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(19) United States (12) Patent Application Publication (10) Pub

(19) United States (12) Patent Application Publication (10) Pub

US 20120319052A1 (19) United States (12) Patent Application Publication (10) Pub. N0.: US 2012/0319052 A1 Brocke et al. (43) Pub. Date: Dec. 20, 2012

(54) COMPOUNDS FOR ELECTRONIC DEVICES Publication Classi?cation

(75) Inventors: Constanze Brocke, Gross-Gerau (DE); (51) Int. Cl. Christof P?umm, Darmstatd (DE); H01 B 1/12 (2006.01) Amir Hossain Parham, Frankfurt am C07D 513/00 (200601) Main (DE); Rocco Fortte, Frankfurt am C08G 73/06 (200601) Main (DE) C07D 401/10 (2006.01) . _ (52) US. Cl...... 252/500; 546/102; 546/58; 546/38; (73) Asslgnee. Merck Patent GmbH, Darmstadt (DE) 544/14; 526/259; 526/257 (21) Appl. N0.: 13/581,543 (22) PCT Filed: Jan. 21, 2011 (57) ABSTRACT (86) PCT N0.: PCT/EP2011/000235 The present invention relates to compounds of the formula (1) (2)’§371(c)(1), (4) Date: Aug 28, 2012 or ( 2 ) d to h e use h ereo f.in'e 1 ectronic. d evices,. an d to electromc devices Wh1ch comprise these compounds. The (30) Foreign Application Priority Data invention furthermore relates to the preparation of the com pounds of the formula (1) or (2) and to formulations compris Mar. 2, 2010 (DE) ...... 10 2010 009 903.1 ing one or more compounds of the formula (1) or (2). US 2012/0319052 A1 Dec. 20, 2012

COMPOUNDS FOR ELECTRONIC DEVICES materials in electronic devices. In the triarylamine com pounds, the individual aryl groups are bridged to one another [0001] The present invention relates to compounds of the formula (1) or (2) and to the use thereof in electronic devices, in a de?ned manner and are additionally substituted by car and to electronic devices Which comprise these compounds. baZole derivatives. HoWever, the compounds disclosed The invention furthermore relates to the preparation of the therein contain three carbaZole groups, Which are arranged compounds of the formula (1) or (2) and to formulations symmetrically around the central triarylamine group. comprising one or more compounds of the formula (1) or (2). [0011] Bridged triarylamine derivatives are furthermore [0002] The compounds of the formula (1) or (2) are used in disclosed in the application WO 2010/083871. accordance With the invention in electronic devices, prefer ably in organic electroluminescent devices (OLEDs). The [0012] HoWever, there continues to be a demand for func general structure of these devices is described, for example, in tional materials for use in OLEDs Which preferably effect Us. Pat. No. 4,539,507, US Pat. No. 5,151,629, EP improvements in relation to the performance data of the elec 0676461 and WO 98/27136. tronic devices, in particular in relation to the lifetime and [0003] Hole-transport and -injection materials Which are ef?ciency of the devices. knoWn from the prior art for organic electroluminescent devices are, inter alia, arylamine compounds. Materials of [0013] In particular, there is a demand for compounds this type based on an indeno?uorene skeleton are disclosed, Which have high hole mobility. This facilitates a loW depen for example, in WO 2006/ 100896 and WO 2006/ 122630. dence of the operating voltage on the thickness of the hole [0004] HoWever, the hole-transport materials knoWn from transport layer, Which represents a highly desirable property. the prior art frequently have loW electron stability, Which Furthermore, there is a demand for oxidation- and tempera reduces the lifetime of electronic devices comprising these ture-stable compounds, since this improves the proccessabil compounds. Overall, further improvements are desirable ity on use in electronic devices. With respect to the ef?ciency of ?uorescent organic electrolu [0014] The present invention provides compounds of the minescent devices and the lifetime, especially in the case of formula (1) and (2) in order to achieve the technical object blue-?uorescent devices. There is also potential for improve described above. ment in the operating voltage of the electronic devices. [0005] There is therefore a demand for alternative com [0015] The invention thus relates to a compound of the pounds Which can be used, inter alia, as hole-transport mate formula (1) or (2) rials in organic electroluminescent devices and Which prefer ably effect an improvement in the above-mentioned performance data of the devices. formula (1) [0006] Matrix materials Which are knoWn from the prior art for phosphorescent dopants are, inter alia, carbaZole deriva tives, for example bis(carbaZolyl)-biphenyl. The use of ketones (WO 2004/093207), phosphine oxides and sulfones (WO 2005/003253) as matrix materials for phosphorescent dopants is furthermore known. Metal complexes, for example BAlq or Zinc(II) bis[2-(2-benZothiaZolyl)phenolate], are also used as matrix materials for phosphorescent dopants. [0007] HoWever, there continues to be a demand for alter native matrix materials for phosphorescent dopants, in par ticular those Which effect an improvement in the performance data of the electronic devices. [0008] Also of particular interest is the provision of alter native materials as matrix components of mixed-matrix sys tems. A mixed-matrix system in the sense of this application formula (2) is taken to mean a system in Which tWo or more different matrix compounds are used as a mixture together With one (or more) dopant compounds in an emitting layer. These systems are, in particular, of interest in the case of phosphorescent organic electroluminescent devices. For more detailed infor mation, reference is made to the application WO 2010/ 108579. [0009] Compounds knoWn from the prior art Which may be mentioned as matrix components in mixed-matrix systems are, inter alia, CBP (biscarbaZolylbiphenyl) and TCTA (tri scarbaZolyltriphenylamine) (?rst component). Suitable as the second component are compounds such as, for example, benZophenone derivatives, diaZaphospholes (see the applica tion WO 2010/054730) and . HoWever, there contin ues to be a demand for alternative compounds for use as matrix components in mixed-matrix systems. In particular, there is a demand for compounds Which effect an improve ment in the operating voltage and lifetime of the electronic devices. [0010] The applications WO 2007/031165 and WO 2006/ 033563 disclose triarylamine derivatives for use as functional US 2012/0319052 A1 Dec. 20, 2012

