ORGANIC MOLECULES FOR OPTOELECTRONIC DEVICES

Abstract

The invention relates to an organic molecule for optoelectronic devices. According to the invention, the organic molecule has a structure of Formula I:

##STR00001## wherein X.sup.1, X.sup.2, X.sup.3, X.sup.4, X.sup.5, X.sup.6, X.sup.7, X.sup.8, X.sup.9, X.sup.10, X.sup.11, X.sup.12, X.sup.13, and X.sup.14 is independently selected from the group consisting of N and CR.sup.a; and Z is at each occurrence independently selected from the group consisting of a direct bond, CR.sup.3R.sup.4, CCR.sup.3R.sup.4, CO, CNR.sup.3, NR.sup.3, O, SiR.sup.3R.sup.4, S, S(O), and S(O).sub.2.

Claims

1-15. (canceled)

16. An organic molecule, comprising a structure of Formula I: ##STR00117## wherein X.sup.1, X.sup.2, X.sup.3, X.sup.4, X.sup.5, X.sup.6, X.sup.7, X.sup.8, X.sup.9, X.sup.10, X.sup.11, X.sup.12, X.sup.13, and X.sup.14 is independently from each other selected from the group consisting of N and CR.sup.a; Z is at each occurrence independently from one another selected from the group consisting of a direct bond, CR.sup.3R.sup.4, CCR.sup.3R.sup.4, CO, CNR.sup.3, NR.sup.3, O, SiR.sup.3R.sup.4, S, S(O) and S(O).sub.2; R.sup.1 and R.sup.2 is at each occurrence independently from one another selected from the group consisting of hydrogen; deuterium; N(R.sup.5).sub.2; OR.sup.5; Si(R.sup.5).sub.3; B(OR.sup.5).sub.2; OSO.sub.2R.sup.5; CF.sub.3; CN; F; Br; I; C.sub.1-C.sub.40-alkyl, which is optionally substituted with one or more substituents R.sup.5 and wherein one or more non-adjacent CH.sub.2-groups are optionally substituted by R.sup.5CCR.sup.5, CC, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, CO, CS, CSe, CNR.sup.5, P(O)(R.sup.5), SO, SO.sub.2, NR.sup.5, O, S or CONR.sup.5; C.sub.1-C.sub.40-alkoxy, which is optionally substituted with one or more substituents R.sup.5 and wherein one or more non-adjacent CH.sub.2-groups are optionally substituted by R.sup.5CCR.sup.5, CC, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, CO, CS, CSe, CNR.sup.5, P(O)(R.sup.5), SO, SO.sub.2, NR.sup.5, O, S or CONR.sup.5; C.sub.1-C.sub.40-thioalkoxy, which is optionally substituted with one or more substituents R.sup.5 and wherein one or more non-adjacent CH.sub.2-groups are optionally substituted by R.sup.5CCR.sup.5, CC, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, CO, CS, CSe, CNR.sup.5, P(O)(R.sup.5), SO, SO.sub.2, NR.sup.5, O, S or CONR.sup.5; C.sub.2-C.sub.40-alkenyl, which is optionally substituted with one or more substituents R.sup.5 and wherein one or more non-adjacent CH.sub.2-groups are optionally substituted by R.sup.5CCR.sup.5, CC, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, CO, CS, CSe, CNR.sup.5, P(O)(R.sup.5), SO, SO.sub.2, NR.sup.5, O, S or CONR.sup.5; C.sub.2-C.sub.40-alkynyl, which is optionally substituted with one or more substituents R.sup.5 and wherein one or more non-adjacent CH.sub.2-groups are optionally substituted by R.sup.5CCR.sup.5, CC, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, CO, CS, CSe, CNR.sup.5, P(O)(R.sup.5), SO, SO.sub.2, NR.sup.5, O, S or CONR.sup.5; C.sub.6-C.sub.60-aryl, which is optionally substituted with one or more substituents R.sup.5; and C.sub.3-C.sub.57-heteroaryl, which is optionally substituted with one or more substituents R.sup.5; and a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system formed by ring-closure with one or more other substituent selected from the group consisting of R.sup.1, R.sup.2 and R.sup.5; R.sup.a, R.sup.3 and R.sup.4 is at each occurrence independently from one another selected from the group consisting of hydrogen; deuterium; N(R.sup.5).sub.2; OR.sup.5; Si(R.sup.5).sub.3, B(OR.sup.5).sub.2; OSO.sub.2R.sup.5; CF.sub.3; CN; F; Br; I; C.sub.1-C.sub.40-alkyl, which is optionally substituted with one or more substituents R.sup.5 and wherein one or more non-adjacent CH.sub.2-groups are optionally substituted by R.sup.5CCR.sup.5, CC, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, CO, CS, CSe, CNR.sup.5, P(O)(R.sup.5), SO, SO.sub.2, NR.sup.5, O, S or CONR.sup.5; C.sub.1-C.sub.40-alkoxy, which is optionally substituted with one or more substituents R.sup.5 and wherein one or more non-adjacent CH.sub.2-groups are optionally substituted by R.sup.5CCR.sup.5, CC, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, CO, CS, CSe, CNR.sup.5, P(O)(R.sup.5), SO, SO.sub.2, NR.sup.5, O, S or CONR.sup.5; C.sub.1-C.sub.40-thioalkoxy, which is optionally substituted with one or more substituents R.sup.5 and wherein one or more non-adjacent CH.sub.2-groups are optionally substituted by