WO2009092671A2 - Organic light emitting systems - Google Patents

Organic light emitting systems Download PDF

Info

Publication number
WO2009092671A2
WO2009092671A2 PCT/EP2009/050494 EP2009050494W WO2009092671A2 WO 2009092671 A2 WO2009092671 A2 WO 2009092671A2 EP 2009050494 W EP2009050494 W EP 2009050494W WO 2009092671 A2 WO2009092671 A2 WO 2009092671A2
Authority
WO
WIPO (PCT)
Prior art keywords
substituted
group
alkyl
unsubstituted
ring
Prior art date
Application number
PCT/EP2009/050494
Other languages
French (fr)
Other versions
WO2009092671A3 (en
Inventor
Natalia Chebotareva
Roger PRÉTÔT
Annemarie Wolleb
Heinz Wolleb
Original Assignee
Basf Se
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Se filed Critical Basf Se
Publication of WO2009092671A2 publication Critical patent/WO2009092671A2/en
Publication of WO2009092671A3 publication Critical patent/WO2009092671A3/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/0033—Iridium compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
    • H05B33/28—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode of translucent electrodes

Definitions

  • the present invention pertains to some novel copolymers, processes for their preparation, novel precursors thereof, electroluminiscent materials and electronic devices containing the novel copolymers, and corresponding uses.
  • Organic light emitting devices inter alia require a charge transmitting material and a light emitter connected by a heterojunction in their active layer.
  • Common classes of light emitters include fluorescent and phosphorescent organic (usually organometallic) compounds; an especially efficient class of light emitters is based on phosphorescent metal complexes (see, for example, WO06000544, and publications cited therein). Since application of the 2 materials usually requires differing techniques, and brings about the danger of unwanted phase separation, migration and/or crystallization processes, a number of modifications to such materials have been proposed, such as chemical bonding of some light emitting metal complexes to acrylic copolymers (WO02/031896) or certain fluorescent polyaryls (EP-A- 1 138746, EP-A-1245659).
  • WO02/068435 features some phosphorescent Iridium complexes with recommendation to incorporate them e.g. into polyfluorenes, polycarbazoles, polythiophenes.
  • Some conjugated or semiconducting polymers containing a phosphorescent organometallic compound bonded to the backbone are disclosed in WO03/091355.
  • US-5518824 teaches the in situ preparation of a polymeric charge transport material by radiation induced crosslinking.
  • WO03/001616 describes some reactive electrophosphorescent metal complexes which may be crosslinked or contain oxadiazole (electron transporting) or carbazole (hole transporting) moieties.
  • US-6803124 discloses a number of carbazole copolymers for use in OLEDs based on a monomeric triplet emitter.
  • a 1 is an organic radical of a phosphorescent light emitting moiety
  • a 2 is an organic radical providing host functionality
  • a 3 is an organic radical providing electron transport functionality
  • a 4 is an organic radical providing hole transport functionality
  • a 5 is a radical derived from aliphatic or aromatic organic monomers; x1 is a number from 1 to about 1000; x2, x3, x4 and x5 independently are numbers from 0 to about 100 000, with the proviso that the sum (x1 + x2 + x3 + x4 + x5) is at least 5, especially greater than 9;
  • a 1 is of the formula (I)
  • n is an integer of 1 to 3
  • n1 and n2 are an integer 0, 1 or 2
  • M 1 is a metal with an atomic weight of greater than 40
  • L 1 is a monodentate ligand or a bidentate ligand
  • L 2 is a monodentate ligand
  • Q 1 and Q 2 are independently of each other hydrogen or an organic substituent, or Q 1 and Q 2 together with the carbon atoms, to which they are bonded, form a condensed ring, for example an aromatic or heteroaromatic ring, which optionally may be substituted, or a carbocyclic or heterocyclic, non-aromatic ring, which optionally may be substituted; and
  • Q 3 represents a group of forming a condensed aromatic or heteroaromatic ring, preferably a phenyl or naphthyl ring, which optionally may be substituted, and wherein 1-3, preferably one, of L 1 , L 2 , Q 1 , Q 2 and/or the substituents contains a divalent group derived from a polymerizable aliphatic or aromatic momomer moiety;
  • a 2 is selected from repeating unit(s) of the formula
  • A is a 5-, 6-, or 7-membered heteroaromatic ring, containing at least one heteroatom selected from nitrogen, oxygen and sulfur, especially one nitrogen atom and at least one further heteroatom selected from nitrogen, substituted nitrogen, oxygen and sulfur;
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently of each other hydrogen, halogen, or an organic substituent, or R 1 and R 2 , R 4 and R 6 , R 2 and R 3 , R 5 and R 3 and/or R 5 and R 6 , which are adjacent to each other, together form an aromatic, or heteroaromatic ring, or ring system, which can optionally be substituted; - A -
  • R 7 is an organic substituent, wherein two or more substituents R 7 in the same molecule may have different meanings, or can form together an aromatic, or heteroaromatic ring, or ring system;
  • G a , G 1 , G 2 , G 3 , G 4 , G 1' , G 2' , G 3' and G 4' are independently of each other hydrogen, halogen, especially fluorine, or an organic substituent, or
  • G a , G 1 , G 2 , G 3 , G 4 , G 1' , G 2' , G 3' and G 4' if possible, together form an aromatic, or heteroaromatic ring, or ring system, which can optionally be substituted,
  • G 7 is halogen, especially fluorine, or an organic substituent, wherein two or more substituents G 7 in the same molecule may have different meanings, or can form together an aromatic, or heteroaromatic ring, or ring system, wherein at least one of G a , G 1 , G 2 , G 3 , G 4 , G 1' , G 2' , G 3' and G 4' in a repeating unit is a group R 10 , wherein
  • R 10 is a trivalent group -(Sp) x i 0 -[PG'] ⁇ , wherein x10 is 0, or 1 ; Sp is a spacer unit; PG' is a group derived from a polymerisable group.
  • the present copolymers show especially good results with regard to solution processing or printing (e.g. in case of non-crosslinked copolymers), long-term stability of the electroluminescent device (e.g. resistance against migration/segregation/crystallization as well as against oxidation/heat) as well as its brightness and efficiency.
  • ligand is intended to mean a molecule, ion, or atom that is attached to the coordination sphere of a metallic ion.
  • a "monodentate ligand” contains only 1 coordination site, while a “bidentate ligand” contains 2 coordination sites, both of which are attached to the metallic centre.
  • complex when used as a noun, is intended to mean a compound having at least one metallic ion and at least one ligand.
  • group or “moiety” is intended to mean a part of a compound, such as a substituent in an organic compound or a ligand in a complex.
  • substituted is intended to mean replacement of a hydrogen atom in an organic group or compound by a (typically organic) substituent.
  • organic substituent stands for an organic (i.e. C, H containing) or
  • hetero (hetero)functional radical (e.g. consisting of heteroatoms and optionally either of C or H); usually, any organic substituent, if present, makes up a minor part of the compound; examples for organic substituents are organic radicals containing 1 to 20 carbon atoms and optionally further (e.g. 1-10) heteroatoms, heterofunctional radicals typically comprising 1 to 5 heteroatoms.
  • Heteroatoms in organic or heterofunctional radicals are usually selected from O, S, N, P, Si, B, as well as halogen (i.e. any of F, Cl, Br, I) making up such a radical.
  • Organic substituents if present, preferably are selected from halogen, OH, CrC 24 alkoxy, d- C 24 alkyl, Ci-C 24 haloalkyl, C 2 -C 24 alkenyl, C 2 -C 24 alkynyl, Ci-C 24 alkylthio, Ci-C 24 acyl, C 5 -Ci 0 aryl, Ci-Cioheteroaryl, C 3 -Ci 2 cycloalkyl, Ci-C 24 acyloxy, C 5 -Ci 0 aryloxy, C 3 -Ci 2 cycloalkyloxy, or from the residues COR (i.e.
  • Common substituents are often selected from Ci-Ci 2 alkyl, a hydroxyl group, a mercapto group, Ci-Ci 2 alkoxy, Ci-Ci 2 alkylthio, halogen, halo-Ci-Ci 2 alkyl, a cyano group, an aldehyde group, a ketone group, a carboxyl group, an ester group, a carbamoyl group, an amino group, a nitro group or a silyl group.
  • haloalkyl means groups given by partially or wholly substituting the above-mentioned alkyl group with halogen, the term includes Ci-C 24 perfluoroalkyl, which is branched or unbranched, such as for example -CF 3 (trifluoromethyl), -CF 2 CF 3 , -CF 2 CF 2 CF 3, -CF(CF 3 ) 2 , -(CF 2 ) 3 CF 3 , and -C(CFa) 3 .
  • aldehyde group, ketone group, ester group, carbamoyl group and amino group include those substituted by an Ci-C 24 alkyl group, a C 4 -Ci 8 cycloalkyl group, an C 6 -C 30 aryl group, an C 7 -C 24 aralkyl group or a heterocyclic group, wherein the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group and the heterocyclic group may be unsubstituted or substituted.
  • sil group more specifically means a group of formula -SiR 105 R 106 R 107 , wherein R 105 , R 106 and R 107 are independently of each other a Ci-C 8 alkyl group, in particular a CrC 4 alkyl group, a C 6 -C 24 aryl group or a C 7 -Ci 2 aralkylgroup, such as a trimethylsilyl group.
  • a substituent occurs more than one time in a group, it can be different in each occurrence.
  • alkyl whereever used, thus mainly embraces especially uninterrupted and, where appropriate, substituted Ci-C 22 alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, sec- butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1 ,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3-tetramethylbutyl, 1-methylheptyl, 3- methylheptyl, n-octyl, 2-ethylhexyl, 1 ,1 ,3-trimethylhexyl, 1 ,1 ,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl
  • alkenyl whereever used, thus mainly embraces especially uninterrupted and, where appropriate, substituted C 2 -C 22 alkenyl such as vinyl, allyl, etc.
  • Alkynyl including C 2 - 24 alkynyl, is straight-chain or branched, preferred is C 2 - 8 alkynyl.
  • any alkyl or alkylene moiety of more than one, especially more than 2 carbon atoms, or such alkyl or alkylene moieties which are part of another moiety may be interrupted by a non-aromatic cyclic or aromatic cyclic (arylene or heteroarylene) moiety as defined below and/or preferably by a heterofunction such as O, S, CO, COO, OCNR22, OCOO, OCONR22, NR22CNR22, or NR22, where R22 is H, C r Ci 2 alkyl, C 3 -Ci 2 cycloalkyl, phenyl.
  • They can be interrupted by one or more of these spacer groups, one group in each case being inserted, in general, into one carbon-carbon bond, with hetero-hetero bonds, for example 0-0, S-S, NH-NH, etc., not occurring; if the interrupted alkyl is additionally substituted, the substituents are generally not ⁇ to the heteroatom. If two or more interrupting groups of the type -0-, -NR22-, -S- occur in one radical, they often are identical.
  • Acyl stands for a residue of an organic carboxylic acid, from which it may be formally derived by abstraction of the acid OH; examples are formyl, acetyl, propionyl, benzoyl.
  • d- Ci8 acyl stands for a radical X'-R 2 i, wherein X' is CO or SO 2 and R 2 i is selected from monovalent aliphatic or aromatic organic residues, usually from molecular weight up to 300; for example, R 2 i may be selected from CrCi 8 alkyl, C 2 -Ci 8 alkenyl, C 5 -Ci 0 aryl which may be unsubstituted or substituted by Ci-C 8 alkyl or halogen or d-C 8 alkoxy, C 6 -Ci 5 arylalkyl which may be unsubstituted or substituted in the aromatic part by Ci-C 8 alkyl or halogen or d- C 8 alkoxy, C 4 -Ci 2
  • Acyl is preferably an aliphatic or aromatic residue of an organic acid -CO-R 2 - I , usually of 1 to 30 carbon atoms, wherein R 21 embraces aryl, alkyl, alkenyl, alkynyl, cycloalkyl, each of which may be substituted or unsubstituted and/or interrupted as described elsewhere inter alia for alkyl residues, or R' may be H (i.e. COR' being formyl).
  • Preferences consequently are as described for aryl, alkyl etc.; more preferred acyl residues are substituted or unsubstituted benzoyl, substituted or unsubstituted Ci-Ci 7 alkanoyl or alkenoyl such as acetyl or propionyl or butanoyl or pentanoyl or hexanoyl, substituted or unsubstituted C 5 -Ci 2 cycloalkylcarbonyl such as cyclohexylcarbonyl.
  • Aralkyl is, within the definitions given, usually selected from C 7 -C 24 aralkyl radicals, preferably C 7 -Ci 5 aralkyl radicals, which may be substituted, such as, for example, benzyl, 2-benzyl-2- propyl, ⁇ -phenethyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, ⁇ -phenyl-butyl, ⁇ -phenyl-octyl, ⁇ -phenyl-dodecyl; or phenyl-Ci-C 4 alkyl substituted on the phenyl ring by one to three Cr C 4 alkyl groups, such as, for example, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2,4- dimethylbenzyl, 2,6-dimethylbenzyl or 4-tert-butylbenzyl.or 3-methyl-5-(1 ',1',3',3'-tetramethyl-
  • Non-aromatic cyclic (i.e. cycloaliphatic) moieties include cycloalkyl, aliphatic heterocyclic moieties, as well as unsaturated variants thereof such as cycloalkenyl.
  • Cycloalkyl such as C 3 -Ci 8 cycloalkyl, is preferably C 3 -Ci 2 cycloalkyl or said cycloalkyl substituted by one to three Ci-C 4 alkyl groups, and includes cyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tert-butylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cyclododecyl, 1-
  • C 3 - Ci 2 cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl; preferred among these residues are C 3 - C ⁇ cycloalkyl as well as cyclododecyl, especially cyclohexyl.
  • heterocyclic aliphatic rings usually containing 5 to 7 ring members, among them at least 1 , especially 1-3, heteromoieties, usually selected from O, S, NR22, where R22 is as explained above for interrupting NR22-groups; examples include C 4 -Ci 8 cycloalkyl, which is interrupted by S, O, or NR22, such as piperidyl, tetrahydrofuranyl, piperazinyl and morpholinyl.
  • Unsaturated variants may be derived from these structures by abstraction of a hydrogen atom on 2 adjacent ring members with formation of a double bond between them.; an example for such a moiety is cyclohexenyl.
  • aryl e.g. in C 5 -Ci 0 aryl, Ci-Ci 4 -heteroaryl
  • aryl denotes an aromatic ring or polycyclic ring system containing the highest possible number of double bonds, such as preferably phenyl, naphthyl, anthrachinyl, anthracenyl, phenanthrenyl or fluorenyl.
  • aryl mainly embraces hydrocarbon aromatic rings, examples mainly are C 6 -Ci 8 aryl including phenyl, naphthyl, anthrachinyl, anthracenyl, phenanthrenyl, fluorenyl.
  • Heteroaromatic rings such as Ci-Ci8heteroaryl moieties contain, as part of the ring structure, one or more heteroatoms mainly selected from O, N and S; heteroaryl such as C 4 -Ci8heteroaryl stands for an aryl group containing at least one heteroatom, especially selected from N, O, S, among the atoms forming the aromatic ring; examples include pyridyl, pyrimidyl, pyridazyl, pyrazyl, thienyl, benzothienyl, pyrryl, furyl, benzofuryl, indyl, carbazolyl, benzotriazolyl, thiazolyl, chinolyl, isochinolyl, triazinyl, tetrahydronaphthyl, thienyl, pyrazolyl, imidazolyl.
  • heteroaryl such as C 4 -Ci8heteroaryl stands for an ary
  • C 6 -Ci 0 aryl or C 4 -Ci 8 heteroaryl e.g. selected from phenyl, naphthyl, pyridyl, tetrahydronaphthyl, furyl, thienyl, pyrryl, chinolyl, isochinolyl, anthrachinyl, anthracenyl, phenanthrenyl, pyrenyl, benzothiazolyl, benzoisothiazolyl, benzothienyl, especially C 6 - Cioaryl; most preferred is phenyl, naphthyl. Any "arylene” stands for the corresponding divalent "aryl”.
  • the structural units (organic radicals) A 1 -A 5 making up the present copolymer are generally derived from polymerizable aliphatic or aromatic monomers. These monomers mainly include those known in the art to undergo condensation or especially addition polymerization reactions; examples are monomers containing one or more polymerizable groups (PG) such as ethylenically unsaturated moieties or strained ring systems.
  • PG polymerizable groups
  • PG' is a group derived from a polymerisable group
  • R 212 -AHG AHG is an aromatic, or heteroaromatic residue, which can optionally be substituted, such as
  • R 211 and R 212 are independently of each other halogen, -C ⁇ CH, boronic acid, or boronic esters, -Mg-HaI, -Zn-HaI, -Sn (R 213 ) 3 , wherein Hal is halogen, and R 213 is d-Ci 8 alkyl,
  • R 214 and R 214 are independently of each other H, Ci-Cisalkyl, d-C-isalkyl which is interrupted by D, Ci-Ci8perfluoroalkyl, d-Ci 8 alkoxy, Ci-Ci 8 alkoxy which is interrupted by D, or C 7 -
  • Examples for preferred groups PG are vinyl, allyl, (meth)acryloyl, styryl, oxetanyl, oxiranyl, glycidyl.
  • nickel-coupling reaction was disclosed by Yamamoto in Progress in Polymer Science 17 (1992) 1153 wherein a mixture of dihaloaromatic compounds was treated with an excess amount of nickel (1 ,5-cyclooctadiene) complex in an inert solvent. All nickel-coupling reactions when applied to reactant mixtures of two or more aromatic dihalides yield essentially random copolymers. Such polymerization reactions may be terminated by the addition of small amounts of water to the polymerization reaction mixture, which will replace the terminal halogen groups with hydrogen groups. Alternatively, a monofunctional aryl halide may be used as a chain-terminator in such reactions, which will result in the formation of a terminal aryl group.
  • Nickel-coupling polymerizations may yield random copolymers, e.g. comprising units of formula I, III, IV and/or units derived from other co-monomers.
  • the desired functional moieties of the present copolymers may be provided as an integral part of the copolymer's main chain, or may be attached as a side chain to the copolymer's main chain.
  • the latter architecture brings about some advantages, e.g. in the synthesis of the compounds since it opens the possibility to attach the desired functionality via grafting reactions, and simplifies certain in situ formations of the desired polymers, e.g. by coating the substrate with a suitable monomer mixture, with or without addition of a photoinitiator, and polymerizing the mixture by exposure to radiation (e.g. UV, electron beam etc.) and/or temperature.
  • radiation e.g. UV, electron beam etc.
  • the present copolymers may be linear or crosslinked.
  • crosslinked copolymers a certain fraction of the monomers making up the present copolymer are crosslinkers (crosslinking agents), usually containing 2 or more polymerizable groups.
  • Preferred copolymers of the present invention have a glass transition temperature above 100 0 C.
  • Another aspect of this invention is related to polymer blends containing 1 to 99 percent of at least one copolymer of the invention. The remainder 1 to 99 percent of the blend is composed of one or more polymeric materials selected from among chain growth polymers such as polystyrene, polybutadiene, poly(methyl methacrylate), and poly(ethylene oxide); step-growth polymers such as phenoxy resins, polycarbonates, polyamides, polyesters, polyurethanes, and polyimides; and crosslinked polymers such as crosslinked epoxy resins, crosslinked phenolic resins, crosslinked acrylate resins, and crosslinked urethane resins.
  • chain growth polymers such as polystyrene, polybutadiene, poly(methyl methacrylate), and poly(ethylene oxide)
  • step-growth polymers such as phenoxy resins, polycarbonates, polyamides, polyesters, polyurethanes, and polyimides
  • poly(phenylene vinylene), substituted poly(phenylene vinylene)s, substituted polyphenylenes and polythiophenes examples of these conjugated polymers are given by Greenham and Friend in Solid State Physics, Vol. 49, pp. 1-149 (1995).
  • electroluminescent materials of the invention often contain at least one further component, especially selected from triplett emitters, electron transporters, hole transporters, inert polymers (such as aromatic homo- or copolymers like polystyrene or further polymers listed above, e.g. as viscosity modifiers), initiators, organic salts (especially if soluble in the matrix, e.g. organic ammonium salts).
  • the electroluminescent materials of the invention thus often contain 1 to 99 percent of at least one copolymer of the invention, and 99 to 1 percent of one or more of the additional (auxiliary) components listed above, which often will make up the remainder of the material.
  • Monomers for the preparation of linear copolymers usually contain only 1 class of polymerizable group and only 1 PG per monomer unit, or for grafting one or more further class(es) of PGs.
  • Crosslinkers i.e. monomers suitable to provide crosslinking of the final copolymer product
  • PGs which may be of the same class (such as ethylenically unsaturated groups; example: divinylbenzene) or 2 or more different classes of PGs (such as an ethylenically unsaturated group and a strained ring; example: vinylbenzene-Sp-oxetanyl).
  • Any of the structural units A 1 , A 2 , A 3 , A 4 , A 5 may function as a crosslinker.
  • Any moiety containing a divalent group derived from a polymerizable aliphatic or aromatic monomer thus typically is a group R 10 : -(Sp) x i 0 -[PG'] ⁇ , wherein x10 is 0, or 1.
  • the spacer unit Sp which may be present in the group R 10 , typically is of the formula wherein x11 is 0 or 1 ;
  • X 3 , X 2 independently are O, Ci-C 4 alkylene-O, S, Ci-C 4 alkylene-S, NR22, Ci-C 4 alkylene-NR22, COO, C r C 4 alkylene-COO or C r C 4 alkylene-OCO, CONR22, C 1 - C 4 alkylene-CONR22 or C r C 4 alkylene-NR22CO, NR22CONR22, C r C 4 alkylene- NR22CONR22, C r C 4 alkylene, or a direct bond, and
  • D is CrC 24 alkylene, interrupted C 3 -C 24 alkylene, C 2 -C 24 alkenylene, C 2 -C 24 alkynylene, C 6 - Cioarylene.
  • PG' is a group derived from a polymerisable group, it is trivalent since it is anchored on Sp (or its anchor position in formula (I), (II) or (IV)) and it is integrated in the copolymer chain, or crosslinked copolymer network, of the present invention.
  • a typical group of moieties PG' thus are derived from ethylenically unsaturated monomers or strained oxygen ring systems, including those of the formulae
  • moieries PG' are those derived from from moieties PG described further above, e.g. those introducing the desired functionalities into the main chain of the copolymer of the invention. More specific copolymers of the invention comprise
  • a 1 is an organic radical of a phosphorescent light emitting moiety
  • x1 is a number from 1 to about 1000
  • x2, x3, x4 and x5 independently are numbers from 0 to about 100 000, with the proviso that the sum (x2 + x3 + x4 + x5) is at least 5, especially greater than 9;
  • a 2 , A 3 , A 4 and A 5 independently are radicals derived from aliphatic or aromatic monomers
  • a 1 is of the formula (I)
  • n is an integer of 1 to 3
  • n1 and n2 are an integer 0, 1 or 2
  • M 1 is a metal with an atomic weight of greater than 40
  • L 1 is a monodentate ligand or a bidentate ligand
  • L 2 is a monodentate ligand
  • Q 1 and Q 2 are independently of each other hydrogen or an organic substituent, or
  • Q 1 and Q 2 together with the carbon atoms, to which they are bonded, form a condensed ring, for example an aromatic or heteroaromatic ring, which optionally may be substituted, or a carbocyclic or heterocyclic, non-aromatic ring, which optionally may be substituted; and
  • Q 3 represents a group of forming a condensed aromatic or heteroaromatic ring, preferably a phenyl or naphthyl ring, which optionally may be substituted, and wherein 1-3, preferably one, of L 1 , L 2 , Q 1 , Q 2 and/or the substituents contains a divalent group derived from a polymerizable aliphatic or aromatic monomer moiety; orand, in case that x2 is at least 1 , and A 2 is selected from repeating unit(s) of the formula
  • M 1 is as defined above; each of L and L 1 is a monodentate ligand or a bidentate ligand; L 2 is a monodentate ligand; and at least one of L, L 1 and L 2 contains a divalent group derived from a polymerizable aliphatic or aromatic momomer moiety;
  • A is a 5-, 6-, or 7-membered heteroaromatic ring, containing at least one heteroatom selected from nitrogen, oxygen and sulfur, especially one nitrogen atom and at least one further heteroatom selected from nitrogen, substituted nitrogen, oxygen and sulfur;
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently of each other hydrogen, halogen, or an organic substituent, or
  • R 1 and R 2 , R 4 and R 6 , R 2 and R 3 , R 5 and R 3 and/or R 5 and R 6 which are adjacent to each other, together form an aromatic, or heteroaromatic ring, or ring system, which can optionally be substituted;
  • R 7 is an organic substituent, wherein two or more substituents R 7 in the same molecule may have different meanings, or can form together an aromatic, or heteroaromatic ring, or ring system;
  • G a , G 1 , G 2 , G 3 , G 4 , G 1' , G 2' , G 3' and G 4' are independently of each other hydrogen, halogen, especially fluorine, or an organic substituent, or
  • G a , G 1 , G 2 , G 3 , G 4 , G 1' , G 2' , G 3' and G 4' if possible, together form an aromatic, or heteroaromatic ring, or ring system, which can optionally be substituted,
  • G 7 is halogen, especially fluorine, or an organic substituent, wherein two or more substituents
  • G 7 in the same molecule may have different meanings, or can form together an aromatic, or heteroaromatic ring, or ring system, wherein at least one of G a , G 1 , G 2 , G 3 , G 4 , G 1' , G 2' , G 3' and G 4' in a repeating unit is a group R 10 , wherein
  • R 10 is a trivalent group -(Sp) x i 0 -[PG'] ⁇ , wherein x10 is 0, or 1 ;
  • Sp is a spacer unit
  • PG' is a group derived from a polymerisable group
  • a 1 as the phosphorescent light emitting moiety contains a metal M 1 selected from the group consisting of Fe, Ru, Ni, Cu, Co, Ir, Pt, Pd, Rh, Re, Os,TI, Pb, Bi, In, Sn, Sb, Te, Ag and Au; and any substituent, if present, is selected from halogen, OH, CrC 24 alkoxy, CrC 24 alkyl, d-
  • C 24 haloalkyl C 2 -C 24 alkenyl, C 2 -C 24 alkynyl, Ci-C 24 alkylthio, Ci-C 24 acyl, C 5 -Ci 0 aryl, d-
  • R, R' and R" independently are selected from Ci-Ci 2 alkyl, Ci-Ci 2 haloalkyl, C 5 -Ci 0 aryl,
  • the invention includes a process for the preparation of the present copolymers, electronic devices comprising them, as well as their use in electronic devices, especially organic light emitting diodes (OLEDs), as oxygen sensitive indicators, as phosphorescent indicators in bioassays, and as catalysts.
  • OLEDs organic light emitting diodes
  • the present invention is directed to copolymers comprising a metal complex containing at least one ligand derived from (2H-benzo)triazole, as well as to copolymers comprising, besides a metal complex, a heteroaryl-derivate of phenanthrene.
  • a 1 as an organic radical of a phosphorescent light emitting moiety may be selected from moieties of the formula (II)
  • the metal is generally a metal M 1 with an atomic weight of greater than 40.
  • the metal M 1 is selected from the group consisting of Fe, Ru, Ni, Cu, Co, Ir, Pt, Pd, Rh, Re, Os 1 TI, Pb, Bi, In, Sn, Sb, Te, Ag and Au.
  • the metal is selected from Ir, Rh and Re as well as Pt and Pd, wherein Ir is most preferred.
  • a bidentate ligand containing a divalent group derived from a polymerizable aliphatic or aromatic momomer moiety may be selected from:
  • ring A represents an optionally substituted aryl group which may contain a heteroatom
  • ring B represents an optionally substituted nitrogen containing aryl group, which may contain further heteroatoms,
  • ring C represents a ligand derived from a nucleophilic carbene, which may contain a heteroatom
  • Y-Z " is a group R 10 of the formula -(Sp) x i 0 -[PG'] ⁇ , as defined above;
  • R 11 is unsubstituted or substituted Ci-C 4 alkyl
  • R 12 is CF 3 or a ring A;
  • R 13 is H, unsubstituted or substituted CrC 4 alkyl
  • R 14 , R 14 independently are a ring A, unsubstituted or substituted Ci-C 8 alkyl, d-
  • W is N or CH.
  • Preferred metal complex moieties including A 1 , and formulae (I) and (II), are electroneutral, i.e. wherein the total charge of ligands balances the charge of the central metal atom.
  • ligands especially in moieties of the formula (II), may be selected from those of the above formulae IX-1 to IX-17 wherein Y-Z " is hydrogen.
  • Bidentate ligands of specific interest are often selected from (2H-benzo)triazole, o- phenylpyridine, each of which may be unsubstituted or substituted.
  • Moieties A 1 containing 2 or 3 bidentate ligands are preferred. Likewise preferred are moieties A 1 containing at least one bidentate ligand of the class 2-aryl-1 ,2,3-triazole as contained in the formula (I)
  • Q 1 and Q 2 together with the carbon atoms, to which they are bonded, form a condensed ring, for example an aromatic or heteroaromatic ring, which optionally may be substituted, or a carbocyclic or heterocyclic, non-aromatic ring, which optionally may be substituted; and Q 3 represents a group of forming a condensed aromatic or heteroaromatic ring, preferably a phenyl or naphthyl ring, which optionally may be substituted, and wherein Q 1 , Q 2 and/or the substituents contains a group Y-Z " which is H or is derived from a polymerizable aliphatic or aromatic momomer moiety such as a group R 10 as defined above.
  • a preferred class of structural units A 1 are of the formula (I).
  • Q 1 and Q 2 together with the carbon and nitrogen atoms, to which they are bonded, often form a group , wherein Q 4 represents a group of forming a condensed aromatic, or heteroaromatic ring, which can optionally be substituted.
  • Some phosphorescent moieties A 1 of specific interest contain a bidentate ligand L 1 , which conforms to the formula (LII)
  • W is selected from O, S, NR 4 , CR 5 R 6 , X is N or CR 7 , Y is selected from O, S, NR 8 ;
  • Ri, R 2 , R 4 , R 5 , R 6 independently are H, unsubstituted or substituted CrCi 8 alkyl, unsubstituted or substituted C 2 -Ci 8 alkenyl, unsubstituted or substituted C 5 -Ci 0 aryl, unsubstituted or substituted C 2 -Ci 0 heteroaryl, Ci-Ci 8 acyl, or R 10 ;
  • R 1 , R 2 may stand for a substituent ; or the neighbouring residues R 1 and R 2 form an organic bridging group completing, together with the carbon atoms they are bonding to, a carbocyclic or heterocyclic, non-aromatic or preferably aromatic ring of 5 to 7 ring atoms in total, which optionally may be substituted;
  • R 7 if present, together with its neighbouring residue R 3 forms an organic bridging group completing, with the carbon atoms they are bonding to, a carbocyclic or heterocyclic, non- aromatic or preferably aromatic ring of 5 to 7 ring atoms in total, which optionally may be substituted; or R 7 embraces the meanings given for R 4 , or is halogen, OR, SR, NRR', COOR, CONRR', CN, OCN, SCN, or is C 2 -C 5 alkynyl, C 3 -C 5 cycloalkyl, hetero-C 2 -C 5 cycloalkyl, or C 3 -C 5 cycloalkenyl, each unsubstituted or substituted; or R 3 is H, unsubstituted or substituted Ci-Ci 8 alkyl, unsubstituted or substituted C 2 - Ci 8 alkenyl, unsubstituted or substituted C 5 -Cioaryl, un
  • R' 3 is unsubstituted or substituted CrCi 8 alkylene, unsubstituted or substituted C 2 - Ci 8 alkenylene, unsubstituted or substituted C 5 -Ci 0 arylene, unsubstituted or substituted C 2 - Cioheteroarylene, C 2 -Ci 8 diacylene;
  • R' 3 is unsubstituted or substituted Ci-Ci 8 alkylene, unsubstituted or substituted C 2 - Ci 8 alkenylene, unsubstituted or substituted C 5 -Ci 0 arylene, unsubstituted or substituted C 2 - Cioheteroarylene, C 2 -Ci 8 diacylene; R 8 is hydrogen or a substituent.
  • a 2 as an organic radical providing host functionality may be selected from suitable divalent radicals providing the desired functionality in the main chain (as in the units of formulae III, Ilia and 1Mb above), or corresponding radicals in the side chain (as in formula IV).
  • the ring A in units A 2 as of the above formulae IN-IV often is selected from A is a 5-, 6-, or 7- membered heteroaromatic ring, containing at least one heteroatom selected from nitrogen, oxygen and sulphur, which can be substituted and/or can be part of a fused aromatic or heteroaromatic ring system.
  • A is a 5-, 6-, or 7- membered heteroaromatic ring, containing at least one heteroatom selected from nitrogen, oxygen and sulphur, which can be substituted and/or can be part of a fused aromatic or heteroaromatic ring system.
  • Non-limiting examples of A are:
  • R 8 , R 8' has the meaning of R 8
  • X is O, S, N-R 17
  • R 205 , R 206 , R 207 , R 208 , R 209 , R 210 , R 8 , R 9 , R 9' , R 9 " , R", R 99' , R 10 and R 17 are as defined below
  • p' is 0, 1 , or 2 and the dotted line indicates the bonding to the benzene ring.
  • A is one of the above 5-, 6-, or 7-membered heteroaromatic rings, containing one nitrogen atom and at least one further heteroatom selected from nitrogen, oxygen and sulphur.
  • R 1 and R 4 are independently of each other hydrogen, halogen, CrCi 8 alkyl, d-Ci 8 alkyl which is substituted by E and/or interrupted by D, Ci-Ci 8 perfluoroalkyl, C 2 -Ci 8 alkenyl, C 2 -Ci 8 alkynyl, d-Ci 8 alkoxy, Ci-Ci 8 alkoxy which is substituted by E and/or interrupted by D, CN, or -CO-R 28 , R 2 , R 3 R 5 and R 6 are independently of each other H, halogen, Ci-Ci 8 alkyl, Ci-Ci 8 alkyl which is substituted by E and/or interrupted by D, Ci-Ci 8 perfluoroalkyl, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 20 heteroaryl, C 2 -C 20 heteroaryl which is substituted by G, C 2 -
  • R and R together form a group , wherein R 206' R 208' R 205 , R 206 , R 207 , R 208 , R 209 and R 210 are independently of each other H, d-C 18 alkyl, Ci-Ci 8 alkyl which is substituted by E and/or interrupted by D, Ci-Ci 8 alkoxy, or d-Ci 8 alkoxy which is substituted by E and/or interrupted by D, Ci-Ci 8 perfluoroalkyl, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 2 oheteroaryl, C 2 -C 2 oheteroaryl which is substituted by G, C 2 - Ci 8 alkenyl, C 2 -Ci 8 alkynyl, C 7 -C 25 aralkyl, CN, or -CO-R 28 ,
  • R 110 is H, Ci-Ci 8 alkyl, Ci-Ci 8 alkyl which is substituted by E and/or interrupted by D, d- Ci 8 perfluoroalkyl, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 20 heteroaryl, C 2 - C 20 heteroaryl which is substituted by G, C 2 -Ci 8 alkenyl, C 2 -Ci 8 alkynyl, Ci-Ci 8 alkoxy, d- Ci 8 alkoxy which is substituted by E and/or interrupted by D, C 7 -C 25 aralkyl, or -CO-R 28 , R 11 and R 14 are independently of each other hydrogen, halogen, Ci-Ci 8 alkyl, Ci-Ci 8 alkyl which is substituted by E and/or interrupted by D, Ci-Ci 8 perfluoroalkyl, C 2 -Ci 8 alkenyl, C 2 - Ci 8 al
  • C 20 heteroaryl which are substituted by Ci-Ci 8 alkyl, Ci-Ci 8 perfluoroalkyl, or Ci-Ci 8 alkoxy; d- Ci 8 alkyl; or Ci-Ci 8 alkyl which is interrupted by -O-; or two substituents R 2 and R 3 , R 5 and R 6 , R 12 and R 13 and/or R 15 and R 16 , R 1 and R 2 , R 4 and R 6 , R 11 and R 12 and/or R 14 and R 16 , which are adjacent to each other, together form a group
  • R 121 and R 122 are independently of each other H, Ci-Ci 8 alkyl, Ci-Ci 8 alkyl which is substituted by E and/or interrupted by D, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, or C 2 -
  • R 119 and R 120 together form a five or six membered ring, which optionally can be substituted by Ci-Ci 8 alkyl, Ci-Ci 8 alkyl which is substituted by E and/or interrupted by D, C 6 -C 24 aryl, C 6 -
  • R 127 is H; C 6 -Ci 8 aryl; C 6 -Ci 8 aryl which is substituted by Ci-Ci 8 alkyl, or Ci-Ci 8 alkoxy; d- Ci 8 alkyl; or Ci-Ci 8 alkyl which is interrupted by -O-,
  • E is -OR 29 ; -SR 29 ; -NR 25 R 26 ; -COR 28 ; -COOR 27 ; -CONR 25 R 26 ; -CN; or halogen;
  • G is E, d-
  • Ci 8 alkyl Ci-Ci 8 alkyl which is interrupted by D
  • Ci-Ci 8 perfluoroalkyl Ci-Ci 8 alkoxy
  • Ci-Ci 8 alkoxy Ci-Ci 8 alkoxy which is substituted by E and/or interrupted by D
  • R 23 , R 24 , R 25 and R 26 are independently of each other H; C 6 -d 8 aryl; C 6 -d 8 aryl which is substituted by Ci-Ci 8 alkyl, or Ci-Ci 8 alkoxy; Ci-Ci 8 alkyl; or Ci-Ci 8 alkyl which is interrupted by
  • R 25 and R 26 together form a five or six membered ring, in particular
  • R ⁇ ' and R ⁇ b are independently of each other H; C 6 -d 8 aryl; C 6 -d 8 aryl which is substituted by Ci-Ci 8 alkyl, or Ci-Ci 8 alkoxy; Ci-Ci 8 alkyl; or Ci-Ci 8 alkyl which is interrupted by -0-, R 29 is H; C 6 -Ci 8 aryl; C 6 -Ci 8 aryl, which is substituted by Ci-Ci 8 alkyl, or d-Ci 8 alkoxy; d-
  • Ci 8 alkyl or Ci-Ci 8 alkyl which is interrupted by -O-,
  • R 30 and R 31 are independently of each other Ci-Ci 8 alkyl, C 6 -Ci 8 aryl, or C 6 -Ci 8 aryl, which is substituted by Ci-Ci 8 alkyl, and
  • R 32 is Ci-Ci 8 alkyl, C 6 -Ci 8 aryl, or C 6 -Ci 8 aryl, which is substituted by Ci-Ci 8 alkyl.
  • R 2 , R 3 R 5 and R 6 are independently of each other H, C r Ci 8 alkyl, C r Ci 8 alkyl which is interrupted by D, Ci-Ci 8 perfluoroalkyl, Ci-Ci 8 alkoxy, Ci-Ci 8 alkoxy which is interrupted by D, C 7 -C 25 aralkyl, or a group -X 2 -R 18 , R 8 and R 9 are independently of each other H, Ci-Ci 8 alkyl, Ci-Ci 8 alkyl which is interrupted by D, Ci-Ci 8 perfluoroalkyl, Ci-Ci 8 alkoxy, Ci-Ci 8 alkoxy which is interrupted by D, or a group -X 2 - R 18 , wherein X 2 is a spacer, such as C 6 -Ci 2 aryl, or C 6 -Ci 2 heteroaryl, especially phenyl, or naphthyl, which can be substituted one more, especially one to two times with Ci-C
  • R 105 , R 106 , R 107 and R 108 are independently of each other H, or Ci-C 8 alkyl, or R 8 and R 9 together form a group
  • R 209 and R 210 are independently of each other H, Ci-Ci 8 alkyl, d-Ci 8 alkyl which is substituted by E and/or interrupted by D, Ci-Ci 8 alkoxy, or d-Ci 8 alkoxy which is substituted by E and/or interrupted by D, Ci-Ci 8 perfluoroalkyl
  • R 110 is H, C 6 -Ci 8 aryl, which can be substituted by G, C 2 -Ci 8 heteroaryl, which can be substituted by G, Ci-Ci 8 alkyl, Ci-Ci 8 alkyl which is interrupted by D, Ci-Ci 8 perfluoroalkyl, d- Ci 8 alkoxy, Ci-Ci 8 alkoxy which is substituted by E and/or interrupted by D, or a group -X 2 - R 18 , wherein X 2 is a spacer, such as C 6 -Ci 2 aryl, or C 6 -Ci 2 heteroaryl, especially pheny
  • R 25 and R 26 together form a five or six membered ring, in particular
  • R 1 and R 1 are independently of each other hydrogen, halogen, CrCi 8 alkyl, d-Ci 8 alkyl which is substituted by E and/or interrupted by D, Ci-Ci 8 perfluoroalkyl, C 2 -Ci 8 alkenyl, C 2 -Ci 8 alkynyl, Ci-Ci 8 alkoxy, Ci-Ci 8 alkoxy which is substituted by E and/or interrupted by D, CN, or -CO-R 28 , R 2 , R 3 R 4 , R 2' , R 3' and R 4' are independently of each other H, halogen, C r Ci 8 alkyl, d- Ci 8 alkyl which is substituted by E and/or interrupted by D, Ci-Ci 8 perfluoroalkyl, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 2 oheteroaryl, C 2 -C 2 oheteroary
  • R 8 is H, Ci-Ci 8 alkyl, Ci-Ci 8 alkyl which is substituted by E and/or interrupted by D, d- Ci 8 perfluoroalkyl, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 20 heteroaryl, C 2 - C 20 heteroaryl which is substituted by G, C 2 -Ci 8 alkenyl, C 2 -Ci 8 alkynyl, Ci-Ci 8 alkoxy, d- Ci 8 alkoxy which is substituted by E and/or interrupted by D, C 7 -C 25 aralkyl, CN, or -CO-R 28 , R 9 , R 9' , R 9 " , R” and R 99' is H, C r Ci 8 alkyl, R 10 , C r Ci 8 alkyl which is substituted by E and/or interrupted by D, Ci-Ci 8 perfluoroalkyl, C 6 -C
  • R 10 is a group -(Sp) x i 0 -[PG'] ⁇ , wherein Sp is a spacer unit, PG' is a group derived from a polymerisable group, with preferences as described above, and x10 is 0, or 1 , or
  • R and R together form a group , wherein one of the substituents R 205 , R 206 , R 207 and R 208 , and one of the substituents R 209 and R 210 is a group R 10 and the other substituents are independently of each other H, Ci-Ci 8 alkyl, Ci-Ci 8 alkyl which is substituted by E and/or interrupted by D, Ci-Ci 8 alkoxy, or Ci-Ci 8 alkoxy which is substituted by E and/or interrupted by D,
  • R and R ⁇ > i r are independently of each other hydrogen, halogen, especially fluorine, d- Ci 8 alkyl, Ci-Ci 8 alkyl which is substituted by E and/or interrupted by D, Ci-Ci 8 perfluoroalkyl, C 2 -Ci 8 alkenyl, R 10 , C 2 -Ci 8 alkynyl, Ci-Ci 8 alkoxy, Ci-Ci 8 alkoxy which is substituted by E and/or interrupted by D, CN, or -CO-R 28 , SiRR'R", GeRR'R", POAr 2 , PAr 2 ;
  • R 12 , R 13 R 14 , R 12' , R 13' and R 14' are independently of each other H, halogen, especially fluorine, Ci-Ci 8 alkyl, R 10 , CrCi 8 alkyl which is substituted by E and/or interrupted by D, d-
  • Ci 8 alkoxy which is substituted by E and/or interrupted by D, C 7 -C 25 aralkyl, CN or -CO-R 28 , and R 13 R 14 , R 13' and R 14' may also be SiRR'R", GeRR'R", POAr 2 , PAr 2 ;
  • X is O, S, or NR 17 , wherein R 17 is Ci-Ci 8 alkyl, Ci-Ci 8 alkyl which is substituted by E and/or interrupted by D, Ci-Ci 8 perfluoroalkyl, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -
  • C 20 heteroaryl C 2 -C 20 heteroaryl which is substituted by G, C 2 -Ci 8 alkenyl, C 2 -Ci 8 alkynyl, C 7 -
  • R , R and R which are adjacent to each other, together form a group , or
  • R 121 and R 122 are independently of each other H, Ci-Cisalkyl, Ci-C- ⁇ 8 alkyl which is substituted by E and/or interrupted by D, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, or C 2 - C 2 oheteroaryl, or C 2 -C 20 heteroaryl which is substituted by G, or R 119 and R 120 are independently of each other H, Ci-Ci 8 alkyl, d-Ci 8 alkyl which is substituted by E and/or interrupted by D, C6-C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 - C 20 heteroaryl, C 2 -C 20 heteroaryl which is substituted by G, C 2 -Ci 8 alkenyl, C 2 -Ci 8 alkynyl, d- Ci 8 alkoxy, Ci-Ci 8 alkoxy which is substituted by E and/or interrupted by D, or
  • E is -OR 29 ; -SR 29 ; -NR 25 R 26 ; -COR 28 ; -COOR 27 ; -CONR 25 R 26 ; -CN; or halogen;
  • G is E, C r
  • Ci 8 alkyl Ci-Ci 8 alkyl which is interrupted by D
  • Ci-Ci 8 perfluoroalkyl Ci-Ci 8 perfluoroalkyl
  • Ci-Ci 8 alkoxy which is substituted by E and/or interrupted by D
  • R 23 , R 24 , R 25 and R 26 are independently of each other H; C 6 -Ci 8 aryl; C 6 -Ci 8 aryl which is substituted by Ci-Ci 8 alkyl, or Ci-Ci 8 alkoxy; Ci-Ci 8 alkyl; or Ci-Ci 8 alkyl which is interrupted by -0-; or
  • R 25 and R 26 together form a five or six membered ring, in particular
