ORGANIC MOLECULES FOR USE IN OPTOELECTRONIC DEVICES

Abstract

The invention relates to an organic compound, in particular for the application in optoelectronic devices. According to the invention, the organic compound has a structure of Formula I,

##STR00001## wherein n is 0 or 1; m=1-n; X is N or CR.sup.X; V is N or CR.sup.V; Z is N or CR.sup.II; R.sup.1 and R.sup.2 are independently from each other selected from the group consisting of: C.sub.1-C.sub.5-alkyl, which is optionally substituted with one or more substituents R.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.

Claims

1. An organic molecule having a structure of Formula I: ##STR00020## wherein n is 0 or 1; m=1-n; X is N or CR.sup.X; V is N or CR.sup.V; Z is N or CR.sup.II; W is selected from the group consisting of Si(R.sup.3).sub.2, C(R.sup.3).sub.2 and BR.sup.3; R.sup.1, R.sup.2 and R.sup.3 is independently from each other selected from the group consisting of: C.sub.1-C.sub.5-alkyl, which is optionally substituted with one or more substituents R.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.I, R.sup.II, R.sup.III, R.sup.IV, R.sup.V, R.sup.VI, R.sup.VII, R.sup.VIII, R.sup.IX, R.sup.X, and R.sup.XI are 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, halogen, 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 another selected from the group consisting of: hydrogen, deuterium, OPh, CF.sub.3, CN, F, C.sub.1-C.sub.5-alkyl, wherein optionally one or more hydrogen atoms are independently from each other substituted by deuterium, CN, CF.sub.3, or F; C.sub.1-C.sub.5-alkoxy, wherein optionally one or more hydrogen atoms are independently from each other substituted by deuterium, CN, CF.sub.3, or F; C.sub.1-C.sub.5-thioalkoxy, wherein optionally one or more hydrogen atoms are independently from each other substituted by deuterium, CN, CF.sub.3, or F; C.sub.2-C.sub.5-alkenyl, wherein optionally one or more hydrogen atoms are independently from each other substituted by deuterium, CN, CF.sub.3, or F; C.sub.2-C.sub.5-alkynyl, wherein optionally one or more hydrogen atoms are 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); R.sup.6 is at each occurrence independently from another selected from the group consisting of hydrogen, deuterium, OPh, CF.sub.3, CN, F, C.sub.1-C.sub.5-alkyl, wherein optionally one or more hydrogen atoms are independently from each other substituted by deuterium, CN, CF.sub.3, or F; C.sub.1-C.sub.5-alkoxy, wherein optionally one or more hydrogen atoms are independently from each other substituted by deuterium, CN, CF.sub.3, or F; C.sub.1-C.sub.5-thioalkoxy, wherein optionally one or more hydrogen atoms are independently from each other substituted by deuterium, CN, CF.sub.3, or F; C.sub.2-C.sub.5-alkenyl, wherein optionally one or more hydrogen atoms are independently from each other substituted by deuterium, CN, CF.sub.3, or F; C.sub.2-C.sub.5-alkynyl, wherein optionally one or more hydrogen atoms are 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); wherein at least one substituent selected from the group consisting of R.sup.I, R.sup.II, R.sup.III, R.sup.IV, R.sup.V, R.sup.VI, R.sup.VII, R.sup.VI, R.sup.IX, R.sup.X, and R.sup.XI optionally forms a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system with one or more substituents of the same group that is/are positioned adjacent to the at least one substituent.

2. The organic molecule according to claim 1, wherein n is 0, X is N, V is N and Z is N.

3. The organic molecule according to claim 1, wherein n is 0, X is CR.sup.X, V is CR.sup.V and Z is CR.sup.II.

4. The organic molecule according to claim 1, wherein R.sup.I, R.sup.II, R.sup.III, R.sup.IV, R.sup.V, R.sup.VI, R.sup.VII, R.sup.VIII, R.sup.IX, R.sup.X and R.sup.XI are independently selected from the group consisting of: hydrogen, deuterium, halogen, 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; R.sup.1 and R.sup.2 each independently from each other are selected from the group consisting of C.sub.1-C.sub.5-alkyl, which is optionally substituted with one or more substituents R.sup.6; C.sub.6-C.sub.30-aryl, which is optionally substituted with one or more substituents R.sup.6; and C.sub.3-C.sub.30-heteroaryl, which is optionally substituted with one or more substituents R.sup.6.

5. The organic molecule according to claim 4, wherein R.sup.I, R.sup.III, R.sup.IV, R.sup.V, R.sup.IX, and R.sup.X are independently selected from the group consisting of: hydrogen, deuterium, halogen, 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, and 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 R.sup.II, R.sup.V, R.sup.VII, R.sup.VIII and R.sup.X are independently selected from the group consisting of: hydrogen, deuterium, Me, .sup.iPr, .sup.tBu, 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, 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, and N(Ph).sub.2.

