Patent Application
20240251676
The object of the present invention is to provide molecules which are suitable for use in optoelectronic devices.
This object is achieved by the invention which provides a new class of organic molecules.
According to the invention the organic molecules are purely organic molecules, i.e., they do not contain any metal ions in contrast to metal complexes known for use in optoelectronic devices.
According to the present invention, the organic molecules exhibit emission maxima in the blue, sky-blue or green spectral range. The organic molecules exhibit in particular emission maxima between 420 nm and 520 nm, preferably between 440 nm and 495 nm, more preferably between 450 nm and 470 nm, or the organic molecules exhibit in particular emission maxima below 560 nm, more preferably below 550 nm, even more preferably below 545 nm or even below 540 nm. It will typically be above 500 nm, more preferably above 510 nm, even more preferably above 515 nm or even above 520 nm. The photoluminescence quantum yields of the organic molecules according to the invention are, in certain embodiments, more than 20%, preferably more than 30%, more than 35%, more than 40%, or more than 45%, and most preferably more than 50%. The use of the molecules according to the invention in an optoelectronic device, for example an organic light-emitting diode (OLED), leads to higher efficiencies or higher color purity, expressed by the full width at half maximum (FWHM) of emission, of the device. Corresponding OLEDs have a higher stability than OLEDs with known emitter materials and comparable color.
The organic light-emitting molecule (oligomer) of the invention includes or consists of a structure of Formula I
Examples for the substituents Ra, Rd, Re, R1, R2, R3, R4, R5, RI, RII, RIII, RIV, and RV include C6-C60-aryl, preferably C6-C30-aryl, more preferably C6-C18-aryl, and even preferably C5-C10-aryl.
Specific aryl substituents include monocyclic benzene, bicyclic biphenyl, condensed bicyclic naphthalene, tricyclic terphenyl (m-terphenyl, o-Terphenyl, p-terphenyl), condensed tricyclic systems such as acenaphthylene, fluorene, phenalene, phenanthrene, condensed tetracyclic systems such as triphenylene, pyrene, naphthacene, condensed pentacyclic system examples include a perylene and a pentacene.
Examples for the substituents Ra, Rd, Re, R1, R2, R3, R4, R5, RI, RII, RIII, RIV, and RV include C2-C57-heteroaryl, preferably C2-C30-heteroaryl, more preferably C2-C17-heteroaryl, and even preferably C2-C10-heteroaryl.
Specific heteroaryl substituents include pyrrole, oxazole, isoxazole, thiazole, isothiazole, imidazole, oxadiazole, thiadiazole, triazole, tetrazole, pyrazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, indole, isoindole, 1H-indazole, benzimidazole, benzoxazole, benzothiazole, 1H-benzotriazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, phthalazine, naphthyridine, purine, pteridine, carbazole, acridine, phenoxathiin, phenoxazine ring, phenothiazine, phenazine, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, dibenzothiophene, furazan, oxadiazole, and thianthrene.
Examples for the substituents Ra, Rd, Re, R1, R2, R3, R4, R5, RI, RII, RIII, RIV, and RV include C1-C40-alkyl, preferably C1-C24-alkyl or branched or cyclic C3-C40-alkyl, more preferably C1-C18-alkyl or branched or cyclic C3-C18-alkyl, even preferably C1-C12-alkyl or branched or cyclic C3-C12-alkyl, even more preferably C1-C6-alkyl or branched or cyclic C3-C6-alkyl, and particularly preferably C1-C4-alkyl or branched C3-C4-alkyl.
Specific alkyl substituents include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, and 1-methyl, pentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propyl Pentyl, n-nonyl, cyclo-hexyl 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-Tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, such as n-eicosyl, and the like.
Examples for the substituents Ra, Rd, Re, R1, R2, R3, R4, R5, RI, RII, RIII, RIV, and RV include C1-C40-alkoxy, preferably C1-C24-alkoxy or branched or cyclic C3-C40-alkoxy, more preferably C1-C18-alkoxy or branched or cyclic C3-C18-alkoxy, even preferably C1-C12-alkoxy or branched or cyclic C3-C12-alkoxy, even more preferably C1-C4-alkoxy or branched or cyclic C3-C6-alkoxy, and particularly preferably C1-C4-alkoxy or branched C3-C4-alkoxy.
Specific alkoxy substituents include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, and the like.
Examples for the substituents Ra, Rd, Re, R1, R2, R3, R4, R5, RI, RII, RIII, RIV, and RV include C1-C40-thioalkyl, preferably C1-C24-thioalkyl or branched or cyclic C3-C40-thioalkyl, more preferably C1-C18-thioalkyl or branched or cyclic C3-Cle-thioalkyl, even preferably C1-C12-thioalkyl or branched or cyclic C3-C12-thioalkyl, even more preferably C1-C5-thioalkyl or branched or cyclic C3-C6-thioalkyl, and particularly preferably C1-C4-thioalkyl or branched C3-C4-thioalkyl.
Examples for the substituents Ra, Rd, Re, R1, R2, R3, R4, R5, RI, RII, RIII, RIV, and RV include C1-C40-alkenyl, preferably C2-C24-alkenyl or branched or cyclic C3-C40-alkenyl, more preferably C2-C18-alkenyl or branched or cyclic C3-C18-alkenyl, even preferably C2-C12-alkenyl or branched or cyclic C3-C12-alkenyl, even more preferably C2-C5-alkenyl or branched or cyclic C3-C6-alkenyl, and particularly preferably C1-C4-alkenyl or branched C3-C4-alkenyl.
Examples for the substituents Ra, Rd, Re, R1, R2, R3, R4, R5, RI, RII, RIII, RIV, and RV include C1-C40-alkynyl, preferably C2-C24-alkynyl or branched or cyclic C3-C40-alkynyl, more preferably C2-C18-alkynyl or branched or cyclic C3-C18-alkynyl, even preferably C2-C12-alkynyl or branched or cyclic C3-C12-alkynyl, even more preferably C2-C6-alkynyl or branched or cyclic C3-C6-alkynyl, and particularly preferably C1-C4-alkynyl or branched C3-C4-alkynyl.
In a preferred embodiment, R1, R2, R3, R4, RI, RII, RIII, RIV, and RV are each independently from each other selected from the group consisting of: hydrogen;
R5 is at each occurrence independently from each other selected from the group consisting of: hydrogen; deuterium; N(R6)2; OR6; Si(R6)3; B(OR6)2; B(R6)2; OSO2R6; CF3; CN; F; Br; I:
In a preferred embodiment, n=1.
In another embodiment, n=0.
In a preferred embodiment, R1, R2, R3, R4, RI, RII, RIII, RIV, and RV are each independently from each other selected from the group consisting of: hydrogen;
In a preferred embodiment, R1, R2, R3, R4, RI, RII, RIII, RIV, and RV are each independently from each other selected from the group consisting of: hydrogen;
In a preferred embodiment, R1, R2, R3, R4, RI, RII, RIII, RIV, and RV are each independently from each other selected from the group consisting of: hydrogen;
In a preferred embodiment, R1, R2, R3, R4, RI, RII, RIII, RIV, and RV are each independently from each other selected from the group consisting of: hydrogen;
In one embodiment, R1, R2, R3, R4, RI, RII, RIII, RIV, and RV are each independently from each other selected from the group consisting of: hydrogen;
In one embodiment, R1, R2, RI, RII, RIII, RIV, and RV are each independently from each other selected from the group consisting of: hydrogen;
In one embodiment, R3 and R4 are independently from each other selected from the group consisting of:
In one embodiment, R1, R2, R3, R4, RI, RII, RIII, RIV, and RV are each independently from each other selected from the group consisting of:
In another embodiment, R1, R2, R3, R4, RI, RII, RIII, RIV, and RV are each independently from each other selected from the group consisting of:
In another embodiment, R1, R2, R3, R4, RI, RII, RIII, RIV, and RV are each independently from each other selected from the group consisting of:
In a preferred embodiment, R3 is independently from each other selected from the group consisting of:
In a preferred embodiment, R3 is independently from each other selected from the group consisting of:
In a more preferred embodiment, R3 is independently from each other selected from the group consisting of:
In a more preferred embodiment, R3 is a C6-C18-aryl, which is optionally substituted with one or more substituents R6.
In a more preferred embodiment, R3 is a Phenyl (Ph), which is optionally substituted with one or more substituents R5.
In a certain embodiment, R3 is a Phenyl (Ph), which is optionally substituted with one or more substituents R6.
In a certain embodiment, R3 is a Phenyl (Ph), which is optionally substituted with one or more C1-C5-alkyl substituents.
In a certain embodiment, R3 is a Phenyl (Ph), which is independently from each other optionally substituted with one or more
In a certain embodiment, R3 is Ph.
In one embodiment, R1, R2, R3, R4, RI, RII, RIII, RIV, and RV are each independently from each other selected from the group consisting of:
In one embodiment, at least one substituent selected from the group consisting of R1, R2, RI, RII, RIII, RIV, RV, and Ra is
In one embodiment, at least one substituent selected from the group consisting of R1, R2, RI, RII, RIII, RIV, RV, and R8 is
In one embodiment, Ra is at each occurrence independently from each other selected from the group consisting of: hydrogen;
In one embodiment, Ra is at each occurrence independently from each other selected from the group consisting of: hydrogen;
In one embodiment, Ra is at each occurrence independently from each other selected from the group consisting of: hydrogen,
In one embodiment, at least one Ra is
In a preferred embodiment, at least one substituent selected from the group consisting of R1, R2, RI, RII, RIII, RIV, and RV
In a more preferred embodiment, at least one substituent selected from the group consisting of R1, R2, RI, RII, RIII, RIV, and RV
In a more preferred embodiment, at least one substituent selected from the group consisting of R1, R2, RI, RII, RIII, RIV, and RV
In a more preferred embodiment, at least one substituent selected from the group consisting of R1, R2, RI, RII, RIII, RIV, and RV
In a preferred embodiment, at least one substituent selected from the group consisting of R1, R2, RI, RII, RIII, RIV, and RV
In a preferred embodiment, at least one substituent selected from the group consisting of R1, R2, RI, RII, RIII, RIV, and RV
In a preferred embodiment the attachment points are positioned adjacent to each other. This means that R1 preferably forms a ring system with RI; RI preferably forms a ring system with RII and/or R1; RII preferably forms a ring system with RIII and/or R1; RIII preferably forms a ring system with RII; R2 preferably forms a ring system with RV; RV preferably forms a ring system with R2 and/or RIV; and RIV preferably forms a ring system with RV.
Specific examples are listed below:
In one embodiment, at least one substituent selected from the group consisting of R1, R2, RI, RII, RIII, RIV, and RV forms a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and/or benzo-fused ring system with one or more substituents R1, R2, RI, RII, RIII, RIV, and/or RV, wherein the ring system is selected from the following group:
In a preferred embodiment the attachment points are positioned adjacent to each other.
In another embodiment, at least one substituent selected from the group consisting of R1, RI, RII, and RIII
In another embodiment, at least one substituent selected from the group consisting of R1, RI, RII, and RIII
In a preferred embodiment the attachment points are positioned adjacent to each other. This means that R1 preferably forms a ring system with RI; RI preferably forms a ring system with RII and/or R1; RII preferably forms a ring system with RIII and/or RI; and RIII preferably forms a ring system with RII.
In one embodiment, at least one substituent selected from the group consisting of R1, R2, RI, RII, RIII, RIV, and RV forms a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and/or benzo-fused ring system with one or more substituents R1, R2, RI, RII, RIII, RIV, and/or RV, wherein the ring system is selected from the following group:
In a preferred embodiment the attachment points are positioned adjacent to each other.
In a preferred embodiment, Rd and Re are at each occurrence independently selected from the group consisting of: hydrogen: deuterium; CF3; CN; F; Br; I;
In a preferred embodiment, R8 is at each occurrence independently from each other selected from the group consisting of: hydrogen;
In one embodiment, at least one Ra is different from hydrogen.
In one embodiment, Ra is at each occurrence independently from each other selected from the group consisting of: hydrogen;
In one embodiment, Ra is at each occurrence independently from each other selected from the group consisting of: hydrogen;
In one embodiment of the invention, Ra is at each occurrence independently selected from the group consisting of:
In one embodiment of the invention, Ra is at each occurrence independently selected from the group consisting of:
In a further embodiment of the invention, Ra is at each occurrence independently selected from the group consisting of:
In one embodiment of the invention, Ra is at each occurrence independently selected from the group consisting of:
In a further embodiment of the invention, Ra is at each occurrence independently selected from the group consisting of:
In a further embodiment of the invention, Ra is at each occurrence independently selected from the group consisting of:
In a further embodiment of the invention, Ra is at each occurrence independently selected from the group consisting of:
In a further embodiment of the invention, Ra is at each occurrence independently selected from the group consisting of:
In one embodiment, Ra is at each occurrence independently from each other selected from the group consisting of: hydrogen;
In one embodiment, Ra is at each occurrence independently from each other selected from the group consisting of: hydrogen;
In a preferred embodiment the attachment points are positioned adjacent to each other. This means that Ra preferably forms a ring system with Ra positioned adjacent to each other.
Specific examples are listed below:
In one embodiment, at least one Ra forms a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and/or benzo-fused ring system with one or more substituents Ra and/or R5, wherein the ring system is selected from the following group:
wherein X1 is S, O or NR5.
In a preferred embodiment the attachment points are positioned adjacent to each other.
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula I, with the proviso, if X is NR3 and Rd and Re are connected to each other to form an aromatic ring system, RV is N(R5)2 or forms a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and/or benzo-fused ring system with one or more substituents R2, R3, R5, and/or RIV.
Specific examples are listed below:
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula I, with the proviso, if X is NR3 and Rd and Re are connected to each other to form an aromatic ring system, RV is selected from
N(R6)2 or forms a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and/or benzo-fused ring system with one or more substituents R2, R3, R5, and/or RIV.
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula I, with the proviso, if X is NR3 and Rd and Re are connected to each other to form an aromatic ring system, RV is selected from
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula I, with the proviso, if X is NR3 and Rd and Re are connected to each other to form an aromatic ring system, RV is selected from
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula I, with the proviso, if X is NR3 and Rd and Re are connected to each other to form an aromatic ring system, RV is
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula I, with the proviso, if X is NR3 and Rd and Re are connected to each other to form an aromatic ring system, RV is
In another preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula I, with the proviso, if X is NR3 and Rd and Re are connected to each other to form an aromatic ring system, RV forms a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and/or benzo-fused ring system with one or more substituents R2, R3, R5, and/or RIV.
In more preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula I, with the proviso, if X is NR3 and Rd and Re are connected to each other to form an aromatic ring system, RV forms a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and/or benzo-fused ring system with one or more adjacent substituents R2 and/or RIV.
Below, examples for n=0 and n=1 with different substituents X are shown:
Additional examples of the organic molecules according to the invention include:
In a preferred embodiment, X is at each occurrence independently from each other selected from the group consisting of a direct bond, NR3, CR3R4, S, and O.
In a more preferred embodiment, X is at each occurrence independently from each other selected from the group consisting of a direct bond, NR3, S, and O.
In a certain embodiment, X is at each occurrence independently from each other selected from the group consisting of a direct bond and NR3.