  • R ⁇ ' and R ⁇ b are independently of each other H; C 6 -Ci 8 aryl; C 6 -Ci 8 aryl which is substituted by Ci-Ci 8 alkyl, or Ci-Ci 8 alkoxy; Ci-Ci 8 alkyl; or Ci-Ci 8 alkyl which is interrupted by -0-, R 29 is H; C 6 -Ci 8 aryl; C 6 -Ci 8 aryl, which is substituted by Ci-Ci 8 alkyl, or d-Ci 8 alkoxy; d- Ci 8 alkyl; or Ci-Ci 8 alkyl which is interrupted by -O-,
  • R 30 and R 31 are independently of each other Ci-Ci 8 alkyl, C 6 -Ci 8 aryl, or C 6 -Ci 8 aryl, which is substituted by Ci-Ci 8 alkyl, and R 32 is Ci-Ci 8 alkyl, C 6 -Ci 8 aryl, or C 6 -Ci 8 aryl, which is substituted by Ci-Ci 8 alkyl,
  • R, R' and R" independently are selected from d-C ⁇ alkyl, d-C ⁇ haloalkyl, d.-d o aryl, C 3 - Ci 2 cycloalkyl, preferably from d-C 6 alkyl, phenyl, cyclopentyl, cyclohexyl; and Ar independently is selected from C 5 -d o aryl, especially phenyl; x1 is 0, or 1 , with the proviso that in case of the moieties of the formulae XIV and XXM' and XXIII' at least one of the substituents R 11 , R 13 , R 14 , R 9' , R 13' and R 14' or, if present, of the substituents R 9 , R 12 and R 12 , is a group R 10 .
  • a preferred A 2 is selected from R5 2 -(Sp) x i 0 -[PG'] ⁇ , wherein R5 2 is unsubstituted or substituted carbazolyl, or a residue of the formula
  • R 9 or R 10 being an open bond linking the residue to Sp or PG', while the remaining R 9' , R 10' , R 11 , R 11' , R 12 , R 13 R 14 , R 12' , R 13' and R 14' are independently of each other H or a substituent.
  • a 3 as an organic radical providing electron-injection or electron-transport functionality often is a group (HEf)-R 10 , which increases the electron-injection or electron-transport properties.
  • Preferred groups HEl" are: wherein R 41 and m and n are as defined below and p is 0,1 , or 2, especially O or 1 , R 42 ' is H, or R 42 .
  • R 41 and m and n are as defined below and p is 0,1 , or 2, especially O or 1
  • R 42 ' is H, or R 42 .
  • Another group of units A 3 introduces the electron transport functionality into the copolymer's main chain; examples are (Mice), (lllkk). (lllkl), (lllmm), (Minn), (lllpp),
  • a moiery A 3 of special interest is selected from R53-(Sp) x i 0 -[PG'] ⁇ , wherein R 5 3 is a residue of the formula
  • n can be the same or different at each occurence and is 0, 1 , 2, or 3; and each R 3 4 41' is a substituent, or 2 neighbouring are linked together to form, together with the carbon atoms they are bonding to, an unsubstituted or substituted 5- or 6-membered carbocyclic or heterocyclic ring.
  • a 4 as an organic radical providing hole transport functionality often is a group (HEl')-R 10 , wherein R 10 is as defined above and
  • HEl' which increase the hole-injection or hole-transport properties of the copolymers, is preferably selected from:
  • R can be the same or different at each occurence and is Cl, F, CN, Rio, a d-
  • Ar 1 and Ar 1 are independently of each other a C 6 -C 24 aryl group, a C 2 -C 30 heteroaryl group, which can be substituted by one or more non-aromatic groups R 41 , or NO 2 , especially phenyl, naphthyl, anthryl, biphenylyl, 2-fluorenyl, phenanthryl, or perylenyl, which can be substituted by one or more non-aromatic groups R , such as
  • Ar 2 is a C 6 -C 3 oarylene group, or a C 2 -C 24 heteroarylene group, which can optionally be substituted, especially
  • C 20 heteroaryl, C 2 -C 20 heteroaryl which is substituted by G, C 2 -Ci 8 alkenyl, C 2 -Ci 8 alkynyl, d- Ci 8 alkoxy, Ci-Ci 8 alkoxy which is substituted by E and/or interrupted by D, or C 7 -C 25 aralkyl, or R 119 and R 120 together form a group of formula CR 121 R 122 , wherein R 121 and R 122 are independently of each other H, Ci-Ci 8 alkyl, Ci-Ci 8 alkyl which is substituted by E and/or interrupted by D, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, or C 2 - C 20 heteroaryl, or C 2 -C 20 heteroaryl which is substituted by G, or
  • R 63 , R 64 , R 65 and R 66 are independently of each other H; C 6 -Ci 8 aryl; C 6 -Ci 8 aryl which is substituted by CrCi 8 alkyl, d-Ci 8 alkoxy; Ci-Ci 8 alkyl; or Ci-Ci 8 alkyl which is interrupted by 0-; or
  • R 65 and R 66 together form a five or six membered ring, in particular
  • R 67 and R 68 are independently of each other H; C 6 -Ci 8 aryl; C 6 -Ci 8 aryl which is substituted by
  • R 70 and R 71 are independently of each other Ci-Ci 8 alkyl, C 6 -Ci 8 aryl, or C 6 -Ci 8 aryl, which is substituted by Ci-Ci 8 alkyl, and
  • R 72 is Ci-Ci 8 alkyl, C 6 -Ci 8 aryl, or C 6 -Ci 8 aryl, which is substituted by Ci-Ci 8 alkyl.
  • Ar 1 is preferably a phenyl group, which is substituted by Ci-C 4 alkyl, or NO 2 , in particular , , or an anthryl group, in particular an anthr-2-yl group.
  • R 116 and R 117 are independently of each other H, d-C ⁇ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, t-butyl, 2-methylbutyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, or n-heptyl, Ci-Ci 2 alkyl which is substituted by E and/or interrupted by D, such as -CH 2 OCH 3 , -CH 2 OCH 2 CH 3 , -CH 2 OCH 2 CH 2 OCH 3 , or -CH 2 OCH 2 CH 2 OCH 2 CH 3 , C 6 -Ci 4 aryl, such as phenyl, naphthyl, or biphenylyl, C 5 - Ci 2 cycloalkyl, such as cyclohexyl, C 6
  • R 65 is preferably H, d-C ⁇ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, t-butyl, 2-methylbutyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, n-heptyl, or C 6 - Ci 4 aryl, such as phenyl, naphthyl, or biphenylyl, which can optionally be substituted.
  • d-C ⁇ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, t-butyl, 2-methylbutyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, n-
  • D is preferably -CO-, -COO-, -S-, -SO-, -SO 2 -, -0-, -NR 65 -, wherein R 65 is C r Ci 2 alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, or sec-butyl, or C 6 -Ci 4 aryl, such as phenyl, naphthyl, or biphenylyl.
  • E is preferably -OR 69 ; -SR 69 ; -NR 65 R 65 ; -COR 68 ; -COOR 67 ; -CONR 65 R 65 ; or -CN; wherein R 65 , R 67 , R 68 and R 69 are independently of each other Ci-Ci 2 alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or C 6 -Ci 4 aryl, such as phenyl, naphthyl, or biphenylyl.
  • Ci-Ci 2 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octy
  • G has the same preferences as E, or is Ci-Ci 8 alkyl, especially Ci-Ci 2 alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl.
  • Another group of units A 4 introduces the hole transport functionality into the copolymer's main chain; examples are in particular selected from the group consisting of ortho-, meta- or para-phenylene, 1 ,4-naphthylene, 9,10-anthracenylene, 2,7-phenanthrenylene, 1 ,6-, 2,7-, 4,9-pyrene, 2,7-tetrahydropyrene, oxadiazolylene, 2,5-thiophenylene, 2,5-pyrrolylene; 2,5- furanylene, 2,5-pyridylene, 2,5-pyrimidinylene, 5,8-chinolinylene, fluorene, spiro-9,9'- bifluorene, indenofluorene, heteroindenofluorene, 2,7-N-alkylcarbazol, 2,7-N-arylcarbazol, 3,6- N-alkylcarbazol, and 3,6-N-arylcarbazol.
  • R 41 ; R 116 and R 117 are independently of each other H, CrCi 8 alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, t-butyl, 2-methylbutyl, n-pentyl, isopentyl, n-hexyl, 2- ethylhexyl, or n-heptyl; CrCisalkyl which is substituted by E and/or interrupted by D, such as -CH 2 OCH 3 , -CH 2 OCH 2 CH 3 , -CH 2 OCH 2 CH 2 OCH 3 , Or -CH 2 OCH 2 CH 2 OCH 2 CH 3 ; Ci-Ci 8 alkoxy, such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, isobutoxy, sec-butoxy, t-butoxy, 2-methylbut
  • a moiety A 4 of special interest is selected from R 54 -(Sp) x io-[PG'] ⁇ , wherein
  • R 5 4 is (ll'c), n can be the same or different at each occurence and is 0, 1 , 2, or 3; and each R is a substituent.
  • a 5 as an organic radical derived from aliphatic or aromatic organic monomers often is selected from those of the formula R 1 0-H or R 10 -RiO in case of crosslinking monomers.
  • Examples are repeating structural units derived from (meth)acrylic acid, d- C 8 alkyl(meth)acrylates, C 2 -C 8 hydroxyalkyl(meth)acrylates, styrene, isopropenylbenzene, diisopropenylbenzene, divinylbenzene, C 2 -Ci 2 hydroxyalkylstyrene, C 2 - Ci 2 hydroxyalkoxystyrene.
  • R 55 -(Sp) x io-[PG'] ⁇ wherein R 55 is Ci-Ci 2 alkyl, C 3 - Ci 2 cycloalkyl, C 6 -Cioaryl, C 4 -Cioheteroaryl, each of which is unsubstituted or substituted, or is H or R 10 ; any substituent, if present, is selected from Ci-Ci 2 alkyl, a hydroxyl group, a mercapto group, Ci-Ci 2 alkoxy, Ci-Ci 2 alkylthio, halogen, halo-Ci-Ci 2 alkyl, a cyano group, an aldehyde group, a ketone group, a carboxyl group, an ester group, a carbamoyl group, an amino group, a nitro group, R 10 , a silyl group, where halogen stands for Cl, F; R 10 is a group -(Sp) x i
  • PG' is , where the asterisk marks the atom bonding to (Sp) x i 0 -;
  • PG is oxiranyl, oxetanyl, glycidyl, or is PG'; any Sp, if present, independently is a spacer of the formula (X 3 -D) x11 -X 2 , wherein x11 is 0 or 1 ; X 3 , X 2 independently are O, Ci-C 4 alkylene-O, COO, Ci-C 4 alkylene-
  • copolymers of this invention preferably have a weight average molecular weight of 2,000
  • the number of phosphorescent metal complex units A 1 (i.e. x1 ) often is from 1 to about 500, e.g. 2-500 or preferably 3-300.
  • the sum (x2 + x3 + x4 + x5) often is from the range 5-10000, e.g. 8-5000.
  • Structural units (organic radicals) A 1 often make up about 0.1-25 %, especially 1-10 %, by weight of the present copolymer.
  • Structural units (organic radicals) A 2 if present, often make up about 25-99.9 %, especially
  • Structural units (organic radicals) A 3 and/or A 4 if present, often make up about 0.9-99.9 or, if used concomitantly to radicals A 2 and/or A 5 , about 1-75 %, e.g. 0.9-74.9 %, especially 10-50
  • Structural units (organic radicals) A 5 if present, often make up about 0.01-50 %, e.g. 0.1-20
  • the copolymers of the invention may be prepared following techniques known in the art, e.g. for preparing linear or crosslinked polymers by condensation and/or addition polymerization methods.
  • a basic polymer network is formed by addition polymerization of suitable monomers containing ethylenically unsaturated moieties as PGs, e.g. by radical copolymerization using chemical radical starters, photoinitiators, actinic radiation and/or heat for the generation of radicals and initiation of the reaction.
  • (Co)polymers formed in a first preparation step may be further modified e.g. by grafting one or more further monomers and/or functional groups on the polymer skeleton. Reaction conditions and methods may follow, for example, those described in WO06/097419 or WO07/090773.
  • the present copolymers may also be formed in situ on the substrate.
  • the invention thus further pertains to a reactive intermediate obtainable by radical copolymerization of a compound of the formula (XII), (XIH) and/or (XXII) (XXII, i.e. vinylcarbazole or a vinylcarbazole derivative)
  • X is NR 9" ; each of R 9 , R 9' , R 11 , R 11' , R 12 , R 12' , R 13 , R 13' , R 14 , R 14' is H, d-Ci 2 alkyl, halogen, C r Ci 2 alkoxy;
  • R 9" is H, Ci-Ci 2 alkyl
  • R 10 is a group -(Sp) x i 0 -vinyl, xiO is O oM ;
  • Sp if present, is a spacer unit (X 3 -D) x11 -X 2 , wherein x1 1 is 0 or 1 ;
  • X 3 , X 2 independently are O, Ci-C 4 alkylene-O, S, Ci-C 4 alkylene-S,
  • D is Ci-C 24 alkylene, interrupted C 3 -C 24 alkylene, C 2 -C 24 alkenylene, C 2 -C 24 alkynylene, C 6 -
  • RG is a reactive group selected from OH, COOR, oxiranyl, oxetanyl, where R is hydrogen
  • Ci-C 6 alkyl phenyl, cyclopentyl, cyclohexyl.
  • the reactive copolymers advantageously are prepared using the monomer of formula XII,
  • XIII and/or XXII in excess over the crosslinking monomer, e.g. 50-99, especially 80-95 % b.w. of the functional monomer XII, XIII, XXII and 1-50, especially 5-20 % b.w. of the crosslinker.
  • novel intermediate polymers may be obtained from the above monomers by methods known per se for the polymerization of vinyl compounds.
  • the vinyl monomers are largely known compounds or analogous to known compounds (see, for example, WO06/097419 or WO07/090773).
  • the invention further provides novel monomers useful for preparing the present copolymers, which are of the formulae:
  • M 1 is a metal with an atomic weight of greater than 40, L 1 is a bidentate ligand containing the substituent R 10 ; Q 1 and Q 2 are independently of each other hydrogen or an organic substituent, or
  • Q 1 and Q 2 together with the carbon atoms, to which they are bonded, form a condensed ring, for example an aromatic or heteroaromatic ring, which optionally may be substituted, or a carbocyclic or heterocyclic, non-aromatic ring, which optionally may be substituted; and
  • Q 3 represents a group of forming a condensed aromatic or heteroaromatic ring, preferably a phenyl or naphthyl ring, which optionally may be substituted, and wherein 1-3, preferably one, of L 1 , L 2 , Q 1 , Q 2 and/or the substituents contains a divalent group derived from a polymerizable aliphatic or aromatic monomer moiety; with preferred residues and/or substituents as described above.
  • L 1 as a bidentate ligand containing the substituent R 10 is, for example, selected from
  • R 10 is a group -(Sp) x i 0 -PG, where PG is selected from vinyl, allyl, acryloyl, methacryloyl, styryl, oxetanyl, oxiranyl, glycidyl; and Sp and x10 are as described above;
  • ring A represents an optionally substituted aryl group which may contain a heteroatom
  • ring B represents an optionally substituted nitrogen containing aryl group, which may contain further heteroatoms,
  • R 11 is unsubstituted or substituted Ci-C 4 alkyl
  • R 12 is CF 3 or a ring A
  • R 13 is H, unsubstituted or substituted Ci-C 4 alkyl
  • R 14 , R 14 independently are a ring A, unsubstituted or substituted Ci-C 8 alkyl, d-
  • W is N or CH.
  • Examples for (co)polymerizable phosphorescent moieties of the invention are compounds of the formulae:
  • the present invention is also directed to an electronic device comprising the present metal complex copolymer and its fabrication process.
  • the electronic device can comprise at least one organic active material positioned between two electrical contact layers, wherein at least one of the layers of the device includes the metallic complex compound.
  • the electronic device can comprise an anode layer (a), a cathode layer (e), and an active layer (c). Adjacent to the anode layer (a) is an optional hole-injecting/transport (electron blocking) layer (b), and adjacent to the cathode layer (e) is an optional electron-injection/transport (hole blocking) layer (d). Layers (b) and (d) are examples of charge transport layers.
  • the active layer (c) may be split into a layer comprising the present copolymer containing units A 3 (electron transport) and a further layer comprising the present copolymer containing units A 4 (hole transport).
  • the active layer (c) preferably comprises at least approximately 1 weight percent of luminiscent metal complex, e.g. in the form of recurring units of the present copolymer or in admixture with non-polymeric complex.
  • the active layer (c) may be substantially 100% of the present metal complex copolymer because a host charge transporting material, such as AIq 3 is not needed.
  • substantially 100% it is meant that the present copolymer is the only material in the layer, with the possible exception of impurities or adventitious by-products from the process to form the layer.
  • the present copolymer containing metal complex moieties may be a dopant within a host material, which is typically used to aid charge transport within the active layer (c).
  • the active layer (c) may include an additional other luminescent material, for example a luminescent metal complex, especially a phosphorescent one (i.e. a triplett emitter), which can be a small molecule active material.
  • the device may include a support or substrate adjacent to the anode layer (a) or the cathode layer (e). Most frequently, the support is adjacent the anode layer (a).
  • the support can be flexible or rigid, organic or inorganic. Generally, glass or flexible organic films are used as a support.
  • the anode layer (a) is an electrode that is more efficient for injecting holes compared to the cathode layer (e).
  • the anode can include materials containing a metal, mixed metal, alloy, metal oxide or mixed-metal oxide. Suitable metal elements within the anode layer (a) can include the Groups 4, 5, 6, and 8-1 1 transition metals.
  • anode layer (a) is to be light transmitting, mixed-metal oxides of Groups 12, 13 and 14 metals, such as indium-tin-oxide, may be used.
  • Some non-limiting, specific examples of materials for anode layer (a) include indium-tin-oxide ("ITO"), aluminum-tin-oxide, gold, silver, copper, nickel, and selenium.
  • the anode layer (a) may be formed by a chemical or physical vapor deposition process or spin-cast process, inject or gravure printing process. Chemical vapor deposition may be performed as a plasma-enhanced chemical vapor deposition ("PECVD") or metal organic chemical vapor deposition (“MOCVD").
  • PECVD plasma-enhanced chemical vapor deposition
  • MOCVD metal organic chemical vapor deposition
  • Physical vapor deposition can include all forms of sputtering (e. g., ion beam sputtering), e- beam evaporation, and resistance evaporation.
  • physical vapor deposition examples include rf magnetron sputtering or inductively- coupled plasma physical vapor deposition ("ICP- PVD"). These deposition techniques are well-known within the semiconductor fabrication arts.
  • a hole-transport layer (b) may be adjacent to the anode; this layer may be split into a hole injecting (b1 ) and a hole transporting (b2) layer. Both hole transporting small molecule compounds and polymers can be used.
  • Commonly used hole transporting molecules include: N, N'-diphenyl-N, N'-bis(3- methylphenyl)-[1 ,1 '-biphenyl]-4,4'-diamine (TPD), 1 ,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC), N,N'-bis(4-methylphenyl)-N,N'-bis(4-ethylphenyl)-[1 ,1 '-(3,3'-dimethyl)biphenyl]4,4'- diamine (ETPD), tetrakis-(3-methylphenyl)-N,N,N',N'-2,5-phenylenediamine (PDA), a-phenyl- 4-N,N-diphenylaminostyrene (TPS), p- (diethylamino)benzaldehydediphenylhydrazone (DEH), tripheny
  • TTB 4,4'-N,N-dicarbazole-biphenyl
  • CBP 4,4'-N,N-dicarbazole-biphenyl
  • DCB N,N-dicarbazoyl-1 ,4-dimethene-benzene
  • NPD N,N'-Di(naphthalen-1-yl)-N,N'-diphenyl-benzidine
  • mCP 1 ,3-fc>/s(9-carbazolyl)benzene
  • mCP 1,3-fc>/s(9-carbazolyl)benzene
  • hole transporting polymers are polyvinylcarbazole, (phenylmethyl) polysilane, poly(3,4-ethylendioxythiophene) (PEDOT), triarylamine polymers (such as poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'- (N-(4-sec- butylphenyl))diphenylamine)] [TFB]), polypyrrole, and polyaniline.
  • Hole-transporting polymers can be obtained by doping hole- transporting molecules such as those mentioned above into polymers such as polystyrene and polycarbonate.
  • the hole-injection/transport layer (b) can be formed using any conventional means, including spin-coating, casting, and printing, such as gravure printing.
  • the layer can also be applied by ink jet printing, thermal patterning, or chemical or physical vapor deposition.
  • the anode layer (a) and the hole-injection/transport layer (b), if present, are patterned during the same lithographic operation.
  • the pattern may vary as desired.
  • the layers can be formed in a pattern by, for example, positioning a patterned mask or resist on the first flexible composite barrier structure prior to applying the first electrical contact layer material.
  • the layers can be applied as an overall layer (also called blanket deposit) and subsequently patterned using, for example, a patterned resist layer and wet- chemical or dry-etching techniques. Other processes for patterning that are well known in the art can also be used.
  • the anode layer (a) and hole injection/transport layer (b) typically are formed into substantially parallel strips having lengths that extend in substantially the same direction, layer (b) can be crosslinked.
  • the active layer (c) comprises the luminescent copolymer of the present invention.
  • the particular material chosen may depend on the specific application, potentials used during operation, or other factors.
  • the active layer (c) may comprise a host material capable of transporting electrons and/or holes, doped with an emissive material that may trap electrons, holes, and/ or excitons, such that excitons relax from the emissive material via a photoemissive mechanism.
  • Active layer (c) may comprise a single material that combines transport and emissive properties. Whether the emissive material is a dopant or a major constituent, the active layer may comprise other materials, such as dopants that tune the emission of the emissive material.
  • Active layer (c) may include a plurality of emissive materials capable of, in combination, emitting a desired spectrum of light.
  • phosphorescent emissive materials include the copolymers of the present invention, as well as phosphorescent metal compounds disclosed in WO06000544, WO06067074, WO07074093, and publications cited therein.
  • fluorescent emissive materials include DCM and DMQA, and certain fluorescent polyaryls (EP-A- 1 138746, EP-A-1245659).
  • host materials include AIq 3 , CBP and mCP. Examples of emissive and host materials are disclosed in US 6,303,238 B, which is incorporated by reference in its entirety.
  • Examples of methods for forming the active layer (c) include deposition by solution processing.
  • Examples of film-forming methods from a solution include application methods, such as spin-coating, casting, microgravure coating, roll-coating, wire bar-coating, dip- coating, spray-coating, screen-printing, flexography, offset-printing, gravure printing and ink- jet-printing.
  • composition used for forming the active layer (c) at least one kind of present copolymers and at least one solvent are contained, and additives, such as hole transport material, electron transport material, luminescent material, rheology modifier or stabilizer, may be added.
  • additives such as hole transport material, electron transport material, luminescent material, rheology modifier or stabilizer.
  • the amount of solvent in the composition is 1 to 99 wt% of the total weight of the composition and preferably 60 to 99 wt% and more preferably 80 to 99 wt%.
  • the solvent used in the solution processing method is not particularly limited and preferable are those which can dissolve or uniformly disperse the materials.
  • the materials may be dissolved in a solvent, the solution deposited onto a substrate, and the solvent removed to leave a solid film.
  • Any suitable solvents may be used to dissolve the ionic compounds, provided it is inert, may dissolve at least some material and may be removed from the substrate by conventional drying means (e.g. application of heat, reduced pressure, airflow, etc.).
  • Suitable organic solvents include, but are not limited to, are aromatic or aliphatic hydrocarbons, halogenated such as chlorinated hydrocarbons, esters, ethers, ketones, amide, such as chloroform, dichloroethane, tetrahydrofuran, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, acetone, dimethyl formamide, dichlorobenzene, chlorobenzene, propylene glycol monomethyl ether acetate (PGMEA), and alcohols, and mixtures thereof. Also water and mixtures with water miscible solvents are possible. Layer (c) can be crosslinked.
  • halogenated such as chlorinated hydrocarbons, esters, ethers, ketones, amide, such as chloroform, dichloroethane, tetrahydrofuran, toluene, xylene, ethyl acetate, buty
  • Optional layer (d) can function both to facilitate electron injection/transport, hole blocking, and also serve as a buffer layer or confinement layer to prevent quenching reactions at layer interfaces. More specifically, layer (d) may promote electron mobility and reduce the likelihood of a quenching reaction if layers (c) and (e) would otherwise be in direct contact.
  • materials for optional layer (d) include metal-chelated oxinoid compounds (e. g., tris(8-hydroxyquinolato)aluminum (AIq 3 ) or the like); phenanthroline-based compounds (e.
  • DDPA 2,9-dimethyl-4,7-diphenyl-1 ,10-phenanthroline
  • DPA 4,7-diphenyl-1 ,10-phenanthroline
  • azole compounds e. g., 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1 ,3,4- oxadiazole ("PBD”) or the like, 3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1 ,2,4-triazole (“TAZ”) or the like; other similar compounds; or any one or more combinations thereof.
  • optional layer (d) may be inorganic and comprise BaO, LiF, Li 2 O, or the like. Layer (d) can be crosslinked.
  • the electron injection/transport layer (d) can be formed using any conventional means, including spin-coating, casting, and printing, such as gravure printing.
  • the layer can also be applied by ink jet printing, thermal patterning, or chemical or physical vapor deposition.
  • the cathode layer (e) is an electrode that is particularly efficient for injecting electrons or negative charge carriers.
  • the cathode layer (e) can be any metal or nonmetal having a lower work function than the first electrical contact layer (in this case, the anode layer (a)).
  • Materials for the second electrical contact layer can be selected from alkali metals of Group 1 (e. g., Li, Na, K, Rb, Cs), the Group 2 (alkaline earth) metals, the Group 12 metals, the rare earths, the lanthanides (e. g. , Ce, Sm, Eu, or the like), and the actinides.
  • Materials, such as aluminum, indium, calcium, barium, yttrium, and magnesium, and combinations thereof, may also be used.
  • Li-containing organometallic compounds, LiF, and Li 2 O can also be deposited between the organic layer and the cathode layer to lower the operating voltage.
  • Specific non- limiting examples of materials for the cathode layer (e) include barium, lithium, cerium, cesium, europium, rubidium, yttrium, magnesium, or samarium.
  • the cathode layer (e) is usually formed by a chemical or physical vapor deposition process.
  • the cathode layer will be patterned, as discussed above in reference to the anode layer (a) and optional hole injecting layer (b).
  • the cathode layer (e) may be patterned into substantially parallel strips, where the lengths of the cathode layer strips extend in substantially the same direction and substantially perpendicular to the lengths of the anode layer strips.
  • Electronic elements called pixels are formed at the cross points (where an anode layer strip intersects a cathode layer strip when the array is seen from a plan or top view).
  • additional layer(s) may be present within organic electronic devices.
  • a layer between the hole injecting layer (b) and the active layer (c) may facilitate positive charge transport, band-gap matching of the layers, function as a protective layer, or the like.
  • additional layers between the electron injecting layer (d) and the cathode layer (e) may facilitate negative charge transport, band-gap matching between the layers, function as a protective layer, or the like.
  • Layers that are known in the art generally may be used. Some or all of the layers may be surface treated to increase charge carrier transport efficiency. The choice of materials for each of the component layers may be determined by balancing the goals of providing a device with high device efficiency with the cost of manufacturing, manufacturing complexities, or potentially other factors.
  • the materials of the charge transport layers (b) and (d) often are of the same type as the materials of the active layer (c). More specifically, if the active layer (c) comprises a small molecule compound, then the charge transport layers (b) and (d), if either or both are present, often comprises a different small molecule compound. If the active layer (c) contains a polymer, the charge transport layers (b) and (d), if either or both are present, often contain a polymer, too. Still, the active layer (c) may contain a small molecule compound, and any of its adjacent layers (e.g. charge transport layers) may be polymers.
  • Each functional layer may be made up of more than one layer.
  • the cathode layer may comprise a layer of a Group I metal and a layer of aluminum.
  • the Group I metal may lie closer to the active layer (c), and the aluminum may help to protect the Group I metal from environmental contaminants, such as water.
  • the different layers may have the following range of thicknesses: inorganic anode layer (a), usually no greater than approximately 500 nm, for example, approximately 50-200 nm; optional hole-injecting layer (b), usually no greater than approximately 100 nm, for example, approximately 50-200 nm; active layer (c), usually no greater than approximately 100 nm, for example, approximately 10-80 nm; optional electron- injecting layer (d), usually no greater than approximately 100 nm, for example, approximately 10-80 nm; and cathode layer (e), usually no greater than approximately 1000 nm, for example, approximately 30-500 nm. If the anode layer (a) or the cathode layer (e) needs to transmit at least some light, the thickness of such layer may not exceed approximately 100 nm.
  • the location of the electron-hole recombination zone in the device, and thus the emission spectrum of the device, can be affected by the relative thickness of each layer.
  • the thickness of the electron-transport layer should be chosen so that the electron-hole recombination zone lies within the light-emitting layer (i.e., active layer (c)).
  • the desired ratio of layer thicknesses can depend on the exact nature of the materials used.
  • the efficiency of the devices made with metal complexes can be further improved by optimizing the other layers in the device.
  • more efficient cathodes such as Ca, Ba, Mg/Ag, or LiF/AI can be used.
  • Shaped substrates and hole transport materials that result in a reduction in operating voltage or increase quantum efficiency are also applicable.
  • Additional layers can also be added to tailor the energy levels of the various layers and facilitate electroluminescence.
  • the active layer (c) can be a light- emitting layer that is activated by a signal (such as in a light-emitting diode) or a layer of material that responds to radiant energy and generates a signal with or without an applied potential (such as detectors or voltaic cells).
  • a signal such as in a light-emitting diode
  • a layer of material that responds to radiant energy and generates a signal with or without an applied potential (such as detectors or voltaic cells).
  • Examples of electronic devices that may respond to radiant energy are selected from photoconductive cells, photoresistors, photoswitches, phototransistors, and phototubes, and photovoltaic cells. After reading this specification, skilled artisans will be capable of selecting material (s) that for their particular applications.
  • the electroluminescent devices may be employed for full color display panels in, for example, mobile phones, televisions and personal computer screens. Accordingly the present invention relates also to a device selected from stationary and mobile displays, such as displays for computers, mobile phones, laptops, pdas, TV sets, displays in printers, kitchen equipment, billboards, lightings, information boards and destination boards in trains and buses, containing an organic light emitting diode according to the present invention.
  • OLEDs electrons and holes, injected from the cathode (e) and anode (a) layers, respectively, into the photoactive layer (c), form negative and positively charged polarons in the active layer (c).
  • a sufficient potential difference between the anode and cathode usually less than approximately 20 volts, and in some instances no greater than approximately 5 volts, may be applied to the device. The actual potential difference may depend on the use of the device in a larger electronic component.
  • the anode layer (a) is biased to a positive voltage and the cathode layer (e) is at substantially ground potential or zero volts during the operation of the electronic device.
  • a battery or other power source (s) may be electrically connected to the electronic device as part of a circuit.
  • the compound does not need to be in a solid matrix diluent (e. g., host charge transport material) when used in layer (b) (c), or (d) in order to be effective.
  • a layer greater than approximately 1 % by weight of the metal complex compound, based on the total weight of the layer, and up to substantially 100% of the present copolymer can be used as the active layer (c).
  • Additional materials can be present in the active layer (c) with the complex compound. For example, a fluorescent dye may be present to alter the color of emission.
  • a diluent may also be added.
  • the diluent can be a polymeric material, such as poly (N-vinyl carbazole) and polysilane. It can also be a small molecule, such as 4,4'-N,N'-dicarbazole biphenyl or tertiary aromatic amines.
  • the present copolymer is generally present in a small amount, usually less than 20% by weight, preferably less than 10% by weight, based on the total weight of the layer.
  • the present copolymers may be used in applications other than electronic devices.
  • they may be used as catalysts or indicators (e. g., sensors, oxygen-sensitive indicators, phosphorescent indicators in bioassays, or the like).
  • Room temperature depicts a temperature in the range 20-25 0 C; over night denotes a time period in the range 12-16 hours. Percentages are by weight unless otherwise indicated.
  • PEDOT:PSS poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate)
  • Triplet Emitters The compounds (intermediate complexes) in Table 1 are prepared according to the method shown in example 10 of WO 2006/000544.
  • the compounds (intermediate complexes) in Table 2 are prepared starting from the compounds in Table 1 and 3-Hydroxypicolinic acid according to the method shown in example 1 1 of WO 2006/000544.
  • the combined organic phases are washed three times with 50 ml of water, dried over Magnesiumsulfate, filtered and evaporated.
  • the crude product is purified by flash chromatography using Ethylacetate as eluent.
  • the desired product is isolated in 49% yield as a yellow powder.
  • the photoluminescence spectrum in toluene shows emission maxima at 539 and 563 nm.
  • the following compound is prepared in 59% yield according to Example 1.7, starting from the compound prepared in example 1.5.
  • the photoluminescence spectrum in toluene shows an emission maximum at 510 nm.
  • the following compound is prepared in 58% yield according to Example 1.7, starting from the compound prepared in example 1.6.
  • the photoluminescence spectrum in toluene shows an emission maximum at 510 nm.
  • the crude product is purified by flash chromatography using Ethylacetate as eluent.
  • the product is added to 50 ml of Diisopropylether and stirred for five hours.
  • the suspension is filtered and dried at 50 0 C and 25 mbar over night.
  • the desired product is isolated in 67% yield as a yellow powder.
  • Example 1.10 The following compound is prepared according to Example 1.10, starting from the compound prepared in example 1.5.
  • the photoluminescence spectrum in toluene shows an emission maximum at 515 nm.
  • Example 1.10 The following compound is prepared according to Example 1.10, starting from the compound prepared in example 1.6.
  • the photoluminescence spectrum in toluene shows an emission maximum at 514 nm.
  • the following compound is prepared according to Example 1.7 but using Octylbromide instead of 3-(6-Bromo-hexyloxymethyl)-3-methyl-oxetane.
  • the photoluminescence spectrum in toluene shows emission maxima at 540 and 568 nm.
  • the following compound is prepared according to Example 1.9 but using Octylbromide instead of 3-(6-Bromo-hexyloxymethyl)-3-methyl-oxetane.
  • the photoluminescence spectrum in toluene shows an emission maximum at 511 nm.
  • 6-(4-Vinyl-phenyl)- hexane-2,4-dione is isolated in 66% yield.
  • the compound prepared in example 1.1 and 6-(4-Vinyl-phenyl)-hexane-2,4-dione are reacted according to example 1.4.
  • the final product shows in the photoluminescence spectrum an emission maximum at 559 nm in toluene.
  • Example 1.4 0.57 g (0.60 mmol) of the compound prepared in Example 1.4 are dissolved in 10 ml of dry CH 2 Cb in a 25 ml three necked round bottomed flask, equipped with magnetic stirrer. 50 mg of Dimetylaminopyridine and 0.35 g (3.02 mmol) of Diisopropyethylamine are added and the clear orange solution is cooled to 3°C with an ice bath.
  • the following compound is prepared in 84% yield according to Example 1.18, starting from the compound prepared in example 1.5.
  • the photoluminescence spectrum in toluene shows an emission maximum at 510 nm.
  • Example 1.18 The following compound is prepared in 33% yield according to Example 1.18, starting from the compound prepared as an intermediate in example 1.1 1.
  • the photoluminescence spectrum in toluene shows an emission maximum at 513 nm.
  • the following compound is prepared according to Example 2.1 , starting from 9,10- Phenantrenequinone and 4-Hydroxybenzaldehyde.
  • the following compound is prepared according to Example 2.2, starting from 9,10- Phenantrenequinone and 4-Hydroxybenzaldehyde.
  • the reaction mixture is stirred at the same temperature for one hour, then 13.3 g (182.3 mmol) DMF (dried over Calcium hydride) are added within 30 minutes while keeping the internal temperature below - 75°C.
  • the reaction mixture is stirred at the same temperature for one hour.
  • 18 ml of 0.5 M HCI are added drop by drop and the reaction mixture is warmed to room temperature.
  • the reaction mixture is diluted with 300 ml of water and extracted twice with 250 ml of Ethylacetate.
  • the combined organic phases are washed twice with 50 ml of saturated Ammonium chloride solution and once with 100 ml of brine, dried over Magnesiumsulfate, filtered and evaporated.
  • the crude product is crystallized from 2-Propanol. 4-(1-0ctyl-1- phenanthro[9,10]imidazol-2-yl)-benzaldehyde is isolated in 79% yield.
  • 4N,4'N-Diphenyl-4N,4'N-di-p-tolyl-biphenyl-4,4'-diamine is prepared according to WO/061562, Example 6, compound 21 , but using N,N-Diphenylbenzidine and 4-lodotoluene as starting materials.
  • 4N ! 4'N-Diphenyl-4N ! 4'N-di-p-tolyl-biphenyl-4,4'-diamine 4N,4'N-Di(4- formylphenyl-4N,4'N-di-p-tolyl-biphenyl-4,4'-diamine is prepared according to EP795791 Preparation Example.
  • N-(4-hydroxymethylphenyl)-N'-phenyl-N,N'-bis(4-methylphenyl)-[1 ,1 '-biphenyl]-4,4'-diamine is prepared according to M. Tamada, Polymer 41 (2000) 5661.
  • N-(4-hydroxymethylphenyl)-N'-phenyl-N,N'-bis(4-methylphenyl)-[1 ,1 '-biphenyl]-4,4'-diamine is reacted according to Example 3.2 step 1 to yield 6-(4- ⁇ [4'-(Phenyl-p-tolyl-amino)-biphenyl-4- yl]-p-tolyl-amino ⁇ -benzyloxy)-hexan-1-ol.
  • Example 4.1 The following compound is prepared in 35% yield according to Example 4.1 , starting from 3,3'-Dimethyl-N4,N4,N4',N4'-tetra-m-tolyl-biphenyl-4,4'-diamine (prepared according to WO05061562, Example 6).
  • Example 4.6 The following compound is prepared in analogy to compound 20 of WO05061562 (Example 6):
  • Compound 5.5 is prepared according to Macromolecules (2005), 38(5), 1640-1647.
  • Copolymerization in analogy to examples 6.1 to 6.18 is carried out using the starting monomers of Examples 1.19 (10 wt%), 2.1 1 (30 wt%), 3.8 (30 wt%), and 4.6 (30 wt%), yielding the copolymer of the formula:
  • Copolymerization in analogy to examples 6.1 to 6.18 is carried out using the starting monomers of Examples 1.16 (10 wt%), 2.1 1 (30 wt%), 3.8 (30 wt%), and 4.6 (30 wt%), yielding the copolymer of the formula:
  • Example 6.30 a) Copolymerization in analogy to examples 6.1 to 6.18 is carried out using the starting monomers of Examples 1.19 (10 wt%), 2.1 1 (30 wt%), 3.8 (25 wt%), 4.6 (25 wt%), and 5.3 (10 wt%), yielding the copolymer of the formula:
  • Example 6.31 a) Copolymerization in analogy to examples 6.1 to 6.18 is carried out using the starting monomers of Examples 1.16 (10 wt%), 2.1 1 (30 wt%), 3.8 (25 wt%), 4.6 (25 wt%), and 5.3 (10 wt%), yielding the copolymer of the formula:
  • Example 6.32 Copolymerization in analogy to examples 6.1 to 6.18 is carried out using the starting monomers of Examples 1.19 (10 wt%), 2.12 (30 wt%), 3.8 (30 wt%), and 4.6 (30 wt%), yielding the copolymer of the formula:
  • Copolymerization in analogy to examples 6.1 to 6.18 is carried out using the starting monomers of Examples 1.16 (10 wt%), 2.12 (30 wt%), 3.8 (30 wt%), and 4.6 (30 wt%), yielding the copolymer of the formula:
  • Example 6.34 a) Copolymerization in analogy to examples 6.1 to 6.18 is carried out using the starting monomers of Examples 1.19 (10 wt%), 2.12 (30 wt%), 3.8 (25 wt%), 4.6 (25 wt%), and 5.3 (10 wt%), yielding the copolymer of the formula:
  • Example 6.35 a) Copolymerization in analogy to examples 6.1 to 6.18 is carried out using the starting monomers of Examples 1.16 (10 wt%), 2.1 1 (30 wt%), 3.8 (25 wt%), 4.6 (25 wt%), and 5.3 (10 wt%), yielding the copolymer of the formula:
  • Examples 6.36-6.40 Polymers are prepared using the monomer units as identified in the below table. Procedures are analogous to those of examples 6.1 - 6.18 above.
  • Examples 6.41-6.42 (polymer modification) are carried out in analogy to examples 6.23 6.27 above. Polymers as prepared are identified in the below table.
  • An organic luminescence device having a single organic layer is prepared in the following manner: On a glass substrate, a 80 nm thick ITO film is formed by sputtering and subsequently patterned. Onto the oxygen-plasma treated ITO film, a hole-injection layer of 80 nm thickness is formed by spin-coating using PEDOT:PSS (Baytron® P), followed by heating at 200 0 C (10 minutes). A solution of 15 mg of polymer of example 6.6 (compound 1 ), 5 mg of TPD (compound 2), and 5 mg of PBD (compound 3) in 1.1 ml of toluene is applied by spin coating (3100 rpm.; 40 seconds) to obtain a thickness of 80 nm.
  • the film is dried under nitrogen atmosphere at 80 0 C for 30 minutes.
  • the substrate is placed in a vacuum deposition chamber, and a cathode having a two-layer structure is formed by depositing a 5 nm layer of barium followed by a 70 nm layer of aluminum.
  • a current density of 22 mA/cm 2 at 10 V
  • a bright (1000 cd/m 2 ) yellow (CIE 0.46, 0.50) emission is observed. This corresponds to a device efficiency of 4.6 cd/A.
  • Copolymers of the invention can be formed by in-situ crosslinking.