R.sup.5CCR.sup.5, CC, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, CO, CS, CSe, CNR.sup.5, P(O)(R.sup.5), SO, SO.sub.2, NR.sup.5, O, S or CONR.sup.5; C.sub.2-C.sub.40-alkenyl, which is optionally substituted with one or more substituents R.sup.5 and wherein one or more non-adjacent CH.sub.2-groups are optionally substituted by R.sup.5CCR.sup.5, CC, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, CO, CS, CSe, CNR.sup.5, P(O)(R.sup.5), SO, SO.sub.2, NR.sup.5, O, S or CONR.sup.5; C.sub.2-C.sub.40-alkynyl, which is optionally substituted with one or more substituents R.sup.5 and wherein one or more non-adjacent CH.sub.2-groups are optionally substituted by R.sup.5CCR.sup.5, CC, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, CO, CS, CSe, CNR.sup.5, P(O)(R.sup.5), SO, SO.sub.2, NR.sup.5, O, S or CONR.sup.5; C.sub.6-C.sub.60-aryl, which is optionally substituted with one or more substituents R.sup.5; and C.sub.3-C.sub.57-heteroaryl, which is optionally substituted with one or more substituents R.sup.5; R.sup.5 is at each occurrence independently from one another selected from the group consisting of hydrogen; deuterium; N(R.sup.6).sub.2; OR.sup.6; Si(R.sup.6).sub.3; B(OR.sup.6).sub.2; OSO.sub.2R.sup.6; CF.sub.3; CN; F; Br; I; C.sub.1-C.sub.40-alkyl, which is optionally substituted with one or more substituents R.sup.6 and wherein one or more non-adjacent CH.sub.2-groups are optionally substituted by R.sup.6CCR.sup.6, CC, Si(R.sup.6).sub.2, Ge(R.sup.6).sub.2, Sn(R.sup.6).sub.2, CO, CS, CSe, CNR.sup.6, P(O)(R.sup.6), SO, SO.sub.2, NR.sup.6, O, S or CONR.sup.6; C.sub.1-C.sub.40-alkoxy, which is optionally substituted with one or more substituents R.sup.6 and wherein one or more non-adjacent CH.sub.2-groups are optionally substituted by R.sup.6CCR.sup.6, CC, Si(R.sup.6).sub.2, Ge(R.sup.6).sub.2, Sn(R.sup.6).sub.2, CO, CS, CSe, CNR.sup.6, P(O)(R.sup.6), SO, SO.sub.2, NR.sup.6, O, S or CONR.sup.6; C.sub.1-C.sub.40-thioalkoxy, which is optionally substituted with one or more substituents R.sup.6 and wherein one or more non-adjacent CH.sub.2-groups are optionally substituted by R.sup.6CCR.sup.6, CC, Si(R.sup.6).sub.2, Ge(R.sup.6).sub.2, Sn(R.sup.6).sub.2, CO, CS, CSe, CNR.sup.6, P(O)(R.sup.6), SO, SO.sub.2, NR.sup.6, O, S or CONR.sup.6; C.sub.2-C.sub.40-alkenyl, which is optionally substituted with one or more substituents R.sup.6 and wherein one or more non-adjacent CH.sub.2-groups are optionally substituted by R.sup.6CCR.sup.6, CC, Si(R.sup.6).sub.2, Ge(R.sup.6).sub.2, Sn(R.sup.6).sub.2, CO, CS, CSe, CNR.sup.6, P(O)(R.sup.6), SO, SO.sub.2, NR.sup.6, O, S or CONR.sup.6; C.sub.2-C.sub.40-alkynyl, which is optionally substituted with one or more substituents R.sup.6 and wherein one or more non-adjacent CH.sub.2-groups are optionally substituted by R.sup.6CCR.sup.6, CC, Si(R.sup.6).sub.2, Ge(R.sup.6).sub.2, Sn(R.sup.6).sub.2, CO, CS, CSe, CNR.sup.6, P(O)(R.sup.6), SO, SO.sub.2, NR.sup.6, O, S or CONR.sup.6; C.sub.6-C.sub.60-aryl, which is optionally substituted with one or more substituents R.sup.6; and C.sub.3-C.sub.57-heteroaryl, which is optionally substituted with one or more substituents R.sup.6; R.sup.6 is at each occurrence independently from one another selected from the group consisting of hydrogen; deuterium; OPh; CF.sub.3; CN; F; C.sub.1-C.sub.5-alkyl, wherein one or more hydrogen atoms are optionally, independently from each other substituted by deuterium, CN, CF.sub.3, or F; C.sub.1-C.sub.5-alkoxy, wherein one or more hydrogen atoms are optionally, independently from each other substituted by deuterium, CN, CF.sub.3, or F; C.sub.1-C.sub.5-thioalkoxy, wherein one or more hydrogen atoms are optionally, independently from each other substituted by deuterium, CN, CF.sub.3, or F; C.sub.2-C.sub.5-alkenyl, wherein one or more hydrogen atoms are optionally, independently from each other substituted by deuterium, CN, CF.sub.3, or F; C.sub.2-C.sub.5-alkynyl, wherein one or more hydrogen atoms are optionally, independently from each other substituted by deuterium, CN, CF.sub.3, or F; C.sub.6-C.sub.18-aryl, which is optionally substituted with one or more C.sub.1-C.sub.5-alkyl substituents; C.sub.3-C.sub.17-heteroaryl, which is optionally substituted with one or more C.sub.1-C.sub.5-alkyl substituents; N(C.sub.6-C.sub.18-aryl).sub.2; N(C.sub.3-C.sub.17-heteroaryl).sub.2; and N(C.sub.3-C.sub.17-heteroaryl)(C.sub.6-C.sub.18-aryl); and wherein any of the substituents R.sup.1, R.sup.2, R.sup.a, R.sup.3, R.sup.4 or R.sup.5 independently from each other optionally form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system with one or more other substituent R.sup.1, R.sup.2, R.sup.a, R.sup.3, R.sup.4 or R.sup.5.

