US 2015 0340627A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2015/0340627 A1 JATSCH et al. (43) Pub. Date: Nov. 26, 2015

(54) MATERIALS FOR ELECTRONIC DEVICES C07D40 L/04 (2006.01) C08G 6/12 (2006.01) (71) Applicant: MERCK PATENT GMBH, Darmstadt C07D 403/2 (2006.01) (DE) C07D 403/4 (2006.01) (72) Inventors: Anja JATSCH, Frankfurt Am Main C07D40 L/4 (2006.01) (DE); Christof PFLUMM, Darmstadt C07D 209/94 (2006.01) Frankfurt Am Main (DE); Thomas EBERLE, Landau (DE); Philipp (52) U.S. Cl. STOESSEL, Frankfurt Am Main (DE); CPC ...... HOIL 51/0072 (2013.01); C07D 209/94 Jonas Valentin KROEBER, Frankfurt (2013.01); C07D 209/86 (2013.01); C07D Am Main (DE); Rouven LINGE, 401/04 (2013.01); C07D 487/04 (2013.01); Darmstadt (DE) C07D 403/12 (2013.01); C07D 403/14 (21) Appl. No.: 14/758,978 stoo,2013.01); O 3.01); C07D HOIL 401/14 so (2013.01); tleHOIL (22) PCT Filed: Dec. 10, 2013 HOIL 51/0058 (2013.01); HOIL 51/006 (2013.01); HOIL 51/0061 (2013.01); C08G (86). PCT No.: PCT/EP2013/003722 61/124 (2013.01); C08G 2261/3241 (2013.01); S371 (c)(1), C08G 2261/3221 (2013.01); C08G 2261/312 (2) Date: Jul. 2, 2015 (2013.01); C08G 2261/314 (2013.01); C08G 2261/3142 (2013.01); C08G 2261/95 (2013.01); (30) Foreign Application Priority Data C08G 2261/5.14 (2013.01); C08G 2261/3162 Jan. 3, 2013 (EP) ...... 13OOOO13.6 (2013.01); HOIL 5 1/5024 (2013.01) Publication Classification (57) ABSTRACT (51) Int. Cl. The present application relates to a compound of a formula HOIL 5L/00 (2006.01) (I), (II) or (III). The compound can be used in an electronic CO7D 209/86 (2006.01) device, preferably an organic electronic device. US 2015/0340627 A1 Nov. 26, 2015

MATERALS FOR ELECTRONIC DEVICES ticular in the aspects operating Voltage and power efficiency 0001. The present application relates to a compound of a of devices comprising the compounds. formula (I), (II) or (III) which contains a carbazole group and 0013 Surprisingly, it has now been found that excellent an electron-deficient heteroaryl group. The compound can be values for operating Voltage and power efficiency can be used in an electronic device, preferably an organic electronic achieved with compounds which contain a carbazole group or device. The present application furthermore relates to a pro indenocarbazole group which are connected to a donor-Sub cess for the preparation of the compound. stituted electron-deficient six-membered heteroaromatic ring 0002 Electronic devices in the sense of this application via a linker group on the Natom. are taken to mean, in particular, so-called organic electronic devices, which comprise organic semiconductor materials as 0014. The present application thus relates to a compound functional materials. They are again taken to mean, in par of a formula (I), (II) or (III) ticular, organic electroluminescent devices (OLEDs) and other electronic devices which are mentioned below in the detailed description of the invention. formula (I) 0003. The precise structure of OLEDs is described, inter R4 alia, in U.S. Pat. No. 4,539,507, U.S. Pat. No. 5,151,629, EP 0676461 and WO 98/27136. In general, the term OLED is CBZ taken to mean electronic devices which comprise at least one formula (II) organic material and emit light on application of an electrical Voltage. f R1 R1 0004. In the case of electronic devices, in particular Z N Z Z N Z OLEDs, there is great interest in improving the performance data, in particular lifetime and efficiency and operating Volt rrn Srry age. An important role is played here by organic emitter Z s Z 2 Z 2 4 Z layers, in particular the matrix materials present therein, and formula (III) organic layers having electron-transporting function. formula (I)-HT--formula (I), 0005. In order to achieve this technical object, there is a continuous search for novel materials which are suitable for use as matrix materials in emitting layers, in particular phos where: phorescent emitting layers. Furthermore, materials having electron-transporting properties for use in electron-transport 0015 Cbz is a carbazole group which is optionally substi ing layers are being sought. tuted by one or more radicals R' and which may be 0006 Phosphorescent emitting layers in the sense of the extended by means of one or more condensed-on indeno present application are organic layers which comprise at least groups to form an indenocarbazole, and in which one or one phosphorescent emitting compound (phosphorescent more aromatic groups =C(R')— or =C(H)— may be dopant). replaced by =N , and which is bonded to the group R' 0007. In accordance with the present application, the term via the carbazole nitrogen atom; phosphorescent emitters encompasses compounds in the case of which the light emission takes place through a spin-forbid 0016 formula (I) is on each occurrence, identically or den transition, for example a transition from an excited triplet differently, any desired unit of the formula (1), where the state or a state having a higher spin quantum number, Such as group T may be bonded to this unit at any desired position; a quintet state. 0017 Z is on each occurrence, identically or differently, 0008. A matrix material in a system comprising a matrix CR' or N: material and a dopant is taken to mean the component whose proportion in the mixture is the greater. Correspondingly, a I0018) R' is on each occurrence, identically or differently, dopant in a system comprising a matrix material and a dopant H, D, F, C(=O)R, CN, Si(R), N(R), P(=O)(R), is taken to mean the component whose proportion in the S(=O)R. S(=O).R., a straight-chain alkyl or alkoxy mixture is the smaller. group having 1 to 20 C atoms or a branched or cyclic alkyl 0009. In accordance with the prior art, carbazole deriva or alkoxy group having 3 to 20 C atoms or an alkenyl or tives, such as, for example, bis(carbazolyl)biphenyl, or car alkynyl group bazole compounds or indenocarbazole compounds, such as, for example, in accordance with WO 2005/039246, US 2005/ 0019 having 2 to 20 C atoms, where the above-mentioned 0069729, JP 2004/288381, EP 1205527 or WO 2008/086851, groups may each be substituted by one or more radicals R are frequently used as matrix materials for phosphorescent and where one or more CH groups in the above-mentioned emitters. groups may be replaced by R°C=CR , —C=C , 0010 Triazine compounds, for example in accordance Si(R), C=O, C-NR, C(=O)C , C(=O)NR , with WO 2010/015306, WO 2007/063754 or WO 2008/ NR, P(=O)(R), -O-, -S. , SO or SO, or an aromatic 056746, are likewise used in this function. or heteroaromatic ring system having 5 to 30 aromatic ring 0011. The prior art furthermore discloses compounds in which a carbazole group or indenocarbazole group is bonded atoms, which may in each case be substituted by one or more to a triazine group, for example in WO 2011/057706, WO radicals R. or an aryloxy or heteroaryloxy group having 5 to 2010/136109 or WO 2011 FOOO455. 30 aromatic ring atoms, which may be substituted by one or 0012 However, there continues to be a need for improve more radicals R, where two or more radicals R' may be ment over the compounds known from the prior art, in par linked to one another and may form a ring; US 2015/0340627 A1 Nov. 26, 2015

(0029 Ar' is an aromatic ring system having 6 to 30 aro formula (A) matic ring atoms, which may be substituted by one or more X radicals R'; h Sx x1's x 0030 T is a single bond or an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which may salsNx E. El 2 k be substituted by one or more radicals R'. inLI 0031. For the purposes of the present application, the defi nition that the group Cbz is a carbazole group, which may be extended by means of indeno groups to form an indenocar bazole, is taken to mean that indeno groups may be condensed 0021 where the dashed line denotes the bond to the onto one or both of the six-membered rings of the carbazole. remainder of the formula, or R is equal to R', where at If indeno groups are present, one or two are preferably least one group R" performula unit of the formula (I) or present. If two indeno groups are present, they are preferably (II) conforms to the formula (A): not both bonded to the same six-membered ring of the carba 0022. L' is an aromatic or heteroaromatic ring system Zole. having 6 to 30 aromatic ring atoms, which may be substi 0032. An indeno group here is taken to mean the following tuted by one or more radicals R'; Structure: 0023 E is on each occurrence, identically or differently, O, S, or NAr"; 0024 X is on each occurrence, identically or differently, N R1 RI or CR, where at least one group Xper six-membered ring R1 is equal to N: 0025 i is on each occurrence, identically or differently, 0 or 1, where at least one index i per group of the formula : R1 (A) is equal to 1; RI 0026 R is on each occurrence, identically or differently, H, D, F, C(=O)R, CN, Si(R), S(=O)R’, S(=O),R, a straight-chain alkyl group having 1 to 20 C atoms or a 0033 Condensation of the indeno group is taken to mean branched orcyclic alkyl group having 3 to 20 Catoms oran that it shares two ring atoms with two ring atoms of the alkenyl or alkynyl group having 2 to 20 C atoms, where the six-membered ring of the carbazole. These two ring atoms are above-mentioned groups may each be substituted by one or preferably the ring atoms labelled with *. more radicals R and where one or more CH groups in the 0034. The condensation of indeno groups onto the carba above-mentioned groups may be replaced by Zole group in the group CbZ preferably takes place in posi RC—CR , -C=C , Si(R), C=O, C=NR, tions 2 and 3 and/or positions 6 and 7, where the numbering of C(=O)C , C(=O)NR NR, P(=O)(R), the positions on the carbazole, as generally customary, takes —O— —S , SO or SO, or an aromatic or heteroaro place as shown below. However, it may also take place in matic ring system having 5 to 30 aromatic ring atoms, positions 1 and 2, 3 and 4, 5 and 6 and/or 7 and 8. which may in each case be substituted by one or more radicals R: 0027 R’ is on each occurrence, identically or differently, H, D, F, C(=O)R, CN, Si(R), N(R), P(=O)(R), S(=O)R. S(=O).R., a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above mentioned groups may each be substituted by one or more radicals R and where one or more CH groups in the above-mentioned groups may be replaced by 0035 An illustrative carbazole group Cbz onto which an RC—CR , -C=C , Si(R), C=O, C=NR, indeno group is condensed is the following: C(=O)C , C(=O)NR NR, P(=O)(R), —O— —S , SO or SO, or an aromatic or heteroaro matic ring system having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R. or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R, where two or more radicals R may be linked to one another and may form a ring; I0028 R is on each occurrence, identically or differently, H. D. For an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 Catoms, in which, in addition, one or more H atoms may be replaced by D or F: two or more where the group may be substituted by radicals R' at all free substituents Rhere may be linked to one another and form positions, and where the dashed line denotes the bond to the a ring, group L'. US 2015/0340627 A1 Nov. 26, 2015