Abstract

Novel electrophosphorescent copolymers of the composition [A1]x1, [A2]x2, [A3]x3, [A4]x4, [A5]x5 wherein the structural units A1, A2, A3, A4 and/or A5 are in blocks or at random, and the copolymer is linear or crosslinked, and A1 is an organic radical of a phosphorescent light emitting moiety; A2 is an organic radical providing host functionality; A3 is an organic radical providing electron transport functionality; A4 is an organic radical providing hole transport functionality; A5 is a radical derived from aliphatic or aromatic organic monomers; x1 is a number from 1 to about 1000; x2, x3, x4 and x5 independently are numbers from 0 to about 100 000, with the proviso that the sum (x1 + x2 + x3 + x4 + x5) is at least 5, especially greater than 9; are characterized in that A1 contains a metal benzotriazole complex moiety or A2 is selected from repeating unit(s) of the formulae (III), (IV), where the symbols are as defined in claim 1. The novel copolymers are useful as active materials e.g. in electroluminescent devices.

Description

Organic Light Emitting Systems
The present invention pertains to some novel copolymers, processes for their preparation, novel precursors thereof, electroluminiscent materials and electronic devices containing the novel copolymers, and corresponding uses.
Organic light emitting devices inter alia require a charge transmitting material and a light emitter connected by a heterojunction in their active layer. Common classes of light emitters include fluorescent and phosphorescent organic (usually organometallic) compounds; an especially efficient class of light emitters is based on phosphorescent metal complexes (see, for example, WO06000544, and publications cited therein). Since application of the 2 materials usually requires differing techniques, and brings about the danger of unwanted phase separation, migration and/or crystallization processes, a number of modifications to such materials have been proposed, such as chemical bonding of some light emitting metal complexes to acrylic copolymers (WO02/031896) or certain fluorescent polyaryls (EP-A- 1 138746, EP-A-1245659). Similarly, WO02/068435 features some phosphorescent Iridium complexes with recommendation to incorporate them e.g. into polyfluorenes, polycarbazoles, polythiophenes. Some conjugated or semiconducting polymers containing a phosphorescent organometallic compound bonded to the backbone are disclosed in WO03/091355.
US-5518824 teaches the in situ preparation of a polymeric charge transport material by radiation induced crosslinking. WO03/001616 describes some reactive electrophosphorescent metal complexes which may be crosslinked or contain oxadiazole (electron transporting) or carbazole (hole transporting) moieties. US-6803124 discloses a number of carbazole copolymers for use in OLEDs based on a monomeric triplet emitter.
Certain copolymers have now been found which provide especially good properties in electroluminescent application. The present invention therefore pertains to a copolymer of the composition
[A1]X1, [AJx2, [A3Ix3, [A4Jx4, [A5]χ5
wherein the structural units A1, A2, A3, A4 and/or A5 are in blocks or at random, and the copolymer is linear or crosslinked, and
A1 is an organic radical of a phosphorescent light emitting moiety;
A2 is an organic radical providing host functionality;
A3 is an organic radical providing electron transport functionality;
A4 is an organic radical providing hole transport functionality;
A5 is a radical derived from aliphatic or aromatic organic monomers; x1 is a number from 1 to about 1000; x2, x3, x4 and x5 independently are numbers from 0 to about 100 000, with the proviso that the sum (x1 + x2 + x3 + x4 + x5) is at least 5, especially greater than 9;
characterized in that A1 is of the formula (I)
Figure imgf000003_0001
(I), wherein n is an integer of 1 to 3, n1 and n2 are an integer 0, 1 or 2,
M1 is a metal with an atomic weight of greater than 40,
L1 is a monodentate ligand or a bidentate ligand,
L2 is a monodentate ligand,
Q1 and Q2 are independently of each other hydrogen or an organic substituent, or Q1 and Q2 together with the carbon atoms, to which they are bonded, form a condensed ring, for example an aromatic or heteroaromatic ring, which optionally may be substituted, or a carbocyclic or heterocyclic, non-aromatic ring, which optionally may be substituted; and
Q3 represents a group of forming a condensed aromatic or heteroaromatic ring, preferably a phenyl or naphthyl ring, which optionally may be substituted, and wherein 1-3, preferably one, of L1, L2, Q1, Q2 and/or the substituents contains a divalent group derived from a polymerizable aliphatic or aromatic momomer moiety;
or x2 is at least 1 , and A2 is selected from repeating unit(s) of the formula
Figure imgf000004_0001
especially
Figure imgf000004_0002
(Ilia) or (MIb),
Figure imgf000004_0003
where in the formulae (III) and (IV) x is 0, or an integer of 1 to 5, A is a 5-, 6-, or 7-membered heteroaromatic ring, containing at least one heteroatom selected from nitrogen, oxygen and sulfur, especially one nitrogen atom and at least one further heteroatom selected from nitrogen, substituted nitrogen, oxygen and sulfur;
R1, R2, R3, R4, R5 and R6 are independently of each other hydrogen, halogen, or an organic substituent, or R1 and R2, R4 and R6, R2 and R3, R5 and R3 and/or R5 and R6, which are adjacent to each other, together form an aromatic, or heteroaromatic ring, or ring system, which can optionally be substituted; - A -
R7 is an organic substituent, wherein two or more substituents R7 in the same molecule may have different meanings, or can form together an aromatic, or heteroaromatic ring, or ring system;
Ga, G1, G2, G3, G4, G1', G2', G3' and G4' are independently of each other hydrogen, halogen, especially fluorine, or an organic substituent, or
Ga, G1, G2, G3, G4, G1', G2', G3' and G4', if possible, together form an aromatic, or heteroaromatic ring, or ring system, which can optionally be substituted,
G7 is halogen, especially fluorine, or an organic substituent, wherein two or more substituents G7 in the same molecule may have different meanings, or can form together an aromatic, or heteroaromatic ring, or ring system, wherein at least one of Ga, G1, G2, G3, G4, G1', G2', G3' and G4' in a repeating unit is a group R10, wherein
R10 is a trivalent group -(Sp)xi0-[PG']<, wherein x10 is 0, or 1 ; Sp is a spacer unit; PG' is a group derived from a polymerisable group.
The present copolymers show especially good results with regard to solution processing or printing (e.g. in case of non-crosslinked copolymers), long-term stability of the electroluminescent device (e.g. resistance against migration/segregation/crystallization as well as against oxidation/heat) as well as its brightness and efficiency.
The term "ligand" is intended to mean a molecule, ion, or atom that is attached to the coordination sphere of a metallic ion. A "monodentate ligand" contains only 1 coordination site, while a "bidentate ligand" contains 2 coordination sites, both of which are attached to the metallic centre. The term "complex", when used as a noun, is intended to mean a compound having at least one metallic ion and at least one ligand. The term "group" or "moiety" is intended to mean a part of a compound, such as a substituent in an organic compound or a ligand in a complex. The term "substituted" is intended to mean replacement of a hydrogen atom in an organic group or compound by a (typically organic) substituent.
The term "organic substituent" stands for an organic (i.e. C, H containing) or
(hetero)functional radical (e.g. consisting of heteroatoms and optionally either of C or H); usually, any organic substituent, if present, makes up a minor part of the compound; examples for organic substituents are organic radicals containing 1 to 20 carbon atoms and optionally further (e.g. 1-10) heteroatoms, heterofunctional radicals typically comprising 1 to 5 heteroatoms.
Heteroatoms in organic or heterofunctional radicals are usually selected from O, S, N, P, Si, B, as well as halogen (i.e. any of F, Cl, Br, I) making up such a radical.
Organic substituents, if present, preferably are selected from halogen, OH, CrC24alkoxy, d- C24alkyl, Ci-C24haloalkyl, C2-C24alkenyl, C2-C24alkynyl, Ci-C24alkylthio, Ci-C24acyl, C5-Ci0aryl, Ci-Cioheteroaryl, C3-Ci2cycloalkyl, Ci-C24acyloxy, C5-Ci0aryloxy, C3-Ci2cycloalkyloxy, or from the residues COR (i.e. aldehyde or keto group), CH=NR, CH=N-OH, CH=N-OR, COOR, OCOR, CONHR, CONRR', CONH-NHR, CONH-NRR', SR, SO2R, SO3R, SO2NHR, SO2NRR', SO2NH-NHR, SO2NH-NRR', S(O)R, S(O)OR, S(O)NHR, S(O)NRR', S(O)NH- NHR, S(O)NH-NRR', a silyl group (SiRR1R"), PORR', PO(OR)R', PO(OR)2, PO(NHR)2, P0(NRR')2, cyano (CN), NO2, NHR, NRR', NH-NHR, NH-NRR', CONROH; where R, R' and R" independently are selected from Ci-Ci2alkyl, Ci-Ci2haloalkyl, C5-Ci0aryl, C3-Ci2cycloalkyl, preferably from d-C6alkyl, phenyl, cyclopentyl, cyclohexyl; and R may also be hydrogen. Common substituents are often selected from Ci-Ci2alkyl, a hydroxyl group, a mercapto group, Ci-Ci2alkoxy, Ci-Ci2alkylthio, halogen, halo-Ci-Ci2alkyl, a cyano group, an aldehyde group, a ketone group, a carboxyl group, an ester group, a carbamoyl group, an amino group, a nitro group or a silyl group.
Any condensed ring or ring system formed by two neighbouring residues such as Q1 and Q2 or two residues R41 (see below) as an organic bridging group, together with their anchor atoms form a carbocyclic or heterocyclic, non-aromatic or preferably aromatic ring, typically of 5 to 7 ring atoms in total, often is selected from aryl, heteroaryl, cycloalkyl, or cycloaliphatic unsaturated moieties as explained below.
The term "haloalkyl" means groups given by partially or wholly substituting the above-mentioned alkyl group with halogen, the term includes Ci-C24perfluoroalkyl, which is branched or unbranched, such as for example -CF3 (trifluoromethyl), -CF2CF3, -CF2CF2CF3, -CF(CF3)2, -(CF2)3CF3, and -C(CFa)3.
The "aldehyde group, ketone group, ester group, carbamoyl group and amino group" include those substituted by an Ci-C24alkyl group, a C4-Ci8cycloalkyl group, an C6-C30aryl group, an C7-C24aralkyl group or a heterocyclic group, wherein the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group and the heterocyclic group may be unsubstituted or substituted. The term "silyl group" more specifically means a group of formula -SiR105R106R107, wherein R105, R106 and R107 are independently of each other a Ci-C8alkyl group, in particular a CrC4 alkyl group, a C6-C24aryl group or a C7-Ci2aralkylgroup, such as a trimethylsilyl group.
If a substituent occurs more than one time in a group, it can be different in each occurrence.
Alkyl stands for any acyclic saturated monovalent hydrocarbyl group; alkenyl denotes such a group but containing at least one carbon-carbon double bond (such as in allyl); similarly, alkynyl denotes such a group but containing at least one carbon-carbon triple bond (such as in propargyl). In case that an alkenyl or alkynyl group contains more than one double bond, these bonds usually are not cumulated, but may be arranged in an alternating order, such as in -[CH=CH-]n or -[CH=C(CH3)-]n, where n may be, for example, from the range 2-50. Where not defined otherwise, preferred alkyl contains 1-22 carbon atoms; preferred alkenyl and alkynyl each contains 2-22 carbon atoms, especially 3-22 carbon atoms.
The term alkyl, whereever used, thus mainly embraces especially uninterrupted and, where appropriate, substituted Ci-C22alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, sec- butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1 ,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3-tetramethylbutyl, 1-methylheptyl, 3- methylheptyl, n-octyl, 2-ethylhexyl, 1 ,1 ,3-trimethylhexyl, 1 ,1 ,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1 ,1 ,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl. Alkoxy is alkyl-O-; alkylthio is alkyl-S-.
The term alkenyl, whereever used, thus mainly embraces especially uninterrupted and, where appropriate, substituted C2-C22alkenyl such as vinyl, allyl, etc.
Alkynyl, including C2-24alkynyl, is straight-chain or branched, preferred is C2-8alkynyl. For example, ethynyl, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1 ,4-pentadiyn-3-yl, 1 ,3-pentadiyn-5-yl, 1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1-yl, trans-3- methyl-2-penten-4-yn-1-yl, 1 ,3-hexadiyn-5-yl, 1-octyn-8-yl, 1-nonyn-9-yl, 1-decyn-10-yl, or 1- tetracosyn-24-yl. Where indicated as interrupted, any alkyl or alkylene moiety of more than one, especially more than 2 carbon atoms, or such alkyl or alkylene moieties which are part of another moiety, may be interrupted by a non-aromatic cyclic or aromatic cyclic (arylene or heteroarylene) moiety as defined below and/or preferably by a heterofunction such as O, S, CO, COO, OCNR22, OCOO, OCONR22, NR22CNR22, or NR22, where R22 is H, Cr Ci2alkyl, C3-Ci2cycloalkyl, phenyl. They can be interrupted by one or more of these spacer groups, one group in each case being inserted, in general, into one carbon-carbon bond, with hetero-hetero bonds, for example 0-0, S-S, NH-NH, etc., not occurring; if the interrupted alkyl is additionally substituted, the substituents are generally not α to the heteroatom. If two or more interrupting groups of the type -0-, -NR22-, -S- occur in one radical, they often are identical.
Acyl stands for a residue of an organic carboxylic acid, from which it may be formally derived by abstraction of the acid OH; examples are formyl, acetyl, propionyl, benzoyl. Generally, d- Ci8 acyl stands for a radical X'-R2i, wherein X' is CO or SO2 and R2i is selected from monovalent aliphatic or aromatic organic residues, usually from molecular weight up to 300; for example, R2i may be selected from CrCi8alkyl, C2-Ci8alkenyl, C5-Ci0aryl which may be unsubstituted or substituted by Ci-C8alkyl or halogen or d-C8alkoxy, C6-Ci5arylalkyl which may be unsubstituted or substituted in the aromatic part by Ci-C8alkyl or halogen or d- C8alkoxy, C4-Ci2cycloalkyl, and in case that X' is CO, R2i may also be H. Acyl is preferably an aliphatic or aromatic residue of an organic acid -CO-R2-I, usually of 1 to 30 carbon atoms, wherein R21 embraces aryl, alkyl, alkenyl, alkynyl, cycloalkyl, each of which may be substituted or unsubstituted and/or interrupted as described elsewhere inter alia for alkyl residues, or R' may be H (i.e. COR' being formyl). Preferences consequently are as described for aryl, alkyl etc.; more preferred acyl residues are substituted or unsubstituted benzoyl, substituted or unsubstituted Ci-Ci7alkanoyl or alkenoyl such as acetyl or propionyl or butanoyl or pentanoyl or hexanoyl, substituted or unsubstituted C5-Ci2cycloalkylcarbonyl such as cyclohexylcarbonyl.
Aralkyl is, within the definitions given, usually selected from C7-C24aralkyl radicals, preferably C7-Ci5aralkyl radicals, which may be substituted, such as, for example, benzyl, 2-benzyl-2- propyl, β-phenethyl, α-methylbenzyl, α,α-dimethylbenzyl, ω-phenyl-butyl, ω-phenyl-octyl, ω-phenyl-dodecyl; or phenyl-Ci-C4alkyl substituted on the phenyl ring by one to three Cr C4alkyl groups, such as, for example, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2,4- dimethylbenzyl, 2,6-dimethylbenzyl or 4-tert-butylbenzyl.or 3-methyl-5-(1 ',1',3',3'-tetramethyl- butyl)-benzyl.
Non-aromatic cyclic (i.e. cycloaliphatic) moieties include cycloalkyl, aliphatic heterocyclic moieties, as well as unsaturated variants thereof such as cycloalkenyl. Cycloalkyl such as C3-Ci8cycloalkyl, is preferably C3-Ci2cycloalkyl or said cycloalkyl substituted by one to three Ci-C4alkyl groups, and includes cyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tert-butylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cyclododecyl, 1- adamantyl, or 2-adamantyl. Cyclohexyl, 1-adamantyl and cyclopentyl are most preferred. C3- Ci2cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl; preferred among these residues are C3- Cβcycloalkyl as well as cyclododecyl, especially cyclohexyl. Further ring structures occuring are heterocyclic aliphatic rings usually containing 5 to 7 ring members, among them at least 1 , especially 1-3, heteromoieties, usually selected from O, S, NR22, where R22 is as explained above for interrupting NR22-groups; examples include C4-Ci8cycloalkyl, which is interrupted by S, O, or NR22, such as piperidyl, tetrahydrofuranyl, piperazinyl and morpholinyl. Unsaturated variants may be derived from these structures by abstraction of a hydrogen atom on 2 adjacent ring members with formation of a double bond between them.; an example for such a moiety is cyclohexenyl.
Wherever "aryl" is used (e.g. in C5-Ci0aryl, Ci-Ci4-heteroaryl), it denotes an aromatic ring or polycyclic ring system containing the highest possible number of double bonds, such as preferably phenyl, naphthyl, anthrachinyl, anthracenyl, phenanthrenyl or fluorenyl. The term aryl mainly embraces hydrocarbon aromatic rings, examples mainly are C6-Ci8aryl including phenyl, naphthyl, anthrachinyl, anthracenyl, phenanthrenyl, fluorenyl. Heteroaromatic rings such as Ci-Ci8heteroaryl moieties contain, as part of the ring structure, one or more heteroatoms mainly selected from O, N and S; heteroaryl such as C4-Ci8heteroaryl stands for an aryl group containing at least one heteroatom, especially selected from N, O, S, among the atoms forming the aromatic ring; examples include pyridyl, pyrimidyl, pyridazyl, pyrazyl, thienyl, benzothienyl, pyrryl, furyl, benzofuryl, indyl, carbazolyl, benzotriazolyl, thiazolyl, chinolyl, isochinolyl, triazinyl, tetrahydronaphthyl, thienyl, pyrazolyl, imidazolyl. Preferred are C6-Ci0aryl or C4-Ci8heteroaryl, e.g. selected from phenyl, naphthyl, pyridyl, tetrahydronaphthyl, furyl, thienyl, pyrryl, chinolyl, isochinolyl, anthrachinyl, anthracenyl, phenanthrenyl, pyrenyl, benzothiazolyl, benzoisothiazolyl, benzothienyl, especially C6- Cioaryl; most preferred is phenyl, naphthyl. Any "arylene" stands for the corresponding divalent "aryl".
The structural units (organic radicals) A1-A5 making up the present copolymer are generally derived from polymerizable aliphatic or aromatic monomers. These monomers mainly include those known in the art to undergo condensation or especially addition polymerization reactions; examples are monomers containing one or more polymerizable groups (PG) such as ethylenically unsaturated moieties or strained ring systems. PG often is a polymerisable group selected from -C(R44)=CH2, -NHC(O )-C(R45)=CH2, -OCH2CH2OC(O )-C(R45)=CH2, - OC(O)-C(R45)=CH2, -C(O)-C(R46)=CH2, -C≡C-, -C≡CR46, -N≡C, -O-CH(CH2CH2CH=CH2)2; C5-C8cycloalkenyl, bicycloalkenyl (a substituted or unsubstituted bicycloalkenyl group having
5 to 30 carbon atoms),
Figure imgf000010_0001
(1 ,2-epoxyether), (oxetanyl),
(CH2)m 1 -CH - C - R8
Figure imgf000010_0002
/0^l -N CO
N ^ ' (CH2)S 1 and , wherein s is an integer from 1 to 6, ml is an integer from 1 to 6, R6 is hydrogen, or CrC20alkyl, R44 is hydrogen, or d-C4alkyl, or halogen, R45 is hydrogen, d-C4alkyl, or halogen, and R46 is hydrogen, CrC4alkyl, or C6-Ci2aryl, or
211
PG' is a group derived from a polymerisable group | , wherein
R212-AHG AHG is an aromatic, or heteroaromatic residue, which can optionally be substituted, such as
Figure imgf000011_0001
or
wherein each dotted line marks the bonding position of PG',
R211 and R212 are independently of each other halogen, -C≡CH, boronic acid, or boronic esters, -Mg-HaI, -Zn-HaI, -Sn (R213)3, wherein Hal is halogen, and R213 is d-Ci8alkyl,
R214 and R214 are independently of each other H, Ci-Cisalkyl, d-C-isalkyl which is interrupted by D, Ci-Ci8perfluoroalkyl, d-Ci8alkoxy, Ci-Ci8alkoxy which is interrupted by D, or C7-
C25aralkyl. Examples for preferred groups PG are vinyl, allyl, (meth)acryloyl, styryl, oxetanyl, oxiranyl, glycidyl.
R212-AHG
If PG is a polymerisable group , the following processes can be used for the production of polymers:
Polymerization processes involving only dihalo-functional reactants may be carried out using nickel coupling reactions. One such coupling reaction was described by Colon et al. in J. Pol. ScL, Part A, Polymer Chemistry Edition 28 (1990) 367, and by Colon et al. in J. Org. Chem. 51 (1986) 2627. The reaction is typically conducted in a polar aprotic solvent (e.g., dimethylacetamide) with a catalytic amount of nickel salt, a substantial amount of triphenylphosphine and a large excess of zinc dust. A variant of this process is described by loyda et al. in Bull. Chem. Soc. Jpn, 63 (1990) 80 wherein an organo-soluble iodide was used as an accelerator.
Another nickel-coupling reaction was disclosed by Yamamoto in Progress in Polymer Science 17 (1992) 1153 wherein a mixture of dihaloaromatic compounds was treated with an excess amount of nickel (1 ,5-cyclooctadiene) complex in an inert solvent. All nickel-coupling reactions when applied to reactant mixtures of two or more aromatic dihalides yield essentially random copolymers. Such polymerization reactions may be terminated by the addition of small amounts of water to the polymerization reaction mixture, which will replace the terminal halogen groups with hydrogen groups. Alternatively, a monofunctional aryl halide may be used as a chain-terminator in such reactions, which will result in the formation of a terminal aryl group.
Nickel-coupling polymerizations may yield random copolymers, e.g. comprising units of formula I, III, IV and/or units derived from other co-monomers.
In general, polymerization methods and workup procedures known in the pertinent art may be applied in analogy for the present copolymers, including those known as Heck, Sonogashira, Kumada reactions; reactions may be carried out e.g. in analogy to WO07/090773 (see passage from page 21 , line 12, to page 26, line 17) or WOOΘ/097419 (see passage from page 41 line 12 to page 44 line 10, and page 45, lines 15 to 34); the passages from the latter 2 documents mentioned are hereby incorporated by reference.
In general, the desired functional moieties of the present copolymers may be provided as an integral part of the copolymer's main chain, or may be attached as a side chain to the copolymer's main chain. The latter architecture brings about some advantages, e.g. in the synthesis of the compounds since it opens the possibility to attach the desired functionality via grafting reactions, and simplifies certain in situ formations of the desired polymers, e.g. by coating the substrate with a suitable monomer mixture, with or without addition of a photoinitiator, and polymerizing the mixture by exposure to radiation (e.g. UV, electron beam etc.) and/or temperature.
The present copolymers may be linear or crosslinked. In the case of crosslinked copolymers, a certain fraction of the monomers making up the present copolymer are crosslinkers (crosslinking agents), usually containing 2 or more polymerizable groups.
Preferred copolymers of the present invention have a glass transition temperature above 1000C. Another aspect of this invention is related to polymer blends containing 1 to 99 percent of at least one copolymer of the invention. The remainder 1 to 99 percent of the blend is composed of one or more polymeric materials selected from among chain growth polymers such as polystyrene, polybutadiene, poly(methyl methacrylate), and poly(ethylene oxide); step-growth polymers such as phenoxy resins, polycarbonates, polyamides, polyesters, polyurethanes, and polyimides; and crosslinked polymers such as crosslinked epoxy resins, crosslinked phenolic resins, crosslinked acrylate resins, and crosslinked urethane resins. Examples of these polymers may be found in Preparative Methods of Polymer Chemistry, W. R. Sorenson and T. W. Campbell, Second Edition, lnterscience Publishers (1968). Also may be used in the blends are conjugated polymers such as poly(phenylene vinylene), substituted poly(phenylene vinylene)s, substituted polyphenylenes and polythiophenes. Examples of these conjugated polymers are given by Greenham and Friend in Solid State Physics, Vol. 49, pp. 1-149 (1995).
Besides the present copolymers, in general, electroluminescent materials of the invention often contain at least one further component, especially selected from triplett emitters, electron transporters, hole transporters, inert polymers (such as aromatic homo- or copolymers like polystyrene or further polymers listed above, e.g. as viscosity modifiers), initiators, organic salts (especially if soluble in the matrix, e.g. organic ammonium salts). The electroluminescent materials of the invention thus often contain 1 to 99 percent of at least one copolymer of the invention, and 99 to 1 percent of one or more of the additional (auxiliary) components listed above, which often will make up the remainder of the material.
Monomers for the preparation of linear copolymers usually contain only 1 class of polymerizable group and only 1 PG per monomer unit, or for grafting one or more further class(es) of PGs.
Crosslinkers (i.e. monomers suitable to provide crosslinking of the final copolymer product) generally contain 2 or more PGs, which may be of the same class (such as ethylenically unsaturated groups; example: divinylbenzene) or 2 or more different classes of PGs (such as an ethylenically unsaturated group and a strained ring; example: vinylbenzene-Sp-oxetanyl). Any of the structural units A1, A2, A3, A4, A5 may function as a crosslinker. Any moiety containing a divalent group derived from a polymerizable aliphatic or aromatic monomer (such as L1, L2, Q1, Q2 and/or a substituent of formula (I); or L, L1 and/or L2 of formula (II)) thus typically is a group R10 : -(Sp)xi0-[PG']<, wherein x10 is 0, or 1.
The spacer unit Sp, which may be present in the group R10, typically is of the formula
Figure imgf000014_0001
wherein x11 is 0 or 1 ; X3, X2 independently are O, Ci-C4alkylene-O, S, Ci-C4alkylene-S, NR22, Ci-C4alkylene-NR22, COO, CrC4alkylene-COO or CrC4alkylene-OCO, CONR22, C1- C4alkylene-CONR22 or CrC4alkylene-NR22CO, NR22CONR22, CrC4alkylene- NR22CONR22, CrC4alkylene, or a direct bond, and
D is CrC24alkylene, interrupted C3-C24alkylene, C2-C24alkenylene, C2-C24alkynylene, C6- Cioarylene.
PG' is a group derived from a polymerisable group, it is trivalent since it is anchored on Sp (or its anchor position in formula (I), (II) or (IV)) and it is integrated in the copolymer chain, or crosslinked copolymer network, of the present invention. A typical group of moieties PG' thus are derived from ethylenically unsaturated monomers or strained oxygen ring systems, including those of the formulae
Figure imgf000014_0002
where the asterisk (*) indicates its bonding position to Sp or the moieties of formula (I), (II) or IV) and R is as defined above, while the 2 further open bonds provide integration into the copolymer chain. These moieties are especially suitable for introducing the desired functionalities as side chains into the final copolymer of the invention, or as crosslinking moieties. Corresponding polymerizable groups PG include vinyl, allyl, 1-methylvinyl
(isopropenyl), (meth)acryloyl, vinylphenyl (styryl), oxiranyl, glycidyl, oxetanyl etc. Other moieries PG' are those derived from from moieties PG described further above, e.g. those introducing the desired functionalities into the main chain of the copolymer of the invention. More specific copolymers of the invention comprise
[Ai]χi , [A2]χ2, [A3]χ3, [A4]X4, [A5] |x5
wherein the structural units A1, A2, A3, A4 and/or A5 are contained in blocks or at random, and the copolymer is linear or crosslinked, and
A1 is an organic radical of a phosphorescent light emitting moiety; x1 is a number from 1 to about 1000; x2, x3, x4 and x5 independently are numbers from 0 to about 100 000, with the proviso that the sum (x2 + x3 + x4 + x5) is at least 5, especially greater than 9;
A2, A3, A4 and A5 independently are radicals derived from aliphatic or aromatic monomers;
characterized in that A1 is of the formula (I)
Figure imgf000015_0001
(I), wherein n is an integer of 1 to 3, n1 and n2 are an integer 0, 1 or 2,
M1 is a metal with an atomic weight of greater than 40,
L1 is a monodentate ligand or a bidentate ligand,
L2 is a monodentate ligand,
Q1 and Q2 are independently of each other hydrogen or an organic substituent, or
Q1 and Q2 together with the carbon atoms, to which they are bonded, form a condensed ring, for example an aromatic or heteroaromatic ring, which optionally may be substituted, or a carbocyclic or heterocyclic, non-aromatic ring, which optionally may be substituted; and
Q3 represents a group of forming a condensed aromatic or heteroaromatic ring, preferably a phenyl or naphthyl ring, which optionally may be substituted, and wherein 1-3, preferably one, of L1, L2, Q1, Q2 and/or the substituents contains a divalent group derived from a polymerizable aliphatic or aromatic monomer moiety; orand, in case that x2 is at least 1 , and A2 is selected from repeating unit(s) of the formula
Figure imgf000016_0001
A1 generally embraces a phosphorescent light emitting moiety, especially of the formula (II)
Figure imgf000016_0002
where in formula (II) n = 1 ,2 or 3; n1 = 0, 1 or 2; n2 = 0, 1 or 2;
M1 is as defined above; each of L and L1 is a monodentate ligand or a bidentate ligand; L2 is a monodentate ligand; and at least one of L, L1 and L2 contains a divalent group derived from a polymerizable aliphatic or aromatic momomer moiety;
and where in the formulae (III) and (IV) x is 0, or an integer of 1 to 5,
A is a 5-, 6-, or 7-membered heteroaromatic ring, containing at least one heteroatom selected from nitrogen, oxygen and sulfur, especially one nitrogen atom and at least one further heteroatom selected from nitrogen, substituted nitrogen, oxygen and sulfur; R1, R2, R3, R4, R5 and R6 are independently of each other hydrogen, halogen, or an organic substituent, or
R1 and R2, R4 and R6, R2 and R3, R5 and R3 and/or R5 and R6, which are adjacent to each other, together form an aromatic, or heteroaromatic ring, or ring system, which can optionally be substituted; R7 is an organic substituent, wherein two or more substituents R7 in the same molecule may have different meanings, or can form together an aromatic, or heteroaromatic ring, or ring system;
Ga, G1, G2, G3, G4, G1', G2', G3' and G4' are independently of each other hydrogen, halogen, especially fluorine, or an organic substituent, or
Ga, G1, G2, G3, G4, G1', G2', G3' and G4', if possible, together form an aromatic, or heteroaromatic ring, or ring system, which can optionally be substituted,