6. The organic molecule according to claim 5, wherein R.sup.I, R.sup.III, R.sup.IV, R.sup.VI, R.sup.IX, and R.sup.XI are independently selected from the group consisting of: hydrogen, deuterium, Me, .sup.iPr, .sup.tBu, CN, CF.sub.3, and 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; and R.sup.II, R.sup.V, R.sup.VII, R.sup.VIII and R.sup.X are independently selected from the group consisting of hydrogen, deuterium, Me, .sup.iPr, .sup.tBu, 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, and Ph; carbazolyl, which is optionally substituted with one or more substituents independently from each other selected from the group consisting of Me, .sup.tBu, and Ph; and N(Ph).sub.2.

7. The organic molecule according to claim 1, wherein R.sup.1 and R.sup.2 independently from each other are C.sub.6-C.sub.30-aryl, 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.

8. The organic molecule according to claim 7, wherein R.sup.1 and R.sup.2 are each independently phenyl or mesityl.

9. The organic molecule according to claim 1, having a structure of one of Formulas II to XXVII: ##STR00021## ##STR00022## ##STR00023## ##STR00024## ##STR00025## ##STR00026## ##STR00027##

10.-15. (canceled)

16. A composition comprising: (a) at least one organic molecule according to claim 1 as an emitter and/or host; (b) one or more emitter and/or host materials different from the at least one organic molecule according to claim 1, and (c) optionally one or more dyes and/or one or more solvents.

17. An optoelectronic device comprising the organic molecule according to claim 1, wherein the optoelectronic device is an organic light-emitting diode, light-emitting electrochemical cell, organic light-emitting sensor, an organic diode, an organic solar cell, an organic transistor, an organic field-effect transistor, an organic laser or a down-conversion element.

18. The optoelectronic device according to claim 17, comprising: a substrate; an anode; a cathode, wherein the anode or the cathode is applied to the substrate; and at least one light-emitting layer disposed between the anode and the cathode and which comprises the organic molecule.

19. An optoelectronic device comprising the organic molecule according to claim 1, wherein the organic molecule is one of a luminescent emitter, an electron transport material, a hole injection material or a hole blocking material in the optoelectronic device.

20. The optoelectronic device according to claim 19, wherein the optoelectronic device is an organic light-emitting diode, light-emitting electrochemical cell, organic light-emitting sensor, an organic diode, an organic solar cell, an organic transistor, an organic field-effect transistor, an organic laser or a down-conversion element.

21. An optoelectronic device comprising the organic molecule according to claim 2, wherein the optoelectronic device is an organic light-emitting diode, light-emitting electrochemical cell, organic light-emitting sensor, an organic diode, an organic solar cell, an organic transistor, an organic field-effect transistor, an organic laser or a down-conversion element.

22. The optoelectronic device according to claim 21, comprising: a substrate; an anode; a cathode, wherein the anode or the cathode is applied to the substrate; and at least one light-emitting layer disposed between the anode and the cathode and which comprises the organic molecule.

23. An optoelectronic device comprising the composition according to claim 14, wherein the optoelectronic device is an organic light-emitting diode, light-emitting electrochemical cell, organic light-emitting sensor, an organic diode, an organic solar cell, an organic transistor, an organic field-effect transistor, an organic laser or a down-conversion element.

24. The optoelectronic device according to claim 23, comprising: a substrate; an anode; a cathode, wherein the anode or the cathode is applied to the substrate; and at least one light-emitting layer disposed between the anode and the cathode and which comprises the composition.

25. A process for producing an optoelectronic device, comprising processing of the organic molecule according to claim 1 by a vacuum evaporation method or from a solution.

26. A process for producing an optoelectronic device, comprising processing of the composition according to claim 16 by a vacuum evaporation method or from a solution.

Description

EXAMPLES

[0204] ##STR00014##

General Procedure for Synthesis:

[0205] I0 (1.00 equivalents) was dissolved in diethyl ether and the solution was cooled to 30 C. tert-Butyllithium (.sup.tBuLi) (4.00 equivalents) was added dropwise and the reaction mixture was allowed to warm up to 0 C. After stirring for 30 minutes at 0 C., the reaction mixture was cooled again to 30 C.

[0206] A solution of boron tribromide (BBr.sub.3, 2.2 equivalents) was added dropwise, the bath was removed and the reaction mixture was allowed to warm to room temperature (rt). Subsequently, the reaction mixture was heated at reflux at 120 C. for 5 h. Volatiles were removed under reduced pressure to obtain I1.

[0207] A solution of Grignard compound/compounds [R.sup.1MgBr (1.2 equivalents)/R.sup.2MgBr (1.2 equivalents)] was added dropwise to I1 over a period of 30 min. After stirring for 1 h, MeOH was added to the reaction mixture and the solvents were evaporated under reduced pressure. The residue was dissolved in toluene and filtered with a pad of silica gel (toluene was used as eluent). The solvent was removed under reduced pressure. The crude product was dissolved in a minimum amount of toluene and then a small amount of heptane was added. The resulting precipitate was filtered to obtain Z1 as a solid product.

Cyclic Voltammetry

[0208] 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 SCE.

