KR20200080326A - Metal complexes comprising diazabenzimidazol carbene-ligands and the use thereof in oleds - Google Patents

Abstract

The present invention includes a central atom selected from iridium and platinum, and a metal-carbene complex comprising diazabenzimidazole carbene-ligand, an organic photodiode comprising the complex, and at least one metal-carbene complex A device selected from the group comprising a light emitting layer, a light emitting element comprising an OLED, a still image display device and a moving image display device and OLEDs, for example emitters, matrix materials, charge transport materials and/or charge or exciton blockers In metal-carbene complexes.

Description

Metal complexes containing diazabenzimidazolocarben ligands and their use in OLEDs METAL COMPLEXES COMPRISING DIAZABENZIMIDAZOL CARBENE-LIGANDS AND THE USE THEREOF IN OLEDS}

The present invention is a metal-carbene complex comprising a central atom selected from iridium and platinum and a diazabenzimidazolocarbene ligand, an organic light emitting diode (OLED) comprising the complex, and at least one metal-carbene complex A device selected from the group comprising a light emitting layer comprising, the OLED, a lighting element, a stationary image display device and a moving image display device, and for example, emitters, matrix materials, charge transport materials and And/or the use of metal-carbene complexes in OLEDs as charge or exciton blockers.

Organic light emitting diodes (OLEDs) use the tendency of a material to emit light when excited by an electric current. OLEDs are particularly important as an alternative to liquid crystal displays and cathode ray tubes for the manufacture of flat panel image display devices. Due to the very compact design and inherent low power consumption, devices comprising OLEDs are suitable for the field of mobile communications, for example in mobile phones, laptop computers and the like. In addition, white light OLEDs offer significant advantages, particularly in terms of high efficiency, compared to the lighting techniques known to date.

The prior art proposes various materials that emit light when excited by electric current.

WO 2005/019373 discloses transition metal complexes using carbene ligands as emitters for organic light emitting diodes (OLEDs). The ligands of these transition metal complexes are preferably bound by metal-carbene bonds and by bonds between metal atoms and aromatic radicals. A number of heterocycles attached to metal atoms via carbene bonds have been disclosed, but complexes with diazabenzimidazolocarben ligands have not been disclosed.

WO 2006/056418 A2 discloses the use of transition metal-carbene complexes in organic light-emitting diodes. In this transition metal complex, the metal atom is bound to the ligand by one or more metal-carbene bonds and by a bond between the metal atom and the aromatic radical. The metal-carbene bond is preferably via an imidazole ring, according to the cited literature, aromatic cycles may also be fused thereto. However, complexes with diazabenzimidazolocarben ligands are not disclosed.

WO 2007/088093 A1 and WO 2007/185981 A1 disclose transition metal complexes comprising a ligand bound by a metal-carbene bond. Preferred carbene ligands are mentioned imidazole ligands. It also has a fused aromatic 6-membered ring, where 1 to 4 of the carbon atoms present in the aromatic 6-membered ring can be substituted with nitrogen. The cited document does not disclose the position of nitrogen in the aromatic 6-membered ring.

WO 2007/115970 A1 likewise discloses transition metal-carbene complexes, imidazole units being preferred as carbene ligands. Aromatic 6-membered rings can likewise be fused to these imidazole units, where 1 to 4 carbon atoms can be substituted with nitrogen atoms. There is no disclosure as to the location of the nitrogen atom in this document.

Although compounds that exhibit electroluminescence in the visible region, especially in the blue region of the electromagnetic spectrum, are already known, there is a need to provide compounds that exhibit long diode lifetimes. In the context of the present invention, electroluminescence is understood to mean both electrofluorescence and electrophosphorescence.

Therefore, it is an object of the present invention to provide alternative iridium and platinum complexes suitable for electroluminescence in the visible region of the electromagnetic spectrum, more particularly in the blue region, capable of manufacturing a full color display and a white light OLED. A further object of the present invention is to provide a corresponding complex which can be used as a mixture with a host compound (matrix material) as a light emitting layer in an OLED. It is a further object of the present invention to provide a corresponding complex having high quantum yield and high stability in a diode. The complex must be usable as an emitter, matrix material, charge transport material, especially hole transport material or charge blocker in OLED.

This object is achieved according to the invention by metal-carbene complexes of the formula (I):

<Formula I>

In the above formula,

M, n, Y, A ² , A ³ , A ⁴ , A ⁵ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , K, L, m and o are each as defined below:

M is Ir or Pt,

n is an integer selected from 1, 2 and 3,

Y is NR ¹ , O, S or C(R ¹⁰ ) ₂ ,

A ² , A ³ , A ⁴ , A ⁵ are each independently N or C, where two A are nitrogen atoms, and one or more carbon atoms are present between two nitrogen atoms in the ring,

R ¹ is optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having a linear or branched alkyl radical having 1 to 20 carbon atoms; A cycloalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A substituted or unsubstituted aryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 6 to 30 carbon atoms; Is a substituted or unsubstituted heteroaryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having a total of 5 to 18 carbon atoms and/or heteroatoms,

R ² , R ³ , R ⁴ , R ⁵ are each a free electron pair when A ² , A ³ , A ⁴ and/or A ⁵ is N, or A ² , A ³ , A ⁴ and/or A ⁵ is In the case of C, each independently hydrogen; A linear or branched alkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups and having 1 to 20 carbon atoms; A cycloalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A substituted or unsubstituted aryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 6 to 30 carbon atoms; A substituted or unsubstituted heteroaryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having a total of 5 to 18 carbon atoms and/or heteroatoms; Is a group with donor or acceptor action or

R ³ and R ⁴ together with A ³ and A ⁴ are optionally interrupted by one or more additional heteroatoms and form an optionally substituted unsaturated ring having a total of 5 to 18 carbon atoms and/or heteroatoms,

R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently hydrogen; A linear or branched alkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups and having 1 to 20 carbon atoms; A cycloalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A cycloheteroalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A substituted or unsubstituted aryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 6 to 30 carbon atoms; A substituted or unsubstituted heteroaryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having a total of 5 to 18 carbon atoms and/or heteroatoms; Is a group with donor or acceptor action or

R ⁶ and R ⁷ , R ⁷ and R ⁸ or R ⁸ and R ⁹ together with the carbon atom to which they are attached are optionally interrupted by one or more heteroatoms and are unsaturated or having a total of 5 to 18 carbon atoms and/or heteroatoms, or Form an aromatic, optionally substituted ring, and/or

When A ⁵ is C, R ⁵ and R ⁶ together optionally include heteroatoms, aromatic units, heteroaromatic units and/or functional groups and have a total of 1 to 30 carbon atoms and/or heteroatoms, wherein carbon atoms and / Or a substituted or unsubstituted, 5- to 8-membered ring containing heteroatoms optionally forms a saturated or unsaturated, linear or branched bridge,

R ¹⁰ is independently optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having a linear or branched alkyl radical having 1 to 20 carbon atoms; A cycloalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A substituted or unsubstituted aryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 6 to 30 carbon atoms; Is a substituted or unsubstituted heteroaryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having a total of 5 to 18 carbon atoms and/or heteroatoms,

K is an uncharged monodentate or monodentate ligand,

L is a monovalent or divalent anionic ligand, preferably a monovalent anionic ligand, which may be a monodentate ligand or a bidentate ligand,

m is 0, 1 or 2, wherein when m is 2, the K ligands can be the same or different,

o is 0, 1 or 2, where o is 2, the L ligands may be the same or different.

1 is a chemical formula of the metal-carbene complex of the present invention.

When m and o are each 0, according to the present invention, an alloligand metal-carbene complex of formula (I) is present. When at least one of m and o is 1 or 2, according to the present invention, a heteroligand metal-carbene complex of formula (I) is present.

In the context of the present invention, the terms aryl radicals, units or groups, heteroaryl radicals, units or groups, alkyl radicals, units or groups and cycloalkyl radicals, units or groups, respectively, are defined as follows unless stated otherwise: :

An aryl radical, unit or group is understood to mean a radical having a basic skeleton of 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms, formed from an aromatic ring or a plurality of fused aromatic rings. Examples of suitable basic skeletons include phenyl, naphthyl, anthracenyl or phenanthrenyl. Such a basic skeleton may be unsubstituted, meaning that all substitutable carbon atoms have hydrogen atoms, or may be substituted at one or more or all substitutable positions of the basic skeleton.

Examples of suitable substituents are alkyl radicals, preferably alkyl radicals having 1 to 8 carbon atoms, more preferably methyl, ethyl, i-propyl, t-butyl, neopentyl, aryl radicals, preferably in turn substituted or An unsubstituted C ₆ -aryl radical, a heteroaryl radical, preferably a heteroaryl radical comprising at least one nitrogen atom, more preferably a pyridyl radical, an alkenyl radical, preferably one double bond Genie includes alkenyl radicals, more preferably alkenyl radicals having one double bond and 1 to 8 carbon atoms, or groups having donor or acceptor functions. A group having a donor action is understood to mean a group having a +I and/or +M effect, and a group having a receptor action is understood to mean a group having a -I and/or -M effect. Groups with suitable donor or acceptor functions include halogen radicals, preferably F, Cl, Br, more preferably F, alkyl radicals, silyl radicals, siloxy radicals, alkoxy radicals, aryloxy radicals, carbonyl radicals, ester radicals , Amine radical, amide radical, CH ₂ F group, CHF ₂ group, CF ₃ group, CN group, thio group or SCN group. The aryl radical is most preferably from the group consisting of methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl, tert-butyl, neopentyl, CF ₃ , aryloxy, amine, thio groups and alkoxy. The substituent selected or the aryl radical is unsubstituted. The aryl radical or aryl group is preferably a C ₆ -aryl radical optionally substituted with one or more of the aforementioned substituents. The C ₆ -aryl radical more preferably has 0, 1, 2 or 3 of the aforementioned substituents.

Heteroaryl radicals or heteroaryl units or groups are understood to mean radicals having 5 to 30 carbon atoms and/or heteroatoms that differ from the aforementioned aryl radicals in which one or more carbon atoms in the basic skeleton of the aryl radical are substituted with heteroatoms. . Preferred heteroatoms are N, O and S. Most preferably, 1 or 2 carbon atoms of the basic skeleton of the aryl radical are substituted with heteroatoms. The basic skeleton is particularly preferably an electron-poor system, such as pyridyl, pyrimidyl, pyrazil and triazolyl and 5-membered heteroaromatics such as pyrrole, furan, thiophene, imidazole, pyrazole, triazole, oxazole And thiazole. The base skeleton can be substituted at one, more than one, or all of the substitutable positions of the base skeleton. Suitable substituents are the same as those already specified above for aryl groups.

An alkyl radical or alkyl group is understood to mean a radical having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 8 carbon atoms. These alkyl radicals may or may not be branched and may optionally be interrupted by one or more heteroatoms, preferably N, O or S. In addition, these alkyl radicals may be substituted by one or more of the substituents already specified for the aryl group. Likewise, it is possible for the alkyl radical to have one or more aryl groups. All of the aryl groups presented above are suitable. Methyl, ethyl, i-propyl, n-propyl, i-butyl, n-butyl, t-butyl, sec-butyl, i-pentyl, n-pentyl, sec-pentyl, neopentyl, n-hexyl, i-hexyl And an alkyl radical selected from the group consisting of sec-hexyl. Methyl, i-propyl, tert-butyl and neopentyl are very particularly preferred.

Cycloalkyl radicals or cycloalkyl groups are understood to mean cyclic radicals having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, and more preferably 3 to 8 carbon atoms. The alkyl radical may optionally be interrupted by one or more heteroatoms, preferably N, O or S. Moreover, these cycloalkyl radicals may be unsubstituted or substituted, ie substituted with one or more of the substituents already specified for the aryl group. Likewise, a cycloalkyl radical can have one or more aryl groups. All aryl groups listed above are suitable.

Reference to aryl, heteroaryl, alkyl and cycloalkyl radicals applies according to the invention independently to the radicals mentioned herein, wherein R ² , R ³ , R ⁴ and R ⁵ are A ² , A ³ , A ^{When 4} and/or A ⁵ is N, it is a free electron pair which means that a substituent selected from the groups described above is not present on these ring nitrogen atoms. When A ² , A ³ , A ⁴ and/or A ⁵ is C, R ² , R ³ , R ⁴ and R ⁵ are each independently hydrogen and/or the specified substituent.

K in formula (I) is an uncharged monodentate or bidentate ligand, and L in formula (I) is a monovalent or divalent anionic ligand, preferably a monovalent anionic ligand, which may be a monodentate or bidentate ligand. to be.

The bidentate ligand is understood to mean a ligand coordinated to the transition metal atom M at two sites. The monodentate ligand is understood to mean a ligand coordinated to the transition metal atom M at one position on the ligand.

A suitable monovalent or divalent anionic ligand L, which may be a monodentate ligand or a bidentate ligand, preferably a monovalent anionic ligand L is a monodentate ligand or a bidentate ligand monovalent anionic or divalent anionic ligand It is a commonly used ligand.

An example of a suitable first anionic one L ligand, the ligand is a halide, especially Cl ^- by a sigma bond, a hydride, a transition metal M and Br ^-, pseudo halide, in particular CN ^{- -,} cyclopentadienyl (Cp) And bound alkyl radicals, for example CH ₃ , alkylaryl radicals bonded by a sigma bond to the transition metal M, for example benzyl.

Examples of suitable monovalent anionic bidentate ligands include acetylacetonate and derivatives thereof, picolinate, Schiff base, amino acids, arylpyridines such as phenylpyridine and further 2 specified in WO 02/15645. Left ligand monovalent anionic ligands, carbene ligands as specified in WO2006056418 and EP1658343, arylazoles such as 2-arylimidazole, and the like, 2-arylimidazole and carbene ligands are preferred.

Examples of suitable divalent anionic bidentate ligands are dialkoxy, dicarbonate, dicarboxylate, diamide, diimide, dithiolate, biscyclopentadienyl, bisphosphonate, bissulfonate and 3-phenyl And pyrazole.

