Organic molecules for use in optoelectronic devices

Abstract

The invention relates to an organic molecule, in particular for use in organic optoelectronic devices. According to the invention, the organic molecule has a structure of Formula I ##STR00001##
wherein
Q is at each occurrence N or CR.sup.III;
W is at each occurrence N or CR.sup.IV;
Z is at selected from the group consisting of a direct bond, CR.sup.3R.sup.4, C═CR.sup.3R.sup.4, C═O, C═NR.sup.3, NR.sup.3, O, SiR.sup.3R.sup.4, S, S(O) and S(O).sub.2;
R.sup.A is selected from the group consisting of CN and CF.sub.3; and
wherein exactly one Q and exactly one W is N.

Claims

1. An organic molecule represented by Formula I: ##STR00143## wherein Q is at each occurrence N or CR.sup.III; W is at each occurrence N or CR.sup.IV; Z is a direct bond; R.sup.A is selected from the group consisting of CN and CF.sub.3; R.sup.1 and R.sup.2 is independently from another selected from the group consisting of: hydrogen, deuterium, C.sub.1-C.sub.5-alkyl, wherein one or more hydrogen atoms are optionally substituted by deuterium; C.sub.2-C.sub.8-alkenyl, wherein one or more hydrogen atoms are optionally substituted by deuterium; C.sub.2-C.sub.8-alkynyl, wherein one or more hydrogen atoms are optionally substituted by deuterium; and C.sub.6-C.sub.18-aryl, which is optionally substituted with one or more substituents selected from the group consisting of: deuterium, C.sub.1-C.sub.5-alkyl and C.sub.6-C.sub.18-aryl, which is optionally substituted with one or more C.sub.1-C.sub.5-alkyl substituents; R.sup.I, R.sup.II, R.sup.III and R.sup.IV is at each occurrence independently from another selected from the group consisting of: hydrogen, deuterium, C.sub.1-C.sub.5-alkyl, wherein one or more hydrogen atoms are optionally substituted by deuterium; C.sub.2-C.sub.8-alkenyl, wherein one or more hydrogen atoms are optionally substituted by deuterium; C.sub.2-C.sub.8-alkynyl, wherein one or more hydrogen atoms are optionally substituted by deuterium; C.sub.3-C.sub.57-heteroaryl, which is optionally substituted with one or more substituents R.sup.6; and C.sub.6-C.sub.18-aryl, which is optionally substituted with one or more substituents R.sup.6; R.sup.a is at each occurrence independently from 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.5C═CR.sup.5, C≡C, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, C═O, C═S, C═Se, C═NR.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.5C═CR.sup.5, C≡C, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, C═O, C═S, C═Se, C═NR.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.5C═CR.sup.5, C≡C, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, C═O, C═S, C═Se, C═NR.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.5C═CR.sup.5, C≡C, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, C═O, C═S, C═Se, C═NR.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.5C═CR.sup.5, C≡C, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, C═O, C═S, C═Se, C═NR.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, 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.6C═CR.sup.6, C≡C, Si(R.sup.6).sub.2, Ge(R.sup.6).sub.2, Sn(R.sup.6).sub.2, C═O, C═S, C═Se, C═NR.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.6C═CR.sup.6, C≡C, Si(R.sup.6).sub.2, Ge(R.sup.6).sub.2, Sn(R.sup.6).sub.2, C═O, C═S, C═Se, C═NR.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.6C═CR.sup.6, C≡C, Si(R.sup.6).sub.2, Ge(R.sup.6).sub.2, Sn(R.sup.6).sub.2, C═O, C═S, C═Se, C═NR.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.6C═CR.sup.6, C≡C, Si(R.sup.6).sub.2, Ge(R.sup.6).sub.2, Sn(R.sup.6).sub.2, C═O, C═S, C═Se, C═NR.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.6C═CR.sup.6, C≡C, Si(R.sup.6).sub.2, Ge(R.sup.6).sub.2, Sn(R.sup.6).sub.2, C═O, C═S, C═Se, C═NR.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 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 exactly one Q is N and exactly one W is N.

2. The organic molecule according to claim 1, wherein R.sup.1 and R.sup.2 are at each occurrence independently from another selected from the group consisting of H, methyl, mesityl, tolyl and phenyl.

3. The organic molecule according to claim 1, wherein R.sup.I, R.sup.II, R.sup.III and R.sup.IV are independently from each other selected from the group consisting of H, methyl, mesityl, tolyl and phenyl.

4. The organic molecule according to claim 1, wherein R.sup.I and R.sup.II are independently from each other selected from the group consisting of mesityl, tolyl and phenyl and R.sup.III and R.sup.IV are both H.

