(12) United States Patent (10) Patent No.: US 7.414,133 B2 Stössel Et Al

USOO7414133B2

(12) United States Patent (10) Patent No.: US 7.414,133 B2 Stössel et al. (45) Date of Patent: Aug. 19, 2008

(54) PALLADIUMAND PLATINUM COMPLEXES (58) Field of Classification Search ...... 546/2: 549/3, 206; 313/504; 257/40: 528/423; (75) Inventors: Philipp Stössel, Frankfurt (DE); Ingrid 526/265 Bach, Bad Soden (DE); Hubert See application file for complete search history. Spreitzer, Viernheim (DE) (56) References Cited (73) Assignee: Merck Patent GmbH U.S. PATENT DOCUMENTS 4,539,507 A 9/1985 VanSlyke et al. (*) Notice: Subject to any disclaimer, the term of this 5,151,629 A 9/1992 VanSlyke patent is extended or adjusted under 35 5,621,131 A 4/1997 Kreuder et al. U.S.C. 154(b) by 637 days. 5,679,760 A 10, 1997 Mullen et al. 5,763,636 A 6/1998 Kreuder et al. (21) Appl. No.: 10/534,173 6,653,438 B1 1 1/2003 Spreitzer et al. 2004/O1384.55 A1 7/2004 Stossel et al. (22) PCT Filed: Nov. 4, 2003 FOREIGN PATENT DOCUMENTS EP O 707 O2O 4f1996 (86). PCT No.: PCT/EPO3/12279 EP O 842 208 5, 1998 EP O 894 107 2, 1999 S371 (c)(1), EP 1 O28 136 8, 2000 (2), (4) Date: May 6, 2005 EP 1 191 613 3, 2002 EP 1238981 9, 2002 WO WO-92, 18552 10, 1992 (87) PCT Pub. No.: WO2004/041835 WO WO-O2, 15645 2, 2000 WO WO-OO.22026 4/2000 PCT Pub. Date: May 21, 2004 WO WO-O2/O68435 9, 2002 (65) Prior Publication Data Primary Examiner P. Nazario Gonzalez US 2006/OO712O6A1 Apr. 6, 2006 (57) ABSTRACT (30) Foreign Application Priority Data The invention relates to novel metallo-organic compounds which are phosphorescence emitters. Such compounds can be Nov. 8, 2002 (DE) ...... 10251986 used as active components (functional materials) in a range of different applications which form part of the electronics (51) Int. Cl. industry in the broadest sense. The inventive compounds are C07F 15/00 (2006.01) described by the formulae (1), (1a), (2), (2a), (3), (4), (5), (6), HOIL 5/54 (2006.01) (7) and (8). (52) U.S. Cl...... 546/2:549/3; 549/206; 313/504; 257/40: 528/423: 526/265 27 Claims, No Drawings US 7,414,133 B2 1. 2 PALLADIUMAND PLATINUM COMPLEXES typical C–C bond-forming reactions (for example Stille or Suzuki coupling), or else C-heteroatom bond-forming reac RELATED APPLICATIONS tions (for example, for C. N. Hartwig-Buchwald coupling, similarly also for C O and C P) are possible here, in order This application is a national stage application (under 35 thus either to further functionalize the halogen-functionalized U.S.C. 371) of PCT/EP2003.012279 filed Nov.4, 2003 which compounds or to use them as (co)monomers in the prepara claims benefit to German application 10251986.2 filed Nov. tion of corresponding polymers. 8, 2002. 5'-mono-, 5.5"-di-halo-functionalized mono- and bis Organometallic compounds, especially compounds of the ortho-metalated organopalladium and organoplatinum com d metals, will find use as functional components in the near 10 pounds (according to compounds (1), (1a) or (2), (2a)), 5'5"- future as active components (functional materials) in a mono- or di-halo-functionalized bis-ortho-metalated bridged series of different types of application which can be classed organopalladium and organoplatinum compounds (according within the electronics industry in the broadest sense. to compound (3) and (4)) and cationic, uncharged or anionic The organic electroluminescent devices based on organic 5'-mono-halo-functionalized mono-ortho-metalated organo components (for a general description of the construction, see 15 palladium and organoplatinum compounds (according to U.S. Pat. No. 4,539,507 and U.S. Pat. No. 5,151,629) and compound (4), (6), (7) and (8)) have not been described to their individual components, the organic light-emitting date in the literature, but their efficient preparation and avail diodes (OLEDs), have already been introduced onto the mar ability as pure materials is of great significance for various ket, as demonstrated by the car radios having organic displays electrooptical applications. from Pioneer. For the polymeric OLEDs (PLEDs) too, a first The closest prior art may be regarded as being the mono product in the form of a relatively small display (in a shaver bromination and monoiodination of a cationic ruthenium(II) from PHILIPS N.V.) has become available on the market. complex which, in addition to the ortho-metalated 2-phe Further products of this type will shortly be introduced. In nylpyridine ligand, also bears 2,2'-bipyridine ligands C. spite of this, distinct improvements are still necessary here for Coudret, S. Fraysse, J.-P-Luanay, Chem. Commun., 1998, these displays to provide real competition to the currently 25 663-664. The brominating agent used is N-bromosuccinim market-leading liquid crystal displays (LCDS) or to overtake ide, the iodinating agent a mixture of iodobenzene diacetate them. and elemental iodine in a molar ratio of one to one. The A development in this direction which has emerged in isolated yield after chromatographic purification is reported recent years is the use of organometallic complexes which as 95% in the case of bromination, and as 50% in the case of exhibit phosphorescence instead of fluorescence M. A. 30 iodination. Baldo, S. Lamansky, P. E. Burrows, M. E. Thompson, S. R. The bromination, described by Clarket al., of ortho-meta Forrest, Applied Physics Letters, 1999, 75, 4-6. lated 2-phenylduinoline and 2,3-diphenyl-quinoxaline For theoretical reasons relating to the spin probability, up ligands of ruthenium(II) carbonyl chloro and osmium(II) car to four times the energy efficiency and performance effi bonyl chloro complexes with pyridinium perbromide should ciency are possible using organometallic compounds as phos 35 also be regarded analogously. After chromatographic purifi phorescence emitters. Whether this new development will cation, yields of from 27% to 92% were obtained A. M. establish itself firstly depends strongly upon whether corre Clark, C. E. F. Rickard, W. R. Roper, L. J. Wright, J. Orga sponding device compositions can be found which can utilize nomet. Chem., 2000, 598, 262-275. these advantages (triplet emission phosphorescence com In addition, it has been shown in the application WO pared to single emission fluorescence) in OLEDs too. The 40 02/068435 that the halogenation of octahedral homo- and essential conditions for practical use are in particular a long heteroleptic rhodium and iridium complexes with an ortho operative lifetime, a high stability against thermal stress and metalated ligand set proceeds very selectively and in good to a low use and operating Voltage, in order to enable mobile very good yields. applications. In addition, there has to be efficient chemical However, this prior art described in the abovementioned access to the corresponding organometallic compounds. Of 45 references has the following disadvantages: particular interest in this context are organopalladium and (1) only the halogenation of Ru, Os, Rh and Ir complexes, but -platinum compounds. Especially taking into account the cost not that of Pd or Pt compounds, is described. of palladium and platinum, it is of crucial importance here (2) no viable teaching is provided as to how square planar, that efficient access to the corresponding derivatives is homo- and heteroleptic palladium and platinum complexes enabled. 