 8.20 (dd, J=6.5, 3.2 Hz, 1H), 8.07-8.02 (m, 2H), 7.91 (dt, J=7.8, 1.4 Hz, 1H), 7.87-7.80 (m, 4H), 7.72 (t, J=7.8 Hz, 1H), 7.68-7.64 (m, 1H), 7.62-7.42 (m, 11H), 7.40-7.30 (m, 4H), 7.20-7.09 (m, 3H)
TABLE-US-00014 Compound MW M.P. C-1 510.6 258° C.
EXAMPLE 15: PREPARATION OF COMPOUND C-14
[0150] ##STR00295##
[0151] 3.3 g of 5-bromo-2,3-diphenylquinoxaline (9.4 mmol), 7 g of 7-phenyl-9-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-7,9-dihydrobenzo[g]indolo[2,3-b]carbazole (21.1 mmol), 494 mg of Pd(PPh.sub.3).sub.4 (0.43 mmol), and 3.5 g of K.sub.2CO.sub.3 (25.6 mmol) were dissolved in a mixture solvent of 50 mL of toluene, 25 mL of ethanol, and 25 mL of H.sub.2O in a flask, and the mixture was stirred under reflux at 130° C. for 4 hours. After completion of the reaction, the reactant was filtered with celite, dried, and separated by column chromatography to obtain 3 g of compound C-14 (yield: 47.5%).
[0152] .sup.1H NMR (600 MHz, CDCl.sub.3, δ) 9.36 (d, J=0.8 Hz, 1H), 9.08 (d, J=8.3 Hz, 1H), 8.94-8.90 (m, 2H), 8.45-8.40 (m, 1H), 8.38 (d, J=2.3 Hz, 1H), 8.31 (d, J=8.8 Hz, 1H), 8.06 (ddd, J=13.7, 8.6, 1.6 Hz, 2H), 7.87-7.82 (m, 2H), 7.62-7.57 (m, 3H), 7.57-7.52 (m, 3H), 7.49-7.39 (m, 4H)
TABLE-US-00015 Compound MW M.P. C-14 738.89 271.3° C.
EXAMPLE 16: PREPARATION OF COMPOUND C-400
[0153] ##STR00296##
[0154] 5.9 g of compound 1-1 (18.6 mmol), 5 g of 14H-benzo[c]benzo[4,5]thieno[2,3-a]carbazole (15.46 mmol), 704 mg of Pd.sub.2(dba).sub.3 (0.773 mmol), 635 mg of s-Phos (1.546 mmol), and 4.5 g of NaOtBu (46.4 mmol) were dissolved in 130 mL of o-xylene in a flask, and the mixture was stirred under reflux at 180° C. for 3 hours. After completion of the reaction, the reactant was filtered with celite, dried, and separated by column chromatography to obtain 8.2 g of compound C-400 (yield: 87.8%).
[0155] .sup.1H NMR (600 MHz, CDCl.sub.3, δ) 9.23 (d, J=8.3 Hz, 1H), 9.11 (dd, J=8.2, 1.3 Hz, 1H), 8.93 (d, J=8.4 Hz, 1H), 8.75 (d, J=8.0 Hz, 1H), 8.51 (dd, J=2.3, 0.5 Hz, 1H), 8.45 (dd, J=8.6, 0.6 Hz, 1H), 7.92 (dd, J=8.7, 2.3 Hz, 1H), 7.84 (ddd, J=8.2, 6.9, 1.2 Hz, 1H), 7.78-7.72 (m, 2H), 7.68-7.64 (m, 2H), 7.63-7.59 (m, 2H), 7.53 (dddd, J=38.4, 8.1, 7.0, 1.2 Hz, 2H), 7.48-7.32 (m, 8H)
TABLE-US-00016 Compound MW M.P. C-400 603.74 290° C.
Comparative Example 1: Production of a Red Light-Emitting OLED not According to the Present Disclosure
[0156] An OLED not according to the present disclosure was produced. A transparent electrode indium tin oxide (ITO) thin film (10 Ω/sq) on a glass substrate for an OLED device (Geomatec, Japan) was subjected to an ultrasonic washing with acetone and isopropyl alcohol, sequentially, and was then stored in isopropanol. Next, the ITO substrate was mounted on a substrate holder of a vacuum vapor depositing apparatus. Compound HI-1 was introduced into a cell of said vacuum vapor depositing apparatus, and then the pressure in the chamber of said apparatus was controlled to 10.sup.−7 torr. Thereafter, an electric current was applied to the cell to evaporate the above-introduced material, thereby forming a first hole injection layer having a thickness of 80 nm on the ITO substrate. Compound HI-2 was then introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a second hole injection layer having a thickness of 5 nm on the first hole injection layer. Compound HT-1 was introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a first hole transport layer having a thickness of 10 nm on the second hole injection layer. Compound HT-2 was introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a second hole transport layer having a thickness of 60 nm on the first hole transport layer. After forming the hole injection layers and the hole transport layers, a light-emitting layer was then deposited as follows. Compound X was introduced into one cell of the vacuum vapor depositing apparatus as a host, and compound D-71 was introduced into another cell as a dopant. The two materials were evaporated at different rates and were deposited in a doping amount of 3 wt % based on the total amount of the host and dopant to form a light-emitting layer having a thickness of 40 nm on the second hole transport layer. Next, compound ETL-1 and compound EIL-1 were evaporated in a weight ratio of 50:50 as electron transport materials to form an electron transport layer having a thickness of 35 nm on the light-emitting layer. After depositing Compound EIL-1 as an electron injection layer having a thickness of 2 nm on the electron transport layer, an Al cathode having a thickness of 80 nm was deposited by another vacuum vapor deposition apparatus on the electron injection layer. Thus, an OLED device was produced. All the materials used for producing the OLED device were purified by vacuum sublimation at 10.sup.−6 torr.