Density Functional Theory Calculation

[0209] Molecular structures are optimized employing the BP86 functional and the resolution of identity approach (R.sup.I). 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

[0210] Sample pretreatment: Spin-coating

[0211] Apparatus: Spin150, SPS euro.

[0212] The sample concentration is 10 mg/ml, dissolved in a suitable solvent.

[0213] Program: 1) 3 s at 400 U/min; 20 s at 1000 U/min at 1000 Upm/s. 3) 10 s at 4000 U/min at 1000 Upm/s. After coating, the films are tried at 70 C. for 1 min.

Photoluminescence Spectroscopy and TCSPC (Time-Correlated Single-Photon Counting)

[0214] Steady-state emission spectroscopy is measured by a Horiba Scientific, Modell FluoroMax-4 equipped with a 150 W Xenon-Arc lamp, excitation- and emissions monochromators and a Hamamatsu R928 photomultiplier and a time-correlated single-photon counting option. Emissions and excitation spectra are corrected using standard correction fits.

[0215] Excited state lifetimes are determined employing the same system using the TCSPC method with FM-2013 equipment and a Horiba Yvon TCSPC hub.

[0216] Excitation sources:

NanoLED 370 (wavelength: 371 nm, puls duration: 1.1 ns)
NanoLED 290 (wavelength: 294 nm, puls duration: <1 ns)
SpectraLED 310 (wavelength: 314 nm)
SpectraLED 355 (wavelength: 355 nm).

[0217] Data analysis (exponential fit) is done using the software suite DataStation and DAS6 analysis software. The fit is specified using the chi-squared-test.

Photoluminescence Quantum Yield Measurements

[0218] 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.

[0219] Emission maxima are given in nm, quantum yields Q) in % and CIE coordinates as x,y values. PLQY is determined using the following protocol: [0220] 1) Quality assurance: Anthracene in ethanol (known concentration) is used as reference [0221] 2) Excitation wavelength: the absorption maximum of the organic molecule is determined and the molecule is excited using this wavelength [0222] 3) Measurement [0223] Quantum yields are measured, for sample, of solutions or films under nitrogen atmosphere. The yield is calculated using the equation:

[00001]${}_{P.Math.L}=\frac{n_{\mathrm{photon}},\mathrm{emited}}{n_{\mathrm{photon}},\mathrm{absorbed}}=\frac{\frac{}{h.Math.c}\left[{\mathrm{Int}}_{\mathrm{emitted}}^{\mathrm{sample}}\left(\right)-{\mathrm{Int}}_{\mathrm{absorbed}}^{\mathrm{sample}}\left(\right)\right].Math.d.Math.}{\frac{}{h.Math.c}\left[{\mathrm{Int}}_{\mathrm{emitted}}^{\mathrm{reference}}\left(\right)-{\mathrm{Int}}_{\mathrm{emitted}}^{\mathrm{reference}}\left(\right)\right].Math.d.Math.}$ [0224] wherein n.sub.photon denotes the photon count and Int. the intensity.

Production and Characterization of Organic Electroluminescence Devices

[0225] OLED devices comprising 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%.

[0226] 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. 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:

[00002]$\mathrm{LT}.Math..Math.80.Math.\left(5.Math.0.Math.0.Math.\frac{c.Math.d^2}{m^2}\right)=L.Math.T.Math.8.Math.0.Math.\left(L_0\right).Math.{\left(\frac{L_0}{5.Math.0.Math.0.Math.\frac{c.Math.d^2}{m^2}}\right)}^{1.6}$

wherein L.sub.0 denotes the initial luminance at the applied current density.

[0227] The values correspond to the average of several pixels (typically two to eight), the standard deviation between these pixels is given.

HPLC-MS:

[0228] HPLC-MS spectroscopy is performed on a HPLC by Agilent (1100 series) with MS-detector (Thermo LTQ XL). A reverse phase column 4.6 mm150 mm, particle size 5.0 m from Waters (without pre-column) is used in the HPLC. The HPLC-MS measurements are performed at room temperature (rt) with the solvents acetonitrile, water and THF in the following concentrations:

TABLE-US-00001 solvent A: H.sub.2O (90%) MeCN (10%) solvent B: H.sub.2O (10%) MeCN (90%) solvent C: THF (100%)

[0229] From a solution with a concentration of 0.5 mg/ml an injection volume of 15 L is taken for the measurements. The following gradient is used:

TABLE-US-00002 Flow rate [ml/min] time [min] A [%] B [%] D [%] 3 0 40 50 10 3 10 10 15 75 3 16 10 15 75 3 16.01 40 50 10 3 20 40 50 10
Ionisation of the probe is performed by APCI (atmospheric pressure chemical ionization).

Example 1

[0230] ##STR00015##

[0231] Example 1 was synthesized according to the general procedure for synthesis, wherein 2,6-dichloro-N,N-diphenylbenzeneamine and 2-mesitylmagensium bromide solution (1.0 mol/I in THF) were used as reactants.

Additional Examples of Organic Molecules of the Invention

[0232] ##STR00016## ##STR00017## ##STR00018## ##STR00019##