17. The organic molecule according to claim 16, comprising a structure of Formula Ib: ##STR00118##

18. The organic molecule according to claim 16, wherein Z is a direct bond.

19. The organic molecule according to claim 16, wherein R.sup.1 and R.sup.2 is independently selected from the group consisting of: phenyl, which is optionally substituted with one or more substituents R.sup.5; and pyridine, which is optionally substituted with one or more substituents R.sup.5.

20. The organic molecule according to claim 16, wherein the substituents R.sup.2 and R.sup.1 are the same.

21. The organic molecule according to claim 17, comprising a structure selected from the group consisting of Formula IIIa, Formula IIIb, Formula IIIc, Formula IIId, Formula IIIe, Formula IIIf, Formula IIIg, Formula IIIh, and Formula IIIi: ##STR00119## ##STR00120## ##STR00121##

22. The organic molecule according to claim 16, wherein R.sup.a is at each occurrence independently from one another selected from the group consisting of: hydrogen, Me, .sup.iPr, .sup.tBu, CN, CF.sub.3, Ph, which is optionally substituted with one or more substituents independently from each other selected from the group consisting of Me, .sup.iPr, .sup.tBu, CN, CF.sub.3, and Ph, pyridinyl, which is optionally substituted with one or more substituents independently from each other selected from the group consisting of Me, .sup.iPr, .sup.tBu, CN, CF.sub.3, and Ph, pyrimidinyl, which is optionally substituted with one or more substituents independently from each other selected from the group consisting of Me, .sup.iPr, .sup.tBu, CN, CF.sub.3, and Ph, carbazolyl, which is optionally substituted with one or more substituents independently from each other selected from the group consisting of Me, .sup.iPr, .sup.tBu, CN, CF.sub.3, and Ph, triazinyl, which is optionally substituted with one or more substituents independently from each other selected from the group consisting of Me, .sup.iPr, .sup.tBu, CN, CF.sub.3, and Ph, and N(Ph).sub.2.

23. The organic molecule according to claim 16, wherein R.sup.5 is at each occurrence independently from one another selected from the group consisting of: hydrogen, Me, .sup.iPr, .sup.tBu, CN, CF.sub.3, Ph, which is optionally substituted with one or more substituents independently from each other selected from the group consisting of Me, .sup.iPr, .sup.tBu, CN, CF.sub.3, and Ph, pyridinyl, which is optionally substituted with one or more substituents independently from each other selected from the group consisting of Me, .sup.iPr, .sup.tBu, CN, CF.sub.3, and Ph, pyrimidinyl, which is optionally substituted with one or more substituents independently from each other selected from the group consisting of Me, .sup.iPr, .sup.tBu, CN, CF.sub.3, and Ph, carbazolyl, which is optionally substituted with one or more substituents independently from each other selected from the group consisting of Me, .sup.iPr, .sup.tBu, CN, CF.sub.3, and Ph, triazinyl, which is optionally substituted with one or more substituents independently from each other selected from the group consisting of Me, .sup.iPr, .sup.tBu, CN, CF.sub.3, and Ph, and N(Ph).sub.2.