50 with an ortho-metalated ligand set can be halogenated The present invention provides 5'-mono-, 5'5"-di-halo selectively on the coordinated ligand. Rather, it is known functionalized mono- and bis-ortho-metalated organo-palla that these complexes are readily amenable to oxidative dium and organoplatinum compounds (according to com addition by halogens (L. Chassot, E. Müller, A. Zelewsky, pounds (1), (1a) or (2), (2a)), 5'5"-mono- or di-halo Inorg. Chem. 1984, 23, 4249-4253) and thus, according to functionalized bis-ortho-metalated bridged organopalladium 55 the prior art, change from square planar to octahedral and organoplatinum compounds (according to compound (3) geometry. and (4)), and cationic, uncharged or anionic 5'-mono-halo It has now been found that, Surprisingly, the novel com functionalized mono-ortho-metalated organopalladium and pounds (1), (1a), (2), (2a), according to Scheme 2, are organoplatinum compounds (according to compound (5), (6), obtained starting from the bis-ortho-metalated organopalla (7) and (8)), which will be the central key building blocks for 60 dium or organoplatinum compounds (9), (9a), (10), (10a), and obtaining highly efficient triplet emitters, since the halogen that the novel compounds (3) or (4), according to scheme 3, function can be converted to a multitude of functions with the are obtained starting from the bis-ortho-metalated, bridged aid of common methods described in the literature. This organopalladium and organoplatinum compounds (11) or allows not only the covalent incorporation of these active, (12), and that the novel compounds (5), (6), (7) or (8), accord light-emitting centers into a multitude of polymers, but also 65 ing to scheme 4, are obtained starting from the cationic, the tailoring of the optoelectronic properties of these building uncharged or anionic functionalized mono-ortho-metalated blocks. For instance, starting from the structure mentioned, organopalladium and organoplatinum compounds (13), (14), US 7,414,133 B2 3 (15) and (16) with a halogen or interhalogen, optionally in the presence of a base and optionally of a Lewis acid, and in the -continued presence or with Subsequent addition of a reducing agentor of an organic N-halogen compound, optionally in the presence N of a Bronsted acid, and in the presence or with Subsequent addition of a reducing agent, or with a halogenating agent 2N consisting of an organic O-halogen compound and a halogen X M1 He X, in the presence or with subsequent addition of a reducing Yx reduction agent, with suitable selection of the stoichiometric ratio of the appropriate halogenating agent to the compounds (9), (10), 10 (11), (12), (13), (14), (15) or (16) and with suitable selection of the reaction parameters such as reaction temperature, reac X 2 octahedral tion medium, concentration and reaction times, reproducibly M(IV) complex in more than 80% yield, without use of chromatographic with halogenated purification processes, in some cases after recrystallization, 15 ligand set in purities of >99% by NMR or HPLC (see Example 1-3). The above-described process is notable particularly for N several features which have not been described to date in the literature: 2N 1) without wishing to be bound thereby to a particular theory, we suspect that the exceptional tendency of square planar palladium and platinum complexes to the oxidative addi tion of electrophiles, here of halogens or their analogs 25 which transfer halogenium ions, always has the conse X quence that a rapid oxidative addition to the metal center square planar occurs initially with consumption of one equivalent of M(II) complex with halogenated halogen and formation of octahedral dihalopalladium(IV) ligand set and -platinum(IV) complexes. In a second, Subsequent 30 step, these react with further equivalents of halogen to halogenate the ligands and form octahedral dihalopalla 2) The selective 5'-mono- and 5'5"-dihalogenation on square dium(IV) and -platinum(IV) complexes with a haloge planar palladium(II) and platinum(II) complexes via the nated, ortho-metalated ligand set. The Subsequent reduc above-described dihalo-palladium(IV) and -platinum(IV) tion of these octahedral dihalopalladium(IV) and 35 -platinum(IV) complexes with a halogenated ortho-meta complexes is Wunexpected and not known in this form. The lated ligand set then leads to the square planar palladium observed high selectivity is suspected to result from the (II) and platinum(II) complexes with a correspondingly activation which is experienced by the position para to the halogenated ligand set described here. Scheme 1 shows palladium or platinum atom as a result of this atom. The this reaction sequence schematically. 40 unexpectedly high activity of this position compared to an electrophilic Substitution, here halogenation, is utilized selectively by the use of mild halogenating agents. Scheme 1: 3) A crucial factor for the achievement of high selectivities and high reaction rates is frequently, depending on the N 45 halogenating agent, working in the presence of an acid binding agent which binds hydrohalic acid formed in the 2N -- X2 course of the Substitution. This is a Surprising finding, by He M oxidative addition which the side reactions are apparently Suppressed effec 50 tively. The inventive halogenating agents accordingly com prise an acid-binding agent, Such as a base, which is either an intrinsic part of the halogenating agent or is added H 2 additionally to the halogenating agent. square planar M(II) complex 4) The high conversion achieved, which is reflected in the 55 reproducibly very good yields of isolated product, is unex N pected and unique for the halogenation of ortho-metalated 2N ligands bound to metals of the nickel group. M1 X + 2 X 5) The resulting compounds are obtained without costly and Nx Herhalogenation of 60 inconvenient chromatographic purification, in Some cases the ligands after recrystallization, in very good purities of >99% by NMR or HPLC. This is essential for the use in optoelec H 2 tronic components, and the utilization as valuable interme diates for the preparation of corresponding compounds. octahedral 65 M(II) complex As outlined above, the inventive compounds have not been described before and are thus novel. US 7,414,133 B2 5 The present invention thus provides the compounds (1) and (2) according to scheme 2