5. The organic molecule according to claim 1, wherein the organic molecule is represented by Formula IIb: ##STR00144## wherein R.sup.b is at each occurrence independently from another selected from the group consisting of: 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.5C═CR.sup.5, C≡C, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, C═O, C═S, C═Se, C═NR.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.5C═CR.sup.5, C≡C, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, C═O, C═S, C═Se, C═NR.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.5C═CR.sup.5, C≡C, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, C═O, C═S, C═Se, C═NR.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.5C═CR.sup.5, C≡C, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, C═O, C═S, C═Se, C═NR.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.5C═CR.sup.5, C≡C, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, C═O, C═S, C═Se, C═NR.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.

6. The organic molecule according to claim 1, wherein the organic molecule is represented by Formula IIc: ##STR00145## wherein R.sup.b is selected from the group consisting of 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.5C═CR.sup.5, C≡C, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, C═O, C═S, C═Se, C═NR.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.5C═CR.sup.5, C≡C, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, C═O, C═S, C═Se, C═NR.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.5C═CR.sup.5, C≡C, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, C═O, C═S, C═Se, C═NR.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.5C═CR.sup.5, C≡C, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, C═O, C═S, C═Se, C═NR.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.5C═CR.sup.5, C≡C, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, C═O, C═S, C═Se, C═NR.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.

7. The organic molecule according to claim 5, wherein R.sup.b is independently from another selected from the group consisting of: 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.

8. 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.

Description

EXAMPLES

(1) ##STR00026##

General Procedure for Synthesis AAV1

(2) ##STR00027##

(3) 4-fluoro-3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-benzonitrile E1 (1.00 equivalents), 2-chloro-4,6-diphenylpyrimidine (3.00 equivalents), Pd.sub.2(dba).sub.3 (0.04 equivalents), 2-dicyclohexylphosphino-2′,4′,6′-tri-isopropyl-1, 1-biphenyl (XPhos) (0.08 equivalents) and tribasic potassium phosphate (5.00 equivalents) are stirred under nitrogen atmosphere in a dioxane/water mixture (ratio of 10:1) at 80° C. overnight. The precipitated product is filtered and washed with water and dioxane. The solid is dissolved in a dichloromethane/ethyl acetate mixture and washed with brine. The organic phase is dried with MgSO.sub.4 and concentrated under reduced pressure. The product is obtained as a solid (60%).

General procedure for synthesis A AV1-CF3

(4) ##STR00028##

(5) The synthesis of Z1-CF.sub.3 is done analogously to AAV1 except that 4-fluoro-3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-trifluorotoluene is used instead of 4-fluoro-3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-benzonitrile.

General Procedure for Synthesis AAV2

(6) ##STR00029##

(7) The synthesis of Z2 is done analogously to AAV1 except 4-chloro-2,6-diphenylpyrimidine is used instead of 2-chloro-4,6-diphenylpyrimidine.

General Procedure for Synthesis AAV2-CF3

(8) ##STR00030##

(9) The synthesis of Z2-CF.sub.3 is done analogously to AAV2 except that 4-fluoro-3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-trifluorotoluene is used instead of 4-fluoro-3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-benzonitrile.

General Procedure for Synthesis AAV3

(10) ##STR00031##

(11) The synthesis of Z3 is done analogously to AAV1 except 1 equivalent of 4-chloro-2,6-diphenylpyrimidine and subsequently 1 equivalent of 2-chloro-4,6-diphenylpyrimidine is used instead of 3 equivalents of 2-chloro-4,6-diphenylpyrimidine.

General Procedure for Synthesis AAV3-II

(12) ##STR00032##

(13) Alternatively, the synthesis of Z3 is done analogously to AAV1 except 1 equivalent of 2-chloro-4,6-diphenylpyrimidine and subsequently 1 equivalent of 4-chloro-2,6-diphenylpyrimidine is used instead of 3 equivalents of 2-chloro-4,6-diphenylpyrimidine.

General Procedure for Synthesis AAV3-CF3

(14) ##STR00033##

(15) The synthesis of Z3-CF.sub.3 is done analogously to AAV3 except that 4-fluoro-3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-trifluorotoluene is used instead of 4-fluoro-3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-benzonitrile.

General procedure for synthesis AAV3-II-CF3

(16) ##STR00034##

(17) Alternatively, the synthesis of Z3-CF.sub.3 is done analogously to AAV3-II except that 4-fluoro-3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-trifluorotoluene is used instead of 4-fluoro-3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-benzonitrile.