In one embodiment of the invention, R1, R2, R3, R4, RI, RII, RIII, RIV, and RV are at each occurrence independently from each other selected from the group consisting of:
In one embodiment of the invention, the organic molecule includes or consists of a structure of Formula II
In a preferred embodiment of the invention, X is at each occurrence independently from each other selected from the group consisting of a direct bond, NR3, and O.
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula II, with the proviso, if X is NR3 and Rd and Re are connected to each other to form an aromatic ring system, RV is selected from
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula II, with the proviso, if X is NR3 and Rd and Re are connected to each other to form an aromatic ring system, RV is selected from
In one embodiment of the invention the organic molecule includes or consists of a structure of Formula II-1
In one embodiment of the invention, the organic molecule includes or consists of a structure of Formula II-1, wherein R3 is selected from the group consisting of
In a preferred embodiment of the invention the organic molecule includes or consists of a structure of Formula II-1, wherein R3 is a C6-C18-aryl, which is optionally substituted with one or more substituents R5.
In another embodiment of the invention the organic molecule includes or consists of a structure of Formula II-1, wherein R3 is a C6-C18-aryl, which is optionally substituted with one or more substituents R6.
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula II-1, with the proviso, if Rd and Re are connected to each other to form an aromatic ring system, RV is selected from
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula II-1, with the proviso, if Rd and Re are connected to each other to form an aromatic ring system, RV is selected from
In a preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula II-1a
This means a structure of Formula II-1a is build-up of the following three structure Formula II-1aa, Formula II-1ab, and Formula II-1ac:
In a more preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula II-1a, wherein
In a more preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula II-1a, wherein
In a more preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula II-1a, wherein
In a preferred embodiment the attachment points are positioned adjacent to each other. This means that R2 preferably forms a ring system with RV: RV preferably forms a ring system with R2 and/or RIV; and RIV preferably forms a ring system with RV.
In a more preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula II-1a, wherein
In an even more preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula II-1a, wherein
In an even more preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula II-1a, wherein
In a certain embodiment of the invention, the organic molecule includes or consists of a structure of Formula II-1a, wherein
In a preferred embodiment, the organic molecule includes or consists of a structure of Formula II-1ac
In another embodiment, the organic molecule includes or consists of a structure of Formula II-1ab
In one embodiment of the invention, the organic molecule includes or consists of a structure of Formula IIa
Apart from that, the aforementioned definitions apply.
In a further embodiment of the invention, Rb is at each occurrence independently from each other selected from the group consisting of:
In a further embodiment of the invention, Rb is at each occurrence independently from each other selected from the group consisting of:
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIa, with the proviso, if X is NR3 and Rd and Re are connected to each other to form an aromatic ring system, RV is selected from
In a preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula III
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula III, with the proviso, if X is NR3, RV is selected from
In a preferred embodiment of the invention the organic molecule includes or consists of a structure of Formula III-1
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula III-1, wherein RV is selected from
In a preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula III-2
In a preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula III-2 wherein R3 is a C6-C18-aryl, which is optionally substituted with one or more substituents R6, and
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula III-2, wherein RV is selected from
In a preferred embodiment, the organic molecule includes or consists of a structure of Formula III-2, wherein RV is N(C6-C18-aryl)2.
In a preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula III-2a
In a preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula III-2a, wherein R3 is a C6-C18-aryl, which is optionally substituted with one or more substituents R5 and
In a preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula III-2b
In a more preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula III-2b, wherein
In an even more preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula III-2b, wherein
In a certain embodiment of the invention, the organic molecule includes or consists of a structure of Formula III-2b, wherein
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula III-2b, wherein at least one Ra is different from hydrogen.
In a preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula III-2c
In a more preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula III-2c, wherein
In an even more preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula III-2c, wherein
In an even more preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula III-2c, wherein
In a certain embodiment of the invention, the organic molecule includes or consists of a structure of Formula III-2c, wherein
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula III-2c, wherein at least one Ra is different from hydrogen.
In a preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula III-2d-I, Formula III-2d-II, Formula III-2d-II, or Formula III-2d-IV:
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula III-2d-I, Formula III-2d-II, Formula III-2d-II, or Formula III-2d-IV, wherein at least one Ra is different from hydrogen.
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula III-2d-I, Formula III-2d-II, Formula III-2d-II, or Formula III-2d-IV, wherein X1 is O.
In a more preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula III-2d-III:
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula III-2d-III, wherein at least one Ra is different from hydrogen.
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula III-2d-II, wherein X1 is O.
In a more preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula III-2d-IIIa:
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula III-2d-IIIa, wherein at least one Ra is different from hydrogen.
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula III-2d-IIIa, wherein X1 is O.
In a more preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula III-2d-IIIb:
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula III-2d-IIIb, wherein at least one Ra is different from hydrogen.
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula III-2d-IIIb, wherein X1 is O.
In a certain embodiment of the invention, the organic molecule includes or consists of a structure of Formula III-2d-IIIc:
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula III-2d-IIIc, wherein at least one Ra is different from hydrogen.
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula III-2d-IIIc, wherein X1 is O.
In another preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula III-3, Formula III-4, or Formula III-5
In one embodiment, the organic molecule includes or consists of a structure of Formula III-3, Formula III-4, or Formula III-5, wherein RV is selected from the group consisting of
Different exemplary embodiments for Formula III are shown in the following:
Additional examples of the organic molecule:
In one embodiment, Ra and R5 are at each occurrence independently from each other selected from the group consisting of hydrogen (H), methyl (Me), i-propyl (CH(CH3)2) (iPr), t-butyl (tBu), phenyl (Ph), CN, CF3, and diphenylamine (NPh2).
In a preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula IIIa
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIa, with the proviso that, if X is NR3, RV is selected from
In a preferred embodiment of the invention, the organic molecule includes or consists of a structure selected from the group consisting of Formula IIIa-1 and Formula IIIa-2
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIa-1 or IIIa-2, with the proviso, if X is NR3, RV is selected from
N(R5)2 or forms a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and/or benzo-fused ring system with one or more substituents R2, R3, R5, and/or RIV.
In a preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula IIIb
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIb, wherein RV is selected from
In a preferred embodiment of the invention, the organic molecule includes or consists of a structure selected from the group consisting of Formula IIIb-1 and Formula IIIb-2
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIb-1 or IIIb-2, wherein RV is selected from
In a preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula IIIc
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIc, with the proviso, if X is NR3, RV is selected from
In a preferred embodiment of the invention, the organic molecule includes or consists of a structure selected from the group consisting of Formula IIIc-1 and Formula IIIc-2
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIc-1 or IIIc-2, with the proviso, if X is NR3, RV is selected from
In a preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula IIId
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIId, wherein RV is selected from
In a preferred embodiment of the invention, the organic molecule includes or consists of a structure selected from the group consisting of Formula IIId-1 and Formula IIId-2
In a preferred embodiment, RV is selected from the group consisting of
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIId-1 or IIId-2, wherein RV is selected from
In a preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula IIIe-0
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe-0, wherein RV is selected from
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe-0, wherein RV forms a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and/or benzo-fused ring system with one or more substituents R2, R3, R5, and/or RIV.
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe-0, wherein at least one substituent selected from the group consisting of R1, R2, RIII, RIV, RV forms a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and/or benzo-fused ring system with one or more substituents R1, R2, R3, R4, R5, RI, RII, RIII, RIV, and/or RV.
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe-0, wherein R3 is independently from each other selected from the group consisting of:
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe-0, wherein R3 is independently from each other selected from the group consisting of:
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe-0, wherein Q4 is CR1.
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe-0, wherein R8 is at each occurrence independently from each other selected from the group consisting of: hydrogen;
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe-0, wherein Ra is at each occurrence independently from each other selected from the group consisting of: hydrogen;
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe-0, wherein R8 is at each occurrence independently from each other selected from the group consisting of: hydrogen;
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe-0, wherein R1, R2, R3, R4, RI, RII, RIII, RIV, and RV are each independently from each other selected from the group consisting of: hydrogen;
This means a structure of Formula IIIe-0 is build-up of the following three structure Formula IIIe-0a, Formula IIIe, and Formula IIIe-b:
In a preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula IIIe-0b
In a preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula IIIe
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe, wherein RV is selected from
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe, wherein RV forms a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and/or benzo-fused ring system with one or more substituents R2, R3, R5, and/or RIV.
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe, wherein at least one substituent selected from the group consisting of R1, R2, RIII, RIV, RV forms a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and/or benzo-fused ring system with one or more substituents R1, R2, R3, R4, R5, RI, RII, RIII, RIV, and/or RV.
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe, wherein R3 is independently from each other selected from the group consisting of:
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe, wherein R3 is independently from each other selected from the group consisting of:
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe, wherein Ra is at each occurrence independently from each other selected from the group consisting of: hydrogen;
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe, wherein Ra is at each occurrence independently from each other selected from the group consisting of: hydrogen;
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe, wherein R8 is at each occurrence independently from each other selected from the group consisting of: hydrogen,
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe, wherein R1, R2, R3, R4, RI, RII, RIII, RIV, and RV are each independently from each other selected from the group consisting of: hydrogen;
In a preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula IIIe-2
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe-2, wherein RV is selected from
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe-2, wherein RV forms a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and/or benzo-fused ring system with one or more substituents R2, R3, R5, and/or RIV.
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe-2, wherein at least one substituent selected from the group consisting of R1, R2, RIII, RIV, and RV forms a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and/or benzo-fused ring system with one or more other substituents R1, R2, R3, R4, R5, RI, RII, RIII, RIV, and/or RV.
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe-2, wherein R3 is independently from each other selected from the group consisting of:
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe-2, wherein R3 is independently from each other selected from the group consisting of:
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe-2, wherein R8 is at each occurrence independently from each other selected from the group consisting of: hydrogen;
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe-2, wherein R8 is at each occurrence independently from each other selected from the group consisting of: hydrogen;
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe-2, wherein Ra is at each occurrence independently from each other selected from the group consisting of: hydrogen;
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe-2, wherein R1, R2, R3, R4, RI, RII, RIII, RIV, and RV are each independently from each other selected from the group consisting of: hydrogen;
In a preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula IIIe-3
In a preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula IIIe-4
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe-4, wherein RV is selected from
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe-4, wherein RV forms a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and/or benzo-fused ring system with one or more substituents R2, R3, R5, and/or RIV.
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe-4, wherein at least one substituent selected from the group consisting of R1, R2, RIII, RIV, and RV forms a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and/or benzo-fused ring system with one or more other substituents R1, R2, R3, R4, R5, RI, RII, RIII, RIV, and/or RV
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe-4, wherein R3 is independently from each other selected from the group consisting of:
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe-4, wherein R3 is independently from each other selected from the group consisting of:
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe-4, wherein R8 is at each occurrence independently from each other selected from the group consisting of: hydrogen;
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe-4, wherein R8 is at each occurrence independently from each other selected from the group consisting of: hydrogen;
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe-4, wherein Ra is at each occurrence independently from each other selected from the group consisting of: hydrogen,
In one embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IIIe-4, wherein R1, R2, R3, R4, RI, RII, RIII, RIV, and RV are each independently from each other selected from the group consisting of: hydrogen;
In preferred embodiments, at least one substituent selected from the group of R1, R2, R3, R4, RI, RII, RIII, RIV and RV is different from hydrogen.
The present invention also provides an organic molecule in the form of an oligomer for the use as an emitter in an optoelectronic device. The oligomer includes or consists of a plurality (i.e., 2, 3, 4, 5, or 6) of units represented by the Formula IV
The oligomer is a dimer to hexamer (m=2, 3, 4, 5, or 6), in particular a dimer (m=2) to trimer (m=3), or preferably a dimer (m=2). The oligomer
is shared by at least one other adjacent unit of the oligomer, or
Below different examples are shown:
In some embodiments of the oligomer, a part of the unit shown in Formula VI (ring a and/or b and/or ring c) is bonded so as to be shared by an adjacent unit, as shown in the following exemplary structures:
Additional examples for oligomers in form of dimers (m=2) according to the invention:
In one embodiment of the invention, the oligomer includes or consists of a structure selected from the following group:
In certain embodiments of the invention, the oligomer is a dimer (m=2) or trimer (m=3), preferably a dimer.
In a preferred embodiment, R1, R2, R3, R4, RI, RII, RIII, RIV, and RV are each independently from each other selected from the group consisting of: hydrogen;
In certain embodiments of the oligomer, R1, R2, R3, R4, RI, RII, RIII, RIV, and RV are each independently from each other selected from the group consisting of: hydrogen;
In certain embodiments of the oligomer, R1, R2, R3, R4, RI, RII, RIII, RIV, RV, and Ra are each independently from each other selected from the group consisting of: hydrogen;
In one embodiment of the invention, the organic molecule consists of a dimer or trimer, wherein R1, R2, Ra, Rd, Re, RI, RII, RIII, RIV and RV is at each occurrence independently from each other selected from the group consisting of:
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IV, wherein at least one Ra is different from hydrogen.
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IV, with the proviso, if X is NR3 and Rd and Re are connected to each other to form an aromatic ring system, RV is selected from
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IV, wherein X is at each occurrence independently from each other selected from the group consisting of a direct bond, NR3, CR3R4, S, and O.
In a more preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IV, wherein X is at each occurrence independently from each other selected from the group consisting of a direct bond, NR3, S, and O.
In a certain embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IV, wherein X is at each occurrence independently from each other selected from the group consisting of a direct bond and NR3.
In a certain embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IV, wherein X is NR3.
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IV, wherein R3 is independently from each other selected from the group consisting of:
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IV, wherein RV is at each occurrence independently from each other selected from the group consisting of:
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVa-0, Formula IVb-0, or Formula IVf (dimers):
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVa, Formula IVb-0, or Formula IVf:
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVa, Formula IVb-0, or Formula IVf, wherein at least one Ra is different from hydrogen.
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IVa, Formula IVb-0, or Formula IVf, with the proviso, if X is NR3 and Rd and Re are connected to each other to form an aromatic ring system, RV is selected from
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVa, Formula IVb-0, or Formula IVf, wherein X is at each occurrence independently from each other selected from the group consisting of a direct bond, NR3, CR3R4, S, and O.
In a more preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVa, Formula IVb-0, or Formula IVf, wherein X is at each occurrence independently from each other selected from the group consisting of a direct bond, NR3, S, and O.
In a certain embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVa, Formula IVb-0, or Formula IVf, wherein X is at each occurrence independently from each other selected from the group consisting of a direct bond and NR3.
In a certain embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVa, Formula IVb-0, or Formula IVf, wherein X is NR3.
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVa, Formula IVb-0, or Formula IVf, wherein R3 is independently from each other selected from the group consisting of:
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVa, Formula IVb-0, or Formula IVf, wherein RV is at each occurrence independently from each other selected from the group consisting of:
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVa-0 (dimer)
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVa
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVa-2
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVa-3
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVa-4
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb-0
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb-0, wherein at least one Ra is different from hydrogen.
