ORGANIC MOLECULES FOR OPTOELECTRONIC DEVICES

Abstract

The invention relates to a light-emitting organic molecule, in particular for the application in optoelectronic devices. According to the invention, the organic molecule has a first chemical moiety with a structure of Formula I:

##STR00001##

and a second chemical moiety with a structure of Formula II:

##STR00002##

Claims

1.-16. (canceled)

17. An organic molecule, comprising a first chemical moiety comprising of a structure of Formula I: ##STR00109## and a second chemical moiety comprising a structure of Formula II: ##STR00110## wherein: the first chemical moiety is linked to the second chemical moiety via a single bond; W is a binding site of the single bond linking the first chemical moiety to the second chemical moiety; # represents a binding site of the first chemical moiety to the second chemical moiety; Z is at each occurrence independently from each other 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.EWG is selected from the group consisting of F, CF.sub.3, CN, a substituted C.sub.6-C.sub.60-aryl, an unsubstituted C.sub.6-C.sub.60-aryl, a substituted C.sub.2-C.sub.57-heteroaryl, and an unsubstituted C.sub.2-C.sub.57-heteroaryl; Ar.sup.1 is independently selected from the group consisting of a substituted C.sub.6-C.sub.60-aryl and an unsubstituted C.sub.6-C.sub.60-aryl; R.sup.1 is at each occurrence independently selected from the group consisting of hydrogen, deuterium, C.sub.1-C.sub.6-alkyl, and C.sub.6-C.sub.12-aryl, which is optionally substituted with one or more C.sub.1-C.sub.6-alkyl substituents; R.sup.a, R.sup.3, and R.sup.4 are at each occurrence independently from each other 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 each other 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 each other 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 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 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 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 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 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.5-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); wherein, optionally, the substituents R.sup.a, R.sup.3, R.sup.4, and/or R.sup.5, independently form a mono- or polycyclic, aliphatic, aromatic, or heteroaromatic ring system with one or more other substituents R.sup.a, R.sup.3, R.sup.4 and/or R.sup.5; and wherein, optionally, two Ar.sup.1 form a ring system with each other.

18. The organic molecule according to claim 17, wherein R.sup.EWG is selected from the group consisting of F, CF.sub.3, CN, and a group E, the group E being an aryl group or a heteroaryl group each having 6 to 14 aromatic ring atoms, the group being optionally substituted by one or more substituents R.sup.5, and the group E comprising, as constituents of the aryl group or the heteroaryl group, one or more groups V, the one or more groups V being independently selected from the group consisting of N, =C(F), =C(CN) and =C(CF.sub.3), and the heteroaryl group being not bonded via a nitrogen atom.

19. The organic molecule according to claim 17, wherein R.sup.EWG is selected from the group A consisting of the following structures: Group A ##STR00111## ##STR00112## ##STR00113## ##STR00114## ##STR00115## ##STR00116## ##STR00117## wherein a dashed line represents a single bond linking the substituent R.sup.EWG to the rest of the organic molecule as represented by Formula I; and wherein, optionally, two or more adjacent substituents R.sup.5 independently form a mono- or polycyclic, aliphatic, aromatic, and/or benzo-fused ring system, wherein one or more hydrogen atoms of the formed ring system are optionally substituted by R.sup.6.

20. The organic molecule according to claim 17, wherein R.sup.EWG is at each occurrence independently selected from the group B consisting of the following structures: ##STR00118## wherein a dashed line represents a single bond linking the substituent R.sup.EWG to the rest of the organic molecule as represented by Formula I; and wherein, optionally, two or more adjacent substituents R.sup.5 independently form a mono- or polycyclic, aliphatic, aromatic, and/or benzo-fused ring system, wherein one or more hydrogen atoms of the formed ring system are optionally substituted by R.sup.6.

21. The organic molecule according to claim 17, wherein Z is a direct bond.

22. The organic molecule according to claim 17, wherein Ar.sup.1 is Ph, which is optionally substituted with one or more substituents independently selected from the group consisting of Me, .sup.iPr, .sup.tBu, and Ph.

