ORGANIC MOLECULES FOR USE IN OPTOELECTRONIC DEVICES

Abstract

An organic molecule is disclosed having a structure of Formula I:

##STR00001##

wherein X is O or S; Y is O or S; R.sup.1 is selected from the group consisting of: hydrogen, deuterium, C.sub.1-C.sub.5-alkyl, which is optionally substituted with one or more substituents R.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.

Claims

1. An organic molecule having a structure of Formula ##STR00031## wherein X is O or S; Y is O or S; R.sup.1 is selected from the group consisting of: hydrogen, deuterium, C.sub.1-C.sub.5-alkyl, which is optionally substituted with one or more substituents R.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.2, R.sup.3, and R.sup.4 are independently from each other selected from the group consisting of: hydrogen, deuterium, C.sub.1-C.sub.40-alkyl, which is optionally substituted with one or more substituents R.sup.5; C.sub.1-C.sub.40-alkoxyl, which is optionally substituted with one or more substituents R.sup.5; C.sub.2-C.sub.40-alkenyl, which is optionally substituted with one or more substituents R.sup.5; C.sub.2-C.sub.40-alkynyl, which is optionally substituted with one or more substituents R.sup.5; C.sub.6-C.sub.60-aryl, which is optionally substituted with one or more substituents R.sup.5; C.sub.3-C.sub.57-heteroaryl, which is optionally substituted with one or more substituents R.sup.5; CN; CF.sub.3; N(R.sup.5).sub.2; OR.sup.5, and Si(R.sup.5).sub.3; R.sup.I, R.sup.II, R.sup.III, R.sup.IV, R.sup.V and R.sup.VI is independently from each other selected from the group consisting of: hydrogen, deuterium, C.sub.1-C.sub.40-alkyl, which is optionally substituted with one or more substituents R.sup.5; C.sub.1-C.sub.40-alkoxyl, which is optionally substituted with one or more substituents R.sup.5; C.sub.2-C.sub.40-alkenyl, which is optionally substituted with one or more substituents R.sup.5; C.sub.2-C.sub.40-alkynyl, which is optionally substituted with one or more substituents R.sup.5; C.sub.6-C.sub.60-aryl, which is optionally substituted with one or more substituents R.sup.5; C.sub.3-C.sub.57-heteroaryl, which is optionally substituted with one or more substituents R.sup.5; CN; CF.sub.3; N(R.sup.5).sub.2; OR.sup.5, and Si(R.sup.5).sub.3; 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.1-heteroaryl)(C.sub.6-C.sub.18-aryl).

2. The organic molecule according to claim 1, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.I, R.sup.II, R.sup.III, R.sup.IV, R.sup.V and R.sup.VI are independently from 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.

3. The organic molecule according to claim 1, wherein R.sup.2, R.sup.4, R.sup.I, R.sup.II, R.sup.III, R.sup.V, and R.sup.VI 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.3, R.sup.II, and R.sup.V is independently from another 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.

4. The organic molecule according to claim 3, wherein R.sup.2, R.sup.4, R.sup.I, R.sup.II, R.sup.III, R.sup.IV, and R.sup.VI 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; R.sup.3, R.sup.II and R.sup.V is independently from another 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.

5. The organic molecule according to claim 1, wherein R.sup.1 is 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.

6. The organic molecule according to claim 5, wherein R.sup.1 is phenyl or mesityl.

7. The organic molecule according to claim 1, comprising a structure of one of Formulas II to XXI: ##STR00032## ##STR00033## ##STR00034## ##STR00035## ##STR00036## ##STR00037##

8.-13. (canceled)

14. 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.

15. 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.

16. The optoelectronic device according to claim 15, 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.

17. 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.

18. The optoelectronic device according to claim 17, 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.

19. 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.

20. The optoelectronic device according to claim 19, 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.

21. An optoelectronic device comprising the organic molecule according to claim 2, 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.

22. The optoelectronic device according to claim 21, 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.

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 14 by a vacuum evaporation method or from a solution.

Description

EXAMPLES

[0284] ##STR00013## ##STR00014## ##STR00015## ##STR00016##

[0285] General Procedure for Synthesis:

[0286] Synthesis of Z1:

[0287] E1 (1.1 equivalents), E2 (1.1 equivalents), E3 (1.0 equivalent), K.sub.2CO.sub.3 (4.0 equivalents) and copper powder (6.0 equivalents) were mixed in dry o-dichlorobenzene (ODCB) and stirred at 180 C. for 110 h. The insoluble materials were filtered off and washed with CH.sub.2Cl.sub.2. The combined filtrate was washed with water and extracted with CH.sub.2Cl.sub.2. The organic phase was dried over MgSO.sub.4, filtered off, and concentrated under reduced pressure. The obtained crude product was washed with hexane to give Z1.

[0288] Synthesis of Z2:

[0289] To a microwave tube was added Z1 (1.0 equivalent) and 1-n-butyl-3-methylimidazolium bromide ([bmim][Br]; 3.0 equivalents). The reaction tube was flushed with argon and then was irradiated at 20 W for the 10 min with air-flow cooling to prevent overheating. After cooled to room temperature, the reaction mixture was acidified with 1 M HCl solution and extracted with ethyl acetate. The combined organic layer was washed with water and brine, and dried over anhydrous MgSO.sub.4 and the solvent was evaporated under vacuum. Crude product was purified on silica gel to afford Z2.