0036) An illustrative carbazole group Cbz onto which two defined above, which is bonded via an oxygen atom. An indeno groups are condensed is the following: analogous definition applies to heteroaryloxy groups. 0042. An aromatic ring system in the sense of this inven

tion contains 6 to 60 Catoms in the ring system. A heteroaro matic ring system in the sense of this invention contains 5 to 60 aromatic ring atoms, at least one of which is a heteroatom. The heteroatoms are preferably selected from N, O and/or S. An aromatic or heteroaromatic ring system in the sense of this invention is intended to be taken to mean a system which does not necessarily contain only aryl or heteroaryl groups, but instead in which, in addition, a plurality of aryl or heteroaryl groups may be connected by a non-aromatic unit (preferably less than 10% of the atoms other than H), such as, for example, an sp-hybridised C, Si, Nor O atom, an sp-hybri where the group may be substituted by radicals R at all free dised C or N atom or an sp-hybridised C atom. Thus, for positions, and where the dashed line denotes the bond to the example, systems such as 9.9'-spirobifluorene, 9.9'-dia group L'. rylfluorene, triarylamine, diaryl ether, stilbene, etc., are also 0037 General definitions of chemical groups in accor intended to be taken to be aromatic ring systems in the sense dance with the present application follow. of this invention, as are systems in which two or more aryl 0038 An aryl group in the sense of this invention contains groups are connected, for example, by a linear or cyclic alkyl, 6 to 60 aromatic ring atoms; a heteroaryl group in the sense of alkenyl or alkynyl group or by a silyl group. Furthermore, this invention contains 5 to 60 aromatic ring atoms, at least systems in which two or more aryl or heteroaryl groups are one of which is a heteroatom. The heteroatoms are preferably linked to one another via single bonds are also taken to be selected from N, O and S. This represents the basic definition. aromatic or heteroaromatic ring systems in the sense of this If other preferences are indicated in the description of the invention, such as, for example, systems such as biphenyl, present invention, for example with respect to the number of terphenyl or diphenyltriazine. aromatic ring atoms or the heteroatoms present, these apply. 10043. An aromatic or heteroaromatic ring system having 0039. An aryl group or heteroaryl group here is taken to 5-60 aromatic ring atoms, which may in each case also be mean either a simple aromatic ring, i.e. benzene, or a simple Substituted by radicals as defined above and which may be heteroaromatic ring, for example pyridine, pyrimidine or linked to the aromatic or heteroaromatic group via any thiophene, or a condensed (annellated) aromatic or heteroaro desired positions, is taken to mean, in particular, groups matic polycycle, for example naphthalene, phenanthrene, derived from benzene, naphthalene, anthracene, benzan quinoline or carbazole. A condensed (annellated) aromatic or thracene, phenanthrene, benzophenanthrene, pyrene, chry heteroaromatic polycycle in the sense of the present applica Sene, perylene, fluoranthene, naphthacene, pentacene, ben tion consists of two or more simple aromatic or heteroaro Zopyrene, biphenyl, biphenylene, terphenyl, terphenylene. matic rings condensed with one another. quaterphenyl, fluorene, spirobifluorene, dihydrophenan 0040. An aryl or heteroaryl group, which may in each case threne, dihydropyrene, tetrahydropyrene, cis- or trans-inde be substituted by the above-mentioned radicals and which nofluorene, truxene, isotruxene, spiro-truxene, spiroisotrux may be linked to the aromatic or heteroaromatic ring system ene, furan, benzofuran, isobenzofuran, dibenzofuran, Via any desired positions, is taken to mean, in particular, thiophene, benzothiophene, isobenzothiophene, diben groups derived from benzene, naphthalene, anthracene, Zothiophene, pyrrole, indole, isoindole, carbazole, indolocar phenanthrene, pyrene, dihydropyrene, chrysene, perylene, bazole, indenocarbazole, pyridine, quinoline, isoquinoline, fluoranthene, benzanthracene, benzophenanthrene, tet acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7- racene, pentacene, benzopyrene, furan, benzofuran, isoben quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, Zofuran, dibenzofuran, thiophene, benzothiophene, isoben pyrazole, indazole, imidazole, benzimidazole, naphthimida Zothiophene, dibenzothiophene, pyrrole, indole, isoindole, Zole, phenanthrimidazole, pyridimidazole, pyrazinimida carbazole, pyridine, quinoline, isoquinoline, acridine, Zole, quinoxalinimidazole, oxazole, benzoxazole, naphthox phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, azole, anthroxazole, phenanthroxazole, isoxazole, 1.2- benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, thiazole, 1,3-thiazole, benzothiazole, pyridazine, indazole, imidazole, benzimidazole, naphthimidazole, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, phenanthrimidazole, pyridimidazole, pyrazinimidazole, qui 1,5-diazaanthracene, 2.7-diazapyrene, 2,3-diazapyrene, 1.6- noxalinimidazole, oxazole, benzoxazole, naphthoxazole, diazapyrene, 1,8-diazapyrene, 4.5-diazapyrene, 4.5.9,10-tet anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3- raazaperylene, pyrazine, phenazine, phenoxazine, phenothi thiazole, benzothiazole, pyridazine, benzopyridazine, pyri azine, fluorubin, naphthyridine, aZacarbazole, midine, benzopyrimidine, quinoxaline, pyrazine, phenazine, benzocarboline, phenanthroline, 1.2.3-triazole, 1,2,4-triaz naphthyridine, azacarbazole, benzocarboline, phenanthro ole, benzotriazole, 1.2.3-oxadiazole, 1,2,4-oxadiazole, 1.2.5- line, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxa oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thia diazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiaz diazole, 1.2.5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, ole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1.2, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triaz 3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine ine, tetrazole, 1,2,4,5-tetrazine, 1.2.3,4-tetrazine, 1,2,3,5-tet and benzothiadiazole, or combinations of these groups. razine, purine, pteridine, indolizine and benzothiadiazole. 0044) For the purposes of the present invention, a straight 0041 An aryloxy group in accordance with the definition chain alkyl group having 1 to 40 C atoms or a branched or of the present invention is taken to mean an aryl group, as cyclic alkyl group having 3 to 40 C atoms or an alkenyl or US 2015/0340627 A1 Nov. 26, 2015

alkynyl group having 2 to 40 C atoms, in which, in addition, -continued individual H atoms or CH groups may be substituted by the groups mentioned above under the definition of the radicals, is preferably taken to mean the radicals methyl, ethyl, n-pro ring formation pyl, i-propyl. n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, —e. n-pentyl, S-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclo of the radicals R hexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2.2.2-trifluo H CH3 roethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl or octynyl. An alkoxy or thioalkyl group having 1 to 40 C atoms is preferably taken to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, S-butoxy, CH t-butoxy, n-pentoxy, S-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy, 2.2.2- 0047. The compound of the formula (I), (II) or (III) pref trifluoroethoxy, methylthio, ethylthio, n-propylthio, i-propy erably contains no condensed aryl or heteroaryl groups hav lthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio, n-pen ing more than 14 aromatic ring atoms, particularly preferably tylthio, s-pentylthio, n-hexylthio, cyclohexylthio. no aryl or heteroaryl groups having more than 10 aromatic n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio. ring atoms. 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio. 2.2.2-trifluoroethylthio, ethenylthio, propenylthio, bute 0048. It is preferred in accordance with the invention for nylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclo one index i performula (A) to be equal to one and for the other hexenylthio, heptenylthio, cycloheptenylthio, octenylthio. index i to be equal to Zero. cyclooctenylthio, ethynylthio, propynylthio, butynylthio. 0049 Furthermore preferably, two or three groups X per pentynylthio, hexynylthio, heptynylthio or octynylthio. six-membered ring are equal to N. 0045. The formulation that two or more radicals may form a ring with one another is, for the purposes of the present 0050. Furthermore preferably, groups X which represent application, intended to be taken to mean, interalia, that the N are not adjacent in a six-membered ring. two radicals are linked to one another by a chemical bond. 10051) Ar' is furthermore preferably selected from an aro This is illustrated by the following scheme: matic ring system having 6 to 18 aromatic ring atoms, which may be substituted by one or more radicals R'. Ar' is particu larly preferably selected from phenyl, biphenyl, terphenyl, naphthyl, fluorenyl or spirobifluorenyl, each of which is optionally substituted by radicals R'. 0.052 Groups of the formula (A) preferably conform to R R one of the following formulae (A-1) to (A-8) ring formation Rd of the radicals R

CH CH formula (A-1) s N R NY N CH CH El 0046. Furthermore, however, the above-mentioned for mulation is also intended to be taken to mean that, in the case where one of the two radicals represents hydrogen, the second radical is bonded at the position to which the hydrogenatom formula (A-2) was bonded, with formation of a ring. This is illustrated by the following scheme: s N R N 2 R El Ll US 2015/0340627 A1 Nov. 26, 2015

-continued -continued formula (A-8) R. N R formula (A-3) R s N1 N R R afn El R 2N

where the groups occurring are as defined above, and where the dashed line denotes the bond to the remainder of the formula (A-4) formula. 0053 For groups of the formulae (A-1) to (A-8), the embodiments indicated as preferred in the present application relating to the groups L', E' and R are likewise regarded as preferred. 10054 E is furthermore preferably selected identically on E each occurrence. E' is furthermore preferably on each occur rence, identically or differently, O or S, particularly prefer Ll ably O. I0055 L is furthermore preferably an aromatic or het eroaromatic ring system having 6 to 24 aromatic ring atoms, formula (A-5) R particularly preferably an aromatic ring system having 6 to 24 aromatic ring atoms, where the ring systems may be substi R. R tuted by one or more radicals R'. rs I0056. The group L' furthermore preferably contains at least one meta- or ortho-phenylene group, which may option NY ally be substituted by one or more radicals R'. El I0057 Very particularly preferred groups L are selected Ll from groups of the following formulae (L-1) to (L-18)

formula (L-1) formula (A-6) R 1s N1N R formula (L-2) R afn O o El O formula (L-3) Ll O-O-O- formula (A-7) formula (L-4) R 1N N 1sN 1s R. s O N49 Selse formula (L-5) Na2 R

El Ll US 2015/0340627 A1 Nov. 26, 2015

-continued -continued formula (L-12) formula (L-6)

N | 21-- - CO)2-Cy formula (L-7) f la (L-13) - + N 1s-O syn s/n formula (L-14) formula (L-8) -- Sl-O s ul-/ \ 2N/ \ s^ \ K o formula (L-15) 1S-S 1s formula (L-9) 2N/ y 2 / \ S formula (L-16) s^ \ 1 N o 2N/ \ -N -? y formula (L-17) N N formula (L-10) o 4-4 \ 21 s/n O S T- 1S-N formula (L-18) -CO--(y Null-/- \ y

formula (L-11) where the groups may be substituted by radicals R at all free ( ) positions and where the dashed lines denote the bonds to the remainder of the compound in the case where the sum of the indices i is equal to 1 and only one group E" is present. In the case where the Sum of the indices i is equal to 2, so that two N O groups E' are present, preferably both groups E are bonded - to the same aryl group. Correspondingly modified groups of 21 / \ the formulae (L-1) to (L-18) which correspondingly contain s^ three dashed lines which denote the bonds to the remainder of the formula instead of two dashed lines should then be called into play. US 2015/0340627 A1 Nov. 26, 2015