G7 is halogen, especially fluorine, or an organic substituent, wherein two or more substituents
G7 in the same molecule may have different meanings, or can form together an aromatic, or heteroaromatic ring, or ring system, wherein at least one of Ga, G1, G2, G3, G4, G1', G2', G3' and G4' in a repeating unit is a group R10, wherein
R10 is a trivalent group -(Sp)xi0-[PG']<, wherein x10 is 0, or 1 ;
Sp is a spacer unit; PG' is a group derived from a polymerisable group;
an example is a copolymer of the constitution
[Ai]xi-[A2]χ2 -[A3]X3-[A4]X4 -[A5Jx5 wherein the structural units A1, and, if present, A2, A3, A4 and A5 are contained in blocks or at random, and the copolymer is linear or crosslinked; each Of A2, A3, A4 and A5 independently is selected from radicals containing 2 to 200 carbon atoms;
A1 as the phosphorescent light emitting moiety contains a metal M1 selected from the group consisting of Fe, Ru, Ni, Cu, Co, Ir, Pt, Pd, Rh, Re, Os,TI, Pb, Bi, In, Sn, Sb, Te, Ag and Au; and any substituent, if present, is selected from halogen, OH, CrC24alkoxy, CrC24alkyl, d-
C24haloalkyl, C2-C24alkenyl, C2-C24alkynyl, Ci-C24alkylthio, Ci-C24acyl, C5-Ci0aryl, d-
Cioheteroaryl, C3-Ci2cycloalkyl, Ci-C24acyloxy, C5-Ci0aryloxy, C3-Ci2cycloalkyloxy, or from the residues COR, CH=NR, CH=N-OH, CH=N-OR, COOR, OCOR, CONHR, CONRR',
CONH-NHR, CONH-NRR', SR, SO2R, SO3R, SO2NHR, SO2NRR', SO2NH-NHR, SO2NH-
NRR', S(O)R, S(O)OR, S(O)NHR, S(O)NRR', S(O)NH-NHR, S(O)NH-NRR', a silyl group
(SiRR1R"), PORR', PO(OR)R', PO(OR)2, PO(NHR)2, PO(NRR')2, cyano (CN), NO2, NHR,
NRR', NH-NHR, NH-NRR', CONROH; where R, R' and R" independently are selected from Ci-Ci2alkyl, Ci-Ci2haloalkyl, C5-Ci0aryl,
C3-Ci2cycloalkyl; and R may also be hydrogen.
The invention includes a process for the preparation of the present copolymers, electronic devices comprising them, as well as their use in electronic devices, especially organic light emitting diodes (OLEDs), as oxygen sensitive indicators, as phosphorescent indicators in bioassays, and as catalysts.
The present invention is directed to copolymers comprising a metal complex containing at least one ligand derived from (2H-benzo)triazole, as well as to copolymers comprising, besides a metal complex, a heteroaryl-derivate of phenanthrene.
Phosphorescent Emitters
In general, A1 as an organic radical of a phosphorescent light emitting moiety may be selected from moieties of the formula (II)
Figure imgf000018_0001
where in formula (II) n = 1 ,2 or 3; n1 = 0, 1 or 2; n2 = 0, 1 or 2; M1 is as defined above; each of L and L2 is a monodentate ligand or a bidentate ligand; L1 is a monodentate ligand; and at least one of L, L1 and L2 contains a divalent group derived from a polymerizable aliphatic or aromatic momomer moiety.
In both formulae (I) and (II), the metal is generally a metal M1 with an atomic weight of greater than 40. Preferably, the metal M1 is selected from the group consisting of Fe, Ru, Ni, Cu, Co, Ir, Pt, Pd, Rh, Re, Os1TI, Pb, Bi, In, Sn, Sb, Te, Ag and Au.
More preferably the metal is selected from Ir, Rh and Re as well as Pt and Pd, wherein Ir is most preferred.
For example, a bidentate ligand containing a divalent group derived from a polymerizable aliphatic or aromatic momomer moiety may be selected from:
Figure imgf000019_0002
),
Figure imgf000019_0001
(IX-2), (IX-3), (IX-4),
Figure imgf000019_0003
(IX-8),
Figure imgf000019_0005
(IX-10),
Figure imgf000019_0004
(IX-12), (IX-16),
Figure imgf000020_0001
and (IX- 17), wherein
Figure imgf000020_0002
ring A, , represents an optionally substituted aryl group which may contain a heteroatom,
ring B,
Figure imgf000020_0003
, represents an optionally substituted nitrogen containing aryl group, which may contain further heteroatoms,
Figure imgf000020_0004
ring C, , represents a ligand derived from a nucleophilic carbene, which may contain a heteroatom,
G is -C(=O)-, or -C(X1)2-, wherein X1 is H, or unsubstituted or substituted Ci-C4alkyl, preferably H; y is 0, or 1 , preferably 0;
Y-Z" is a group R10 of the formula -(Sp)xi0-[PG']<, as defined above;
R11 is unsubstituted or substituted Ci-C4alkyl;
R12 is CF3 or a ring A; R13 is H, unsubstituted or substituted CrC4alkyl
R14, R14 independently are a ring A, unsubstituted or substituted Ci-C8alkyl, d-
Cβperfluoralkyl or a ring B, unsubstituted or substituted Ci-C8alkoxy; and
W is N or CH. Preferred metal complex moieties including A1, and formulae (I) and (II), are electroneutral, i.e. wherein the total charge of ligands balances the charge of the central metal atom.
Further ligands, especially in moieties of the formula (II), may be selected from those of the above formulae IX-1 to IX-17 wherein Y-Z" is hydrogen.
Bidentate ligands of specific interest are often selected from (2H-benzo)triazole, o- phenylpyridine, each of which may be unsubstituted or substituted.
Moieties A1 containing 2 or 3 bidentate ligands are preferred. Likewise preferred are moieties A1 containing at least one bidentate ligand of the class 2-aryl-1 ,2,3-triazole as contained in the formula (I)
Figure imgf000021_0001
(I), wherein Q1 and Q2 are independently of each other hydrogen or an organic substituent, or
Q1 and Q2 together with the carbon atoms, to which they are bonded, form a condensed ring, for example an aromatic or heteroaromatic ring, which optionally may be substituted, or a carbocyclic or heterocyclic, non-aromatic ring, which optionally may be substituted; and Q3 represents a group of forming a condensed aromatic or heteroaromatic ring, preferably a phenyl or naphthyl ring, which optionally may be substituted, and wherein Q1, Q2 and/or the substituents contains a group Y-Z" which is H or is derived from a polymerizable aliphatic or aromatic momomer moiety such as a group R10 as defined above.
Further symbols shown in formula (I) are as defined above.
A preferred class of structural units A1 are of the formula (I). In the moieties of the above formula (I), Q1 and Q2 together with the carbon and nitrogen atoms, to which they are bonded, often form a group
Figure imgf000022_0001
, wherein Q4 represents a group of forming a condensed aromatic, or heteroaromatic ring, which can optionally be substituted.
Some phosphorescent moieties A1 of specific interest contain a bidentate ligand L1, which conforms to the formula (LII)
Figure imgf000022_0002
wherein W is selected from O, S, NR4, CR5R6, X is N or CR7, Y is selected from O, S, NR8;
Ri, R2, R4, R5, R6 independently are H, unsubstituted or substituted CrCi8alkyl, unsubstituted or substituted C2-Ci8alkenyl, unsubstituted or substituted C5-Ci0aryl, unsubstituted or substituted C2-Ci0heteroaryl, Ci-Ci8acyl, or R10;
or R1, R2 may stand for a substituent ; or the neighbouring residues R1 and R2 form an organic bridging group completing, together with the carbon atoms they are bonding to, a carbocyclic or heterocyclic, non-aromatic or preferably aromatic ring of 5 to 7 ring atoms in total, which optionally may be substituted;
R7, if present, together with its neighbouring residue R3 forms an organic bridging group completing, with the carbon atoms they are bonding to, a carbocyclic or heterocyclic, non- aromatic or preferably aromatic ring of 5 to 7 ring atoms in total, which optionally may be substituted; or R7 embraces the meanings given for R4, or is halogen, OR, SR, NRR', COOR, CONRR', CN, OCN, SCN, or is C2-C5alkynyl, C3-C5cycloalkyl, hetero-C2-C5cycloalkyl, or C3-C5cycloalkenyl, each unsubstituted or substituted; or R3 is H, unsubstituted or substituted Ci-Ci8alkyl, unsubstituted or substituted C2- Ci8alkenyl, unsubstituted or substituted C5-Cioaryl, unsubstituted or substituted C2- Cioheteroaryl, Ci-Ci8acyl, OR, SR, NRR', or is C2-C5alkynyl, C3-C5cycloalkyl, hetero-C2-C5cycloalkyl or C3-C5cycloalkenyl each unsubstituted or mono- or poly-substituted by COR, COOR, CONRR', CN, halogen and/or by OR;
R'3 is unsubstituted or substituted CrCi8alkylene, unsubstituted or substituted C2- Ci8alkenylene, unsubstituted or substituted C5-Ci0arylene, unsubstituted or substituted C2- Cioheteroarylene, C2-Ci8diacylene; R8 is hydrogen or a substituent; any substituent is selected from halogen, Ci-Ci8alkoxy, Ri0, CrCi8alkylthio, Ci-Ci8acyl, C5- Cioaryl, C3-Ci2cycloalkyl, Ci-Ci8acyloxy, C5-Ci0aryloxy, C3-Ci2cycloalkyloxy, or from the residues COR, CH=NR, CH=N-OH, CH=N-OR, COOR, CONHR, CONRR', CONH-NHR, CONH-NRR', SO2R, SO3R, SO2NHR, SO2NRR', SO2NH-NHR, SO2NH-NRR', S(O)R, S(O)OR, S(O)NHR, S(O)NRR', S(O)NH-NHR, S(O)NH-NRR', SiRR'R", PORR', PO(OR)R', PO(OR)2, PO(NHR)2, PO(NRR')2, CN, NO2, NHR, NRR', NH-NHR, NH-NRR', CONROH; R, R' and R" independently are selected from Ci-Ci2alkyl, C5-Ci0aryl, C3-Ci2cycloalkyl, preferably from d-C6alkyl, phenyl, cyclopentyl, cyclohexyl; and R may also be hydrogen; L in formula Il is a bidentate ligand; and L or L1 contains a residue Ri0; especially wherein R7, if present, together with its neighbouring residue R3 forms an organic bridging group completing, with the carbon atoms they are bonding to, a carbocyclic or heterocyclic, non-aromatic or preferably aromatic ring of 5 to 7 ring atoms in total, which optionally may be substituted; or R7 embraces the meanings given for R4, or is NRR', COR, COOR, CONRR', CN, or is C2-C5alkynyl, C3-C5cycloalkyl, hetero-C2-C5cycloalkyl, or C3-C5cycloalkenyl, each unsubstituted or substituted; or R3 is H, unsubstituted or substituted Ci-Ci8alkyl, unsubstituted or substituted C2- Ci8alkenyl, unsubstituted or substituted C5-Ci0aryl, unsubstituted or substituted C2- Cioheteroaryl, Ci-Ci8acyl, or is C2-C5alkynyl, C3-C5cycloalkyl, hetero-C2-C5cycloalkyl or C3-C5cycloalkenyl each unsubstituted or mono- or poly-substituted by COR, COOR, CONRR', CN, halogen and/or by OR;
R'3 is unsubstituted or substituted Ci-Ci8alkylene, unsubstituted or substituted C2- Ci8alkenylene, unsubstituted or substituted C5-Ci0arylene, unsubstituted or substituted C2- Cioheteroarylene, C2-Ci8diacylene; R8 is hydrogen or a substituent.
Hosts
A2 as an organic radical providing host functionality may be selected from suitable divalent radicals providing the desired functionality in the main chain (as in the units of formulae III, Ilia and 1Mb above), or corresponding radicals in the side chain (as in formula IV).
The ring A in units A2 as of the above formulae IN-IV often is selected from A is a 5-, 6-, or 7- membered heteroaromatic ring, containing at least one heteroatom selected from nitrogen, oxygen and sulphur, which can be substituted and/or can be part of a fused aromatic or heteroaromatic ring system. Non-limiting examples of A are:
Figure imgf000024_0001
' ' , ' , or , wherein R has the meaning of
R8, R8' has the meaning of R8, X is O, S, N-R17, wherein R205, R206, R207, R208, R209, R210, R8, R9, R9', R9 ", R", R99', R10 and R17 are as defined below, p' is 0, 1 , or 2 and the dotted line indicates the bonding to the benzene ring.
Preferably, A is one of the above 5-, 6-, or 7-membered heteroaromatic rings, containing one nitrogen atom and at least one further heteroatom selected from nitrogen, oxygen and sulphur. If the heteroatom is nitrogen, it can be a group =N-, or -NR-, especially -N-R17, or - NR10-, wherein R is an organic substituent, R17 and R10 are as defined below. Some preferred structural units A2 of the type integrated into the main chain are as described in WO06/097419, especially of the formulae
Figure imgf000025_0001
(XVIII), wherein R1 and R4 are independently of each other hydrogen, halogen, CrCi8alkyl, d-Ci8alkyl which is substituted by E and/or interrupted by D, Ci-Ci8perfluoroalkyl, C2-Ci8alkenyl, C2-Ci8alkynyl, d-Ci8alkoxy, Ci-Ci8alkoxy which is substituted by E and/or interrupted by D, CN, or -CO-R28, R2, R3 R5 and R6 are independently of each other H, halogen, Ci-Ci8alkyl, Ci-Ci8alkyl which is substituted by E and/or interrupted by D, Ci-Ci8perfluoroalkyl, C6-C24aryl, C6-C24aryl which is substituted by G, C2-C20heteroaryl, C2-C20heteroaryl which is substituted by G, C2- Ci8alkenyl, C2-Ci8alkynyl, Ci-Ci8alkoxy, Ci-Ci8alkoxy which is substituted by E and/or interrupted by D, C7-C25aralkyl, CN, or -CO-R28, R8 and R9 are independently of each other H, Ci-Ci8alkyl, Ci-Ci8alkyl which is substituted by E and/or interrupted by D, Ci-Ci8perfluoroalkyl, C6-C24aryl, C6-C24aryl which is substituted by G, C2-C20heteroaryl, C2-C20heteroaryl which is substituted by G, C2-Ci8alkenyl, C2-Ci8alkynyl, Ci-Ci8alkoxy, Ci-Ci8alkoxy which is substituted by E and/or interrupted by D, C7-C25aralkyl, CN, or -CO-R28, or 210 .
R and R together form a group
Figure imgf000026_0001
, wherein R206' R208' R205, R206, R207, R208, R209 and R210 are independently of each other H, d-C18alkyl, Ci-Ci8alkyl which is substituted by E and/or interrupted by D, Ci-Ci8alkoxy, or d-Ci8alkoxy which is substituted by E and/or interrupted by D, Ci-Ci8perfluoroalkyl, C6-C24aryl, C6-C24aryl which is substituted by G, C2-C2oheteroaryl, C2-C2oheteroaryl which is substituted by G, C2- Ci8alkenyl, C2-Ci8alkynyl, C7-C25aralkyl, CN, or -CO-R28,
R110 is H, Ci-Ci8alkyl, Ci-Ci8alkyl which is substituted by E and/or interrupted by D, d- Ci8perfluoroalkyl, C6-C24aryl, C6-C24aryl which is substituted by G, C2-C20heteroaryl, C2- C20heteroaryl which is substituted by G, C2-Ci8alkenyl, C2-Ci8alkynyl, Ci-Ci8alkoxy, d- Ci8alkoxy which is substituted by E and/or interrupted by D, C7-C25aralkyl, or -CO-R28, R11 and R14 are independently of each other hydrogen, halogen, Ci-Ci8alkyl, Ci-Ci8alkyl which is substituted by E and/or interrupted by D, Ci-Ci8perfluoroalkyl, C2-Ci8alkenyl, C2- Ci8alkynyl, Ci-Ci8alkoxy, Ci-Ci8alkoxy which is substituted by E and/or interrupted by D, CN, or -CO-R28, R12, R13 R15 and R16 are independently of each other H, halogen, CrCi8alkyl, CrCi8alkyl which is substituted by E and/or interrupted by D, Ci-Ci8perfluoroalkyl, C6-C24aryl, C6-C24aryl which is substituted by G, C2-C20heteroaryl, C2-C20heteroaryl which is substituted by G, C2- Ci8alkenyl, C2-Ci8alkynyl, Ci-Ci8alkoxy, Ci-Ci8alkoxy which is substituted by E and/or interrupted by D, C7-C25aralkyl, CN or -CO-R28, X is O, S, or NR17, wherein R17 is H; C6-Ci8aryl, C2-C20heteroaryl; C6-Ci8aryl, or C2-
C20heteroaryl, which are substituted by Ci-Ci8alkyl, Ci-Ci8perfluoroalkyl, or Ci-Ci8alkoxy; d- Ci8alkyl; or Ci-Ci8alkyl which is interrupted by -O-; or two substituents R2 and R3, R5 and R6, R12 and R13 and/or R15 and R16, R1 and R2, R4 and R6, R11 and R12 and/or R14 and R16, which are adjacent to each other, together form a group
Figure imgf000026_0002
, or two substituents R15 and R13, and/or R5 and R3, which
are adjacent to each other, together form a group
Figure imgf000026_0003
, wherein X is O, S, C(R119XR120), or NR17, wherein R17 is as defined above, R105, R106, R107, R108, R106' and R108' are independently of each other H, CrCi8alkyl, d-Ci8alkyl which is substituted by E and/or interrupted by D, d-Ci8alkoxy, or d-Ci8alkoxy which is substituted by E and/or interrupted by D, R119 and R120 together form a group of formula =CR121R122, wherein
R121 and R122 are independently of each other H, Ci-Ci8alkyl, Ci-Ci8alkyl which is substituted by E and/or interrupted by D, C6-C24aryl, C6-C24aryl which is substituted by G, or C2-
C2oheteroaryl, or C2-C20heteroaryl which is substituted by G, or
R119 and R120 together form a five or six membered ring, which optionally can be substituted by Ci-Ci8alkyl, Ci-Ci8alkyl which is substituted by E and/or interrupted by D, C6-C24aryl, C6-
C24aryl which is substituted by G, C2-C20heteroaryl, C2-C20heteroaryl which is substituted by
G, C2-Ci8alkenyl, C2-Ci8alkynyl, Ci-Ci8alkoxy, Ci-Ci8alkoxy which is substituted by E and/or interrupted by D, C7-C25aralkyl, or -C(=O)-R127, and
R127 is H; C6-Ci8aryl; C6-Ci8aryl which is substituted by Ci-Ci8alkyl, or Ci-Ci8alkoxy; d- Ci8alkyl; or Ci-Ci8alkyl which is interrupted by -O-,
D is -CO-; -COO-; -S-; -SO-; -SO2-; -0-; -NR25-; -SiR30R31-; -POR32-; -CR23=CR24-; or -C≡C-; and
E is -OR29; -SR29; -NR25R26; -COR28; -COOR27; -CONR25R26; -CN; or halogen; G is E, d-
Ci8alkyl, Ci-Ci8alkyl which is interrupted by D, Ci-Ci8perfluoroalkyl, Ci-Ci8alkoxy, or d- Ci8alkoxy which is substituted by E and/or interrupted by D, wherein
R23, R24, R25 and R26 are independently of each other H; C6-d8aryl; C6-d8aryl which is substituted by Ci-Ci8alkyl, or Ci-Ci8alkoxy; Ci-Ci8alkyl; or Ci-Ci8alkyl which is interrupted by
-0-; or
R25 and R26 together form a five or six membered ring, in particular
Figure imgf000027_0001
Figure imgf000027_0002
R^' and R^b are independently of each other H; C6-d8aryl; C6-d8aryl which is substituted by Ci-Ci8alkyl, or Ci-Ci8alkoxy; Ci-Ci8alkyl; or Ci-Ci8alkyl which is interrupted by -0-, R29 is H; C6-Ci8aryl; C6-Ci8aryl, which is substituted by Ci-Ci8alkyl, or d-Ci8alkoxy; d-
Ci8alkyl; or Ci-Ci8alkyl which is interrupted by -O-,
R30 and R31 are independently of each other Ci-Ci8alkyl, C6-Ci8aryl, or C6-Ci8aryl, which is substituted by Ci-Ci8alkyl, and
R32 is Ci-Ci8alkyl, C6-Ci8aryl, or C6-Ci8aryl, which is substituted by Ci-Ci8alkyl.
Repeating units of the formula X, Xl and XII, which are suitable as conjugated polymers for EL devices, especially of the formula XII, are preferred.
Repeating units of the formula X and Xl (XVI and XVII) are of special interest, wherein R1 and R4 are hydrogen,
R2, R3 R5 and R6 are independently of each other H, CrCi8alkyl, CrCi8alkyl which is interrupted by D, Ci-Ci8perfluoroalkyl, Ci-Ci8alkoxy, Ci-Ci8alkoxy which is interrupted by D, C7-C25aralkyl, or a group -X2-R18, R8 and R9 are independently of each other H, Ci-Ci8alkyl, Ci-Ci8alkyl which is interrupted by D, Ci-Ci8perfluoroalkyl, Ci-Ci8alkoxy, Ci-Ci8alkoxy which is interrupted by D, or a group -X2- R18, wherein X2 is a spacer, such as C6-Ci2aryl, or C6-Ci2heteroaryl, especially phenyl, or naphthyl, which can be substituted one more, especially one to two times with Ci-Ci8alkyl, Ci-Ci8alkyl which is interrupted by D, Ci-Ci8perfluoroalkyl, Ci-Ci8alkoxy, or Ci-Ci8alkoxy which is substituted by E and/or interrupted by D, and R18 is H, Ci-Ci8alkyl, Ci-Ci8alkyl which is interrupted by D, Ci-Ci8perfluoroalkyl, Ci-Ci8alkoxy, Ci-Ci8alkoxy which is interrupted by D, or -NR25R26-; or two substituents R2 and R3 and/or R5 and R6, which are adjacent to each other, together form
a group
Figure imgf000028_0001
, or two substituents R5 and R3, which are adjacent to each other,
together form a group
Figure imgf000028_0002
, wherein R105, R106, R107 and R108 are independently of each other H, or Ci-C8alkyl, or R8 and R9 together form a group
Figure imgf000029_0001
R209 and R210 are independently of each other H, Ci-Ci8alkyl, d-Ci8alkyl which is substituted by E and/or interrupted by D, Ci-Ci8alkoxy, or d-Ci8alkoxy which is substituted by E and/or interrupted by D, Ci-Ci8perfluoroalkyl, R110 is H, C6-Ci8aryl, which can be substituted by G, C2-Ci8heteroaryl, which can be substituted by G, Ci-Ci8alkyl, Ci-Ci8alkyl which is interrupted by D, Ci-Ci8perfluoroalkyl, d- Ci8alkoxy, Ci-Ci8alkoxy which is substituted by E and/or interrupted by D, or a group -X2- R18, wherein X2 is a spacer, such as C6-Ci2aryl, or C6-Ci2heteroaryl, especially phenyl, or naphthyl, which can be substituted one more, especially one to two times with Ci-Ci8alkyl, Ci-Ci8alkyl which is interrupted by D, Ci-Ci8perfluoroalkyl, Ci-Ci8alkoxy, or Ci-Ci8alkoxy which is substituted by E and/or interrupted by D, and R18 is H, Ci-Ci8alkyl, Ci-Ci8alkyl which is interrupted by D, Ci-Ci8perfluoroalkyl, Ci-Ci8alkoxy, Ci-Ci8alkoxy which is interrupted by D, Or -NR25R26; D is -CO-; -COO-; -S-; -SO-; -SO2-; -O-; -NR25-; -CR23=CR24-; or -C≡C-; wherein R23, R24, R25 and R26 are independently of each other H; C6-Ci8aryl; C6-Ci8aryl which is substituted by Ci-C8alkyl, or Ci-C8alkoxy; Ci-C8alkyl; or Ci-C8alkyl which is interrupted by -
O-, or R25 and R26 together form a five or six membered ring, in particular
Figure imgf000029_0002
Figure imgf000029_0003
Some preferred structural units A2 containing the host functionality in the side chain are as described in WO07/090773 especially selected from those of the formulae
Figure imgf000030_0001
Figure imgf000031_0001
(XXII'), and/or (XXIII'), wherein
R1 and R1 are independently of each other hydrogen, halogen, CrCi8alkyl, d-Ci8alkyl which is substituted by E and/or interrupted by D, Ci-Ci8perfluoroalkyl, C2-Ci8alkenyl, C2-Ci8alkynyl, Ci-Ci8alkoxy, Ci-Ci8alkoxy which is substituted by E and/or interrupted by D, CN, or -CO-R28, R2, R3 R4, R2', R3' and R4' are independently of each other H, halogen, CrCi8alkyl, d- Ci8alkyl which is substituted by E and/or interrupted by D, Ci-Ci8perfluoroalkyl, C6-C24aryl, C6-C24aryl which is substituted by G, C2-C2oheteroaryl, C2-C2oheteroaryl which is substituted by G, C2-Ci8alkenyl, C2-Ci8alkynyl, Ci-Ci8alkoxy, Ci-Ci8alkoxy which is substituted by E and/or interrupted by D, C7-C25aralkyl, CN, or -CO-R28,
R8 is H, Ci-Ci8alkyl, Ci-Ci8alkyl which is substituted by E and/or interrupted by D, d- Ci8perfluoroalkyl, C6-C24aryl, C6-C24aryl which is substituted by G, C2-C20heteroaryl, C2- C20heteroaryl which is substituted by G, C2-Ci8alkenyl, C2-Ci8alkynyl, Ci-Ci8alkoxy, d- Ci8alkoxy which is substituted by E and/or interrupted by D, C7-C25aralkyl, CN, or -CO-R28, R9, R9', R9 ", R" and R99' is H, CrCi8alkyl, R10, CrCi8alkyl which is substituted by E and/or interrupted by D, Ci-Ci8perfluoroalkyl, C6-C24aryl, C6-C24aryl which is substituted by G, C2- C20heteroaryl, C2-C20heteroaryl which is substituted by G, C2-Ci8alkenyl, C2-Ci8alkynyl, d- Ci8alkoxy, Ci-Ci8alkoxy which is substituted by E and/or interrupted by D, C7-C25aralkyl, SiRR'R", GeRR'R", POAr2, PAr2, or is -CO-R28;
R10 is a group -(Sp)xi0-[PG']<, wherein Sp is a spacer unit, PG' is a group derived from a polymerisable group, with preferences as described above, and x10 is 0, or 1 , or
R and R together form a group
Figure imgf000031_0002
, wherein one of the substituents R205, R206, R207 and R208, and one of the substituents R209 and R210 is a group R10 and the other substituents are independently of each other H, Ci-Ci8alkyl, Ci-Ci8alkyl which is substituted by E and/or interrupted by D, Ci-Ci8alkoxy, or Ci-Ci8alkoxy which is substituted by E and/or interrupted by D,
R and R ■> i r are independently of each other hydrogen, halogen, especially fluorine, d- Ci8alkyl, Ci-Ci8alkyl which is substituted by E and/or interrupted by D, Ci-Ci8perfluoroalkyl, C2-Ci8alkenyl, R10, C2-Ci8alkynyl, Ci-Ci8alkoxy, Ci-Ci8alkoxy which is substituted by E and/or interrupted by D, CN, or -CO-R28, SiRR'R", GeRR'R", POAr2, PAr2;
R12, R13 R14, R12', R13' and R14' are independently of each other H, halogen, especially fluorine, Ci-Ci8alkyl, R10, CrCi8alkyl which is substituted by E and/or interrupted by D, d-
Ci8perfluoroalkyl, C6-C24aryl, C6-C24aryl which is substituted by G, C2-C20heteroaryl, C2-
C20heteroaryl which is substituted by G, C2-Ci8alkenyl, C2-Ci8alkynyl, Ci-Ci8alkoxy, d-
Ci8alkoxy which is substituted by E and/or interrupted by D, C7-C25aralkyl, CN or -CO-R28, and R13 R14, R13' and R14' may also be SiRR'R", GeRR'R", POAr2, PAr2;
X is O, S, or NR17, wherein R17 is Ci-Ci8alkyl, Ci-Ci8alkyl which is substituted by E and/or interrupted by D, Ci-Ci8perfluoroalkyl, C6-C24aryl, C6-C24aryl which is substituted by G, C2-
C20heteroaryl, C2-C20heteroaryl which is substituted by G, C2-Ci8alkenyl, C2-Ci8alkynyl, C7-
C25aralkyl, or -CO-R28; or two substituents R1, R2, R3 and R4; R1', R2', R3' and R4'; R9, R11, R12, R13 and R14; R9', R11',
R , R and R , which are adjacent to each other, together form a group
Figure imgf000032_0001
, or
Figure imgf000032_0002
or two substituents R and R , which are adjacent to each other, together
form a group
Figure imgf000032_0003
or two substituents R and R , and/or R and R , which are adjacent to each other, together
form a group
Figure imgf000032_0004
, wherein X3 is O, S, C(R119)(R120), or NR17, wherein R17 is as defined above, R105, R106, R107, R108, R105',R106', R107' and R108' are independently of each other H, Ci-Ci8alkyl, Ci-Ci8alkyl which is substituted by E and/or interrupted by D, Ci-Ci8alkoxy, or Ci-Ci8alkoxy which is substituted by E and/or interrupted by D, R119 and R120 together form a group of formula =CR121R122, wherein
R121 and R122 are independently of each other H, Ci-Cisalkyl, Ci-C-ι8alkyl which is substituted by E and/or interrupted by D, C6-C24aryl, C6-C24aryl which is substituted by G, or C2- C2oheteroaryl, or C2-C20heteroaryl which is substituted by G, or R119 and R120 are independently of each other H, Ci-Ci8alkyl, d-Ci8alkyl which is substituted by E and/or interrupted by D, C6-C24aryl, C6-C24aryl which is substituted by G, C2- C20heteroaryl, C2-C20heteroaryl which is substituted by G, C2-Ci8alkenyl, C2-Ci8alkynyl, d- Ci8alkoxy, Ci-Ci8alkoxy which is substituted by E and/or interrupted by D, or C7-C25aralkyl, or R119 and R120 together form a five or six membered ring, which optionally can be substituted by Ci-Ci8alkyl, Ci-Ci8alkyl which is substituted by E and/or interrupted by D, C6-C24aryl, C6- C24aryl which is substituted by G, C2-C20heteroaryl, C2-C20heteroaryl which is substituted by G, C2-Ci8alkenyl, C2-Ci8alkynyl, Ci-Ci8alkoxy, Ci-Ci8alkoxy which is substituted by E and/or interrupted by D, C7-C25aralkyl, or -C(=O)-R127, and R127 is H; C6-Ci8aryl; C6-Ci8aryl which is substituted by Ci-Ci8alkyl, or Ci-Ci8alkoxy; d- Ci8alkyl; or Ci-Ci8alkyl which is interrupted by -O-,
D is -CO-; -COO-; -S-; -SO-; -SO2-; -0-; -NR25-; -SiR30R31-; -POR32-; -CR23=CR24-; or -C≡C-; and
E is -OR29; -SR29; -NR25R26; -COR28; -COOR27; -CONR25R26; -CN; or halogen; G is E, Cr
Ci8alkyl, Ci-Ci8alkyl which is interrupted by D, Ci-Ci8perfluoroalkyl, or Ci-Ci8alkoxy which is substituted by E and/or interrupted by D, wherein
R23, R24, R25 and R26 are independently of each other H; C6-Ci8aryl; C6-Ci8aryl which is substituted by Ci-Ci8alkyl, or Ci-Ci8alkoxy; Ci-Ci8alkyl; or Ci-Ci8alkyl which is interrupted by -0-; or
R25 and R26 together form a five or six membered ring, in particular
Figure imgf000033_0001
Figure imgf000033_0002
R^' and R^b are independently of each other H; C6-Ci8aryl; C6-Ci8aryl which is substituted by Ci-Ci8alkyl, or Ci-Ci8alkoxy; Ci-Ci8alkyl; or Ci-Ci8alkyl which is interrupted by -0-, R29 is H; C6-Ci8aryl; C6-Ci8aryl, which is substituted by Ci-Ci8alkyl, or d-Ci8alkoxy; d- Ci8alkyl; or Ci-Ci8alkyl which is interrupted by -O-,
R30 and R31 are independently of each other Ci-Ci8alkyl, C6-Ci8aryl, or C6-Ci8aryl, which is substituted by Ci-Ci8alkyl, and R32 is Ci-Ci8alkyl, C6-Ci8aryl, or C6-Ci8aryl, which is substituted by Ci-Ci8alkyl,
R, R' and R" independently are selected from d-C^alkyl, d-C^haloalkyl, d.-doaryl, C3- Ci2cycloalkyl, preferably from d-C6alkyl, phenyl, cyclopentyl, cyclohexyl; and Ar independently is selected from C5-doaryl, especially phenyl; x1 is 0, or 1 , with the proviso that in case of the moieties of the formulae XIV and XXM' and XXIII' at least one of the substituents R11, R13, R14, R9', R13' and R14' or, if present, of the substituents R9, R12 and R12 , is a group R10.
A preferred A2 is selected from R52-(Sp)xi0-[PG']<, wherein R52 is unsubstituted or substituted carbazolyl, or a residue of the formula
Figure imgf000034_0001
with either R9 or R10 being an open bond linking the residue to Sp or PG', while the remaining R9', R10', R11, R11', R12, R13 R14, R12', R13' and R14' are independently of each other H or a substituent.
Electron Transport
A3 as an organic radical providing electron-injection or electron-transport functionality often is a group (HEf)-R10, which increases the electron-injection or electron-transport properties. Preferred groups HEl" are:
Figure imgf000035_0001
wherein R41 and m and n are as defined below and p is 0,1 , or 2, especially O or 1 , R42' is H, or R42. Among the above units of group III the units of formula IH'a, MIi, MIj, and IHk are more preferred. Another group of units A3 introduces the electron transport functionality into the copolymer's main chain; examples are
Figure imgf000036_0001
(Mice),
Figure imgf000036_0002
(lllkk). (lllkl), (lllmm), (Minn),
Figure imgf000037_0001
(lllpp),
Figure imgf000037_0003
Figure imgf000037_0002
(lllrr), wherein vn
R4' can be the same or different at each occurence and is Cl, F, CN, N(R45)2, a Ci-C25alkyl group, a C4-Ci8cycloalkyl group, a Ci-C25alkoxy group, in which one or more carbon atoms which are not in neighbourhood to each other could be replaced by -NR45-, -O-, -S-, -C(=O)- O-, or -O-C(=O)-O-, and/or wherein one or more hydrogen atoms can be replaced by F, a C6- C24aryl group, or a C6-C24aryloxy group, wherein one or more carbon atoms can be replaced by O, S, or N, and/or which can be substituted by one or more non-aromatic groups R41, or two or more groups R41 form a ring system; m can be the same or different at each occurence and is 0, 1 , 2, or 3, especially 0, 1 , or 2, very especially 0 or 1 ; n can be the same or different at each occurence and is 0, 1 , 2, or 3, especially 0, 1 , or 2, very especially 0 or 1 ; p is 0,1 , or 2, especially 0 or 1. Among the above units of group III the units of formula IHe, IHj, and IHk are more preferred.
A moiery A3 of special interest is selected from R53-(Sp)xi0-[PG']<, wherein R53 is a residue of the formula
Figure imgf000037_0004
wherein n can be the same or different at each occurence and is 0, 1 , 2, or 3; and each R 3 441' is a substituent, or 2 neighbouring are linked together to form, together with the carbon atoms they are bonding to, an unsubstituted or substituted 5- or 6-membered carbocyclic or heterocyclic ring.
Hole Transport
A4 as an organic radical providing hole transport functionality often is a group (HEl')-R10, wherein R10 is as defined above and
HEl', which increase the hole-injection or hole-transport properties of the copolymers, is preferably selected from:
Figure imgf000038_0001
R can be the same or different at each occurence and is Cl, F, CN,
Figure imgf000038_0002
Rio, a d-
C25alkyl group, a C4-Ci8cycloalkyl group, a Ci-C25alkoxy group, in which one or more carbon atoms which are not in neighbourhood to each other could be replaced by -NR45-, -O-, -S-, - C(=O)-O-, or -O-C(=O)-O-, and/or wherein one or more hydrogen atoms can be replaced by F, a C6-C24aryl group, or a C6-C24aryloxy group, wherein one or more carbon atoms can be replaced by O, S, or N, and/or which can be substituted by one or more non-aromatic groups R41, or two or more groups R41 form a ring system;
R42 can be the same or different at each occurence and is CN, a Ci-C25alkyl group, a C4- C-iscycloalkyl group, a CrC2SaIkOXy group, in which one or more carbon atoms which are not in neighbourhood to each other could be replaced by -NR45-, -O-, -S-, -C(=O)-O-, or -O- C(=O)-O-, and/or wherein one or more hydrogen atoms can be replaced by F, a C6-C24aryl group, or a C6-C24aryloxy group, wherein one or more carbon atoms can be replaced by O, S, or N, and/or which can be substituted by one or more non-aromatic groups R41, or two or more groups R41 form a ring system;