Suitable uncharged monodentate ligands or bidentate ligands K are preferably both phosphine, mono- and bisphosphine; Phosphonates, both mono- and bisphosphonates and derivatives thereof, both arsenates, mono- and bisarsenates and derivatives thereof; Phosphites, mono- and bisphosphites; CO; Both pyridine, mono- and bispyridine; Nitrile, dinitrile, allyl, diimine, non-conjugated diene and conjugated diene forming π complexes with M ¹ . Particularly preferred uncharged monodentate ligands or bidentate ligands K are phosphine, mono- and bisphosphine, preferably trialkyl-, triaryl- or alkylarylphosphine, more preferably PAr ₃ (where Ar Is a substituted or unsubstituted aryl radical, and the _three aryl radicals in PAr ₃ may be the same or different), more preferably PPh ₃ , PEt ₃ , PnBu ₃ , PEt ₂ Ph, PMe ₂ Ph, PnBu ₂ Ph; Phosphonates and derivatives thereof, acenate and derivatives thereof, phosphite, CO; Pyridine, mono- and bispyridine (where pyridine may be substituted with an alkyl or aryl group); Nitrile and diene forming π complexes with M ¹ , preferably η ⁴ -diphenyl-1,3-butadiene, η ⁴ -1,3-pentadiene, η ^4-1 -phenyl-1,3-pentadiene , η ⁴ -1,4-dibenzyl-1,3-butadiene, η ⁴ -2,4-hexadiene, η ⁴ -3-methyl-1,3-pentadiene, η ⁴ -1,4-ditolyl -1,3-butadiene, η ⁴ -1,4-bis(trimethylsilyl)-1,3-butadiene and η ² -or η ⁴ -cyclooctadiene (1,3 and 1,5 respectively), more preferably 1,4-diphenyl-1,3-butadiene, 1-phenyl-1,3-pentadiene, 2,4-hexadiene, butadiene, η ² -cyclooctene, η ⁴ -1,3-cyclooctane Diene and η ⁴ -1,5-cyclooctadiene. Very particularly preferred uncharged monodentate ligands are selected from the group consisting of PPh ₃ , P(OPh) ₃ , AsPh ₃ , CO, pyridine, nitrile and derivatives thereof. Suitable uncharged monodentate ligands or bidentate ligands are preferably 1,4-diphenyl-1,3-butadiene, 1-phenyl-1,3-pentadiene, 2,4-hexadiene, η ⁴ -cyclo Octadiene and η ² -cyclooctadiene (1,3 and 1,5 respectively).

In the above-mentioned case, the number o of the monovalent anionic ligand L is 0, 1, 2. When o>1, the L ligands are the same or different, preferably the same.

The number m of uncharged ligand K depends on whether coordination number 6 of Ir(III) or coordination number 4 of Pt(II) has already been achieved with the aid of carbene ligand and ligand L. In the case of using Ir(III), n is 3, and when three monovalent anionic bidentate carbene ligands are used, m is 0 in the above case. When using Pt(II), n is 2, and when using two monovalent anionic bidentate carbene ligands, m in this case is likewise 0.

In a further preferred embodiment, the invention relates to metal-carbene complexes of the invention wherein L in formula I is a carbene ligand of formula II:

<Formula II>

In the above formula,

A ⁶ and A ⁷ are each independently C or N,

R ¹¹ is optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and a linear or branched alkyl radical having 1 to 20 carbon atoms; A cycloalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A cycloheteroalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A substituted or unsubstituted aryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 6 to 30 carbon atoms; Is a substituted or unsubstituted heteroaryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having a total of 5 to 18 carbon atoms and/or heteroatoms,

R ¹² and R ¹³ are each independently, when A is N, a free electron pair, or hydrogen when A is C; A linear or branched alkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups and having 1 to 20 carbon atoms; A cycloalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A cycloheteroalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A substituted or unsubstituted aryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 6 to 30 carbon atoms; A substituted or unsubstituted heteroaryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having a total of 5 to 18 carbon atoms and/or heteroatoms; Is a group with donor or acceptor action,

R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently hydrogen; A linear or branched alkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups and having 1 to 20 carbon atoms; A cycloalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A cycloheteroalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A substituted or unsubstituted aryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 6 to 30 carbon atoms; A substituted or unsubstituted heteroaryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having a total of 5 to 18 carbon atoms and/or heteroatoms; Is a group with donor or acceptor action or

R ¹² and R ¹³ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ or R ¹⁶ and R ¹⁷ are arbitrarily interposed with one or more heteroatoms together with the A or carbon atom to which they are attached, and a total of 5 to 18 carbon atoms And/or form an unsaturated or aromatic, optionally substituted ring with heteroatoms, and/or

When A ⁶ is C, R ¹³ and R ¹⁴ together optionally include heteroatoms, aromatic units, heteroaromatic units and/or functional groups and have a total of 1 to 30 carbon atoms and/or heteroatoms, wherein carbon atoms and / Or a substituted or unsubstituted, 5- to 8-membered ring containing heteroatoms, optionally fused to form a saturated or unsaturated, linear or branched bridge.

In a further preferred embodiment, the invention relates to metal-carbene complexes of the invention wherein L in formula I is a heterocyclic bicarbene ligand of formula III:

<Formula III>

Each of the symbols in the ligand of Formula III is as defined below:

D are each independently CR ¹⁸ or N, preferably CR ¹⁸ ;

W is C, N, preferably C;

E are each independently CR ¹⁹ , N, NR ²⁰ , preferably CR ¹⁹ or N;

G is CR ²¹ , N, NR ²² , S, O, preferably NR ²¹ ;

R ¹⁸ , R ¹⁹ and R ²¹ are each independently hydrogen; A linear or branched alkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups and having 1 to 20 carbon atoms; A cycloalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A cycloheteroalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A substituted or unsubstituted aryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 6 to 30 carbon atoms; A substituted or unsubstituted heteroaryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having a total of 5 to 18 carbon atoms and/or heteroatoms; Is a group with donor or acceptor action or

In each case the two R ¹⁸ , R ¹⁹ and R ²¹ radicals are optionally interrupted by one or more heteroatoms together with the carbon atom to which they are attached, and are saturated, unsaturated or having a total of 5 to 18 carbon atoms and/or heteroatoms. Form an aromatic, optionally substituted ring,

R ²⁰ , R ²² are each independently optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having a linear or branched alkyl radical having 1 to 20 carbon atoms; A cycloalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A cycloheteroalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A substituted or unsubstituted aryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 6 to 30 carbon atoms; A substituted or unsubstituted heteroaryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having a total of 5 to 18 carbon atoms and/or heteroatoms; Groups with donor or acceptor action; Preferably an o,o'-dialkylated aryl radical,

Where the solid line curve is any bridge between one of the D groups and the G group; Here, the crosslinking may be defined as alkylene, arylene, heteroarylene, alkynylene, alkenylene, O, S, SiR ²⁴ R ²⁵ and (CR ²⁶ R ²⁷ ) _d , wherein at least one non-adjacent (CR ²⁶ R ²⁷ ) group may be substituted with O, S, SiR ²⁴ R ²⁵ , wherein

d is 2 to 10;

R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ are each H, alkyl, aryl, heteroaryl, alkenyl, alkynyl.

In each case the two R ¹⁸ , R ¹⁹ and R ²¹ radicals are optionally interrupted by one or more heteroatoms together with the carbon atom to which they are attached, and are saturated, unsaturated or having a total of 5 to 18 carbon atoms and/or heteroatoms. For embodiments of the invention that form an aromatic, optionally substituted ring, for example two R ¹⁸ radicals, two R ¹⁹ radicals or one R ¹⁹ radical and one R ²¹ radical form the corresponding ring.

Very particularly preferred ligands L by the present invention are:

Additional preferred ligands L:

In a preferred embodiment, M, n, Y, A ² , A ³ , A ⁴ , A ⁵ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ in formula I , R ⁹ , R ¹⁰ , K, L, n and o are each as defined below:

According to the present invention, M is Ir or Pt, preferably Ir. Ir is present in the +3 oxidation state in the complex of the present invention. Pt is present in the +2 oxidation state in the complex of the present invention.

*n is usually 1, 2 or 3. When M is Ir, n is preferably 3. When M is Pt, n is preferably 1.

According to the invention, Y is NR ¹ , O, S or C(R ²⁵ ) ₂ , preferably NR ¹ .

According to the present invention, A ² , A ³ , A ⁴ and A ⁵ are each independently C or N, where two A are nitrogen atoms and one or more carbon atoms are present between two nitrogen atoms in the ring. . Typically, one or two carbon atoms are between two nitrogen atoms.

According to the invention, the following embodiments are preferred:

1.A ² and A ⁵ are each N, and A ³ and A ⁴ are each C, that is, the metal-carbene complex of the present invention is bound by a metal-carbene bond in this preferred embodiment, and the formula Ia It includes one or more pyrazinoimidazole units having:

<Formula Ia>

2. A ² and A ⁴ are each N, and A ³ and A ⁵ are each C, that is, the metal-carbene complex of the present invention is bound by a metal-carbene bond in this preferred embodiment, and the formula Ib It includes one or more pyrimidinoimidazole units having:

<Formula Ib>

3. A ³ and A ⁵ are each N, A ² and A ⁴ are each C, that is, the metal-carbene complex of the present invention is bound by a metal-carbene bond in this preferred embodiment, and the formula Ic It includes one or more pyrimidinoimidazole units having:

<Formula Ic>

In Formula Ia, Formula Ib and Formula Ic, the same definition applies as in Formula I.

In the preferred case where Y is NR ¹ , in a preferred embodiment R ¹ is a linear or branched alkyl radical having 1 to 6 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, and a total of 5 It is a substituted or unsubstituted heteroaryl radical having 18 to 18 carbon atoms and/or heteroatoms.

R ¹ is more preferably a linear or branched alkyl radical having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl radical, a substituted or unsubstituted heteroaryl radical having a total of 5 or 6 carbon atoms and/or heteroatoms. .

R ¹ is most preferably selected from phenyl, tolyl, mesityl, thiophenyl, furanyl, pyridyl, methyl, isopropyl and neopentyl.

Therefore, the present invention in particular Y is NR ¹ , where R ¹ is a metal-car of the invention selected from the group consisting of phenyl, tolyl, mesityl, thiophenyl, furanyl, pyridyl, methyl, isopropyl and neopentyl. It's about the Ben complex.

In a preferred embodiment, R ² , R ³ , R ⁴ , R ⁵ are each independently hydrogen, linear or branched alkyl radical having 1 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms Radicals, substituted or unsubstituted heteroaryl radicals having 5 to 18 carbon atoms and/or heteroatoms or silyl radicals.

In a preferred embodiment, R ² , R ³ , R ⁴ , R ⁵ are each a free electron pair when A ² , A ³ , A ⁴ and/or A ⁵ is N, or A ² , A ³ , A ⁴ and And/or when A ⁵ is C, each independently hydrogen, a linear or branched alkyl radical having 1 to 6 carbon atoms, a substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, a total of 5 to 18 carbon atoms And/or a substituted or unsubstituted heteroaryl radical or a silyl radical having heteroatoms, or

R ³ and R ⁴ together with A ³ and A ⁴ are optionally interrupted by one or more additional heteroatoms and form an optionally substituted unsaturated ring having a total of 5 to 18 carbon atoms and/or heteroatoms.

According to the invention, the unsaturated ring is a mono-, bi- or polyunsaturated, preferably monounsaturated ring. According to the invention, aromatic rings are not included in this definition. More particularly, R ³ and R ⁴ together with A ³ and A ⁴ do not form a phenyl ring.

R ² is more preferably a free electron pair when A ² is N or hydrogen when A ² is C.

R ³ is more preferably a free electron pair when A ³ is N, or hydrogen or linear or branched alkyl radical having 1 to 20 carbon atoms or a total of 5 to 18 carbon atoms when A ³ is C and/or Or an optionally substituted, saturated, unsaturated or aromatic ring with heteroatoms, more preferably a branched chain alkyl radical or o,o'-dialkylated phenyl ring.

R ⁴ is more preferably a free electron pair when A ⁴ is N, or hydrogen or linear or branched alkyl radical having 1 to 20 carbon atoms or a total of 5 to 18 carbon atoms when A ⁴ is C and/or Or an optionally substituted, saturated, unsaturated or aromatic ring with heteroatoms, more preferably a branched chain alkyl radical or o,o'-dialkylated phenyl ring.

R ³ and R ⁴ are most preferably A ^3, and A in ^tetravalent form an unsaturated ring optionally substituted with 5 to 18 carbon atoms total with A ³ and A ^4, if each of C, A ² and A ⁵ Is N, respectively, and R ³ and R ⁴ together with A ³ and A ⁴ form a phenyl ring are excluded by the present invention.

R ⁵ is more preferably a free electron pair when A ⁵ is N or hydrogen when A ⁵ is C.

In a further preferred embodiment, R ⁶ , R ⁷ , R ⁸ , R ⁹ are each independently hydrogen or a linear or branched alkyl radical having 1 to 20 carbon atoms or an o,o′-dialkylated phenyl radical, more It is preferably hydrogen.

In a further preferred embodiment, R ⁶ and R ⁷ or R ⁷ and R ⁸ or R ⁸ and R ⁹ are optionally interrupted by one or more heteroatoms with a phenyl ring, ie with a carbon atom to which a radical is attached. And it forms an unsaturated or aromatic, optionally substituted ring having a total of 5, 6 or 7 carbon atoms and/or heteroatoms. The two specific radicals more preferably form the following heterocycle: dibenzofuran, dibenzothiophene, fluorene, acridan, xanthene, thioxanthene, phenazine or penoxazine with the phenyl ring.

Alternatively or additionally, R ⁵ and R ⁶ together optionally contain heteroatoms, aromatic units, heteroaromatic units and/or functional groups and are saturated or unsaturated, linear or having 1 to 30 carbon atoms and/or heteroatoms in total. To form a branched bridge, to which a substituted or unsubstituted, 5- to 8-membered, preferably 6-membered ring containing carbon atoms and/or heteroatoms is optionally fused.

When R ²⁵ is present, preferably independently according to the invention according to the invention a linear or branched alkyl radical having 1 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, 5 to 18 carbons A substituted or unsubstituted heteroaryl radical having atoms and/or heteroatoms, more preferably a linear alkyl radical or a substituted or unsubstituted phenyl radical.

In a particularly preferred embodiment, the invention is M, n, Y, A ² , A ³ , A ⁴ , A ⁵ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , L, m and o are each as defined below:

M is Ir,

n is 1, 2 or 3,

Y is NR ¹ ,

A ² , A ³ , A ⁴ , A ⁵ are each independently N or C, where two A are nitrogen atoms, and one or more carbon atoms are present between two nitrogen atoms in the ring,

R ¹ is a linear or branched alkyl radical having 1 to 6 carbon atoms, substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, substituted or unsubstituted having a total of 5 to 18 carbon atoms and/or heteroatoms Is a heteroaryl radical,

R ² , R ³ , R ⁴ , R ⁵ are each a free electron pair when A ² , A ³ , A ⁴ and/or A ⁵ is N, or A ² , A ³ , A ⁴ and/or A ⁵ is In the case of C, each independently hydrogen, a linear or branched alkyl radical having 1 to 6 carbon atoms, a substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, a total of 5 to 18 carbon atoms and/or heteroatoms Having a substituted or unsubstituted heteroaryl radical, or

R ³ and R ⁴ together with A ³ and A ⁴ are optionally interrupted by one or more additional heteroatoms and form an optionally substituted unsaturated ring having a total of 5 to 18 carbon atoms and/or heteroatoms,

R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently hydrogen; A linear or branched alkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups and having 1 to 20 carbon atoms; A substituted or unsubstituted aryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 6 to 30 carbon atoms; Is a substituted or unsubstituted heteroaryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having a total of 5 to 18 carbon atoms and/or heteroatoms

L is a monovalent anionic bidentate ligand,

*

*

*m is 0,

o relates to the metal-carbene complex of the present invention that is 0, 1 or 2.