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IVb-0, with the proviso, if X is NR3 and Rd and Re are connected to each other to form an aromatic ring system, RV is selected from
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb-0, wherein X is at each occurrence independently from each other selected from the group consisting of a direct bond, NR3, CR3R4, S, and O.
In a more preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb-0, wherein X is at each occurrence independently from each other selected from the group consisting of a direct bond, NR3, S, and O.
In a certain embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb-0, wherein X is at each occurrence independently from each other selected from the group consisting of a direct bond and NR3.
In a certain embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb-0, wherein X is NR3.
In a more preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb-0a
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb-0a, wherein at least one Ra is different from hydrogen.
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IVb-0a, with the proviso, if X is NR3 and Rd and Re are connected to each other to form an aromatic ring system, RV is selected from
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb-0a, wherein X is at each occurrence independently from each other selected from the group consisting of a direct bond, NR3, CR3R4, S, and O.
In a more preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb-0a, wherein X is at each occurrence independently from each other selected from the group consisting of a direct bond, NR3, S, and O.
In a certain embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb-0a, wherein X is at each occurrence independently from each other selected from the group consisting of a direct bond and NR3.
In a certain embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb-0a, wherein X is NR3.
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb-0b
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb-0b, wherein at least one Ra is different from hydrogen.
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IVb-0b, with the proviso, if X is NR3, RV is selected from
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb-0b, wherein X is at each occurrence independently from each other selected from the group consisting of a direct bond, NR3, CR3R4, S, and O.
In a more preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb-0b, wherein X is at each occurrence independently from each other selected from the group consisting of a direct bond, NR3, S, and O.
In a certain embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb-0b, wherein X is at each occurrence independently from each other selected from the group consisting of a direct bond and NR3.
In a certain embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb-0b, wherein X is NR3.
In a more preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb-0c
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb-0c, wherein at least one Ra is different from hydrogen.
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IVb-0c, with the proviso, if X is NR3, RV is selected from
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb-0c, wherein X is at each occurrence independently from each other selected from the group consisting of a direct bond, NR3, CR3R4, S, and O.
In a more preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb-0c, wherein X is at each occurrence independently from each other selected from the group consisting of a direct bond, NR3, S, and O.
In a certain embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb-0c, wherein X is at each occurrence independently from each other selected from the group consisting of a direct bond and NR3.
In a certain embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb-0c, wherein X is NR3.
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb-2
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb-3
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb-3, wherein at least one Ra is different from hydrogen.
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IVb-3, wherein RV is selected from
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb-4
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVb-4, wherein at least one Ra is different from hydrogen.
In a preferred embodiment, the organic light-emitting molecule of the invention includes or consists of a structure of Formula IVb-3, wherein RV is selected from
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVc
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVc-2
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVd
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVd-2
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVe
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVe-2
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVf
Below, examples with different substituents X are shown:
Additional examples of the organic molecules according to the invention include:
In one embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVf, wherein at least one Ra is different from hydrogen.
In a preferred embodiment, the organic molecule of the invention includes or consists of a structure of Formula IVf, with the proviso that, if X is NR3 and Rd and Re are connected to each other to form an aromatic ring system, RV is N(R5)2 or forms a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and/or benzo-fused ring system with one or more substituents R2, R3, R5, and/or RIV.
In a preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula IVf, wherein X is at each occurrence independently from each other selected from the group consisting of a direct bond, NR3, CR3R4, S, and O.
In a more preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVf, wherein X is at each occurrence independently from each other selected from the group consisting of a direct bond, NR3, S, and O.
In a certain embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVf, wherein X is at each occurrence independently from each other selected from the group consisting of a direct bond and NR3.
In a certain embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVf, wherein X is NR3.
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVf, wherein R3 is independently from each other selected from the group consisting of:
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVf, wherein R3 is independently from each other selected from the group consisting of:
In more preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVf, wherein R3 is independently from each other selected from the group consisting of:
In a certain embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVf, wherein R3 is independently from each other selected from the group consisting of:
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVf, wherein RV is at each occurrence independently from each other selected from the group consisting of:
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVf, wherein RV is at each occurrence independently from each other selected from the group consisting of:
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVf, wherein R1, R2, R3, R4, RI, RII, RIII, RIV, and RV are each independently from each other selected from the group consisting of: hydrogen;
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVf, wherein R8 is at each occurrence independently from each other selected from the group consisting of: hydrogen;
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVf, wherein R8 is at each occurrence independently from each other selected from the group consisting of: hydrogen;
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVf, wherein Ra is at each occurrence independently from each other selected from the group consisting of: hydrogen;
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVf, wherein Ra is at each occurrence independently from each other selected from the group consisting of: hydrogen;
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVf-2
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVf-3
In a preferred embodiment of the invention, the organic molecule/oligomer includes or consists of a structure of Formula IVf-4
In one embodiment, at least one substituent of R1, R2, R3, R4, R5, RI, RII, RIII, RIV, and/or RV independently from each other, forms a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and/or benzo-fused ring system together with an adjacent substituent R1, R2, R3, R4, R5, RI, RII, RIII, RIV, and/or RV.
In a preferred embodiment, exactly two substituents of R1, R2, R3, R4, R5, RI, RII, RIII, RIV, and/or RV independently from each other, form a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and/or benzo-fused ring system together with an adjacent substituents R1, R2, R3, R4, R5, RI, RII, RIII, RIV, and/or RV, i.e., in total two ring systems are formed by the aforementioned substituents.
In a preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula Va
A is at each occurrence independently from each other O, S, or NR5.
In a preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula Vb
A is at each occurrence independently from each other O, S, or NR5.
In one embodiment, A is selected from O and NR5.
In a preferred embodiment, A is O.
Examples for structures according to Formula Va are shown in the following for A=O:
In a preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula VIa
In a preferred embodiment of the invention the organic molecule including or consisting of a structure of Formula Via emits green light.
In a preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula VIb
Non-limiting examples for structures according to Formula VIa are shown in the following for A=O:
In a preferred embodiment of the invention, the organic molecule includes or consists of a structure of Formula Vila or Formula VIIb:
In a preferred embodiment of the invention the organic molecule including or consisting of a structure of Formula VIIa is a green emitter.
Examples for structures according to Formula VIIa and Formula VIIb are shown in the following:
As used throughout the present application, the terms “aryl” and “aromatic” may be understood in the broadest sense as any mono-, bi- or polycyclic aromatic moieties. Accordingly, an aryl group contains 6 to 60 aromatic ring atoms, and a heteroaryl group contains 5 to 60 aromatic ring atoms, of which at least one is a heteroatom. Notwithstanding, throughout the application the number of aromatic ring atoms may be given as subscripted number in the definition of certain substituents. In particular, the heteroaromatic ring includes one to three heteroatoms. Again, the terms “heteroaryl” and “heteroaromatic” may be understood in the broadest sense as any mono-, bi- or polycyclic hetero-aromatic moieties that include at least one heteroatom. The heteroatoms may at each occurrence be the same or different and be individually selected from the group consisting of N, O, and S. Accordingly, the term “arylene” refers to a divalent substituent that bears two binding sites to other molecular structures and thereby serving as a linker structure. In case, a group in the exemplary embodiments is defined differently from the definitions given here, for example, the number of aromatic ring atoms or number of heteroatoms differs from the given definition, the definition in the exemplary embodiments is to be applied. According to the invention, a condensed (annulated) aromatic or heteroaromatic polycycle is built of two or more single aromatic or heteroaromatic cycles, which formed the polycycle via a condensation reaction.
In particular, as used throughout, the term “aryl group or heteroaryl group” includes groups which can be bound via any position of the aromatic or heteroaromatic group, derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, fluoranthene, benzanthracene, benzophenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene; pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthoimidazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalinoimidazole, oxazole, benzoxazole, naphthooxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, 1,3,5-triazine, quinoxaline, pyrazine, phenazine, naphthyridine, carboline, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,2,3,4-tetrazine, purine, pteridine, indolizine, and benzothiadiazole, or combinations of the abovementioned groups.
As used throughout, the term “cyclic group” may be understood in the broadest sense as any mono-, bi- or polycyclic moieties.
As used throughout, the term “biphenyl” as a substituent may be understood in the broadest sense as ortho-biphenyl, meta-biphenyl, or para-biphenyl, wherein ortho, meta and para is defined in regard to the binding site to each other chemical moiety.
As used throughout, the term “alkyl group” may be understood in the broadest sense as any linear, branched, or cyclic alkyl substituent. In particular, examples of the term alkyl include the substituents methyl (Me), ethyl (Et), n-propyl (nPr), i-propyl (iPr), cyclopropyl, n-butyl (nBu), i-butyl (tBu), s-butyl (Bu), t-butyl (tBu), cyclobutyl, 2-methylbutyl, n-pentyl, s-pentyl, t-pentyl, 2-pentyl, neo-pentyl, cyclopentyl, n-hexyl, s-hexyl, t-hexyl, 2-hexyl, 3-hexyl, neo-hexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1-methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl, 1-bicyclo[2,2,2]octyl, 2-bicyclo[2,2,2]-octyl, 2-(2,6-dimethyl)octyl, 3-(3,7-dimethyl)octyl, adamantyl, 2,2,2-trifluoroethyl, 1,1-dimethyl-n-hex-1-yl, 1,1-dimethyl-n-hept-1-yl, 1,1-dimethyl-n-oct-1-yl, 1,1-dimethyl-n-dec-1-yl, 1,1-dimethyl-n-dodec-1-yl, 1,1-dimethyl-n-tetradec-1-yl, 1,1-dimethyl-n-hexadec-1-yl, 1,1-dimethyl-n-octadec-1-yl, 1,1-diethyl-n-hex-1-yl, 1,1-diethyl-n-hept-1-yl, 1,1-diethyl-n-oct-1-yl, 1,1-diethyl-n-dec-1-yl, 1,1-diethyl-n-dodec-1-yl, 1,1-diethyl-n-tetradec-1-yl, 1,1-diethyl-n-hexadec-1-yl, 1,1-diethyl-n-octadec-1-yl, 1-(n-propyl)-cyclohex-1-yl, 1-(n-butyl)-cyclohex-1-yl, 1-(n-hexyl)-cyclohex-1-yl, 1-(n-octyl)-cyclohex-1-yl, and 1-(n-decyl)-cyclohex-1-yl.
As used throughout, the term “alkenyl” includes linear, branched, or cyclic alkenyl substituents. Examples of the term “alkenyl group”, for example, includes the substituents ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, and cyclooctadienyl.
As used throughout, the term “alkynyl” includes linear, branched, or cyclic alkynyl substituents. The term “alkynyl group”, for example, includes ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, or octynyl.
As used throughout, the term “alkoxy” includes linear, branched, or cyclic alkoxy substituents. The term “alkoxy group” exemplarily includes methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, or 2-methylbutoxy.
As used throughout, the term “thioalkoxy” includes linear, branched, or cyclic thioalkoxy substituents, in which the O of the exemplarily alkoxy groups is replaced by S.
As used throughout, the terms “halogen” and “halo” may be understood in the broadest sense as being preferably fluorine, chlorine, bromine, or iodine.
Whenever hydrogen (H) is mentioned herein, it could also be replaced by deuterium at each occurrence.
It is understood that when a molecular fragment is described as being a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g., naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g., naphthalene, dibenzofuran). As used herein, these different ways of designating a substituent or attached fragment are considered to be equivalent.
In one embodiment, the organic molecules according to the invention have an excited state lifetime of not more than 5.0 μs, of not more than 2.5 μs, in particular of not more than 2.0 μs, more preferably of not more than 1.0 μs or not more than 0.7 μs in a film of poly(methyl methacrylate) (PMMA) with 1% to 5%, in particular with 2% by weight of organic molecule at room temperature.
In a further embodiment of the invention, the organic molecules according to the invention have an emission peak in the visible or nearest ultraviolet range, i.e., in the range of a wavelength of from 380 to 800 nm, with a full width at half maximum of less than 0.25 eV, preferably less than 0.22 eV, more preferably less than 0.18 eV, even more preferably less than 0.15 eV or even less than 0.12 eV in a film of poly(methyl methacrylate) (PMMA) with 1% to 5%, in particular with 2% by weight of organic molecule at room temperature.
Orbital and excited state energies can be determined either by means of experimental methods. The energy of the highest occupied molecular orbital EHOMO is determined by methods known to the person skilled in the art from cyclic voltammetry measurements with an accuracy of 0.1 eV. The energy of the lowest unoccupied molecular orbital ELUMO is calculated as EHOMO+Egap, wherein Egap is determined as follows: For host compounds, the onset of the emission spectrum of a film with 10% by weight of host in poly(methyl methacrylate) (PMMA) is used as Egap, unless stated otherwise. For emitter molecules, Egap is determined as the energy at which the excitation and emission spectra of a film with 1% to 5%, in particular with 2% by weight of emitter in PMMA cross. For the organic molecules according to the invention, Egap is determined as the energy at which the excitation and emission spectra of a film with 1% to 5%, in particular with 2% by weight of emitter in PMMA cross.
The energy of the first excited triplet state T1 is determined from the onset of the emission spectrum at low temperature, typically at 77 K. For host compounds, where the first excited singlet state and the lowest triplet state are energetically separated by >0.4 eV, the phosphorescence is usually visible in a steady-state spectrum in 2-Me-THF. The triplet energy can thus be determined as the onset of the phosphorescence spectrum. For TADF emitter molecules, the energy of the first excited triplet state T1 is determined from the onset of the delayed emission spectrum at 77 K, if not otherwise stated, measured in a film of PMMA with 1% to 5%, in particular with 2% by weight of emitter and in case of the organic molecules according to the invention with 1% to 5%, in particular with 2% by weight of the organic molecules according to the invention. Both for host and emitter compounds, the energy of the first excited singlet state S1 is determined from the onset of the emission spectrum, if not otherwise stated, measured in a film of PMMA with 10% by weight of host or emitter compound and in case of the organic molecules according to the invention with 1% to 5%, in particular with 2% by weight of the organic molecules according to the invention.
The onset of an emission spectrum is determined by computing the intersection of the tangent to the emission spectrum with the x-axis. The tangent to the emission spectrum is set at the high-energy side of the emission band and at the point at half maximum of the maximum intensity of the emission spectrum.
A further aspect of the invention relates to the use of an organic molecule of the invention as a luminescent emitter or as an absorber, and/or as a host material and/or as an electron transport material, and/or as a hole injection material, and/or as a hole blocking material in an optoelectronic device.
A preferred embodiment relates to the use of an organic molecule according to the invention as a luminescent emitter in an optoelectronic device.
The optoelectronic device may be understood in the broadest sense as any device based on organic materials that is suitable for emitting light in the visible or nearest ultraviolet (UV) range, i.e., in the range of a wavelength of from 380 to 800 nm. More preferably, the optoelectronic device may be able to emit light in the visible range, i.e., of from 400 nm to 800 nm.