R44 can be the same or different at each occurence and are a hydrogen atom, a CrC25alkyl group, a C4-Ci8cycloalkyl group, a Ci-C25alkoxy group, in which one or more carbon atoms which are not in neighbourhood to each other could be replaced by -NR45-, -O-, -S-, -C(=O)- O-, or, -O-C(=O)-O-, and/or wherein one or more hydrogen atoms can be replaced by F, a C6-C24aryl group, or a C6-C24aryloxy group, wherein one or more carbon atoms can be replaced by O, S, or N, and/or which can be substituted by one or more non-aromatic groups R41, or CN, or two or more groups R44, which are in neighbourhood to each other, form a ring;
R45 is H, a Ci-C25alkyl group, a C4-Ci8cycloalkyl group, a Ci-C25alkoxy group, in which one or more carbon atoms which are not in neighbourhood to each other could be replaced by -NR45-, -O-, -S-, -C(=O)-O-, or, -O-C(=O)-O-, and/or wherein one or more hydrogen atoms can be replaced by F, a C6-C24aryl group, or a C6-C24aryloxy group, wherein one or more carbon atoms can be replaced by O, S, or N, and/or which can be substituted by one or more non-aromatic groups R41; m can be the same or different at each occurence and is 0, 1 , 2, or 3, especially 0, 1 , or 2, very especially 0 or 1 ; n can be the same or different at each occurence and is 0, 1 , 2, or 3, especially 0, 1 , or 2, very especially 0 or 1 ;
Ar1 and Ar1 are independently of each other a C6-C24aryl group, a C2-C30heteroaryl group, which can be substituted by one or more non-aromatic groups R41, or NO2, especially phenyl, naphthyl, anthryl, biphenylyl, 2-fluorenyl, phenanthryl, or perylenyl, which can be substituted by one or more non-aromatic groups R , such as
Figure imgf000040_0001
Figure imgf000040_0002
Ar2 is a C6-C3oarylene group, or a C2-C24heteroarylene group, which can optionally be substituted, especially
Figure imgf000040_0003
Figure imgf000040_0004
Figure imgf000041_0001
, wherein
R116 and R117 are independently of each other H, halogen, -CN, CrCi8alkyl, d-Ci8alkyl which is substituted by E and/or interrupted by D, C6-C24aryl, C6-C24aryl which is substituted by G, C2-C2oheteroaryl, C2-C2oheteroaryl which is substituted by G, C2-Ci8alkenyl, C2-Ci8alkynyl, Ci-Ci8alkoxy, Ci-Ci8alkoxy which is substituted by E and/or interrupted by D, C7-C25aralkyl, - C(=O)-R127, -C(=O)OR127, or -C(=O)NR127R126, R119 and R120 are independently of each other H, Ci-Ci8alkyl, Ci-Ci8alkyl which is substituted by E and/or interrupted by D, C6-C24aryl, C6-C24aryl which is substituted by G, C2-
C20heteroaryl, C2-C20heteroaryl which is substituted by G, C2-Ci8alkenyl, C2-Ci8alkynyl, d- Ci8alkoxy, Ci-Ci8alkoxy which is substituted by E and/or interrupted by D, or C7-C25aralkyl, or R119 and R120 together form a group of formula =CR121R122, wherein R121 and R122 are independently of each other H, Ci-Ci8alkyl, Ci-Ci8alkyl which is substituted by E and/or interrupted by D, C6-C24aryl, C6-C24aryl which is substituted by G, or C2- C20heteroaryl, or C2-C20heteroaryl which is substituted by G, or
R119 and R120 together form a five or six membered ring, which optionally can be substituted by Ci-Ci8alkyl, Ci-Ci8alkyl which is substituted by E and/or interrupted by D, C6-C24aryl, C6- C24aryl which is substituted by G, C2-C20heteroaryl, C2-C20heteroaryl which is substituted by G, C2-Ci8alkenyl, C2-Ci8alkynyl, Ci-Ci8alkoxy, Ci-Ci8alkoxy which is substituted by E and/or interrupted by D, C7-C25aralkyl, or -C(=O)-R127, and
R126 and R127 are independently of each other H; C6-Ci8aryl; C6-Ci8aryl which is substituted by Ci-Ci8alkyl, or Ci-Ci8alkoxy; Ci-Ci8alkyl; or Ci-Ci8alkyl which is interrupted by -O-, D is -CO-, -COO-, -S-, -SO-, -SO2-, -O-, -NR65-, -SiR70R71-, -POR72-, -CR63=CR64-, or -C≡C-, and E is -OR69, -SR69, -NR65R66, -COR68, -COOR67, -CONR65R66, -CN, or halogen, G is E, or Ci-Ci8alkyl,
R63, R64, R65 and R66 are independently of each other H; C6-Ci8aryl; C6-Ci8aryl which is substituted by CrCi8alkyl, d-Ci8alkoxy; Ci-Ci8alkyl; or Ci-Ci8alkyl which is interrupted by 0-; or
R65 and R66 together form a five or six membered ring, in particular
Figure imgf000042_0001
Figure imgf000042_0002
R67 and R68 are independently of each other H; C6-Ci8aryl; C6-Ci8aryl which is substituted by
Ci-Ci8alkyl, or Ci-Ci8alkoxy; Ci-Ci8alkyl; or Ci-Ci8alkyl which is interrupted by -O-, R69 is H; C6-Ci8aryl; C6-Ci8aryl, which is substituted by CrCi8alkyl, CrCi8alkoxy; CrCi8alkyl; or Ci-Ci8alkyl which is interrupted by -O-,
R70 and R71 are independently of each other Ci-Ci8alkyl, C6-Ci8aryl, or C6-Ci8aryl, which is substituted by Ci-Ci8alkyl, and
R72 is Ci-Ci8alkyl, C6-Ci8aryl, or C6-Ci8aryl, which is substituted by Ci-Ci8alkyl.
Ar1 is preferably a phenyl group, which is substituted by Ci-C4alkyl, or NO2, in particular
Figure imgf000042_0003
, , or an anthryl group, in particular an anthr-2-yl group.
Preferably, R116 and R117 are independently of each other H, d-C^alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, t-butyl, 2-methylbutyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, or n-heptyl, Ci-Ci2alkyl which is substituted by E and/or interrupted by D, such as -CH2OCH3, -CH2OCH2CH3, -CH2OCH2CH2OCH3, or -CH2OCH2CH2OCH2CH3 , C6-Ci4aryl, such as phenyl, naphthyl, or biphenylyl, C5- Ci2cycloalkyl, such as cyclohexyl, C6-d4aryl which is substituted by G, such as -C6H4OCH3, -C6H4OCH2CH3, -C6H3(OCH3)2, or -C6H3(OCH2CH3)2, -C6H4CH3, -C6H3(CH3)2, -C6H2(CH3)3, or -C6H4tBu. R65 is preferably H, d-C^alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, t-butyl, 2-methylbutyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, n-heptyl, or C6- Ci4aryl, such as phenyl, naphthyl, or biphenylyl, which can optionally be substituted.
Preferably, R119 and R120 are independently of each other H, d-C^alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, d-C^alkyl which is substituted by E and/or interrupted by D, such as -CH2(OCH2CH2)WOCH3, W = 1 , 2, 3, or 4, C6-Ci4aryl, such as phenyl, naphthyl, or biphenylyl, C6-Ci4aryl which is substituted by G, such as -C6H4OCH3, -C6H4OCH2CH3, -C6H3(OCH3)2, -C6H3(OCH2CH3),, -C6H4CH3, -C6H3(CH3)2, -C6H2(CH3)3, or -C6H4tBu, or R9 and R10 together form a 4 to 8 membered ring, especially a 5 or 6 membered ring, such as cyclohexyl, or cyclopentyl, which can optionally be substituted by Ci-C8alkyl.
D is preferably -CO-, -COO-, -S-, -SO-, -SO2-, -0-, -NR65-, wherein R65 is CrCi2alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, or sec-butyl, or C6-Ci4aryl, such as phenyl, naphthyl, or biphenylyl.
E is preferably -OR69; -SR69; -NR65R65; -COR68; -COOR67; -CONR65R65; or -CN; wherein R65, R67, R68 and R69 are independently of each other Ci-Ci2alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or C6-Ci4 aryl, such as phenyl, naphthyl, or biphenylyl.
G has the same preferences as E, or is Ci-Ci8alkyl, especially Ci-Ci2alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl.
Another group of units A4 introduces the hole transport functionality into the copolymer's main chain; examples are in particular selected from the group consisting of ortho-, meta- or para-phenylene, 1 ,4-naphthylene, 9,10-anthracenylene, 2,7-phenanthrenylene, 1 ,6-, 2,7-, 4,9-pyrene, 2,7-tetrahydropyrene, oxadiazolylene, 2,5-thiophenylene, 2,5-pyrrolylene; 2,5- furanylene, 2,5-pyridylene, 2,5-pyrimidinylene, 5,8-chinolinylene, fluorene, spiro-9,9'- bifluorene, indenofluorene, heteroindenofluorene, 2,7-N-alkylcarbazol, 2,7-N-arylcarbazol, 3,6- N-alkylcarbazol, and 3,6-N-arylcarbazol. Preferred examples of additional repeating units are
Figure imgf000044_0001
p is 0, 1 or 2;
R41 can be the same or different at each occurence and is Cl, F, CN, N(R45)2, a Ci-C25alkyl group, a C4-Ci8cycloalkyl group, a Ci-C25alkoxy group, in which one or more carbon atoms which are not in neighbourhood to each other could be replaced by -NR45-, -O-, -S-, -C(=O)- O-, or -O-C(=O)-O-, and/or wherein one or more hydrogen atoms can be replaced by F, a C6- C24aryl group, or a C6-C24aryloxy group, wherein one or more carbon atoms can be replaced by O, S, or N, and/or which can be substituted by one or more non-aromatic groups R41, or two or more groups R41 form a ring system; R44 can be the same or different at each occurence and are a hydrogen atom, a Ci-C25alkyl group, a C4-Ci8cycloalkyl group, a Ci-C25alkoxy group, in which one or more carbon atoms which are not in neighbourhood to each other could be replaced by -NR45-, -O-, -S-, -C(=O)- O-, or, -O-C(=O)-O-, and/or wherein one or more hydrogen atoms can be replaced by F, a C6-C24aryl group, or a C6-C24aryloxy group, wherein one or more carbon atoms can be replaced by O, S, or N, and/or which can be substituted by one or more non-aromatic groups R41, or CN, or two or more groups R44, which are in neighbourhood to each other, form a ring; R45 is H, a Ci-C25alkyl group, a C4-Ci8cycloalkyl group, in which one or more carbon atoms which are not in neighbourhood to each other could be replaced by -NR45-, -O-, -S-, -C(=O)- O-, or, -O-C(=O)-O-, and/or wherein one or more hydrogen atoms can be replaced by F, a C6-C24aryl group, or a C6-C24aryloxy group, wherein one or more carbon atoms can be replaced by O, S, or N, and/or which can be substituted by one or more non-aromatic groups
R41; R116 and R117 are independently of each other H, CrCi8alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, t-butyl, 2-methylbutyl, n-pentyl, isopentyl, n-hexyl, 2- ethylhexyl, or n-heptyl; CrCisalkyl which is substituted by E and/or interrupted by D, such as -CH2OCH3, -CH2OCH2CH3, -CH2OCH2CH2OCH3, Or -CH2OCH2CH2OCH2CH3; Ci-Ci8alkoxy, such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, isobutoxy, sec-butoxy, t-butoxy, 2-methylbutoxy, n-pentyloxy, isopentyloxy, n-hexyloxy, 2-ethylhexyloxy, or n-heptyloxy; C6- Ci4aryl, such as phenyl, naphthyl, or biphenylyl, C5-Ci2cycloalkyl, such as cyclohexyl, C6- Ci4aryl which is substituted by G, such as -C6H4OCH3, -C6H4OCH2CH3, -C6H3(OCH3)2, or -C6H3(OCH2CH3)2, -C6H4CH3, -C6H3(CH3)2, -C6H2(CH3)3, -C6H4OtBu, or -C6H4tBu; R119 and R120 are independently of each other H, Ci-Ci2alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, Ci-Ci2alkyl which is substituted by E and/or interrupted by D, such as -CH2(OCH2CH2)WOCH3, w = 1 , 2, 3, or 4, C6-Ci4aryl, such as phenyl, naphthyl, or biphenylyl, C6-Ci4aryl which is substituted by one to three times by Ci-Ci2alkyl, or Ci-Ci2alkoxy, which can optionally be interrupted by -O-, such as -C6H4OCH3, -C6H4OCH2CH3, -C6H3(OCH3)2, -C6H3(OCH2CH3)2, -C6H4CH3, -C6H3(CH3)2, -C6H2(CH3)3, or -C6H4tBu, or R119 and R120 together form a 4 to 8 membered ring, especially a 5 or 6 membered ring, such as cyclohexyl, or cyclopentyl, which can optionally be substituted by
Ci-C8alkyl.
A moiety A4 of special interest is selected from R54-(Sp)xio-[PG']<, wherein
Figure imgf000046_0001
R54 is (ll'c), n can be the same or different at each occurence and is 0, 1 , 2, or 3; and each R is a substituent.
Further structural units
A5 as an organic radical derived from aliphatic or aromatic organic monomers often is selected from those of the formula R10-H or R10-RiO in case of crosslinking monomers. Examples are repeating structural units derived from (meth)acrylic acid, d- C8alkyl(meth)acrylates, C2-C8hydroxyalkyl(meth)acrylates, styrene, isopropenylbenzene, diisopropenylbenzene, divinylbenzene, C2-Ci2hydroxyalkylstyrene, C2- Ci2hydroxyalkoxystyrene.
Some preferred A5 are selected from R55-(Sp)xio-[PG']<, wherein R55 is Ci-Ci2alkyl, C3- Ci2cycloalkyl, C6-Cioaryl, C4-Cioheteroaryl, each of which is unsubstituted or substituted, or is H or R10; any substituent, if present, is selected from Ci-Ci2alkyl, a hydroxyl group, a mercapto group, Ci-Ci2alkoxy, Ci-Ci2alkylthio, halogen, halo-Ci-Ci2alkyl, a cyano group, an aldehyde group, a ketone group, a carboxyl group, an ester group, a carbamoyl group, an amino group, a nitro group, R10, a silyl group, where halogen stands for Cl, F; R10 is a group -(Sp)xI0-[PG]; x10 is 0 or 1 ,
Figure imgf000046_0002
PG' is , where the asterisk marks the atom bonding to (Sp)xi0-;
PG is oxiranyl, oxetanyl, glycidyl, or is PG'; any Sp, if present, independently is a spacer of the formula (X3-D)x11-X2, wherein x11 is 0 or 1 ; X3, X2 independently are O, Ci-C4alkylene-O, COO, Ci-C4alkylene-
COO or Ci-C4alkylene-OCO, or a direct bond, and D is Ci-C24alkylene or phenylene.
The copolymers of this invention preferably have a weight average molecular weight of 2,000
Daltons or greater, especially 2,000 to 1 ,000,000 Daltons, more preferably 10,000 to 1 ,000,000 and most preferably 20,000 to 500,000 Daltons. Molecular weights are determined according to gel permeation chromatography using polystyrene standards and/or light scattering detectors. In the present copolymers, the number of phosphorescent metal complex units A1 (i.e. x1 ) often is from 1 to about 500, e.g. 2-500 or preferably 3-300.
The sum (x2 + x3 + x4 + x5) often is from the range 5-10000, e.g. 8-5000. Structural units (organic radicals) A1 often make up about 0.1-25 %, especially 1-10 %, by weight of the present copolymer.
Structural units (organic radicals) A2, if present, often make up about 25-99.9 %, especially
50-99 %, by weight of the present copolymer.
Structural units (organic radicals) A3 and/or A4, if present, often make up about 0.9-99.9 or, if used concomitantly to radicals A2 and/or A5, about 1-75 %, e.g. 0.9-74.9 %, especially 10-50
% by weight of the present copolymer.
Structural units (organic radicals) A5, if present, often make up about 0.01-50 %, e.g. 0.1-20
%, especially 1-10 %, by weight of the present copolymer.
The copolymers of the invention may be prepared following techniques known in the art, e.g. for preparing linear or crosslinked polymers by condensation and/or addition polymerization methods. In many cases, a basic polymer network is formed by addition polymerization of suitable monomers containing ethylenically unsaturated moieties as PGs, e.g. by radical copolymerization using chemical radical starters, photoinitiators, actinic radiation and/or heat for the generation of radicals and initiation of the reaction. (Co)polymers formed in a first preparation step may be further modified e.g. by grafting one or more further monomers and/or functional groups on the polymer skeleton. Reaction conditions and methods may follow, for example, those described in WO06/097419 or WO07/090773. As mentioned above, the present copolymers may also be formed in situ on the substrate.
Some valuable intermediate (co)polymers and monomers are novel compounds.
The invention thus further pertains to a reactive intermediate obtainable by radical copolymerization of a compound of the formula (XII), (XIH) and/or (XXII)
Figure imgf000048_0001
(XXII, i.e. vinylcarbazole or a vinylcarbazole derivative)
with a bifunctional crosslinker of the formula
Figure imgf000048_0002
wherein
X is NR9"; each of R9, R9' , R11, R11', R12, R12', R13, R13', R14, R14' is H, d-Ci2alkyl, halogen, CrCi2alkoxy;
R9" is H, Ci-Ci2alkyl;
R10 is a group -(Sp)xi0-vinyl, xiO is O oM ;
Sp, if present, is a spacer unit (X3-D)x11-X2, wherein x1 1 is 0 or 1 ; X3, X2 independently are O, Ci-C4alkylene-O, S, Ci-C4alkylene-S,
NR22, Ci-C4alkylene-NR22, COO, CrC4alkylene-COO or CrC4alkylene-OCO, CONR22, Cr C4alkylene-CONR22 or Ci-C4alkylene-NR22CO, NR22CONR22, CrC4alkylene-
NR22CONR22, CrC4alkylene, or a direct bond, and
D is Ci-C24alkylene, interrupted C3-C24alkylene, C2-C24alkenylene, C2-C24alkynylene, C6-
Cioarylene; and
RG is a reactive group selected from OH, COOR, oxiranyl, oxetanyl, where R is hydrogen
Ci-C6alkyl, phenyl, cyclopentyl, cyclohexyl.
The reactive copolymers advantageously are prepared using the monomer of formula XII,
XIII and/or XXII in excess over the crosslinking monomer, e.g. 50-99, especially 80-95 % b.w. of the functional monomer XII, XIII, XXII and 1-50, especially 5-20 % b.w. of the crosslinker.
The novel intermediate polymers may be obtained from the above monomers by methods known per se for the polymerization of vinyl compounds. The vinyl monomers are largely known compounds or analogous to known compounds (see, for example, WO06/097419 or WO07/090773).
The invention further provides novel monomers useful for preparing the present copolymers, which are of the formulae:
Figure imgf000049_0001
Figure imgf000049_0002
(I"), wherein
M1 is a metal with an atomic weight of greater than 40, L1 is a bidentate ligand containing the substituent R10; Q1 and Q2 are independently of each other hydrogen or an organic substituent, or
Q1 and Q2 together with the carbon atoms, to which they are bonded, form a condensed ring, for example an aromatic or heteroaromatic ring, which optionally may be substituted, or a carbocyclic or heterocyclic, non-aromatic ring, which optionally may be substituted; and
Q3 represents a group of forming a condensed aromatic or heteroaromatic ring, preferably a phenyl or naphthyl ring, which optionally may be substituted, and wherein 1-3, preferably one, of L1, L2, Q1, Q2 and/or the substituents contains a divalent group derived from a polymerizable aliphatic or aromatic monomer moiety; with preferred residues and/or substituents as described above.
L1 as a bidentate ligand containing the substituent R10 is, for example, selected from
(IX-1 )
(IX-5)
Figure imgf000050_0001
Figure imgf000050_0002
Y-Z"
O O
(IX-15) ' , wherein the residue Y-Z" stands for R10, and
R10 is a group -(Sp)xi0-PG, where PG is selected from vinyl, allyl, acryloyl, methacryloyl, styryl, oxetanyl, oxiranyl, glycidyl; and Sp and x10 are as described above;
Figure imgf000051_0001
ring A, , represents an optionally substituted aryl group which may contain a heteroatom,
ring B,
Figure imgf000051_0002
, represents an optionally substituted nitrogen containing aryl group, which may contain further heteroatoms,
R11 is unsubstituted or substituted Ci-C4alkyl;
R12 is CF3 or a ring A;
R13 is H, unsubstituted or substituted Ci-C4alkyl
R14, R14 independently are a ring A, unsubstituted or substituted Ci-C8alkyl, d-
Cβperfluoralkyl or a ring B, unsubstituted or substituted Ci-C8alkoxy; and
W is N or CH.
Examples for (co)polymerizable phosphorescent moieties of the invention are compounds of the formulae:
Figure imgf000051_0003
Figure imgf000052_0001
Figure imgf000052_0002
Figure imgf000053_0001
The present invention is also directed to an electronic device comprising the present metal complex copolymer and its fabrication process. The electronic device can comprise at least one organic active material positioned between two electrical contact layers, wherein at least one of the layers of the device includes the metallic complex compound. The electronic device can comprise an anode layer (a), a cathode layer (e), and an active layer (c). Adjacent to the anode layer (a) is an optional hole-injecting/transport (electron blocking) layer (b), and adjacent to the cathode layer (e) is an optional electron-injection/transport (hole blocking) layer (d). Layers (b) and (d) are examples of charge transport layers.
The active layer (c) may be split into a layer comprising the present copolymer containing units A3 (electron transport) and a further layer comprising the present copolymer containing units A4 (hole transport).
The active layer (c) preferably comprises at least approximately 1 weight percent of luminiscent metal complex, e.g. in the form of recurring units of the present copolymer or in admixture with non-polymeric complex.
In some embodiments, the active layer (c) may be substantially 100% of the present metal complex copolymer because a host charge transporting material, such as AIq3 is not needed. By "substantially 100%" it is meant that the present copolymer is the only material in the layer, with the possible exception of impurities or adventitious by-products from the process to form the layer. Still, in some embodiments, the present copolymer containing metal complex moieties may be a dopant within a host material, which is typically used to aid charge transport within the active layer (c). The active layer (c) may include an additional other luminescent material, for example a luminescent metal complex, especially a phosphorescent one (i.e. a triplett emitter), which can be a small molecule active material.
The device may include a support or substrate adjacent to the anode layer (a) or the cathode layer (e). Most frequently, the support is adjacent the anode layer (a). The support can be flexible or rigid, organic or inorganic. Generally, glass or flexible organic films are used as a support. The anode layer (a) is an electrode that is more efficient for injecting holes compared to the cathode layer (e). The anode can include materials containing a metal, mixed metal, alloy, metal oxide or mixed-metal oxide. Suitable metal elements within the anode layer (a) can include the Groups 4, 5, 6, and 8-1 1 transition metals. If the anode layer (a) is to be light transmitting, mixed-metal oxides of Groups 12, 13 and 14 metals, such as indium-tin-oxide, may be used. Some non-limiting, specific examples of materials for anode layer (a) include indium-tin-oxide ("ITO"), aluminum-tin-oxide, gold, silver, copper, nickel, and selenium. The anode layer (a) may be formed by a chemical or physical vapor deposition process or spin-cast process, inject or gravure printing process. Chemical vapor deposition may be performed as a plasma-enhanced chemical vapor deposition ("PECVD") or metal organic chemical vapor deposition ("MOCVD").
Physical vapor deposition can include all forms of sputtering (e. g., ion beam sputtering), e- beam evaporation, and resistance evaporation.
Specific forms of physical vapor deposition include rf magnetron sputtering or inductively- coupled plasma physical vapor deposition ("ICP- PVD"). These deposition techniques are well-known within the semiconductor fabrication arts.
A hole-transport layer (b) may be adjacent to the anode; this layer may be split into a hole injecting (b1 ) and a hole transporting (b2) layer. Both hole transporting small molecule compounds and polymers can be used.
Commonly used hole transporting molecules include: N, N'-diphenyl-N, N'-bis(3- methylphenyl)-[1 ,1 '-biphenyl]-4,4'-diamine (TPD), 1 ,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC), N,N'-bis(4-methylphenyl)-N,N'-bis(4-ethylphenyl)-[1 ,1 '-(3,3'-dimethyl)biphenyl]4,4'- diamine (ETPD), tetrakis-(3-methylphenyl)-N,N,N',N'-2,5-phenylenediamine (PDA), a-phenyl- 4-N,N-diphenylaminostyrene (TPS), p- (diethylamino)benzaldehydediphenylhydrazone (DEH), triphenylamine (TPA), bis[4-(N,N-diethylamino)-2-methylphenyl](4- methylphenyl)methane (MPMP), 1-phenyl-3-[p-(diethylamino)styryl]-5-[p- (diethylamino)phenyl]pyrazoline (PPR or DEASP), 1 ,2-trans-bis (9H-carbazol-9- yl)cyclobutane (DCZB), N,N,N',N'-tetrakis (4-methylphenyl)-(1 ,1'-biphenyl)-4,4'-diamine
(TTB), 4,4'-N,N-dicarbazole-biphenyl (CBP), N,N-dicarbazoyl-1 ,4-dimethene-benzene (DCB), N,N'-Di(naphthalen-1-yl)-N,N'-diphenyl-benzidine (NPD), 1 ,3-fc>/s(9-carbazolyl)benzene (mCP), porphyrinic compounds, phthalocyanines, and combinations thereof. Further materials and methods of use in this regard may be as described in US-A-2007-0087219 (see sections [0096] - [0154] therein), which passages are hereby incorporated by reference.
Commonly used hole transporting polymers are polyvinylcarbazole, (phenylmethyl) polysilane, poly(3,4-ethylendioxythiophene) (PEDOT), triarylamine polymers (such as poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'- (N-(4-sec- butylphenyl))diphenylamine)] [TFB]), polypyrrole, and polyaniline. Hole-transporting polymers can be obtained by doping hole- transporting molecules such as those mentioned above into polymers such as polystyrene and polycarbonate.
The hole-injection/transport layer (b) can be formed using any conventional means, including spin-coating, casting, and printing, such as gravure printing. The layer can also be applied by ink jet printing, thermal patterning, or chemical or physical vapor deposition.
Usually, the anode layer (a) and the hole-injection/transport layer (b), if present, are patterned during the same lithographic operation. The pattern may vary as desired. The layers can be formed in a pattern by, for example, positioning a patterned mask or resist on the first flexible composite barrier structure prior to applying the first electrical contact layer material. Alternatively, the layers can be applied as an overall layer (also called blanket deposit) and subsequently patterned using, for example, a patterned resist layer and wet- chemical or dry-etching techniques. Other processes for patterning that are well known in the art can also be used. When the electronic devices are located within an array, the anode layer (a) and hole injection/transport layer (b) typically are formed into substantially parallel strips having lengths that extend in substantially the same direction, layer (b) can be crosslinked.
The active layer (c) comprises the luminescent copolymer of the present invention. The particular material chosen may depend on the specific application, potentials used during operation, or other factors. The active layer (c) may comprise a host material capable of transporting electrons and/or holes, doped with an emissive material that may trap electrons, holes, and/ or excitons, such that excitons relax from the emissive material via a photoemissive mechanism. Active layer (c) may comprise a single material that combines transport and emissive properties. Whether the emissive material is a dopant or a major constituent, the active layer may comprise other materials, such as dopants that tune the emission of the emissive material. Active layer (c) may include a plurality of emissive materials capable of, in combination, emitting a desired spectrum of light. Examples of phosphorescent emissive materials include the copolymers of the present invention, as well as phosphorescent metal compounds disclosed in WO06000544, WO06067074, WO07074093, and publications cited therein. Examples of fluorescent emissive materials include DCM and DMQA, and certain fluorescent polyaryls (EP-A- 1 138746, EP-A-1245659). Examples of host materials include AIq3, CBP and mCP. Examples of emissive and host materials are disclosed in US 6,303,238 B, which is incorporated by reference in its entirety.
Examples of methods for forming the active layer (c) include deposition by solution processing. Examples of film-forming methods from a solution include application methods, such as spin-coating, casting, microgravure coating, roll-coating, wire bar-coating, dip- coating, spray-coating, screen-printing, flexography, offset-printing, gravure printing and ink- jet-printing.
As the composition used for forming the active layer (c) at least one kind of present copolymers and at least one solvent are contained, and additives, such as hole transport material, electron transport material, luminescent material, rheology modifier or stabilizer, may be added.The amount of solvent in the composition is 1 to 99 wt% of the total weight of the composition and preferably 60 to 99 wt% and more preferably 80 to 99 wt%.
The solvent used in the solution processing method is not particularly limited and preferable are those which can dissolve or uniformly disperse the materials. Preferably the materials may be dissolved in a solvent, the solution deposited onto a substrate, and the solvent removed to leave a solid film. Any suitable solvents may be used to dissolve the ionic compounds, provided it is inert, may dissolve at least some material and may be removed from the substrate by conventional drying means (e.g. application of heat, reduced pressure, airflow, etc.). Suitable organic solvents include, but are not limited to, are aromatic or aliphatic hydrocarbons, halogenated such as chlorinated hydrocarbons, esters, ethers, ketones, amide, such as chloroform, dichloroethane, tetrahydrofuran, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, acetone, dimethyl formamide, dichlorobenzene, chlorobenzene, propylene glycol monomethyl ether acetate (PGMEA), and alcohols, and mixtures thereof. Also water and mixtures with water miscible solvents are possible. Layer (c) can be crosslinked.
Optional layer (d) can function both to facilitate electron injection/transport, hole blocking, and also serve as a buffer layer or confinement layer to prevent quenching reactions at layer interfaces. More specifically, layer (d) may promote electron mobility and reduce the likelihood of a quenching reaction if layers (c) and (e) would otherwise be in direct contact. Examples of materials for optional layer (d) include metal-chelated oxinoid compounds (e. g., tris(8-hydroxyquinolato)aluminum (AIq3) or the like); phenanthroline-based compounds (e. g., 2,9-dimethyl-4,7-diphenyl-1 ,10-phenanthroline ("DDPA"), 4,7-diphenyl-1 ,10-phenanthroline ("DPA"), or the like; azole compounds (e. g., 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1 ,3,4- oxadiazole ("PBD") or the like, 3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1 ,2,4-triazole ("TAZ") or the like; other similar compounds; or any one or more combinations thereof. Further materials and methods of use in this regard may be as described in US-A-2006- 0210830 (see sections [0076] - [0079] therein), and in US-A-2007-0042220 (see sections [01 10] - [01 14] therein), which passages are hereby incorporated by reference. Alternatively, optional layer (d) may be inorganic and comprise BaO, LiF, Li2O, or the like. Layer (d) can be crosslinked.
The electron injection/transport layer (d) can be formed using any conventional means, including spin-coating, casting, and printing, such as gravure printing. The layer can also be applied by ink jet printing, thermal patterning, or chemical or physical vapor deposition.
The cathode layer (e) is an electrode that is particularly efficient for injecting electrons or negative charge carriers. The cathode layer (e) can be any metal or nonmetal having a lower work function than the first electrical contact layer (in this case, the anode layer (a)). Materials for the second electrical contact layer can be selected from alkali metals of Group 1 (e. g., Li, Na, K, Rb, Cs), the Group 2 (alkaline earth) metals, the Group 12 metals, the rare earths, the lanthanides (e. g. , Ce, Sm, Eu, or the like), and the actinides. Materials, such as aluminum, indium, calcium, barium, yttrium, and magnesium, and combinations thereof, may also be used. Li-containing organometallic compounds, LiF, and Li2O can also be deposited between the organic layer and the cathode layer to lower the operating voltage. Specific non- limiting examples of materials for the cathode layer (e) include barium, lithium, cerium, cesium, europium, rubidium, yttrium, magnesium, or samarium.