compounds (1a)

Scheme 2: compounds (1) (R) 10

compounds (2a)

compounds (2) 25

where the symbols and indices are each defined under the formulae (1) and (2).

35 The present invention likewise provides the compounds (3) and (4) according to scheme 3 where the symbols and indices are each defined as follows: Scheme 3: M is Pd, Pt: 40 compounds (3)

X is Cl, Br, I: Y is O, S, Se, NR'; (R)a R is the same or different at each instance and is H, F, Cl, Br, as I, NO, CN, a straight-chain or branched or cyclic alkyl or y alkoxy group having 1 to 20 carbonatoms, in which one or 45 more nonadjacent CH groups may be replaced by —O—, SiR' - S - NR'— or CONR'—and in which one or more hydrogen atoms may be replaced by F, or an aryl or heteroaryl group having from 4 to 14 carbon atoms which may be substituted by one or more nonaromatic R 50 X radicals, and a plurality of R substituents, either on the compounds (4) same ring or on the two different rings, may together in turn form one furtheraliphatic or aromatic, mono- or polycyclic ring system; R" are the same or different at eachinstance and are each Hor 55 an aliphatic or aromatic hydrocarbon radical having from 1 to 20 carbon atoms; a is 0, 1, 2, 3 or 4, preferably 0, 1 or 2: b is 0, 1, 2 or 3, preferably 0 or 1; 60 n is 1 or 2. A further embodiment of the invention relates to those Pd and Pt complexes which simultaneously have ligands of the type as in compounds (1) and those of compounds (2), i.e. mixed ligand systems. These are described by the formulae where the symbols and indices are each defined as follows: (1a) and (2a): M is Pd, Pt: US 7,414,133 B2 7 X is H, Cl, Br or I, with the proviso that at least one X" per formula is selected from Cl, Br or I; -continued Y is O, S, Se, NR'; Z is identically F, Cl, Br, I, O-R', S-R', N(R'). compounds (8) R is the same or different at each instance and is H, F, Cl, Br, 5 (R) +1 O-1 I, NO, CN, a straight-chain or branched or cyclic alkyl or 2xa alkoxy group having 1 to 20 carbonatoms, in which one or more nonadjacent CH groups may be replaced by —O—, N N SiR' - S - NR'— or CONR'—and in which M-L one or more hydrogen atoms may be replaced by F, or an 10 S. aryl or heteroaryl group having from 4 to 14 carbon atoms Y le which may be substituted by one or more nonaromatic R R radicals, and a plurality of R substituents, either on the X same ring or on the two different rings, may together in turn 15 form one furtheraliphatic or aromatic, mono- or polycyclic ring system; R" are the same or different at eachinstance and are each Hor where the symbols and indices are each defined as follows: an aliphatic or aromatic hydrocarbon radical having from 1 M is Pd, Pt: to 20 carbon atoms; 2O X is Cl, Br, I: a is 0, 1, 2, 3 or 4, preferably 0, 1 or 2: Y is O, S, Se, NR'; b is 0, 1, 2 or 3, preferably 0 or 1. R is the same or different at each instance and is H, F, Cl, Br, The present invention likewise provides the compounds I, NO, CN, a straight-chain or branched or cyclic alkyl or (5), (6), (7) and (8) according to scheme 4 alkoxy group having 1 to 20 carbonatoms, in which one or 25 more nonadjacent CH groups may be replaced by —O—, SiR , —S , NR'— or CONR'—and in which one or more hydrogen atoms may be replaced by F, or an Scheme 4: aryl or heteroaryl group having from 4 to 14 carbon atoms 30 which may be substituted by one or more nonaromatic R compounds (5) radicals, and a plurality of R substituents, either on the (R)a (m-1) same ring or on the two different rings, may together in turn e form one furtheraliphatic or aromatic, mono- or polycyclic r ring System; N N 35 N 1 (L2)2-m R" are the same or different at each instance and are each Hor M an aliphatic or aromatic hydrocarbon radical having from 1 Y(L) to 20 carbon atoms; L is an uncharged, monodentate ligand; r 1. X eX 40 L is a monoanionic, monodentate ligand; (R) L is an uncharged or mono- or dianionic bidentate ligand; a is 0, 1, 2, 3 or 4, preferably 0, 1 or 2: compounds (6) b is 0, 1, 2 or 3, preferably 0 or 1; (R) (m-1) m is 0, 1 or 2. ar 45 Inventive uncharged, monodentate ligands L. are carbon N N monoxide, an isonitrile, for example tert-butylisonitrile, N 1 (L2)2-m cyclohexylisonitrile, adamantylisonitrile, an amine, for MN example trimethylamine, triethylamine, morpholine, phos S. (L1)m 50 phines, for example trifluorophosphine, or else aliphatic, aro Y matic or heteroaromatic phosphines Such as trimeth le ylphoshine, tricyclohexylphosphine, R dicyclohexylphenylphosphine, tri-o-tolylphosphine, tri-tert X butylphosphine, tri-phenylphosphine, tris(pentafluorophe 55 nyl)phosphine, phosphites, for example trimethyl phosphite, compounds (7) triethyl phosphite, arsines, for example trifluoroarsine, trim (R) ethylarsine, tricyclohexylarsine, tri-tert-butylarsine, triph e +1 O-1 enylarsine, tris(pentafluorophenyl)-arsine, Stibines, for y example trifluorostibine, trimethylstibine, tricyclohexylstib N-N 60 ine, tri-tert-butylstibine, triphenylstibine, tris(pentafluoro phenyl)stibine or a nitrogen-containing heterocycle, for )- example pyridine, pyridazine, pyrazine, triazine. N Inventive monoanionic, monodentate ligands L are halides such as F, Cl, Br, I, cyanide, cyanate, isocyanate, X le 65 thiocyanate, isothiocyanate, alkoxides, for example methox (R) ide, ethoxide, propoxide, isopropoxide, tert-butoxide, phe noxide, a thioalkoxide, in particular, for example, meth US 7,414,133 B2 9 10 anethiolate, ethanethiolate, propanethiolate, 3) The access, outlined under 1) and 2), to corresponding isopropanethiolate, tert-thiobutoxide, thiophenoxide, functionalizations is of very high significance, since it is amides, for example dimethylamide, diethylamide, diisopro very important to integrate metal complexes either into pylamide, carboxylates, for example acetate, trifluoroacetate, polymers or into readily soluble low molecular weight propionate, benzoate, and anionic nitrogen-containing het- 5 Substances. erocycles Such as morpholide, pyrrollide, imidazolide, pyra 4) It is likewise advantageous that the claimed complexes can Zolide. be prepared in good purity and high yield. This is of enor Inventive uncharged or mono- or dianionic, bidentate ligands L are diamines, for example ethylenediamine, N.N. mous significance firstly for corresponding applications N',N'-tetramethylethylenediamine, propylenediamine, N.N. 10 (further processing for use in electrical or electronic N',N'-tetramethylpropylenediamine, cis-, trans-diamihocy devices, for example OLED- or PLED-based displays) and clohexane, cis-, trans-N,N,N',N'-tetramethyl also commercially (owing to the high raw material cost). diaminocyclohexane, imines, for example 2 (1- The present invention further provides processes for pre (phenylimino)ethylpyridine, 2(1-(2-methylphenyl-imino) paring the compounds (1), (2), (3), (4), (5), (6), (7) and (8) by ethylpyridine, 2(1-(2,6-diisopropylphenyl-imino)ethyl 15 pyridine, 2(1-methylimino)ethylpyridine, 2(1- reacting the compounds (9), (10), (11), (12), (13), (14), (15) (ethylimino)ethylpyridine, 2(1-(isopropylimino)-ethyl and (16) according to scheme 5 pyridine, 2(1-(tert-butylimino)ethylpyridine, diimines, for example 1.2-bis(methylimino)ethane, 1.2-bis(ethylimino) ethane, 1.2-(bis(isopropylimino)ethane, 1.2-bis(tert-butyl Scheme 5: imino)ethane, 2,3-bis(methyl-imino)butane, 2,3-bis(eth compounds (9) ylimino)butane, 2,3-bis(iso-propylimino)butane, 2,3-bis (tert-butylimino)butane, 1,2-bis(phenylimino)ethane, 1,2-bis (2-methylphenyl-imino)ethane, 1,2-bis(2,6- diisopropylphenylimino)-ethane, 1.2-bis(2,6-di-tert 25 butylphenylimino)ethane, 2,3-bis(phenylimino)butane, 2,3- bis(2-methylphenyl-imino)butane, 2,3-bis(2,6- diisopropylphenylimino)-butane, 2,3-bis(2,6-di-tert butylphenylimino)butane, heterocycles containing two nitrogen atoms, for example 2,2'-bipyridine, o-phenanthro 30 line, diphosphines, for example bis-diphenylphosphi nomethane, bisdiphenyl-phosphinoethane, bis(diphe compounds (10) nylphosphino)propane, bis(di-methylphosphino)methane, bis(dimethylphosphino)ethane, bis(dimethylphosphino)pro pane, bis(diethylphosphino)-methane, bis(diethylphosphino) 35 ethane, bis(diethyl-phosphino)propane, bis(di-tert-bu tylphosphino)methane, bis(di-tert-butylphosphino)ethane, bis(tert-butyl-phosphino)propane, 1,3-diketonates derived from 1,3-diketones, for example acetylacetone, benzoylac etone, 1,5-diphenylacetylacetone, dibenzoylmethane, bis(1, 40 1,1-trifluoroacetyl)methane, 3-ketonates derived from 3-keto esters, for example ethyl acetoacetate, carboxylates derived from aminocarboxylic acids, for example pyridine-2-car compounds (11) boxylic acid, quinoline-2-carboxylic acid, glycine, dimeth 45 ylglycine, alanine, dimethylaminoalanine, salicyliminates (R) (R)a derived from salicylimines, in particular, for example, meth ylsalicylimine, ethylsalicylimine, phenylsalicylimine, dialkoxides derived from dialcohols, in particular, for example, ethylene glycol, 1,3-propylene glycol, dithiolates derived from dithiols, for example 1.2-ethylenedithiol, 1,3- 50 propylenedithiol, or heteroarylborates, for example tetrakis (1-imidazolyl)borate, tetrakis(1-pyrazolyl)-borate. Sa The inventive complexes (1) to (8) and (1a) and (2a) have yS-1N the following advantages over the prior art: (R) 55 compounds (12) 1) As a result of the functionalization, it is simple to covalently incorporate these complexes as (co)monomers, for example, into corresponding polymers or oligomers. This may be effected either in the main chain or at the end of the main chain, or, in the case of appropriate further 60 reactions, into the side chain of the polymer. 2) It is possible analogously by appropriate reactions to pro vide “defined low molecular weight complexes” which, however, have specific properties (for example high Solu bility, low tendency to crystallize). The incorporation into 65 defined oligomers (for example dendrimers) is also pos sible effortlessly by the same reactions. US 7,414,133 B2 11