24. An optoelectronic device comprising the organic molecule according to claim 16 as a luminescent emitter.

25. The optoelectronic device according to claim 24, wherein the optoelectronic device is at least one selected from the group consisting of: organic light-emitting diodes (OLEDs), light-emitting electrochemical cells, OLED-sensors, organic diodes, organic solar cells, organic transistors, organic field-effect transistors, organic lasers, and down-conversion elements.

26. A composition, comprising: (a) the organic molecule according to claim 16 as a luminescent emitter, (b) a triplet-triplet annihilation (TTA) host material, which differs from the organic molecule, (c) optionally, a thermally-activated delayed fluorescence (TADF) material, and (d) optionally, a dye and/or a solvent.

27. An optoelectronic device, comprising the composition according to claim 26, wherein the optoelectronic device is at least one selected from the group consisting of organic light-emitting diodes (OLEDs), light-emitting electrochemical cells, OLED-sensors, organic diodes, organic solar cells, organic transistors, organic field-effect transistors, organic lasers, and down-conversion elements.

28. The optoelectronic device according to claim 24, comprising: a substrate, an anode, and a cathode, wherein the anode or the cathode is on the substrate, and a light-emitting layer between the anode and the cathode and comprising the organic molecule.

29. A method for producing an optoelectronic device, the method comprising depositing the organic molecule according to claim 16 by a vacuum evaporation method and/or a solution deposition method.

30. A method for producing an optoelectronic device, the method comprising depositing the composition according to claim 26 by a vacuum evaporation method and/or a solution deposition method.

31. The optoelectronic device according to claim 27, comprising: a substrate, an anode, and a cathode, wherein the anode or the cathode is on the substrate, and a light-emitting layer between the anode and the cathode and comprising the composition.

32. An optoelectronic device, comprising a layer formed from the composition according to claim 26, wherein the optoelectronic device is at least one selected from the group consisting of organic light-emitting diodes (OLEDs), light-emitting electrochemical cells, OLED-sensors, organic diodes, organic solar cells, organic transistors, organic field-effect transistors, organic lasers, and down-conversion elements.

33. The optoelectronic device according to claim 32, comprising: a substrate, an anode, and a cathode, wherein the anode or the cathode is on the substrate, and a light-emitting layer between the anode and the cathode and comprising the layer formed from the composition.

Description

EXAMPLES

General Synthesis Scheme I

[0417] wherein X.sup.1X.sup.14, X.sup.2X.sup.13, X.sup.3X.sup.12, X.sup.4X.sup.11, X.sup.5X.sup.10, X.sup.6X.sup.9, and X.sup.7X.sup.8:

##STR00051## ##STR00052## ##STR00053##

General Procedure for Synthesis AAV1

[0418] ##STR00054##

[0419] In the first step acetic acid (50 eq) added to a flask which contains 4,7-dibromo-5,6-difluorobenzo[c][1,2,5]thiadiazole (E0; 1 eq) and Zn (1.5 eq) and the mixture stirred at 60 C. Then 1,2-dione compounds E1 were added to the obtained compound and the reaction was stirred at elevated temperature (30 C. or higher) to generate the corresponding 5,8-dibromo-6,7-difluoroquinoxaline derivatives E2. Variations in the amount of compounds and temperature could be employed.

General Procedure for Synthesis AAV2

[0420] ##STR00055##

[0421] The second step was a nucleophilic aromatic substitution reaction between E2 (1 eq) and secondary amines E3 (2.3 eq) in organic solvent (for example DMSO, DMF, NMP, DMAc, DME, EtOH, MeCN, ToI, MeCN, or DCM) in the presence of base (4 eq; for example K.sub.2CO.sub.3, K.sub.3PO.sub.4, NaH, NaOtBu, KOtBu, Cs.sub.2CO.sub.3, KOH, NaOH, LDA, LDEA) at elevated temperature (30 C. or higher, and overnight) to obtain di-substituted compound E4. Variations in the amount of compounds, base, solvent, time, and temperature could be employed.

General Procedure for Synthesis AAV3

[0422] ##STR00056##

[0423] In the last step, CH activation conducted in the presence of Pd.sup.II or Pd.sup.0 catalyst (0.05 eq; for example Pd(OAc).sub.2, PdCl.sub.2(PPh.sub.3).sub.2, Pd(dppf)Cl.sub.2, PdCl.sub.2(PPh.sub.3).sub.2, Pd(PPh.sub.3).sub.4), ligand (0.08 eq; for example PPh.sub.3, PCy.sub.3, PCy.sub.3HBF.sub.4, XPhos, S-Phos, R-Phos, xanphos, (tBu).sub.3P), quaternary ammonium salt (1 eq; for example TBACl, TBAB, TBAl, TBAOH, TMAB, THACl, TOACl, tetrabutylammonium tetrafluoroborate, benzyltrimethylammonium bromide), base (5 eq; for example K.sub.2CO.sub.3, K.sub.3PO.sub.4, NaH, NaOtBu, KOtBu, Cs.sub.2CO.sub.3, KOH, or NaOH), solvent (for example, DMAc, NMP, DMF, DME, MeCN, ToI, 1,4-dioxane, DMSO, EtOH, or THF) and at 140 C. to achieve organic molecules according to the invention, P1. Variations in the amount of compounds, phase catalyst, solvent, and temperature could be employed.