The present invention is more preferably M, n, Y, A ² , A ³ , A ⁴ , A ⁵ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , L, m and o are each as defined below:

M is Ir,

n is 1, 2 or 3,

Y is NR ¹ ,

A ² , A ³ , A ⁴ , A ⁵ are A ² and A ⁵ each N, and A ³ and A ⁴ are each C or

A ² and A ⁴ are each N and A ³ and A ⁵ are each C or

A ³ and A ⁵ are each N and A ² and A ⁴ are each C,

R ¹ is a linear or branched alkyl radical having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl radical, a substituted or unsubstituted heteroaryl radical having a total of 6 to 18 carbon atoms and/or heteroatoms,

R ² , R ³ , R ⁴ , R ⁵ are each a free electron pair when A ² , A ³ , A ⁴ and/or A ⁵ is N, or A ² , A ³ , A ⁴ and/or A ⁵ When C is each independently hydrogen, a linear or branched alkyl radical having 1 to 6 carbon atoms, a substituted, especially o,o'-dialkylated or unsubstituted phenyl radical, or

R ³ and R ⁴ together with A ³ and A ⁴ form an optionally substituted, monounsaturated ring having a total of 5 to 7 carbon atoms,

R ⁶ , R ⁷ , R ⁸ , R ⁹ are each independently hydrogen, linear or branched alkyl radical having 1 to 20 carbon atoms, o,o'-dialkylated aryl radical having 6 to 30 carbon atoms, ,

L is a monovalent anionic bidentate ligand,

m is 0,

o relates to the metal-carbene complex of the present invention that is 0, 1 or 2.

Therefore, the above-mentioned preferred and particularly preferred embodiments apply.

Very particularly preferred metal-carbene complexes of the formula (I) of the invention are presented below:

The homo-ligand metal-carbene complex of the present invention may exist in the form of a cotton or meridian isomer, and a cotton isomer is preferred.

In the case of heteroligand metal-carbene complexes, four different isomers may be present, pseudo-cotton isomers being preferred.

The present invention further relates to a method for preparing the metal-carbene complex of the present invention by contacting a suitable compound comprising M with a suitable ligand or ligand precursor.

In a preferred embodiment of the method according to the invention, a suitable metal M, i.e. iridium or platinum, preferably iridium and a suitable carbene ligand, preferably in deprotonated form as free carbene or in the form of protected carbene As, for example, a suitable compound comprising as a silver-carbene complex is contacted. Suitable precursor compounds include suitable substituents R ¹ to R ⁹ and R ²⁵ which must be present in the complex of formula (I).

Therefore, the present invention more particularly relates to the method according to the present invention wherein the ligand precursor used is the corresponding Ag-carbene complex.

In a further preferred embodiment of the method according to the invention, the ligand precursor used is an organic compound that reacts with a suitable M-containing compound. Carbenes are removed from precursors of carbene ligands by, for example, removing volatiles, such as lower alcohols, such as methanol, ethanol, using molecular sieves that bind alcohol molecules that are removed at and/or under high temperature and/or under reduced pressure. Can be discharged. This process is particularly carried out in the case of compounds of formula XII. The method is known to those skilled in the art.

The invention also relates to the process according to the invention, wherein the ligand precursor used is a compound of formula IV:

<Formula IV>

In the above formula, Y, A ² , A ³ , A ⁴ , A ⁵ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are respectively the same for the compound of formula I As defined, R ²⁸ is defined as follows:

R ²⁸ is independently SiR ²⁹ R ³⁰ R ³¹ , aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl,

*R ²⁹ , R ³⁰ and R ³¹ are each independently aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl.

The definitions of aryl, heteroaryl, alkyl, cycloalkyl and heterocycloalkyl are specified above.

In a particularly preferred embodiment, R ²⁸ is alkyl, especially C ₁ -C ₂₀ -alkyl, preferably C ₁ -C ₁₀ -alkyl, more preferably C ₁ -C ₈ -alkyl, for example methyl, ethyl, Propyl, such as n-propyl, isopropyl, butyl, such as n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl or octyl.

R ²⁸ in the compound of formula IV is most preferably methyl or ethyl.

Compounds of formula IV can generally be obtained by methods known to those skilled in the art. In a particularly preferred case according to the invention where Y is NR ¹ , the corresponding compound of formula IV can be obtained by reacting a compound of formula V with a compound of formula VI:

<Formula V>

<Formula VI>

HC(OR ²⁸ ) ₃

In the above formula, A ² , A ³ , A ⁴ , A ⁵ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ²⁸ are each of formula I or As already defined above for compounds of formula IV.

Preparation of such a compound of formula IV can be carried out with or without a solvent. Suitable solvents are specified below. In a preferred embodiment, the compound of formula IV is produced in the material, or the compound of formula VI is added in excess to act as a solvent.

Compounds of formula V and formula VI are commercially available and/or can be obtained by methods known to those skilled in the art, for example, compounds of formula V can be obtained by reacting a suitable chloride with a suitable amine.

The compound of formula IV is generally produced at a temperature of 10°C to 150°C, preferably 40°C to 120°C, more preferably 60°C to 110°C.

The reaction time is generally 2 to 48 hours, preferably 6 to 24 hours, more preferably 8 to 16 hours.

After the reaction is completed, the desired product can be separated and purified by conventional methods known in the art, such as filtration, recrystallization, column chromatography, and the like.

Suitable compounds, especially complexes comprising a suitable metal M, preferably iridium, are known to those skilled in the art. Particularly suitable compounds comprising platinum or iridium are, for example, ligands such as halides, preferably chlorides, 1,5-cyclooctadiene (COD), cyclooctene (COE), phosphine, cyanide, alkoxide, Pseudohalides and/or alkyls.

Particularly preferred complexes comprising suitable metals, especially iridium, are [Ir(COD)Cl] ₂ , [Ir(COE) ₂ Cl] ₂ IrCl ₃ ×H ₂ O, Ir(acac) ₃ , Ir(COD) ₂ BF ₄ , Ir(COD) ₂ BARF (BARF=tetrakis[3,5-bis(trifluoromethyl)phenyl]borate)), Pt(COD)Cl ₂ , Pt(acac) ₂ , [Pt(C ₆ H ₁₀ )Cl ₂ ] ₂ , K ₂ PtCl ₆ and mixtures thereof.

The carbene ligand precursor is preferably before reaction, for example a basic compound known to those skilled in the art, for example a basic metalate, a basic metal acetate, an acetylacetonate or alkoxide, or a base such as KO ^t Bu,NaO ^t Deprotonated with Bu,LiO ^t Bu,NaH, silylamide, Ag ₂ O and phosphazene bases. It is particularly preferable to deprotonate with Ag ₂ O to obtain the corresponding Ag-carbene, and to react with a compound containing M to obtain the complex of the present invention.

The method according to the present invention to produce a complex of formula I using a compound of formula IV has the advantage that the compound of formula IV is a stable intermediate that can be easily handled and isolated under standard laboratory conditions. In addition, the workup of the desired product, i.e. complex of formula I, is more readily possible, e.g. for separation and/or purification, to enable the preparation of complexes of formula I of the invention in a homogeneous solution. Thus, the compound of formula IV is soluble in conventional organic solvents.

Contacting is preferably carried out in a solvent. Suitable solvents are known per se to the skilled person and are preferably aromatic or aliphatic solvents, for example benzene, toluene, xylene or mesitylene, cyclic or acyclic ethers, for example dioxane or THF, alcohols, esters , Amide, ketone, nitrile, halogenated compound and mixtures thereof. Particularly preferred solvents are toluene, xylene, mesitylene and dioxane.

The molar ratio of metal-bicarbene complex used to carbene ligand precursor used is generally 1:10 to 10:1, preferably 1:1 to 1:6, more preferably 1:2 to 1:5.

The contacting is generally carried out at a temperature of 20°C to 200°C, preferably 50°C to 150°C, more preferably 60°C to 130°C.

The reaction time depends on the desired carbene complex, and is generally 0.02 to 50 hours, preferably 0.1 to 24 hours, more preferably 1 to 12 hours.

The complex of formula I obtained after the reaction can optionally be purified by methods known to those skilled in the art, for example washing, crystallization or chromatography, optionally under conditions known to those skilled in the art, for example under thermal or photochemical acid mediation. Isomerized.

The metal-carbene complexes described above and mixtures thereof are very suitable as emitter molecules in organic light emitting diodes (OLEDs). Changes in the ligand make it possible to provide corresponding complexes that exhibit electroluminescence in the red, green and especially blue regions in the electromagnetic spectrum. Therefore, the metal-carbene complexes of the formula (I) of the present invention are very suitable as emitter materials since they are emitted in the visible region of the electromagnetic spectrum, for example 400 to 800 nm, preferably 400 to 600 nm. The complex of the invention makes it possible to provide compounds with electroluminescence in the red, green and blue regions of the electromagnetic spectrum. It is possible to provide an industrially available OLED with the aid of the complex of the present invention as an emitter material.

Furthermore, the metal-carbene complexes of the formula (I) of the present invention can be used as matrix materials, charge transport materials, in particular hole transport materials and/or charge blockers.

The metal-carbene complexes of the formula (I) of the present invention are preferably used as emitter and/or hole transport materials, more preferably as emitters.

The particular properties of the metal-carbene complexes of the formula (I) of the present invention have particularly good efficiency and long life when used in OLEDs.

Therefore, the present invention further provides an OLED comprising at least one metal-carbene complex of formula I of the present invention. The metal-carbene complexes of formula I of the present invention are preferably emitters, matrix materials, charge transport materials, especially hole transport materials and/or charge blockers in OLEDs, more preferably emitter and/or hole transport As a material, it is most preferably used as an emitter.

In addition, the invention is preferably an emitter, a matrix material, a charge transport material, in particular a hole transport material, and/or a charge blocker, more preferably as an emitter and/or hole transport material, most preferably already This provides the use of metal-carbene complexes of formula I in OLEDs.

Organic photodiodes are in principle from multiple layers, for example

-Anode (1),

-Hole transport layer (2),

-Emitting layer (3),

-Electron transport layer (4),

-It is formed from the cathode (5).

However, also OLEDs may not have all of the layers mentioned, for example OLEDs comprising layers (1) (anode), (3) (light emitting layer) and (5) (cathode) are equally suitable, The functions of layers (2) (hole transporting layer) and (4) (electron transporting layer) in this case are estimated by the adjacent layers. OLEDs having layers (1), (2), (3) and (5) or layers (1), (3), (4) and (5) are likewise suitable.

The metal-carbene complex of formula I is preferably used as emitter molecule and/or matrix material in the light emitting layer 3. The metal-carbene complexes of formula I of the present invention also charge in the hole transport layer 2 or in the electron transport layer 4 in addition to the use as an emitter molecule and/or matrix material in the light emitting layer 3 or instead of the use in the light emitting layer. It can be used as a transport material and/or as a charge blocker, and is preferably used as a charge transport material in the hole transport layer 2 (hole transport material).

Therefore, the present application further provides a light emitting layer comprising at least one of the metal-carbene complexes of formula (I) of the present invention, preferably as emitter molecules. Preferred metal-carbene complexes of formula I have already been specified above.

The metal-carbene complex of formula (I) used by the present invention may be present in the emitting layer in the material, ie it is not added further. However, in addition to the metal-carbene complex of formula I used by the present invention, additional compounds may be present in the light emitting layer. For example, a fluorescent dye may be present to alter the emission color of the metal-carbene complex used as an emitter molecule. In addition, diluent materials (matrix materials) can be used. This diluent material can be a polymer, for example poly(N-vinylcarbazole) or polysilane. However, the diluent material can likewise be a small molecule, for example 4,4'-N,N'-dicarbazolebiphenyl (CDP) or tertiary aromatic amine. When using a diluent material, the proportion of the metal-carbene complex of the formula (I) of the present invention in the light emitting layer is generally less than 40% by weight, preferably 3 to 30% by weight. The metal-carbene complexes of formula (I) of the invention are preferably used in matrices. The light emitting layer thus preferably comprises at least one metal-carbene complex of the formula (I) of the invention and at least one matrix material.

Suitable matrix materials are, in addition to the diluents described above, in principle the materials specified below as hole and electron transport materials and also carbon complexes, for example the carbene complexes of formula I or the carbene complexes mentioned in WO 2005/019373. Carbazole derivatives such as 4,4'-bis(carbazole-9-yl)-2,2'-dimethylbiphenyl (CDBP), 4,4'-bis(carbazole-9-yl)biphenyl (CBP), 1,3-bis(N-carbazolyl)benzene (mCP), matrix materials specified in the following applications: WO2008/034758, WO2009/003919 are particularly suitable.

Dibenzofuran. For example, dibenzofuran disclosed in US 2007/0224446 A1, for example dibenzofuran, wherein at least one of the R ¹ to R ⁸ radicals is a heterocyclic group, for example compound A-15 and WO 2009/069442 A1 , Dibenzofuran disclosed in WO 2010/090077 A1 and JP 2006/321750 A are further suitable as matrix materials.