23. The organic molecule according to claim 17, wherein R.sup.1 is selected from the group consisting of hydrogen, deuterium, Me, .sup.iPr, .sup.tBu, and Ph, which is optionally substituted with one or more substituents independently selected from the group consisting of Me, .sup.iPr, .sup.tBu, and Ph.

24. The organic molecule according to claim 17, wherein R.sup.a is at each occurrence independently from each other selected from the group consisting of: hydrogen, deuterium, Me, .sup.iPr, Bu, CN, CF.sub.3, Ph, which is optionally substituted with one or more substituents independently 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 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 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 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 selected from the group consisting of Me, .sup.iPr, .sup.tBu, CN, CF.sub.3, and Ph, and N(Ph).sub.2, which is optionally substituted with one or more substituents independently selected from the group consisting of Me, .sup.iPr, .sup.tBu, CN, CF.sub.3, and Ph; and wherein two or more adjacent substituents R.sup.a optionally form attachment points for a ring system selected from the group consisting of: ##STR00119## each dashed line indicating a direct bond connecting a respective ring system to the attachment points of two adjacent substituents R.sup.a such that the respective ring system is fused to the structure as shown in Formula II.

25. The organic molecule according to claim 17, comprising a structure of Formula III: ##STR00120## wherein R.sup.b is at each occurrence independently from each other 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.2-C.sub.57-heteroaryl, which is optionally substituted with one or more substituents R.sup.5.

26. An optoelectronic device comprising the organic molecule according to claim 17.

27. The optoelectronic device 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; down-conversion elements; and combinations thereof.

28. The optoelectronic device according to claim 26, wherein the optoelectronic device is an organic light-emitting diode and comprises the organic molecule in a light-emitting layer and/or in a layer that is directly adjacent to the light-emitting layer.

29. A composition, comprising: the organic molecule according to claim 17, a host material H.sup.B, which differs from the organic molecule.

30. The composition according to claim 29, further comprising, a fluorescence emitter F and/or a phosphorescence material P.sup.B, each of which differs from the organic molecule, wherein a fraction of the organic molecule in % by weight is higher than a fraction of the fluorescence emitter F and/or a fraction of the phosphorescence material P.sup.B in % by weight.

31. A method for producing an optoelectronic device, the method comprising depositing the organic molecule according to claim 17 by a vacuum evaporation method and/or a solution deposition method.

32. A method for generating light with a wavelength from 500 nm to 560 nm, the method comprising applying an electrical current to the optoelectronic device according to claim 26 to generate the light.

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

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

35. An optoelectronic device, comprising the composition according to claim 29 or a layer formed from the composition, wherein the optoelectronic device is at least one selected from the group consisting of organic light-emitting diodes (OLED), light-emitting electrochemical cells, OLED-sensors, organic diodes, organic solar cells, organic transistors, organic field-effect transistors, organic lasers, down-conversion elements, and combinations thereof.

36. An optoelectronic device, comprising the composition according to claim 30 or a layer formed from the composition, wherein the optoelectronic device is at least one selected from the group consisting of organic light-emitting diodes (OLED), light-emitting electrochemical cells, OLED-sensors, organic diodes, organic solar cells, organic transistors, organic field-effect transistors, organic lasers, down-conversion elements, and combinations thereof.

Description

EXAMPLES

General Synthesis Scheme

[0535] A further aspect of the invention relates to a process for preparing the organic molecules (with an optional subsequent reaction) of the invention, wherein a palladium catalyzed cross-coupling reaction is used:

Synthesis of E1

[0536] i)

##STR00072## [0537] iia)

##STR00073## [0538] or [0539] iib)