General Synthesis Scheme II

[0424] ##STR00057## ##STR00058## ##STR00059## ##STR00060##

General Procedure for Synthesis AAV2-1

[0425] ##STR00061##

[0426] The synthesis of AAV2-1 is carried out by reacting of E2 (1.05 eq), secondary amine E3 (1 eq) in the presence of base (1.5 eq; for example K.sub.2CO.sub.3, K.sub.3PO.sub.4, NaH, NaOtBu, KOtBu, Cs.sub.2CO.sub.3, KOH, NaOH, LDA, or LDEA), and solvent (for example DMSO, DMF, NMP, DMAc, DME, EtOH, MeCN, ToI, MeCN, or DCM) at ambient temperature up to 120 C.

General Procedure for Synthesis AAV2-2

[0427] ##STR00062##

[0428] The synthesis of E4-2 is carried out from reaction of E4-1 and secondary amine E3-2. To a flask containing E4-1 (1 eq), base (1.5 eq), E3-2 (1.2 eq) was added in a solvent (for example DMSO, DMF, NMP, DMAc, DME, EtOH, MeCN, ToI, MeCN, or DCM) and the reaction mixture stirred at elevated temperature (50 C. or higher) for 12 hours. Variations in the amount of compounds, base, solvent, and temperature could be employed.

General Procedure for Synthesis AAV2-3

[0429] ##STR00063##

[0430] To 1 eq of E4-2, palladium catalyst (0.05 eq; for example Pd(OAc).sub.2, PdCl.sub.2(PPh.sub.3).sub.2, Pd(dppf)Cl.sub.2, PdCl.sub.2(PPh.sub.3).sub.2, Pd(PPh.sub.3).sub.4), ligand (0.08 eq; for example PPh.sub.3, PCy.sub.3, PCy.sub.3HBF.sub.4, XPhos, S-Phos, R-Phos, xanphos, (tBu).sub.3P), quaternary ammonium salt (1 eq; for example TBACl, TBAB, TBAl, TBAOH, TMAB, THACl, TOACl, tetrabutylammonium tetrafluoroborate, benzyltrimethylammonium bromide), base (5 eq; for example K.sub.2CO.sub.3, K.sub.3PO.sub.4, NaH, NaOtBu, KOtBu, Cs.sub.2CO.sub.3, KOH, NaOH, LDA, LDEA) were added to a solvent (for example DMAc, NMP, DMF, DME, MeCN, ToI, 1,4-dioxane, DMSO, THF, EtOH) and at elevated temperatures (60-160 C.). Variations in the amount of compounds, phase catalyst, solvent, and temperature could be employed.

General Synthesis Scheme III

[0431] wherein X.sup.1X.sup.14, X.sup.2X.sup.13, X.sup.3X.sup.12, X.sup.4X.sup.11, X.sup.5X.sup.10, X.sup.6X.sup.9, and X.sup.7=X.sup.8:

##STR00064## ##STR00065## ##STR00066##

General Procedure for Synthesis AAV3-1

[0432] ##STR00067##

[0433] The first step was a nucleophilic aromatic substitution reaction between 4,7-dibromo-5,6-difluorobenzo[c][1,2,5]thiadiazole (E0; 1 eq) and secondary amines E3 (2.1 eq) in organic solvent (for example DMSO, DMF, NMP, DMAc, DME, EtOH, MeCN, ToI, MeCN, or DCM) in the presence of base (4 eq; for example K.sub.2CO.sub.3, K.sub.3PO.sub.4, NaH, NaOtBu, KOtBu, Cs.sub.2CO.sub.3, KOH, NaOH, LDA, LDEA) at elevated temperature (30 C. or higher, and overnight) to obtain di-substituted compound E5. Variations in the amount of compounds, base, solvent, time, and temperature may be employed.