Device Examples 1 to 9: Production of a Red Light-Emitting OLED According to the Present Disclosure
[0157] OLEDs were produced in the same manner as in Comparative Example 1, except that the compounds shown in Table 1 below were used as the light-emitting material instead of compound X.
[0158] The driving voltage, luminous efficiency, and CIE color coordinate at a luminance of 1,000 nit, and the time taken for the luminance to decrease from 100% to 90% at a luminance of 5,000 nit (lifespan; T90) of the OLEDs produced in Comparative Example 1 and Device Examples 1 to 9 are provided in Table 1 below.
TABLE-US-00017 TABLE 1 Light- Driving Luminous Color Color emitting voltage efficiency coordinate coordinate Lifespan layer (V) (cd/A) (x) (y) (T90, hr) Comparative Compound X 3.0 18.2 0.665 0.334 7.2 Example 1 Device C-62 2.7 25.7 0.661 0.338 65.0 Example 1 Device C-2 2.7 25.8 0.666 0.334 190.2 Example 2 Device C-193 3.0 26.0 0.665 0.334 73.0 Example 3 Device C-20 2.9 23.1 0.665 0.334 324.3 Example 4 Device C-50 3.0 22.7 0.666 0.333 178.6 Example 5 Device C-43 2.7 22.7 0.666 0.333 30.5 Example 6 Device C-170 3.0 22.5 0.667 0.333 56.3 Example 7 Device C-200 3.0 23.7 0.665 0.335 56.8 Example 8 Device C-163 3.0 26.1 0.667 0.333 101.0 Example 9
[0159] The organic electroluminescent device using the organic electroluminescent compound of the present disclosure as a host showed similar or lower driving voltage and higher efficiency than the organic electroluminescent device using the compound of the Comparative Example. Particularly, the lifespan characteristic was highly excellent.
Device Examples 10 to 16: Production of a Red Light-Emitting OLED According to the Present Disclosure
[0160] In Device Examples 10 to 16, OLEDs were produced in the same manner as in Comparative Example 1, except that the first and second host compounds shown in Table 2 below as a host were introduced into two cells of the vacuum vapor deposition apparatus and compound D-71 as a dopant was introduced into another cell of the apparatus, the two host materials were evaporated at a rate of 1:1 and the dopant material was simultaneously deposited at a different rate in a doping amount of 3 wt %, based on the total weight of the host and dopant, to form a light-emitting layer having a thickness of 40 nm on the second hole transport layer.
[0161] The driving voltage, luminous efficiency, and CIE color coordinate at a luminance of 1,000 nit, and the time taken for the luminance to decrease from 100% to 90% at a luminance of 5,000 nit (lifespan; T90) of the OLEDs produced in Device Examples 10 to 16 are provided in Table 2 below.
TABLE-US-00018 TABLE 2 Driving Luminous Color Color First Second voltage efficiency coordinate coordinate Lifespan host host (V) (cd/A) (x) (y) (T90, hr) Device C-193 H1-7 3.0 27.0 0.667 0.333 163.6 Example 10 Device C-182 3.2 25.6 0.666 0.333 292.3 Example 11 Device C-43 2.9 24.2 0.665 0.335 39.9 Example 12 Device C-50 3.1 26.4 0.665 0.334 258.5 Example 13 Device C-163 3.2 27.9 0.668 0.332 207.0 Example 14 Device C-163 H1-1 3.2 29.3 0.666 0.334 244.8 Example 15 Device C-163 H1-56 3.0 27.0 0.669 0.331 321.9 Example 16
[0162] From the properties of the OLEDs of Device Examples 10 to 16, it is verified that when using a combination of the first host material of the present disclosure with a second host material as a plurality of host materials, driving voltage is maintained at a similar level or lowered but the luminous efficiency and lifespan characteristic are highly enhanced.
TABLE-US-00019 TABLE 3 Organic electroluminescent materials used in the Device Examples and Comparative Examples Hole Injection Layer/Hole Transport Layer