General Procedure for Synthesis-AAV4

(18) ##STR00035## ##STR00036## ##STR00037## ##STR00038## ##STR00039## ##STR00040##

(19) Z1, Z1-CF.sub.3 Z2, Z2-CF.sub.3, Z3 or Z3-CF.sub.3 (1 equivalent each), the corresponding donor molecule D-H (1.30 equivalents) and tribasic potassium phosphate (2.50 equivalents) are suspended under nitrogen atmosphere in DMSO and stirred at 120° C. (2-20 h). Subsequently the reaction mixture is poured into a saturated sodium chloride solution and the precipitate is filtered and washed with water. The solid is then dissolved in dichloromethane, dried over MgSO.sub.4 and the solvent is evaporated under reduced pressure. The crude product is purified by recrystallization out of ethanol or by flash chromatography. The product is obtained as a solid.

(20) In particular, the donor molecule D-H is a 3,6-substituted carbazole (e.g., 3,6-dimethylcarbazole, 3,6-diphenylcarbazole, 3,6-di-tert-butylcarbazole), a 2,7-substituted carbazole (e.g., 2,7-dimethylcarbazole, 2,7-diphenylcarbazole, 2,7-di-tert-butylcarbazole), a 1,8-substituted carbazole (e.g., 1,8-dimethylcarbazole, 1,8-diphenylcarbazole, 1,8-di-tert-butylcarbazole), a 1-substituted carbazole (e.g., 1-methylcarbazole, 1-phenylcarbazole, 1-tert-butylcarbazole), a 2-substituted carbazole (e.g., 2-methylcarbazole, 2-phenylcarbazole, 2-tert-butylcarbazole), or a 3-substituted carbazole (e.g., 3-methylcarbazole, 3-phenylcarbazole, 3-tert-butylcarbazole).

(21) For example, a halogen-substituted carbazole, particularly 3-bromocarbazole, can be used as D-H.

(22) In a subsequent reaction a boronic acid ester functional group or boronic acid functional group may be exemplarily introduced at the position of the one or more halogen substituents, which was introduced via D-H, to yield the corresponding carbazol-3-ylboronic acid ester or carbazol-3-ylboronic acid, e.g., via the reaction with bis(pinacolato)diboron (CAS No. 73183-34-3). Subsequently, one or more substituents R.sup.a may be introduced in place of the boronic acid ester group or the boronic acid group via a coupling reaction with the corresponding halogenated reactant R.sup.a-Hal, preferably R.sup.a—CI and R.sup.a—Br.

(23) Alternatively, one or more substituents R.sup.a may be introduced at the position of the one or more halogen substituents, which was introduced via D-H, via the reaction with a boronic acid of the substituent R.sup.a [R.sup.a—B(OH).sub.2] or a corresponding boronic acid ester.

(24) Cyclic Voltammetry

(25) 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).

(26) Density Functional Theory Calculation

(27) 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.

(28) Photophysical Measurements

(29) Sample pretreatment: Spin-coating

(30) Apparatus: Spin150, SPS euro.

(31) The sample concentration is 10 mg/ml, dissolved in a suitable solvent.

(32) 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.

(33) Photoluminescence spectroscopy and TCSPC (Time-correlated single-photon counting) 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.

(34) Excited state lifetimes are determined employing the same system using the TCSPC method with FM-2013 equipment and a Horiba Yvon TCSPC hub.

(35) Excitation Sources:

(36) NanoLED 370 (wavelength: 371 nm, puls duration: 1.1 ns)

(37) NanoLED 290 (wavelength: 294 nm, puls duration: <1 ns)

(38) SpectraLED 310 (wavelength: 314 nm)

(39) SpectraLED 355 (wavelength: 355 nm).

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

(41) Photoluminescence Quantum Yield Measurements

(42) 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.

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

(44) ${\Phi }_{\mathrm{PL}}=\frac{n_{\mathrm{photon}},\mathrm{emited}}{n_{\mathrm{photon}},\mathrm{absorbed}}=\frac{\int \frac{\lambda }{\mathrm{hc}}\left[{\mathrm{Int}}_{\mathrm{emitted}}^{\mathrm{sample}}\left(\lambda \right)-{\mathrm{Int}}_{\mathrm{absorbed}}^{\mathrm{sample}}\left(\lambda \right)\right]d\lambda }{\int \frac{\lambda }{\mathrm{hc}}\left[{\mathrm{Int}}_{\mathrm{emitted}}^{\mathrm{reference}}\left(\lambda \right)-{\mathrm{Int}}_{\mathrm{absorbed}}^{\mathrm{reference}}\left(\lambda \right)\right]d\lambda }$ wherein n.sub.photon denotes the photon count and Int. the intensity.
Production and Characterization of Optoelectronic Devices

(45) 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%.