General Procedure for Synthesis AAV3-2

[0434] ##STR00068##

[0435] In the second step, CH activation of E5 (1 eq) conducted in the presence of Pd.sup.II or Pd.sup.0 catalyst (0.15 eq; for example Pd(OAc).sub.2, PdCl.sub.2(PPh.sub.3).sub.2, Pd(dppf)Cl.sub.2, PdCl.sub.2(PPh.sub.3).sub.2, Pd(PPh.sub.3).sub.4), ligand (0.4 eq; for example PPh.sub.3, PCy.sub.3, PCy.sub.3HBF.sub.4, XPhos, S-Phos, R-Phos, xanphos, (tBu).sub.3P), quaternary ammonium salt (1 eq; for example TBACl, TBAB, TBAl, TBAOH, TMAB, THACl, TOACl, tetrabutylammonium tetrafluoroborate, benzyltrimethylammonium bromide), base (5 eq; for example K.sub.2CO.sub.3, K.sub.3PO.sub.4, NaH, NaOtBu, KOtBu, Cs.sub.2CO.sub.3, KOH, or NaOH), solvent (for example, DMAc, NMP, DMF, DME, MeCN, ToI, 1,4-dioxane, DMSO, EtOH, or THF) and at elevated temperature (60 C. or higher, and overnight) to achieve E6. Variations in the amount of compounds, phase catalyst, solvent, and temperature could be employed.

General Procedure for Synthesis AAV3-3

[0436] ##STR00069##

[0437] In the last step acetic acid (50 eq) added to a flask which contains E6 (1 eq) and Zn (10 eq) and the mixture stirred at 60 C. Then 1,2-dione compounds E1 were added to the obtained compound and the reaction was stirred at elevated temperature (30 C. or higher) to generate the corresponding organic molecules according to the invention, P1. Variations in the amount of compounds and temperature could be employed.

[0438] Cyclic Voltammetry

[0439] Cyclic voltammograms are measured from solutions having concentration of 10.sup.3 mol/L of the organic molecules in dichloromethane or a suitable solvent and a suitable supporting electrolyte (e.g., 0.1 mol/L of tetrabutylammonium hexafluorophosphate). The measurements are conducted at room temperature under nitrogen atmosphere with a three-electrode assembly (Working and counter electrodes: Pt wire, reference electrode: Pt wire) and calibrated using FeCp.sub.2/FeCp.sub.2.sup.+ as internal standard. The HOMO data was corrected using ferrocene as internal standard against a saturated calomel electrode (SCE).

[0440] Density Functional Theory Calculation

[0441] Molecular structures are optimized employing the BP86 functional and the resolution of identity approach (RI). Excitation energies are calculated using the (BP86) optimized structures employing Time-Dependent DFT (TD-DFT) methods. Orbital and excited state energies are calculated with the B3LYP functional. Def2-SVP basis sets (and a m4-grid for numerical integration are used. The Turbomole program package is used for all calculations.

[0442] Photophysical Measurements [0443] Sample pretreatment: Spin-coating [0444] Apparatus: Spin150, SPS euro. [0445] The sample concentration is 0.2 mg/ml, dissolved in Toluene/DCM. [0446] Program: 7) 30 sec. at 2000 U/min. After coating, the films are dried at 70 C. for 1 min.

[0447] Fluorescence Spectroscopy and Phosphorescence Spectroscopy

[0448] For the analysis of Phosphorescence and Photoluminescence spectroscopy a fluorescence spectrometer Fluoromax 4P from Horiba is used.

[0449] Time-Resolved PL Spectroscopy in the s-Range and ns-Range (FS5)

[0450] Time-resolved PL measurements were performed on an FS5 fluorescence spectrometer from Edinburgh Instruments. Compared to measurements on the HORIBA setup, better light gathering allows for an optimized signal to noise ratio, which favors the FS5 system especially for transient PL measurements of delayed fluorescence characteristics. The FS5 consists of a xenon lamp providing a broad spectrum. The continuous light source is a 150W xenon arc lamp, selected wavelengths are chosen by a Czerny-Turner monochromator, which is also used to set specific emission wavelengths. The sample emission is directed towards a sensitive R928P photomultiplier tube (PMT), allowing the detection of single photons with a peak quantum efficiency of up to 25% in the spectral range between 200 nm to 870 nm. The detector is a temperature stabilized PMT, providing dark counts below 300 cps (counts per second). Finally, to determine the transient decay lifetime of the delayed fluorescence, a tail fit using three exponential functions is applied. By weighting the specific lifetimes .sub.i with their corresponding amplitudes A.sub.i,

[00001]${}_{\mathrm{DF}}={.Math.}_{i=1}^3\frac{A_i{}_i}{A_i}$ [0451] the delayed fluorescence lifetime .sub.DF is determined.

[0452] Photoluminescence Quantum Yield Measurements

[0453] For photoluminescence quantum yield (PLQY) measurements an Absolute PL Quantum Yield Measurement C.sub.9920-03G system (Hamamatsu Photonics) is used. Quantum yields and CIE coordinates are determined using the software U6039-05 version 3.6.0.

[0454] Emission maxima are given in nm, quantum yields in % and CIE coordinates as x,y values.

[0455] PLQY is determined using the following protocol:

[0456] Quality assurance: Anthracene in ethanol (known concentration) is used as reference.