I0058. Furthermore preferably, no groups =C(R') or 0063 Preferred embodiments of alkyl rings which are =C(H)— in the group Cbz have been replaced by —N—. formed by two radicals R on a methylene group —C(R) - 0059. It is furthermore generally regarded as preferred for in a group Cbz, which represents an indenocarbazole group not more than three groups Z per six-membered ring to be are selected from the following formulae (C-1) to (C-8) equal to N, particularly preferably not more than two groups Z. Furthermore preferably, not more than two adjacent groups Zare equal to N. Furthermore preferably, Z is equal to CR". formula (C-1) 0060 Preferred groups Cbz conform to the following for mulae (Cbz-1) to (Cbz-3) formula (C-2)

formula (Cbz-1)

formula (C-3) 4z/ y ( “aY Zsz 72Z formula (Cbz-2) formula (C-4) z/ N Z R. . \ / N R1 CO Zsz 72 2 Z f y formula (C-5) Z s/ formula (Cbz-3)

R Z. N Z R. formula (C-6) R1 7 \ / N R1

Ses- e |Z N Z Z a Zy O N27 Zs formula (C-7) where the dashed line denotes the bond to the group R', and where the groups occurring are as defined above. CO A I0061) R' is preferably on each occurrence, identically or p differently, H, D, F, C(=O)R, CN, Si(R), a straight-chain formula (C-8) alkyl oralkoxy group having 1 to 10C atoms or a branched or cyclic alkyl oralkoxy group having 3 to 10C atoms, where the s above-mentioned groups may each be substituted by one or more radicals R and where one or more CH groups in the above-mentioned groups may be replaced by —C=C , A. —RC=CR , Si(R) or C=O, or an aromatic or het eroaromatic ring system having 5 to 20 aromatic ring atoms, which may in each case be substituted by one or more radicals each of which may be substituted by radicals R at the free R, where two or more radicals R' may be linked to one positions. another and may form a ring. I0064. For formula (II), both groups Rare preferably each I0062) R' which is bonded to the methylene group of an groups of the formula (A). For formula (II), however, one R' indeno group which is a constituent of a group Cbz or of the may also be a group of the formula (A) and the other R is indenocarbazole group of formula (II) is preferably selected equal to R". For formula (I), R' can by definition not be equal from a straight-chain alkyl group having 1 to 10 C atoms, or to R', but instead must conform to formula (A). a branched or cyclic alkyl group having 3 to 10 C atoms, I0065 R is furthermore preferably on each occurrence, where the above-mentioned groups may each be substituted identically or differently, H, D, F, C(=O)R, CN, Si(R), a by one or more radicals R. or the two radicals R' which are straight-chain alkyl oralkoxy group having 1 to 10C atoms or bonded to the same methylenegroup are linked to one another a branched or cyclic alkyl or alkoxy group having 3 to 10C and form an alkyl ring with the methylene group, where the atoms, where the above-mentioned groups may each be Sub alkyl ring may in each case be substituted by one or more stituted by one or more radicals R and where one or more radicals R. CH2 groups in the above-mentioned groups may be replaced US 2015/0340627 A1 Nov. 26, 2015

by -C=C-, - RC—CR , Si(R) or C=O, or an aro -continued matic or heteroaromatic ring system having 5 to 20 aromatic ring atoms, which may in each case be substituted by one or formula (I-4) more radicals R, where two or more radicals R may be R linked to one another and may form a ring. 0066 R is furthermore preferably on each occurrence, es identically or differently, H. D. F. CN, a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms or an alkenyl or alkynyl group 1. having 2 to 10 C atoms, where the above-mentioned groups El may each be substituted by one or more radicals R and where Ll one or more CH2 groups in the above-mentioned groups may be replaced by R°C—CR , -C=C , Si(R), or N C=O, or an aromatic or heteroaromatic ring system having 5 to 20 aromatic ring atoms, which may in each case be substi tuted by one or more radicals R. 0067 Preferred compounds of the formula (1) conform to one of the following formulae (I-1) to (I-24) formula (I-5) R

R. R formula (I-1) rs s N R N NY N El El Ll Ll N

N

formula (I-6) R formula (I-2) s s R s R N afn R 2 R El El Ll Ll

N N

formula (I-3) formula (I-7) R R

R N1 N R N R R 1. N N 21 R El El Ll Ll

N N US 2015/0340627 A1 Nov. 26, 2015

-continued -continued formula (I-8) R. N R n formula (I-12) R 1Nafn 1. E Ll R 21 R

E Ll CS C N R1 formula (I-9) R. N R R1 N- O El Ll N RI formula (I-13)

C Cy RI R R R rs N 2 N formula (I-10) n R. N R El n

N an N R1 R1 Ll C O N ClyRI O formula (I-14) R formula (I-11) R R 1s-" N N R afn R 2 El

Ll R1 O US 2015/0340627 A1 Nov. 26, 2015

-continued -continued

formula (I-15) formula (I-18) R

R. R N oN R El

N RI

formula (I-19) formula (I-16) R. N R

R an El

N RI C C R1

formula (I-17) formula (I-20) s al,

R 2

E

Ll

N US 2015/0340627 A1 Nov. 26, 2015 11

-continued -continued

formula (I-21) formula (I-24)

where the compounds may each be substituted by radicals R' formula (I-22) at all free positions on the groups Cbz, and where the groups occurring are as defined above. 0068 For compounds of the formulae (I-1) to (I-24), it is preferred for the groups occurring to be defined in accordance with their preferred embodiments. R 0069. E is especially preferably selected from O and S.

0070 L is furthermore especially preferably selected from an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, particularly preferably an aromatic ring system having 6 to 24 aromatic ring atoms, where the ring systems may be substituted by one or more radicals R'. R" is very particularly preferably selected from groups of the formulae (L-1) to (L-18), as defined above. 0071 Preferred compounds of the formula (II) conform to one of the following formulae (II-1) to (II-8)

formula (I-23)

R. formula (II-1)

US 2015/0340627 A1 Nov. 26, 2015

-continued -continued

formula (II-2) formula (II-6)

R N1 N R

R 2 R

formula (II-3) formula (II-7) R R R N1 N R. R N 2 N R N 21 R

formula (II-4) R formula (II-8) 1. R Ns R R 2 R R 21 R

formula (II-5) where the compounds may each be substituted by radicals R' at all positions depicted as unsubstituted, and where the groups occurring are as defined above, and where, in particular, R' may be equal to R' or equal to a group of the formula (A). 0072 For compounds of the formulae (II-1) to (II-8), it is preferred for the groups occurring to be defined in accordance with their preferred embodiments. 0073 R' in formulae (II-1) to (II-8) is preferably a group of the formula (A). R' is particularly preferably selected in Such a way that the two groups bonded to the carbazole nitrogen atoms are identical. (0074 E' is especially preferably selected from O and S. (0075) Furthermore, L' is especially preferably selected from an aromatic or heteroaromatic ring system having 6 to US 2015/0340627 A1 Nov. 26, 2015 13

24 aromatic ring atoms, particularly preferably an aromatic -continued ring system having 6 to 24 aromatic ring atoms, where the ring systems may be substituted by one or more radicals R'. formula (III-3) R" is very particularly preferably selected from groups of the formulae (L-1) to (L-18), as defined above. x1's x 0076 For compounds of the formula (III), T is in general - n - preferably a single bond or an aromatic or heteroaromatic h s: n ring system having 6 to 24 aromatic ring atoms, which may be substituted by one or more radicals R'. T is particularly pref E erably a single bond. L 0077. For compounds of the formula (III), the groups of N the unit of the formula (I) furthermore generally preferably correspond to their preferred embodiments indicated above. The units of the formula (I) especially preferably correspond to the preferred embodiments of the formulae (I-1) to (I-21) indicated above. 0078. Furthermore, the group T is preferably in each case bonded to the group Cbz of the unit of the formula (I). formula (III-4) 007.9 Furthermore, the units of the formula (I) in com- x^s x x^s x pounds of the formula (III) are preferably each selected iden- I I tically. X. X X. X

0080 Particularly preferred embodiments of compounds E E of the formula (III) conform to the following formulae (III-1) to (III-5) N N

formula (III-1) x1 SX x1 Sx

formula (III-5)

El El

where the groups occurring are as defined above. I0081 For compounds of the formulae (III-1) to (III-5), the groups occurring are preferably defined in accordance with their preferred embodiments. I0082 E' is especially preferably selected from O and S. I0083. Furthermore, L' is especially preferably selected from an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, particularly preferably an aromatic ring system having 6 to 24 aromatic ring atoms, where the ring systems may be substituted by one or more radicals R'. US 2015/0340627 A1 Nov. 26, 2015 14

R" is very particularly preferably selected from groups of the -continued formulae (L-1) to (L-18), as defined above. 0084. Furthermore, for compounds of the formulae (III-1) 3 to (III-5), T is especially preferably a single bond or an aro matic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which may be substituted by one or more radicals O R'. T in compounds of the formula (III-1) to (III-5) is par ticularly preferably a single bond. C 0085 Examples of compounds according to the invention are shown below:

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Z US 2015/0340627 A1 Nov. 26, 2015 20

-continued -continued 36 33 Y\ NS o Ns. \ 2

D-O (O C. N \ NS G \ 7 C.O.)

35

I0086. The compounds according to the invention can be prepared by known organochemical synthesis processes. These include, for example, the Hartwig-Buchwald coupling, the Suzuki coupling, halogenation reactions and nucleophilic Substitution reactions on electron-deficient aromatic com pounds. I0087 Illustrative processes for the preparation of the com pounds according to the invention are presented below. The US 2015/0340627 A1 Nov. 26, 2015

processes shown are particularly Suitable for the preparation -continued of compounds according to the invention. However, alterna tive processes are conceivable and possibly to be preferred in certain cases. Correspondingly, the person skilled in the art will be able to modify the processes shown below within the bounds of his general expert knowledge. s: n Hal N 0088 Scheme 1 shows the synthesis of compounds r" s A1NA according to the invention which contain an oxygen- or Sul fur-functionalised electron-deficient heteroaryl group. To this end, firstly a protected oxygen- or Sulfur-functionalised linker Buchwald is coupled to a carbazole derivative in a Buchwald coupling. After deprotection, this linker is reacted with an electron deficientheteroaromatic compound in a Substitution reaction. Hal = halogen, preferably Br This gives a compound according to the invention, which, X=N or CR R = any desired organic radical however, can be functionalised and modified further. Ar = any desired aryl or heteroaryl group