Where the following applies to the symbols and indices occur stituted by one or more radicals R1, or a combination of ring: these systems, Where tWo or more radicals R may be [0016] W is on each occurrence equal to Z, linked to one another and may form a ring; [0017] Where a unit comprising tWo adjacent groups [0023] R1 is, identically or differently on each occur W may optionally be replaced by a group of the for rence, H, D, F, Cl, Br, I, CHO, N(R2)2, C(:O)R2, mula (3) P(:0)(R2)2, S(:O)R2, S(:0)2R2, CR2:C(R2)2, CN, N02, Si(R2)3, B(OR2)2, OSO2R2, OH, COOR2, CON(R2)2, a straight-chain alkyl, alkoxy or thioalkyl formula (3) group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, each of Which may be substituted by one or more radi cals R2, Where one or more non-adjacent CH2 groups may be replaced by iR2C:CR2i, 4CECi, Si(R2) [0018] Where the group of the formula (3) is arranged 2, Ge(R2)2, Sn(R2)2, C:O, C:S, C:Se, C:NR2, in such a Way that the bond betWeen the C atoms P(:O)(R2), SO, S02, NR2, iOi, iSi, iCOOi or iCONRzi and Where one or more H atoms may be labelled With * is condensed onto the six-membered replaced by D, F, Cl, Br, 1, CN or N02, or an aromatic or ring of the carbaZole derivative; heteroaromatic ring system having 5 to 60 aromatic ring [0019] X is a divalent group selected from C(R)2, Si(R)2, atoms, Which may in each case be substituted by one or NR, PR, P(:O)R, BR, 0, S, C:O, C:S, C:NR, more radicals R2, or an aryloxy or heteroaryloxy group 8:0 and S(:O)2, having 5 to 60 aromatic ring atoms, Which may be sub [0020] Z is selected on each occurrence, identically or stituted by one or more radicals R2, or a combination of differently, from CR and N, or is equal to C if a substitu these systems, Where tWo or more radicals Rl may be ent is bonded to the group Z; linked to one another and may form a ring; [0021] L is on each occurrence, identically or differently, [0024] R2 is, identically or differently on each occur a divalent group selected from C(R)2, Si(R)2, NR, PR, rence, H, D, F or an aliphatic, aromatic and/or heteroaro P(:O)R, BR, 0, S, C:O, C:S, C:NR, C:C(R)2, matic organic radical having 1 to 20 C atoms, in Which, 8:0, S(:O)2 and CR:CR; in addition, one or more H atoms may be replaced by D [0022] R is, identically or differently on each occur or F; tWo or more substituents R2 here may also be linked rence, H, D, F, Cl, Br, I, CHO, N(Rl)2, C(:O)Rl, P(:0)(R1)2, S(:0)R1, S<:0)2R1, CR1:C(R1)2, to one another and may form a ring; CN, N02, Si(Rl)3, B(ORl)2, OSOZRI, OH, COORl, [0025] i is equal to 0, 1 or 2, Where, for i:0, the tWo CON(Rl)2, a straight-chain alkyl, alkoxy or thioalkyl groups Which are bonded to the group With the index i are connected directly to one another; group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms [0026] j is equal to 0, 1 or 2, Where, for jIO, the tWo or an alkenyl or alkynyl group having 2 to 40 C atoms, groups Which are bonded to the group With the index j each of Which may be substituted by one or more radi are connected directly to one another; cals R1, Where one or more non-adjacent CH2 groups [0027] k is equal to 0 or 1, Where, for k:0, the may be replaced by iR1C:CRli, *CECi, Si(Rl) atom and the aromatic or heteroaromatic ring Which are 2, Ge(Rl)2, Sn(Rl)2, C:O, C:S, C:Se, C:NRl, bonded to the group With the index k are connected P(:O)(Rl), SO, S02, NR1, 40*, iSi, iCOOi directly to one another; or 4CONR1i and Where one or more H atoms may be [0028] n is on each occurrence, identically or differently, replaced by D, F, Cl, Br, 1, CN or N02, or an aromatic or 0 or 1, Where the sum of the values of the indices n can heteroaromatic ring system having 5 to 60 aromatic ring be equal to 1, 2 or 3; atoms, Which may in each case be substituted by one or and Where furthermore a maximum of one substituent R may more radicals R1, or an aryloxy or heteroaryloxy group represent a carbaZole derivative, having 5 to 60 aromatic ring atoms, Which may be sub and Where the folloWing structures are excluded: Q Q @Q QB