-continued -continued compounds (16) (R) +1 O-1 e 5 compounds (15) (R) +1 O-1 N N M- L3 S. ro 10 Y N N le M-L R H

r2x1 15 H in which M and the radicals and indices X,Y,Z. R. R. L. L. (R) L., a, b and m are each as defined above with halogenating agents, followed by reducing agents. The process according to the invention is illustrated by scheme 6:

Scheme 6:

1) = (n + 1) halogenating agent I, II or III 2) + reducing agent

1) = (n + 1) halogenating agent I, II or III He2) + reducing agent

compounds (2) (R)a (R)a s Kn s -1 NaN2 N N - ZN u-1 N 21 MN Z M e y Y r S. SAS H R R (R) H H compounds (11) compounds (12) 1) +2 or 3 equiv. of halogenating agent I, II or III 2) + reducing agent US 7,414,133 B2 13 14

-continued (R)a (R)a (R)a rSA u-1 N 2 r Sás X (R) compounds (3) compounds (4) (m-I) (R) (m-1)

2N 1) +2 or 3 equiv. of halogenating agent I, II or III N 1 (L2)2-m He2) + reducing agent

(R)a (m-I) (m-I)

1) +2 or 3 equiv. of halogenating agent I, II or III 2) + reducing agent 3

compounds (14) compounds (6)

(R)3. -- $0.8- (R) 3. -- 0.8-

1) +2 or 3 equiv. of halogenating agent I, II or III Her2) + reducing agent

compounds (7) (R) -- $0.8- --AO,-

1) +2 or 3 equiv. of halogenating agent I, II or III He2) + reducing agent

compounds (16) compounds (8)

The compounds (1a) and (2a) may also be prepared analo- 1:100 and optionally a Lewis acid in a molar ratio (halogen to gously. 65 Lewis acid) of from 1:0.1 to 1:0.0001, for example chlorine, Inventive halogenating agents are the halogens X and the bromine or iodine, or chlorine fluoride, bromine fluoride, interhalogens X-X and a base in a molar ratio of from 1:1 to iodine fluoride, bromine chloride, iodine chloride or iodine US 7,414,133 B2 15 16 bromide, in combination with organic bases Such as amines, formly substituted products. It is self-evident that slight for example triethylamine, tri-n-butylamine, duisopropyl deviations from the abovementioned ratios still lead to good ethylamine, morpholine, N-methylmorpholine and pyridine, to acceptable results. According to the invention, a reducing agent is added to the or salts of carboxylic acids such as sodium acetate, sodium reaction mixture in a molar ratio of from 1:1 to 10000:1 based propionate, sodium benzoate, or inorganic bases such as on the compounds (9), (10), (11), (12), (13), (14), (15) or (16). Sodium phosphate or potassium phosphate or Sodium hydro The addition may be effected either simultaneously with the genphosphate or potassium hydrogenphosphate, sodium addition of the halogenating agents (I), (II) or (III), or pref hydrogencarbonate or potassium hydrogencarbonate, sodium erably after a time delay. carbonate or potassium carbonate, or else organic bromine 10 Inventive reducing agents are hydrazine (hydrate) or salts complexes such as pyridinium perbromide, in each case thereof, for example hydrazine hydrochloride, hydrobro optionally in combination with a Lewis acid, for example mide, hydroiodide, hydrazine Sulfate, hydrazine nitrate and borontrifluoride, borontrifluoride etherate, borontrichloride, hydrazine phosphate, hydroxylamine or salts thereof, for borontribromide, borontriiodide, aluminum trichloride, alu example hydroxylamine hydrochloride, hydrobromide, minum tribromide, aluminum triiodide, iron(III) chloride, 15 hydroiodide, hydroxylamine nitrate, hydroxylamine phos iron(III) bromide, zinc.(II) chloride, zinc.(II) bromide, tin(IV) phate and hydroxylamine Sulfate, hydroxylamine-O-sulfonic chloride, tin(IV) bromide, phosphorus pentachloride, arsenic acid and hydroquinones, for example hydroquinone or tet pentachloride and antimony pentachloride. These halogenat ramethylhydroquinone, alkali metal and alkaline earth metal ing agents are referred to below as halogenating agents (I). Sulfites such as lithium, Sodium, potassium and magnesium Further inventive halogenating agents are organic N-halo sulfite, alkali metal and alkaline earth metal dithionites, for gen compounds, N-halocarboxamides, for example example lithium, sodium, potassium and magnesium dithion N-chloro-, N-bromo- and N-iodoacetamide, N-chloro-, ite, alkali metals and alkaline earth metals, for example N-bromo- and N-iodopropionamide, N-chloro-, N-bromo lithium, Sodium, potassium and magnesium, calcium, and N-iodobenzamide, or N-halocarboximides, for example 25 barium, and their amalgams and other corresponding alloys, N-chloro-, N-bromo- and N-iodosuccinimide, N-chloro-, transition metals such as manganese, iron, nickel and Zinc, N-bromo- and N-iodophthalimide, or N-dihalosulfonamides and transition metal alloys, for example Raney nickel. such as N,N-dibromobenzenesulfonamide, or N-halosulr fonamide salts such as chloramine B or T. According to the invention, the reduction may also be 30 effected by dry-heating, under reduced pressure, the palla These halogenating agents are referred to below as halo dium(IV) or platinum(VI) compounds which have been genating agents (II). In the case of the halogenating agents formed as intermediates and isolated in Substance. (II), the additive use of Lewis acids, as are listed above, for Inventive reaction media are protic or aprotic, halogen-free example, may likewise be advantageous. or halogenated solvents, for example alcohols such as metha In the case of the halogenating agents (II), the additive use 35 nol, ethanol, propanol, butanol, polyhydric alcohols such as of Bronsted acids, for example hydrochloric acid, hydrobro ethylene glycol or propylene glycol, nitriles such as acetoni mic acid, hydriodic acid, Sulfuric acid or phosphoric acid, may likewise be advantageous. trile, propionitrile or benzonitrile, ethers such as diethyl ether, THF or dioxane, aromatic hydrocarbons such as benzonitrile, Still further inventive halogenating agents are organic nitrobenzene or chlorobenzene, N,N-dialkylamides such as O-Hal compounds and halogens X in a molar ratio of from 40 0.5:1 to 1:1, such as iodoaryl dicarboxylates in a molar ratio dimethylformamide, dimethylacetamide or N-methylpyrroli of from 0.5:1 to 1:1 with a halogen X, for example iodoben done, Sulfoxides such as dimethyl Sulfoxide, Sulfones such as Zene diacetate or bistrifluoroacetoxyiodobenzene and dimethylsulfone or Sulfolane, halogenated hydrocarbons elemental bromine in a molar ratio of from 0.5:1 to 1:1, or Such as dichloromethane, trichloromethane, 1,1-dichloroet iodobenzene diacetate or bistrifluoroacetoxyiodobenzene 45 hane, 1,2-di-chloroethane, 1.1.2.2-tetrachloroethane; prefer and elemental iodine in a molar ratio of from 0.5:1 to 1:1. ence is given to aromatic or chlorinated solvents. These halogenating agents are referred to below as halo According to the invention, the reaction is carried out genating agents (III). within the temperature range from -78°C. to 150° C., pref In the process according to the invention, a stoichiometric erably from 0°C. to 100° C., very preferably from 10° C. to ratio of the halogenating agents (I), (II) or (III), based on the 50 60° C. content of active halogen, to the compounds (9), (10), (11), According to the invention, the concentration of the palla (12), (13), (14), (15) or (16) of 2:1 leads selectively to the dium-containing or platinum-containing reactants, com compounds (1), (2) where n=1, (3), (4) where one X" is Hand pounds (9), (10), (11), (12), (13), (14), (15) or (16), is in the the other is halogen, and to the compounds (5), (6), (7) or (8). 55 range from 0.0005 mol/l to 2 mol/l, more preferably in the This is a Surprising and unforeseeable result. range from 0.002 mol/l to 0.1 mol/l. In the process according to the invention, a stoichiometric According to the invention, the palladium-containing or ratio of the halogenating agents (I), (II) or (III), based on the platinum-containing reactants may be present dissolved or content of active halogen, to the compounds (9), (10), (11) or Suspended in the reaction medium. 60 According to the invention, the reaction is carried out (12) of from 3:1 to 1000:1 leads selectively to the compounds within from 10 minutes up to 100 hours, preferably within (1), (2) where n=2, or (3), (4) where both of X" are halogen. from 1 h to 40 h. This is a Surprising and unforeseeable result. It is possible with the synthetic methods illustrated here to The stoichiometric ratios described here are preferred prepare the compounds (1), (1a), (2), (2a), (3), (4), (5), (6), (7) embodiments of the present invention since they lead to uni or (8), including the examples shown below. US 7,414,133 B2 17 18