Scheme 1 0090 The preparation of dimeric compounds of the for H mula (III) can be carried out starting from corresponding N modified starting compounds. Alternatively, monomeric Buchwald compounds obtained in accordance with Scheme 1 or 2 can be Y V N O functionalised and coupled or extended to give dimeric com pounds. S/SR 2\sR ill---O) 0091. It is furthermore noted that it is also possible to use E = S, O indenocarbazoles as starting materials instead of the carba Hal = halogen, preferably Br Zoles shown, in which case the corresponding indenocarba X = N or CR Zole derivatives are obtained as compounds according to the R = any desired organic radical invention. Ar = any desired aryl or heteroaryl group 0092. In summary, the invention furthermore relates to a process for the preparation of a compound of the formula (I), (II) or (III), characterised in that at least one transition metal catalysed coupling reaction is employed. 0093. The transition metal-catalysed coupling reaction is preferably a Hartwig-Buchwald coupling, which is particu larly preferably carried out on the nitrogen atom of the car bazole derivative. 0094. The electron-deficient heteroaryl group is further more preferably introduced by a Hartwig-Buchwald reaction if it is Substituted by an amino group, and by a nucleophilic aromatic Substitution reaction if it is Substituted by an oxygen or sulfur in the compound of the formula (I), (II) or (III). 0.095 The compounds according to the invention described above, in particular compounds which are substi tuted by reactive leaving groups, such as bromine, iodine, 0089 Scheme 2 shows the synthesis of compounds which chlorine, boronic acid or boronic acid ester, can be used as contain a nitrogen-functionalised electron-deficient het monomers for the production of corresponding oligomers, eroaryl group. To this end, firstly a halogen-substituted linker dendrimers or polymers. Suitable reactive leaving groups are, is coupled to the carbazole derivative in a Buchwald coupling. for example, bromine, iodine, chlorine, boronic acids, In a second Buchwald reaction, the product is Subsequently boronic acid esters, amines, alkenyl or alkynyl groups having coupled to an amino group which has been functionalised by a terminal C C double bond or C C triple bond, oxiranes, means of an electron-deficient heteroaryl group. This gives a oxetanes, groups which undergo a cycloaddition, for example compound according to the invention, which, however, can be a 1,3-dipolar cycloaddition, Such as, for example, dienes or functionalised and modified further. azides, carboxylic acid derivatives, alcohols and silanes. 0096. The invention therefore furthermore relates to oli gomers, polymers or dendrimers containing one or more Scheme 2 compounds of the formula (I), (II) or (III), where the bond(s) to the polymer, oligomer or dendrimer may be localised at any desired positions informula (I), (II) or (III) which are substi tuted by R' or RX. Depending on the linking of the compound of the formula (I), (II) or (III) the compound is a constituent of a side chain of the oligomer or polymer or a constituent of the main chain. An oligomer in the sense of this invention is taken to mean a compound which is built up from at least three US 2015/0340627 A1 Nov. 26, 2015 22 monomer units. A polymer in the sense of the invention is detail in the literature, for example in WO 2003/048225, WO taken to mean a compound which is built up from at least ten 2004/O37887 and WO 2004/O37887. monomer units. The polymers, oligomers or dendrimers 0103) The present invention thus also relates to a process according to the invention may be conjugated, partially con for the preparation of the polymers, oligomers and dendrim jugated or non-conjugated. The oligomers or polymers ers according to the invention, which is characterised in that according to the invention may be linear, branched or den they are prepared by SUZUKI polymerisation,YAMAMOTO dritic. In the structures linked in a linear manner, the units of polymerisation, STILLE polymerisation or HARTWIG the formula (I), (II) or (III) may be linked directly to one BUCHWALD polymerisation. The dendrimers according to another or they may be linked to one another via a divalent the invention can be prepared by processes known to the group, for example via a substituted or unsubstituted alkylene person skilled in the art or analogously thereto. Suitable pro group, via a heteroatom or via a divalent aromatic or het cesses are described in the literature, such as, for example, in eroaromatic group. In branched and dendritic structures, for Frechet, Jean M. J.; Hawker, Craig J., “Hyperbranched example, three or more units of the formula (I), (II) or (III) polyphenylene and hyperbranched polyesters: new soluble, may be linked via a trivalent or polyvalent group, for example three-dimensional, reactive polymers’. Reactive & Func via a trivalent or polyvalent aromatic or heteroaromatic tional Polymers (1995), 26(1-3), 127-36; Janssen, H. M.: group, to form a branched or dendritic oligomer or polymer. Meijer, E. W. “The synthesis and characterization of den 0097. The same preferences as described above for com dritic molecules', Materials Science and Technology (1999), pounds of the formula (I), (II) or (III) apply to the recurring 20 (Synthesis of Polymers), 403-458; Tomalia, Donald A. units of the formula (I), (II) or (III) in oligomers, dendrimers “Dendrimer molecules”, Scientific American (1995), 272(5), and polymers. 62-6; WO 2002/067343 A1 and WO 2005/026144A1. 0098. For the preparation of the oligomers or polymers, 0104 For the processing of the compounds according to the monomers according to the invention are homopolymer the invention from the liquid phase, for example by spin ised or copolymerised with further monomers. coating or by printing processes, formulations of the com 0099 Suitable and preferred comonomers are selected pounds according to the invention are necessary. These for from fluorenes (for example in accordance with EP 842208 or mulations can be, for example, Solutions, dispersions or WO 00/22026), spirobifluorenes (for example in accordance emulsions. It may be preferred to use mixtures of two or more with EP 707020, EP 894107 or WO 06/061181), paraphe solvents for this purpose. Suitable and preferred solvents are, nylenes (for example in accordance with WO 1992/18552), for example, toluene, anisole, o-, m- or p-Xylene, methyl carbazoles (for example in accordance with WO 04/070772 benzoate, mesitylene, tetralin, Veratrol, THF, methyl-THF, or WO 2004/113468), thiophenes (for example inaccordance THP, chlorobenzene, dioxane, phenoxytoluene, in particular with EP 1028.136), dihydrophenanthrenes (for example in 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylben accordance with WO 2005/014689 or WO 2007/006383), cis Zene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, and trans-indenofluorenes (for example in accordance with 2-methylbenzothiazole, 2-phenoxyethanol. 2-pyrrolidinone, WO 2004/041901 or WO 2004/113412), ketones (for 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3.5- example in accordance with WO 2005/040302), phenan dimethylanisole, acetophenone, ca-terpineol, benzothiazole, threnes (for example in accordance with WO 2005/104264 or butyl benzoate, cumene, cyclohexanol, cyclohexanone, WO 2007/017066) or also a plurality of these units. The cyclohexylbenzene, decalin, dodecyl-benzene, ethyl ben polymers, oligomers and dendrimers usually also contain Zoate, indane, methylbenzoate, NMP p-cymene, phenetol, further units, for example emitting (fluorescent or phospho 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol rescent) units, such as, for example, vinyltriarylamines (for butyl methyl ether, triethylene glycol butyl methyl ether, example in accordance with WO 2007/068325) or phospho diethylene glycol dibutyl ether, triethylene glycol dimethyl rescent metal complexes (for example in accordance with ether, diethylene glycol monobutyl ether, tripropylene glycol WO 2006/003000), and/or charge-transportunits, in particu dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopro lar those based on triarylamines. pylnaphthalene, pentylbenzene, hexylbenzene, heptylben 0100. The polymers, oligomers and dendrimers according Zene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane or to the invention have advantageous properties, in particular mixtures of these solvents. long lifetimes, high efficiencies and good colour coordinates. 0105. The invention therefore furthermore relates to a for 0101 The polymers and oligomers according to the inven mulation, in particular a solution, dispersion or emulsion, tion are generally prepared by polymerisation of one or more comprising at least one compound of the formula (I) or at least types of monomer, at least one monomer of which results in one polymer, oligomer or dendrimer containing at least one recurring units of the formula (I), (II) or (III) in the polymer. unit of the formula (I), and at least one solvent, preferably an Suitable polymerisation reactions are known to the person organic solvent. The way in which solutions of this type can skilled in the art and are described in the literature. Particu be prepared is known to the person skilled in the art and is larly suitable and preferred polymerisation reactions which described, for example, in WO 2002/072714, WO 2003/ result in C C or C N links are the following: O19694 and the literature cited therein. 0106 The compounds according to the invention are suit (A) SUZUKI polymerisation; able for use in electronic devices, in particular in organic (B)YAMAMOTO polymerisation: electroluminescent devices (OLEDs). Depending, interalia, (C) STILLE polymerisation; and on the Substitution, the compounds can be employed in dif (D) HARTWIG-BUCHWALD polymerisation. ferent functions and layers. The compounds are preferably 0102 The way in which the polymerisation can be carried employed as host materials, preferably as host materials for out by these methods and the way in which the polymers can phosphorescent emitters, or as electron-transport materials. then be separated off from the reaction medium and purified 0.107 The invention furthermore relates to the use of the is known to the person skilled in the art and is described in compounds of the formula (I), (II) or (III) in electronic US 2015/0340627 A1 Nov. 26, 2015