(46) 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:

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

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

(49) HPLC-MS:

(50) HPLC-MS spectroscopy is performed on a HPLC by Agilent (1100 series) with MS-detector (Thermo LTQ XL). A reverse phase column 4.6 mm×150 mm, particle size 5.0 μm 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: solvent A: H.sub.2O (90%) MeCN (10%) solvent B: H.sub.2O (10%) MeCN (90%) THF solvent C: (100%)

(51) From a solution with a concentration of 0.5 mg/ml an injection volume of 15 μL is taken for the measurements. The following gradient is used:

(52) 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

(53) ##STR00041##

(54) Example 1 was synthesized according to AAV1 and AAV4, the synthesis AAV4 had a yield of 93%.

(55) TABLE-US-00002 Molecular Retention Formula Time m/z calculated m/z found C.sub.63H.sub.40N.sub.6 14.54 min 881.05 881.08

(56) FIG. 1 depicts the emission spectrum of example 1 (10% by weight in PMMA). The emission maximum (λ.sub.max) is at 471 nm. The photoluminescence quantum yield (PLQY) is 77%, the full width at half maximum (FWHM) is 0.40 eV and the emission lifetime is 15 μs. The resulting CIE.sub.x coordinate is determined at 0.16 and the CIEY coordinate at 0.24.

Example 2

(57) ##STR00042##

(58) Example 2 was synthesized according to AAV1 and AAV4, the synthesis AAV4 had a yield of 93%.

(59) TABLE-US-00003 Molecular Retention Formula Time m/z calculated m/z found C.sub.59H.sub.48N.sub.6 15.66 min 841.07 840.52

(60) FIG. 2 depicts the emission spectrum of example 2 (10% by weight in PMMA). The emission maximum (λ.sub.max) is at 473 nm. The photoluminescence quantum yield (PLQY) is 80%, the full width at half maximum (FWHM) is 0.41 eV and the emission lifetime is 19 μs. The resulting CIE.sub.x coordinate is determined at 0.16 and the CIE.sub.Y coordinate at 0.26.

Example 3

(61) ##STR00043##

(62) Example 3 was synthesized according to AAV1 and AAV4, the synthesis AAV4 had a yield of 82%.

(63) TABLE-US-00004 Molecular Retention m/z calculated m/z found Formula Time C.sub.51H.sub.32N.sub.6 9.82 728.86 728.32

(64) FIG. 3 depicts the emission spectrum of example 3 (10% by weight in PMMA). The emission maximum (λ.sub.max) is at 454 nm. The photoluminescence quantum yield (PLQY) is 49%, the full width at half maximum (FWHM) is 0.42 eV and the emission lifetime is 91 μs.

(65) The resulting CIE.sub.x coordinate is determined at 0.15 and the CIEy coordinate at 0.14.

Example 4

(66) ##STR00044##

(67) Example 4 was synthesized according to AAV and AAV4, wherein the synthesis AAV4 had a yield of 80%.

(68) TABLE-US-00005 Molecular Retention Formula Time m/z calculated m/z found C.sub.57H.sub.36N.sub.6 13.03 804.95 804.43

(69) FIG. 4 depicts the emission spectrum of example 4 (10% by weight in PMMA). The emission maximum (λ.sub.max) is at 465 nm. The photoluminescence quantum yield (PLQY) is 65%, the full width at half maximum (FWHM) is 0.43 eV and the emission lifetime is 28 μs.

(70) The determined CIE.sub.x coordinate is 0.16 and the CIE.sub.Y coordinate is 0.20.

Example 5

(71) ##STR00045##

(72) Example 5 was synthesized according to AAV and AAV4, wherein the synthesis AAV4 had a yield of 77%.

(73) TABLE-US-00006 Molecular Retention Formula Time m/z calculated m/z found C.sub.55H.sub.40N.sub.6 13.6 784.96 784.49

(74) FIG. 5 depicts the emission spectrum of example 5 (10% by weight in PMMA). The emission maximum (λ.sub.max) is at 464 nm. The photoluminescence quantum yield (PLQY) is 68%, the full width at half maximum (FWHM) is 0.42 eV and the emission lifetime is 33 μs.

(75) The determined CIE.sub.x coordinate is 0.16 and the CIEY is 0.19.