Further suitable matrix materials which can be small molecules or (co)polymers of the small molecules mentioned are specified in the following publications:

WO2007108459 (H-1 to H-37), preferably H-20 to H-22 and H-32 to H-37, most preferably H-20, H-32, H-36, H-37, WO2008035571 A1 (Host 1 to Host 6), JP2010135467 (Compounds 1 to 46 and Host-1 to Host-39 and Host-43), WO2009008100 Compound Nos. 1 to 67, preferably Nos. 3, 4 and 7 Number 12, number 55, number 59, number 63 to number 67, more preferably number 4, number 8 to number 12, number 55, number 59, number 64, number 65, and number 67, WO2009008099 Compound number 1 to number 110, WO2008140114 Compounds 1-1 to 1-50, WO2008090912 Polymers of OC-7 to OC-36 and Mo-42 to Mo-51, JP2008084913 H-1 to H-70, WO2007077810 Compounds 1 to 44, preferably 1, 2, 4-6, 8, 19-22, 26, 28-30, 32, 36, 39-44, WO201001830 monomers 1-1 to 1-9, preferably 1-3, 1-7 and 1 -9 polymer, WO2008029729 compounds 1-1 to 1-36 (polymer), WO20100443342 HS-1 to HS-101 and BH-1 to BH-17, preferably BH-1 to BH-17, JP2009182298 monomer 1 (Co)polymers based on 75 to JP2009170764, (Co)polymers based on JP2009135183 monomers 1-14, preferably (co)polymers based on monomers 1-1 to 1-26, WO2008146838 compounds a-1 to a- 43 and 1-1 to 1-46, (co)polymer based on JP2008207520 monomers 1-1 to 1-26, (co)polymer based on JP2008066569 monomers 1-1 to 1-16, WO20 08029652 (co)polymer based on monomers 1-1 to 1-52, (co)polymer based on WO2007114244 monomers 1-1 to 1-18, JP2010040830 compounds HA-1 to HA-20, HB-1 to HB-16, (Co)polymers based on HC-1 to HC-23 and monomers HD-1 to HD-12, JP2009021336, WO2010090077 compounds 1 to 55, WO2010079678 compounds H1 to H42, WO2010067746, WO2010044342 compounds HS-1 to HS-101 and poly -1 to poly-4, JP2010114180 compounds PH-1 to PH-36, US2009284138 compounds 1 to 111 and H1 to H71, WO2008072596 compounds 1 to 45, JP2010021336 compounds H-1 to H-38, preferably H-1, WO2010004877 Compound H-1 to H-60, JP2009267255 Compound 1-1 to 1-105, WO2009104488 Compound 1-1 to 1-38, WO2009086028, US2009153034, US2009134784, WO2009084413 Compound 2-1 to 2-56, JP2009114369 Compound 2- 1 to 2-40, JP2009114370 Compound 1 to 67, WO2009060742 Compound 2-1 to 2-56, WO2009060757 Compound 1-1 to 1-76, WO2009060780 Compound 1-1 to 1-70, WO2009060779 Compound 1-1 to 1- 42, WO2008156105 Compound 1 to 54, JP2009059767 Compound 1 to 20, JP2008074939 Compound 1 to 256, JP2008021687 Compound 1 to 50, WO2007119816 Compound 1 to 37, WO2010087222 Compound H-1 to H-31, WO2010095564 Compound Host-1 to Host- 61, WO2007108362, WO2009003 898, WO2009003919, WO2010040777, US2007224446 and WO06128800.

In a particularly preferred embodiment, at least one compound of formula (X) specified below is used as a matrix material. Preferred embodiments of the compound of formula X are likewise specified below.

Individual layers among the above-described layers of OLEDs may in turn be formed from two or more layers. For example, the hole transport layer may be formed from one layer in which holes are injected from the electrode, and a layer that transports holes from the hole-injection layer to the light emitting layer. The electron transport layer may likewise consist of a plurality of layers, for example, a layer in which electrons are injected through an electrode, and a layer that receives electrons from the electron-injecting layer and transports them to the light emitting layer. These layers mentioned are selected by factors such as energy level, heat resistance and charge carrier mobility, respectively, and also energy difference between the mentioned layer and the organic layer or metal electrode. Those skilled in the art can select the structure of the OLED to optimally conform to the heteroligand complex according to the invention used as the emitter material according to the invention.

In order to obtain a particularly efficient OLED, the hole transport layer's HOMO (highest occupied molecular orbital function) must be aligned with the anode's work function, and the electron transport layer's (lowest occupied molecular orbital function) must be aligned with the cathode's work function.

The present application further provides an OLED comprising at least one light emitting layer of the present invention. Additional layers in OLEDs are commonly used for these layers and can be formed of any material known to those skilled in the art.

Materials suitable for the aforementioned layers (anode, cathode, hole and electron injection materials, hole and electron transport materials and hole and electron blocker materials, matrix materials, fluorescent and phosphorescent emitters) are known to those skilled in the art, for example [H. Meng, N. Herron, Organic Small Molecule Materials for Organic Light-Emitting Devices in Organic Light-Emitting Materials and Devices , eds: Z. Li, H. Meng, Taylor & Francis, 2007, Chapter 3, pages 295 to 411] It is stated.

The anode is an electrode that provides a positive charge carrier. For example, it may be made of a material including a metal, a mixture of various metals, a metal alloy, a metal oxide, or a mixture of various metal oxides. Alternatively, the anode can be a conductive polymer. Suitable metals include metals of groups 11, 4, 5 and 6 of the periodic table of elements and also transition metals of groups 8 to 10. When the anode is transparent, mixed metal oxides of groups 12, 13 and 14 of the periodic table of elements are generally used, for example indium tin oxide (ITO). Similarly, the anode (1), for example, Nature , Vol. 357, pages 477 to 479 (June 11, 1992), for example, organic materials such as polyaniline. At least the anode or cathode must be at least partially transparent in order to be able to emit the formed light.

Hole transport materials suitable for the layer 2 of the OLED of the present invention are described, for example, in Kirk-Othmer Encyclopedia of Chemical Technology , 4th Edition, Vol. 18, pages 837 to 860, 1996. Hole transport molecules or polymers can be used as the hole transport material. Commonly used hole transport molecules are 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl(α-NPD), 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), α-phenyl-4-N,N-diphenylaminostyrene (TPS), p-(diethylamino)benzaldehyde diphenylhydrazone (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-car Bazol-9-yl)-cyclobutane (DCZB), N,N,N',N'-tetrakis(4-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TTB) , Fluorine compounds such as 2,2',7,7'-tetra(N,N-di-tolyl)amino-9,9-spirobifluorene (spiro-TTB), N,N'-bis(naphthalene- 1-yl)-N,N'-bis(phenyl)-9,9-spirobifluorene (spiro-NPB) and 9,9-bis(4-(N,N-bis-biphenyl-4-yl) -Amino)phenyl-9H-fluorene, benzidine compounds such as N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)benzidine and porphyrin compounds, such as selected from the group consisting of copper phthalocyanine The hole transport polymers commonly used are selected from the group consisting of polyvinylcarbazole, (phenylmethyl)polysilane and polyaniline, likewise hole transport polymers by doping hole transport molecules with polymers such as polystyrene and polycarbonate. Suitable hole transport molecules are those already mentioned above.

In addition, in one embodiment, a carbene complex can be used as the hole conductor material, in which case the bandgap of one or more hole conductor materials is generally greater than the bandgap of the emitter material used. In the context of this application, the bandgap is understood to mean triple energy.

Examples of suitable carbene complexes are described in the carbine complexes of formula I of the present invention, WO 2005/019373 A2, WO 2006/056418 A2, WO 2005/113704, WO 2007/115970, WO 2007/115981 and WO 2008/000727 The carbene complex as mentioned is mentioned. An example of a suitable carbene complex is Ir(DPBIC) ₃ of the formula:

The hole transport layer can also be electron doped to improve the transport properties of the materials used, first to make the layer thickness more gentle (prevent pinholes/shorts) and secondly to minimize the operating voltage of the device. Electronic doping is known to those skilled in the art, for example, W. Gao, A. Kahn, J. Appl. Phys. , Vol. 94, No. 1, 1 July2003 (p-doped organic layers)]; [AG Werner, F. Li, K. Harada, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett. , Vol. 82, No. 25, 23 June2003] and [Pfeiffer et al., Organic Electronics 2003, 4, 89-103] and [K. Walzer, B. Maennig, M. Pfeiffer, K. Leo, Chem. Soc. Rev. 2007, 107, 1233. For example, a hole transport layer can be used, in particular a mixture which results in electrical p-doping of the hole transport layer. P-doping is achieved by the addition of oxidizing materials. Such mixtures can be, for example, the following mixtures: the above hole transport material and one or more metal oxides, for example MoO ₂ , MoO ₃ , WOx, ReO ₃ and/or V ₂ O ₅ , preferably MoO ₃ and/or ReO ₃ , more preferably ReO ₃ or a mixture, or 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3,5,6-tetrafluoro-7, 7,8,8-tetracyanoquinodimethane (F ₄ -TCNQ), 2,5-bis(2-hydroxyethoxy)-7,7,8,8-tetracyanoquinodimethane, bis( Tetra-n-butylammonium)-tetracyanodiphenoquinodimethane, 2,5-dimethyl-7,7,8,8-tetracyanoquinodimethane, tetracyanoethylene, 11,11,12,12- Tetracyanonapto-2,6-quinodimethane, 2-fluoro-7,7,8,8-tetracyanoquinodimethane, 2,5-difluoro-7,7,8,8-tetra Cyanoquinodimethane, dicyanomethylene-1,3,4,5,7,8-hexafluoro-6H-naphthalene-2-ylidene)malononitrile (F ₆ -TNAP), Mo(tfd) ₃ (From Kahn et al., J. Am. Chem. Soc. 2009, 131 (35), 12530-12531), selected from compounds as described in EP1988587 and EP2180029 and quinone compounds as mentioned in EP 09153776.1 A mixture comprising at least one compound and the hole transport material described above.

Suitable electron transport materials for the layer 4 of the inventive OLED are oxynoid compounds, such as tris(8-hydroxyquinolato)aluminum (Alq ₃ ), compounds based on phenanthroline, such as 2,9-dimethyl- 4,7-diphenyl-1,10-phenanthroline (DDPA=BCP), 4,7-diphenyl-1,10-phenanthroline (Bphen), 2,4,7,9-tetraphenyl-1 ,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline (DPA) or phenanthroline derivatives and azole compounds disclosed in EP1786050, EP1970371 or EP1097981, such as 2-(4-biphenylyl) -5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD) and 3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)- Metals chelated with 1,2,4-triazole (TAZ). Furthermore, dibenzofuran is, for example, dibenzofuran disclosed in US 2007/0224446 A1, for example, dibenzofuran in which at least one of the R ¹ to R ⁸ radicals is a heterocyclic group, for example compound A-15 and Dibenzofuran disclosed in WO 2009/069442 A1, WO 2010/090077 A1 and JP 2006/321750 A are suitable as electron transport materials. The layer 4 can function as a buffer layer or as a blocking layer and to facilitate electron transport to prevent rapid cooling of excitons at the interface of the layer of the OLED. Layer 4 preferably improves the mobility of electrons and reduces the quenching of excitons.

Similarly, mixtures of two or more materials in the electron transport layer can be used, in which case the one or more materials are electron-conducting. Preferably, in the mixed electron transport layer, one or more phenanthroline compounds, preferably BCP or one or more pyridine compounds according to the following formula VIII, preferably compounds of the following formula VIIIaa are used. More preferably, in the mixed electron transport layer, in addition to at least one phenanthroline compound, an alkaline earth metal or alkali metal hydroxyquinolate complex, for example Liq, is used. Suitable alkaline earth metal or alkali metal hydroxyquinolate complexes are specified below (Formula VII).

The electron transport layer can also be electron doped to improve the transport properties of the materials used, first to make the layer thickness more gentle (prevent pinholes/shorts) and second to minimize the operating voltage of the device. Electronic doping is known to those skilled in the art, for example, W. Gao, A. Kahn, J. Appl. Phys. , Vol. 94, No. 1, 1 July2003 (p-doped organic layers)]; [AG Werner, F. Li, K. Harada, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett. , Vol. 82, No. 25, 23 June2003] and [Pfeiffer et al., Organic Electronics 2003, 4, 89-103] and [K. Walzer, B. Maennig, M. Pfeiffer, K. Leo, Chem. Soc. Rev. 2007, 107, 1233. For example, mixtures that result in electrical n-doping of the electron transport layer can be used. n-doping is achieved by the addition of reducing materials. Such mixtures are, for example, the aforementioned electron transport materials and alkali/alkaline earth metals or alkali/alkaline earth metal salts, for example Li, Cs, Ca, Sr, Cs ₂ CO ₃ , alkali metal complexes, for example 8- Hydroxyquinolatolithium (Liq) and Y, Ce, Sm, Gd, Tb, Er, Tm, Yb, Li ₃ N, Rb ₂ CO ₃ , dipotassium phthalate, W(hpp) ₄ from EP 1786050 or , Mixtures with compounds as described in EP1837926 B1.

Therefore, the present invention relates to an OLED of the present invention comprising an electron transport layer comprising two or more different materials, wherein at least one material is electron-conducting.

In a preferred embodiment, the electron transport layer comprises one or more compounds of formula VII:

<Formula VII>

(In the above formula,

R ³² and R ³³ are each independently F, C ₁ -C ₈ -alkyl, or C ₆ -C ₁₄ -aryl optionally substituted with one or more C ₁ -C ₈ -alkyl groups,

The two R ³² and/or R ³³ substituents together form a fused benzene ring optionally substituted with one or more C ₁ -C ₈ -alkyl groups;

a and b are each independently 0, or 1, 2 or 3,

M ¹ is an alkali metal atom or an alkaline earth metal atom,

If M ¹ is an alkali metal atom and p is 1, and p is 2 if M ¹ is an alkaline earth metal atom.

(Liq)이고, 이는 단일종으로서 또는 기타의 형태, 예컨대 Li_gQ_g(여기서 g는 정수임), 예를 들면 Li₆Q₆로 존재할 수 있다. Q는 8-히드록시퀴놀레이트 리간드 또는 8-히드록시퀴놀레이트 유도체이다.Very particularly preferred compounds of formula VII are

(Liq), which can exist as a single species or in other forms, such as Li _g Q _g (where g is an integer), for example Li ₆ Q ₆ . Q is an 8-hydroxyquinolate ligand or 8-hydroxyquinolate derivative.