##STR00074##

[0540] According to the invention, a 1-fluorobenzene, which is substituted with a coupling group CG.sup.1 in 2-position and which is substituted with a coupling group CG.sup.2 in 4-position, is used as a reactant, which is reacted with two heterocycles, one substituted with a coupling group CG.sup.3 (reactant E3) and one with a coupling group CG.sup.4 (reactant E4). The coupling groups CG.sup.1 and CG.sup.4 are chosen as a reaction pair to introduce the heterocycle of E4 at the position of CG.sup.1. Accordingly, coupling groups CG.sup.2 and CG.sup.3 are chosen reaction pair for introducing the heterocycle of E3 at the position of CG.sup.2. Preferably, a so-called Suzuki coupling reaction is used. Here, either CG.sup.1 is chosen from Cl, Br, or I, and CG.sup.4 is a boronic acid group or a boronic acid ester group, in particular a boronic acid pinacol ester group, or CG.sup.1 is a boronic acid group or a boronic acid ester group, in particular a boronic acid pinacol ester group, and CG.sup.4 is chosen from Cl, Br, or I. Analogously, either CG.sup.2 is chosen from Cl, Br, or I, and CG.sup.3 is a boronic acid group or a boronic acid ester group, in particular a boronic acid pinacol ester group, or CG.sup.2 is a boronic acid group or a boronic acid ester group, in particular a boronic acid pinacol ester group, and CG.sup.3 is chosen from Cl, Br, or I. The person skilled in the art is aware that in order to introduce different heterocycles via the coupling reactions of E3 with E2 and E4 with E2, either first E2 is reacted with E3 and the resulting intermediate is subsequently reacted with E4 to yield E1, or first E2 is reacted with E4 and the resulting intermediate is subsequently reacted with E3 to yield E1. In this constellation, either CG.sup.1 and CG.sup.3 are independently from each other a boronic acid group or a boronic acid ester group and CG.sup.2 and CG.sup.4 are independently from each other chosen from Cl, Br, or I, or CG.sup.2 and CG.sup.4 are independently from each other a boronic acid group or a boronic acid ester group and CG.sup.1 and CG.sup.3 are independently from each other chosen from Cl, Br, or I.

Synthesis of D

##STR00075##

Synthesis of P

##STR00076##

[0541] For the reaction of a nitrogen heterocycle in a nucleophilic aromatic substitution with an aryl halide (Synthesis of P), preferably an aryl fluoride, typical conditions include the use of a base, such as tribasic potassium phosphate or sodium hydride, for example, in an aprotic polar solvent, such as dimethyl sulfoxide (DMSO) or N,N-dimethylformamide (DMF), for example.

[0542] An alternative synthesis route includes the introduction of a nitrogen heterocycle via copper- or palladium-catalyzed coupling to an aryl halide or aryl pseudohalide, preferably an aryl bromide, an aryl iodide, aryl triflate, or an aryl tosylate.

General Procedures for Synthesis:

AAV1Synthesis of D

##STR00077##

[0543] Under nitrogen atmosphere, o-xylene is added to D1 (1.00 equivalents, e.g., CAS 1438427-35-0), the diarylamine D2 (1.30 equivalents, e.g., CAS 122-39-4), tri-tert-butylphosphonium tetrafluoroborate (0.16 equivalents; CAS 131274-22-1), tris(dibenzylideneacetone)dipalladium(0) (0.04 equivalents, CAS 51364-51-3), and Sodium tert-butoxide (3.50 equivalents, CAS 865-48-5) followed by nitrogen-sparging for 10 min. The reaction mixture is stirred at 140 C. for 48 hours. After cooling to room temperature, activate charcoal and Celite (kieselgur) is added to the mixture, stirred for 15 minutes then filtered by vacuum suction. The filtrate is extracted with ethyl acetate and brine. The organic extracts are concentrated under reduced pressure. The resulting crude product is purified by column chromatography to afford D as a solid.

AAV2

[0544] E1 (1.0 equivalents), D (1.1 equivalents), and Potassium phosphate tribasic (2.2 equivalents) are dissolved under nitrogen atmosphere in DMSO and stirred at 100 C. for 42 h (reaction monitored via LC/MS and TLC). Subsequently, the reaction mixture is poured into a stirred mixture of water and ice. The resulting precipitate is filtered off and washed with water and ethanol. The crude product is purified by column chromatography or recrystallization to obtain the organic molecule according to the invention P as a solid.

Cyclic Voltammetry

[0545] Cyclic voltammograms are measured from solutions having concentration of 10.sup.3 mol/L of the respective compound (e.g., the organic molecules according to the present invention, TADF materials E.sup.B in general, host materials H.sup.B in general, phosphorescence materials P.sup.B in general, and fluorescence emitters F in general) 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 (i.e., (approximately) 20 C.) 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.