-continued rs rs Nn 2 Nn 2 Pt Pt

C Br Example 1 F rs 15 Example 6 N n2 O Pt rNin Na2 Pt Br Example 2 25 Br rs Example 7 Na2 Pt 30

2 I-2 35 Example 3 Pt

rs Br Nn 2 40 Example 8 Pt

N 45 Br Na2 Pt

50 2 Example 4 Br Example 9

55 N N Na2 Pt Pt 60

Br ON Br Example 5 65 Example 10 US 7,414,133 B2 19 20

-continued -continued N 5 N N N 2 2 N N 21 Pt Pt

Br 2 Example 11 H Br

15 Example 16

2O 2N Na2 Pt

25 H I

Example 17

30 rs 35 N 2 Po

40 Cl

Example 18

2 N N 2 50 Pt

H C 55 Example 19

2 N N 21 60 Po

65 H Br Example 15 Example 20 US 7,414,133 B2 21 22

-continued -continued

N O

Nrs D - 2 O Po Po 10

Br Br F Example 26 Example 21 15 N N 2N C M \ D - Pt Pt Po V / C

25 Br Br Br Example 26 Example 22 N 30 Y 2N C A V D N S Pt Pt V / - C 35 Po Br Br

F Br 40 Example 27 Example 23 N N - 45 2 N /CO Po V CO

50 Br Example 28 Example 24

CN 55 N

rs N Na2 2 /C Pd 60 C

Example 25 65 Example 29 US 7,414,133 B2 23 24 The invention therefore further provides conjugated or -continued semiconjugated and nonconjugated polymers containing one or more compounds of the formula (1") and/or (2)

N 5 compounds (1) 2N CN M Pt Yo 10

Br Example 30 15 (XX) N N compounds (2) 2 /O \ 2O \-O

Br 25 Example 31 N N O 30 and/or of the formula (1a) and/or (2a") 2 o compounds (1a) P x N sy

Br leS C2 N 1. C

Example 32 Y N 21

40 o SAS H. R. (R) (XX)

-- (R) (R) compounds (2a") N 3. 3.

2N / 45 knN 2s Pt 2

N 21 2 Y B ly o r H X (R) R (XX) Example 33 and/or of the formula (3), (4), (5'), (6'), (7), and/or (8) 55 compounds (3')