US 2012/0319052 A1 Dec. 20, 2012

-c0ntinued US 2012/0319052 A1 Dec. 20, 2012 5 ‘Qcontinued

Q Q Q Q N W CTN %i% %i%

US 2012/0319052 A1 Dec. 20, 2012

d:N add; Q <> i.0 O $2 US 2012/0319052 A1 Dec. 20, 2012

contlnued

O US 2012/0319052 A1 Dec. 20, 2012 10

-continued US 2012/0319052 A1 Dec. 20, 2012

-continued

[0029] An aryl group in the sense of this invention contains [0030] An aryl or heteroaryl group, Which may in each case 6 to 60 C atoms; a heteroaryl group in the sense of this be substituted by the above-mentioned radicals R or R1 and invention contains 1 to 60 C atoms and at least one heteroa Which may be linked to the aromatic or heteroaromatic ring tom, With the proviso that the sum of C atoms and heteroat system via any desired positions, is taken to mean, in particu oms is at least 5. The heteroatoms are preferably selected lar, groups derived from , , , from N, O and/ or S. An aryl group or heteroaryl group here is phenanthrene, pyrene, dihydropyrene, chrysene, perylene, taken to mean either a , i.e. benzene, or a ?uoranthene, benZanthracene, benZophenanthrene, tet simple heteroaromatic ring, for example , pyrimi racene, pentacene, benZopyrene, , , isoben dine, , etc ., or a condensed (fused) aryl or heteroaryl Zofuran, dibenZofuran, thiophene, , isoben group, for example naphthalene, anthracene, phenanthrene, Zothiophene, dibenZothiophene, , , , , , carbaZole, etc. carbaZole, pyridine, quinoline, isoquinoline, acridine, US 2012/0319052 A1 Dec. 20, 2012