[0457] Excitation wavelength: the absorption maximum of the organic molecule is determined and the molecule is excited using this wavelength

[0458] Measurement

[0459] Quantum yields are measured, for sample, of solutions or films under nitrogen atmosphere. The yield is calculated using the equation:

[00002]${}_{\mathrm{PL}}=\frac{n_{\mathrm{photon}},\mathrm{emitted}}{n_{\mathrm{photon}},\mathrm{absorbed}}=\frac{\frac{}{\mathrm{hc}}\left[{\mathrm{Int}}_{\mathrm{emitted}}^{\mathrm{sample}}\left(\right)-{\mathrm{Int}}_{\mathrm{absorbed}}^{\mathrm{sample}}\left(\right)\right]d}{\frac{}{\mathrm{hc}}\left[{\mathrm{Int}}_{\mathrm{emitted}}^{\mathrm{reference}}\left(\right)-{\mathrm{Int}}_{\mathrm{absorbed}}^{\mathrm{reference}}\left(\right)\right]d}$ [0460] wherein n.sub.photon denotes the photon count and Int. the intensity.

[0461] Production and Characterization of Optoelectronic Devices

[0462] Optoelectronic devices, such as OLED devices, including organic molecules according to the invention can be produced via vacuum-deposition methods. If a layer contains more than one compound, the weight-percentage of one or more compounds is given in %. The total weight-percentage values amount to 100%, thus if a value is not given, the fraction of this compound equals to the difference between the given values and 100%.

[0463] The not fully optimized OLEDs are characterized using standard methods and measuring electroluminescence spectra, the external quantum efficiency (in %) in dependency on the intensity, calculated using the light detected by the photodiode, and the current. The OLED device lifetime is extracted from the change of the luminance during operation at constant current density. The LT50 value corresponds to the time, where the measured luminance decreased to 50% of the initial luminance, analogously LT80 corresponds to the time point, at which the measured luminance decreased to 80% of the initial luminance, LT 95 to the time point, at which the measured luminance decreased to 95% of the initial luminance etc.

[0464] Accelerated lifetime measurements are performed (e.g., applying increased current densities). For example, LT80 values at 500 cd/m.sup.2 are determined using the following equation:

[00003]$\mathrm{LT}80\left(500\frac{{\mathrm{cd}}^2}{m^2}\right)=\mathrm{LT}80\left(L_0\right){\left(\frac{L_0}{500\frac{{\mathrm{cd}}^2}{m^2}}\right)}^{1.6}$ [0465] wherein L.sub.0 denotes the initial luminance at the applied current density.

[0466] The values correspond to the average of several pixels (typically two to eight), the standard deviation between these pixels is given.

[0467] HPLC-MS

[0468] HPLC-MS analysis is performed on an HPLC by Agilent (1260 series) with MS-detector (Thermo LTQ XL).

[0469] For example, a typical HPLC method is as follows: a reverse phase column 3.0 mm100 mm, particle size 2.7 m from Agilent (Poroshell 120EC-C18, 3.0100 mm, 2.7 m HPLC column) is used in the HPLC. The HPLC-MS measurements are performed at room temperature (rt) following gradients

TABLE-US-00001 Flow rate [ml/min] Time [min] A[%] B[%] C[%] 1.5 30 40 40 30 1.5 45 10 10 80 1.5 50 40 10 80 1.5 51 30 40 30 1.5 55 30 10 30 [0470] using the following solvent mixtures containing 0.1% formic acid:

TABLE-US-00002 Solvent A: H2O (10%) MeCN (90%) Solvent B: H2O (90%) MeCN (10%) Solvent C: THF (50%) MeCN (50%)

[0471] An injection volume of 2 L from a solution with a concentration of 0.5 mg/mL of the analyte is taken for the measurements.

[0472] Ionization of the probe is performed using an atmospheric pressure chemical ionization (APCI) source either in positive (APCI+) or negative (APCI) ionization mode or an atmospheric pressure photoionization (APPI) source.

##STR00070##

[0473] Example 1 was synthesized according to [0474] AAV1 (69% yield), wherein benzil [134-81-6] was used as E1, reaction temperature set to 40 C. and reaction time of 16 hours; [0475] AAV2 (82% yield), wherein carbazole [201-696-0] was used as E3, DMF as solvent, potassium carbonate [584-08-7] as base, reaction temperature set to 80 C. and reaction time of 24 h; and [0476] AAV3 (80% yield), wherein Pd(OAC).sub.2 [3375-31-3], PPh.sub.3 [603-35-0], tetrabutylammonium bromide [1643-19-2 were used as catalyst system, potassium carbonate [584-08-7] as base, N,N-dimethyl acetamide as a solvent, reaction temperature set to 140 C. and reaction time of 24 h.