The thus obtained inventive compounds may find use, for example, as comonomers to obtain corresponding conjugated s" or else semiconjugated or nonconjugated polymers. The cor- s responding copolymerization is preferably effected via the 2 halogen functionality. It is thus possible to copolymerize 60 them into polymers including soluble polyfluorenes (for example according to EP-A-842 208 or WO 00/22026), polyspirobifluorenes (for example according to EP-A-707 020 or EP-A-894 107), poly-para-phenylenes (for example according to WO 92/18552), polycarbazoles or else poly 65 (XX) thiophenes (for example according to EP-A-1 028 136). US 7,414,133 B2 25 26 SiR' ,—S , NR'— or CONR'—and in which -continued one or more hydrogen atoms may be replaced by F, or an compound (4) aryl or heteroaryl group having from 4 to 14 carbon atoms which may be substituted by one or more nonaromatic R (R) radicals, and a plurality of R substituents, either on the same ring or on the two different rings, may together in turn form one furtheraliphatic or aromatic, mono- or polycyclic 21 ring System; R" are the same or different at each instance and are each Hor 10 an aliphatic or aromatic hydrocarbon radical having from 1 Y to 20 carbon atoms; L is an uncharged, monodentate ligand; (XX) R R (XX) L is a monoanionic, monodentate ligand; compound (5) L is an uncharged or mono- or dianionic bidentate ligand; x (m-1) 15 a is 0, 1, 2, 3 or 4: e b is 0, 1, 2 or 3: y m is 0, 1 or 2: N n is 1 or 2; N N-(L2)2-m (XX) is a bond to the conjugated or semiconjugated or non M 2O conjugated polymer; N Y(L) (XX") is H or a bond to the conjugated or semiconjugated or nonconjugated polymer, but at least one (XX) performula le is a bond to the conjugated or semiconjugated or noncon (XX) (R) jugated polymer. 25 Preference is given to conjugated, semiconjugated or non compound (6') conjugated polymers which have been obtained using one or (R)a (m-1) more compounds of the formula (1), (1a), (2), (2a) and/or (3) to (8). ar Conjugated or semiconjugated polymers refer to polyfluo N renes, polyspirobifluorenes, poly-paraphenylenes, polycar YN (L) 30 bazoles or polythiophenes. N "NL), The conjugated or semiconjugated polymers based on Y polyfluorenes are preferably the polyfluorenes disclosed in EP-A-842 208 and WOOO/22026. 35 The conjugated or semiconjugated polymers based on (XX) R polyspirobifluorenes are preferably the polyspirobifluorenes compound (7) disclosed in EP-A-707 020 and EP-A-894 107. (R)a -- $0.8- The conjugated or semiconjugated polymers based on poly-para-phenylenes are preferably the poly-paraphe ar nylenes disclosed in WO92/18552. N 40 The conjugated or semiconjugated polymers based on N polythiophenes are preferably the polythiophenes disclosed in EP-A-1 (028 136. In addition, the inventive compounds may also be function 45 alized further by the abovementioned reaction types, for (XX) ex example, and thus converted to extended low molecular weight Pd or Pt complexes or defined oligomers (for example compound (8) dendrimers). An example to be mentioned here is the func -- $0.8- tionalization with arylboronic acids according to Suzuki or 50 with amines according to Hartwig-Buchwald. The halogenated complexes or the polymers or else “extended low molecular weight complexes” or else the defined oligomers obtained therefrom may be used in electri cal or electronic components, for example as light-emitting 55 materials in organic or polymeric light-emitting diodes (OLEDs or PLEDs). However, other applications, for example in organic Solar cells, organic lasers, organic photo (XX) R detectors, and the like are also conceivable. The invention therefore also provides electronic compo 60 nents, for example organic or polymeric light-emitting diodes where the symbols and indices are each defined as follows: (OLEDs or PLEDs), organic integrated circuits (O-ICs), M is Pd, Pt: organic field-effect transistors (O-FETs), organic thin-film Y is O, S, Se, NR; transistors (O-TFTs), organic solar cells (O-SCs) or organic R is the same or different at each instance and is H, F, Cl, Br, laser diodes (O-lasers), comprising one or more inventive I, NO, CN, a straight-chain or branched or cyclic alkyl or 65 halogenated palladium or platinum complexes or one or more alkoxy group having 1 to 20 carbonatoms, in which one or inventive polymers which have been obtained using these more nonadjacent CH groups may be replaced by —O—, inventive palladium or platinum complexes. US 7,414,133 B2 27 28 The present invention is illustrated in detail by the Example 2 examples which follow, without any intention that it be restricted thereto. Those skilled in the art can prepare further Bis2-(2-pyridinyl-KN) inventive complexes from the descriptions without inventive (5-bromophenyl-KC)platinum(II) activity, and employ the process according to the invention. 783 mg (4.4 mmol) of N-bromosuccinimide and 170 ul of EXAMPLES 48% by weight HBr were added under exclusion of light to an efficiently stirred solution of 504 mg (1.0 mmol) of bis(2-(2- pyridinyl-KN)phenyl-KCplatinum(II) in 200 ml of dichlo Synthesis of Symmetrically and Asymmaetrically Function 10 romethane. The reaction mixture was stirred at room tem alized Bis-Ortho-Metalated Organopalladium or Organo perature for a further 20 h. Subsequently, 240 ul (5 mmol) of platinum Compounds: hydrazine hydrate and 100 ml of ethanol were added, and the The syntheses which follow have, unless stated otherwise, mixture was heated under reflux for 2 h. After concentration to a volume of 20 ml under reduced pressure, the solution was been carried out under air using commercial solvents. The 15 admixed with 200 ml of ethanol. Subsequently, the microc reactants were purchased from Aldrich N-chlorosuccinim rystalline precipitate was filtered off (P4), washed three times ide, N-bromosuccinimide, HCl, HBr, hydrazine hydrate. with 20 ml of ethanol and then dried under reduced pressure Before the N-haloimides were used, the content of active (60° C., 10 mbar). The yield, at a purity of >99.5% by 'H halogen was determined iodometrically analogously to: K. NMR, was 613 mg, corresponding to 92.7%. W. Rosenmund, W. Kuhnhenn, Ber. 1923, 56, 1262. Bis2 H NMR (DMSO-d6) ppm=8.85 (m, 3H), 7.93 (m, 3H), (2-pyridinyl-KN)phenyl-KCplatinum was prepared by lit 7.78 (m,3H), 7.52 (m, 3H), 7.39 (m, 3H), 7.35 (m, 3H), 7.02 erature methods (L. Chassot, E. Müller, A. Zelewsky, Inorg. (m, 3H). Chem. 1984, 23, 4249-4253). Numbering scheme for the assignment of the "H NMR 25 Example 3 signals analogously to: C. Coudret, S. Fraysse, J.-P-Launay, Bis2-(2-pyridinyl-KN) Chem. Commun., 1998, 663-664: (5-bromophenyl-KC)platinum(II)

Scheme 7: 30 783 mg (4.4 mmol) of N-bromosuccinimide and 170 ul of 48% by weight HBr were added under exclusion of light to an efficiently stirred solution of 504 mg (1.0 mmol) of bis(2-(2- pyridinyl-KN)phenyl-KCplatinum(II) in 200 ml of dichlo romethane. The reaction mixture was stirred at room tem 35 perature for a further 20h. After concentration to a volume of 20 ml under reduced pressure, the solution was admixed with 200 ml of ethanol. Subsequently, the microcrystalline pre cipitate was filtered off (P4), washed three times with 20 ml of ethanol and then dried under reduced pressure (60° C., 10' 40 mbar). The thus obtained platinum(IV) compound was sub limed at a temperature of from 380 to 410°C. under reduced pressure (approx. 5.10 mbar), in the course of which the product (the desired platinum(II) compound) was obtained as Example 1 the sublimate. The yield, at a purity of >99.5% by H NMR, 45 was 569 mg, corresponding to 86.0%. Bis2-(2-pyridinyl-KN)(5-chlorophenyl)-KC)plati H NMR (DMSO-d6): ppm=8.85 (m,3H), 7.93 (m, 3H), num(II) 7.78 (m,3H), 7.52 (m, 3H), 7.39 (m, 3H), 7.35 (m, 3H), 7.02 (m, 3H). 588 mg (4.4 mmol) of N-chlorosuccinimide and 200 ul of so conc. HCl were added under exclusion of light to an effi ciently stirred solution of 504 mg (1.0 mmol) of bis 2-(2- What is claimed is: pyridinyl-KN)phenyl-KCplatinum(II) in 200 ml of dichlo 1. A compound of the formula (1) or (2) romethane. The reaction mixture was stirred at room temperature for a further 20h. Subsequently, 240 ul (5 mmol) 55 of hydrazine hydrate and 100 ml of ethanol were added, and formula (1) the mixture was heated under reflux for 2 h. After concentra tion to a volume of 20 ml under reduced pressure, the solution was admixed with 200 ml of ethanol. Subsequently, the microcrystalline precipitate was filtered off (P4), washed three times with 20 ml of ethanol and then dried under reduced pressure (60°C., 10 bar). The yield, at a purity of >99.5% by "H NMR, was 501 mg, corresponding to 87.5%. "H NMR (CDC1): ppm=8.91 (m, 3H), 7.91 (m, 3H), 65 7.83 (m, 3H), 7.57 (m, 3H), 7.43 (m, 3H), 7.37 (m,3H), 7.09 (m, 3H). US 7,414,133 B2 29 30 Y is O, S, Se or NR'; -continued R is the same or different at each instance and is H, F, Cl, formula (2) Br, I, NO, CN, a straight-chain or branched or cyclic alkyl or alkoxy group having 1 to 20 carbon atoms, in which one or more nonadjacent CH2 groups may be replaced by -O-, -SiR' , —S , —NR'—or —CONR'—and in which one or more hydrogenatoms may be replaced by F, or an aryl or heteroaryl group having from 4 to 14 carbon atoms which may be substi tuted by one or more nonaromatic R radicals, and a plurality of R Substituents, either on the same ring or on the two different rings, may together in turn form one further aliphatic or aromatic, mono- or polycyclic ring system; 15 where the symbols and indices are each defined as follows: R" are the same or different at eachinstance and are each H M is Pd or Pt or an aliphatic or aromatic hydrocarbon radical having X is C1, Br or I; from 1 to 20 carbon atoms; Y is O, S, Se or NR'; a is 0, 1, 2, 3 or 4: R is the same or different at each instance and is H, F, Cl, b is 0, 1, 2 or 3. Br, I., NO, CN, a straight-chain or branched or cyclic alkyl or alkoxy group having 1 to 20 carbon atoms, in 3. A compound of the formula (3) or (4) which one or more nonadjacent CH groups may be replaced by -O-, -SiR'2 , -S-, -NR'— or formula (3)