In a further preferred embodiment, the electron transport layer comprises at least one compound of the formula VIII:

<Formula VIII>

In the above formula,

R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ^34' , R ^35' , R ^36' and R ^37' are each independently substituted with H, C ₁ -C ₁₈ -alkyl, E and/or with D via a C ₁ -C ₁₈ - alkyl, C ₆ -C ₂₄ - aryl, substituted C ₆ -C ₂₄ in G - aryl, C ₂ -C ₂₀ - heteroaryl, or a C ₂ -C ₂₀ substituted with G - heteroaryl Aryl,

*Q is an arylene or heteroarylene group, each optionally substituted with G;

D is -CO-; -COO-; -S-; -SO-; -SO ₂ -; -O-; -NR ⁴⁰ -; -SiR ⁴⁵ R ⁴⁶ -; -POR ⁴⁷ -; -CR ³⁸ =CR ³⁹ -; Or -C≡C-;

E is -OR ⁴⁴ ; -SR ⁴⁴ ; -NR ⁴⁰ R ⁴¹ ; -COR ⁴³ ; -COOR ⁴² ; -CONR ⁴⁰ R ⁴¹ ; -CN; Or F;

G is E, C ₁ -C ₁₈ - alkyl, C ₁ -C ₁₈ substituted with D - alkyl, C ₁ -C ₁₈ - perfluoroalkyl, C ₁ -C ₁₈ - alkoxy, or, or is substituted by E and / Or C ₁ -C ₁₈ -alkoxy interrupted by D,

Wherein R ³⁸ and R ³⁹ are each independently H, C ₆ -C ₁₈ -aryl; C ₁ -C ₁₈ - alkyl or C ₁ -C ₁₈ - a C ₆ -C ₁₈ alkoxy substituted with aryl; C ₁ -C ₁₈ -alkyl; Or C ₁ -C ₁₈ -alkyl interrupted by -O-;

R ⁴⁰ and R ⁴¹ are each independently C ₆ -C ₁₈ -aryl; C ₁ -C ₁₈ - alkyl or C ₁ -C ₁₈ - a C ₆ -C ₁₈ alkoxy substituted with aryl; C ₁ -C ₁₈ -alkyl; Or C ₁ -C ₁₈ -alkyl interrupted by -O-; or

R ⁴⁰ and R ⁴¹ together form a 6-membered ring;

R ⁴² and R ⁴³ are each independently C ₆ -C ₁₈ -aryl; C ₁ -C ₁₈ - alkyl or C ₁ -C ₁₈ - a C ₆ -C ₁₈ alkoxy substituted with aryl; C ₁ -C ₁₈ -alkyl; Or C ₁ -C ₁₈ -alkyl interrupted by -O-;

R ⁴⁴ is C ₆ -C ₁₈ -aryl; C ₁ -C ₁₈ - alkyl or C ₁ -C ₁₈ - a C ₆ -C ₁₈ alkoxy substituted with aryl; C ₁ -C ₁₈ -alkyl; Or C ₁ -C ₁₈ -alkyl interrupted by -O-;

R ⁴⁵ and R ⁴⁶ are each independently C ₆ -C ₁₈ -aryl substituted with C ₁ -C ₁₈ -alkyl, C ₆ -C ₁₈ -aryl or C ₁ -C ₁₈ -alkyl,

R ⁴⁷ is C ₁ -C ₁₈ - alkyl substituted by C ₆ -C ₁₈ -aryl, C ₆ -C ₁₈ - alkyl-aryl or C ₁ -C _18.

Preferred compounds of formula VIII are compounds of formula VIIIa:

<Formula VIIIa>

In the above formula,

,

,

또는

이고,Q is

,

,

or

ego,

R ⁴⁸ is H or C ₁ -C ₁₈ -alkyl,

,

또는

이다.*R ^48' is H, C ₁ -C ₁₈ -alkyl or

,

or

to be.

Particular preference is given to compounds of formula VIIIaa:

<Formula VIIIaa>

Additionally, in a very particularly preferred embodiment, the electron transporting layer comprises a compound of the formula Liq and a compound of the formula VIIIaa:

<Formula Liq>

<Formula VIIIaa>

In a preferred embodiment, the electron transport layer comprises the compound of Formula VII in an amount of 99 to 1% by weight, preferably 75 to 25% by weight, more preferably about 50% by weight, wherein the amount of the compound of Formula VII and The amount of the compound of formula VIII combined is 100% by weight or less in total.

Preparation of compounds of formula VIII is described in J. Kido et al., Chem. Commun . (2008) 5821-5823], [J. Kido et al., Chem. Mater . 20 (2008) 5951-5953] and JP2008-127326, or the compounds can be produced similar to the methods described in the aforementioned documents.

Preparation of compounds of formula VII is described, for example, in Christoph Schmitz et al., Chem. Mater . 12 (2000) 3012-3019] and WO00/32717, or the compounds can be produced in analogy to the methods described in the aforementioned documents.

In a preferred embodiment, the present invention relates to an OLED of the present invention, wherein the electron transport layer comprises one or more phenanthroline derivatives and/or pyridine derivatives.

In a further preferred embodiment, the invention relates to an OLED of the invention, wherein the electron transport layer comprises at least one phenanthroline derivative and/or pyridine derivative and at least one alkali metal hydroxyquinolate complex.

In a further preferred embodiment, the invention relates to an OLED of the invention, wherein the electron transport layer comprises at least one phenanthroline derivative and/or pyridine derivative and 8-hydroxyquinolatolithium.

Some of the above-mentioned materials as hole transport materials and electron transport materials can perform various functions. For example, when a part of the electron transport material has a lower HOMO, it becomes a hole blocking material at the same time.

The cathode 5 becomes an electrode that acts to inject electrons or negative charge carriers. The cathode can be any metal or nonmetal having a lower work function than the anode. Materials suitable for the cathode are selected from the group consisting of alkali metals of group 1 of the periodic table of elements, for example Li, Cs, alkaline earth metals of group 2, rare earth metals and metals of group 12 including lanthanide and actinium groups. In addition, metals such as aluminum, indium, calcium, barium, samarium and magnesium and combinations thereof can be used. In addition, lithium-containing organometallic compounds such as 8-hydroxyquinolatolithium (Liq), CsF, NaF, KF, Cs ₂ CO ₃ or LiF are used as electron injection layers to reduce the operating voltage between the organic layer and cathode. Can be applied to.

The OLED of the present invention may further include additional layers known to those skilled in the art. For example, a layer that facilitates the transport of positive charges and/or conforms to the band gap of the layers relative to each other can be applied between the layer 2 and the light emitting layer 3. Alternatively, this additional layer can act as a protective layer. In a similar manner, additional layers may be present between the light emitting layer 3 and the layer 4 to facilitate the transport of negative charges and/or to match the bandgap of the layers relative to each other. Alternatively, this layer can act as a protective layer.

In a preferred embodiment, in addition to layers (1) to (5), the OLED of the present invention comprises at least one of the additional layers mentioned below:

-A hole injection layer between the anode 1 and the hole transport layer 2;

-A blocking layer for electrons between the hole transport layer 2 and the light emitting layer 3;

-A blocking layer for holes between the light emitting layer 3 and the electron transport layer 4;

-An electron injection layer between the electron transport layer 4 and the cathode 5.

However, as already mentioned above, the OLED may not have all of the layers (1) to (5) mentioned, for example layers (1) (anode), layers (3) (light emitting layer) and layers (5) OLEDs comprising (cathode) are likewise suitable, in which case the functions of layers (2) (hole transporting layer) and (4) (electron transporting layer) are assumed by adjacent layers. OLEDs having layer 1, layer 2, layer 3 and layer 5 or layer 1, layer 3, layer 4 and layer 5 are likewise suitable.

Those skilled in the art will know how to select the appropriate material (eg based on electrochemical investigation). Materials suitable for individual layers are known to those skilled in the art and are disclosed, for example, in WO 00/70655.

In addition, some or all of layer 1, layer 2, layer 3, layer 4 and layer 5 may be surface treated to increase the efficiency of charge carrier transport. The choice of material for each of the layers mentioned is preferably determined by obtaining an OLED with high efficiency.

The OLED of the present invention can be produced by methods known to those skilled in the art. In general, OLEDs are produced by successively depositing individual layers onto a suitable substrate. Examples of suitable substrates include glass, inorganic materials such as ITO or IZO or polymer films. In the case of vapor deposition, conventional techniques such as thermal vapor deposition, chemical vapor deposition (CVD), and physical vapor deposition (PVD) can be used.

Alternatively, the organic layer can be coated from a solution or dispersion in a suitable solvent, using coating techniques known to those skilled in the art. Examples of suitable coating techniques are spin-coating, casting method, Langmuir-Blodgett ("LB") method, inkjet printing method, dip coating, iron plate printing, screen printing, doctor blade printing, slit-coating , Roller printing, reverse roller printing, offset lithography printing, flexographic printing, web printing, spray coating, coating by brush or pad printing. Among the mentioned methods, in addition to the above-described vapor deposition, spin-coating, inkjet printing methods and casting methods are preferable because they are particularly simple and have low implementation cost.

In the case of layers of OLEDs obtained by spin-coating methods, casting methods or inkjet printing methods, the coating is suitable for organic solvents such as benzene, toluene, xylene, tetrahydrofuran, methyltetrahydrofuran, N,N-dimethylformamide , Acetone, acetonitrile, anisole, dichloromethane, dimethyl sulfoxide, water, and mixtures thereof can be obtained by using the resulting solution by dissolving the composition in a concentration of 0.0001 to 90% by weight.

In general, the various layers have the following thickness: anode 2 500 to 5,000 mm 2, preferably 1,000 to 2,000 mm 2 (angstrom); Hole transport layer 3 50 to 1,000 mm 2, preferably 200 to 800 mm 2; The light emitting layer 4 10 to 1,000 Pa, preferably 100 to 800 Pa; Electron transport layer 5 50 to 1,000 kPa, preferably 200 to 800 kPa; Cathode (6) 200 to 10,000 MPa, preferably 300 to 5,000 MPa. Moreover, it is likewise possible to combine several layers by mixing. For example, the hole transport material can be applied together after mixing with the material of the light emitting layer. The position of the recombination zone of holes and electrons in the OLED of the present invention and the emission spectrum of the OLED can be influenced by the relative thickness and concentration ratio of each layer. This means that the thickness of the electron transport layer should preferably be selected so that the electron/hole recombination zone is in the light emitting layer. The ratio of the layer thickness of each layer in the OLED depends on the material used. The layer thickness of any additional layer used is known to those skilled in the art.

In a preferred embodiment, the invention relates to an OLED comprising at least one metal-carbene complex of the invention and at least one compound of formula (X):

<Formula X>

In the above formula,

T is NR ⁵⁷ , S, O or PR ⁵⁷ , preferably S or O, more preferably O;

R ⁵⁷ is aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl;

이고, 여기서Q'is -NR ⁵⁸ R ⁵⁹ , -P(O)R ⁶⁰ R ⁶¹ , -PR ⁶² R ⁶³ , -S(O) ₂ R ⁶⁴ , -S(O)R ⁶⁵ , -SR ⁶⁶ or -OR ⁶⁷ , Preferably -NR ⁵⁸ R ⁵⁹ ; More preferably

And here

R ⁶⁸ and R ⁶⁹ are each independently alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl; Preferably methyl, carbazolyl, dibenzofuryl or dibenzothienyl;

y and z are each independently 0, 1, 2, 3 or 4, preferably 0 or 1;

R ⁵⁵ , R ⁵⁶ are each independently alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, SiR ⁷⁰ R ⁷¹ R ⁷² , Q'group or a group having donor or acceptor action,

a" is 0, 1, 2, 3 or 4;

b'is 0, 1, 2 or 3;

R ⁵⁸ , R ⁵⁹ together with a nitrogen atom have 3 to 10 ring atoms and are substituted with one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and donor or acceptor groups. Or a cyclic radical which may be unsubstituted and/or fused with one or more additional cyclic radicals having 3 to 10 ring atoms, wherein the fused radicals are alkyl, cycloalkyl, heterocycloalkyl , Substituted or unsubstituted with one or more substituents selected from aryl, heteroaryl, and donor or acceptor groups;

R ⁷⁰ , R ⁷¹ , R ⁷² , R ⁶⁰ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ are each independently aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl or,

The two units of formula (X) are crosslinked to each other by linear or branched, saturated or unsaturated crosslinks, by bonds or by O, optionally interrupted by one or more heteroatoms.

T is S or O, preferably O,

이고, 여기서Q'

And here

R ⁶⁸ and R ⁶⁹ are each independently alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl; Preferably methyl, carbazolyl, dibenzofuryl or dibenzothienyl;

y and z are each independently 0, 1, 2, 3 or 4, preferably 0 or 1, preferably a compound of formula (X).

*Especially preferred compounds of formula X have the formula Xa:

<Formula Xa>

In the above formula,

The sign and exponents Q', T, R ⁵⁵ , R ⁵⁶ , a" and b'are each as defined above.

Very particularly preferred compounds of formula X have the formula Xaa:

<Formula Xaa>

Signs and exponents R ⁶⁸ , R ⁶⁹ y, z, T, R ⁵⁵ , R ⁵⁶ , a" and b'are each as defined above.

In a very particularly preferred embodiment, in formula Xaa

T is O or S, preferably O;

a" is 1;

b'is 0;

y and z are each independently 0 or 1;

R ⁶⁸ and R ⁶⁹ are each independently methyl, carbazolyl, dibenzofuryl or dibenzothienyl;

R ⁵⁵ is substituted phenyl, carbazolyl, dibenzofuryl or dibenzothienyl.

In a further preferred embodiment, the compound of formula X has formula XI or XI ^* :

<Formula XI>

<Formula XI ^* >

(In the above formula,

T is NR ⁵⁷ , S, O or PR ⁵⁷ ;

R ⁵⁷ is aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl;

Q'is -NR ⁵⁸ R ⁵⁹ , -P(O)R ⁶⁰ R ⁶¹ , -PR ⁶² R ⁶³ , -S(O) ₂ R ⁶⁴ , -S(O)R ⁶⁵ , -SR ⁶⁶ or -OR ⁶⁷ ;

R ⁷⁰ , R ⁷¹ , R ⁷² are each independently aryl, heteroaryl, alkyl, cycloalkyl, heterocycloalkyl, wherein at least one of the R ⁷⁰ , R ⁷¹ , R ⁷² radicals is at least 2 carbon atoms or OR ⁷³ It includes;

R ⁵⁵ and R ⁵⁶ are each independently an alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, Q group or a group having donor or acceptor action;

a', b'are each independently 0, 1, 2, 3 for compounds of formula (XI); For compounds of formula XI ^* a'is 0, 1, 2, b'is 0, 1, 2, 3, 4;

R ⁵⁸ , R ⁵⁹ , together with the nitrogen atom, have 3 to 10 ring atoms and are substituted with one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and groups having donor or acceptor action Form a cyclic radical which may or may not be substituted and/or fused to one or more additional cyclic radicals having 3 to 10 ring atoms, wherein the fused radicals are alkyl, cycloalkyl, heterocyclo May or may not be substituted with one or more substituents selected from alkyl, aryl, heteroaryl, and donor or acceptor groups;

R ⁷³ is SiR ⁷⁴ R ⁷⁵ R ⁷⁶ , aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, each independently substituted with an OR ⁷⁷ group,

R ⁷⁷ are each independently SiR ⁷⁴ R ⁷⁵ R ⁷⁶ , aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl,

R ⁶⁰ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ are each independently aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl or

The two units of Formula XI and/or Formula XI ^* are crosslinked to each other by linear or branched, saturated or unsaturated bridges optionally interrupted by one or more heteroatoms or by O, where Formulas XI and/or Formula XI This crosslinking in ^* is in each case bonded to a silicon atom instead of R ⁷¹ .