The cathode layer (e) is usually formed by a chemical or physical vapor deposition process. In general, the cathode layer will be patterned, as discussed above in reference to the anode layer (a) and optional hole injecting layer (b). If the device lies within an array, the cathode layer (e) may be patterned into substantially parallel strips, where the lengths of the cathode layer strips extend in substantially the same direction and substantially perpendicular to the lengths of the anode layer strips. Electronic elements called pixels are formed at the cross points (where an anode layer strip intersects a cathode layer strip when the array is seen from a plan or top view).
In other embodiments, additional layer(s) may be present within organic electronic devices. For example, a layer between the hole injecting layer (b) and the active layer (c) may facilitate positive charge transport, band-gap matching of the layers, function as a protective layer, or the like. Similarly, additional layers between the electron injecting layer (d) and the cathode layer (e) may facilitate negative charge transport, band-gap matching between the layers, function as a protective layer, or the like. Layers that are known in the art generally may be used. Some or all of the layers may be surface treated to increase charge carrier transport efficiency. The choice of materials for each of the component layers may be determined by balancing the goals of providing a device with high device efficiency with the cost of manufacturing, manufacturing complexities, or potentially other factors.
The materials of the charge transport layers (b) and (d) often are of the same type as the materials of the active layer (c). More specifically, if the active layer (c) comprises a small molecule compound, then the charge transport layers (b) and (d), if either or both are present, often comprises a different small molecule compound. If the active layer (c) contains a polymer, the charge transport layers (b) and (d), if either or both are present, often contain a polymer, too. Still, the active layer (c) may contain a small molecule compound, and any of its adjacent layers (e.g. charge transport layers) may be polymers.
Each functional layer may be made up of more than one layer. For example, the cathode layer may comprise a layer of a Group I metal and a layer of aluminum. The Group I metal may lie closer to the active layer (c), and the aluminum may help to protect the Group I metal from environmental contaminants, such as water.
Although not meant to limit, the different layers may have the following range of thicknesses: inorganic anode layer (a), usually no greater than approximately 500 nm, for example, approximately 50-200 nm; optional hole-injecting layer (b), usually no greater than approximately 100 nm, for example, approximately 50-200 nm; active layer (c), usually no greater than approximately 100 nm, for example, approximately 10-80 nm; optional electron- injecting layer (d), usually no greater than approximately 100 nm, for example, approximately 10-80 nm; and cathode layer (e), usually no greater than approximately 1000 nm, for example, approximately 30-500 nm. If the anode layer (a) or the cathode layer (e) needs to transmit at least some light, the thickness of such layer may not exceed approximately 100 nm.
The location of the electron-hole recombination zone in the device, and thus the emission spectrum of the device, can be affected by the relative thickness of each layer. Thus, the thickness of the electron-transport layer should be chosen so that the electron-hole recombination zone lies within the light-emitting layer (i.e., active layer (c)). The desired ratio of layer thicknesses can depend on the exact nature of the materials used.
The efficiency of the devices made with metal complexes can be further improved by optimizing the other layers in the device. For example, more efficient cathodes such as Ca, Ba, Mg/Ag, or LiF/AI can be used. Shaped substrates and hole transport materials that result in a reduction in operating voltage or increase quantum efficiency are also applicable. Additional layers can also be added to tailor the energy levels of the various layers and facilitate electroluminescence.
Depending upon the application of the electronic device, the active layer (c) can be a light- emitting layer that is activated by a signal (such as in a light-emitting diode) or a layer of material that responds to radiant energy and generates a signal with or without an applied potential (such as detectors or voltaic cells). Examples of electronic devices that may respond to radiant energy are selected from photoconductive cells, photoresistors, photoswitches, phototransistors, and phototubes, and photovoltaic cells. After reading this specification, skilled artisans will be capable of selecting material (s) that for their particular applications.
The electroluminescent devices may be employed for full color display panels in, for example, mobile phones, televisions and personal computer screens. Accordingly the present invention relates also to a device selected from stationary and mobile displays, such as displays for computers, mobile phones, laptops, pdas, TV sets, displays in printers, kitchen equipment, billboards, lightings, information boards and destination boards in trains and buses, containing an organic light emitting diode according to the present invention. In OLEDs, electrons and holes, injected from the cathode (e) and anode (a) layers, respectively, into the photoactive layer (c), form negative and positively charged polarons in the active layer (c). These polarons migrate under the influence of the applied electric field, forming a polaron exciton with an oppositely charged species and subsequently undergoing radiative recombination. A sufficient potential difference between the anode and cathode, usually less than approximately 20 volts, and in some instances no greater than approximately 5 volts, may be applied to the device. The actual potential difference may depend on the use of the device in a larger electronic component. In many embodiments, the anode layer (a) is biased to a positive voltage and the cathode layer (e) is at substantially ground potential or zero volts during the operation of the electronic device. A battery or other power source (s) may be electrically connected to the electronic device as part of a circuit.
The compound does not need to be in a solid matrix diluent (e. g., host charge transport material) when used in layer (b) (c), or (d) in order to be effective. A layer greater than approximately 1 % by weight of the metal complex compound, based on the total weight of the layer, and up to substantially 100% of the present copolymer can be used as the active layer (c). Additional materials can be present in the active layer (c) with the complex compound. For example, a fluorescent dye may be present to alter the color of emission.
A diluent may also be added. The diluent can be a polymeric material, such as poly (N-vinyl carbazole) and polysilane. It can also be a small molecule, such as 4,4'-N,N'-dicarbazole biphenyl or tertiary aromatic amines. When a diluent is used, the present copolymer is generally present in a small amount, usually less than 20% by weight, preferably less than 10% by weight, based on the total weight of the layer.
The present copolymers may be used in applications other than electronic devices. For example, they may be used as catalysts or indicators (e. g., sensors, oxygen-sensitive indicators, phosphorescent indicators in bioassays, or the like).
The following test methods and examples are for illustrative purposes only and are not to be construed to limit the instant invention in any manner whatsoever. Room temperature (r.t.) depicts a temperature in the range 20-250C; over night denotes a time period in the range 12-16 hours. Percentages are by weight unless otherwise indicated. Abbreviations used in the examples or elsewhere: AIBN azo-bis-isobutyronitrile
CIE colour definition according to Commission Internationale de I'Eclairage
DMF dimethylformamide
EE ethyl acetate
EtOH ethanol
HMPTA hexamethylphosphorus triamide
ITO indium tin oxide
Mw molecular mass weight average
Mn molecular mass number average
PBD 2-(p-tert.butylphenyl)-5-biphenylyl-1 ,3,4-oxadiazole
PDI polydispersity index (= ratio [Mw] / [Mn])
PEDOT:PSS poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate)
PG polymerizable group
TBME tert.-butyl methyl ether
THF tetrahydrofuran
TPD N,N'-biphenyl-N,N'-di-m-tolyl-benzidine
1. Triplet Emitters: The compounds (intermediate complexes) in Table 1 are prepared according to the method shown in example 10 of WO 2006/000544.
Table 1
Example Structure
1.1
Figure imgf000062_0001
Figure imgf000063_0001
The compounds (intermediate complexes) in Table 2 are prepared starting from the compounds in Table 1 and 3-Hydroxypicolinic acid according to the method shown in example 1 1 of WO 2006/000544.
Table 2
Figure imgf000063_0002
Figure imgf000064_0001
Example 1.7
Figure imgf000064_0002
400 mg (0.424 mmol) of the compound prepared in Example 1.4, 124 mg (0.467 mmol) of 3- (6-Bromo-hexyloxymethyl)-3-methyl-oxetane (prepared according to Jungermann, Macromolecules 2006, 39, 891 1 ), 73 mg (0.53 mmol) Potassiumcarbonate and 5 ml of DMF are placed in a 25 ml three necked round bottomed flask, equipped with a magnetic stirrer and a reflux condenser. The reaction mixture is heated to 800C internal temperature for three hours, then cooled to room temperature, added to 100 ml of buffer solution pH = 7 and extracted three times with 100 ml of Dichloromethane. The combined organic phases are washed three times with 50 ml of water, dried over Magnesiumsulfate, filtered and evaporated. The crude product is purified by flash chromatography using Ethylacetate as eluent. The desired product is isolated in 49% yield as a yellow powder. The photoluminescence spectrum in toluene shows emission maxima at 539 and 563 nm.
Example 1.8
The following compound is prepared in 59% yield according to Example 1.7, starting from the compound prepared in example 1.5. The photoluminescence spectrum in toluene shows an emission maximum at 510 nm.
Figure imgf000065_0001
Example 1.9
The following compound is prepared in 58% yield according to Example 1.7, starting from the compound prepared in example 1.6. The photoluminescence spectrum in toluene shows an emission maximum at 510 nm.
Figure imgf000065_0002
Example 1.10
Figure imgf000066_0001
4.2 g (4.45 mmol) of the compound prepared in Example 1.4, 1.66 g (8.91 mmol) of 6- Bromo-1-hexanol, 1.85g (13.36 mmol) Potassiumcarbonate and 50 ml of DMF are placed in a 100 ml three necked round bottomed flask, equipped with a magnetic stirrer and a reflux condenser. The reaction mixture is heated to 800C internal temperature for five hours, then cooled to room temperature, added to 300 ml of buffer solution pH = 7 and extracted three times with 200 ml of Dichloromethane. The combined organic phases are washed three times with 50 ml of water, dried over Magnesiumsulfate, filtered and evaporated. The crude product is purified by flash chromatography using Ethylacetate as eluent. The product is added to 50 ml of Diisopropylether and stirred for five hours. The suspension is filtered and dried at 500C and 25 mbar over night. The desired product is isolated in 67% yield as a yellow powder.
3.1 g (2.97 mmol) of this compound and 65 ml of Dichloromethane are placed in a 100 ml three necked round bottomed flask, equipped with a magnetic stirrer. 0.47 g (3.57 mmol) of Diisopropylethylamine are added and reaction mixture is cooled to -30°C internal temperature with an EtOH/CC>2 bath. 308 mg (3.27 mmol) of Acryloylchloride are added with a syringe within 10 minutes and the resulting mixture stirred for another 30 minutes. The reaction mixture is purified by flash chromatography using Ethylacetate/Methanol = 20:1 as eluent without any workup. The product is added to 50 ml of Diisopropylether and stirred for five hours. The suspension is filtered and dried at RT at the air. The desired product is isolated in 72% yield as a yellow powder. The photoluminescence spectrum in toluene shows emission maxima at 540 and 572 nm. Example 1.11
The following compound is prepared according to Example 1.10, starting from the compound prepared in example 1.5. The photoluminescence spectrum in toluene shows an emission maximum at 515 nm.
Figure imgf000067_0001
Example 1.12
The following compound is prepared according to Example 1.10, starting from the compound prepared in example 1.6. The photoluminescence spectrum in toluene shows an emission maximum at 514 nm.
Figure imgf000067_0002
Example 1.13
The following compound is prepared according to Example 1.7 but using Octylbromide instead of 3-(6-Bromo-hexyloxymethyl)-3-methyl-oxetane. The photoluminescence spectrum in toluene shows emission maxima at 540 and 568 nm.
Figure imgf000068_0001
Example 1.14
The following compound was prepared according to Example 1.8 but using Octylbromide instead of 3-(6-Bromo-hexyloxymethyl)-3-methyl-oxetane. The photoluminescence spectrum in toluene shows an emission maximum at 511 nm.
Figure imgf000068_0002
Example 1.15
The following compound is prepared according to Example 1.9 but using Octylbromide instead of 3-(6-Bromo-hexyloxymethyl)-3-methyl-oxetane. The photoluminescence spectrum in toluene shows an emission maximum at 511 nm.
Figure imgf000069_0001
Example 1.16
Figure imgf000069_0002
3.12 g (130 mmol) of Sodiumhydride and 200 ml of dry THF are placed in a 500 ml three necked round bottomed flask, equipped with a magnetic stirrer, and cooled to 00C with an ice bath. 10.01 g (100 mmol) of Acetyl acetone and 4.48 g (25 mmol) of HMPTA are added within 10 minutes while keeping the temperature below 7°C. The reaction mixture is stirred for another 10 minutes, then 75 ml (120 mmol) of a Butyl lithium solution 1.6M in Hexane is added within 10 minutes. The reaction mixture is stirred for another 20 minutes then 16.78 g (1 10 mmol) of 4-Vinylbenzyl chloride are added within 7 minutes. Then the reaction mixture is warmed to room temperature and stirred for three hours. The orange suspension is added to 100 ml of cold 2N HCI solution, the phases are separated and the aqueous phase extracted with 200 ml of TBME. The combined organic phases are washed once with 200 ml of brine, dried over Magnesiumsulfate, filtered and evaporated. The crude product is purified by flash chromatography using Hexane/Ethylacetate = 9:1 as eluent. 6-(4-Vinyl-phenyl)- hexane-2,4-dione is isolated in 66% yield. The compound prepared in example 1.1 and 6-(4-Vinyl-phenyl)-hexane-2,4-dione are reacted according to example 1.4. The final product shows in the photoluminescence spectrum an emission maximum at 559 nm in toluene.
Example 1.17
Figure imgf000070_0001
2.16 g (10 mmol) of 6-(4-Vinyl-phenyl)-hexane-2,4-dione are hydrogenated with 200 mg of Pd/C 5% in 20 ml of Ethylacetate at room temperature at a pressure of 12 bar H2 for 24 hours. The reaction mixture is filtered and the solvent evaporated. The crude product is purified by flash chromatography using Hexane/Ethylacetate = 9:1 as eluent. 6-(4-Ethyl- phenyl)-hexane-2,4-dione is isolated in 77% yield.
The compound prepared in example 1.1 and 6-(4-Ethyl-phenyl)-hexane-2,4-dione are reacted according to example 1.4. The final product shows in the photoluminescence spectrum an emission maximum at 558 nm in toluene.
Example 1.18
Figure imgf000070_0002
0.57 g (0.60 mmol) of the compound prepared in Example 1.4 are dissolved in 10 ml of dry CH2Cb in a 25 ml three necked round bottomed flask, equipped with magnetic stirrer. 50 mg of Dimetylaminopyridine and 0.35 g (3.02 mmol) of Diisopropyethylamine are added and the clear orange solution is cooled to 3°C with an ice bath. 0.25 g (1.51 mmol) of 4-Vinyl-benzoyl chloride (prepared from 4-Vinyl-benzoic acid and Oxalylchloride according to standard procedures) dissolved in 5 ml of dry CH2CI2 are added with a syringe while keeping the internal temperature below 5°C. The resulting solution is stirred for 90 minutes, then diluted with 100 ml of CH2CI2, washed three times with 50 ml of water, dried over Magnesiumsulfate, filtered and evaporated. The crude product is purified by flash chromatography using CH2CI2/Me0H = 25:1 as eluent. The desired product is isolated in 74% yield as an orange powder. The photoluminescence spectrum in toluene shows an emission maximum at 534nm
Example 1.19
The following compound is prepared in 84% yield according to Example 1.18, starting from the compound prepared in example 1.5. The photoluminescence spectrum in toluene shows an emission maximum at 510 nm.
Figure imgf000071_0001
Example 1.20
The following compound is prepared in 33% yield according to Example 1.18, starting from the compound prepared as an intermediate in example 1.1 1. The photoluminescence spectrum in toluene shows an emission maximum at 513 nm.
Figure imgf000072_0001
2. Hosts
Example 2.1
Figure imgf000072_0002
25 g (120 mmol) of 9,10-Phenantrenequinone, 10.1 g (180 mmol) of Benzaldehyde, 64.8 g (840 mmol) of Ammonium acetate and 600 ml of Ethanol are placed in a 1 I round bottomed flask, equipped with a magnetic stirrer and a reflux condenser. The reaction mixture is heated to reflux for five hours, cooled to room temperature, then to 00C with an ice bath. The suspension is filtered and the residue washed twice with 50 ml of Ethanol, three times with 150 ml of water and then dried at 600C and 25 mbar over night. 2-Phenyl-1- phenanthro[9,10]imidazole is obtained in 92% yield.
4.4 g (15.1 mmol) of 2-Phenyl-1-phenanthro[9,10]imidazole, 8.0 g (30.2 mmol) of 3-(6- Bromo-hexyloxymethyl)-3-methyl-oxetane (prepared according to Jungermann, Macromolecules 2006, 39,891 1 ), 6.26 g (45.3 mmol) of Potassiumcarbonate and 60 ml of DMF are placed in a 250 ml three necked round bottomed flask, equipped with a magnetic stirrer and reflux condenser. The reaction mixture is heated to 1200C internal temperature over night, then cooled to room temperature and filtered. The filtrate is evaporated and the residue dissolved in 100 ml of Ethylacetate. The solution is washed three times with 50 ml of water and once with 50 ml of brine, dried over Magnesiumsulfate, filtered and evaporated. The crude product is purified by flash chromatography using Hexane/Ethylacetate = 2:1 as eluent. The product is treated with 80 ml of Hexane over night, the solvent decanted and the residual solvent evaporated. 1-[6-(3-Methyl-oxetan-3-ylmethoxy)-hexyl]-2-phenyl-1 H- phenanthro[9,10]imidazole is isolated in 65% yield. 1H-NMR (300MHz, CDCI3): 8.83 (d, 1 H)
8.80 (d, 1 H)
8.69 (d, 1 H)
8.25 (d, 1 H)
7.78 - 7.50 (m, 9H)
4.61 (t, 2H)
4.44 (d, 2H)
4.30 (d, 2H) 3.36 (s, 2H)
3.31 (t, 2H) 1.92 (m, 2H) 1.44 (m, 2H) 1.24 (s, 3H) 1.21 (m, 4H)
Example 2.2
Figure imgf000073_0001
10 g (34 mmol) of 2-Phenyl-1-phenanthro[9,10]imidazole, 12.3 g (68 mmol) of 6-Bromo-1- hexanol, 14.1 g (102 mmol) of Potassiumcarbonate and 300 ml of DMF are placed in a 500 ml three necked round bottomed flask, equipped with a magnetic stirrer and a reflux condenser. The reaction mixture is heated to 1200C internal temperature over night, then another 5.3 g (18 mmol) of 6-Bromo-1-hexanol and 7.0 g (50 mmol) of Potassiumcarbonate are added and stirrer for another six hours. The suspension is cooled to room temperature and filtered. The filtrate is evaporated to a solution of about 50 ml, then 400 ml of water are added and the solution is extracted three times with 400 ml of Ethylacetate. The combined organic phases are washed three times with 200 ml of brine, dried over Magnesiumsulfate, filtered and evaporated. The crude product is purified by flash chromatography using Hexane/Ethylacetate = 1 :1 as eluent. The product is crystallized from Toluene. 6-(2-Phenyl- phenanthro[9,10]imidazol-1-yl)-hexan-1-ol is isolated in 63% yield.
3.0 g (7.6 mmol) of 6-(2-Phenyl-phenanthro[9,10]imidazol-1-yl)-hexan-1-ol and 100 ml of Dichloromethane are placed in a 250 ml three necked round bottomed flask, equipped with a magnetic stirrer. 0.74 g (8.36 mmol) of Diisopropylethylamine are added and the reaction mixture is cooled to -300C internal temperature with an EtOH/CC>2 bath. 1.18 g (9.12 mmol) of Acryloylchloride are added with a syringe within 2 minutes and the resulting mixture stirred for another 30 minutes. The reaction mixture is purified by flash chromatography using Hexane/Ethylacetate = 20:1 as eluent without any workup. Acrylic acid 6-(2-phenyl- phenanthro[9,10]imidazol-1-yl)-hexyl ester is isolated in 94% yield. 1H-NMR (300MHz, DMSO): 8.94 (d, 1 H)
8.82 (d, 1 H)
8.56 (d, 1 H)
8.36 (d, 1 H) 7.77 - 7.56 (m, 9H)
6.24 (dxd, 1 H)
6.07 (dxd, 1 H)
5.85 (dxd, 1 H)
4.63 (t, 2H) 3.90 (t, 2H)
1.77 (m, 2H)
1.38 (m, 2H)
1.02 (m, 4H)
Example 2.3
The following compound is prepared according to Example 2.1 , starting from 9,10- Phenantrenequinone and 4-Hydroxybenzaldehyde.
Figure imgf000075_0001
1H-NMR (300MHz, CDCI3): 8.84 (d, 1 H)
8.78 (d, 1 H) 8.71 (d, 1 H) 8.25 (d, 1 H)
7.73 - 7.60 (m, 6H) 7.06 (d, 2H) 4.60 (t, 2H) 4.52 (d, 2H) 4.44 (d, 2H)
4.36 (d, 2H) 4.30 (d, 2H) 4.05 (t, 4H) 3.51 (t, 2H) 3.50 (s, 2H)
3.37 (s, 2H) 3.33 (t, 2H) 1.95 - 1.10 (m, 22H)
Example 2.4
The following compound is prepared according to Example 2.2, starting from 9,10- Phenantrenequinone and 4-Hydroxybenzaldehyde.
Figure imgf000076_0001
1H-NMR (300MHz, DMSO): 8.90 (d, 1 H)
8.78 (d, 1 H) 8.52 (d, 1 H) 8.32 (d, 1 H) 7.74 - 7.56 (m, 6H) 7.08 (d, 2H) 6.26 - 5.76 (m, 6H) 4.59 (t, 2H) 4.12 - 3.86 (m, 6H) 1.80 - 1.00 (m, 16H)
Example 2.5
Figure imgf000076_0002
Starting from 9,10-Phenantrenequinonen and 4-Bromo-benzaldehyde 2-(4-Bromo-phenyl)-1- phenanthro[9,10]imidazole is prepared according to step 1 of the example 2.1. This compound is reacted with Octylbromide according to step 2 of example 2.1 to yield 2-(4- Bromo-phenyl)-1 -octyl-1 -phenanthro[9, 10]imidazole.
17.7 g ( 36.5 mmol) of 2-(4-Bromo-phenyl)-1 -octyl-1 -phenanthro[9,10]imidazole and 200 ml of dry THF are placed in a dried 500 ml three necked round bottomed flask, equipped with a magnetic stirrer and the reaction mixture is cooled to -78°C internal temperature with an EtOH/CO2 bath. 29.6 ml (47.4 mmol) of 1.6 M Butyl lithium solution in Hexane are added within 75 minutes while keeping the internal temperature below -75°C. The reaction mixture is stirred at the same temperature for one hour, then 13.3 g (182.3 mmol) DMF (dried over Calcium hydride) are added within 30 minutes while keeping the internal temperature below - 75°C. The reaction mixture is stirred at the same temperature for one hour. 18 ml of 0.5 M HCI are added drop by drop and the reaction mixture is warmed to room temperature. The reaction mixture is diluted with 300 ml of water and extracted twice with 250 ml of Ethylacetate. The combined organic phases are washed twice with 50 ml of saturated Ammonium chloride solution and once with 100 ml of brine, dried over Magnesiumsulfate, filtered and evaporated. The crude product is crystallized from 2-Propanol. 4-(1-0ctyl-1- phenanthro[9,10]imidazol-2-yl)-benzaldehyde is isolated in 79% yield.
22.7 g (63.7 mmol) of Methyl triphenylphosphonium bromide and 200 ml of dry THF are placed in a dried 500 ml three necked round bottomed flask, equipped with a magnetic stirrer and the reaction mixture is cooled to 00C internal temperature with a NaCI/ice bath. 41.8 ml (66.9 mmol) of 1.6 M Butyl lithium solution in Hexane are added within 30 minutes while keeping the internal temperature below 3°C. The reaction mixture is stirred at the same temperature for 45 minutes, then 20.5 g (47.2 mmol) 4-(1-Octyl-1-phenanthro[9,10]imidazol- 2-yl)-benzaldehyde dissolved in 100 ml of dry THF are added within 30 minutes. After two hours the reaction mixture is warmed to room temperature, added to 500 ml of water and extracted three times with 500 ml of Ethylacetate. The combined organic phases are washed once with 500 ml of a 1 :1 mixture of buffer pH =1 and brine, once with 30 ml of brine, dried over Magnesiumsulfate, filtered and evaporated. The crude product is dissolved in Dichloromethane, 100 g of silica are added and the solvent is evaporated. The resulting powder is added on top of 300 g of silica in a sintered glass funnel and the product eluted with Hexane/Ethylacetate = 8:1. The product is crystallized from 2-Propanol. 1 -Octyl-2-(4- vinyl-phenyl)-1-phenanthro[9,10]imidazole is isolated in 57% yield. 1H-NMR (300MHz, CDCI3)): 8.83 (d, 1 H) 8.78 (d, 1 H)
8.70 (d, 1 H) 8.26 (d, 1 H) 7.74 - 7.56 (m, 8H) 6.81 (dxd, 1 H) 5.86 (d, 1 H) 5.36 (d, 1 H) 4.59 (t, 2H) 1.92 (m, 2H) 1.30 - 1.10 (m, 10H) 0.83 (t, 3H)
Example 2.6
Figure imgf000078_0001
3 g (17.94mmol) of carbazole and 7 ml DMF are placed in a three necked round bottomed flask, equipped with a magnetic stirrer and a reflux condenser, 5.98 g (23.32 mmol) of NaH 55-65% (washed 3 times with Hexane) suspended in 8ml DMF are slowly added at room temperature. The reaction mixture is heated to 800C internal temperature. 5.98 g (23.32 mmol) of 3-(6-Bromo-hexyloxymethyl)-3-methyl-oxetane (prepared according to Jungermann, Macromolecules 2006, 39, 891 1 ) are added within 25 min. The temperature increases to 94°C. The reaction mixture is stirred for 1 hour. After cooling, the reaction mixture is diluted with Ethylacetate and extracted twice with water and once with brine. The organic phase is dried over Na2SO4, the solvent is evaporated and the crude product is purified by column chromatography. (Heptane/Ethylacetate = 4:1 ) After crystallization from Heptane: Ethylacetate = 4:1 9-[6-(3-Methyl-oxetan-3-ylmethoxy)-hexyl]-9H-carbazole is isolated in 66 % yield. 1H-NMR (300MHz, CDCI3): 8.09 (d, 2H)
7.50 - 7.38 (m, 4H) 4.49 (d, 2H) 4.34 (m, 4H)
3.41 (m, 4H) 1.89 (m, 2H) 1.56 (m, 2H) 1.40 (m, 4H) 1.28 (s, 3H) Example 2.7
Figure imgf000079_0001
2,84 g (16,98 mmol) of Carbazole are added to a 50ml three necked round bottomed flask, equipped with a magnetic stirrer, a reflux condenser and an Argon/Vacuum inlet. The flask is sealed and degassed, and then 14 ml of dry DMF and 0.611 g (25.47 mmol) of NaH 55-65% (washed three times with Hexane) are added. When the mixture stops bubbling it is heated to 1000C external temperature. 4.84 ml (22.08mmol) of 2-6-Bromohexyloxyltetrahydro-1 H pyrane are added drop by drop. After 2 hours the mixture is cooled to room temperature. 200 ml of cold water are added and stirred for 20 minutes, and then the mixture is centrifuged. The solvent is removed, the product dissolved in Ethanol and the solvent removed by evaporation. 9-[6-(Tetrahydro-pyran-2-yloxy)-hexyl]-9H-carbazole is isolated in 96% yield as a brown oil.
5.7 g (16.22 mmol) of 9-[6-(Tetrahydro-pyran-2-yloxy)-hexyl]-9H-carbazole and 20 ml of Ethanol are dissolved in a 50ml three necked round bottomed flask, equipped with a magnetic stirrer and a reflux condenser, the solution is degassed three times and saturated with argon, then 5 g of p-Toluenesulfonic acid monohydrate are added. The mixture is stirred under Argon at room temperature for 4 hours. The reaction mixture is poured on 250 ml of water and stirred for 20 minutes. The suspension is filtered and the residue washed extensively with water. The crude product is purified by column chromatography.
(Toluene/Ethylacetate = 10:1 , then 7:3 followed by 6:4). 6-Carbazol-9-yl-hexan-1-ol is isolated in 74% yield.
3.2 g (11.97 mmol) of 6-Carbazol-9-yl-hexan-1-ol are dissolved in 50 ml of dry CH2CI2 in a 250 ml three necked round bottomed flask, equipped with a magnetic stirrer and a reflux condenser. The mixture is cooled to 00C with an ice bath. 2.87 ml (16.76 mmol) of N-
Ethyldiisopropylamine are added. The mixture is stirred for 10 minutes, then 1.26 ml (15.56 mmol) of Acryloylchloride are added within 10 minutes and stirred for another hour. The mixture is filtered twice on silica (Hexane/Ethylacetate 4/1 ) and the solvent is evaporated. The crude product purified by column chromatography. (Hexane, followed by Hexane/Ethylacetate = 9:1 ; then 8:2). Acrylic acid 6-carbazol-9-yl-hexyl ester is isolated in
85% yield.
1H-NMR (300MHz, CDCI3): 8.1 (d, 2H)
7.48-7.4 (m, 4H)
7.25 (m, 2H)
6.40 (d, 1 H)
6.09 (dxd, 1 H)
5.81 (d, 1 H)
4.3 (t, 2H)
4.1 (t, 2H)
1.90 (m, 2H)
1.64 (m, 2H)
1.42 (m 4H)
Example 2.8
Figure imgf000080_0001
39.87 g (0.299 mol) of Aluminium chloride; 50 g (0.299 mol) of Carbazole and 500 ml of CH2CI2 are added to a 1 I three necked round bottomed flask, equipped with a magnetic stirrer. The mixture is cooled to 00C with an ice bath. 65.05 ml (0.6 mol) of tert-Butylchloride are added within 90 minutes. The reaction mixture is warmed to room temperature and stirred over night. The reaction is cooled to 00C and 200 ml of 1 M HCI are added very slowly. The mixture is diluted with 700 ml of CH2CI2 and extracted once with water and twice with brine. The organic phase is dried over Sodiumsulfate, the solvent is evaporated and the crude product is purified by column chromatography (Heptane/Ethylacetate = 10:1 ). After crystallization from Methanol 3,6-Di-tert-butyl-9H-carbazole is isolated in 53 % yield.
3 g (10.74 mmol) of 3,6-Di-tert-butyl-9H-carbazole and 9 ml DMF are placed in a 25 ml three necked round bottomed flask, equipped with a magnetic stirrer and a reflux condenser, 0.7g (16.1 mmol) of NaH 55-65% (washed 3 times with Hexane) suspended in 8ml DMF are slowly added at room temperature. The reaction mixture is heated to 800C internal temperature. 3.58 g (13.96 mmol) of 3-(6-Bromo-hexyloxymethyl)-3-methyl-oxetane (prepared according to Jungermann, Macromolecules 2006, 39, 8911 ) are added within 12 minutes. The temperature increases to 1000C. The reaction mixture is stirred for 1 hour. After cooling, the reaction mixture is diluted with water, then extracted with Ethylacetate. The organic phase is extracted twice with water and once with brine. The organic phase is dried over Sodiumsulfate, the solvent is evaporated and the crude product is purified by column chromatography (Heptane/Ethylacetate = 6:1 followed by CH2CI2/Ethylacetate = 15:0.1 ). 3,6- Di-tert-butyl-9-[6-(3-methyl-oxetan-3-ylmethoxy)-hexyl]-9H-carbazole is isolated in 46% yield. 1H-NMR (300MHz, CDCI3): 8.1 1 (d, 2H)
7.50 (dxd, 2H) 7.31 (d, 2H)
4.50 (d, 2H)