In the context of such use, the optoelectronic device is more particularly selected from the group consisting of:
In a preferred embodiment in the context of such use, the optoelectronic device is a device selected from the group consisting of an organic light emitting diode (OLED), a light emitting electrochemical cell (LEC), and a light-emitting transistor.
In the case of the use, the fraction of the organic molecule according to the invention in the emission layer in an optoelectronic device, more particularly in an OLED, is 0.1% to 99% by weight, more particularly 1% to 80% by weight. In an alternative embodiment, the proportion of the organic molecule in the emission layer is 100% by weight.
In one embodiment, the light-emitting layer includes not only the organic molecules according to the invention, but also a host material whose triplet (T1) and singlet (S1) energy levels are energetically higher than the triplet (T1) and singlet (S1) energy levels of the organic molecule.
A further aspect of the invention relates to a composition including or consisting of:
In one embodiment, the light-emitting layer includes (or essentially consists of) a composition including or consisting of:
In a particular embodiment, the light-emitting layer EML includes (or essentially consists of) a composition including or consisting of:
Preferably, energy can be transferred from the host compound H to the one or more organic molecules according to the invention, in particular transferred from the first excited triplet state T1(H) of the host compound H to the first excited triplet state T1(E) of the one or more organic molecules according to the invention E and/or from the first excited singlet state S1(H) of the host compound H to the first excited singlet state S1(E) of the one or more organic molecules according to the invention E.
In one embodiment, the host compound H has a highest occupied molecular orbital HOMO(H) having an energy EHOMO(H) in the range of from −5 to −6.5 eV and the at least one further host compound D has a highest occupied molecular orbital HOMO(D) having an energy EHOMO(D), wherein EHOMO(H)>EHOMO(D).
In a further embodiment, the host compound H has a lowest unoccupied molecular orbital LUMO(H) having an energy ELUMO(H) and the at least one further host compound D has a lowest unoccupied molecular orbital LUMO(D) having an energy ELUMO(D), wherein ELUMO(H)>ELUMO(D).
In one embodiment, the host compound H has a highest occupied molecular orbital HOMO(H) having an energy EHOMO(H) and a lowest unoccupied molecular orbital LUMO(H) having an energy ELUMO(H), and
In one embodiment of the invention the host compound D and/or the host compound H is a thermally-activated delayed fluorescence (TADF)-material. TADF materials exhibit a ΔEST value, which corresponds to the energy difference between the first excited singlet state (S1) and the first excited triplet state (T1), of less than 2500 cm−1. Preferably the TADF material exhibits a ΔEST value of less than 3000 cm−1, more preferably less than 1500 cm−1, even more preferably less than 1000 cm−1 or even less than 500 cm-1.
In one embodiment, the host compound D is a TADF material and the host compound H exhibits a ΔEST value of more than 2500 cm−1. In a particular embodiment, the host compound D is a TADF material and the host compound H is selected from group consisting of CBP, mCP, mCBP, 9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole, 9-[3-(dibenzothiophen-2-yl)phenyl]-9H-carbazole, 9-[3,5-bis(2-dibenzofuranyl)phenyl]-9H-carbazole, and 9-[3,5-bis(2-dibenzothiophenyl)phenyl]-9H-carbazole.
In one embodiment, the host compound H is a TADF material and the host compound D exhibits a ΔEST value of more than 2500 cm−1. In a particular embodiment, the host compound H is a TADF material and the host compound D is selected from group consisting of T2T (2,4,6-tris(biphenyl-3-yl)-1,3,5-triazine), T3T (2,4,6-tris(triphenyl-3-yl)-1,3,5-triazine), and/or TST (2,4,6-tris(9,9′-spirobifluoren-2-yl)-1,3,5-triazine).
In a further aspect, the invention relates to an optoelectronic device including an organic molecule or a composition of the type described here, more particularly in the form of a device selected from the group consisting of organic light-emitting diode (OLED), light-emitting electrochemical cell, OLED sensor, more particularly gas and vapour sensors not hermetically externally shielded, organic diode, organic solar cell, organic transistor, organic field-effect transistor, organic laser, and down-conversion element.
In a preferred embodiment, the optoelectronic device is a device selected from the group consisting of an organic light emitting diode (OLED), a light emitting electrochemical cell (LEC), and a light-emitting transistor.
In one embodiment of the optoelectronic device of the invention, the organic molecule according to the invention E is used as emission material in a light-emitting layer EML.
In one embodiment of the optoelectronic device of the invention, the light-emitting layer EML consists of the composition according to the invention described here.
When the optoelectronic device is an OLED, it may, for example, have the following layer structure:
Furthermore, the optoelectronic device may, in one embodiment, include one or more protective layers protecting the device from damaging exposure to harmful species in the environment including, for example, moisture, vapor, and/or gases.
In one embodiment of the invention, the optoelectronic device is an OLED, with the following inverted layer structure:
In one embodiment of the invention, the optoelectronic device is an OLED, which may have a stacked architecture. In this architecture, contrary to the typical arrangement in which the OLEDs are placed side by side, the individual units are stacked on top of each other. Blended light may be generated with OLEDs exhibiting a stacked architecture, in particular white light may be generated by stacking blue, green, and red OLEDs. Furthermore, the OLED exhibiting a stacked architecture may include a charge generation layer (CGL), which is typically located between two OLED subunits and typically consists of a n-doped and p-doped layer with the n-doped layer of one CGL being typically located closer to the anode layer.
In one embodiment of the invention, the optoelectronic device is an OLED, which includes two or more emission layers between anode and cathode. In particular, this so-called tandem OLED includes three emission layers, wherein one emission layer emits red light, one emission layer emits green light, and one emission layer emits blue light, and optionally may include further layers such as charge generation layers, blocking or transporting layers between the individual emission layers. In a further embodiment, the emission layers are adjacently stacked. In a further embodiment, the tandem OLED includes a charge generation layer between each two emission layers. In addition, adjacent emission layers or emission layers separated by a charge generation layer may be merged.
The substrate may be formed by any material or composition of materials. Most frequently, glass slides are used as substrates. Alternatively, thin metal layers (e.g., copper, gold, silver, or aluminum films) or plastic films or slides may be used. This may allow for a higher degree of flexibility. The anode layer A is mostly composed of materials allowing to obtain an (essentially) transparent film. As at least one of both electrodes should be (essentially) transparent in order to allow light emission from the OLED, either the anode layer A or the cathode layer C is transparent. Preferably, the anode layer A includes a large content or even consists of transparent conductive oxides (TCOs). Such anode layer A may, for example, include indium tin oxide, aluminum zinc oxide, fluorine doped tin oxide, indium zinc oxide, PbO, SnO, zirconium oxide, molybdenum oxide, vanadium oxide, tungsten oxide, graphite, doped Si, doped Ge, doped GaAs, doped polyaniline, doped polypyrrole, and/or doped polythiophene.
The anode layer A (essentially) may consist of indium tin oxide (ITO) (e.g., (In2O3)0.9(SnO2)0.1). The roughness of the anode layer A caused by the transparent conductive oxides (TCOs) may be compensated by using a hole injection layer (HIL). Further, the HIL may facilitate the injection of quasi charge carriers (i.e., holes) in that the transport of the quasi charge carriers from the TCO to the hole transport layer (HTL) is facilitated. The hole injection layer (HIL) may include poly-3,4-ethylenedioxy thiophene (PEDOT), polystyrene sulfonate (PSS), MoO2, V2O5, CuPC, or CuI, in particular a mixture of PEDOT and PSS. The hole injection layer (HIL) may also prevent the diffusion of metals from the anode layer A into the hole transport layer (HTL). The HIL may, for example, include PEDOT:PSS (poly-3,4-ethylenedioxy thiophene: polystyrene sulfonate), PEDOT (poly-3,4-ethylenedioxy thiophene), mMTDATA (4,4′,4″-tris[phenyl(m-tolyl)amino]triphenylamine), Spiro-TAD (2,2′,7,7′-tetrakis(n,n-diphenylamino)-9,9′-spirobifluorene), DNTPD (N1,N1′-(biphenyl-4,4′-diyl)bis(N1-phenyl-N4,N4-di-m-tolylbenzene-1,4-diamine), NPB (N,N′-nis-(1-naphthalenyl)-N,N′-bis-phenyl-(1,1′-biphenyl)-4,4′-diamine), NPNPB (N,N′-diphenyl-N,N′-di-[4-(N,N-diphenyl-amino)phenyl]benzidine), MeO-TPD (N,N,N′,N′-tetrakis(4-methoxyphenyl)benzidine), HAT-CN (1,4,5,8,9,11-hexaazatriphenylen-hexacarbonitrile), and/or Spiro-NPD (N,N′-diphenyl-N,N′-bis-(1-naphthyl)-9,9′-spirobifluorene-2,7-diamine).
Adjacent to the anode layer A or hole injection layer (HIL), a hole transport layer (HTL) is typically located. Herein, any hole transport compound may be used. For example, electron-rich heteroaromatic compounds such as triarylamines and/or carbazoles may be used as hole transport compound. The HTL may decrease the energy barrier between the anode layer A and the light-emitting layer EML. The hole transport layer (HTL) may also be an electron blocking layer (EBL). Preferably, hole transport compounds bear comparably high energy levels of their triplet states T1. For example, the hole transport layer (HTL) may include a star-shaped heterocycle such as tris(4-carbazol-9-ylphenyl)amine (TCTA), poly-TPD (poly(4-butylphenyl-diphenyl-amine)), [alpha]-NPD (poly(4-butylphenyl-diphenyl-amine)), TAPC (4,4′-cyclohexyliden-bis[N,N-bis(4-methylphenyl)benzenamine]), 2-TNATA (4,4′,4″-tris[2-naphthyl(phenyl)amino]trphenylamine), Spiro-TAD, DNTPD, NPB, NPNPB, MeO-TPD, HAT-CN, and/or TrisPcz (9,9′-diphenyl-6-(9-phenyl-9H-carbazol-3-yl)-9H,9′H-3,3′-bicarbazole). In addition, the HTL may include a p-doped layer, which may be composed of an inorganic or organic dopant in an organic hole-transporting matrix. Transition metal oxides such as vanadium oxide, molybdenum oxide, and/or tungsten oxide may, for example, be used as inorganic dopant. Tetrafluorotetracyanoquinodimethane (F4-TCNQ), copper-pentafluorobenzoate (Cu(I)pFBz) or transition metal complexes may, for example, be used as organic dopant.
The EBL may, for example, include mCP (1,3-bis(carbazol-9-yl)benzene), TCTA, 2-TNATA, mCBP (3,3-di(9H-carbazol-9-yl)biphenyl), tris-Pcz, CzSi (9-(4-tert-butylphenyl)-3,6-bis(triphenylsilyl)-9H-carbazole), and/or DCB (N,N′-dicarbazolyl-1,4-dimethylbenzene).
Adjacent to the hole transport layer (HTL), the light-emitting layer EML is typically located. The light-emitting layer EML includes at least one light emitting molecule. Particularly, the EML includes at least one light emitting molecule according to the invention E. In one embodiment, the light-emitting layer includes only the organic molecules according to the invention. Typically, the EML additionally includes one or more host materials H. For example, the host material H is selected from CBP (4,4′-Bis-(N-carbazolyl)-biphenyl), mCP, mCBP Sif87 (dibenzo[b,d]thiophen-2-yltriphenylsilane), CzSi, Sif88 (dibenzo[b,d]thiophen-2-yl)diphenylsilane), DPEPO (bis[2-(diphenylphosphino)phenyl] ether oxide), 9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole, 9-[3-(dibenzothiophen-2-yl)phenyl]-9H-carbazole, 9-[3,5-bis(2-dibenzofuranyl)phenyl]-9H-carbazole, 9-[3,5-bis(2-dibenzothiophenyl)phenyl]-9H-carbazole, T2T (2,4,6-tris(biphenyl-3-yl)-1,3,5-triazine), T3T (2,4,6-tris(triphenyl-3-yl)-1,3,5-triazine), and/or TST (2,4,6-tris(9,9′-spirobifluoren-2-yl)-1,3,5-triazine). The host material H typically should be selected to exhibit first triplet (T1) and first singlet (S1) energy levels, which are energetically higher than the first triplet (T1) and first singlet (S1) energy levels of the organic molecule.
In one embodiment of the invention, the EML includes a so-called mixed-host system with at least one hole-dominant host and one electron-dominant host. In a particular embodiment, the EML includes exactly one light emitting organic molecule according to the invention and a mixed-host system including T2T as electron-dominant host and a host selected from CBP, mCP, mCBP, 9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole, 9-[3-(dibenzothiophen-2-yl)phenyl]-9H-carbazole, 9-[3,5-bis(2-dibenzofuranyl)phenyl]-9H-carbazole and 9-[3,5-bis(2-dibenzothiophenyl)phenyl]-9H-carbazole as hole-dominant host. In a further embodiment the EML includes 50-80% by weight, preferably 60-75% by weight of a host selected from CBP, mCP, mCBP, 9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole, 9-[3-(dibenzothiophen-2-yl)phenyl]-9H-carbazole, 9-[3,5-bis(2-dibenzofuranyl)phenyl]-9H-carbazole, and 9-[3,5-bis(2-dibenzothiophenyl)phenyl]-9H-carbazole; 10-45% by weight, preferably 15-30% by weight of T2T and 5-40% by weight, preferably 10-30% by weight of light emitting molecule according to the invention.
Adjacent to the light-emitting layer EML, an electron transport layer (ETL) may be located. Herein, any electron transporter may be used. Exemplarily, electron-poor compounds such as, e.g., benzimidazoles, pyridines, triazoles, oxadiazoles (e.g., 1,3,4-oxadiazole), phosphine oxides, and/or sulfone, may be used. An electron transporter may also be a star-shaped heterocycle such as 1,3,5-tri(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl (TPBi). The ETL may include NBphen (2,9-bis(naphthalen-2-yl)-4,7-diphenyl-1,10-phenanthroline), Alq3 (Aluminum-tris(8-hydroxyquinoline)), TSPO1 (diphenyl-4-triphenylsilylphenyl-phosphine oxide), BPyTP2 (2,7-di(2,2′-bipyridin-5-yl)triphenylene), Sif87 (dibenzo[b,d]thiophen-2-yltriphenylsilane), Sif88 (dibenzo[b,d]thiophen-2-yl)diphenylsilane), BmPyPhB (1,3-bis[3,5-di(pyridin-3-yl)phenyl]benzene), and/or BTB (4,4′-bis-[2-(4,6-diphenyl-1,3,5-triazinyl)]-1,1′-biphenyl). Optionally, the ETL may be doped with materials such as Liq. The electron transport layer (ETL) may also block holes or a hole blocking layer (HBL) is introduced.
The HBL may, for example, include BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline=Bathocuproine), BAlq (bis(8-hydroxy-2-methylquinoline)-(4-phenylphenoxy)aluminum), NBphen (2,9-bis(naphthalen-2-yl)-4,7-diphenyl-1,10-phenanthroline), Alq3 (Aluminum-tris(8-hydroxyquinoline)), TSPO1 (diphenyl-4-triphenylsilylphenyl-phosphine oxide), T2T (2,4,6-tris(biphenyl-3-yl)-1,3,5-triazine), T3T (2,4,6-tris(triphenyl-3-yl)-1,3,5-triazine), TST (2,4,6-tris(9,9′-spirobifluoren-2-yl)-1,3,5-triazine), and/or TCB/TCP (1,3,5-tris(N-carbazolyl)benzene/1,3,5-tris(carbazol)-9-yl) benzene).