devices. The electronic devices here are preferably selected The compounds according to the invention may alternatively from the group consisting of organic integrated circuits and/or additionally also be present in the electron-transport (O-ICs), organic field-effect transistors (O-FETs), organic layer or in another layer. thin-film transistors (O-TFTs), organic light-emitting transis 0113. It should be noted that, for the generation of white tors (O-LETs), organic Solar cells (O-SCs), organic optical light, an emitter compound used individually which emits in detectors, organic photoreceptors, organic field-quench a broad wavelength range may also be suitable instead of a devices (O-FQDs), light-emitting electrochemical cells plurality of emitter compounds emitting in colour. (LECs), organic laser diodes (O-lasers) and particularly pref 0114. It is preferred in accordance with the invention if the erably selected from organic electroluminescent devices compound of the formula (I), (II) or (III) is employed in an (OLEDs). electronic device comprising one or more phosphorescent 0108. The invention furthermore relates to an electronic dopants. The compound can be used in various layers here, device comprising anode, cathode and at least one organic preferably in an electron-transport layer or in an emitting layer, where the organic layer comprises at least one com layer. pound of the formula (I), (II) or (III). The electronic device 0.115. In accordance with the present application, the term here is preferably selected from the above-mentioned devices phosphorescent emitters encompasses compounds in which and is particularly preferably an organic electroluminescent the light emission takes place through a spin-forbidden tran device (OLED). sition, for example a transition from an excited triplet State or 0109 Apart from cathode, anode and the emitting layer, a state having a higher spin quantum number, such as a quintet the organic electroluminescent device may also comprise further layers. These are selected, for example, from in each State. case one or more hole-injection layers, hole-transport layers, 0116 Suitable phosphorescent dopants are, in particular, hole-blocking layers, electron-transport layers, electron-in compounds which emit light, preferably in the visible region, jection layers, electron-blocking layers, exciton-blocking on Suitable excitation and in addition contain at least one atom layers, charge-generation layers (IDMC 2003, Taiwan; Ses having an atomic number greater than 20, preferably greater sion 21 OLED (5), T. Matsumoto, T. Nakada, J. Endo, K. than 38 and less than 84, particularly preferably greater than Mori, N. Kawamura, A. Yokoi, J. Kido, Multiphoton Organic 56 and less than 80. The phosphorescent dopants used are EL Device Having Charge Generation Layer), coupling-out preferably compounds which contain copper, molybdenum, layers and/or organic or inorganic pfnjunctions. However, it tungsten, rhenium, ruthenium, osmium, rhodium, iridium, should be pointed out that each of these layers does not palladium, platinum, silver, gold or europium, in particular necessarily have to be present and the choice of layers is compounds which contain iridium, platinum or copper. always dependent on the compounds used and in particular 0117 For the purposes of the present invention, all lumi also on whether the electroluminescent device is fluorescent nescent iridium, platinum or copper complexes are regarded or phosphorescent. The compounds preferably employed in as phosphorescent compounds. the respective layers and functions are explicitly disclosed in 0118. Examples of phosphorescent dopants are revealed later sections. by the applications WO 2000/70655, WO 2001/41512, WO 0110. The sequence of the layers of the organic electrolu 2002/02714, WO 2002/15645, EP 1191613, EP 1191612, EP minescent device is preferably as follows: 1191614, WO 2005/033244, WO 2005/019373 and US 2005/ anode 0258742. In general, all phosphorescent complexes as used in hole-injection layer accordance with the prior art for phosphorescent OLEDs and hole-transport layer as are known to the person skilled in the art in the area of organic electroluminescent devices are Suitable for use in the optionally 1, 2 or 3 further hole-transport layers, preferably 2 devices according to the invention. The person skilled in the further hole-transport layers art will also be able, without inventive step, to employ further emitting layer phosphorescent complexes in OLEDs in combination with electron-transport layer the compounds according to the invention. Further examples electron-injection layer of suitable phosphorescent dopants are revealed by the table cathode. following in a later section. 0111. It should again be pointed out here that not all the 0119. In a preferred embodiment of the present invention, said layers have to be present, and/or that further layers may the compounds of the formula (I), (II) or (III) are employed as matrix material in an emitting layer in combination with one additionally be present. or more dopants, preferably phosphorescent dopants. 0112 The organic electroluminescent device according to the invention may comprise a plurality of emitting layers. 0120 A dopant in a system comprising a matrix material These emission layers in this case particularly preferably and a dopant is taken to mean the component whose propor have in total a plurality of emission maxima between 380 nm tion in the mixture is the Smaller. Correspondingly, a matrix and 750 nm, resulting overall in white emission, i.e. various material in a system comprising a matrix material and a emitting compounds which are able to fluoresce or phospho dopant is taken to mean the component whose proportion in resce and which emit blue or yellow or orange or red light are the mixture is the larger. used in the emitting layers. Particular preference is given to I0121 The proportion of the matrix material in the emitting three-layer systems, i.e. systems having three emitting layers, layer is in this case between 50.0 and 99.9% by vol., prefer where at least one of these layers preferably comprises at least ably between 80.0 and 99.5% by vol. and particularly prefer one compound of the formula (I), (II) or (III) and where the ably between 92.0 and 99.5% by vol. for fluorescent emitting three layers exhibit blue, green and orange or red emission layers and between 85.0 and 97.0% by vol. for phosphores (for the basic structure see, for example, WO 2005/011013). cent emitting layers. US 2015/0340627 A1 Nov. 26, 2015 24

0122 Correspondingly, the proportion of the dopants is 0.130. The compounds shown in the following table repre between 0.1 and 50.0% by vol., preferably between 0.5 and sent particularly Suitable phosphorescent dopants. 20.0% by vol. and particularly preferably between 0.5 and 8.0% by vol. for fluorescent emitting layers and between 3.0 and 15.0% by Vol. for phosphorescent emitting layers. 0123. An emitting layer of an organic electroluminescent device may also comprise systems comprising a plurality of N matrix materials (mixed-matrix systems) and/or a plurality of dopants. In this case too, the dopants are generally the mate- Ir rials whose proportion in the system is the Smaller and the a matrix materials are the materials whose proportion in the system is the larger. In individual cases, however, the propor tion of an individual matrix material in the system may be Smaller than the proportion of an individual dopant. 0.124. In a further preferred embodiment of the invention, the compounds of the formula (I), (II) or (III) are used as a component of mixed-matrix systems. The mixed-matrix sys- N N tems preferably comprise two or three different matrix mate- N N rials, particularly preferably two different matrix materials. 2 2 One of the two materials here is preferably a material having Ir Ir hole-transporting properties and the other material is a mate rial having electron-transporting properties. The two differ ent matrix materials may be present here in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, particularly preferably 1:10 to 1:1 3 3 and very particularly preferably 1:4 to 1:1. Mixed-matrix systems are preferably employed in phosphorescent organic N N electroluminescent devices. More precise information on mixed-matrix systems is given, interalia, in the application WO 2010/108579. Ir Ir 0.125. The mixed-matrix systems may comprise one or more dopants. The dopant compounds or the dopant com pounds together have, in accordance with the invention, a proportion of 0.1 to 50.0% by vol. in the mixture as a whole Me and preferably a proportion of 0.5 to 20.0% by vol. in the mixture as a whole. Correspondingly, the matrix components together have a proportion of 50.0 to 99.9% by vol. in the mixture is a whole and preferably a proportion of 80.0 to 99.5% by vol. in the mixture as a whole. 0126 Particularly suitable matrix materials which can be N used as matrix components of a mixed-matrix system in com bination with the compounds according to the invention are 2N selected from the preferred matrix materials for phosphores cent dopants indicated below or the preferred matrix materi als for fluorescent dopants, depending on what type of dopant compound is employed in the mixed-matrix system. Ir 0127 Preferred phosphorescent dopants for use in mixed matrix systems comprising the compounds according to the invention are the phosphorescent dopants shown above and in O 3 a following table. 0128. In a further preferred embodiment of the invention, the compound of the formula (I), (II) or (III) is employed as electron-transport material in an electron-transport layer or electron-injection layer or hole-blocking layer. The emitting layer here may comprise fluorescent and/or phosphorescent O Ir Ir emitters. 0129. The further functional materials preferably employed in the electronic devices according to the invention are shown below. US 2015/0340627 A1 Nov. 26, 2015 25

-continued -continued

Ir

OMe

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I0131 Preferred fluorescent dopants are selected from the class of the arylamines. An arylamine or aromatic amine in the sense of this invention is taken to meana compound which contains three substituted or unsubstituted aromatic or het eroaromatic ring systems bonded directly to the nitrogen. At least one of these aromatic or heteroaromatic ring systems is preferably a condensed ring system, particularly preferably having at least 14 aromatic ring atoms. I0132 Preferred examples thereof are aromatic anthrace namines, aromatic anthracenediamines, aromatic pyre namines, aromatic pyrenediamines, aromatic chrysenamines or aromatic chrysenediamines. An aromatic anthracenamine is taken to mean a compound in which one diarylamino group is bonded directly to an anthracene group, preferably in the 9-position. An aromatic anthracenediamine is taken to mean a compound in which two diarylamino groups are bonded directly to an anthracene group, preferably in the 9,10-posi tion. Aromatic pyrenamines, pyrenediamines, chrysenamines and chrysenediamines are defined analogously thereto, where the diarylamino groups are preferably bonded to the pyrene in the 1-position or in the 1,6-position. Further preferred dopants are indenofluorenamines or indeno-fluorenedi US 2015/0340627 A1 Nov. 26, 2015 37 amines, for example in accordance with WO 2006/108497 or silanes, for example in accordance with WO 2005/11 1172, WO 2006/122630, benzoindenofluorenamines or benzoinde aZaboroles or boronic esters, for example in accordance with nofluorene-diamines, for example in accordance with WO WO 2006/117052, triazine derivatives, for example in accor 2008/006449, and dibenzoindenofluorenamines or diben dance with WO 2010/015306, WO 2007/063754 or WO Zoindenofluorenediamines, for example in accordance with 2008/056746, Zinc complexes, for example in accordance WO 2007/140847, and the indenofluorene derivatives con with EP 652273 or WO 2009/062578, diazasilole or tetraa taining condensed aryl groups which are disclosed in WO Zasilole derivatives, for example in accordance with WO 2010/012328. Preference is likewise given to the pyrenary 2010/054729, diazaphosphole derivatives, for example in lamines disclosed in WO 2012/048780 and the as yet unpub accordance with WO 2010/054730, bridged carbazole deriva lished EP 12004426.8. Preference is likewise given to the tives, for example inaccordance with US 2009/0136779, WO benzoindenofluorenamines disclosed in the as yet unpub 2010/050778, WO 2011/042107, WO 2011/088877 or WO lished EP 12006239.3. 2012/143080, triphenylene derivatives, for example in accor 0133) Suitable matrix materials, preferably for fluorescent dance with WO 2012/048781, or lactams, for example in emitters, besides the compounds according to the invention, accordance with WO 2011/116865 or WO 2011/137951. are materials from various classes of substance. Preferred 0.135 Suitable charge-transport materials, as can be used matrix materials are selected from the classes of the oli in the hole-injection or hole-transport layer or in the electron goarylenes (for example 2.2.7.7'-tetraphenylspirobifluorene transport layer of the organic electroluminescent device in accordance with EP 676461 or dinaphthylanthracene), in according to the invention, besides the compounds according particular the oligoarylenes containing condensed aromatic to the invention, are, for example, the compounds disclosed in groups, the oligoarylenevinylenes (for example DPVBi or Y. Shirota et al., Chem. Rev. 2007, 107(4),953-1010, or other spiro-DPVBi in accordance with EP 676.461), the polypodal materials as are employed in these layers in accordance with metal complexes (for example in accordance with WO 2004/ the prior art. 08.1017), the hole-conducting compounds (for example in 0.136. Materials which can be used for the electron-trans accordance with WO 2004/058911), the electron-conducting port layer, besides the compounds according to the invention, compounds, in particular ketones, phosphine oxides, Sulfox are all materials as are used in accordance with the prior art as ides, etc. (for example in accordance with WO 2005/084081 electron-transport materials in the electron-transport layer. and WO 2005/084082), the atropisomers (for example in Particularly suitable are aluminium complexes, for example accordance with WO 2006/048268), the boronic acid deriva Ald, Zirconium complexes, for example Zrqa, benzimida tives (for example in accordance with WO 2006/117052) or Zole derivatives, triazine derivatives, pyrimidine derivatives, the benzanthracenes (for example in accordance with WO pyridine derivatives, pyrazine derivatives, quinoxaline 2008/145239). Particularly preferred matrix materials are derivatives, quinoline derivatives, oxadiazole derivatives, selected from the classes of the oligoarylenes, comprising aromatic ketones, lactams, boranes, diaZaphosphole deriva naphthalene, anthracene, benzanthracene and/or pyrene or tives and phosphine oxide derivatives. Furthermore suitable atropisomers of these compounds, the oligoarylenevinylenes, materials are derivatives of the above-mentioned compounds, the ketones, the phosphine oxides and the sulfoxides. Very as disclosed in JP 2000/053957, WO 2003/060956, WO particularly preferred matrix materials are selected from the 2004/028217, WO 2004/080975 and WO 2010/072300. classes of the oligoarylenes, comprising anthracene, benzan 0.137 Preferred hole-transport materials which can be thracene, benzophenanthrene and/or pyrene or atropisomers used in a hole-transport, hole-injection or electron-blocking of these compounds. An oligoarylene in the sense of this layer in the electroluminescent device according to the inven invention is intended to be taken to mean a compound in tion are indenofluorenamine derivatives (for example in which at least three aryl or arylene groups are bonded to one accordance with WO 06/122630 or WO 06/100896), the another. Preference is furthermore given to the anthracene amine derivatives disclosed in EP 1661888, hexaazatriph derivatives disclosed in WO 2006/097208, WO 2006/ enylene derivatives (for example in accordance with WO 131192, WO 2007/065550, WO 2007/11012.9, WO 2007/ 01/049806), amine derivatives containing condensed aro 065678, WO 2008/145239, WO 2009/100925, WO 2011/ matic rings (for example in accordance with U.S. Pat. No. 0544.42 and EP 1553154, and also the pyrene compounds 5,061,569), the amine derivatives disclosed in WO95/09147, disclosed in EP 1749809, EP 1905754 and US 2012/ monobenzoindenofluorenamines (for example in accordance O1878.26. with WO 08/006449), dibenzoindenofluorenamines (for 0134 Preferred matrix materials for phosphorescent emit example in accordance with WO 07/140847), spirobifluore ters, besides the compounds according to the invention, are namines (for example in accordance with WO 2012/034627 aromatic ketones, aromatic phosphine oxides or aromatic or WO 2013/120577), fluorenamines (for example in accor sulfoxides or sulfones, for example in accordance with WO dance with the as yet unpublished applications EP 12005369. 2004/013080, WO 2004/093207, WO 2006/005627 or WO 9, EP 12005370.7 and EP 12005371.5), spirodibenzopyran 2010/006680, triarylamines, carbazole derivatives, for amines (for example in accordance with WO 2013/083216) example CBP (N.N-bis-carbazolylbiphenyl) or the carbazole and dihydroacridine derivatives (for example in accordance derivatives disclosed in WO 2005/039246, US 2005/ with WO 2012/150001). 0069729, JP 2004/288381, EP 1205527 or WO 2008/086851, 0.138. The cathode of the organic electroluminescent indolocarbazole derivatives, for example in accordance with device preferably comprises metals having a low work func WO 2007/063754 or WO 2008/056746, indenocarbazole tion, metal alloys or multilayered structures comprising Vari derivatives, for example in accordance with WO 2010/ ous metals, such as, for example, alkaline-earth metals, alkali 136109, WO 2011/000455 or WO 2013/041176, azacarba metals, main-group metals or lanthanoids (for example Ca, Zole derivatives, for example in accordance with EP 1617710, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Also suitable are alloys EP 1617711, EP 1731584, JP 2005/347160, bipolar matrix comprising an alkali metal or alkaline-earth metal and silver, materials, for example in accordance with WO 2007/137725, for example an alloy comprising magnesium and silver. In the US 2015/0340627 A1 Nov. 26, 2015