[0546] The HOMO and the LUMO data is corrected using ferrocene (FeCp.sub.2) as an internal standardwith the literature values of ferrocene used for this purpose.

Density Functional Theory Calculation

[0547] 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.

Photophysical Measurements

Sample Pretreatment: Spin-Coating

[0548] Unless stated otherwise, photophysical measurements of components are performed from spin-coated films of the respective component (e.g., the organic molecules according to the present invention, TADF materials E.sup.B in general, host materials H.sup.B in general, phosphorescence materials P.sup.B in general, and fluorescence emitters F in general) in poly(methyl methacrylate), PMMA. Unless stated differently, the concentration of the components in these spin-coated PMMA films is as follows: [0549] all organic molecules according to the present invention: 10% by weight in PMMA [0550] TADF materials E.sup.B as defined herein: 10% by weight in PMMA [0551] phosphorescence materials P.sup.B as defined herein: 10% by weight in PMMA [0552] fluorescence emitters F as defined herein that do not form part of the organic molecules according to the invention, in particular if they are small FWHM emitters S.sup.B in the context of the present invention: 1-5%, preferably 2%, by weight in PMMA.

[0553] However, host materials H.sup.B are not organic molecules according to the invention and that are not TADF materials E.sup.B or phosphorescence materials P.sup.B or fluorescence emitters F as defined herein, a spin-coated neat film of H.sup.B is used instead of a PMMA film.

[0554] Apparatus: Spin150, SPS euro.

[0555] The sample concentration is 1.0 mg/ml, typically dissolved in Toluene/DCM as suitable solvent.

[0556] Program: 7-30 sec. at 2000 U/min. After coating, the films are dried at 70 C. for 1 min.

Absorption Measurements

[0557] A Thermo Scientific Evolution 201 UV-Visible Spectrophotometer is used to determine the wavelength of the absorption maximum of the sample in the wavelength region above 270 nm. This wavelength is used as excitation wavelength for photoluminescence spectral and quantum yield measurements.

Photoluminescence Spectroscopy

[0558] For the measuring of Photoluminescence spectroscopy, a fluorescence spectrometer Fluoromax 4P from Horiba is used.

[0559] Steady state fluorescence spectra and phosphorescence spectra from phosphorescent emitters are recorded at room temperature. The basic scheme of operation is as follows: A continuous source of light (Xenon arc lamp) shines onto an excitation monochromator, which selects a suitable band of wavelengths. This monochromatic excitation light is directed onto the sample, which emits luminescence. If the sample is a spin coated or evaporated film, it is placed in a cuvette and kept under nitrogen atmosphere during the measurement. The luminescence is directed into a second, emission monochromator, which selects a band of wavelengths, being changed during measurement, and shines them onto a photon counting detector (R928P photomultiplier tube). The signal from the detector is reported to a system controller and host computer, where the data can be processed and presented.

[0560] Phosphorescent spectra from TADF emitters are recorded at 77 K. The basic scheme of operation is as follows: A pulsed source of light (pulsed xenon lamp) is used for excitation, operating at 25 Hz. A control module including a gate-and-delay generator is used to control the timing between excitation and detection. A typical sequence of data-acquisition starts with a flash from the pulsed lamp, sensed by the control module. The light enters an excitation monochromator, where it is dispersed. Monochromatic light from the monochromator excites the sample. The sample is placed in a glass dewar container that is filled with liquid nitrogen during the measurement. Luminescence emission from the sample then passes through an emission monochromator to a photon counting photomultiplier-tube detector. The control module intercepts the signal from the detector and collects only a gated portion of the signal only the flash (the initial delay) for a pre-determined length of sampling time (the sample window). Any signal arriving before or after the gating is ignored. The initial delay can be varied between 0 and 10000 ms and is set to exclude any contribution from initial fluorescent emission and lamp decay, preferably 50 ms. The sample window may be varied between 0.01 and 10000 ms and is set to gather phosphorescent emission, preferably 40 ms.