The compound of formula (X) can be used as a matrix (diluent material), hole/exciton blocker, electron/exciton blocker, electron transport material or hole transport material with the claimed complex, and thus acts as an emitter. The OLED of the present invention comprising both the compound of formula (X) and the compound of formula (I) exhibits particularly good efficiency and lifetime. Depending on the action using the compound of formula (X), it is present in pure form or in various mixing ratios. In a particularly preferred embodiment, at least one compound of formula (X) is used as a matrix material in the light emitting layer.

For compounds of formula X, especially for R ⁵⁵ to R ⁷⁷ radicals,

The terms aryl radicals or groups, heteroaryl radicals or groups, alkyl radicals or groups, cycloalkyl radicals or groups, heterocycloalkyl radicals or groups, alkenyl radicals or groups, alkynyl radicals or groups, and donor and/or acceptor functions Each group having is defined as follows:

An aryl radical (or group) is understood to mean a radical having a basic skeleton of 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms, formed from an aromatic ring or a plurality of fused aromatic rings. Examples of suitable basic skeletons include phenyl, naphthyl, anthracenyl or phenanthrenyl, indenyl or fluorenyl. This base skeleton may be unsubstituted (which means that all substitutable carbon atoms have hydrogen atoms) or may be substituted at one, more than one or all substitutable positions of the base skeleton.

Examples of suitable substituents are deuterium, alkoxy radicals, aryloxy radicals, alkylamino groups, arylamino groups, carbazolyl groups, silyl groups, SiR ⁷⁸ R ⁷⁹ R ⁸⁰ , (suitable silyl groups SiR ⁷⁸ R ⁷⁹ R ⁸⁰ are below Specified), alkyl radicals, preferably alkyl radicals having 1 to 8 carbon atoms, more preferably methyl, ethyl or i-propyl, which in turn can be substituted or unsubstituted aryl radicals, preferably C _6- An aryl radical, a heteroaryl radical, preferably a heteroaryl radical comprising one or more nitrogen atoms, more preferably a pyridyl radical and a carbazolyl radical, an alkenyl radical, preferably an alkenyl having one double bond Radical, more preferably alkenyl radical having 1 double bond and 1 to 8 carbon atoms, alkynyl radical, preferably alkynyl radical having triple bond, more preferably 1 triple bond and 1 to 8 Alkynyl radicals having two carbon atoms and/or groups having donor or acceptor functions. Groups with suitable donor or acceptor functions are specified below. The substituted aryl radicals most preferably have a substituent selected from the group consisting of methyl, ethyl, isopropyl, alkoxy, heteroaryl, halogen, pseudohalogen and amino, preferably arylamino. The aryl radical or aryl group is preferably a C ₆ -C ₁₈ -aryl radical, more preferably a C ₆ -aryl radical, optionally substituted with one or more or more than one of the aforementioned substituents. The C ₆ -C ₁₈ -aryl radical, preferably the C ₆ -aryl radical, more preferably has 0, 1, 2, 3 or 4 of the aforementioned substituents, most preferably 0, 1 or 2.

The heteroaryl radical or heteroaryl group is substituted with at least one carbon atom in the basic skeleton of the aryl radical as a heteroatom, and the basic skeleton of the heteroaryl radical preferably has a radical different from the aforementioned aryl radical having 5 to 18 ring atoms I understand it as meaning. Preferred heteroatoms are N, O and S. Particularly preferably suitable heteroaryl radicals are nitrogen-containing heteroaryl radicals. Most preferably, one or two carbon atoms of the basic skeleton are substituted with heteroatoms, preferably nitrogen. The basic skeleton is particularly preferably selected from systems such as pyridine, pyrimidine and 5-membered heteroaromatics such as pyrrole, furan, pyrazole, imidazole, thiophene, oxazole, thiazole, triazole. In addition, heteroaryl radicals may be fused ring systems such as benzofuryl, benzothienyl, benzopyrrole, dibenzofuryl, dibenzothienyl, phenanthrolinyl, carbazolyl radicals, azacarbazolyl radicals or dia It can be a jacarbazolyl radical. The base skeleton may be substituted at one, more than one or all substitutable positions of the base skeleton. Suitable substituents are the same as already specified for the aryl group.

An alkyl radical or alkyl group is understood to mean a radical having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8, most preferably 1 to 4 carbon atoms. . These alkyl radicals may be branched or unbranched, optionally interposed with one or more heteroatoms, preferably Si, N, O or S, more preferably N, O or S. Moreover, these alkyl radicals may be substituted with one or more of the substituents specified for the aryl group. Moreover, the alkyl radicals present by the present invention may have one or more halogen atoms, for example F, Cl, Br or I, especially F. In a further embodiment, the alkyl radicals present by the present invention can be fully fluorinated. Likewise, an alkyl radical can have one or more (hetero)aryl groups. In the context of the present application, for example, the benzyl radical is thus a substituted alkyl radical. In this regard, all of the (hetero)aryl groups presented above are suitable. The alkyl radical is more preferably selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, n-butyl, iso-butyl and tert-butyl, with methyl and ethyl being very particularly preferred.

Cycloalkyl radicals or cycloalkyl groups are understood to mean radicals having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, and more preferably 3 to 8 carbon atoms. This base skeleton may be unsubstituted (which means that all substitutable carbon atoms have hydrogen atoms) or may be substituted at one, more than one or all substitutable positions of the base skeleton. Suitable substituents are those already mentioned above for aryl radicals. Likewise, a cycloalkyl radical can have one or more (hetero)aryl groups. Examples of suitable cycloalkyl radicals are cyclopropyl, cyclopentyl and cyclohexyl.

Heterocycloalkyl radicals or heterocycloalkyl groups are understood to mean radicals different from the aforementioned cycloalkyl radicals in which at least one carbon atom in the basic skeleton of the cycloalkyl radical is substituted with a heteroatom. Preferred heteroatoms are N, O and S. Most preferably, 1 or 2 carbon atoms of the basic skeleton of the cycloalkyl radical are substituted with heteroatoms. Examples of suitable heterocycloalkyl radicals are radicals derived from pyrrolidine, piperidine, piperazine, tetrahydrofuran, dioxane.

An alkenyl radical or alkenyl group corresponds to the aforementioned alkyl radical having 2 or more carbon atoms, and it is understood that the substitution of one or more C-C single bonds of an alkyl radical with a C-C double bond means different radicals. The alkenyl radical preferably has 1 or 2 double bonds.

An alkynyl radical or an alkynyl group corresponds to the aforementioned alkyl radical having 2 or more carbon atoms, and it is understood that the substitution of one or more C-C single bonds of an alkyl radical with a C-C triple bond means different radicals. The alkynyl radical preferably has 1 or 2 triple bonds.

SiR ⁷⁸ R ⁷⁹ R ⁸⁰ group is understood to mean a silyl radical wherein R ⁷⁸ , R ⁷⁹ and R ⁸⁰ are each independently alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or OR ⁷³ .

The group SiR ⁷⁴ R ⁷⁵ R ⁷⁶ is understood to mean a silyl radical wherein R ⁷⁴ , R ⁷⁵ and R ⁷⁶ are each independently alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or OR ⁷³ .

In the context of this application, groups or substituents with donor or acceptor action are understood to mean the following groups:

A group having a donor action is understood to mean a group having a +I and/or +M effect, and a group having a receptor action is understood to mean a group having a -I and/or -M effect. Preferred suitable groups are C ₁ -C ₂₀ -alkoxy, C ₆ -C ₃₀ -aryloxy, C ₁ -C ₂₀ -alkylthio, C ₆ -C ₃₀ -arylthio, SiR ⁸¹ R ⁸² R ⁸³ , OR ⁷³ , halogen radical , Halogenated C ₁ -C ₂₀ -alkyl radical, carbonyl(-CO(R ⁸¹ )), carbonylthio(-C=O(SR ⁸¹ )), carbonyloxy(-C=O(OR ⁸¹ )), Oxycarbonyl (-OC=O(R ⁸¹ )), thiocarbonyl(-SC=O(R ⁸¹ )), amino(-NR ⁸¹ R ⁸² ), pseudohalogen radical, amido(-C=O(NR ⁸¹ )), -NR ⁸¹ C=O(R ⁸³ ), phosphonate (-P(O)(OR ⁸¹ ) ₂ , phosphate (-OP(O)(OR ⁸¹ ) ₂ ), phosphine (-PR ⁸¹ R ⁸² ), phosphine oxide (-P(O)R ⁸¹ ₂ ), sulfate (-OS(O) ₂ OR ⁸¹ ), sulfoxide (-S(O)R ⁸¹ ), sulfonate (-S( O) ₂ OR ⁸¹ ), sulfonyl (-S(O) ₂ R ⁸¹ ), sulfonamide (-S(O) ₂ NR ⁸¹ R ⁸² ), NO ₂ , boronic ester (-OB(OR ⁸¹ ) ₂ ) , Imino (-C=NR ⁸¹ R ⁸² )), borane radical, stannane radical, hydrazine radical, hydrazone radical, oxime radical, nitroso group, diazo group, vinyl group, sulfoximine, allan, germane, borok Sim and Borazine.

The R ⁸¹ , R ⁸² and R ⁸³ radicals mentioned in the groups having the donor or acceptor functions described above are each independently substituted or unsubstituted C ₁ -C ₂₀ -alkyl or substituted or unsubstituted C ₆ -C ₃₀ -aryl, or OR ⁷⁶ , suitable and preferred alkyl and aryl radicals being specified above. The R ⁸¹ , R ⁸² and R ⁸³ radicals are more preferably C ₁ -C ₆ -alkyl, for example methyl, ethyl or i-propyl or phenyl. In a preferred embodiment,-for SiR ⁸¹ R ⁸² R ⁸³ -R ⁸¹ , R ⁸² and R ⁸³ are preferably each independently substituted or unsubstituted C ₁ -C ₂₀ -alkyl or substituted or unsubstituted aryl, preferably Is phenyl.

Preferred substituents with donor or acceptor action are C ₁ -C ₂₀ -alkoxy, preferably C ₁ -C ₆ -alkoxy, more preferably ethoxy or methoxy; C ₆ -C ₃₀ -aryloxy, preferably C ₆ -C ₁₀ -aryloxy, more preferably phenyloxy; SiR ⁸¹ R ⁸² R ⁸³ wherein R ⁸¹ , R ⁸² and R ⁸³ are each independently independently substituted or unsubstituted alkyl or substituted or unsubstituted aryl, preferably phenyl; more preferably, R ⁸¹ , R ^{At least one of the 82} and R ⁸³ radicals is substituted or unsubstituted phenyl (appropriate substituents are specified above); halogen radicals, preferably F, Cl, more preferably F, halogenated C ₁ -C ₂₀ -alkyl radicals, Preferably a halogenated C ₁ -C ₆ -alkyl radical, most preferably a fluorinated C ₁ -C ₆ -alkyl radical, for example CF ₃ , CH ₂ F, CHF ₂ or C ₂ F ₅ ; amino, preferably Dimethylamino, diethylamino or diarylamino, more preferably diarylamino; pseudohalogen radicals, preferably CN, -C(O)OC ₁ -C ₄ -alkyl, preferably -C(O)OMe , P(O)R ₂ , preferably P(O)Ph ₂ .

Substituents with very particularly preferred donor or acceptor action are methoxy, phenyloxy, halogenated C ₁ -C ₄ -alkyl, preferably CF ₃ , CH ₂ F, CHF ₂ , C ₂ F ₅ , halogen, preferably F , CN, SiR ⁸¹ R ⁸² R ⁸³ (the appropriate R ⁸¹ , R ⁸² and R ⁸³ radicals have already been specified), diarylamino (NR ⁸⁴ R ⁸⁵ , where R ⁸⁴ , R ⁸⁵ are each C ₆ -C _30- Aryl), -C(O)OC ₁ -C ₄ -alkyl, preferably -C(O)OMe, P(O)Ph ₂ .

Halogen groups are understood to mean preferably F, Cl and Br, more preferably F and Cl, most preferably F.

Pseudohalogen groups are understood to mean preferably CN, SCN and OCN, more preferably CN.

Groups with the donor or acceptor functions described above do not exclude the possibility of having donor or acceptor action, although additional radicals and substituents mentioned in this application but not included in the above list of donor or acceptor function groups.

Aryl radicals or groups, heteroaryl radicals or groups, alkyl radicals or groups, cycloalkyl radicals or groups, heterocycloalkyl radicals or groups, alkenyl radicals or groups and groups having donor and/or acceptor functions are substituted as mentioned above Or it can be unsubstituted. In the context of the present application, an unsubstituted group is understood to mean a group in which the substitutable atom of the group has a hydrogen atom. In the context of the present application, a substituted group is understood to mean that at least one substitutable atom(s) has a substituent in place of a hydrogen atom in at least one position. Suitable substituents are the substituents specified above for the aryl radical or group.

When radicals having the same number occur more than once in the compounds according to the present application, these radicals may each have independently specified definitions.

The T radical in the compound of formula X is NR ⁵⁷ , S, O or PR ⁵⁷ , preferably NR ⁵⁷ , S or O, more preferably O or S, most preferably O.

The R ⁵⁷ radical is aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, preferably aryl, heteroaryl or alkyl, more preferably aryl, wherein the radicals described above may be unsubstituted or substituted. Suitable substituents are specified above. R ⁶⁵ is more preferably phenyl which may or may not be substituted with the substituents described above. R ⁵⁷ is most preferably unsubstituted phenyl.

The Q'group in the compound of formula X is -NR ⁵⁸ R ⁵⁹ , -P(O)R ⁶⁰ R ⁶¹ , -PR ⁶² R ⁶³ , -S(O) ₂ R ⁶⁴ , -S(O)R ⁶⁵ , -SR ⁶⁶ or -OR ⁶⁷ ; Preferably NR ⁵⁸ R ⁵⁹ , -P(O)R ⁶⁰ R ⁶¹ or -OR ⁶⁷ , more preferably -NR ⁵⁸ R ⁵⁹ .