—CONR'—and in which one or more hydrogenatoms 25 may be replaced by F, or an aryl or heteroaryl group having from 4 to 14 carbon atoms which may be substi tuted by one or more nonaromatic R radicals, and a s plurality of R Substituents, either on the same ring or on the two different rings, may together in turn form one 30 further aliphatic or aromatic, mono- or polycyclic ring System; R" are the same or different at each instance and are each H or an aliphatic or aromatic hydrocarbon radical having from 1 to 20 carbon atoms; 35 a is 0, 1, 2, 3 or 4: formula (4) b is 0, 1, 2 or 3; and n is 1 or 2. 2. A compound of the formula (1a) or (2a) 40

formula (1a)

where the symbols and indices are each defined as follows: M is Pd or Pt: 50 X is H. Cl, Br or I, with the proviso that at least one Xper formula is selected from Cl, Br or I; formula (2a) Y is O, S, Se or NR'; Z is identically F, Cl, Br, I, O-R', S-R' or N(R'); 55 R is the same or different at each instance and is H, F, Cl, Br, I, NO, CN, a straight-chain or branched or cyclic alkyl or alkoxy group having 1 to 20 carbon atoms, in which one or more nonadjacent CH2 groups may be replaced by -O-, -SiR'2 , -S-, -NR'— or 60 —CONR'—and in which one or more hydrogenatoms may be replaced by F, or an aryl or heteroaryl group having from 4 to 14 carbon atoms which may be substi tuted by one or more nonaromatic R radicals, and a plurality of R Substituents, either on the same ring or on where the symbols and indices are each defined as follows: 65 the two different rings, may together in turn form one M is Pd or Pt further aliphatic or aromatic, mono- or polycyclic ring X is C1, Br or I; system; US 7,414,133 B2 31 32 R" are the same or different at each instance and are each H plurality of R Substituents, either on the same ring or on or an aliphatic or aromatic hydrocarbon radical having the two different rings, may together in turn form one from 1 to 20 carbon atoms; further aliphatic or aromatic, mono- or polycyclic ring a is 0, 1, 2, 3 or 4; and system; b is 0, 1, 2 or 3. R" are the same or different at each instance and are each H 4. A compound of the formula (5), (6), (7) or (8) or an aliphatic or aromatic hydrocarbon radical having from 1 to 20 carbon atoms; L is an uncharged, monodentate ligand; formula (5) L is a monoanionic, monodentate ligand; (R)a (m-1) 10 e L is an unchanged or mono- or dianionic bidentate ligand; e a is 0, 1, 2, 3 or 4: N b is 0, 1, 2 or 3; and N N 1. (L2)2-m m is 0, 1 or 2. M 5. A compound as claimed in claim 4, characterized in that N Y(L) 15 L is carbon monoxide, an isonitrile, an amine, morpholine, phosphine, aliphatic, aromatic or heteroarornatic phosphines, X eX phosphate, arsine, Stibine, or a nitrogen-containing hetero (R) cycle. formula (6) 6. A compound as claimed in claim 4, characterized in that (R)a (m-1) L is a halide, cyanide, cyanate, isocyanate, thiocyanate, e isothiocyanate, an alkoxide, methanethiolate, ethanethiolate, e r propanethiolate, isopropanethiolate, tert-thiobutoxide, N thiophenoxide, an amide, a carboxylate, propionate, ben N N-(L)-n 25 Zoate, or an anionic nitrogen-containing heterocycle. M Y(L) 7. A compound as claimed in claim 4, characterized in that 1N L is a diamine, cis-, trans-diaminocyclohexane, cis-, trans N.N.N',N'-tetramethyldiaminocyclohexane, imine, dimine, diphosphine, heterocycles containing two nitrogen atoms, X R 30 1,3-diketonates derived from 1,3-diketones, 3-ketonates formula (7) derived from 3-keto esters, carhoxylates derived from ami (R)a -- $0.8- nocarboxylic acids, salicyliminates derived from sali e cylimines, dialkoxides derived from dialcohols, dithiolates e o derived from dithiols heteroarylborate. N s 35 8. A process for preparing the compounds defined in claim M- L3 1, by reacting the compounds (9) or (10)

r compounds (9) X 2x 40 (R) formula (8)

xe -- $0.8- e N s 45 M- L3

50 compounds (10)

where the symbols and indices are each defined as follows: 55 M is Pd or Pt X is C1, Br or I; Y is O, S, Se or NR; R is the same or different at each instance and is H, F, Cl, Br, I., NO, CN, a straight-chain or branched or cyclic 60 alkyl or alkoxy group having 1 to 20 carbon atoms, in which one or more nonadjacent CH2 groups may be replaced by -O-, -SiR' , -S-, -NR'— or in which M and the radicals and indices Y. R. R', a and bare —CONR'—and in which one or more hydrogenatoms each as defined in claim 1 with halogenating agents and may be replaced by F, or an aryl or heteroaryl group 65 Subsequently reducing them. having from 4 to 14 carbon atoms which may be substi 9. A process for preparing the compounds defined in claim tuted by one or more nonaromatic R radicals, and a 3, by reacting the compounds (11) or (12) US 7,414,133 B2 34