case of multilayered structures, further metals which have a (III) are necessary for this purpose. High solubility can be relatively high work function, such as, for example, Agor Al, achieved through suitable substitution of the compounds. can also be used in addition to the said metals, in which case 0145 For the production of an organic electroluminescent combinations of the metals, such as, for example, Ca/Ag, device according to the invention, it is furthermore preferred Mg/Agor Ag/Ag, are generally used. It may also be preferred to apply one or more layers from Solution and one or more to introduce a thin interlayer of a material having a high layers by a Sublimation process. dielectric constant between a metallic cathode and the organic 0146 In accordance with the invention, the electronic semiconductor. Suitable for this purpose are, for example, devices comprising one or more compounds of the formula alkali metal fluorides or alkaline-earth metal fluorides, but (I), (II) or (III) can be employed in displays, as light sources also the corresponding oxides or carbonates (for example LiF. in lighting applications and as light Sources in medical and/or LiO, BaF, MgO, NaF. CsF, CsCO, etc.). Furthermore, cosmetic applications (for example light therapy). lithium quinolinate (LiO) can be used for this purpose. The layer thickness of this layer is preferably between 0.5 and 5 WORKING EXAMPLES 0147 The following working examples serve to illustrate 0.139. The anode preferably comprises materials having a the present invention. They should not be interpreted as being high workfunction. The anode preferably has a work function restrictive. of greater than 4.5 eV VS. Vacuum. 0140) Suitable for this purpose are on the one hand metals A) Synthesis Examples having a high redox potential. Such as, for example, Ag, Pt or Au. On the other hand, metal/metal oxide electrodes (for 0.148. The following syntheses are carried out, unless indi example AI/Ni/NiO, AI/PtO) may also be preferred. For cated otherwise, in dried solvents under a protective-gas Some applications, at least one of the electrodes must be atmosphere. The compounds according to the invention can transparent or partially transparent in order to facilitate either be prepared by means of synthetic processes known to the irradiation of the organic material (organic Solar cells) or the person skilled in the art. coupling-out of light (OLEDs, O-lasers). Preferred anode materials here are conductive mixed metal oxides. Particular Example 1 preference is given to indium tin oxide (ITO) or indium zinc oxide (IZO). Preference is furthermore given to conductive, Precursor doped organic materials, in particular conductive, doped (O149 polymers. Furthermore, the anode may also consist of a plu rality of layers, for example of an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide. 0141. The device is appropriately (depending on the appli cation) structured, pro-vided with contacts and finally sealed, since the lifetime of the devices according to the invention is shortened in the presence of water and/or air. CSC 0142. In a preferred embodiment, the organic electrolumi nescent device according to the invention is characterised in that one or more layers are coated by means of a Sublimation process, in which the materials are applied by vapour depo sition in vacuum Sublimation unitsatan initial pressure of less than 10 mbar, preferably less than 10 mbar. However, it is also possible here for the initial pressure to be even lower, for example less than 107 mbar. 0143 Preference is likewise given to an organic electrolu minescent device, characterised in that one or more layers are coated by means of the OVPD (organic vapour phase depo sition) process or with the aid of carrier-gas Sublimation, in which the materials are applied at a pressure of between 10 mbar and 1 bar. A special case of this process is the OVJP (organic vapour jet printing) process, in which the materials are applied directly through a nozzle and are thus structured (for example M. S. Arnold et al., App. Phys. Lett. 2008, 92, 053301). 0144 Preference is furthermore given to an organic elec troluminescent device, characterised in that one or more lay (O150 30.2 g (81 mmol) of the compound CAS 1257248 ers are produced from Solution, Such as, for example, by spin 71-7, 18.36 g (90 mmol) of iodobenzene, 22.4 g (162 mmol) coating, or by means of any desired printing process, such as, of potassium carbonate, 1.84 g (8.1 mmol) of 1,3-di(2-py for example, screen printing, flexographic printing, nozzle ridyl)-1,3-propanedione, 1.55 g (8.1 mmol) of copper iodide printing or offset printing, but particularly preferably LITI and 1000 ml of DMF are heated under reflux for 30 h. The (light induced thermal imaging, thermal transfer printing) or Solution is Subsequently evaporated to dryness in a rotary ink-jet printing. Soluble compounds of the formula (I), (II) or evaporator. The residue is dissolved in THF and filtered US 2015/0340627 A1 Nov. 26, 2015 39 through a short silica-gel bed. The solvent is then removed by -continued means of vacuum. The Solid is Subsequently recrystallised J. from heptane/THF and subsequently extracted with hot hep- O tane/toluene over aluminium oxide. The solid which precipi tates out on cooling is filtered and dried. 0151. Yield: 19.3 g (43 mmol), 53% N Example 2a C O Precursor C 3-(12,12-Dimethyl-12H-10-azaindeno2,1-bifluoren- O 10-yl)phenol 0152 0153. 18.5 g (65mmol) of 12,12-dimethyl-10,12-dihydro 10-azaindeno.2.1-bifluorene, 21.8 g. (85 mmol) of 2-(3-bro mophenoxyl)tetrahydropyran and 42.9 g (196 mmol) of OH potassium phosphate are Suspended in 1 I of toluene.879 mg (3.9 mmol) of palladium(II) acetate and 1.7 ml (6.6 mmol) of tri-tert-butylphosphine are added to this suspension, and the mixture is subsequently stirred at 120° C. for 16 h. After cooling, the organic phase is separated off filtered through Br silica gel, washed three times with 200 ml of water and H N Subsequently evaporated to dryness. The Solid is Subse quently dissolved in 600 ml of THF, and 1 g (5.8 mmol) of p-toluenesulfonic acid is added, and the mixture is stirred at C room temperature for 16 h. The mixture is subsequently fil tered twice through silica gel with heptane/ethyl acetate 5:1. After evaporation of the solvents, the product precipitates out as white solid. The yield is 17 g (45 mmol; 70%) 0154 The following compounds can be prepared analo gously (precursors)

Starting material 1 Starting material 2 Product Yield

SC) or36603-49-3 729% 1257220-47-5 N O O

SH 68%

C CO C.N 1257220-47-5 Br 70O868-02-6 K) () US 2015/0340627 A1 Nov. 26, 2015 40

-continued

Starting material 1 Starting material 2 Product Yield

c. c. O CN 1257220-47-5 57999-46-9 K) Q)

HS 7396

SC CO140712-68-1 t

HO 75%

135981-73-6

1257248-57-9

HO OH 63% O O C() () O'? O Or, 1257248-57-9

O OH 62%

36603-49-3

1257248-71-7 US 2015/0340627 A1 Nov. 26, 2015 41

-continued

Starting material 1 Starting material 2 Product Yield Clus r OO C OH 59% 21 C-C \ 4N Br 103.012-26-6 1163715-11-4 K) O C -() s- Osu O 70O868-02-6 O N CO

1379.585-41-7

co (O S.C () O US 2015/0340627 A1 Nov. 26, 2015 42

-continued

Starting material 1 Starting material 2 Yield 42% CO O o-() O 36603-49-3

"C-C, H

1257248-38-6

Example 3a -continued Compound According to the Invention 10-3-(4,6-Diphenylpyrimidin-2-yloxy)phenyl-212 dimethyl-10,12-dihydro-10-azaindeno2,1-bifluorene 0155

OH

0156 3.32 g (83 mmol) of sodium hydride are suspended in 200 ml of DMF. 24 g (64 mmol) of 3-(12,12-dimethyl 12H-10-azaindeno.2.1-bfluoren-10-yl)phenol, dissolved in 100 ml of DMF, are subsequently slowly added via a dropping funnel. When the addition is complete, the mixture is stirred at room pyrimidine, dissolved in 10 ml of anhydrous THF, are slowly added dropwise via a dropping funnel. The mixture is stirred at room temperature for 3 hours until the conversion is complete. The reaction mixture is added to 300 ml of ice and warmed to room temperature with stirring. The solid which precipitates out is filtered and washed with 300 ml of ethanol and 300 ml of n-heptane. The solid is recrystallised from toluene and subsequently sublimed in a high vacuum (3:10 bar). The purity is 99.9% (HPLC). The yield is 8 g (13.2 mmol; 21%) US 2015/0340627 A1 Nov. 26, 2015 43