phenanthridine, benZo-5,6-quinoline, benZo-6,7-quinoline, naphthyridine, aZacarbaZole, benZocarboline, phenanthro benZo-7,8-quinoline, phenothiaZine, phenoxaZine, , line, 1,2,3-, 1,2,4-triaZole, benZotriaZole, 1,2,3-oxa , , , naphthimidaZole, diaZole, 1,2,4-oxadiaZole, 1,2,5-oxadiaZole, 1,3,4-oxadiaZ phenanthrimidaZole, pyridimidaZole, pyraZinimidaZole, qui ole, 1,2,3-thiadiaZole, 1,2,4-thiadiaZole, 1,2,5-thiadiaZole, noxalinimidaZole, , , naphthoxaZole, 1,3,4-thiadiaZole, 1,3,5-, 1,2,4-triaZine, 1,2,3-triaZ anthroxaZole, phenanthroxaZole, , 1,2-, 1,3 ine, , 1,2,4,5-, 1,2,3,4-tetraZine, 1,2,3,5-tet thiaZole, , , benZopyridaZine, pyri raZine, , pteridine, indoliZine and benZothiadiaZole or midine, benZopyrimidine, , , phenaZine, combinations of these groups. naphthyridine, aZacarbaZole, benZocarboline, phenanthro [0033] For the purposes of the present invention, a straight line, 1,2,3-triaZole, 1,2,4-triaZole, benZotriaZole, 1,2,3-oxa chain alkyl group having 1 to 40 C atoms or a branched or diaZole, 1,2,4-oxadiaZole, 1,2,5-oxadiaZole, 1,3,4-oxadiaZ cyclic alkyl group having 3 to 40 C atoms or an alkenyl or ole, 1,2,3-thiadiaZole, 1,2,4-thiadiaZole, 1,2,5-thiadiaZole, alkynyl group having 2 to 40 C atoms, in Which, in addition, 1,3,4-thiadiaZole, 1,3,5-triaZine, 1,2,4-triaZine, 1,2,3-triaZ individual H atoms or CH2 groups may be substituted by the ine, tetraZole, 1,2,4,5-tetraZine, 1,2,3,4-tetraZine, 1,2,3,5-tet groups mentioned above under the de?nition of the radicals R raZine, purine, pteridine, indoliZine and benZothiadiaZole. and R1, is preferably taken to mean the radicals methyl, ethyl, [0031] An aromatic ring system in the sense of this inven n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-meth tion contains 6 to 60 C atoms in the ring system. A heteroaro ylbutyl, n-pentyl, s-pentyl, cyclopentyl, neopentyl, n-hexyl, matic ring system in the sense of this invention contains 5 to cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, 60 aromatic ring atoms, at least one of Which is a heteroatom. cyclooctyl, 2-ethylhexyl, tri?uoromethyl, penta?uoroethyl, The heteroatoms are preferably selected from N, O and/ or S. 2,2,2-tri?uoroethyl, ethenyl, propenyl, butenyl, pentenyl, An aromatic or heteroaromatic ring system in the sense of this cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cyclohepte invention is intended to be taken to mean a system Which does nyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pen not necessarily contain only aryl or heteroaryl groups, but tynyl, hexynyl or octynyl. An alkoxy or thioalkyl group hav instead in Which, in addition, a plurality of aryl or heteroaryl ing 1 to 40 C atoms is preferably taken to mean methoxy, groups may be connected by a non-aromatic unit (preferably tri?uoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, less than 10% of the atoms other than H), such as, for i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methyl example, an spZ-hybridised C, Si, N or O atom, an sp2-hybri butoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cyclohepty dised C or N atom or an sp-hybridised C atom. Thus, for loxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, penta?uo example, systems such as 9,9'-spirobi?uorene, 9,9'-dia roethoxy, 2,2,2-tri?uoroethoxy, methylthio, ethylthio, ryl?uorene, triarylamine, diaryl ether, stilbene, etc., are also n-propylthio, i-propylthio, n-butylthio, i-butylthio, s-bu intended to be taken to be aromatic ring systems in the sense tylthio, t-butylthio, n-pentylthio, s-pentylthio, n-hexylthio, of this invention, as are systems in Which tWo or more aryl cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, groups are connected, for example, by a linear or cyclic alkyl, cyclooctylthio, 2-ethylhexylthio, tri?uoromethylthio, pen alkenyl or alkynyl group or by a silyl group. Furthermore, ta?uoroethylthio, 2,2,2-tri?uoroethylthio, ethenylthio, pro systems in Which tWo or more aryl or heteroaryl groups are penylthio, butenylthio, pentenylthio, cyclopentenylthio, hex linked to one another via one or more single bonds are also enylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, taken to be aromatic or heteroaromatic ring systems in the octenylthio, cyclooctenylthio, ethynylthio, propynylthio, sense of this invention. butynylthio, pentynylthio, hexynylthio, heptynylthio or octy [0032] An aromatic or heteroaromatic ring system having nylthio. 5-60 aromatic ring atoms, Which may also in each case be [0034] For the purposes of the present description, the for substituted by radicals as de?ned above and Which may be mulation that tWo or more radicals R (or R1 or R2) may form linked to the aromatic or heteroaromatic group via any a ring With one another is intended to be taken to mean, inter desired positions, is taken to mean, in particular, groups alia, that the tWo radicals are linked to one another by a derived from benZene, naphthalene, anthracene, benZan chemical bond. This is intended to be illustrated by the fol thracene, phenanthrene, benZophenanthrene, pyrene, chry loWing scheme: sene, perylene, ?uoranthene, naphthacene, pentacene, ben Zopyrene, biphenyl, biphenylene, terphenyl, terphenylene, ?uorene, spirobi?uorene, dihydrophenanthrene, dihydropy rene, tetrahydropyrene, cis- or trans-indeno?uorene, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benZofuran, , dibenZofuran, thiophene, benZothiophene, isobenZothiophene, dibenZothiophene, pyrrole, indole, isoin dole, carbaZole, pyridine, quinoline, isoquinoline, acridine, cyclisation phenanthridine, benZo-5,6-quinoline, benZo-6,7-quinoline, benZo-7,8-quinoline, phenothiaZine, phenoxaZine, pyraZole, of the indaZole, imidaZole, benZimidaZole, naphthimidaZole, radicals R phenanthrimidaZole, pyridimidaZole, pyraZinimidaZole, qui CH3 CH3 noxalinimidaZole, oxaZole, benZoxaZole, naphthoxaZole, anthroxaZole, phenanthroxaZole, isoxaZole, 1,2-thiaZole, 1,3 thiaZole, benZothiaZole, pyridaZine, benZopyridaZine, pyri midine, benZopyrimidine, quinoxaline, 1,5-diaZaanthracene, 2,7-diaZapyrene, 2,3-diaZapyrene, 1,6-diaZapyrene, 1,8-di CH2 CH2 aZapyrene, 4,5 -diaZapyrene, 4,5,9,10-tetraaZaperylene, pyra Zine, phenaZine, phenoxaZine, phenothiaZine, ?uorubin, US 2012/0319052 A1 Dec. 20, 2012