-continued compounds (11) compound (16) -- $0.8-

(R) (R) ySS

compounds (12) 15 in which M and the radicals and indices L. L2, La, Y. R. R', a, b and m are each as defined in claim 4, with halogenating agents and Subsequently reducing them. 11. The process as claimed in claim 8, characterized in that the halogenating agent used is a halogen X2 or an interhalo gen X X and a base in a molar ratio of from 1:1 to 1:100, or an organic bromine complex Such as pyridinium perbromide, and in each case optionally a Lewis acid in a molar ratio (halogen to Lewis acid) of from 1:0.1 to 1:0.0001. 25 12. The process as claimed in claim 8, characterized in that in which Mand the radicals and indices Z.Y. R. R', a and bare the halogenating agent used is an organic N-Hal compound. each as defined in claim 3 with halogenating agents and 13. The process as claimed in claim 8, characterized in that Subsequently reducing them. the halogenating agent used comprises organic O-Hal com 10. A process for preparing the compounds defined in 30 pounds and halogens X in a molar ratio of from 0.5:1 to 1:1. claim 4, by reacting the compounds (13), (14), (15) or (16), 14. The process as claimed in claim 11, characterized in that a stoichiometric ratio of the halogenating agents as compound (13) claimed in claim 11 based on the content of active halogen, to (R) (m-I) the compounds (9) and (10), of 2:1 is used. 35 15. The process as claimed in claim 11, characterized in er that a stoichiometric ratio of the halogenating agents as N N N-(L2)2-m claimed in claim 11, based on the content of active halogen, to M the compounds (9) and (10), of from 3:1 to 1000:1 is used. N S(L) 40 16. The process as claimed in claim 11, characterized in that a reducing agent is added to the reaction mixture in a molar ratio of from 1:1 to 10 000:1 based on the compounds 1.x H (R) (9) and (10), and the addition is effected simultaneously with the addition of the halogenating agents (I), (II) or (III), or after compound (14) 45 (m-I) a time delay. "ve3. e 17. The process as claimed in claim 11, characterized in that the reducing agent used is hydrazine (hydrate) or salts N thereof, hydroxylamine or salts thereof, hydroxylamine-O- N 50 Sulfonic acid and hydroquinones, alkali metal and alkaline S. earth metal sulfites, alkali metal and alkaline earth metal Y dithionites, alkali metals and alkaline earth metals and their amalgams and other corresponding alloys, transition metals Such as manganese, iron, nickel and Zinc, and transition metal H R 55 alloys. compound (15) 18. The process as claimed in claim 11, characterized in (R)a -- 0.8- that the reduction may also be effected by dry-heating, under reduced pressure, the palladium(IV) or platinum(VI) com N pounds which have been formed as intermediates and isolated N 60 in Substance. M-L 19. A compound as claimed in claim 1, characterized in that N its purity (determined by means of H NMR or HPLC) is more than 99%. H ex 65 20. A conjugated or semiconjugated or nonconjugated (R) polymer containing one or more compounds of the formula (1") and/or (2) US 7,414,133 B2 35 36

formula (1) -continued formula (4) (R) 5 s 2 N N 21 N M / 7. M 1 10 N/ 4N

R (XX) formula (5) formula (2) 15 (m-1) (R)

N C (L2)2-m22 2O N (L1)m

Y (XX) ex (R) (XX) 25 formula (6') (R)a (m-1) and/or of the formula (1a) and/or (2a") er N

formula (1a) 30 S N 1 (L2)2-m M 1\s n (L1)m

35 (XX) R formula (7) (R)a -- $0.8- (XX) e oe formula (2a") 40 N-N N s"s N M-L 21 45 eX (XX) (R) Y formula (8) (R)a -- $0.8-

(XX) 50 and/or of the formula (3'), (4), (5'), (6'), (7) and/or (8)

55 formula (3)

(XX) R

60 where the symbols and indices are each defined as follows: M is Pd or Pt: Y is O, S, Se or NR'; R is the same or different at each instance and is H, F, Cl, Br, I., NO, CN, a straight-chain or branched or cyclic 65 alkyl or alkoxy group having 1 to 20 carbon atoms, in (XX) which one or more nonadjacent CH2 groups may be replaced by -O-, -SiR'2 , -S-, -NR'— or US 7,414,133 B2 37 38 —CONR'—and in which one or more hydrogenatoms may be replaced by F, or an aryl or heteroaryl group -continued having from 4 to 14 carbon atoms which may be substi

formula (1a) tuted by one or more nonaromatic R radicals, and a 5 plurality of R Substituents, either on the same ring or on the two different rings, may together in turn form one further aliphatic or aromatic, mono- or polycyclic ring system; 10 R" are the same or different at each instance and are each H or an aliphatic or aromatic hydrocarbon radical having from 1 to 20 carbon atoms; L is an uncharged, monodentate ligand; L is a monoanionic, monodentate ligand; 15 L is an uncharged or mono—or dianionic bidentate ligand; formula (2a) a is 0, 1, 2, 3 or 4: b is 0, 1, 2 or 3: m is 0, 1 or 2: n is 1 or 2; (XX) is a bond to the conjugated or semiconjugated or nonconjugated polymer, 25 (XX") is Hora bond to the conjugated or semiconjugated or nonconjugated polymer, but at least one (XX) perfor R mula is a bond to the conjugated or semiconjugated or nonconjugated polymer. 30 21. A polymeras claimed in claim 20, characterized in that formula (3) it has been obtained using one or more compounds of the formula (1), (1a), (2), (2a) and/or (3) to (8) 35

formula (1) 40

formula (4)

formula (2) 55 formula (5) (R)a

60 Y(L)

65 (R) US 7,414,133 B2 39 40 which one or more nonadjacent CH2 groups may be -continued replaced by -O-, -SiR' , -S-, -NR'— or formula (6) —CONR'—and in which one or more hydrogenatoms (m-1) may be replaced by F, or an aryl or heteroaryl group having from 4 to 14 carbon atoms which may be substi tuted by one or more nonaromatic R radicals, and a plurality of R Substituents, either on the same ring or on the two different rings, may together in turn form one further aliphatic or aromatic, mono- or polycyclic ring 10 system; R" are the same or different at eachinstance and are each H or an aliphatic or aromatic hydrocarbon radical having from 1 to 20 carbon atoms; formula (7) L is an uncharged, monodentate ligand; (R)a -- $0.8- 15 L is a monoanionic, monodentate ligand; L is an uncharged or mono- or dianionic bidentate ligand; e o X is H. Cl, Br or I, with the proviso that at least one Xper N-N formula is selected from Cl, Br or I; M- L3 Z is identically F, Cl, Br, I, O-R', S-R' or N(R'); a is 0, 1, 2, 3 or 4: r b is 0, 1, 2 or 3: eX m is 0, 1 or 2 and X (R) n is 1 or 2. 22. A polymer as claimed in claim 20 characterized in that $0.8- formula (8) 25 the polymer contains repeat units taken from polyfluorenes, (R) -$():- polyspirobifluorenes, poly-para-phenylenes, polycarbazoles or polythiophenes. ar 23. A polymeras claimed in claim 20, characterized in that N N the polymer is a homo- or copolymer. 30 24. A polymeras claimed in claim 20, characterized in that the polymer is soluble in organic solvents. 25. An electronic component comprising at least one com pound as claimed in claim 1. 35 26. An electronic component comprising at least one poly meras claimed in claim 20. 27. An electronic component as claimed in claim 25, char where the symbols and indices are each defined as follows: acterized in that it comprises organic or polymeric light M is Pd or Pt emitting diodes (OLEDs or PLEDs), organic integrated cir X is C1, Br or I; cuits (O-ICs), organic field-effect transistors (OFETs), Y is O, S, Se or NR; 40 organic thin-film transistors (OTFTs), organic Solar cells R is the same or different at each instance and is H, F, Cl, (O-SCs) or else organic laser diodes (O-lasers). Br, I, NO, CN, a straight-chain or branched or cyclic alkyl or alkoxy group having 1 to 20 carbon atoms, in k k k k k