The R ⁵⁸ to R ⁶⁷ and R ⁷⁴ to R ⁷⁶ radicals are respectively defined below:

R ⁵⁸ , R ⁵⁹ , together with the nitrogen atom, have 3 to 10 ring atoms and are substituted with one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and groups having donor or acceptor action Forms a cyclic radical which may or may not be substituted and/or fused with one or more additional cyclic radicals having 3 to 10 ring atoms, wherein the fused radicals are alkyl, cycloalkyl, heterocyclo May or may not be substituted with one or more substituents selected from alkyl, aryl, heteroaryl, and donor or acceptor groups;

로부터 선택된 라디칼 중 1종 이상으로 비치환 또는 치환될 수 있으며, 여기서 T 기 및 R⁷⁰, R⁷¹ 및 R⁷² 라디칼은 각각 독립적으로 화학식 XI 또는 화학식 XI^*의 화합물에 대하여 정의된 바와 같다.R ⁶⁰ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ are each independently aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, Preferably aryl or heteroaryl, wherein the radicals are alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and groups with donor or acceptor action, more preferably unsubstituted or substituted phenyl, (appropriate substituents Specified above), e.g. tolyl or formula

It may be unsubstituted or substituted with one or more of the radicals selected from, wherein the T group and the R ⁷⁰ , R ⁷¹ and R ⁷² radicals are each independently as defined for the compound of Formula XI or Formula XI ^* .

의 기이며, 여기서 T는 NPh, S 또는 O이다.R ⁶⁰ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ are most preferably each independently phenyl, tolyl or a chemical formula

Is a group, wherein T is NPh, S or O.

Examples of suitable -NR ⁵⁸ R ⁵⁹ groups are preferably pyrrolyl, 2,5-dihydro-1-pyrrolyl, pyrrolidinyl, indolyl, indolinyl, isoindolinyl, carbazolyl, azacarba Zolyl, diazacarbazolyl, imidazolyl, imidazolinyl, benzimidazolyl, pyrazolyl, indazolyl, 1,2,3-triazolyl, benzotriazolyl, 1,2,4-triazolyl, Selected from the group consisting of tetrazolyl, 1,3-oxazolyl, 1,3-thiazolyl, piperidyl, morpholinyl, 9,10-dihydroacridinyl and 1,4-oxazinyl, as described above One group may or may not be substituted with one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and donor or acceptor groups; -NR ⁵⁸ R ⁵⁹ group is preferably selected from carbazolyl, pyrrolyl, indolyl, imidazolyl, benzimidazolyl, azacarbazolyl and diazacarbazolyl, wherein the groups described above are alkyl, cycloalkyl , Substituted or unsubstituted with one or more substituents selected from heterocycloalkyl, aryl, heteroaryl, and groups having donor or acceptor action; The -NR ⁵⁸ R ⁵⁹ group is more preferably alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and carbazolyl, which may or may not be substituted with one or more substituents selected from donors or groups having acceptor action. to be.

이고, 여기서 R⁶⁸, R⁶⁹는 각각 독립적으로 알킬, 시클로알킬, 헤테로시클로알킬, 아릴 또는 헤테로아릴; 바람직하게는 메틸, 카르바졸릴, 디벤조푸릴 또는 디벤조티에닐이고;A particularly preferred -NR ⁵⁸ R ⁵⁹ group

Wherein R ⁶⁸ and R ⁶⁹ are each independently alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl; Preferably methyl, carbazolyl, dibenzofuryl or dibenzothienyl;

y and z are each independently 0, 1, 2, 3 or 4, preferably 0 or 1;

For example

,

,

(여기서 X는 NPh, S 또는 O임),

,

,

,

,

(여기서 X는 NPh, S 또는 O임),

,

,

,

,

,

이다.

,

,

(Where X is NPh, S or O),

,

,

,

,

(Where X is NPh, S or O),

,

,

,

,

,

to be.

및

이다.A particularly preferred -P(O)R ⁶⁰ R ⁶¹ group

And

to be.

이다.The particularly preferred PR ⁶² R ⁶³ group

to be.

,

,

및

이다.*Especially preferred groups -S(O) ₂ R ⁶⁴ and -S(O)R ⁶⁵ are

,

,

And

to be.

,

,

,

,

및

이고, 여기서 T는 각각의 경우에서 NPh, S 또는 O이다.Particularly preferred groups -SR ⁶⁶ and -OR ⁶⁷ are

,

,

,

,

And

Where T is NPh, S or O in each case.

,

또는

,

일 수 있으며, 여기서 X는 NPh, S 또는 O이다.R ⁵⁵ and R ⁵⁶ in the compound of the formula (X) are each independently alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, additional A groups or groups having donor or acceptor action; Preferably each independently alkyl, aryl, heteroaryl or donor or acceptor group. For example, R ⁵⁵ or R ⁵⁶ are each independently

,

or

,

Can be, where X is NPh, S or O.

In the compounds of formula (X), a" R ⁵⁵ group and/or b'R ⁵⁶ group may be present, where a" and b'are

a" is 0, 1, 2, 3 or 4, preferably independently 0, 1 or 2;

b'is 0, 1, 2 or 3; It is preferably 0, 1 or 2 independently.

Most preferably at least a" or b'is 0, very particularly preferably a" and b'are each 0 or a" is 1 and b'is 0.

R ⁷³ in compounds of formula (XI) is generally independently SiR ⁷⁴ R ⁷⁵ R ⁷⁶ , aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, optionally substituted with an OR ⁷⁷ group.

R ⁷⁷ in the compound of formula XI is generally independently aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl.

The optionally present OR ⁷⁷ substituents can be present in the radicals mentioned at all sites generally found to be suitable for those skilled in the art.

In a further embodiment, the two units of formula XI and/or formula XI ^* are crosslinked to one another by one or more heteroatoms or by linear or branched, saturated or unsaturated crosslinks, optionally interrupted by O. This bridge in XI and/or formula XI ^* is in each case bonded to a silicon atom instead of R ⁷¹ .

Such crosslinking is preferably -CH ₂ -, -C ₂ H ₄ -, -C ₃ H ₆ -, -C ₄ H ₈ -, -C ₆ H ₁₂ -, -C ₈ H ₁₆ -, -C ₉ H ₁₈ -, -CH(C ₈ H ₁₇ )CH ₂ -, -C ₂ H ₄ (CF ₂ ) ₈ C ₂ H ₄ -, -C≡C-, -1,4-(CH ₂ ) ₂ -phenyl- (CH ₂ ) ₂ -, 1,3-(CH ₂ ) ₂ -phenyl-(CH ₂ ) ₂ -, -1,4-phenyl-, -1,3-phenyl-, -O-, -O-Si (CH ₃ ) ₂ -O-, -O-Si(CH ₃ ) ₂ -O- Si(CH ₃ ) ₂ -O-, -O-.

In a preferred embodiment of the invention, the compound of formula (X) is to have a formula XIa, the formula XIb, the formula XIc, the formula XId or the formula XIe, i.e. these are the preferred embodiments of formula XI or a compound of formula XI ^* :

<Formula XIa>

<Formula XIb>

<Formula XIc>

<Formula XId>

<Formula XIe>

In the above formula, Q', T, R ⁷⁰ , R ⁷¹ , R ⁷² , R ⁵⁵ , R ⁵⁶ radicals and groups, and a'and b', are each as defined above.

In another preferred embodiment according to the invention, R ⁷⁰ , R ⁷¹ or R ⁷² in the compound of the formula XI or formula XI ^* is an aromatic unit of the formula XIi and/or formula XIi*:

<Formula XIi>

<Formula XIi*>

In the above formula, R ⁵⁵ , R ⁵⁶ , Q', T, a'and b'are each as defined above.

Therefore, the invention in one embodiment, a compound of formula XI) or (XI ^* R ^70, R ⁷¹ or R ⁷² is relates to the OLED of the present invention, the aromatic unit of formula XIi and / or formula XIi *:

<Formula XIi>

<Formula XIi*>

In the above formula, R ⁵⁵ , R ⁵⁶ , Q', T, a'and b'are each as defined above.

In a preferred embodiment, the present invention relates to an OLED is selected from the group of the compound of formula XI) or (XI ^*:

.

.

In these particularly preferred compounds of formula XI or formula XI ^* ,

T is S or O,

R'is H or CH ₃ ,

R ⁷⁰ , R ⁷¹ , R ⁷² are each phenyl, carbazolyl, dibenzofuran or dibenzothiophene.

Further particularly suitable compounds of formula XI or formula XI ^* are as follows:

In this particularly preferred compound of formula (XI) or formula (XI ^* ) also T is O or S, preferably O.

Further compounds of Formula XI or Formula XI ^* of the present invention correspond to Formula XII:

<Formula XII>

In formula XII, R ⁷⁰ , R ⁷¹ , R ⁷² are each defined as follows:

In the table above,

이다.R ⁸⁶ silver

to be.

Two units of Formula XI and/or Formula XI ^* are cross-linked to each other by linear or branched, saturated or unsaturated bridges or by O, optionally interrupted by one or more heteroatoms, wherein Formula XI and/or Formula XI Particularly preferred compounds in which such crosslinking in ^* is bonded to a silicon atom instead of R ⁷¹ in each case correspond to the formula (XIII):

<Formula XIII>

In formula XIII, U, R ⁷⁰ , R ⁷¹ , R ⁷² , R ⁸⁷ , R ⁸⁸ and R ⁸⁹ are each defined as follows:

이다.In the above table, R ⁸⁶ is

to be.

Further suitable compounds of Formula XI and/or Formula XI ^* are specified below. Wherein R is independently Me, phenyl or R ⁸⁶ , wherein at least one R radical is R ⁸⁶ :

In a very particularly preferred embodiment, the invention relates to an OLED comprising at least one metal-carbene complex of formula I, as well as at least one compound of formula X, in which case the compound of formula X is most preferably Is one or more of the compounds specified below:

In the aforementioned compounds, T is O or S, preferably O. If more than one T is present in the molecule, all T groups have the same definition.

In addition to the compounds of formula X, according to the invention, it is possible to use crosslinked or polymeric materials comprising repeating units based on formula X in crosslinked or polymerized form with one or more metal-carbene complexes of formula I. Like the compound of formula X, the latter is preferably used as a matrix material.

Crosslinked or polymeric materials have good solubility in organic solvents, excellent film forming properties and relatively high glass transition temperatures. Moreover, high charge carrier mobility, high stability of color emission and long operating time of the component can be observed when the crosslinked or polymeric material according to the present invention is used in organic light emitting diodes (OLEDs).

The crosslinked or polymeric material is thermally and mechanically stable and is relatively flawless, making it particularly suitable as a coating or for thin films.

A crosslinked or polymeric material comprising repeating units based on formula (X) can be produced by a method comprising steps (a) and (b) below:

(a) Preparation of a crosslinkable or polymerizable compound of formula (X) wherein at least one of the a"R ⁵⁵ radicals or at least one of the ^b'R56 radicals is a crosslinkable or polymerizable group bonded by a spacer, and

(b) Crosslinking or polymerization of the compound of formula (X) obtained from step (a).

The crosslinked or polymeric material can be a homopolymer, meaning that the units of formula X are present in crosslinked or polymerized form. They may also be copolymers, meaning that additional monomers are present in addition to the unit of formula (X) in units of hole-conducting electron-conducting properties, for example in cross-linked or polymerized form.

In a further preferred embodiment of the inventive OLEDs, it comprises at least one metal-carbene complex of the formula I of the invention, at least one matrix material of the formula X and optionally at least one further hole transport matrix material. It includes a light emitting layer.

The OLED of the present invention can be used in any device in which electroluminescence is useful. Suitable devices are preferably selected from still and moving image display devices and lighting means. Therefore, the present invention also relates to a device selected from the group consisting of a still image display apparatus and a moving image display apparatus and lighting means, comprising the OLED of the present invention.

Examples of still image display devices include computer image display devices, televisions, video display devices in printers, kitchen appliances and advertising panels, lighting and information panels. Examples of mobile video display devices include mobile phones, laptops, digital cameras, mp-3 players, smart phones, video display devices in automobiles, and destination displays in buses and trains.

The metal-carbene complexes of the formula (I) of the present invention can further be used in OLEDs having an inverse structure. In such reversed OLEDs, the complexes of the invention are in turn preferably used in light emitting layers. The structure of inverted OLEDs and materials commonly used herein is known to those skilled in the art.

The present invention further provides a white light OLED comprising at least one metal-carbene complex of formula I of the present invention. In a preferred embodiment, the metal-carbene complex of formula I is used as an emitter material in white light OLEDs. Preferred embodiments of the metal-carbene complex of formula I are specified above. In addition to one or more metal-carbene complexes of formula I, white light OLEDs

(i) at least one compound of formula X (the compound of formula X is preferably used as a matrix material. Preferred compounds of formula X are specified); And/or

(ii) one or more compounds of Formula VII and/or Formula IX (the compounds of Formula VII and/or Formula IX are preferably used as electron transport materials. Preferred compounds of Formula VII and Formula IX are specified above) It may include.

To obtain white light, the OLED must produce light that colors the entire visible range of the spectrum. However, organic emitters are usually only emitted in a limited portion of the visible spectrum, ie colored. White light can be generated by a combination of various emitters. Typically, red, green and blue emitters are combined. However, the prior art also discloses other methods for the formation of white light OLEDs, such as the triple harvesting approach. Structures suitable for white light OLEDs or methods for forming white light OLEDs are known to those skilled in the art.

In one embodiment of a white light OLED, several dyes are combined by stacking layer by layer in the light emitting layer of the OLED (stacked device). This can be achieved by mixing all dyes or by direct continuous connection of differently colored layers. The term "stacked OLED" and suitable embodiments are known to those skilled in the art.

In general, the different layers thereafter are from 500 to 5,000 kPa (angstrom) of the anode 2, preferably from 1,000 to 2,000 kPa; The hole transport layer 3 has a thickness of 50 to 1,000 mm 2, preferably 200 to 800 mm 2, and a light emitting layer 4 comprising a mixture of different emitters: 10 to 1,000 mm 2, preferably 100 to 800 mm 2 or continuous Several light emitting layers, each individual layer comprising different emitters (4a, b, c, ...): 10 to 1,000 Pa, respectively 50 to 600 Pa, and electron transport layer 5 50 to 1,000 Pa, respectively , Preferably 200 to 800 MPa, cathode 6 200 to 10,000 MPa, preferably 300 to 5,000 MPa.

In a further embodiment of a white light OLED, several different-colored OLEDs are stacked on top of one another (stacked devices). In the case of stacking two OLEDs, an OLED, a so-called charge generating layer (CG layer) is used. Such a CG layer can be formed, for example, from one electrically n-doped and one electrically p-doped transport layer. The term "stacked OLED" and suitable embodiments are known to those skilled in the art.