0157. The following compounds according to the inven tion can be obtained analogously:

Starting material 1 Starting material 2 Product Yield

3b HO 24% NeN C Ns N O 3842-55-5

19%

22%

70484-36-5 O US 2015/0340627 A1 Nov. 26, 2015 44

-continued

Starting material 1 Starting material 2 Product Yield

25% HS O-O r 928.53-85-5 ( )-(N N \ -(

23% CO-O NeNn C 126O393-65-4 US 2015/0340627 A1 Nov. 26, 2015 45

-continued

Starting material 1 Starting material 2 Product Yield

3g ro O-u(ON Cy " r ( ) 2915-16-4 / N W -C

oon W

O--O C r ( ) O \ Z CSO-O" 2915-16-4 O US 2015/0340627 A1 Nov. 26, 2015

-continued

Starting material 1 Starting material 2 Product Yield

13% N N a 133785-60-1 O O rna N

3k C Cla-C O 12%

Example 4a -continued Br Precursor 10-(4-Bromophenyl)-12,12-dimethyl-10.12dihydro 10-azaindeno2,1-b-fluorene 0158 N C Oy () - O O 0159 23 g (81 mmol) of 12,12-dimethyl-10,12-dihydro I 10-azaindeno.2.1-bifluorene, 115 g (406 mmol) of 1-bromo 4-iodobenzene, 22.4 g (162 mmol) of potassium carbonate, US 2015/0340627 A1 Nov. 26, 2015 47

1.84 g (8.1 mmol) of 1,3-di(2-pyridyl)-1,3-propanedione, quently extracted with hot heptane/toluene over aluminium 1.55 g (8.1 mmol) of copper iodide and 1000 ml of DMF are oxide. The solid which precipitates out on cooling is filtered heated under reflux for 30 h. The solution is subsequently and dried. evaporated to dryness in a rotary evaporator. The residue is dissolved in THF and filtered through a short silica-gel bed. (0160 Yield: 26.3 g (60 mmol), 74% The solvent is then removed by means of vacuum. The solid 0.161 The following compounds can be obtained analo is subsequently recrystallised from heptane/THF and subse gously (precursors):

Starting material 1 Starting material 2 Product Yield

H 61%

N O Br Q) I C 583-55-1 1257220-47-5 CC) H 7396 N O Q) (y 1257220-47-5 31.9906-45-1 C C

43%

Br O

39655-12-4

1257248-57-9 CSC Br Br S8% 86-74-8

77332-64-0 US 2015/0340627 A1 Nov. 26, 2015 48

-continued

Starting material 1 Starting material 2 Product Yield

O -O-O 33% C- -COC) 790674-48-5

I Br 46%

Br 589-87-7

Br

1257248-38-6

Example 5a -continued

precursor (4,6-Diphenyl-1,3,5-triazin-2-yl)phenylamine N (0162 N Z \

N ls N H

NH2

-- -e- % \ 0163 7.76 g (29 mmol) of 2-chloro-4,6-diphenyl-1,3,5- triazine, dissolved in 50 ml of THF, are slowly added drop SN wise to 2.7 g (29 mmol) of aniline in 180 ml of THF/pyridine, C and the mixture is stirred at room temperature. After 20h, the solvents are removed. The product is obtained as white solid US 2015/0340627 A1 Nov. 26, 2015 49

(7.79 g) after precipitation from heptane. This corresponds to 0164. The following compounds can be obtained analo a yield of 24 mmol (83%) gously:

Starting material 1 Starting material 2 Product Yield

82% HN O O rs 62-53-3 N N

N 2915-16-4

65%

HN

2243-47-2 1384.480-21-0

81%

HN

N n 91-59-8

70484-36 US 2015/0340627 A1 Nov. 26, 2015 50

-continued

Starting material 1 Starting material 2 Product Yield O O 80% N N

n n N n 2 N NH2 C 63OO6-66-6 928.53-85-5

78%

N N NH2

C CSC 1257982-95-8 2915-16-4

Example 6a -continued Compound According to the Invention 4-(12,12-Dimethyl-12H-10-azaindeno.2.1-bfluo ren-10-yl)phenyl-(4,6-diphenyl-1,3,5-triazin-2-yl) phenylamine (0165 %

N -Ass

Br CO

0166 13 g (29.7 mmol) of 3a, 9.6 g (29.7 mmol) of 4a, 4.6 N Ho- g (48 mmol) of sodium tert-butoxide, 0.84 g (3 mmol) of tricyclohexylamine, 337 mg (1.5 mmol) of palladium(II) acetate and 300 ml of toluene are heated under reflux for 24h. After cooling, 200 ml of water are added, the mixture is stirred for a further 30 min., the org. phase is separated off, filtered through a short Celite bed, and the solvent is then removed in vacuo. The residue is recrystallised a number of times from toluene/heptane and finally subjected to fractional sublimation twice (p about 10-6 mbar, T=330–340°C.). US 2015/0340627 A1 Nov. 26, 2015 51

(0167. Yield: 6.3 g (9.2 mmol),31%; purity: 99.9% accord- 0.168. The following compounds according to the inven ing to HPLC. tion are obtained analogously:

Starting material 1 Starting material 2 Product Yield

CO) ão Z N Oil

6c 29% Ns N Br n

OC OO K) US 2015/0340627 A1 Nov. 26, 2015 52 US 2015/0340627 A1 Nov. 26, 2015 53

-continued

Starting material 1 Starting material 2 Product

N N N N

B) Device Examples proportion of 10%. Analogously, the electron-transport layer may also consist of a mixture of two materials. Production of the OLEDS 0173 The OLEDs are characterised by standard methods. For this purpose, the electroluminescence spectra, the current 0169. The data of various OLEDs are presented in the efficiency (measured in cd/A), the power efficiency (mea following examples V1 to E11 (see Tables 1 and 2). Glass sured in lm/V) and the external quantum efficiency (EQE, plates which have been coated with structured ITO (indium measured in percent) as a function of the luminous density, tin oxide) in a thickness of 50 nm are coated with 20 nm of calculated from current/voltage/luminous density character PEDOT:PSS (poly(3,4-ethylenedioxythiophene)poly(styre istic lines (IUL characteristic lines) assuming Lambert emis nesulfonate), purchased as CLEVIOSTM PVP AI 4083 from sion characteristics, are determined. The electrolumines Heraeus Precious Metals GmbH, Germany, applied by spin cence spectra are determined at a luminous density of 1000 coating from aqueous solution) for improved processing. cd/m, and the CIE 1931 x and y colour coordinates are These coated glass plates form the substrates to which the calculated therefrom. The term U1000 in Table 2 denotes the OLEDs are applied. voltage required for a luminous density of 1000 cd/m. (0170 The OLEDs have in principle the following layer CE1000 and PE1000 denote the current and power efficiency structure: substrate/hole-transport layer (HTL)/interlayer respectively which are achieved at 1000 cd/m. Finally, (IL)/electron-blocking layer (EBL)/emission layer (EML)/ EQE 1000 denotes the external quantum efficiency at an oper optional hole-blocking layer (HBL)/electron-transport layer ating luminous density of 1000 cd/m. (ETL) and finally a cathode. The cathode is formed by an 0.174. The data obtained for the various OLEDs are sum aluminium layer with a thickness of 100 nm. The precise marised in Table 2. Example V1 is a comparative example in structure of the OLEDs is shown in Table 1. The materials accordance with the prior art, Examples E1-11 show data of required for the production of the OLEDs are shown in Table OLEDS comprising materials according to the invention. 3. 0.175. Some of the examples are explained in greater detail 0171 All materials are applied by thermal vapour deposi below in order to illustrate the advantages of the compounds tion in a vacuum chamber. according to the invention. However, it should be pointed out that this only represents a selection of the data shown in Table 0172. The emission layer here always consists of at least 2. one matrix material (host material) and an emitting dopant (emitter), which is admixed with the matrix material or matrix Use of Compounds According to the Invention as Matrix materials in a certain proportion by Volume by co-evapora Materials in Phosphorescent OLEDs tion. An expression such as 6 g:IC2:TEG1 (55%:35%:10%) here means that material 6 g is present in the layer in a 0176 Compounds 3a, 3b, 3c, 3e, 3g, 3i, 6a, 6b, 6e, 6f and proportion by volume of 55%. IC2 is present in the layer in a 6g according to the invention are employed as matrix mate proportion of 35% and TEG1 is present in the layer in a rials for phosphorescent emitters in the OLEDs shown in US 2015/0340627 A1 Nov. 26, 2015 54

Table 1 (devices E1 to E11). Furthermore, the compound TABLE 2 known from the prior art is employed in an analogous func tion for comparison (device V1). Data of the OLEDS 0177. In general, very good values in relation to lifetime, efficiency and operating Voltage are obtained with the com U1OOO CE1 OOO PE1OOO EQE CIE x/y at pounds according to the invention, both on use in combina- Ex. (V) (cd/A) (lm/W) 1OOO 1000 ccd/m? tion with green-emitting triplet emitters and also on use with red-emitting triplet emitters. V1 5.3 8.7 5.2 9.4% O67.O.33 (0178 For example, excellent performance data are E1 4.7 10 7.0 11.3% O67.O.33 obtained (virtually 17% EQE) in combination with the green emitting dopant TEG 1 with compound 3a as matrix material E2 3.7 60 51 16.8% O.33,0.62 (Example E2). E3 3.3 55 52 15.4% 0.320.62 0179 A corresponding situation applies to compound 3i 54 3.6 57 49 15.9% O.33,0.62 as matrix material (Example E6), for which a very low oper- E5 4.9 10.3 6.6 11.1% O67.O.33 ating Voltage was obtained (3.2 V). E6 3.2 48 47 13.6% O.33,0.63 0180. In combination with the red-emitting dopant TER1. E7 3.5 53 47 14.7% O.33,0.63 very good performance data are likewise achieved. E8 3.7 57 48 16.1% O.33,0.62 0181 For example, a more than 30% or 25% higher power E9 4.9 10.9 7.0 11.8% O67.O.33 efficiency respectively is obtained with compound 6e or 6a E10 3.4 49 45 13.8% O.33,0.62 according to the invention than with compound SdT1 in E11 3.6 51 45 14.4% O.33,0.62 accordance with the prior art (Examples V1 and E9 or V1 and E8). TABLE 1.