Time-Resolved (Transient) Photoluminescence (PL) Spectroscopy in the s-Range and ns-Range (FS5)

[0561] Time-resolved PL measurements are performed on a 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. As continuous light source, the spectrometer includes a 150 W xenon arc lamp and specific wavelengths may be selected by a Czerny-Turner monochromator. However, the standard measurements are instead performed using an external VPLED variable pulsed LED with an emission wavelength of 310 nm. 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 and 870 nm. The detector is a temperature stabilized PMT, providing dark counts below 300 cps (counts per second).

[0562] Data acquisition is made using the well-established technique of time correlated single photon counting (TCSPC). The FS5 is equipped with an emission monochromator, a temperature stabilized photomultiplier as detector unit and a pulsed LED (310 nm central wavelength, 910 s pulse width) as excitation source. If the sample is a spin coated or evaporated film, it is placed in a cuvette and kept under nitrogen atmosphere during the measurement.

[0563] To determine the average decay time i of a measured transient photoluminescence signal, the data is fitted with a sum of n exponential functions:

[00003]${.Math.}_{i=1}^n{A}_i\exp \left(-\frac{t}{t_i}\right),$ [0564] wherein n is between 1 and 3. By weighting the specific lifetimes .sub.i with the corresponding amplitudes A.sub.i, the delayed fluorescence lifetime .sub.DF is determined:

[00004]${}_{\mathrm{DF}}=\frac{{.Math.}_{i=1}^n{A}_i{}_i}{{.Math.}_{i=1}^n{A}_i}.$

TCSPC (Time-Correlated Single-Photon Counting)

[0565] Excited state population dynamics are determined employing Edinburgh Instruments FS5 Spectrofluorometers, equipped with an emission monochromator, a temperature stabilized photomultiplier as detector unit and a pulsed LED (310 nm central wavelength, 910 s pulse width) as excitation source. The samples are placed in a cuvette and flushed with nitrogen during the measurements.

Full Decay Dynamics

[0566] The full excited state population decay dynamics over several orders of magnitude in time and signal intensity is achieved by carrying out TCSPC measurements in 4 time windows: 200 ns, 1 s, and 20 s, and a longer measurement spanning >80 s. The measured time curves are then processed in the following way:

[0567] A background correction is applied by determining the average signal level before excitation and subtracting.

[0568] The time axes are aligned by taking the initial rise of the main signal as reference.

[0569] The curves are scaled onto each other using overlapping measurement time regions.

[0570] The processed curves are merged to one curve.

Data Analysis

[0571] Data analysis is done using mono-exponential and bi-exponential fitting of prompt fluorescence (PF) (usually in the order of nanoseconds) and delayed fluorescence (DF) (usually in the order of microseconds) decays separately. The ratio of delayed fluorescence to prompt fluorescence (n-value) is calculated by the integration of respective photoluminescence decays in time.

[00005]$\frac{I_{\mathrm{DF}}\left(t\right)\mathrm{dt}}{I_{\mathrm{PF}}\left(t\right)\mathrm{dt}}=n$

[0572] The average excited state life time is calculated by taking the average of prompt and delayed fluorescence decay time, weighted with the respective contributions of PF and DF.

Photoluminescence Quantum Yield Measurements

[0573] For photoluminescence quantum yield (PLQY) measurements, an Absolute PL Quantum Yield Measurement C9920-03G system (Hamamatsu Photonics) is used. Quantum yields and CIE coordinates are determined using the software U6039-05 version 3.6.0.

[0574] Emission maxima are given in nm, quantum yields 0 in % and CIE coordinates as x,y values.

[0575] The photoluminescence quantum yield (PLQY) is determined using the following protocol:

[0576] Quality assurance: Anthracene in ethanol (known concentration) is used as reference.

[0577] Excitation wavelength: the absorption maximum of the organic molecule is determined and the molecule is excited using this wavelength

Measurement

[0578] Quantum yields are measured at room temperature (i.e., (approximately) 20 C.) from the aforementioned spin-coated films under nitrogen atmosphere. The PLQY is calculated using the following equation:

[00006]${}_{\mathrm{PL}}=\frac{n_{\mathrm{photon}},\mathrm{emitted}}{n_{\mathrm{photon}},\mathrm{absorbed}}=\frac{{}_{{}_3}^{{}_4}\frac{}{\mathrm{hc}}\left[I_{\mathrm{sample}}\left(\right)-I_{\mathrm{reference}}\left(\right)\right]d}{{}_{{}_1}^{{}_2}\frac{}{\mathrm{hc}}\left[I_{\mathrm{reference}}\left(\right)-I_{\mathrm{sample}}\left(\right)\right]d},$

[0579] wherein n.sub.photon denotes the photon count and I the intensity. The index reference refers to a reference measurement without the emitting sample, the index sample refers to a measurement with the emitting sample. The wavelengths .sub.1 and .sub.2 mark the region of the excitation light, the wavelengths .sub.3 and .sub.4 mark the region of the sample emission.