Adjacent to the electron transport layer (ETL), a cathode layer C may be located. The cathode layer C may, for example, include or may consist of a metal (e.g., Al, Au, Ag, Pt, Cu, Zn, Ni, Fe, Pb, LiF, Ca, Ba, Mg, In, W, or Pd) or a metal alloy. For practical reasons, the cathode layer may also consist of (essentially) intransparent metals such as Mg, Ca, or Al. Alternatively or additionally, the cathode layer C may also include graphite and or carbon nanotubes (CNTs). Alternatively, the cathode layer C may also consist of nanoscale silver wires.
An OLED may further, optionally, include a protection layer between the electron transport layer (ETL) and the cathode layer C (which may be designated as electron injection layer (EIL)). This layer may include lithium fluoride, cesium fluoride, silver, Liq (8-hydroxyquinolinolatolithium), Li2O, BaF2, MgO, and/or NaF.
Optionally, the electron transport layer (ETL) and/or a hole blocking layer (HBL) may also include one or more host compounds H.
In order to modify the emission spectrum and/or the absorption spectrum of the light-emitting layer EML further, the light-emitting layer EML may further include one or more further emitter molecules F. Such an emitter molecule F may be any emitter molecule known in the art. Preferably such an emitter molecule F is a molecule with a structure differing from the structure of the molecules according to the invention E. The emitter molecule F may optionally be a TADF emitter. Alternatively, the emitter molecule F may optionally be a fluorescent and/or phosphorescent emitter molecule which is able to shift the emission spectrum and/or the absorption spectrum of the light-emitting layer EML. Exemplarily, the triplet and/or singlet excitons may be transferred from the organic emitter molecule according to the invention to the emitter molecule F before relaxing to the ground state S0 by emitting light typically red-shifted in comparison to the light emitted by an organic molecule. Optionally, the emitter molecule F may also provoke two-photon effects (i.e., the absorption of two photons of half the energy of the absorption maximum).
Optionally, an optoelectronic device (e.g., an OLED) may, for example, be an essentially white optoelectronic device. For example, such a white optoelectronic device may include at least one (deep) blue emitter molecule and one or more emitter molecules emitting green and/or red light. Then, there may also optionally be energy transmittance between two or more molecules as described above.
As used herein, if not defined more specifically in the particular context, the designation of the colors of emitted and/or absorbed light is as follows:
With respect to emitter molecules, such colors refer to the emission maximum. Therefore, for example, a deep blue emitter has an emission maximum in the range of from >420 to 480 nm, a sky blue emitter has an emission maximum in the range of from >480 to 500 nm, a green emitter has an emission maximum in a range of from >500 to 560 nm, and a red emitter has an emission maximum in a range of from >620 to 800 nm.
A deep blue emitter may preferably have an emission maximum of below 480 nm, more preferably below 470 nm, even more preferably below 465 nm or even below 460 nm. It will typically be above 420 nm, preferably above 430 nm, more preferably above 440 nm or even above 450 nm.
A green emitter has an emission maximum of below 560 nm, more preferably below 550 nm, even more preferably below 545 nm or even below 540 nm. It will typically be above 500 nm, more preferably above 510 nm, even more preferably above 515 nm or even above 520 nm.
Accordingly, a further aspect of the present invention relates to an OLED, which exhibits an external quantum efficiency at 1000 cd/m2 of more than 8%, more preferably of more than 10%, more preferably of more than 13%, even more preferably of more than 15% or even more than 20%, and/or exhibits an emission maximum between 420 nm and 500 nm, preferably between 430 nm and 490 nm, more preferably between 440 nm and 480 nm, even more preferably between 450 nm and 470 nm, and/or exhibits a LT80 value at 500 cd/m2 of more than 100 h, preferably more than 200 h, more preferably more than 400 h, even more preferably more than 750 h or even more than 1000 h. Accordingly, a further aspect of the present invention relates to an OLED, whose emission exhibits a CIEy color coordinate of less than 0.45, preferably less than 0.30, more preferably less than 0.20, or even more preferably less than 0.15 or even less than 0.10.
A further aspect of the present invention relates to an OLED, which emits light at a distinct color point. According to the present invention, the OLED emits light with a narrow emission band (small full width at half maximum (FWHM)). In one aspect, the OLED according to the invention emits light with a FWHM of the main emission peak of less than 0.25 eV, preferably less than 0.20 eV, more preferably less than 0.17 eV, even more preferably less than 0.15 eV or even less than 0.13 eV.
A further aspect of the present invention relates to an OLED, which emits light with CIEx and CIEy color coordinates close to the CIEx (=0.131) and CIEy (=0.046) color coordinates of the primary color blue (CIEx=0.131 and CIEy=0.046) as defined by ITU-R Recommendation BT.2020 (Rec. 2020) and thus is suited for the use in Ultra High Definition (UHD) displays, e.g., UHD-TVs. Accordingly, a further aspect of the present invention relates to an OLED, whose emission exhibits a CIEx color coordinate of between 0.02 and 0.30, preferably between 0.03 and 0.25, more preferably between 0.05 and 0.20, or even more preferably between 0.08 and 0.18 or even between 0.10 and 0.15, and/or a CIEy color coordinate of between 0.00 and 0.45, preferably between 0.01 and 0.30, more preferably between 0.02 and 0.20, or even more preferably between 0.03 and 0.15 or even between 0.04 and 0.10.
Another embodiment of the present invention relates to an OLED, which emits light with CIEx and CIEy color coordinates close to the CIEx (=0.170) and CIEy (=0.797) color coordinates of the primary color green (CIEx=0.170 and CIEy=0.797) as defined by ITU-R Recommendation BT.2020 (Rec. 2020) and thus is suited for the use in Ultra High Definition (UHD) displays, e.g., UHD-TVs. In this context, the term “close to” refers to the ranges of CIEx and CIEy coordinates provided at the end of this paragraph. In commercial applications, typically top-emitting (top-electrode is transparent) devices are used, whereas test devices as used throughout the present application represent bottom-emitting devices (bottom-electrode and substrate are transparent). Accordingly, a further aspect of the present invention relates to an OLED, whose emission exhibits a CIEx color coordinate of between 0.15 and 0.45, preferably between 0.15 and 0.35, more preferably between 0.15 and 0.30, or even more preferably between 0.15 and 0.25 or even between 0.15 and 0.20, and/or a CIEy color coordinate of between 0.60 and 0.92, preferably between 0.65 and 0.90, more preferably between 0.70 and 0.88, or even more preferably between 0.75 and 0.86 or even between 0.79 and 0.84.
Accordingly, a further aspect of the present invention relates to an OLED, which exhibits an external quantum efficiency at 14500 cd/m2 of more than 8%, more preferably of more than 10%, more preferably of more than 13%, even more preferably of more than 15% or even more than 17%, or even more than 20%, and/or exhibits an emission maximum between 485 nm and 560 nm, preferably between 500 nm and 560 nm, more preferably between 510 nm and 550 nm, even more preferably between 515 nm and 540 nm, and/or exhibits a LT97 value at 14500 cd/m2 of more than 100 h, preferably more than 250 h, more preferably more than 50 h, even more preferably more than 750 h or even more than 1000 h.
In a further embodiment of the invention, the composition has a photoluminescence quantum yield (PLQY) of more than 20%, preferably more than 30%, more preferably more than 35%, more preferably more than 40%, more preferably more than 45%, more preferably more than 50%, more preferably more than 55%, even more preferably more than 60% or even more than 70% at room temperature.
In a further aspect, the invention relates to a method for producing an optoelectronic component. In this case an organic molecule of the invention is used.
The optoelectronic device, in particular the OLED according to the present invention can be fabricated by any means of vapor deposition and/or liquid processing. Accordingly, at least one layer is
The methods used to fabricate the optoelectronic device, in particular the OLED according to the present invention are known in the art. The different layers are individually and successively deposited on a suitable substrate by means of subsequent deposition processes. The individual layers may be deposited using the same or differing deposition methods.
Vapor deposition processes, for example, include thermal (co)evaporation, chemical vapor deposition and physical vapor deposition. For active matrix OLED display, an AMOLED backplane is used as substrate. The individual layer may be processed from solutions or dispersions employing adequate solvents. Examples of solution deposition process include spin coating, dip coating and jet printing. Liquid processing may optionally be carried out in an inert atmosphere (e.g., in a nitrogen atmosphere) and the solvent may be completely or partially removed by means known in the state of the art.
In another aspect, the invention also refers to an organic light-emitting molecule including or consisting of a structure of Formula 100
wherein the substituents R1, R2, R3, R4, R5, RI, RII, RIII, RIV, and RV independently from each other, optionally form a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and/or benzo-fused ring system with one or more other substituents R1, R2, R3, R4, R5, RI, RII, RIII, RIV, and/or RV.
AAV1: I0 (1.00 equivalents), 3,5-dichloro-iodobenzene (I0-1, 0.8 equivalents), palladium(II) acetate (0.03 equivalents), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (S-Phos, CAS: 657408-07-6, 0.06 equivalents) and tribasic potassium phosphate (K3PO4; 3.00 equivalents) are stirred under nitrogen atmosphere in a dioxane/water mixture at 90° C. for 12 h. After cooling down to room temperature (rt) the reaction mixture is extracted between DCM and brine and the phases are separated and then the solvent is removed under reduced pressure. The crude material is purified by column chromatography and I-1 is obtained with a yield of 84%. GC-MS: 313.02 m/z.
AAV2: I-1 (1.00 equivalents), diphenylamine (CAS: 122-39-4, 2.5 equivalents), tris(dibenzylideneacetone)dipalladium(0) (CAS: 51364-51-3, 0.01 equivalents), tri-tert-butyl phosphine (CAS: 13716-12-6, 0.04 equivalents) and sodium tert-butoxide (CAS: 865-48-5, 4.00 equivalents) are stirred under nitrogen atmosphere in dry toluene at 100° C. for 12 h. After cooling down to room temperature (rt) the reaction mixture is washed with water and brine and the phases are separated and then the solvent is removed under reduced pressure. The crude material is purified by recrystallization and I-2 is obtained with a yield of 45%. LC-MS: 578.40 m/z at rt: 4.69 min.
AAV3: I-2 (1.00 equivalents) is placed in a round bottom flask under nitrogen. The solvent (1,2-dichlorobenzene is added. Boron tribromide (CAS: 10294-33-4, 6.00 equivalents) is added dropwise and it is heated to 180° C. After cooling to rt, it is further cooled to 0° C. DIPEA (CAS: 7087-68-5, 10.00 equivalents) is added and it is stirred for 1 h. The reaction mixture is washed with water and the phases are separated and then the solvent is removed under reduced pressure. The crude material is purified by column chromatography and P is obtained with a yield of 32%. LC-MS: 586 m/z at rt: 5.73 min.
AAV4: E1 (1.00 equivalents), Bis(pinacolato)diboron (CAS: 73183-34-3, 1.0 equivalents), Tris(dibenzylideneacetone)dipalladium (CAS: 51364-51-3, 0.02 equivalents), 2-dicyclohexylphosphino-2′,4′,6′-tri-isopropyl-1,1′-biphenyl (X-Phos, CAS: 564483-18-7, 0.08 equivalents) and potassium acetate (KOAc; CAS: 127-08-2, 2.00 equivalents) are stirred under nitrogen atmosphere in dry toluene at 105° C. for 24 h. After cooling down to room temperature (rt) the reaction mixture is extracted between ethyl acetate and brine and the combined organic layers concentrated under reduced pressure. The crude material is purified by column chromatography or by recrystallization and I-4 is obtained as a solid.
AAV5: I-4 (1.00 equivalents), E2 (1.0 equivalents), tris(dibenzylideneacetone)dipalladium(0) (CAS: 51364-51-3, 0.01 equivalents), S-Phos (CAS: 657408-07-6, 0.04 equivalents) and potassium phosphate tribasic (K3PO4, CAS: 7778-53-2, 3.00 equivalents) are stirred under nitrogen atmosphere in a dioxane/water mixture at 100° C. for 2 h. After cooling down to room temperature (rt) the reaction mixture is washed with water and brine. The combined organic layers are dried over MgSO4, filtered and concentrated under reduced pressure. The crude material is purified by recrystallization or column chromatography and I-5 is obtained as a solid.
AAV6: I-5 (1.00 equivalents) is placed in a round bottom flask under nitrogen. The solvent (1,2-dichlorobenzene is added. Boron tribromide (CAS: 10294-33-4, 4.00 equivalents) is added dropwise and it is heated to 180° C. overnight. After cooling to rt, it is further cooled to 0° C. DIPEA (CAS: 7087-68-5, 10.00 equivalents) is added and it is stirred for 1 h. The reaction mixture is washed with water and the phases are separated and then the solvent is removed under reduced pressure. The crude material is purified by column chromatography or by recrystallization and P-1 is obtained as a solid.
AAV7: E3 (2.00 equivalents), E4 (1.0 equivalents), tris(dibenzylideneacetone)dipalladium(0) (CAS: 51364-51-3, 0.01 equivalents), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (S-Phos, CAS: 657408-07-6, 0.04 equivalents) and tribasic potassium phosphate (K3PO4: 3.00 equivalents) are stirred under nitrogen atmosphere in a THF/water mixture at 80° C. After cooling down to room temperature (rt), the reaction mixture is extracted between ethyl acetate and brine and the phases are separated and then the solvent is removed under reduced pressure. The crude material is purified by column chromatography or by recrystallization and I-6 is obtained as solid.
AAV8: I-6 (1.00 equivalents), E5 (1.00 equivalents), tris(dibenzylideneacetone)dipalladium(0) (CAS: 51364-51-3, 0.01 equivalents), tri-tert-butyl phosphine (CAS: 13716-12-6, 0.04 equivalents) and sodium tert-butoxide (CAS: 865-48-5, 3.00 equivalents) are stirred under nitrogen atmosphere in dry toluene at 110° C. for 72 h. After cooling down to room temperature (rt) the reaction mixture is washed with water and brine and the phases are separated and then the solvent is removed under reduced pressure. The crude material is purified by recrystallization or column chromatography and I-7 is obtained as a solid.
AAV9: I-7 (1.00 equivalents) is placed in a round bottom flask under nitrogen. The solvent 1,2-dichlorobenzene is added. Boron tribromide (CAS: 10294-33-4, 4.00 equivalents) is added dropwise and it is heated to 180° C. After cooling to rt, it is further cooled to 0° C. DIPEA (CAS: 7087-68-5, 10.00 equivalents) is added and it is stirred for 1 h. The reaction mixture is washed with water and the phases are separated and then the solvent is removed under reduced pressure. The crude material is purified by column chromatography or by recrystallization and P-2 is obtained as a solid.