[0035] Furthermore, however, the above-mentioned for [0039] The C atoms labelled With * here adopt the positions mulation is also intended to be taken to mean that, in the case in the six-membered ring Which Were previously occupied by Where one of the tWo radicals represents hydrogen, the second the unit WiW. Consequently, the group of the formula (3) is radical is bonded at the position at Which the hydrogen atom condensed onto the six-membered ring Which had previously Was bonded, With formation of a ring. This is intended to be contained the unit WiW. illustrated by the following scheme: [0040] It is preferred for a maximum of one unit WiW per six-membered ring in the compound according to the inven tion to have been replaced by a group of the formula (3). All other groups W in this siX-membered ring are in this case equal to Z. [0041] An example of a compound according to the inven R R tion in Which a unit WiW has been replaced by a group of cyclisation the formula (3) is the folloWing compound of the formula (8).

of the radicals R formula (8) H CH3

CH2

[0036] It should furthermore be emphasized for clarity that, for the purposes of the present description, an aromatic or heteroaromatic ring may also be represented by a central circle in the ring as an alternative to the classical LeWis notation.

[0042] In a further preferred embodiment of the invention, only one unit WiW in the compounds of the formula (1) or (2) according to the invention has been replaced by a group of [0037] Furthermore, the numbering used for the purposes the formula (3). of the present description in the carbaZole skeleton Will be [0043] In a further preferred embodiment of the invention, presented at this point: all groups W in formula (1) or (2) are equal to Z, and no unit WiW has been replaced by a group of the formula (3). [0044] In a further preferred embodiment of the invention, the compounds according to the invention are represented by the formulae (4) to (14).

6 3 formula (4)

[0038] For the purposes of the present description, the for mulation that a unit comprising tWo adjacent groups W (unit WiW) has been replaced by a group of the formula (3) is taken to mean that a group of the formula (3)

formula (3)

is present instead of the tWo adjacent groups W. US 2012/0319052 A1 Dec. 20, 2012 14

-continued -c0ntinued formula fonnula

fonnula (9)

T/CSZ formula (1 0) Z Z US 2012/0319052 A1 Dec. 20, 2012 15

-continued -continued formula (1 1) formula (14)

Z—Z QZ >_ Z\/ 1 L1”, formula (12) >i Z/ Z G/ Z—Z

Where the symbols and indices occurring are as de?ned above. [0045] It is preferred in accordance With the invention for the bond from the carbaZole group in the compounds of the formula (2) to emanate from the 2- or 3-position. [0046] Particularly preferred embodiments of the com pounds of the formula (1) or (2) conform to the following formulae (15) to (74):

formula (13) US 2012/0319052 A1 Dec. 20, 2012 16

-c0ntinued -continued formula (17) formula (21)

formula (19)

formula (23)

formula (24)

fm m Fa ( 2 O )

US 2012/0319052 A1 Dec. 20, 2012

-c0ntinued -continued formula (37) formula (40) Z —Z / \ Z Z

formula (3 8)

formula (42)

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