[0477] The drawing depicts the emission spectrum of example 1 (0,001 mg/ml in toluene). The emission maximum (.sub.max) is at 461 nm. The photoluminescence quantum yield (PLQY) is 68%, the full width at half maximum (FWHM) is 0.22 eV. The resulting CIE.sub.x coordinate is 0.13 and the CIE.sub.y coordinate is 0.15.

##STR00071##

[0478] Example 2 was synthesized according to [0479] AAV1 (69% yield), wherein benzil [134-81-6] was used as E1, reaction temperature set to 40 C. and reaction time of 16 hours; [0480] AAV2 (96% yield), wherein 3,6-diphenyl-9H-carbazole [56525-79-2] was used as E3, DMF as solvent, potassium carbonate [584-08-7] as base, reaction temperature set to 80 C. and reaction time of 24 h; and [0481] AAV3 (73% yield), wherein Pd(OAC).sub.2 [3375-31-3], PPh.sub.3 [603-35-0], tetrabutylammonium bromide [1643-19-2 were used as catalyst system, potassium carbonate [584-08-7] as base, N,N-dimethyl acetamide as a solvent, reaction temperature set to 140 C. and reaction time of 36 h.

[0482] The emission spectrum of example 2 (0.001 mg/ml in DCM) has an emission maximum (.sub.max) at 477 nm. The photoluminescence quantum yield (PLQY) is 70%, the full width at half maximum (FWHM) is 0.21 eV. The resulting CIE.sub.x coordinate is 0.129 and the CIE.sub.y coordinate is 0.344.

##STR00072##

[0483] Example 3 was synthesized according to [0484] AAV3-1 (37% yield), wherein 3,6-Di-tert-butylcarbazole [37500-95-1] was used as E3, DMF as solvent, potassium carbonate [584-08-7] as base, reaction temperature set to 100 C. and reaction time of 100 h; and [0485] AAV3-2 (54% yield), wherein Pd(OAC).sub.2 [3375-31-3], PPh.sub.3 [603-35-0], tetrabutylammonium bromide [1643-19-2] were used as catalyst system, potassium carbonate [584-08-7] as base, N,N-dimethyl acetamide as a solvent, reaction temperature set to 140 C. and reaction time of 3 h; and [0486] AAV3-3 (22% yield), wherein cyclohexane-1,2-dione [765-87-7] was used as E1, reaction temperature set to 40 C. and reaction time of 11 hours.

[0487] The emission spectrum of example 3 (0.001 mg/ml in toluene) has an emission maximum (.sub.max) at 450 nm. The photoluminescence quantum yield (PLQY) is 57%, the full width at half maximum (FWHM) is 0.15 eV. The resulting CIE.sub.x coordinate is 0.139 and the CIE.sub.y coordinate is 0.104.

##STR00073##

[0488] Example 4 was synthesized according to [0489] AAV1 (69% yield), wherein benzil [134-81-6] was used as E1, reaction temperature set to 40 C. and reaction time of 16 hours; [0490] AAV2 (58% yield), wherein 7H-dibenzo[c,g]carbazole [194-59-2] was used as E3, DMF as solvent, potassium carbonate [584-08-7] as base, reaction temperature set to 100 C. and reaction time of 24 h; and [0491] AAV3 (21% yield), wherein Pd(OAC).sub.2 [3375-31-3], PPh.sub.3 [603-35-0], tetrabutylammonium bromide [1643-19-2 were used as catalyst system, potassium carbonate [584-08-7] as base, N,N-dimethyl acetamide as a solvent, reaction temperature set to 140 C. and reaction time of 72 h.

[0492] The emission spectrum of example 4 (0.001 mg/ml in toluene) has an emission maximum (.sub.max) at 501 nm. The full width at half maximum (FWHM) is 0.13 eV. The resulting CIE.sub.x coordinate is 0.21 and the CIE.sub.y coordinate is 0.59.

ADDITIONAL EXAMPLES OF ORGANIC MOLECULES OF THE INVENTION

[0493] ##STR00074## ##STR00075## ##STR00076## ##STR00077## ##STR00078## ##STR00079## ##STR00080## ##STR00081## ##STR00082## ##STR00083## ##STR00084## ##STR00085## ##STR00086## ##STR00087## ##STR00088## ##STR00089## ##STR00090## ##STR00091## ##STR00092## ##STR00093## ##STR00094## ##STR00095## ##STR00096## ##STR00097## ##STR00098## ##STR00099## ##STR00100## ##STR00101## ##STR00102## ##STR00103## ##STR00104## ##STR00105## ##STR00106## ##STR00107## ##STR00108## ##STR00109## ##STR00110## ##STR00111## ##STR00112## ##STR00113## ##STR00114## ##STR00115## ##STR00116##

BRIEF DESCRIPTION OF THE DRAWINGS

[0494] The drawing illustrates an emission spectrum of example 1 (0.001 mg/ml) in toluene.