AAV10: E5 (1.05 equivalents), E6 (1.00 equivalents), tris(dibenzylideneacetone)dipalladium(0) (CAS: 51364-51-3, 0.005 equivalents), Sodium tert-butoxide (NaOtBu, CAS: 865-48-5, 1.50 equivalents) and Tri-tert-butylphosphonium tetrafluoroborate (P(tBu)3HBF4; CAS: 131274-22-1, 0.02 equivalents) are stirred under nitrogen atmosphere in dry toluene at 100° C. overnight. After cooling down to room temperature (rt) the reaction mixture is added water, the phases are separated and the combined organic layers dried over MgSO4, filtered and concentrated under reduced pressure. The crude material is purified by column chromatography or by recrystallization and I-8 is obtained as solid.
AAV11: I-8 (1.00 equivalents), E3 (1.2 equivalents), tris(dibenzylideneacetone)dipalladium(0) (CAS: 51364-51-3, 0.01 equivalents), X-Phos (CAS: 564483-18-7, 0.04 equivalents) and Potassium phosphate tribasic (K3PO4, CAS: 7778-53-2, 2.00 equivalents) are stirred under nitrogen atmosphere in a THF/water mixture at 80° C. for 96 h. After cooling down to room temperature (rt) the reaction mixture is washed with water and brine, the combined organic layers are dried over MgSO4, filtered and concentrated under reduced pressure. The crude material is purified by recrystallization or column chromatography and I-9 is obtained as a solid.
The last reaction step was proceed as described in AAV9, where chlorobenzene was used as the solvent and where the reaction temperature was 135° C.
The first reaction step was proceed as described in AAV7.
AAV12: I-6 (2.00 equivalents), E7 (1.0 equivalents), tris(dibenzylideneacetone)dipalladium(0) (CAS: 51364-51-3, 0.01 equivalents), tri-tert-butyl phosphine (CAS: 13716-12-6, 0.04 equivalents) and sodium tert-butoxide (CAS: 865-48-5, 6.00 equivalents) are stirred under nitrogen atmosphere in dry toluene at 110° C. for 72 h. After cooling down to room temperature (rt) the reaction mixture extracted between ethyl acetate and brine and the phases are separated and the solvent is removed under reduced pressure. The crude material is purified by recrystallization or by column chromatography and I-9 is obtained as a solid.
AAV13: I-9 (1.00 equivalents) is placed in a round bottom flask under nitrogen. The solvent (1,2-dichlorobenzene is added. Boron tribromide (CAS: 10294-33-4, 6.00 equivalents) is added dropwise and it is heated to 180° C. After cooling to rt, it is further cooled to 0° C. DIPEA (CAS: 7087-68-5, 10.00 equivalents) is added and it is stirred for 1 h. The reaction mixture is washed with water and the phases are separated and then the solvent is removed under reduced pressure. The crude material is purified by column chromatography or recrystallization and P-3 is obtained as a solid.
AAV14: E5 (2.10 equivalents), E8 (1.00 equivalents), tris(dibenzylideneacetone)-dipalladium(0) (CAS: 51364-51-3, 0.01 equivalents), Sodium tert-butoxide (NaOtBu, CAS: 865-48-5, 3.15 equivalents) and Tri-tert-butylphosphine (P(tBu)3; CAS: 13716-12-6, 0.04 equivalents) are stirred under nitrogen atmosphere in dry toluene at 110° C. for 1 h. After cooling down to room temperature (rt) the reaction mixture is extracted between ethyl acetate and brine and the combined organic layers concentrated under reduced pressure. The crude material is purified by column chromatography or by recrystallization and I-10 is obtained as solid.
AAV15: I-10 (1.00 equivalents), E3 (1.2 equivalents), Palladium(II) acetate (CAS: 3375-31-3, 0.06 equivalents), X-Phos (CAS: 564483-18-7, 0.12 equivalents) and Potassium phosphate tribasic (K3PO4, CAS: 7778-53-2, 3.00 equivalents) are stirred under nitrogen atmosphere in a dioxane/water mixture at 100° C. for 55 h. After cooling down to room temperature (rt) the reaction mixture is extracted between toluene and brine and the combined organic layers concentrated under reduced pressure. The crude material is purified by recrystallization or column chromatography and I-11 is obtained as a solid.
AAV0-3: Under nitrogen, I-11 (1.00 equivalents) is dissolved in tert-butylbenzene. At 20° C., n-BuLi (2.5 M in hexane, CAS: 109-72-8, 1.1 equivalents) is injected and the mixture stirred for 15 min. Subsequently, t-BuLi (1 M in pentane, CAS: 594-19-4, 2.2 equivalents) is added and the mixture stirred at 60° C. for 2 h. Subsequently, the mixture is cooled down below −60° C., followed by dropwise addition of BBr3 CAS: 10294-33-4, 1.3 equivalents). The mixture is allowed to warm to rt, followed by stirring at rt for 16 h. The mixture is extracted between ethyl acetate and water and the combined organic layers concentrated under reduced pressure. The crude is purified with column chromatography or by recrystallization to obtain the target compound as a solid.
AAV16: E3 (1.00 equivalents), E9 (1.1 equivalents), Tetrakis(triphenylphosphine)palladium(0)
(Pd(PPh3)4, CAS: 14221-01-3, 0.02 equivalents) and potassium carbonate (K2CO3; 2.00 equivalents) are stirred under nitrogen atmosphere in a THF/water mixture at 80° C. for 48 h. After cooling down to room temperature (rt) the phases are separated and the aqueous layer extracted with ethyl acetate. The combined organic layers are dried over MgSO4, filtered and concentrated under reduced pressure. The crude material is purified by column chromatography or by recrystallization and I-12 is obtained as solid.
AAV17: I-12 (1.00 equivalents), Di-tert-butyl dicarbonate (CAS: 24424-99-5, 1.4 equivalents), 4-Dimethylaminopyridine (4-DMAP, CAS: 1122-58-3, 1.00 equivalents) are stirred under nitrogen atmosphere in dry MeCN at room temperature for 16 h. The reaction mixture is added NaOH solution (1 M), the phases are separated and the aqueous layer is extracted with ethyl acetate. The combined organic layers are washed with water and brine, dried over MgSO4, filtered and concentrated under reduced pressure. The crude material is purified by column chromatography or by recrystallization and I-13 is obtained as solid.
AAV18: I-13 (1.00 equivalents), E5 (1.20 equivalents), tris(dibenzylideneacetone)dipalladium(0) (CAS: 51364-51-3, 0.01 equivalents), tri-tert-butylphosphonium tetrafluoroborate (CAS: 131274-22-1, 0.04 equivalents) and sodium tert-butoxide (CAS: 865-48-5, 2.00 equivalents) are stirred under nitrogen atmosphere in dry toluene at 110° C. for 16 h. After cooling down to room temperature (rt) the reaction mixture is washed with water and the aqueous layer extracted with ethyl acetate. The combined organic layers are dried over MgSO4, filtered and concentrated under reduced pressure. The crude material is purified by recrystallization or column chromatography and I-14 is obtained as a solid.
AAV19: I-14 (1.00 equivalents) is solved in dichloromethane (DCM). Trifluoroacetic Acid (CAS: 76-05-1; 99.7 equivalents) is added at room temperature and the reaction mixture is stirred for 2 h. Subsequently, the phases are separated and the TFA layer extracted with DCM. The combined organic layers are washed with a saturated NaHCO3 solution and water, dried over MgSO4 and filtered. After removal of the solvent under reduced pressure, the crude material is purified by recrystallization or column chromatography and I-15 is obtained as a solid.
AAV20: I-15 (1.00 equivalents) is placed in a round bottom flask under nitrogen. The solvent o-xylene is added. At 0° C., n-Butyllithium (2.5 M in hexane, CAS: 109-72-8, 1.10 equivalents) is added dropwise and the mixture stirred for 15 min. Subsequently, tert-Butyllithium (1.6 M in hexane, CAS: 594-19-4, 2.20 equivalents) is added dropwise, the temperature is increased to 65° C. and the reaction mixture is stirred for 2 h. The reaction mixture is cooled down to room temperature. At −20° C., boron tribromide (1 M in heptane, CAS: 10294-33-4, 1.30 equivalents) is added dropwise, the mixture stirred at 0° C. for 1 h, followed by stirring at rt for 6 h. The reaction mixture is poured in 5% NH3 solution, the phases are separated and the organic layer washed with water. The organic layer is dried over MgSO4, filtered and concentrated under reduced pressure. The crude material is purified by column chromatography or by recrystallization and P-5 is obtained as a solid.
AAV21: In dry DMSO, E10 (1.10 equivalents), E11 (1.00 equivalents) and tribasic potassium phosphate (1.50 equivalents, CAS: 7778-53-2) are heated at 100° C. for 48 h. After cooling down to rt, the mixture is poured onto ice water. The precipitate is filtered off, washed with water and ethanol and collected. The crude is purified by recrystallization or column chromatography to yield compound I-16 as a solid.
AAV22: Under nitrogen, in a mixture of toluene/water (8:1 by vol.), I-16 (1.00 equivalents) is reacted with E3 (1.00 equivalents), tribasic potassium phosphate (1.80 equivalents, CAS: 7778-53-2), tris(dibenzylideneacetone)dipalladium(0) (0.01 equivalents, CAS: 51364-51-3) and X-Phos (0.04 equivalents, CAS: 564483-18-7) at 95° C. for 48 h. After cooling down to rt, the phases are separated and the aqueous layer extracted with ethyl acetate. The combined organic layers are dried over MgSO4, filtered and concentrated under reduced pressure. The crude is purified by column chromatography or recrystallization to yield compound I-17 as a solid.
AAV23: Under nitrogen, in a mixture of dioxane/water (5:1 by vol.), I-17 (1.00 equivalents) is reacted with E12 (1.50 equivalents), tribasic potassium phosphate (3.00 equivalents, CAS: 7778-53-2), tris(dibenzylideneacetone)dipalladium(0) (0.01 equivalents, CAS: 51364-51-3) and X-Phos (0.04 equivalents, CAS: 564483-18-7) at 100° C. for 5 h. After cooling down to rt, the phases are separated and the aqueous layer extracted with ethyl acetate. The combined organic layers are dried over MgSO4, filtered and concentrated under reduced pressure. The crude is purified by column chromatography or recrystallization to yield compound I-18 as a solid.
The last reaction step was proceed as described in AAV0-3.
AAV24: In dry DMSO, E13 (1.10 equivalents), E11 (1.00 equivalents) and tribasic potassium phosphate (1.50 equivalents, CAS: 7778-53-2) are heated at 100° C. for 48 h. After cooling down to rt, the mixture is poured onto ice water. The precipitate is filtered off, washed with water and ethanol and collected. The crude is purified by recrystallization or column chromatography to yield compound I-19 as a solid.
AAV25: Under nitrogen, in a mixture of toluene/water (8:1 by vol.), I-19 (1.00 equivalents) is reacted with E3 (1.20 equivalents), tribasic potassium phosphate (2.00 equivalents, CAS: 7778-53-2), tris(dibenzylideneacetone)dipalladium(0) (0.01 equivalents, CAS: 51364-51-3) and X-Phos (0.04 equivalents, CAS: 564483-18-7) at 100° C. for 5 h. After cooling down to rt, the phases are separated and the aqueous layer extracted with ethyl acetate. The combined organic layers are dried over MgSO4, filtered and concentrated under reduced pressure. The crude is purified by column chromatography or recrystallization to yield compound I-20 as a solid.
The last reaction step was proceed as described in AAV0-3.
AAV26: Under nitrogen, in a mixture of dioxane/water (10:1 by vol.), E14 (1.00 equivalents) is reacted with E3 (1.00 equivalents), potassium carbonate (2.00 equivalents, CAS: 584-08-7), tris(dibenzylideneacetone)dipalladium(0) (0.02 equivalents, CAS: 51364-51-3) and S-Phos (0.08 equivalents, CAS: 657408-07-6) at 90° C. for 72 h. After cooling down to rt, the phases are separated and the aqueous layer extracted with ethyl acetate. The combined organic layers are dried over MgSO4, filtered and concentrated under reduced pressure. The crude is purified by column chromatography or recrystallization to yield compound I-21 as a solid.
AAV27: E5 (1.00 equivalents), I-21 (1.00 equivalents), tris(dibenzylideneacetone)-dipalladium(0) (CAS: 51364-51-3, 0.01 equivalents), Sodium tert-butoxide (NaOtBu, CAS: 865-48-5, 3.00 equivalents) and Tri-tert-butylphosphine (P(tBu)3; CAS: 13716-12-6, 0.04 equivalents) are stirred under nitrogen atmosphere in dry toluene at 110° C. for 24 h. After cooling down to room temperature (rt) the reaction mixture is extracted between ethyl acetate and brine and the combined organic layers concentrated under reduced pressure. The crude material is purified by column chromatography or by recrystallization and I-22 is obtained as solid.
AAV28: Under nitrogen in dry dichlorobenzene, I-22 (1.00 equivalents) is reacted with BBr3 (3.00 equivalents, CAS: 10294-33-4) at 135° C. for 45 min. After cooling down to rt, the mixture is further cooled down to 0° C., followed by the addition of DIPEA (10.0 equivalents, CAS: 7087-68-5). Water is added, the phases separated and the aqueous layer extracted with dichloromethane. The combined organic layers are washed with water, dried over MgSO4, filtered and concentrated. The crude is purified by column chromatography or recrystallization to yield compound P-8 as a solid.
AAV29: E5 (1.05 equivalents), E14 (1.00 equivalents), tris(dibenzylideneacetone)-dipalladium(0) (CAS: 51364-51-3, 0.005 equivalents), Sodium tert-butoxide (NaOtBu, CAS: 865-48-5, 1.50 equivalents) and Tri-tert-butylphosphonium tetrafluoroborate (HP(tBu)3BF4; CAS: 131274-22-1, 0.02 equivalents) are stirred under nitrogen atmosphere in dry toluene at 100° C. for 1 h. After coaling down to room temperature (rt) the reaction mixture is extracted between ethyl acetate and brine and the combined organic layers concentrated under reduced pressure. The crude material is purified by column chromatography or by recrystallization and I-23 is obtained as solid.
AAV30: Under nitrogen, in a mixture of dioxane/water (5:1 by vol.), I-23 (1.00 equivalents) is reacted with E3 (1.10 equivalents), tribasic potassium phosphate (2.00 equivalents, CAS: 7778-53-2), tris(dibenzylideneacetone)dipalladium(0) (0.01 equivalents, CAS: 51364-51-3) and S-Phos (0.04 equivalents, CAS: 657408-07-6) at 100° C. for 48 h. After cooling down to rt, the phases are separated and the aqueous layer extracted with ethyl acetate. The combined organic layers are dried over MgSO4, filtered and concentrated under reduced pressure. The crude is purified by column chromatography or recrystallization to yield compound I-24 as a solid.
AAV31: Under nitrogen in dry dichlorobenzene, I-24 (1.00 equivalents) is reacted with BBr3 (3.00 equivalents, CAS: 10294-33-4) at 90° C. for 1 h. After cooling down to rt, the mixture is further cooled down to 0° C., followed by the addition of DIPEA (10.0 equivalents, CAS: 7087-68-5). Water is added, the phases separated and the aqueous layer extracted with dichloromethane. The combined organic layers are washed with water, dried over MgSO4, filtered and concentrated. The crude is purified by column chromatography or recrystallization to yield compound P-9 as a solid.