[0290] Synthesis of Z3:

[0291] Z2 (1.0 equivalent) was dissolved in DMF. K.sub.2CO.sub.3 (3.0 equivalents) was added and the mixture was stirred at 100 C. for 19 h. After addition of 1 mol/L HCl, the products were extracted with CH.sub.2Cl.sub.2. The organic phase was dried over Na.sub.2SO.sub.4, filtered off, and concentrated under reduced pressure. The obtained crude product was purified by silica gel short column chromatography (CH.sub.2Cl.sub.2) to give Z3.

[0292] Synthesis of P1:

[0293] Z3 (1.00 equivalents) was dissolved in diethyl ether and the solution was cooled to 78 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 78 C.

[0294] A solution of boronate ester compound [R.sup.1B(OMe).sub.2 (1.2 equivalents)] in diethyl ether 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 overnight. Volatiles were removed under reduced pressure and the crude purified by column chromatography to afford the compound P1 as a solid product.

[0295] Cyclic Voltammetry

[0296] 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.

[0297] Density Functional Theory Calculation

[0298] 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.

[0299] Photophysical Measurements

[0300] Sample pretreatment: Spin-coating

[0301] Apparatus: Spin150, SPS euro.

[0302] The sample concentration is 10 mg/ml, dissolved in a suitable solvent.

[0303] 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.

[0304] Photoluminescence Spectroscopy and TCSPC (Time-Correlated Single-Photon Counting)

[0305] 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.

[0306] Excited state lifetimes are determined employing the same system using the TCSPC method with FM-2013 equipment and a Horiba Yvon TCSPC hub.

[0307] Excitation Sources:

[0308] NanoLED 370 (wavelength: 371 nm, puls duration: 1.1 ns)

[0309] NanoLED 290 (wavelength: 294 nm, puls duration: <1 ns)

[0310] SpectraLED 310 (wavelength: 314 nm)

[0311] SpectraLED 355 (wavelength: 355 nm).

[0312] Data analysis (exponential fit) is done using the software suite DataStation and DAS6 analysis software. The fit is specified using the chi-squared-test.

[0313] Photoluminescence Quantum Yield Measurements

[0314] 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.

[0315] Emission maxima are given in nm, quantum yields in % and CIE coordinates as x,y values. PLQY is determined using the following protocol: [0316] 1) Quality assurance: Anthracene in ethanol (known concentration) is used as reference [0317] 2) Excitation wavelength: the absorption maximum of the organic molecule is determined and the molecule is excited using this wavelength [0318] 3) Measurement [0319] Quantum yields are measured, for sample, of solutions or films under nitrogen atmosphere. The yield is calculated using the equation:

[00001]${}_{P.Math.L}=\frac{n_{\mathrm{photon}},\mathrm{emi}.Math.t.Math.e.Math.d}{n_{\mathrm{photon}},\mathrm{absorbed}}=\frac{\frac{}{h.Math.c}\left[{\mathrm{Int}}_{\mathrm{emitted}}^{\mathrm{smple}}\left(\right)-I.Math.n.Math.t_{.Math.b.Math.\mathrm{sorbed}}^{\mathrm{smple}}\left(\right)\right].Math.d.Math.}{\frac{}{h.Math.c}\left[I.Math.n.Math.t_{\mathrm{emitted}}^{\mathrm{reference}}\left(\right)-I.Math.n.Math.t_{.Math.b.Math.\mathrm{sorbed}}^{\mathrm{reference}}\left(\right)\right].Math.d.Math.}$ [0320] wherein n.sub.photon denotes the photon count and Int. the intensity.

[0321] Production and Characterization of Optoelectronic Devices

[0322] Optoelectronic devices, such as 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%.

[0323] 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). Exemplarily LT80 values at 500 cd/m.sup.2 are determined using the following equation:

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

[0324] wherein L.sub.0 denotes the initial luminance at the applied current density.

[0325] The values correspond to the average of several pixels (typically two to eight), the standard deviation between these pixels is given.

[0326] HPLC-MS:

[0327] 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:

[0328] solvent A: H.sub.2O (90%) MeCN (10%)

[0329] solvent B: H.sub.2O (10%) MeCN (90%) [0330] THF

[0331] solvent C: (100%)

[0332] 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-00001 Flow rate time A B D [ml/min] [min] [%] [%] [%] 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

[0333] ##STR00017##

[0334] Example 1 was synthesized according to the general procedure for synthesis, wherein 1-chloro-2-iodo-3-(phenylmethoxy)benzene (E1 and E2) and 4-amino-3,5-difluorobenzonitrile (E3) were used as reactants.

[0335] Additional examples of organic molecules of the invention

##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022## ##STR00023## ##STR00024## ##STR00025## ##STR00026## ##STR00027## ##STR00028## ##STR00029## ##STR00030##