4.35 (d, 2H)
4.25 (t, 2H)
3.43 (m, 4H) 1.88 (m, 2H)
1.61-1.41 (m, 24H)
1.29 (s, 3H)
Example 2.9
Figure imgf000081_0001
5 g (17.89 mmol) of 3,6-Di-tert-butyl-9H-carbazole are placed in a 25 ml three necked round bottom flask, equipped with a magnetic stirrer, a reflux condenser and an Argon/Vacuum inlet. The flask is sealed and degassed, then 15 ml of dry DMF and 1.17 g (26.84 mmol)) of NaH (55-65%) are added. When the mixture stops bubbling it is heated to 1000C external temperature. 5.26 ml (23.2 mmol) of 2-6-Bromohexyloxyltetrahydro-1 H pyran are added drop by drop within 18 minutes and stirred for another hour. Then the mixture is cooled to room temperature. 300 ml of cold water are added and stirred for 20 minutes. The phases are separated. The solvent is decanted and the residue is dissolved in Methanol and the solvent is distilled off. This procedure is repeated three times. 3,6-Di-tert-butyl-9-[6-(tetrahydro-pyran-2-yloxy)-hexyl]-9H-carbazole is isolated in 99% yield. 9.25 g (19.09 mmol) of 3,6-Di-tert-butyl-9-[6-(tetrahydro-pyran-2-yloxy)-hexyl]-9H-carbazole are dissolved in 24 ml of Ethanol in a 50 ml three necked round bottom flask, equipped with an Argon/Vacuum inlet and a magnetic stirrer, the solution is degassed three times and saturated with argon, then 363 mg (1.91 mmol) p-Toluenesulfonic acid monohydrate are added. The mixture is stirred under Argon at 400C internal temperature over night. The mixture is diluted with CH2Cb and extracted twice with water and once with brine. The organic phase is dried over Sodiumsulfate, the solvent is evaporated and the crude product purified by column chromatography. (Heptane/Ethylacetate = 10 : 1 , followed by 9:1 ). 6-(3,6- Di-tert-butyl-carbazol-9-yl)-hexan-1-ol is isolated in 70%yield.
5.12 g (13.49 mmol) of 6-(3,6-Di-tert-butyl-carbazol-9-yl)-hexan-1-ol are dissolved in 70 ml of dry CH2CI2 in a 100 ml three necked round bottom flask, equipped with a magnetic stirrer. The mixture is cooled to 00C with an ice bath. 4.7 ml (26.98 mmol) of N- Ethyldiisopropylamine are added and the mixture is stirred for 10 minutes. Then 1.69 ml (20.23 mmol) of Acyloylchloride are added within 10 minutes. After one hour the reaction is extracted twice with water and once with brine. The organic phase is dried over Sodiumsulfate and the solvent is evaporated. After crystallization from Methanol Acrylic acid 6-(3,6-di-tert-butyl-carbazol-9-yl)-hexyl ester is isolated in 72 % yield. 1H-NMR (300MHz, CDCI3): 8.1 1 (d, 2H)
7.50 (dxd, 2H) 7.31 (d, 2H) 6.35 (d, 1 H) 6.1 1 (dxd, 1 H) 5.82 (d 1 H)
4.25 (t, 2H) 4.13 (t, 2H) 1.89 (m, 2H) 1.67 (m, 2H) 1.50-1.39 (m, 22H) Example 2.10
Figure imgf000083_0001
30 g (0.107 mol) of 3,6-Di-tert-butyl-9H-carbazole are dissolved in 1.71 I of Acetone in a 2 I three necked round bottom flask, equipped with a magnetic stirrer and a reflux condenser. 42.94 g (1.07 mol) of NaOH dissolved in 32.2 ml of water are slowly added at room temperature. 66.2 ml (0.36 mol) of Chloroethyl-p-toluensulfonate are added within six minutes. The reaction is refluxed over night. 17.18 g (0.43 mol) of NaOH dissolved in 6.44 ml of water and 32.99 ml (0.18 mol) of Chloroethyl-p-toluensulfonate are slowly added. The reaction is refluxed again over night. The mixture is cooled to room temperature, filtered and washed with Acetone. The filtrate is evaporated and the crude product purified by column chromatography (Heptane/Toluene = 4:1 ). 3,6-Di-tert-butyl-9-(2-chloro-ethyl)-9H-carbazole is isolated in 59 % yield.
21.75 g (63.61 mmol) of 3,6-Di-tert-butyl-9-(2-chloro-ethyl)-9H-carbazole, 144 g of KOH and 670 ml of Ethanol are added to a 1 I three necked round bottomed flask equipped with a magnetic stirrer and a reflux condenser. The reaction mixture is refluxed over night. The solvent is evaporated and the crude product is purified by column chromatography (basic Aluminiumoxid, activity III, Heptane). 3,6-Di-tert-butyl-9-vinyl-9H-carbazole is isolated in 66% yield. 1H-NMR (300MHz, CDCI3): 8.07 (d, 2H)
7.60-755 (d, 2H) 7.53-7.49 (dxd, 1 H) 7.25 (dxd, 2H) 5.5 (d, 1 H) 5.05 (d, 1 H)
1.46 (m, 18H)
Example 2.11
16.09 g (0.259 mol) of Potassium hydroxide (86%) are placed in a 500 ml three necked round bottomed flask equipped with a magnetic stirrer and a reflux condenser. 200 ml of THF and 6.5 ml of Dichloromethane are added. The mixture is refluxed. After 1 hour the mixture is cooled to room temperature. A solution of 8 g (37.74 mmol) dibenzofuran-4-boronic acid, 0.8 g (3.02 mmol) of Triphenylphosphine, 339 mg (0.7 mmol) of Palladium (II) acetate and 200 ml of Methanol are added. The reaction mixture is heated to 600C internal temperature. After 2 hours the reaction is complete and cooled down to room temperature. The mixture is diluted with H2O and Ethylacetate. The organic phase is extracted twice with water and once with brine. The organic phase is dried over Sodiumsulfate and the solvent evaporated. The crude product is purified by column chromatography (Heptane). 4-Vinyl-dibenzofuran is isolated in 42% yield.
Figure imgf000084_0001
1H-NMR (300MHz, CDCI3): 7.94 (d,1 H) 7.84 (d, 1 H) 7.61 (d, 1 H) 7.50 (m, 2H) 7.36 (m, 2H) 7.12 (dxd 1 H) 6.32 (d,1 H) 5.60 (d, 1 H)
Example 2.12
Figure imgf000084_0002
Dibenzofuran-2-carboxaldehyde is reacted with Methyl triphenylphosphonium bromide according to example 2.5, Step 3 do give 2-Vinyl-dibenzofuran in 95% yield. 1H-NMR (300MHz, CDCI3): 7.94 (d,1 H)
7.98 - 7.92 (m, 2H) 7.64 - 7.32 (m, 5H) 6.92 (dxd 1 H) 5.82 (d,1 H) 5.30 (d, 1 H)
3. Electron Transporters
Example 3.1
Figure imgf000085_0001
25 g (0.098 mol) of 4-Cyano-4'-pentylbiphenyl (98%), 9.58 g (0.147 mol) of Sodiumazide, 7,88 g (0.147 mol) of Ammonium chloride and 175 ml of dry DMF are placed in a dried 250 ml three necked round bottomed flask equipped with a magnetic stirrer and a reflux condenser and stirred under N2. The reaction mixture is heated to 1000C over night and then cooled to room temperature. 150 ml of water are added while keeping the internal temperature below 300C. 10 ml HCI 4M are added and stirred for 45 min. The suspension is filtered and washed with water. 5-(4'-Pentyl-biphenyl-4-yl)-5H-tetrazole is isolated in 99 % yield.
5 g (17.10 mmol) of 5-(4'-Pentyl-biphenyl-4-yl)-5H-tetrazole and 40 ml of dry Pyridine are placed in a dried 100 ml three necked round bottomed flask equipped with a magnetic stirrer and a reflux condenser and stirred under N2. 3.89 g (18.81 mmol) of 3,5-Dimethoxybenzoyl chloride (97%) are added. The reaction is heated to reflux and stirred over night and then cooled to room temperature. 150 ml of water are added. The suspension is filtrated and washed with water. 2-(3,5-Dimethoxy-phenyl)-5-(4'-pentyl-biphenyl-4-yl)-[1 ,3,4]oxadiazole is isolated in 77 % yield. 7.12 g (16.46 mmol) of 2-(3!5-Dimethoxy-phenyl)-5-(4'-pentyl-biphenyl-4-yl)-[1 !3,4]oxadiazole and 250 ml of dry CH2Cb are placed in a dried 500 ml three necked round bottomed flask, equipped with a magnetic stirrer, and stirred under N2. The reaction mixture is cooled to - 500C internal temperature. 41.15 ml (41.15 mmol) of 1.0 M Boron tribromide solution in CH2CI2 are added within 30 minutes while the reaction mixture is cooled down to -700C. The reaction mixture is warmed to 0°C and stirred over night. 18 ml of Diethylether and 50 ml of H2O are slowly added. The temperature increases to 13°C. The mixture is extracted twice with water and once with brine. The organic phase is dried over Sodiumsulfate and the solvent is evaporated. 5-[5-(4'-Pentyl-biphenyl-4-yl)-[1 ,3,4]oxadiazol-2-yl]-benzene-1 ,3-diol is isolated in 96 % yield.
2.5 g (6.24 mmol) of 5-[5-(4'-Pentyl-biphenyl-4-yl)-[1 ,3,4]oxadiazol-2-yl]-benzene-1 ,3-diol, 4.7 g (17.72 mmol) of 3-(6-Bromo-hexyloxymethyl)-3-methyl-oxetane (prepared according to Jungermann, Macromolecules 2006, 39,8911 ), 3.02 g (21. 85 mmol) of Potassiumcarbonate and 142 ml of DMF are placed in a 250 ml three necked round bottomed flask, equipped with a magnetic stirrer and a reflux condenser. The reaction mixture is heated to 1200C internal temperature over night and then cooled to room temperature. The solvent is evaporated. The crude product is purified by column chromatography (Heptane/EE = 3:2). 2-{3-[6-(3-Methyl- oxetan-3-ylmethoxy)-hexyloxy]-5-[5-(3-methyl-oxetan-3-ylmethoxy)-pentyloxy]-phenyl}-5-(4'- pentyl-biphenyl-4-yl)-[1 ,3,4]oxadiazole is isolated in 76 % yield. 1H-NMR (300MHz, CDCI3): 8.19 (d, 2H)
7.75 (d, 2H) 7.55 (d, 2H)
7.30 (m, 4H) 6.61 (m, 1 H)
4.49 (d, 4H) 4.35 (d,4H) 4.03 (t, 4H) 3.47 (m, 8H) 2.66 (t, 2H)
1.83 (m, 4H) 1.64-1.35 (m, 18H)
1.31 (s, 6H) 0.91 (t, 3H) Example 3.2
Figure imgf000087_0001
2.5 g (6.24 mmol) of 5-[5-(4'-Pentyl-biphenyl-4-yl)-[1 !3!4]oxadiazol-2-yl]-benzene-1 ,3-diol! 1.76 ml (37.44 mmol) Chlor-1-hexanol, 3.2 g (23.41 mmol) of Potassiumcarbonate; 311 mg of Potassium iodide and 20ml of dry DMF are placed in a 50 ml three necked round bottomed flask, equipped with a magnetic stirrer and a reflux condenser, and stirred under N2. The reaction mixture is heated to 800C internal temperature over night and then cooled to room temperature. The mixture is diluted with Ethylacetate and extracted twice with water and once with brine. The organic phase is dried over Sodiumsulfate, the solvent evaporated and the crude product is purified by column chromatography (Ethylacetate/CH2CI2 = 7:2 then slowly changing to Methanol). 6-{3-(5-Hydroxy-pentyloxy)-5-[5-(4'-pentyl-biphenyl-4-yl)- [1 ,3,4]oxadiazol-2-yl]-phenoxy}-hexan-1-ol is isolated in 37 % yield.
1.39 g (2,32 mmol) of 6-{3-(5-Hydroxy-pentyloxy)-5-[5-(4'-pentyl-biphenyl-4-yl)- [1 ,3,4]oxadiazol-2-yl]-phenoxy}-hexan-1-ol are placed in a 25 ml three necked round bottomed flask, equipped with an argon/vacuum inlet and a magnetic stirrer. 16 ml of Dichloromethane are added and the mixture is cooled to 00C. 1.1 1 ml (6.5 mmol) of N- Ethyldiisopropylamine and then 0.49 ml (6.01 mmol) Acryloylchloride are slowly added. After 1 hour the mixture is filtered on Silica (Heptane, then Heptane/Etylacetate = 2:1 ). The crude product purified by column chromatography (Heptane then slowly changing to Heptane/Ethylacetate = 2:1 ). Acrylic acid 6-{3-(5-acryloyloxy-pentyloxy)-5-[5-(4'-pentyl- biphenyl-4-yl)-[1 ,3,4]oxadiazol-2-yl]-phenoxy}-hexyl ester is isolated in 74 % yield. 1H-NMR (300MHz, CDCI3): 8.17 (d, 2H)
7.76 (d, 2H) 7.56 (d, 2H)
7.25 (m,4H)
6.62 (t, 1 H)
6.37 (m, 2H) 6.13 (m 2x, 2H) 5.82 (d 2x, 2H) ? 4.21-4.02 (m, 8H) 2.67 (t, 2H) 1.86-0.84 (m, 25H)
Example 3.3
Figure imgf000088_0001
Starting from 4-Cyano-4'-pentylbiphenyl and 4-Methoxybenzoyl chloride 2-{4-[6-(3-Methyl- oxetan-3-ylmethoxy)-hexyloxy]-phenyl}-5-(4'-pentyl-biphenyl-4-yl)-[1 ,3,4]oxadiazole is prepared according to Example 3.1 in 52% over all yield. 1H-NMR (300MHz, CDCI3): 8.14 (d, 2H)
8.07 (d,2H)
7.74 (d, 2H) 7.54 (d, 2H)
7.29 (d, 2H)
7.02 (d 2H)
4.50 (d, 2H)
4.35 (d, 2H) 4.03 (t, 2H)
3.47 (m, 4H)
2.65 (t, 2H)
1.82 (m, 2H)
1.63-1.34 (m, 14H) 1.31 (s, 3H)
0.91 (t, 3H) Example 3.4
Figure imgf000089_0001
Starting from 4-Cyano-4'-pentylbiphenyl and 4-Methoxybenzoyl chloride Acrylic acid 6-{4-[5- (4'-pentyl-biphenyl-4-yl)-[1 ,3,4]oxadiazol-2-yl]-phenoxy}-hexyl ester oxadiazole is prepared according to Example 3.2 in 51 % over all yield. 1H-NMR (300MHz, CDCI3): 8.13 (d, 2H)
8.04 (d,2H) 7.73 (d, 2H) 7.54 (d, 2H)
7.28 (d, 2H)
7.01 (d 2H) 6.37 (d, 1 H) 6.13 (dxd, 1 H) 5.82 (d, 2H)
4.18 (t, 2H)
4.02 (t, 2H) 2.65 (t, 2H) 1.85-1.32 (m, 14H) 0.90 (t, 3H)
Example 3.5
Figure imgf000089_0002
12 g (0.081 mol) 4-Vinylbenzoic acid and 0.446 g (0.04 mol) of Hydroquinone are added to a 500 ml three necked round bottomed flask, equipped with an Argon/Vacuum inlet and a magnetic stirrer, under N2. 355 ml dry of Toluene and 4.3 ml of dry Pyridine are added. The mixture is stirred and cooled to 00C with an ice bath. 34.3 ml (0.405 mol) of Oxalyl chloride are added drop by drop within 45 minutes and stirred over night at room temperature. The mixture is filtered on cotton wool and the solvent is removed by evaporation. The acid chloride is used directly for the following reaction.
13.5 g (0.081 mol) 4-Vinylbenzoicacid chloride is dissolved in 80 ml of dry Pyridine in a 100 ml three necked round bottomed flask, equipped with a magnetic stirrer and a reflux condenser, then 10 g (0.034 mol) of 5-(4'-Pentyl-biphenyl-4-yl)-5H-tetrazole are added. The reaction is heated to reflux and stirred over night and cooled to room temperature. 500ml of cold water are added and the suspension filtered and dried. The crude product is purified by column chromatography (Heptane/Ethylacetate = 7:1 then slowly changing to Ethylacetate). The product is dissolved in a small amount of CH2CI2 and added drop by drop on Methanol; the suspension is filtrated and washed with Methanol. 2-(4'-Pentyl-biphenyl-4-yl)-5-(4-vinyl- phenyl)-[1 ,3,4]oxadiazole is isolated in 70%yield. 1H-NMR (300MHz, CDCI3): 8.20 (m, 2H)
8.17 (m, 2H)
7.76 (m, 2H) 7.58(m, 4H) 7.28 (d, 2H)
6.77 (dxd, 1 H) 5.90 (d, 1 H) 5.42 (d, 1 H) 2.67 (t, 2H) 1.67 (m, 2H)
1.38 (m, 4H) 0.91 (t, 3H) Example 3.6
Figure imgf000091_0001
O -J
4-[5-(4-tert-Butyl-phenyl)-1 ,3,4-oxadiazol-2-yl]-phenol, prepared according to X. Jiang, Chemistry of Materials (2000), 12(9), 2542-2549, is reacted with 3-(6-Bromo- hexyloxymethyl)-3-methyl-oxetane according to the last step in Example 3.1 in 36% yield. 1H-NMR (300MHz, DMSO): 8.00 (d, 4H)
7.63 (d, 2H)
7.14 (d, 2H)
4.34 (d, 2H)
4.16 (d, 2H)
4.05 (t, 2H)
3.44-3.36 (m,4H)
1.80-1.35 (m, 8H)
1.32 (s, 9H)
1.20 (s, 3H)
Example 3.7
Figure imgf000091_0002
4-[5-(4-tert-Butyl-phenyl)-1 ,3,4-oxadiazol-2-yl]-phenol, prepared according to X. Jiang, Chemistry of Materials (2000), 12(9), 2542-2549, is reacted with 6-Bromo-1-hexanol and then with Acryloylchloride according to Example 1.10 in 52% yield. 1H-NMR (300MHz, DMSO): 8.00 (d, 4H)
7.63 (d, 2H)
7.14 (d, 2H) 6.34-6.07 (m, 3H) 4.1 1-4.00 (m, 4H) 1.80-1.35 (m, 8H) 1.32 (s, 9H)
The following compounds (examples 3.8 and 3.9) are prepared according to L. Boiteau et al., Macromolecules (2002), 35(5) 1543-1548:
Figure imgf000092_0001
Example 3.8:
Example 3.9:
Figure imgf000092_0002
4. Hole Transporters
Example 4.1
Figure imgf000092_0003
4N,4'N-Diphenyl-4N,4'N-di-p-tolyl-biphenyl-4,4'-diamine is prepared according to WO/061562, Example 6, compound 21 , but using N,N-Diphenylbenzidine and 4-lodotoluene as starting materials. Starting from 4N!4'N-Diphenyl-4N!4'N-di-p-tolyl-biphenyl-4,4'-diamine 4N,4'N-Di(4- formylphenyl-4N,4'N-di-p-tolyl-biphenyl-4,4'-diamine is prepared according to EP795791 Preparation Example.
Starting from 4N,4'N-Di(4-formylphenyl-4N!4'N-di-p-tolyl-biphenyl-4,4'-diamine 4N,4'N-Di(4- hydroxymethyl-phenyl-4N,4'N-di-p-tolyl-biphenyl-4,4'-diamine is prepared according to EP710893 Example 1.
1.6 g (2.77 mmol) of Di(4-hydroxymethyl-phenyl-4N,4'N-di-p-tolyl-biphenyl-4,4'-diamine and 50 ml of DMF are placed in a 250 ml three necked round bottomed flask, equipped with a magnetic stirrer and reflux condenser. The reaction mixture is heated to 400C internal temperature and 1.17 g ( 48.5 mmol) of Sodium hydride (washed with Hexane) are added.
1.94 g (6.94 mmol) of 3-(6-Bromo-hexyloxymethyl)-3-ethyl-oxetane (prepared according to
Jungermann, Macromolecules 2006, 39, 891 1 ) are added and the reaction mixture stirred at 900C internal temperature over night, then cooled to room temperature. The reaction mixture is poured on 250 g of ice and extracted three times with 250 ml of Ethylacetate. The combined organic phases are washed three times with 200 ml of water, dried over
Magnesiumsulfate, filtered and evaporated. The crude product is purified by flash chromatography using Hexane/Ethylacetate = 4:1 as eluent. 1 g of the desired product is isolated.
1H-NMR (300MHz, CDCI3): 7.41 (d, 4H)
7.20 (d, 4H) 7.12 - 7.00 (m, 16H) 4.55 - 4.30 (m, 12H) 3.60 - 3.40 (m, 12H)
2.33 -1.20 (m, 26H) 0.89 (t, 6H)
Example 4.2
Figure imgf000093_0001
2 g (3.47 mmol) 4N,4'N-Di(4-hydroxymethyl-phenyl-4N,4'N-di-p-tolyl-biphenyl-4,4'-diamine and 70 ml of THF are placed in a 250 ml three necked round bottomed flask, equipped with a magnetic stirrer and reflux condenser. 8.2 g ( 69.4 mmol) of 1 ,6-Hexanediol are added and the reaction mixture is heated to 400C internal temperature. 0.36 g (1.9 mmol) of p- Toluenesulfonic acid monohydrate are added and reacted for 30 minutes. The reaction mixture is cooled to room temperature, 8.2 g (69.4 mmol) of 1 ,6-Hexanediol are added and stirred for 20 minutes. 80 ml of water are added and the THF is evaporated. The residue is diluted with 200 ml of Ethylacetate, the organic phase is washed three times with 100 ml of water, dried over Magnesiumsulfate, filtered and evaporated. The crude product is purified by flash chromatography using Hexane/Ethylacetate = 1 :2 as eluent. 1.34 g of 6-{4-[(4'-{[4-(6- Hydroxy-hexyloxymethyl)-phenyl]-p-tolyl-amino}-biphenyl-4-yl)-p-tolyl-amino]-benzyloxy}- hexan-1-ol are isolated.
Hydroxy-hexyloxymethyl)-phenyl]-p-tolyl-amino}-biphenyl-4-yl)-p-tolyl-amino]-benzyloxy} - hexan-1-ol is reacted according to Example 2.2 step 2 to yield the desired product after flash chromatography using Hexane/Ethylacetate =5:1 as eluent. 1H-NMR (300MHz, CDCI3): 7.42 (d, 4H)
7.20 (d, 4H) 7.14 - 7.00 (m, 16H) 6.38 (d, 2H)
6.1 1 (dxd, 2H) 5.80 (d, 2H) 4.44 (s, 4H) 4.15 (t, 4H) 3.49 (t, 4H)
2.32 (s, 6H) 1.80 -1.25 (m, 16H) Example 4.3
Figure imgf000095_0001
N-(4-hydroxymethylphenyl)-N'-phenyl-N,N'-bis(4-methylphenyl)-[1 ,1 '-biphenyl]-4,4'-diamine is prepared according to M. Tamada, Polymer 41 (2000) 5661.
N-(4-hydroxymethylphenyl)-N'-phenyl-N,N'-bis(4-methylphenyl)-[1 ,1 '-biphenyl]-4,4'-diamine is reacted according to Example 3.2 step 1 to yield 6-(4-{[4'-(Phenyl-p-tolyl-amino)-biphenyl-4- yl]-p-tolyl-amino}-benzyloxy)-hexan-1-ol.
6-(4-{[4'-(Phenyl-p-tolyl-amino)-biphenyl-4-yl]-p-tolyl-amino}-benzyloxy)-hexan-1-ol is reacted according to example 2.2, step 2 to yield Acrylic acid 6-(4-{[4'-(phenyl-p-tolyl-amino)- biphenyl-4-yl]-p-tolyl-amino}-benzyloxy)-hexyl after flash chromatography using Hexane/Ethylacetate =95:5 as eluent. 1H-NMR (300MHz, CDCI3): 7.52 (m, 4H)
7.31 - 6.93 (m, 21 H)
6.33 (d, 1 H)
6.13 (dxd, 1 H)
5.84 (d, 1 H)
4.44 (s, 2H)
4.13 (t, 2H)
3.49 (t, 2H)
2.31 (s 6H)
1.72 - 1.58 (m, 4H)
1.49 - 1.37 (m, 4H) Example 4.4
Figure imgf000096_0001
4-{[4'-(Phenyl-p-tolyl-methyl)-biphenyl-4-yl]-p-tolyl-methyl}-benzaldehyde, which is obtained as a side product during the synthesis of 4N,4'N-Di(4-formylphenyl-4N,4'N-di-p-tolyl-biphenyl- 4,4'-diamine (second step of Example 4.1 ) is reacted with Methyl-triphenyl-phosphonium; bromide using standard Wittig reaction to give the desired product in 95% yield. 1H-NMR (300MHz, CDCI3): 8.00-7.92 (m, 2H)
7.57-7.31 (m, 5H)
6.80 (dxd, 1 H)
5.80 (d, 1 H)
5.26 (d, 1 H)
Example 4.5
The following compound is prepared in 35% yield according to Example 4.1 , starting from 3,3'-Dimethyl-N4,N4,N4',N4'-tetra-m-tolyl-biphenyl-4,4'-diamine (prepared according to WO05061562, Example 6).
Figure imgf000096_0002
1H-NMR (300MHz, CDCI3): 7.50-7.41 (m, 5H)
7.17-7.07 (m, 5H) 6.82 - 6.70 (m, 10H) 4.50 - 4.48 (m, 4H) 4.42 (s, 4H) 4.36-4.32 (m, 4H) 3.52-3.45 (m, 12H) 2.24 (s, 12H) 2.08 (s, 6H) 1.66-1.35 (m, 16H) 1.30 (s, 6H)
Example 4.6: The following compound is prepared in analogy to compound 20 of WO05061562 (Example 6):
Figure imgf000097_0001
5. Crosslinkers/further Comonomers
Example 5.1
Figure imgf000097_0002
5 g (41 mmol) of 4-Hydroxy-benzaldehyde, 13.6 g (61.5 mmol) of 2-(6-Chloro-hexyloxy)- tetrahydro-pyran, 17.0 g (123 mmol) Potassiumcarbonate and 100 ml of DMF are placed in a 250 ml three necked round bottomed flask, equipped with a magnetic stirrer and a reflux condenser. The reaction mixture is heated to 800C internal temperature for four hours, then cooled to room temperature, added to 500 ml of water and extracted four times with 250 ml of Ethylacetate. The combined organic phases are washed four times with 200 ml of water and once with 100 ml of brine, dried over Magnesiumsulfate, filtered and evaporated. The crude product is purified by flash chromatography using Hexane/Ethylacetate = 4:1 as eluent. 4-[6-(Tetrahydro-pyran-2-yloxy)-hexyloxy]-benzaldehyde is isolated in 89% yield.
13.54 g (37.9 mmol) of Methyltriphenylphosphonium bromide are dissolved in 175 ml of dry THF in a 500 ml three necked round bottomed flask, equipped with a magnetic stirrer. The solution is cooled to 00C with a Sodium chloride/ice bath. Within 30 minutes 24.9 ml of 1.6M Butyl lithium solution in Hexane are added drop by drop while keeping the internal temperature below 2°C. The resulting orange solution is stirred at 00C internal temperature for another 30 minutes. 8.6 g (28.1 mmol) of 4-[6-(Tetrahydro-pyran-2-yloxy)-hexyloxy]- benzaldehyde dissolved in 130 ml of dry THF are added drop by drop within 25 minutes while keeping the temperature below 2°C. The reaction mixture is stirred for another 2 hours at the same temperature, then added to 500 ml of water and extracted twice with 500 ml of Ethylacetate. The combined organic phases are washed twice with 200 ml of water and once with 100 ml of brine, dried over Magnesiumsulfate, filtered and evaporated. The crude product is purified by flash chromatography on basic Aluminumoxide using Hexane/Ethylacetate = 10:1 as eluent. 2-[6-(4-Vinyl-phenoxy)-hexyloxy]-tetrahydro-pyran is isolated in 98% yield.
1 1.4 g (37.4 mmol) of 2-[6-(4-Vinyl-phenoxy)-hexyloxy]-tetrahydro-pyran and 500 ml of Methanol are added to a 2 I three necked round bottomed flask, equipped with a magnetic stirrer. 1.4 g of p-Toluenesulfonic acid monohydrate are added and the solution stirred at room temperature for 75 minutes. The reaction mixture was hydrolysed with 200 ml of saturated NaHCO3 solution and the organic solvent is evaporated. The aqueous phase was extracted three times with 200 ml of Ethylacetate; the combined organic phases are washed twice with 100 ml of brine, dried over Magnesiumsulfate, filtered and evaporated. The crude product is purified by flash chromatography using Hexane/Ethylacetate = 2:1 as eluent. 6-(4- Vinyl-phenoxy)-hexan-1-ol is isolated in 85% yield. 1H-NMR (300MHz, CDCI3): 7.31 (d, 2H)
6.82 (d, 2H) 6.64 (dxd, 1 H)
5.58 (d, 1 H) 5.09 (d, 1 H) 3.93 (t, 2H) 3.61 (t, 2H) 2.00 - 1.30 (m, 9H) Example 5.2
Figure imgf000099_0001
4-Hydroxy-benzaldehyde is reacted with 3-(6-Bromo-hexyloxymethyl)-3-methyl-oxetane (prepared according to Jungermann, Macromolecules 2006, 39, 8911 ) according to Example 1.7. 4-[6-(3-Methyl-oxetan-3-ylmethoxy)-hexyloxy]-benzaldehyde is isolated in 74% yield.
4-[6-(3-Methyl-oxetan-3-ylmethoxy)-hexyloxy]-benzaldehyde is reacted with
Methyltriphenylphosphonium bromide according to Example 5.1 , step 2. 3-Methyl-3-[6-(4- vinyl-phenoxy)-hexyloxymethyl]-oxetane is isolated in 77% yield. 1H-NMR (300MHz, CDCI3): 7.26 (d, 2H)
6.78 (d, 2H) 6.59 (dxd, 1 H) 5.55 (d, 1 H) 5.04 (d, 1 H) 4.44 (d, 2H)
4.28 (d, 2H) 3.89 (t, 2H) 3.44 - 3.37 (m, 4H) 1.80 - 1.30 (m, 8H) 1.24 (s, 3H)
Example 5.3
The following compound is prepared in 68% yield according to A. Hall, Journal of Organic Chemistry (2005), 12, 1732, starting from 3-lsopropenyl-dimethylbenzylisocyanate and Ethanolamine.
Figure imgf000099_0002
1H-NMR (300MHz, DMSO): 7.42 (s, 1H)
7.29-7.21 (m, 3H) 6.36 (s, 1H) 5.86 (t, 1H) 5.33 (s, 1H)
5.05(s, 1H) 4.60 (t, 1H) 3.35 (t, 2H) 2.98 (q, 2H) 2.08(s, 3H)
1.50(s, 6H)
Example 5.4
The following compound is prepared in 24% yield according to E. Bacher, Macromolecules (2005), 38, 1640 starting from the compound prepared in Example 5.3 and 3-(Chloromethyl- 2-methyloxetane.
Figure imgf000100_0001
1H-NMR (300MHz, CDCI3): 7.55 (s, 1 H) 7.40-7.26 (m, 3H)
5.35(s, 1H) 5.10 (m, 1H) 4.48 (d, 2H) 4.28 (d, 2H) 3.42- 3.28 (m, 6H)
2.15(s, 3H) 1.65 (s, 6H) 1.20(s, 3H) Examples 5.5
Figure imgf000101_0001
Compound 5.5 is prepared according to Macromolecules (2005), 38(5), 1640-1647.
6. Polymers
General procedure: The starting materials in the ratio as indicated in the below table plus 3 weight-% of AIBN are dissolved in the minimal amount of Toluene. The solution is placed in a Schlenk apparatus equipped with a magnetic stirrer. N2 is bubbled through the solution for 1 hour and then stirred at 800C over night. The mixture is cooled to room temperature and added drop by drop to 30 ml of Methanol per ml of Toluene. The resulting suspension is filtered and washed with Methanol. The product is dissolved in as little Toluene or CH2CI2 as possible and added drop by drop to 30 ml of Methanol per ml of solvent. The resulting suspension is filtered, washed with Methanol and dried. Indices such as n, m, p, q, x, y in the product formula reflect the amounts of starting monomer incorporated into the product. Where not otherwise indicated, the product is characterized by gel permeation chromatography (GPC).
Figure imgf000101_0002
Figure imgf000102_0001
Figure imgf000103_0001
Figure imgf000104_0001
Figure imgf000105_0001
The polymers of the following table are prepared in an analogous manner as intermediates:
Figure imgf000105_0002
Figure imgf000106_0001
Polymer modification. General procedure: the starting material is dissolved in dichloromethane and cooled down to 0 0C. Excess of acryloyl chloride is added dropwise and the reaction mixture is stirred for 30 min at 0 0C and let warm to r.t. The reaction mixture is added drop by drop to 30 ml of Methanol per ml of solvent. The resulting suspension is filtered, washed with Methanol and dried.
Figure imgf000107_0001
Example 6.28
Copolymerization in analogy to examples 6.1 to 6.18 is carried out using the starting monomers of Examples 1.19 (10 wt%), 2.1 1 (30 wt%), 3.8 (30 wt%), and 4.6 (30 wt%), yielding the copolymer of the formula:
Figure imgf000108_0001
Mn (GPC absolute calibration) = 33600, PDI = 1.47.
Example 6.29
Copolymerization in analogy to examples 6.1 to 6.18 is carried out using the starting monomers of Examples 1.16 (10 wt%), 2.1 1 (30 wt%), 3.8 (30 wt%), and 4.6 (30 wt%), yielding the copolymer of the formula:
Figure imgf000108_0002
Mn (GPC ) = 28300, PDI = 1.28.
Example 6.30 a) Copolymerization in analogy to examples 6.1 to 6.18 is carried out using the starting monomers of Examples 1.19 (10 wt%), 2.1 1 (30 wt%), 3.8 (25 wt%), 4.6 (25 wt%), and 5.3 (10 wt%), yielding the copolymer of the formula:
Figure imgf000109_0001
Mn (GPC) = 18600, PDI = 1.81.
b) Modification of the above product with acryloyl chloride as described above for examples 6.23 to 6.27 yields the product:
Figure imgf000109_0002
Mn (GPC) = 22900, PDI = 1.77.
Example 6.31 a) Copolymerization in analogy to examples 6.1 to 6.18 is carried out using the starting monomers of Examples 1.16 (10 wt%), 2.1 1 (30 wt%), 3.8 (25 wt%), 4.6 (25 wt%), and 5.3 (10 wt%), yielding the copolymer of the formula:
Figure imgf000110_0001
Mn (GPC) = 26600, PDI = 1.55.
b) Modification of the above product with acryloyl chloride as described above for examples 6.23 to 6.27 yields the product:
Figure imgf000110_0002
Mn (GPC) = 31200, PDI = 2.09.
Example 6.32 Copolymerization in analogy to examples 6.1 to 6.18 is carried out using the starting monomers of Examples 1.19 (10 wt%), 2.12 (30 wt%), 3.8 (30 wt%), and 4.6 (30 wt%), yielding the copolymer of the formula:
Figure imgf000111_0001
Mn (GPC absolute calobration) = 45500, PDI = 2.56.
Example 6.33
Copolymerization in analogy to examples 6.1 to 6.18 is carried out using the starting monomers of Examples 1.16 (10 wt%), 2.12 (30 wt%), 3.8 (30 wt%), and 4.6 (30 wt%), yielding the copolymer of the formula:
Figure imgf000111_0002
Mn (GPC ) = 22300, PDI = 2.23.
Example 6.34 a) Copolymerization in analogy to examples 6.1 to 6.18 is carried out using the starting monomers of Examples 1.19 (10 wt%), 2.12 (30 wt%), 3.8 (25 wt%), 4.6 (25 wt%), and 5.3 (10 wt%), yielding the copolymer of the formula:
Figure imgf000112_0001
Mn (GPC) = 25200, PDI = 2.43.
b) Modification of the above product with acryloyl chloride as described above for examples 6.23 to 6.27 yields the product:
Figure imgf000112_0002
Mn (GPC) =31600, PDI = 1.98.
Example 6.35 a) Copolymerization in analogy to examples 6.1 to 6.18 is carried out using the starting monomers of Examples 1.16 (10 wt%), 2.1 1 (30 wt%), 3.8 (25 wt%), 4.6 (25 wt%), and 5.3 (10 wt%), yielding the copolymer of the formula:
Figure imgf000113_0001
Mn (GPC) = 21900, PDI = 1.76.
b) Modification of the above product with acryloyl chloride as described above for examples 6.23 to 6.27 yields the product:
Figure imgf000113_0002
Mn (GPC) = 26700, PDI = 1.69.
Examples 6.36-6.40: Polymers are prepared using the monomer units as identified in the below table. Procedures are analogous to those of examples 6.1 - 6.18 above.
Figure imgf000114_0001
Figure imgf000115_0001
Examples 6.41-6.42 (polymer modification) are carried out in analogy to examples 6.23 6.27 above. Polymers as prepared are identified in the below table.
Figure imgf000115_0002
7. Application Examples
Application Example 7.1 using PBD/TPD (20/20)
An organic luminescence device having a single organic layer is prepared in the following manner: On a glass substrate, a 80 nm thick ITO film is formed by sputtering and subsequently patterned. Onto the oxygen-plasma treated ITO film, a hole-injection layer of 80 nm thickness is formed by spin-coating using PEDOT:PSS (Baytron® P), followed by heating at 2000C (10 minutes). A solution of 15 mg of polymer of example 6.6 (compound 1 ), 5 mg of TPD (compound 2), and 5 mg of PBD (compound 3) in 1.1 ml of toluene is applied by spin coating (3100 rpm.; 40 seconds) to obtain a thickness of 80 nm. The film is dried under nitrogen atmosphere at 800C for 30 minutes. The substrate is placed in a vacuum deposition chamber, and a cathode having a two-layer structure is formed by depositing a 5 nm layer of barium followed by a 70 nm layer of aluminum. When driving the device at a current density of 22 mA/cm2 (at 10 V), a bright (1000 cd/m2) yellow (CIE 0.46, 0.50) emission is observed. This corresponds to a device efficiency of 4.6 cd/A.
The following examples are prepared and evaluated in analogous manner, using the materials and showing the results compiled in the below table.
Figure imgf000117_0001
Application examples 7.37-7.39: Cross-linking experiments. General procedure.
20mg/ml toluene solution of X-linkable materials (copmpounds 1 , 2 and 3 as indicated in the below table) without initiator is spin coated at 2000 rpm for 1 min and at 5000 rpm for 15 sec. Each sample is transferred into a nitrogen-filled glove-box and X-linked with UV light (8W, 254 nm) at 120 0C. The sample is washed with toluene. Degree of X-linking is determined by UV. Results are compiled in the below table
Figure imgf000118_0001
Copolymers of the invention can be formed by in-situ crosslinking.