AAV32: Under nitrogen, in a mixture of dioxane/water (4:1 by vol.), E3 (1.00 equivalents) is reacted with E9 (1.30 equivalents), potassium carbonate (2.00 equivalents, CAS: 584-08-7) and tetrakis(triphenylphosphine)palladium(0) (0.03 equivalents, CAS: 14221-01-3) at 80° C. for 8 h. After coaling down to rt, the phases are separated and the aqueous layer extracted with ethyl acetate. The combined organic layers are dried over MgSO4, filtered and concentrated under reduced pressure. The crude is purified by column chromatography or recrystallization to yield compound I-12 as a solid.
AAV33: E5 (1.10 equivalents), I-12 (1.00 equivalents), tris(dibenzylideneacetone)-dipalladium(0) (CAS: 51364-51-3, 0.01 equivalents), Sodium tert-butoxide (NaOtBu, CAS: 865-48-5, 3.20 equivalents) and Tri-tert-butylphosphonium tetrafluoroborate (HP(tBu)3BF4; CAS: 131274-22-1, 0.04 equivalents) are stirred under nitrogen atmosphere in dry toluene at 110° C. for 3 h. After cooling down to room temperature (rt) the reaction mixture is extracted between ethyl acetate and brine and the combined organic layers concentrated under reduced pressure. The crude material is purified by column chromatography or by recrystallization and I-15 is obtained as solid.
AAV34: Under nitrogen, a solution of I-15 (1.00 equivalents) in dry tert-butylbenzene is added n-BuLi (2.5 M in hexane, 1.10 equivalents, CAS: 109-72-8) at rt. After 15 min of stirring, t-BuLi (1.6 M in pentane, 2.20 equivalents, CAS: 594-19-4) is added and the mixture heated at 60° C. for 2 h. Subsequently, the mixture is cooled below −60° C., followed by dropwise addition of BBr3 (1.50 equivalents, CAS: 10294-33-4). Subsequently, the mixture is stirred at 0° C. for 1 h, followed by stirring at rt for 16 h. The mixture is poured onto a saturated solution of NaHCO3. The phases are separated, and the aqueous layers extracted with ethyl acetate. The combined organic layers are washed with water, dried over MgSO4, filtered and concentrated. The crude is purified by column chromatography or recrystallization to obtain compound P5 as a solid.
AAV35: E15 (1.10 equivalents), E16 (1.00 equivalents), tris(dibenzylideneacetone)-dipalladium(0) (CAS: 51364-51-3, 0.01 equivalents), Sodium tert-butoxide (NaOtBu, CAS: 865-48-5, 2.00 equivalents) and Tri-tert-butylphosphine (P(tBu)3; CAS: 13716-12-6, 0.04 equivalents) are stirred under nitrogen atmosphere in dry toluene at 60° C. until completion of the reaction (TLC control). After cooling down to room temperature (rt) the reaction mixture is extracted between ethyl acetate and brine and the combined organic layers concentrated under reduced pressure. The crude material is purified by column chromatography or by recrystallization and E-5 is obtained as solid.
AAV36: E5 (1.00 equivalents), I-21 (1.00 equivalents), tris(dibenzylideneacetone)-dipalladium(0) (CAS: 51364-51-3, 0.01 equivalents), Sodium tert-butoxide (NaOtBu, CAS: 865-48-5, 2.00 equivalents) and Tri-tert-butylphosphonium tetrafluoroborate (HP(t-Bu)3BF4; CAS: 131274-22-1, 0.02 equivalents) are stirred under nitrogen atmosphere in dry toluene under reflux until completion of the reaction (TLC control). After cooling down to room temperature (rt) the reaction mixture is extracted between toluene and brine and the combined organic layers concentrated under reduced pressure. The crude material is purified by column chromatography or by recrystallization and I-22 is obtained as solid.
AAV37: I-22 (1.00 equivalents) is placed in a round bottom flask under nitrogen. The solvent 1,2-dichlorobenzene is added. Boron tribromide (CAS: 10294-33-4, 3.00 equivalents) is added dropwise and it is heated to 180° C. until completion of the reaction (TLC control). After cooling to rt, it is further cooled to 0° C. DIPEA (CAS: 7087-68-5, 10.00 equivalents) is added and it is stirred for 1 h. The reaction mixture is washed with water and the phases are separated and then the solvent is removed under reduced pressure. The crude material is purified by column chromatography or by recrystallization and P-8 is obtained as a solid.
AAV38: E17 (1.40 equivalents), E18 (0.9 equivalents), hydroiodic acid (CAS: 10034-85-2, 0.20 equivalents) are stirred under nitrogen atmosphere in dry acetonitrile at 100° C. for 16 h. The reaction mixture is cooled down to 0° C.; the precipitate is filtered and washed with cold acetonitrile. The solid is solved in acetonitrile; iodine (CAS: 7553-56-2, 0.40 equivalents) is added and the mixture is stirred at 100 CC until reaction completion (monitored by TLC). The reaction mixture is quenched with a saturated sodium thiosulfite solution and the precipitate is washed with cold acetonitrile, methanol, and hexane. The crude material is purified by recrystallization or by column chromatography and I-25 is obtained as a solid.
AAV39: I-25 (1.00 equivalents), E19 (6.0 equivalents), tris(dibenzylideneacetone)dipalladium(0) (CAS: 51364-51-3, 0.04 equivalents), Tri-tert-butylphosphonium tetrafluoroborate (CAS: 131274-22-1, 0.16 equivalents) and sodium tert-butoxide (CAS: 865-48-5, 7.00 equivalents) are stirred under nitrogen atmosphere in dry toluene at 110° C. for 72 h. After cooling down to room temperature (rt) the reaction mixture extracted between ethyl acetate and brine and the phases are separated and the solvent is removed under reduced pressure. The crude material is purified by recrystallization or by column chromatography and I-26 is obtained as a solid.
AAV40: I-26 (1.00 equivalents) is placed in a round bottom flask under nitrogen. The solvent (1,2-dichlorobenzene is added. Boron tribromide (CAS: 10294-33-4, 4.00 equivalents) is added dropwise and it is heated to 180° C. until reaction completion (TLC control). After cooling to rt, it is further cooled to 0° C. DIPEA (CAS: 7087-68-5, 10.00 equivalents) is added and it is stirred for 1 h. The reaction mixture is washed with water and the phases are separated and then the solvent is removed under reduced pressure. The crude material is purified by column chromatography or recrystallization and P-10 is obtained as a solid.
AAV41: E17 (2.00 equivalents), E20 (1.0 equivalents), and Bis(trifluoromethyl)methanol (CAS: 920-66-1, 300 ml) are stirred under nitrogen atmosphere at room temperature until reaction completion (TLC control). The reaction mixture is cooled down to 0° C.; the precipitate is filtered and washed with cold acetonitrile. The solid is re-dissolved in acetonitrile; 1,4-Benzoquinone (CAS: 106-51-4, 0.20 equivalents) is added and the mixture is stirred at room temperature until reaction completion (monitored by TLC). The solvent is removed under reduced pressure. The crude material is purified by recrystallization or by column chromatography and I-27 is obtained as a solid.
AAV42: I-27 (1.00 equivalents), E21 (1.00 equivalents), are stirred under nitrogen atmosphere in dichloromethane at room temperature. Iodine (CAS: 7553-56-2, 0.03 equivalents) is added and the mixture is stirred at room temperature until reaction completion (monitored by TLC). The solvent is removed under reduced pressure. The crude material is purified by recrystallization or by column chromatography and I-28 is obtained as a solid.
AAV43: I-28 (1.00 equivalents), E19 (2.5 equivalents), tris(dibenzylideneacetone)dipalladium(0) (CAS: 51364-51-3, 0.03 equivalents), Tri-tert-butylphosphonium tetrafluoroborate (CAS: 131274-22-1, 0.12 equivalents) and sodium tert-butoxide (CAS: 865-48-5, 4.00 equivalents) are stirred under nitrogen atmosphere in dry toluene at 110° C. until reaction completion (TLC control). After cooling down to room temperature (rt) the reaction mixture extracted between ethyl acetate and brine and the phases are separated and the solvent is removed under reduced pressure. The crude material is purified by recrystallization or by column chromatography and I-29 is obtained as a solid.
AAV44: I-29 (1.00 equivalents) is placed in a round bottom flask under nitrogen. The solvent chlorobenzene is added. Boron tribromide (CAS: 10294-33-4, 4.00 equivalents) is added dropwise and it is heated to 70° C. until reaction completion (TLC control). After cooling to rt, it is further cooled to 0° C. DIPEA (CAS: 7087-68-5, 10.00 equivalents) is added and it is stirred for 1 h. The reaction mixture is washed with water and the phases are separated and then the solvent is removed under reduced pressure. The crude material is purified by column chromatography or recrystallization and P-11 is obtained as a solid.
AAV45: E22 (1.00 equivalents) is solved in dry chloroform and N-bromosuccinimide (CAS: 128-08-5, 1.1 equivalents) is added portionwise under nitrogen atmosphere at 0° C. The mixture is stirred at room temperature for 4 h and subsequently extracted between dichloromethane and water and the combined organic layers concentrated under reduced pressure. The crude material is purified by column chromatography or by recrystallization and E2 is obtained as a solid.
AAV46: E2 (1.00 equivalents), bis(pinacolato)diboron (CAS: 73183-34-3, 1.5 equivalents), [1,1′-bis(diphenylphosphino)ferrocene]palladium (II) dichloride (CAS: 72287-26-4, 0.02 equivalents) and potassium acetate (KOAc; CAS: 127-08-2, 3.00 equivalents) are stirred under nitrogen atmosphere in dry dioxane at 95° C. for 24 h. After cooling down to room temperature (rt) the reaction mixture is extracted between dichloromethane and water and the combined organic layers concentrated under reduced pressure. The crude material is purified by column chromatography or by recrystallization and E3 is obtained as a solid.
AAV47: Under nitrogen, in a mixture of dry dioxane, E14 (1.00 equivalents) is reacted with bis(pinacolato)diboron (1.50 equivalents, CAS: 73183-34-3), potassium acetate (3.00 equivalents, CAS: 127-08-2), [1,1′-bis(diphenylphosphino)ferrocene]palladium (II) dichloride (0.04 equivalents, CAS: 72287-26-4) at 100° C. for 16 h. After cooling down to rt, water is added, the phases are separated and the aqueous layer extracted with ethyl acetate. The combined organic layers are dried over MgSO4, filtered and concentrated under reduced pressure. The crude is purified by column chromatography or recrystallization to yield compound I-30 as a solid.
AAV48: E2 (1.00 equivalents), I-30 (1.00 equivalents), [1,1′-bis(diphenylphosphino)ferrocene]palladium (II) dichloride (CAS: 72287-26-4, 0.02 equivalents) and potassium phosphate tribasic (K3PO4; CAS: 7778-53-2, 3.00 equivalents) are stirred under nitrogen atmosphere in dioxane/water (4:1 by vol.) at 80° C. for 4 h. After cooling down to room temperature (rt) the reaction mixture is extracted between ethyl acetate and water and the combined organic layers concentrated under reduced pressure. The crude material is purified by column chromatography or by recrystallization and I-21 is obtained as a solid.
The last two reaction steps were performed as described in AAV27 and AAV28.
AAV49: E23 (1.00 equivalents) is solved in dry THF and N-bromosuccinimide (CAS: 128-08-5, 2 equivalents) is added portionwise under nitrogen atmosphere at 0° C. The mixture is stirred at room temperature for 4 h and subsequently extracted between dichloromethane and water and the combined organic layers concentrated under reduced pressure. The crude material is purified by column chromatography or by recrystallization and I-29 is obtained as a solid.
AAV50: I-29 (1.00 equivalents), E24 (2.3 equivalents), tris(dibenzylideneacetone)dipalladium(0) (CAS: 51364-51-3, 0.02 equivalents), S-Phos (CAS: 657408-07-6, 0.08 equivalents) and potassium phosphate tribasic (K3PO4, CAS: 7778-53-2, 6.00 equivalents) are stirred under nitrogen atmosphere in a toluene/water mixture at 90° C. for 5 h. After cooling down to room temperature (rt) the reaction mixture is washed with water and brine. The combined organic layers are dried over MgSO4, filtered and concentrated under reduced pressure. The crude material is purified by recrystallization or column chromatography and I-30 is obtained as a solid.
AAV51: Under nitrogen in dry chlorobenzene, I-30 (1.00 equivalents) is reacted with BBr3 (12.00 equivalents, CAS: 10294-33-4) at 135° C. for 45 min. After cooling down to rt, the mixture is further cooled down to 0° C., followed by the addition of DIPEA (30.0 equivalents, CAS: 7087-68-5). Water is added, the phases separated and the aqueous layer extracted with dichloromethane. The combined organic layers are washed with water, dried over MgSO4, filtered and concentrated. The crude is purified by column chromatography or recrystallization to yield compound P-12 as a solid.
Cyclic voltammograms are measured from solutions having concentration of 103 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 FeCp2/FeCp2+ as internal standard. The HOMO data is corrected using ferrocene as internal standard against a saturated calomel electrode (SCE).
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.
Sample pretreatment: Spin-coating
Apparatus: Spin150, SPS euro.
The sample concentration is 10 mg/ml, dissolved in a suitable solvent.
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.
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.
Excited state lifetimes are determined employing the same system using the TCSPC method with FM-2013 equipment and a Horiba Yvon TCSPC hub.
NanoLED 370 (wavelength: 371 nm, pulse duration: 1.1 ns)
NanoLED 290 (wavelength: 294 nm, pulse duration: <1 ns)
SpectraLED 310 (wavelength: 314 nm)
SpectraLED 355 (wavelength: 355 nm).
Data analysis (exponential fit) is done using the software suite DataStation and DAS6 analysis software. The fit is specified using the chi-squared-test.
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.
Emission maxima are given in nm, quantum yields D in % and CIE coordinates as x,y values.
Quality assurance: Anthracene in ethanol (known concentration) is used as reference.
Excitation wavelength: the absorption maximum of the organic molecule is determined and the molecule is excited using this wavelength.
Quantum yields are measured, for sample, of solutions or films under nitrogen atmosphere. The yield is calculated using the equation:
Optoelectronic devices, such as OLED devices including organic molecules according to the invention can be produced via vacuum-deposition methods. If a layer contains more than one compound, the weight-percentage of one or more compounds is given in %. The total weight-percentage values amount to 100%, thus if a value is not given, the fraction of this compound equals to the difference between the given values and 100%.
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/m2 are determined using the following equation:
The values correspond to the average of several pixels (typically two to eight), the standard deviation between these pixels is given.
HPLC-MS analysis is performed on an HPLC by Agilent (1100 series) with MS-detector (Thermo LTQ XL). Exemplary, a typical HPLC method is as follows: a reverse phase column 4.6 mm×150 mm, particle size 3.5 μm from Agilent (ZORBAX Eclipse Plus 95 Å C18, 4.6×150 mm, 3.5 μm HPLC column) is used in the HPLC. The HPLC-MS measurements are performed at room temperature (rt) following gradients:
An injection volume of 5 μL from a solution with a concentration of 0.5 mg/mL of the analyte is taken for the measurements.