Example 6

(76) ##STR00046##

(77) Example 6 was synthesized according to

(78) ##STR00047##
wherein 4-fluoro-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-chlorobenzonitrile E1-6 (1.00 equivalents), 2-chloro-4,6-diphenylpyrimidine (1.00 equivalents), tetrakis(triphenylphosphine)palladium(0) (0.05 equivalents), and potassium carbonate (3.00 equivalents) are stirred under nitrogen atmosphere in a dioxane/water mixture (ratio of 10:1) at 80° C. overnight. The precipitated product was filtered and washed with water and dioxane. The solid was purified by chromatography (38%).

(79) Subsequently, Z1-6 was reacted with bis(pinacolato)diboron (CAS 73183-34-3) to achieve

(80) ##STR00048##

(81) Subsequently, Z1-6 (1.00 equivalents), bis(pinacolato)diboron (1.50 equivalents), [1,1′-bis(diphenylphosphino)ferrocene]palladium (II) dichloride (0.1 equivalents) potassium acetate (2.50 equivalents) are stirred under nitrogen atmosphere in toluene at 100° C. overnight. To the reaction mixture, active carbon and Celite® were added and hot filtered. After concentration of the solvent under reduced pressure, the residue is purified by chromatography and product 2 is obtained as a solid (84%).

(82) ##STR00049##

(83) 2 (1.00 equivalents), 4-chloro-2,6-diphenylpyrimidine (1.10 equivalents), Pd(dba).sub.3 (0) (0.02 equivalents), X-Phos (0.08 equivalents) and potassium acetate (2.50 equivalents) were stirred under nitrogen atmosphere in a dioxane/water mixture (ratio of 10:1) at 80° C. overnight. The precipitated product was filtered off and washed with water and dioxane. The solid was recrystallized from ethanol to yield product 3 (yield 77%), which was used as Z3 in AA V4 (yield of 57%).

(84) TABLE-US-00007 Molecular Retention Formula Time m/z calculated m/z found C.sub.55H.sub.40N.sub.6 16.86 784.96 784.32

(85) FIG. 6 depicts the emission spectrum of example 6 (10% by weight in PMMA). The emission maximum (λ.sub.max) is at 468 nm. The photoluminescence quantum yield (PLQY) is 56%, the full width at half maximum (FWHM) is 0.43 eV and the emission lifetime is 21 μs. The CIE.sub.x coordinate is 0.16 and the CIE.sub.y coordinate is 0.21.

Example 1C

(86) ##STR00050##

(87) FIG. 7 depicts the emission spectrum of comparison example 1C (10% by weight in PMMA). The emission maximum (λ.sub.max) is at 448 nm. The photoluminescence quantum yield (PLQY) is 20% and the full width at half maximum (FWHM) is 0.45 eV. The CIE.sub.x coordinate is 0.15 and the CIE.sub.y coordinate is 0.13.

Additional Examples of Organic Molecules of the Invention

(88) ##STR00051## ##STR00052## ##STR00053## ##STR00054## ##STR00055## ##STR00056## ##STR00057## ##STR00058## ##STR00059## ##STR00060## ##STR00061## ##STR00062## ##STR00063## ##STR00064## ##STR00065## ##STR00066## ##STR00067## ##STR00068## ##STR00069## ##STR00070## ##STR00071## ##STR00072## ##STR00073## ##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##

(89) ##STR00107## ##STR00108## ##STR00109## ##STR00110## ##STR00111## ##STR00112## ##STR00113## ##STR00114## ##STR00115## ##STR00116## ##STR00117## ##STR00118## ##STR00119## ##STR00120## ##STR00121## ##STR00122## ##STR00123## ##STR00124## ##STR00125## ##STR00126## ##STR00127## ##STR00128## ##STR00129## ##STR00130## ##STR00131## ##STR00132## ##STR00133## ##STR00134## ##STR00135## ##STR00136## ##STR00137## ##STR00138## ##STR00139## ##STR00140## ##STR00141## ##STR00142##

FIGURES

(90) FIG. 1 Emission spectrum of example 1 (10% by weight) in PMMA.

(91) FIG. 2 Emission spectrum of example 2 (10% by weight) in PMMA.

(92) FIG. 3 Emission spectrum of example 3 (10% by weight) in PMMA.

(93) FIG. 4 Emission spectrum of example 4 (10% by weight) in PMMA.

(94) FIG. 5 Emission spectrum of example 5 (10% by weight) in PMMA.

(95) FIG. 6 Emission spectrum of example 6 (10% by weight) in PMMA.

(96) FIG. 7 Emission spectrum of example 1C (10% by weight) in PMMA.