Production and Characterization of Optoelectronic Devices

[0580] Via vacuum-deposition methods OLED devices including organic molecules according to the invention can be produced. 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%.

[0581] 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, LT97 to the time point, at which the measured luminance decreased to 97% of the initial luminance etc.

[0582] Accelerated lifetime measurements are performed (e.g., applying increased current densities). Exemplarily LT80 values at 500 cd/m.sup.2 are determined using the following equation:

[00007]$\mathrm{LT}80\left(500\frac{{\mathrm{cd}}^2}{m^2}\right)=\mathrm{LT}80\left(L_0\right){\left(\frac{L_0}{500\frac{{\mathrm{cd}}^2}{m^2}}\right)}^{1.6}$ [0583] wherein L.sub.0 denotes the initial luminance at the applied current density.

[0584] The values correspond to the average of several pixels (typically two to eight), the standard deviation between these pixels is given. Figures show the data series for one OLED pixel.

HPLC-MS

[0585] The purity of organic compounds can be assessed using high pressure liquid chromatography (HPLC) coupled with mass spectrometry (MS). Such HPLC-MS measurements were performed using a HPLC1260 Infinity HPLC-MS system by Agilent with a single quadrupole MS-detector. 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 45 C. and a typical gradient is as follows:

TABLE-US-00001 Flow rate [ml/min] Time [min] A[%] B[%] C[%] 2.1 0.0 40 50 10 2.1 1.00 40 50 10 2.1 3.50 10 65 25 2.1 6.00 10 40 50 2.1 8.00 10 10 80 2.1 11.50 10 10 80 2.1 11.51 40 50 10 2.1 12.50 40 50 10 [0586] and the following solvent mixtures (all solvents contain 0.1% (VN) of formic acid):

TABLE-US-00002 Solvent A: H.sub.2O (10%) MeCN (90%) Solvent B: H.sub.2O (90%) MeCN (10%) Solvent C: THF (50%) MeCN (50%)

[0587] An injection volume of 2 L of a solution with a concentration of 0.5 mg/mL of the analyte is used for the measurements.

[0588] 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.

Example 1

##STR00078##

[0589] Example 1 was synthesized according to

[0590] AAV1 (yield: 25%), wherein

##STR00079##

was used as reactant D1, and diphenylamine was used reactant as D2 (CAS 122-39-4).

[0591] AAV2 (yield: 42%), wherein

##STR00080##

was used as reactant E1 in the reaction with D.

[0592] MS (HPLC-MS), m/z (retention time): 757 (5.9 min).

[0593] The emission spectrum of example 1 (10% by weight in PMMA) at room temperature (i.e., approximately 20 C.) has an emission maximum (.sub.max) at 508 nm. The photoluminescence quantum yield (PLQY) is 71%. The resulting CIE.sub.x coordinate is determined at 0.27 and the CIE.sub.y coordinate at 0.49.

Example 2

##STR00081##

[0594] Example 2 was synthesized according to

[0595] AAV1 yield: 33%), wherein

##STR00082##

was used as reactant D1, and diphenylamine was used reactant as D2 (CAS 122-39-4).

[0596] AAV2 (yield: 56%), wherein

##STR00083##

was used as reactant E1 in the reaction with D.

[0597] MS (HPLC-MS), m/z (retention time): 820 (6.2 min).

[0598] The emission spectrum of example 2 (10% by weight in PMMA) at room temperature (i.e., approximately 20 C.) has an emission maximum (.sub.max) at 524 nm. The photoluminescence quantum yield (PLQY) is 61%. The resulting CIE.sub.x coordinate is determined at 0.31 and the CIE.sub.y coordinate at 0.51.