Ionization of the probe is performed using an APCI (atmospheric pressure chemical ionization) source either in positive (APCI +) or negative (APCI −) ionization mode.
AA V14 (33% yield), wherein 1,5-dibromo-2,3-dichlorobenzene (CAS: 81067-42-73) and 2,2′-dinaphthylamine (CAS: 532-18-3) was used as reactant E8 and E5, respectively,
AAV15 (34% yield), wherein 1-(tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (CAS: 1219637-88-3) was used as reactant E3, and
AAV0-3 (3% yield).
MS (LC-MS, APCI ion source): 786.5 m/z at rt: 7.00 min.
The emission maximum of example 1 (2% by weight in PMMA) is at 434 nm, the CIEx coordinate is 0.16 and the CIEy coordinate is 0.11.
AAV4 (30% yield), wherein 5-bromo-N1,N1,N3,N3-tetraphenyl-1,3-benzenediamine (CAS: 1290039-73-4) was used as reactant E1,
AA V5 (21% yield), wherein 6-bromo-5H-benzofuro[3,2-c]carbazole (CAS: 1438427-35-0) was used as reactant E2, and
AAV6 (4% yield).
MS (LC-MS, APCI ion source): 676.7 m/z at rt: 6.87 min.
The emission maximum of example 3 (2% by weight in PMMA) is at 440 nm, the full width at half maximum (FWHM) is 0.21 eV. The CIEx coordinate is 0.15 and the CIEy coordinate is 0.06. The photoluminescence quantum yield (PLQY) is 56%.
AAV7 (71% yield), wherein 1-(tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (CAS: 1219637-88-3) and 3,5-dichloro-N,N-diphenylaniline (CAS: 1329428-05-8) was used as reactant E3 and E4, respectively,
AAV8 (52% yield), wherein N,N,N′-triphenyl-benzene-1,3-diamine (CAS: 1554227-26-7) was used as reactant E5, and
AAV9 (3% yield).
MS (LC-MS, APCI ion source): 753.9 m/z at rt: 6.62 min.
The emission maximum of example 3 (2% by weight in PMMA) is at 427 nm, the full width at half maximum (FWHM) is 0.13 eV. The CIEx coordinate is 0.16 and the CIEy coordinate is 0.05. The photoluminescence quantum yield (PLQY) is 58%.
AAV10 (68% yield), wherein 2,2′-dinaphthylamine (CAS: 532-18-3) and 1-bromo-3-chlorodibenzo[b,d]furan (CAS: 2043962-13-4) was used as reactant E5 and E6, respectively,
AAV11 (90% yield), wherein 1-(tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (CAS: 1219637-88-3) was used as reactant E3, and
AAV9 (38% yield).
MS (LC-MS, APCI ion source): 609.5 m/z at rt: 6.26 min.
The emission maximum of example 4 (2% by weight in PMMA) is at 462 nm, the full width at half maximum (FWHM) is 0.14 eV. The CIEx coordinate is 0.14 and the CIEy coordinate is 0.22. The photoluminescence quantum yield (PLQY) is 65%.
AAV7 (71% yield), wherein 1-(tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (CAS: 1219637-88-3) and 3,5-dichloro-N,N-diphenylaniline (CAS: 1329428-05-8) was used as reactant E3 and E4, respectively,
AAV12 (54% yield), wherein N,N′-diphenyl-m-phenylenediamine (CAS: 5905-36-2) was used as reactant E7, and
AAV13 (2% yield).
MS (LC-MS, APCI ion source): 1094.1 m/z at rt: 8.18 min.
The emission maximum of example 5 (2% by weight in PMMA) is at 443 nm, the full width at half maximum (FWHM) is 0.13 eV. The CIEx coordinate is 0.15 and the CIEy coordinate is 0.07. The photoluminescence quantum yield (PLQY) is 61%.
AAV16 (49% yield), wherein 1-(tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (CAS: 1219637-88-3) and 1,3-dibromo-2-chlorobenzene (CAS: 19230-27-4) was used as reactant E3 and E9, respectively,
AAV17 (78% yield),
AAV18 (56% yield), wherein 2,2′-dinaphthylamine (CAS: 532-18-3) was used as reactant E5,
AAV19 (69% yield), and
AAV20 (5% yield).
MS (LC-MS, APPI ion source): 519.6 m/z at rt: 5.54 min.
The emission maximum of example 6 (2% by weight in PMMA) is at 480 nm, the full width at half maximum (FWHM) is 0.18 eV. The CIEx coordinate is 0.13 and the CIEy coordinate is 0.33. The photoluminescence quantum yield (PLQY) is 53%.
AAV21 (85% yield), wherein 1-bromo-2,5-dichloro-3-fluorobenzene (CAS: 202865-57-4) and 7H-dibenzo[c,g]carbazole (CAS: 194-59-2) were used as reactants E10 and E11, respectively;
AAV22 (62% yield), wherein 1-(tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (CAS: 1219637-88-3) was used as the substrate E3;
AAV23 (78% yield), wherein 2,4,6-trimethylphenylboronic acid (CAS: 5980-97-2) represented reactant E12; and
AAV0-3 (2% yield).
MS (LC-MS, APCI ion source): m/z=635.7 at rt=7.72 min.
The emission maximum of example 7 (2% by weight in PMMA) is at 470 nm, the full width at half maximum (FWHM) is 0.24 eV. The CIEx coordinate is 0.15 and the CIEy coordinate is 0.25. The photoluminescence quantum yield (PLQY) is 48%.
AAV24 (70% yield), wherein 1-bromo-2-chloro-3-fluorobenzene (CAS: 883499-24-9) and 7H-dibenzo[c,g]carbazole (CAS: 194-59-2) were used as the reactants E13 and E11, respectively;
AAV25 (51% yield), wherein 1-(tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (CAS: 1219637-88-3) was used as reactant E3; and
AAV0-3 (2% yield).
MS (LC-MS, APCI ion source): m/z=517 at rt=6.45 min.
The emission maximum of example 8 (2% by weight in PMMA) is at 478 nm, the full width at half maximum (FWHM) is 0.26 eV. The CIEx coordinate is 0.16 and the CIEy coordinate is 0.36. The photoluminescence quantum yield (PLQY) is 37%.
AAV21 (85% yield), wherein 1-bromo-2,5-dichloro-3-fluorobenzene (CAS: 202865-57-4) and 7H-dibenzo[c,g]carbazole (CAS: 194-59-2) were used as reactants E10 and E11, respectively;
AAV22 (62% yield), wherein 1-(tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (CAS: 1219637-88-3) was used as the substrate E3;
AAV23 (69% yield), wherein phenylboronic acid (CAS: 98-80-6) represented reactant E12; and
AAV0-3 (1% yield).
MS (LC-MS, APPI ion source): m/z=593 at rt=7.25 min.
The emission maximum of example 9 (2% by weight in PMMA) is at 485 nm.
AAV26 (34% yield), wherein 1-bromo-3-chlorodibenzo[b,d]furan (CAS: 2043962-13-4) and 1-(tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (CAS: 1219637-88-3) were used as the reactants E14 and E3;
AAV27 (37% yield), wherein 2,2′-dinaphthylamine (CAS: 532-18-3) was used as reactant E5; and
AAV28 (3% yield).
MS (LC-MS, APPI ion source): m/z=609.5 at rt=6.38 min.
The emission maximum of example 10 (2% by weight in PMMA) is at 456 nm, the full width at half maximum (FWHM) is 0.22 eV. The CIEx coordinate is 0.15 and the CIEy coordinate is 0.13. The photoluminescence quantum yield (PLQY) is 45%.
MS (LC-MS, APCI ion source): m/z=1275.2 at rt=8.99 min.
The emission maximum of example 11 (2% by weight in PMMA) is at 459 nm, the full width at half maximum (FWHM) is 0.15 eV. The CIEx coordinate is 0.14 and the CIEy coordinate is 0.13. The photoluminescence quantum yield (PLQY) is 53%.
AAV29 (71% yield), where 4-bromo-3-chlorodibenzo[b,d]furan (CAS: 1960445-63-9) and 2,2′-dinaphthylamine (CAS: 532-18-3) were used as the reactants E14 and E5, respectively;
AAV30 (54% yield), where 1-(tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (CAS: 1219637-88-3) was used as compound E3; and
AAV31 (31% yield).
MS (LC-MS, APCI ion source): m/z=609.7 at rt=6.23 min.
The emission maximum of example 12 (2% by weight in PMMA) is at 464 nm, the full width at half maximum (FWHM) is 0.13 eV. The CIEx coordinate is 0.14 and the CIEy coordinate is 0.18. The photoluminescence quantum yield (PLQY) is 58%.
AAV32 (31% yield), where 3,6-bis(1,1-dimethylethyl)-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-Carbazole (CAS: 1510810-80-6) and 1,3-dibromo-5-tert-butyl-2-chlorobenzene (CAS: 1000578-25-5) were used as the reactants E3 and E9, respectively;
AAV33 (48% yield), wherein N-[1,1′-biphenyl]-4-yl-[1,1′-Biphenyl]-4-amine (CAS: 102113-98-4) was used as compound E5; and
AAV33 (24% yield).
MS (LC-MS, APPI ionization source): m/z=740.0 at rt=7.90 min.
The emission maximum of example 13 (2% by weight in PMMA) is at 440 nm, the full width at half maximum (FWHM) is 0.22 eV. The CIEx coordinate is 0.15 and the CIEy coordinate is 0.06. The photoluminescence quantum yield (PLQY) is 74%.
AAV38 (25% yield), where Indole (CAS: 120-72-9) and 3,5-Dibromobenzaldehyde (CAS: 56990-02-4) were used as the reactants E17 and E18, respectively;
AAV39 (51% yield), where diphenylamine (CAS: 122-39-4) was used as E19; and
AAV40 (38% yield).
MS (LC-MS, APPI ionization source): m/z=1094.0 at rt=8.14 min.
The emission maximum of example 14 (2% by weight in PMMA) is at 515 nm, the full width at half maximum (FWHM) is 0.13 eV. The CIEx coordinate is 0.31 and the CIEy coordinate is 0.64. The photoluminescence quantum yield (PLQY) is 31%.
AAV38 (25% yield), where indole (CAS: 120-72-9) and 3,5-dibromobenzaldehyde (CAS: 56990-02-4) were used as the reactants E17 and E18, respectively;
AAV39 (70% yield), where 2,2′-dinaphthylamine (CAS: 532-18-3) was used as E19; and
AAV40 (47% yield).
MS (LC-MS, APPI ionization source): m/z=1494.0 at rt=8.74 min.
The emission maximum of example 15 (2% by weight in PMMA) is at 522 nm, the full width at half maximum (FWHM) is 0.09 eV. The photoluminescence quantum yield (PLQY) is 48%.
AAV41 (34% yield), wherein 4,7-dihydro-1H-indole (CAS: 26686-10-2) and 3,5-dibromobenzaldehyde (CAS: 56990-02-4) were used as the reactants E17 and E20;
AAV42 (15% yield), where trimethyl orthoformate (CAS: 149-73-5) was used as E21;
AAV43 (19% yield), where bis(3-biphenylyl)amine (CAS: 169224-65-1) was used as E19; and
AAV44 (27% yield).
MS (LC-MS, APPI ionization source): m/z=988.0 at rt=8.56 min.
The emission maximum of example 16 (2% by weight in PMMA) is at 444 nm, the full width at half maximum (FWHM) is 0.29 eV. The CIEx coordinate is 0.15 and the CIEy coordinate is 0.09. The photoluminescence quantum yield (PLQY) is 45%.
AAV45 (85% yield), wherein 3,6-di-tert-butylcarbazole (CAS: 37500-95-1) was used as the substrate E22;
AAV46 (83% yield);
AAV21 (85% yield), wherein 1-bromo-2,5-dichloro-3-fluorobenzene (CAS: 202865-57-4) and 7H-dibenzo[c,g]carbazole (CAS: 194-59-2) were used as reactants E10 and E11, respectively;
AAV22 (46% yield);
AAV23 (87% yield), wherein 2,4,6-trimethylphenylboronic acid (CAS: 5980-97-2) represented reactant E12; and
AAV0-3 (7.2% yield).
MS (LC-MS, APCI ion source): m/z=746 at rt=8.90 min.
The emission maximum of example 17 (2% by weight in PMMA) is at 471 nm, the full width at half maximum (FWHM) is 0.24 eV. The CIEx coordinate is 0.14 and the CIEy coordinate is 0.25. The photoluminescence quantum yield (PLQY) is 48%.
AAV47 (74% yield), wherein 4-bromo-2-chlorodibenzo[b,d]furan (CAS: 2087889-86-7) was used as the substrate E14;
AAV45 (85% yield), wherein 3,6-di-tert-butylcarbazole (CAS: 37500-95-1) was used as the substrate E22;
AAV48 (74% yield);
AAV27 (33% yield), where bis(4-tert-butylphenyl)amine (CAS: 4627-22-9) was used as compound E5; and
AAV28 (6.1% yield).
MS (LC-MS, APPI ion source): m/z=734.8 at rt=8.73 min.
The emission maximum of example 18 (2% by weight in PMMA) is at 471 nm, the full width at half maximum (FWHM) is 0.16 eV. The CIEx coordinate is 0.13 and the CIEy coordinate is 0.26. The photoluminescence quantum yield (PLQY) is 76%.
AAV49 (64.7% yield), wherein 5,11-dihydroindolo[3,2-b]carbazole (CAS: 6336-32-9) was used as the substrate E23;
AAV50 (45.3% yield), wherein N,N-diphenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzo[b,d]furan-2-amine was used as the substrate E24; and
AAV51 (51.9% yield).
MS (LC-MS, APPI ion source): m/z=939.6 at rt=7.01 min.
The emission maximum of example 19 (2% by weight in PMMA) is at 548 nm, the full width at half maximum (FWHM) is 0.11 eV. The CIEx coordinate is 0.41 and the CIEy coordinate is 0.58. The photoluminescence quantum yield (PLQY) is 39%.
Example 4 was tested in the OLED Dl, which was fabricated with the following layer structure:
OLED D1 yielded an external quantum efficiency (EQE) at 1000 cd/m2 of 8.7%. The emission maximum is at 466 nm with a FWHM of 18 nm at 3.9 V. The corresponding CIEx value is 0.13 and the CIEy value is 0.16. A LT95-value at 1200 cd/m2 of 55.2 h was determined.
| Number | Date | Country | Kind |
|---|---|---|---|
| 21170181.8 | Apr 2021 | EP | regional |
| PCT/EP2021/060703 | Apr 2021 | WO | international |
| 21201489.8 | Oct 2021 | EP | regional |
The present application is a U.S. National Phase Patent Application of International Patent Application Number PCT/EP2022/060940, filed on Apr. 25, 2022, which claims priority to and the benefit of European Patent Application Number 21170181.8, filed on Apr. 23, 2021, International Patent Application Number PCT/EP2021/060703, filed on Apr. 23, 2021, and European Patent Application Number 21201489.8, filed on Oct. 7, 2021, the entire content of each of which is incorporated herein by reference. The invention relates to light-emitting organic molecules and their use in organic light-emitting diodes (OLEDs) and in other optoelectronic devices.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/060940 | 4/25/2022 | WO |