Structure of the OLEDS

HTL EBL EML HBL ETL Ex. Thickness Thickness Thickness Thickness Thickness Thickness

V1 SpA HATCN SMA1 ST1:TER1 ST1:LiQ 90 mm 5 nm. 130 nm (92%:8%) (50%:50%) 40 mm 40 mm E1. SpA HATCN SMA1 3e:TER ST1:LiQ 90 mm 5 nm. 130 nm (92%:8%) (50%:50%) 40 mm 40 mm E2 SA HATCN SMA1 3al:TEG IC1 ST1:LiQ 70 mm 5 nm. 90 mm (90%:10%) 10 mm (50%:50%) 30 mm 30 mm E3 SA HATCN SMA1 3b:TEG ST1:LiQ 70 mm 5 nm. 90 mm (90%:10%) (50%:50%) 30 mm 40 mm E4 SA HATCN SMA1 3C:TEG IC1 ST1:LiQ 70 mm 5 nm. 90 mm (90%:10%) 10 mm (50%:50%) 30 mm 30 mm ES S.A HATCN SpMA1 3g:TER ST1:LiQ 90 mm 5 nm. 130 nm (92%:8%) (50%:50%) 40 mm 40 mm E6 SpA HATCN SMA1 3:TEG1 IC1 ST1:LiQ 70 mm 5 nm. 90 mm (90%:10%) 10 mm (50%:50%) 30 mm 30 mm E7 SA HATCN SMA1 6a:TEG1 ST1:LiQ 70 mm 5 nm. 90 mm (90%:10%) (50%:50%) 30 mm 40 mm E8 SA HATCN SMA1 6b:TEG1 ST1:LiQ 70 mm 5 nm. 90 mm (90%:10%) (50%:50%) 30 mm 40 mm E9 SA HATCN SMA1 6e:TER1 ST1:LiQ 90 mm 5 nm. 130 nm (92%:8%) (50%:50%) 40 mm 40 mm E10 SA HATCN SMA1 6f:IC2:TEG1 IC1 ST1:LiQ 70 mm 5 nm. 90 mm (45%:45%:10%) 10 nm (50%:50%) 30 mm 30 mm E11 SA HATCN SpMA1 6g:IC2:TEG1 IC1 ST1:LiQ 70 mm 5 nm. 90 mm (45%:45%:10%) 10 nm (50%:50%) 30 mm 30 mm US 2015/0340627 A1 Nov. 26, 2015 55

TABLE 3

Structural formulae of the materials used in the devices HATCN gigs SpA1

SpMA1 IC1

IC2 TEG1 US 2015/0340627 A1 Nov. 26, 2015 56

TABLE 3-continued

Structural formulae of the materials used in the devices

1 CR) 3. 1. \ / C C C’s

C O ( ) O C US 2015/0340627 A1 Nov. 26, 2015 57

TABLE 3-continued

Structural formulae of the materials used in the devices

US 2015/0340627 A1 Nov. 26, 2015 58

TABLE 3-continued

Structural formulae of the materials used in the devices

US 2015/0340627 A1 Nov. 26, 2015 59

1.-19. (canceled) where the dashed line denotes the bond to the remainder 20. A compound of a formula (I), (II) or (III) of the formula, or R is equal to R', where at least one group R" performula unit of the formula (I) or (II) conforms to the formula (A): formula (I) L' is an aromatic or heteroaromatic ring system having 6 to R4 30 aromatic ring atoms, which is optionally substituted by one or more radicals R'; Cbz E" is on each occurrence, identically or differently, O, S, or formula (II) NAr; i R1 RI f X is on each occurrence, identically or differently, N or CR, where at least one group X per six-membered ring Z N Z Z N Z is equal to N: i is on each occurrence, identically or differently, 0 or 1, Znfr11111 2 2 27, where at least one index i per group of the formula (A) is n Z Z 2 equal to 1; formula (III) R is on each occurrence, identically or differently, H. D. F. formula (I)-HT--formula (I), C(=O)R, CN, Si(R), S(=O)R, S(=O),R, a straight-chain alkyl group having 1 to 20 C atoms or a where: branched or cyclic alkyl group having 3 to 20 C atoms or Cbz is a carbazole group which is optionally substituted by an alkenyl or alkynyl group having 2 to 20 C atoms, one or more radicals R and which is optionally where the above-mentioned groups may each be substi extended by means of one or more condensed-on indeno tuted by one or more radicals R and where one or more groups to form an indenocarbazole, and in which one or CH2 groups in the above-mentioned groups is optionally more aromatic groups =C(R')— or =C(H)— is replaced by R°C—CR -, -C=C-, Si(R), optionally replaced by —N , and which is bonded to C—O, C-NR, C(=O)C , C(=O)NR , the group R via the carbazole nitrogen atom; NR, P(=O)(R), -O-, -S. , SO or SO, or an formula (I) is on each occurrence, identically or differ aromatic or heteroaromatic ring system having 5 to 30 ently, any desired unit of the formula (I), where the aromatic ring atoms, which may in each case be substi group T is optionally bonded to this unit at any desired tuted by one or more radicals R; position; R’ is on each occurrence, identically or differently, H. D. F. C(=O)R, CN, Si(R), N(R), P(=O)(R), S(=O) Z is on each occurrence, identically or differently, CR' or R. S(=O).R., a straight-chain alkyl or alkoxy group N: having 1 to 20 C atoms or a branched or cyclic alkyl or R" is on each occurrence, identically or differently, H.D., F. alkoxy group having 3 to 20 C atoms or an alkenyl or C(=O)R, CN, Si(R), N(R), P(=O)(R), S(=O) alkynyl group having 2 to 20 C atoms, where the above R. S(=O),R, a straight-chain alkyl or alkoxy group mentioned groups may each be substituted by one or having 1 to 20 C atoms or a branched or cyclic alkyl or more radicals R and where one or more CH2 groups in alkoxy group having 3 to 20 C atoms or an alkenyl or the above-mentioned groups is optionally replaced by alkynyl group having 2 to 20 C atoms, where the above RC–CR C=C , Si(R), C-O, C=NR, mentioned groups may each be substituted by one or C(=O)C , C(=O)NR NR, P(=O)(R), more radicals R and where one or more CH2 groups in —O— —S , SO or SO, or an aromatic or heteroaro the above-mentioned groups is optionally replaced by matic ring system having 5 to 30 aromatic ring atoms, RC–CR C=C , Si(R), C-O, C=NR, which may in each case be substituted by one or more C(=O)C , C(=O)NR NR, P(=O)(R), radicals R. or an aryloxy or heteroaryloxy group having —O— —S , SO or SO, or an aromatic or heteroaro 5 to 30 aromatic ring atoms, which is optionally Substi matic ring system having 5 to 30 aromatic ring atoms, tuted by one or more radicals R, where two or more which may in each case be substituted by one or more radicals R is optionally linked to one another and may radicals R. or an aryloxy or heteroaryloxy group having form a ring; 5 to 30 aromatic ring atoms, which is optionally Substi R is on each occurrence, identically or differently, H. D. F tuted by one or more radicals R, where two or more or an aliphatic, aromatic or heteroaromatic organic radi radicals R' is optionally linked to one another and may cal having 1 to 20 C atoms, in which, in addition, one or form a ring; more H atoms is optionally replaced by D or F: two or R" is a group of the formula (A) more substituents R here is optionally linked to one another and form a ring; Ar" is an aromatic ring system having 6 to 30 aromatic ring formula (A) atoms, which is optionally substituted by one or more radicals R'; T is a single bond or an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R'. 21. The compound according to claim 20, wherein the condensation of indeno groups onto the carbazole group in the group Cbztakes place in positions 2 and 3 and/or positions 6 and 7. US 2015/0340627 A1 Nov. 26, 2015 60

22. The compound according to claim 20, wherein the -continued compound contains no condensed aryl or heteroaryl groups having more than 14 aromatic ring atoms. formula (A-5) R 23. The compound according to claim 20, wherein one R. R index i performula (A) is equal to one and the other index i is N equal to Zero. 24. The compound according to claim 20, wherein two or three groups X per six-membered ring are equal to N. NY N 25. The compound according to claim 20, wherein Ar" is El selected from an aromatic ring system having 6 to 18 aromatic ring atoms, which is optionally Substituted by one or more radicals R. 26. The compound according to claim 20, wherein groups formula (A-6) of the formula (A) conform to one of the following formulae R (A-1) to (A-8) N1 N R R afn formula (A-1) El s Ns R Ll

formula (A-7) NY N R El R. R Ll N

N formula (A-2) afn s s R El N 2 R

El formula (A-8) Ll R. s R

formula (A-3) R afn R El ---1 El where the groups occurring are as defined in claim 20, and Ll where the dashed line denotes the bond to the remainder of the formula.

formula (A-4) 27. The compound according to claim 20, wherein E' is on R each occurrence, identically or differently, O or S. 28. The compound according to claim 20, wherein L' is an aromatic ring system having 6 to 24 aromatic ring atoms, s which is optionally substituted by one or more radicals R'. R afn 29. The compound according to claim 20, wherein L' El contains at least one meta- or ortho-phenylene group, which may optionally be substituted by one or more radicals R'. L 30. The compound according to claim 20, wherein the group Cbz conforms to one of the following formulae (Cbz-1) to (Cbz-3) US 2015/0340627 A1 Nov. 26, 2015

above-mentioned groups is optionally replaced by formula (Cbz-1) —RC—CR -C=C , Si(R) or C=O, oranaromatic or heteroaromatic ring system having 5 to 20 aromatic ring atoms, which may in each case be substituted by one or more A Z “a radicals R. 32. The compound according to claim 20, wherein the 4 y ( , group T represents a single bond. Zsz 72Z 33. An oligomer, polymer or dendrimer containing one or formula (Cbz-2) more compounds according to claim 20, where the bond(s) to the polymer, oligomer or dendrimer is optionally localised at 7 N Z R. any desired positions in formula (I), (II) or (III) that are substituted by R' or R. . \ / N R1 34. A formulation comprising at least one compound Zsz 72 2 Z according to claim 20 and at least one solvent. y 35. A formulation comprising at least one polymer, oligo Z mer or dendrimer according to claim 33 and at least one s/ solvent. formula (Cbz-3) 36. An electronic device, selected from the group consist ing of an organic integrated circuit (OIC), an organic field effect transistor (OFET), an organic thin-film transistor R Z. N Z R. (OTFT), an organic light-emitting transistor (OLET), an organic Solar cell (OSC), an organic optical detector, an R1 7 \ / N R1 organic photoreceptor, an organic field-quench device Sea- e (OFOD), an organic light-emitting electrochemical cell Z N Z Z a Z (OLEC), an organic laser diode (O-laser) and an organic | y electroluminescent device (OLED), wherein the device com N27 Zs prises at least one compound according to claim 20. 37. An organic electroluminescent device which comprises where the dashed line denotes the bond to the group R", anode, cathode and at least one organic layer, where the at and where the groups occurring are as defined in claim least one compound according to claim 20 is employed as 20. matrix material in an emitting layer in combination with one 31. The compound according to claim 20, wherein R is on or more dopants, or in that it is employed as electron-transport each occurrence, identically or differently, H. D. F. CN, a material in an electron-transport layer, an electron-injection straight-chain alkyl group having 1 to 10 C atoms or a layer or a hole-blocking layer. branched or cyclic alkyl group having 3 to 10 C atoms or an 38. A process for the preparation of the compound accord alkenyl or alkynyl group having 2 to 10 C atoms, where the ing to claim 20, which comprises employing at least one above-mentioned groups may each be substituted by one or transition metal-catalysed coupling reaction. more radicals R and where one or more CH groups in the k k k k k