Example 3

##STR00084##

[0599] Example 3 was synthesized according to

[0600] AAV1 (yield: 46%), wherein

##STR00085##

was used as reactant D1, and diphenylamine was used reactant as D2 (CAS 122-39-4).

[0601] AAV2 (yield: 69%), wherein

##STR00086##

was used as reactant E1 in the reaction with D.

[0602] MS (HPLC-MS), m/z (retention time): 819 (5.9 min).

[0603] The emission spectrum of example 3 (10% by weight in PMMA) at room temperature (i.e., approximately 20 C.) has an emission maximum (.sub.max) at 501 nm. The photoluminescence quantum yield (PLQY) is 75%. The resulting CIE.sub.x coordinate is determined at 0.25 and the CIE.sub.y coordinate at 0.46.

Example 4

##STR00087##

[0604] Example 4 was synthesized according to

[0605] AAV1 (yield: 46%), wherein

##STR00088##

was used as reactant D1, and diphenylamine was used reactant as D2 (CAS 122-39-4).

[0606] AAV2 (yield: 40%), wherein

##STR00089##

was used as reactant E1 in the reaction with D.

[0607] MS (HPLC-MS), m/z (retention time): 896 (6.7 min).

[0608] The emission spectrum of example 4 (10% by weight in PMMA) at room temperature (i.e., approximately 20 C.) has an emission maximum (.sub.max) at 500 nm. The photoluminescence quantum yield (PLQY) is 77%. The resulting CIE.sub.x coordinate is determined at 0.24 and the CIE.sub.y coordinate at 0.45.

Example OLED Devices

Stack Material

##STR00090## ##STR00091## ##STR00092##

[0609] Example 2 was tested in the OLED D1 and OLED D2, which was fabricated with the following layer structure:

TABLE-US-00003 Layer # Thickness D1 D2 9 100 nm Al Al 8 2 nm Liq Liq 7 20 nm ETM1 (50%):Liq ETM1 (50%):Liq (50%) (50%) 6 10 nm ETM2 ETM2 5 50 nm Host1 (70%):Example 2 Host1 (67%):Phos1 (30%) (3%):Example 2 (30%) 4 10 nm EBM1 EBM1 3 60 nm NPB NPB 2 9 nm NPB (95%):NDP-9 NPB (95%):NDP-9 (5%) (5%) 1 50 nm ITO ITO Substrate Glass Glass

[0610] OLED D1 yielded an external quantum efficiency (EQE) at 1000 cd/m.sup.2 of 19.9%. The emission maximum is at 541 nm with a FWHM of 92 nm at 3.7 V. The corresponding CIEx value is 0.380 and the CIEy value is 0.576.

[0611] OLED D2 yielded an external quantum efficiency (EQE) at 1000 cd/m.sup.2 of 20.42%. The emission maximum is at 538 nm with a FWHM of 90 nm at 5.2 V. The corresponding CIEx value is 0.376 and the CIEy value is 0.587.

[0612] Example 3 was tested in the OLED D3, which was fabricated with the following layer structure:

TABLE-US-00004 Layer # Thickness D3 9 100 nm Al 8 2 nm Liq 7 20 nm ETM1 (50%):Liq (50%) 6 10 nm ETM2 5 50 nm Host1 (66%):Phos1 (3%):Example 3 (30%):Fluo1 (1%) 4 10 nm EBM1 3 60 nm NPB 2 9 nm NPB (95%):NDP-9 (5%) 1 50 nm ITO Substrate Glass

[0613] OLED D3 yielded an external quantum efficiency (EQE) at 1000 cd/m.sup.2 of 27.3%. The emission maximum is at 532 nm with a FWHM of 38 nm at 5.2 V. The corresponding CIEx value is 0.320 and the CIEy value is 0.648.

Additional Examples of Organic Molecules of the Invention

##STR00093## ##STR00094## ##STR00095## ##STR00096## ##STR00097## ##STR00098## ##STR00099## ##STR00100## ##STR00101## ##STR00102## ##STR00103## ##STR00104## ##STR00105## ##STR00106## ##STR00107## ##STR00108##