Claims

Claims
1. Copolymer comprising
[A1]X1, [A2]χ2, [A3]χ3, [A4]X4, [A5]χ5
wherein the structural units A1, A2, A3, A4 and/or A5 are in blocks or at random, and the copolymer is linear or crosslinked, and A1 is an organic radical of a phosphorescent light emitting moiety;
A2 is an organic radical providing host functionality;
A3 is an organic radical providing electron transport functionality;
A4 is an organic radical providing hole transport functionality;
A5 is a radical derived from aliphatic or aromatic organic monomers; x1 is a number from 1 to about 1000; x2, x3, x4 and x5 independently are numbers from 0 to about 100 000, with the proviso that the sum (x1 + x2 + x3 + x4 + x5) is at least 5, especially greater than 9;
characterized in that A1 is of the formula (I)
Figure imgf000119_0001
(I), wherein n is an integer of 1 to 3, n1 and n2 are an integer 0, 1 or 2,
M1 is a metal with an atomic weight of greater than 40,
L1 is a monodentate ligand or a bidentate ligand,
L2 is a monodentate ligand,
Q1 and Q2 are independently of each other hydrogen or an organic substituent, or
Q1 and Q2 together with the carbon atoms, to which they are bonded, form a condensed ring, for example an aromatic or heteroaromatic ring, which optionally may be substituted, or a carbocyclic or heterocyclic, non-aromatic ring, which optionally may be substituted; and Q3 represents a group of forming a condensed aromatic or heteroaromatic ring, preferably a phenyl or naphthyl ring, which optionally may be substituted, and wherein 1-3, preferably one, of L1, L2, Q1, Q2 and/or the substituents contains a divalent group derived from a polymerizable aliphatic or aromatic momomer moiety;
or
x2 is at least 1 , and A2 is selected from repeating unit(s) of the formula
Figure imgf000120_0001
especially
Figure imgf000120_0002
(Ilia) or (1Mb),
Figure imgf000120_0003
where in the formulae (III) and (IV) x is 0, or an integer of 1 to 5,
A is a 5-, 6-, or 7-membered heteroaromatic ring, containing at least one heteroatom selected from nitrogen, oxygen and sulfur, especially one nitrogen atom and at least one further heteroatom selected from nitrogen, substituted nitrogen, oxygen and sulfur; R1, R2, R3, R4, R5 and R6 are independently of each other hydrogen, halogen, or an organic substituent, or
R1 and R2, R4 and R6, R2 and R3, R5 and R3 and/or R5 and R6, which are adjacent to each other, together form an aromatic, or heteroaromatic ring, or ring system, which can optionally be substituted;
R7 is an organic substituent, wherein two or more substituents R7 in the same molecule may have different meanings, or can form together an aromatic, or heteroaromatic ring, or ring system;
Ga, G1, G2, G3, G4, G1', G2', G3' and G4' are independently of each other hydrogen, halogen, especially fluorine, or an organic substituent, or
Ga, G1, G2, G3, G4, G1', G2', G3' and G4', if possible, together form an aromatic, or heteroaromatic ring, or ring system, which can optionally be substituted,
G7 is halogen, especially fluorine, or an organic substituent, wherein two or more substituents G7 in the same molecule may have different meanings, or can form together an aromatic, or heteroaromatic ring, or ring system, wherein at least one of Ga, G1, G2, G3, G4, G1', G2', G3' and G4' in a repeating unit is a group R10, wherein
R10 is a trivalent group -(Sp)xi0-[PG']<, wherein x10 is 0, or 1 ; Sp is a spacer unit; PG' is a group derived from a polymerisable group.
2. Copolymer according to claim 1 comprising
[Ai]χi , [A2]χ2, [A3]χ3, [A4]X4, [A5]χ5
wherein the structural units A1, A2, A3, A4 and/or A5 are contained in blocks or at random, and the copolymer is linear or crosslinked, and
A1 is an organic radical of a phosphorescent light emitting moiety; x1 is a number from 1 to about 1000; x2, x3, x4 and x5 independently are numbers from 0 to about 100 000, with the proviso that the sum (x2 + x3 + x4 + x5) is at least 5, especially greater than 9;
A2, A3, A4 and A5 independently are radicals derived from aliphatic or aromatic monomers; characterized in that A1 is of the formula (I)
Figure imgf000122_0001
(I), wherein n is an integer of 1 to 3, n1 and n2 are an integer 0, 1 or 2,
M1 is a metal with an atomic weight of greater than 40,
L1 is a monodentate ligand or a bidentate ligand,
L2 is a monodentate ligand,
Q1 and Q2 are independently of each other hydrogen or an organic substituent, or
Q1 and Q2 together with the carbon atoms, to which they are bonded, form a condensed ring, for example an aromatic or heteroaromatic ring, which optionally may be substituted, or a carbocyclic or heterocyclic, non-aromatic ring, which optionally may be substituted; and
Q3 represents a group of forming a condensed aromatic or heteroaromatic ring, preferably a phenyl or naphthyl ring, which optionally may be substituted, and wherein 1-3, preferably one, of L1, L2, Q1, Q2 and/or the substituents contains a divalent group derived from a polymerizable aliphatic or aromatic monomer moiety;
or, in case that x2 is at least 1 , and A2 is selected from repeating unit(s) of the formula
Figure imgf000123_0001
A1 generally embraces a phosphorescent light emitting moiety, especially of the formula (II)
Figure imgf000123_0002
where in formula (II) n = 1 ,2 or 3; n1 = 0, 1 or 2; n2 = 0, 1 or 2;
M1 is as defined above; each of L and L1 is a monodentate ligand or a bidentate ligand;
L2 is a monodentate ligand; and at least one of L, L1 and L2 contains a divalent group derived from a polymerizable aliphatic or aromatic momomer moiety;
and where in the formulae (III) and (IV) x is 0, or an integer of 1 to 5, A is a 5-, 6-, or 7-membered heteroaromatic ring, containing at least one heteroatom selected from nitrogen, oxygen and sulfur, especially one nitrogen atom and at least one further heteroatom selected from nitrogen, substituted nitrogen, oxygen and sulfur; R1, R2, R3, R4, R5 and R6 are independently of each other hydrogen, halogen, or an organic substituent, or
R1 and R2, R4 and R6, R2 and R3, R5 and R3 and/or R5 and R6, which are adjacent to each other, together form an aromatic, or heteroaromatic ring, or ring system, which can optionally be substituted;
R7 is an organic substituent, wherein two or more substituents R7 in the same molecule may have different meanings, or can form together an aromatic, or heteroaromatic ring, or ring system;
Ga, G1, G2, G3, G4, G1', G2', G3' and G4' are independently of each other hydrogen, halogen, especially fluorine, or an organic substituent, or Ga, G1, G2, G3, G4, G1', G2', G3' and G4', if possible, together form an aromatic, or heteroaromatic ring, or ring system, which can optionally be substituted,
G7 is halogen, especially fluorine, or an organic substituent, wherein two or more substituents
G7 in the same molecule may have different meanings, or can form together an aromatic, or heteroaromatic ring, or ring system, wherein at least one of Ga, G1, G2, G3, G4, G1', G2', G3' and G4' in a repeating unit is a group R10, wherein
R10 is a trivalent group -(Sp)xi0-[PG']<, wherein x10 is 0, or 1 ;
Sp is a spacer unit; PG' is a group derived from a polymerisable group.
3. Copolymer of claim 1 or 2 which is of the constitution
[Ai]xi-[A2]χ2 -[A3]X3-[A4]X4 -[A5Jx5 wherein the structural units A1, and, if present, A2, A3, A4 and A5 are contained in blocks or at random, and the copolymer is linear or crosslinked; each of A2, A3, A4 and A5 independently is selected from radicals containing 2 to 200 carbon atoms;
A1 as the phosphorescent light emitting moiety contains a metal M1 selected from the group consisting of Fe, Ru, Ni, Cu, Co, Ir, Pt, Pd, Rh, Re, Os,TI, Pb, Bi, In, Sn, Sb, Te, Ag and Au; and any substituent, if present, is selected from halogen, OH, CrC24alkoxy, CrC24alkyl, d-
C24haloalkyl, C2-C24alkenyl, C2-C24alkynyl, Ci-C24alkylthio, Ci-C24acyl, C5-Ci0aryl, d-
Cioheteroaryl, C3-Ci2cycloalkyl, Ci-C24acyloxy, C5-Ci0aryloxy, C3-Ci2cycloalkyloxy, or from the residues COR, CH=NR, CH=N-OH, CH=N-OR, COOR, OCOR, CONHR, CONRR',
CONH-NHR, CONH-NRR', SR, SO2R, SO3R, SO2NHR, SO2NRR', SO2NH-NHR, SO2NH-
NRR', S(O)R, S(O)OR, S(O)NHR, S(O)NRR', S(O)NH-NHR, S(O)NH-NRR', a silyl group
(SiRR1R"), PORR', PO(OR)R', PO(OR)2, PO(NHR)2, PO(NRR')2, cyano (CN), NO2, NHR,
NRR', NH-NHR, NH-NRR', CONROH; where R, R' and R" independently are selected from Ci-Ci2alkyl, Ci-Ci2haloalkyl, C5-Ci0aryl,
C3-Ci2cycloalkyl; and R may also be hydrogen.
4. Copolymer according to any of claims 1 to 3, wherein A1 contains a bidentate ligand selected from
Figure imgf000125_0001
Figure imgf000125_0003
(IX-5),
Figure imgf000125_0002
(IX-8),
Figure imgf000125_0005
(IX-9),
Figure imgf000125_0004
(IX-12), (IX-16),
Figure imgf000126_0001
and (IX- 17), wherein
Figure imgf000126_0002
ring A, , represents an optionally substituted aryl group which may contain a heteroatom,
ring B,
Figure imgf000126_0003
, represents an optionally substituted nitrogen containing aryl group, which may contain further heteroatoms,
Figure imgf000126_0004
ring C, , represents a ligand derived from a nucleophilic carbene, which may contain a heteroatom,
G is -C(=O)-, or -C(X1)2-, wherein X1 is H, or unsubstituted or substituted Ci-C4alkyl, preferably H; y is 0, or 1 , preferably 0;
Y-Z" is a group R10 of the formula -(Sp)xi0-[PG']<;
R11 is unsubstituted or substituted Ci-C4alkyl;
R12 is CF3 or a ring A; R13 is H, unsubstituted or substituted CrC4alkyl
R14, R14 independently are a ring A, unsubstituted or substituted Ci-C8alkyl, d-
Cβperfluoralkyl or a ring B, unsubstituted or substituted Ci-C8alkoxy;
Sp is of the formula (X3-D)x11-X2, wherein x11 is 0 or 1 ; X3, X2 independently are O, Ci-C4alkylene-O, S, Ci-C4alkylene-S, NR22, Ci-C4alkylene-NR22, COO, CrC4alkylene-COO or CrC4alkylene-OCO, CONR22, Cr C4alkylene-CONR22 or Ci-C4alkylene-NR22CO, NR22CONR22, CrC4alkylene- NR22CONR22, CrC4alkylene, or a direct bond, and
D is Ci-C24alkylene, interrupted C3-C24alkylene, C2-C24alkenylene, C2-C24alkynylene, C6- Cioarylene; PG' is a group derived from a polymerisable group and is integrated in the copolymer chain; W is N or CH; and a further ligand optionally is selected from those of the above formulae IX-1 to IX-17 wherein Y-Z" is hydrogen.
5. Copolymer according to any of claims 1 to 4, wherein structural units A1 make up about 0.1-25 %, structural units A2, if present, make up about 25-99.9 %, structural units A3 and/or A4, if present, make up about 0.9-99.9 or, if used concomitantly to radicals A2 and/or A5, about 1-75 %, structural units A5, if present, make up about 0.01-50 %, each percentage referring to the total weight of the present copolymer.
6. Copolymer according to any of claims 1 to 5, wherein A2 is selected from R52-(Sp)xi0-[PG']<, wherein R52 is unsubstituted or substituted carbazolyl, or a residue of the formula
Figure imgf000127_0001
with either R9 or R10 being an open bond linking the residue to Sp or PG', while the remaining R9', R10', R11, R11', R12, R13 R14, R12', R13' and R14' are independently of each other H or a substituent;
A3 is selected from R53-(Sp)xi0-[PG']<, wherein R53 is a residue of the formula
Figure imgf000128_0001
wherein n can be the same or different at each occurence and is 0, 1 , 2, or 3; and each R 3441' is a substituent, or 2 neighbouring are linked together to form, together with the carbon atoms they are bonding to, an unsubstituted or substituted 5- or 6-membered carbocyclic or heterocyclic ring;
A4 is selected from R54-(Sp)xio-[PG']<, wherein )n
Figure imgf000128_0002
R54 is (ll'c), n can be the same or different at each occurence and is 0, 1 , 2, or 3; and each R is a substituent;
A5 is selected from R55-(Sp)xi0-[PG']<, wherein R55 is d-C^alkyl, C3-Ci2cycloalkyl, C6- Cioaryl, C4-Ci0heteroaryl, each of which is unsubstituted or substituted, or is H or R10;
any substituent, if present, is selected from d-C^alkyl, a hydroxyl group, a mercapto group, Ci-Ci2alkoxy, d-C^alkylthio, halogen, halo-Ci-Ci2alkyl, a cyano group, an aldehyde group, a ketone group, a carboxyl group, an ester group, a carbamoyl group, an amino group, a nitro group, R , a silyl group, where halogen stands for Cl, F;
R'υ is a group -(Sp)xI0-[PG]; x10 is O or 1 ,
Figure imgf000128_0003
PG' is , where the asterisk marks the atom bonding to (Sp)xI0-; PG is oxiranyl, oxetanyl, glycidyl, or is PG'; any Sp, if present, independently is a spacer of the formula (X3-D)x11-X2, wherein x11 is 0 or 1 ; X3, X2 independently are O, Ci-C4alkylene-O, COO, Ci-C4alkylene- COO or Ci-C4alkylene-OCO, or a direct bond, and D is Ci-C24alkylene or phenylene.
7. Copolymer according to any of claims 1 to 6, wherein x1 is at least 1 and L1 is a bidentate ligand of the formula LII
Figure imgf000129_0001
wherein
W is selected from O, S, NR4, CR5R6, X is N or CR7, Y is selected from O, S, NR8;
Ri, R2, R4, R5, Re independently are H, unsubstituted or substituted CrCi8alkyl, unsubstituted or substituted C2-Ci8alkenyl, unsubstituted or substituted C5-Ci0aryl, unsubstituted or substituted C2-Ci0heteroaryl, Ci-Ci8acyl, or R10;
or R1, R2 may stand for a substituent ; or the neighbouring residues Ri and R2 form an organic bridging group completing, together with the carbon atoms they are bonding to, a carbocyclic or heterocyclic, non-aromatic or preferably aromatic ring of 5 to 7 ring atoms in total, which optionally may be substituted;
R7, if present, together with its neighbouring residue R3 forms an organic bridging group completing, with the carbon atoms they are bonding to, a carbocyclic or heterocyclic, non- aromatic or preferably aromatic ring of 5 to 7 ring atoms in total, which optionally may be substituted; or R7 embraces the meanings given for R4, or is halogen, OR, SR, NRR', COOR, CONRR', CN, OCN, SCN, or is C2-C5alkynyl, C3-C5cycloalkyl, hetero-C2-C5cycloalkyl, or C3-C5cycloalkenyl, each unsubstituted or substituted; or R3 is H, unsubstituted or substituted Ci-Ci8alkyl, unsubstituted or substituted C2- Ci8alkenyl, unsubstituted or substituted C5-Cioaryl, unsubstituted or substituted C2- Cioheteroaryl, Ci-Ci8acyl, OR, SR, NRR', or is C2-C5alkynyl, C3-C5cycloalkyl, hetero-C2-C5cycloalkyl or C3-C5cycloalkenyl each unsubstituted or mono- or poly-substituted by COR, COOR, CONRR', CN, halogen and/or by OR;
R'3 is unsubstituted or substituted CrCi8alkylene, unsubstituted or substituted C2- Ci8alkenylene, unsubstituted or substituted C5-Ci0arylene, unsubstituted or substituted C2- Cioheteroarylene, C2-Ci8diacylene; R8 is hydrogen or a substituent; any substituent is selected from halogen, Ci-Ci8alkoxy, Ri0, CrCi8alkylthio, Ci-Ci8acyl, C5- Cioaryl, C3-Ci2cycloalkyl, Ci-Ci8acyloxy, C5-Ci0aryloxy, C3-Ci2cycloalkyloxy, or from the residues COR, CH=NR, CH=N-OH, CH=N-OR, COOR, CONHR, CONRR', CONH-NHR, CONH-NRR', SO2R, SO3R, SO2NHR, SO2NRR', SO2NH-NHR, SO2NH-NRR', S(O)R, S(O)OR, S(O)NHR, S(O)NRR', S(O)NH-NHR, S(O)NH-NRR', SiRR'R", PORR', PO(OR)R', PO(OR)2, PO(NHR)2, PO(NRR')2, CN, NO2, NHR, NRR', NH-NHR, NH-NRR', CONROH; R, R' and R" independently are selected from Ci-Ci2alkyl, C5-Ci0aryl, C3-Ci2cycloalkyl, preferably from d-C6alkyl, phenyl, cyclopentyl, cyclohexyl; and R may also be hydrogen; L in formula Il is a bidentate ligand; and L or L1 contains a residue Ri0.
8. Copolymer of claim 7, wherein R7, if present, together with its neighbouring residue R3 forms an organic bridging group completing, with the carbon atoms they are bonding to, a carbocyclic or heterocyclic, non-aromatic or preferably aromatic ring of 5 to 7 ring atoms in total, which optionally may be substituted; or R7 embraces the meanings given for R4, or is NRR', COR, COOR, CONRR', CN, or is C2-C5alkynyl, C3-C5cycloalkyl, hetero-C2-C5cycloalkyl, or C3-C5cycloalkenyl, each unsubstituted or substituted; or R3 is H, unsubstituted or substituted Ci-Ci8alkyl, unsubstituted or substituted C2- Ci8alkenyl, unsubstituted or substituted C5-Ci0aryl, unsubstituted or substituted C2- Cioheteroaryl, Ci-Ci8acyl, or is C2-C5alkynyl, C3-C5cycloalkyl, hetero-C2-C5cycloalkyl or C3-C5cycloalkenyl each unsubstituted or mono- or poly-substituted by COR, COOR, CONRR', CN, halogen and/or by OR; R'3 is unsubstituted or substituted Ci-Ci8alkylene, unsubstituted or substituted C2- Ci8alkenylene, unsubstituted or substituted C5-Cioarylene, unsubstituted or substituted C2- Cioheteroarylene, C2-Ci8diacylene; R8 is hydrogen or a substituent.
9. Electroluminescent material comprising a copolymer according to claim 1 or 2 and at least one further component, especially selected from phosphorescent metal complexes, electron transporters, hole transporters, inert polymers, viscosity modifiers, initiators, organic salts.
10. Reactive intermediate obtainable by radical copolymerization of a compound of the formula (XII), (XIII) and/or (XXII)
Figure imgf000131_0001
with a bifunctional crosslinker of the formula
Figure imgf000131_0002
wherein
X is NR9"; each of R9, R9' , R11, R11', R12, R12', R13, R13', R14, R14' is H, d-C^alkyl, halogen, CrCi2alkoxy; R9" is H, Ci-Ci2alkyl;
R10 is a group -(Sp)xi0-vinyl, x10 is 0 or 1 ;
Sp, if present, is a spacer unit (X3-D)x11-X2, wherein x11 is 0 or 1 ; X3, X2 independently are O, Ci-C4alkylene-O, S, Ci-C4alkylene-S, NR22, Ci-C4alkylene-NR22, COO, CrC4alkylene-COO or CrC4alkylene-OCO, CONR22, d- dalkylene-CONR22 or Ci-C4alkylene-NR22CO, NR22CONR22, d-dalkylene-
NR22CONR22, d-dalkylene, or a direct bond, and
D is d-C24alkylene, interrupted C3-C24alkylene, C2-C24alkenylene, C2-C24alkynylene, C6-
Cioarylene; and RG is a reactive group selected from OH, COOR, oxiranyl, oxetanyl, where R is hydrogen
Ci-C6alkyl, phenyl, cyclopentyl, cyclohexyl.
1 1. Monomer of the formula I"
Figure imgf000132_0001
wherein
M1 is a metal with an atomic weight of greater than 40,
L1 is a bidentate ligand containing the substituent R10;
Q1 and Q2 are independently of each other hydrogen or an organic substituent, or
Q1 and Q2 together with the carbon atoms, to which they are bonded, form a condensed ring, for example an aromatic or heteroaromatic ring, which optionally may be substituted, or a carbocyclic or heterocyclic, non-aromatic ring, which optionally may be substituted; and
Q3 represents a group of forming a condensed aromatic or heteroaromatic ring, preferably a phenyl or naphthyl ring, which optionally may be substituted, and R10 is a group -(Sp)xi0-vinyl, where x10 is 0 or 1 and Sp, if present, is a divalent spacer unit.
12. An organic electronic device, especially organic light emitting diode or light emitting cell, comprising an emitting layer wherein the emitting layer comprises a copolymeric compound according to any of claims 1 to 8 or polymeric or monomeric compound according to any of claims 10 or 11.
13. Use of a copolymeric compound according to any of claims 1 to 8 or polymeric or monomeric compound according to any of claims 10 or 11 in an electronic device, especially as active component in an organic light emitting diode or light emitting cell, as oxygen sensitive indicator, as pH sensitive indicator, as phosphorescent indicator in a bioassay, or as a catalyst.
14. Method for the preparation of a light emitting device, especially an organic light emitting diode or light emitting cell, which method comprises providing an organic substance layer containing a copolymeric compound according to any of claims 1 to 8 or polymeric or monomeric compound according to any of claims 10 or 1 1 between a pair of electrodes on a substrate.
15. A device selected from stationary and mobile displays, such as displays for computers, mobile phones, laptops, pdas, TV sets, displays in printers, kitchen equipment, billboards, lightings, information boards and destination boards for example in trains and buses, containing an organic light emitting diode according to claim 12.
PCT/EP2009/050494 2008-01-25 2009-01-16 Organic light emitting systems WO2009092671A2 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP08150646 2008-01-25
EP08150646.1 2008-01-25
EP08157393 2008-06-02
EP08157393.3 2008-06-02

Publications (2)

Publication Number Publication Date
WO2009092671A2 true WO2009092671A2 (en) 2009-07-30
WO2009092671A3 WO2009092671A3 (en) 2009-10-08

Family

ID=40473706

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2009/050494 WO2009092671A2 (en) 2008-01-25 2009-01-16 Organic light emitting systems

Country Status (1)

Country Link
WO (1) WO2009092671A2 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8685541B2 (en) 2008-06-02 2014-04-01 Basf Se Dibenzofurane polymers for electroluminiscent devices
US9233930B2 (en) 2009-05-27 2016-01-12 Basf Se Polycyclic dithiophenes
US9487548B2 (en) 2009-12-14 2016-11-08 Udc Ireland Limited Metal complexes comprising diazabenzimidazolocarbene ligands and the use thereof in OLEDs
CN113314688A (en) * 2021-05-28 2021-08-27 深圳德诚达光电材料有限公司 OLED material based on halogen atom batching
WO2021203663A1 (en) * 2020-04-10 2021-10-14 华南理工大学 Electroluminescent polymer based on phenanthroimidazole units, preparation method therefor, and use thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030091862A1 (en) * 2001-08-31 2003-05-15 Nippon Hoso Kyokai Phosphorescent compound, a phosphorescent composition and an organic light-emitting device
WO2007119629A1 (en) * 2006-03-27 2007-10-25 Showa Denko K.K. An organic light-emitting device using a compound having a carrier transport property and a phosphorescent property
US20080015355A1 (en) * 2004-06-28 2008-01-17 Thomas Schafer Electroluminescent Metal Complexes With Triazoles And Benzotriazoles

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030091862A1 (en) * 2001-08-31 2003-05-15 Nippon Hoso Kyokai Phosphorescent compound, a phosphorescent composition and an organic light-emitting device
US20080015355A1 (en) * 2004-06-28 2008-01-17 Thomas Schafer Electroluminescent Metal Complexes With Triazoles And Benzotriazoles
WO2007119629A1 (en) * 2006-03-27 2007-10-25 Showa Denko K.K. An organic light-emitting device using a compound having a carrier transport property and a phosphorescent property

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8685541B2 (en) 2008-06-02 2014-04-01 Basf Se Dibenzofurane polymers for electroluminiscent devices
US9233930B2 (en) 2009-05-27 2016-01-12 Basf Se Polycyclic dithiophenes
US9716241B2 (en) 2009-05-27 2017-07-25 Basf Se Polycyclic dithiophenes
US9487548B2 (en) 2009-12-14 2016-11-08 Udc Ireland Limited Metal complexes comprising diazabenzimidazolocarbene ligands and the use thereof in OLEDs
US10090476B2 (en) 2009-12-14 2018-10-02 Udc Ireland Limited Metal complexes comprising diazabenzmidazolocarbene ligands and the use thereof in OLEDs
US10916716B2 (en) 2009-12-14 2021-02-09 Udc Ireland Limited Metal complexes comprising diazabenzmidazolocarbene ligands and the use thereof in OLEDS
US11444254B2 (en) 2009-12-14 2022-09-13 Udc Ireland Limited Metal complexes comprising diazabenzmidazolocarbene ligands and the use thereof in OLEDs
US11839140B2 (en) 2009-12-14 2023-12-05 Udc Ireland Limited Metal complexes comprising diazabenzmidazolocarbene ligands and the use thereof in OLEDS
WO2021203663A1 (en) * 2020-04-10 2021-10-14 华南理工大学 Electroluminescent polymer based on phenanthroimidazole units, preparation method therefor, and use thereof
CN113314688A (en) * 2021-05-28 2021-08-27 深圳德诚达光电材料有限公司 OLED material based on halogen atom batching
CN113314688B (en) * 2021-05-28 2022-11-25 深圳德诚达光电材料有限公司 OLED material based on halogen atom batching

Also Published As

Publication number Publication date
WO2009092671A3 (en) 2009-10-08

Similar Documents

Publication Publication Date Title
JP5214237B2 (en) Triarylamine compounds used as charge transport materials
EP1892259B1 (en) Hole transport polymers
KR101539789B1 (en) Light emitting cu(i) complexes
KR101011883B1 (en) Polymeric Charge Transport Compositions and Electronic Devices Made with Such Compositions
KR20040019935A (en) Polymer compound and polymer light-emitting device using the same
WO2005082969A1 (en) Polymer and polymeric luminescent element comprising the same
EP2297272B1 (en) Dibenzofurane polymers for electroluminiscent devices
EP2139907B1 (en) Electroluminescent metal complex
WO2009092671A2 (en) Organic light emitting systems
JP5613941B2 (en) Blue light-emitting polymer compound, organic electroluminescence device and use thereof
KR20210024966A (en) Organic light emitting device
US8084935B2 (en) Organic electroluminescent element and display panel using said element
WO2009087064A1 (en) Electroluminescent ionic host-guest dendritic materials
KR20210022435A (en) Organic light emitting device

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09703695

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09703695

Country of ref document: EP

Kind code of ref document: A2