In general, the different layers have the following thickness: anode (2) 500 to 5,000 kPa (angstroms), preferably 1,000 to 2,000 kPa; Primary hole transport layer (3) 50 to 1,000 Å, preferably 200 to 800 Å, primary light emitting layer (4) 10 to 1,000 Å, preferably 50 to 600 Å, primary electron transport layer (5) 50 to 1,000 Å , Preferably 200 to 800 mm 2, electrical n-doped layers 50 to 1,000 mm 2, preferably 100 to 800 mm 2, electrical p-doped layers 50 to 1,000 mm 2, preferably 100 to 800 mm 2, secondary holes Transport layer (3) 50 to 1,000 Pa, preferably 200 to 800 Pa, secondary light emitting layer (4) 10 to 1,000 Pa, preferably 50 to 600 Pa, secondary electron transport layer (5) 50 to 1,000 Pa, preferably Is 200 to 800 kPa, electrical n-doped layer 50 to 1,000 kPa, preferably 100 to 800 kPa, electrical p-doped layer 50 to 1,000 kPa, preferably 100 to 800 kPa, tertiary hole transport layer (3 ) 1,000 Å, preferably up to 200 to 800 ,, tertiary light emitting layer 4 10 to 1,000 Å, preferably 50 to 600 Å, tertiary electron transport layer 5, 50 to 1,000 Å, preferably 200 to 800 Å Å, cathode 6 200 to 10,000 Å, preferably 300 to 5,000 Å.

In a further embodiment of this "stacked device concept", only two OLEDs can be stacked or more than three OLEDs can be stacked.

In a further embodiment of a white light OLED, the two concepts mentioned for white light generation can also be combined. For example, a single color OLED (for example blue) can be stacked as a multicolor OLED (for example red-green). Additional combinations of the two concepts are conceivable and are known to those skilled in the art.

The metal-carbene complexes of formula I of the present invention can be used in any of the above-mentioned layers in white light OLEDs. In a preferred embodiment, it is used in one or more or all of the light emitting layer(s) of the OLED(s), in which case the structure of the metal-carbene complex of the present invention is varied depending on the function of the use of the complex. Suitable and preferred matrix materials as suitable and preferred component or matrix material in the light emitting layer(s) for further layers of the optical OLED(s) are likewise specified above.

The present invention is also an organic electronic component, preferably an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic field effect transistor (OFET) comprising at least one metal-carbene complex of formula I of the present invention. ) Or a luminescent electrochemical cell (LEEC).

Example

The following examples, more particularly the methods, materials, conditions, process variables, devices, etc., described in the Examples are intended to support the invention, but should not limit the scope of the invention.

All experiments are conducted in a protective gas atmosphere.

The ratios (%) and ratios mentioned in the examples below are weight percents and weight ratios, unless specified otherwise.

Example 1:

2,3-bis(N-phenylamino)pyrazine

A mixture of 2,3-dichloropyrazine (10.0 g, 67 mmol) in aniline (35.3 mL, 376 mmol) is stirred at 105°C overnight. After cooling to 80° C., water (100 mL) is added. The mixture was adjusted to pH 11 with a 50% sodium hydroxide solution and extracted with dichloromethane and ethyl acetate. The combined organic phases are concentrated to dryness, and the crude product is purified by column chromatography (silica gel, n-hexane/ethyl acetate 4:1). Yield: 16.2 g (92%).

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 6.27 (br s, 2H), 7.00 (m _c , 2H), 7.26-7.30 (m, 8H), 7.72 (s, 2H).

1,3-diphenylpyrazinoimidazolium iodide

A mixture of 2,3-bis(N-phenylamino)pyrazine (15.5 g, 59 mmol) in triethyl orthoformate (100 mL) was mixed with ammonium iodide (17.1 g, 118 mmol) and stirred at 80° C. overnight. do. After cooling to room temperature, the solid is filtered off with suction, washed with petroleum ether and dried at 70° C. in a vacuum drying cabinet. Yield: 19.5 g (82%).

¹ H NMR (d ₆ -DMSO, 500 MHz): δ = 7.77 (m _c , 2H), 7.84 (m _c , 4H), 8.03-8.08 (m, 4H), 9.08 (s, 2H), 11.20 (s , 1H).

Complex fac-Em1 :

A suspension of 1,3-diphenylpyrazinoimidazolium iodide (1.6 g, 4.0 mmol) in dioxane (95 ml) was mixed with molecular sieve (14 g) and silver oxide (I) (742 mg, 3.2 mmol) Stir overnight at room temperature. Then a solution of chloro(1,5-cyclooctadiene)iridium(I) dimer (269 mg, 0.4 mmol) in o-xylene (130 mL) is added. The mixture was stirred at reflux overnight. After cooling to 80° C., the residue is filtered off with suction and washed with o-xylene. The combined filtrates were concentrated to dryness, and the residue was dissolved in toluene (40 ml) at 75°C. The solution is concentrated and left at room temperature overnight. The precipitate is filtered off, washed with cyclohexane and dried at 65° C. in a vacuum drying cabinet. Yield: 0.8 g (95%).

¹ H NMR (d ₆ -DMSO, 500 MHz, 100°C): δ = 6.51-6.59 (m, 9H), 6.70 (m _c , 3H), 6.81 (m _c , 3H), 6.90 (br m, 6H) , 7.09 (m _c , 3H), 8.16 (d, 3H), 8.42 (d, 3H), 8.66 (dd, 3H).

Photoluminescence (2% in PMMA film):

λ _max =474 nm, CIE: (0.16;0.24), QY=93%

Example 2:

2-N-isopropylamino-3-chloropyrazine

A solution of 2-amino-3-chloropyrazine (2.7 g, 20.8 mmol) in dichloromethane (54 mL) and glacial acetic acid (27 mL) at 1°C with acetone (4.1 mL, 56.3 mmol) and borane-dimethyl sulfide complex ( 2.2 ml, 22.9 mmol) and stir overnight at room temperature. A second fraction (0.8 mL) of the borane-dimethyl sulfide complex is added at 1° C. and the mixture is stirred again overnight at room temperature. Finally, the tertiary fraction of borane-dimethyl sulfide complex (0.6 mL) and acetone (1.0 mL) are added at 1° C. and the mixture is stirred again overnight at room temperature. The solution is adjusted to pH 9 with aqueous ammonia (38 mL) at <10°C. The organic phase is removed and washed with water. After drying over sodium sulfate, the solution is concentrated and left to stand overnight. The formed precipitate is filtered off and washed with a small amount of dichloromethane. The combined filtrates are concentrated to dryness and dried at 40° C. in a vacuum drying cabinet. Yield: 2.3 g (64%).

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 1.22 (d, 6H), 4.16 (sept, 1H), 5.00 (br s, 1H), 7.46 (d, 1H), 7.88 (d, 1H) .

2-N-phenylamino-3-N-isopropylaminopyrazine

A mixture of 2-isopropylamino-3-chloropyrazine (5.1 g, 30 mmol) in aniline (9 mL, 99 mmol) is stirred overnight at 125°C. After cooling to 90° C., water is added. Dichloromethane is added at room temperature and the solution is adjusted to pH 9 with aqueous ammonia. The organic phase is removed, washed with water, dried over sodium sulfate and concentrated to dryness. The crude product is purified by column chromatography (silica gel, toluene/ethyl acetate 8:1). Yield: 4.6 g (68%).

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 1.23 (d, 6H), 4.15 (br s, 1H), 4.18 (sept, 1H), 5.95 (br s, 1H), 6.96-7.02 (m , 1H), 7.23-7.32 (m, 4H), 7.45 (d, 1H), 7.64 (d, 1H).

1-phenyl-3-isopropylpyrazinoimidazolium iodide

*

*

*

A mixture of 2-N-phenylamino-3-N-isopropylaminopyrazine (1.2 g, 5.2 mmol) in triethyl orthoformate (6 mL) was mixed with ammonium iodide (0.8 g, 5.7 mmol) and 80 overnight Stir at °C. After cooling to room temperature, the solid is filtered off with suction, washed with a small amount of ethanol and petroleum ether and dried at 50° C. in a vacuum drying cabinet. Yield: 1.1 g (60%).

¹ H NMR (d ₆ -DMSO, 500 MHz): δ = 1.76 (d, 6H), 5.23 (sept, 1H), 7.67-7.84 (m, 3H), 7.91-8.02 (m, 2H), 8.98 (d , 1H), 9.02 (d, 1H), 10.72 (s, 1H).

Complex mer-Em2:

*

*

*

A suspension of 1-phenyl-3-isopropylpyrazinoimidazolium iodide (166 mg, 0.48 mmol) in dioxane (8 ml) was prepared with molecular sieve (1 g) and silver oxide (I) (89 mg, 0.38 mmol). Mix and stir overnight at room temperature. Chloro(1,5-cyclooctadiene)-iridium(I) dimer (30 mg, 0.05 mmol) is added and the mixture is stirred at reflux overnight. After cooling to room temperature, the residue is filtered off with suction and washed with dichloromethane. The combined filtrates are concentrated to dryness, and the residue is purified by column chromatography (silica gel, toluene/ethyl acetate 4:1). Yield: 65 mg (80%).

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 0.72 (d, 3H), 0.77 (d, 3H), 0.87 (d, 3H), 1.36 (d, 3H), 1.45 (d, 3H), 1.77 (d, 3H), 4.37-4.53 (m, 2H), 4.65 (sept, 1H), 6.57 (dd, 1H), 6.65-6.74 (m, 3H), 6.94-7.24 (m, 5H), 8.17 ( d, 1H), 8.22 (d, 1H), 8.23 (d, 1H), 8.28 (d, 1H), 8.30 (d, 1H), 8.33 (d, 1H), 8.60 (dd, 1H), 8.63 (dd , 1H), 8.67 (dd, 1H).

Photoluminescence (2% in PMMA film):

λ _max =516 nm, CIE: (0.29;0.51), QY=66%

Complex fac-Em2:

A solution of mer-Em2 (720 mg, 0.80 mmol) in butanone (70 mL) was mixed with hydrochloric acid (1 N, 10 mL) and stirred under reflux overnight. The solution is concentrated, diluted with dichloromethane and washed with water. The organic phase is dried over sodium sulfate and concentrated to anhydrous state. The residue is purified by column chromatography (silica gel, toluene/ethyl acetate 10:1). Yield: 327 mg (45%).

¹ H NMR (CD ₂ Cl ₂ , 500 MHz, 100°C): δ = 0.86 (d, 9H), 1.70 (d, 9H), 4.54 (sept, 3H), 6.36 (d, 3H), 6.64 (dd, 3H), 7.02 (dd, 3H), 8.17 (d, 3H), 8.28 (d, 3H), 8.60 (d, 3H).

Photoluminescence (2% in PMMA film):

λ _max =474 nm, CIE: (0.16;0.27), QY=90%

Example 3:

2-N-phenylamino-3-aminopyrazine

A mixture of 2-amino-3-chloropyrazine (5.0 g, 39 mmol) in aniline (12 mL, 131 mmol) is stirred twice at 100° C. overnight. After cooling to room temperature, the mixture is diluted with dichloromethane (80 mL), stirred overnight and filtered. The solid was dissolved in dichloromethane (200 mL) and washed with saturated aqueous sodium hydrogen carbonate solution. The organic phase is concentrated to dryness, and the residue is dried at 70° C. in a vacuum drying cabinet. Yield: 5.3 g (74%).

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 4.43 (br s, 2H), 6.23 (br s, 1H), 7.03 (dd, 1H), 7.32 (dd, 2H), 7.40 (d, 2H) ), 7.59 (d, 1H), 7.62 (d, 1H).

1-phenylpyrazinoimidazole

A solution of 2-N-phenylamino-3-aminopyrazine (5.3 g, 29 mmol) in formic acid (160 ml) was stirred under reflux overnight, then concentrated to anhydrous state. The residue was taken in dichloromethane (100 mL) and washed with saturated aqueous sodium hydrogen carbonate solution. The aqueous phase was extracted with dichloromethane (2 x 50 mL), and the combined organic phases were concentrated to anhydrous state. Yield: 5.6 g (98%).

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 7.49 (dd, 1H), 7.60 (dd, 2H), 7.76 (d, 2H), 8.39 (d, 1H), 8.56 (d, 1H), 8.63 (s, 1 H).

1-phenyl-3-methylpyrazinoimidazolium tetrafluoroborate

A solution of 1-phenylpyrazinoimidazole (5.5 g, 28 mmol) in dichloromethane (400 mL) is mixed with trimethyloxonium tetrafluoroborate (4.2 g, 28 mmol) and stirred under reflux overnight. The precipitate is filtered off and dried. The product is obtained with a purity of about 75%. Yield: 7.3 g (87%).

¹ H NMR (d ₆ -DMSO, 500 MHz): δ = 4.19 (s, 3H), 7.71 (dd, 1H), 7.78 (dd, 2H), 7.91 (d, 2H), 8.99 (d, 1H), 9.04 (d, 1H), 10.70 (s, 1H).

1-phenyl-3-methylpyrazinoimidazolium iodide

A solution of 1-phenyl-3-methylpyrazinoimidazolium tetrafluoroborate (7.3 g, 25 mmol, purity: 75%) in acetonitrile (70 mL) was tetrabutylammonium iodide in acetonitrile (67 mL) 27.2 g, 74 mmol) and stirred overnight at room temperature. The precipitate is filtered off with suction and washed with petroleum ether. The product is obtained with a purity of about 75%. Yield: 6.0 g (72%).

¹ H NMR (d ₆ -DMSO, 500 MHz): δ = 4.19 (s, 3H), 7.71 (dd, 1H), 7.78 (dd, 2H), 7.92 (d, 2H), 8.99 (d, 1H), 9.04 (d, 1H), 10.72 (s, 1H).

Complex mer-Em3:

A suspension of 1-phenyl-3-methylpyrazinoimidazolium iodide (1.0 g, 2.3 mmol) in dioxane (60 mL) is mixed with molecular sieve (8.4 g) and silver oxide (I) (0.4 g, 1.8 mmol) And stirred overnight at room temperature. A solution of chloro(1,5-cyclooctadiene)iridium(I) dimer (153 mg, 0.2 mmol) in o-xylene (83 ml) is added and the mixture is stirred under reflux overnight. After cooling to room temperature, the residue is filtered off with suction and washed with acetone. The combined filtrates are concentrated to dryness, and the residue is purified by column chromatography (silica gel, dichloromethane). Yield: 44 mg (13%).

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 3.22 (s, 3H), 3.36 (s, 3H), 3.37 (s, 3H), 6.60 (dd, 1H), 6.70-6.78 (m, 3H ), 6.87 (dd, 1H), 6.92 (dd, 1H), 7.01-7.10 (m, 3H), 8.22 (d, 1H), 8.27 (d, 1H), 8.28 (d, 1H), 8.32 (d, 1H), 8.35 (d, 1H), 8.36 (d, 1H), 8.60 (dd, 1H), 8.67 (dd, 1H), 8.68 (dd, 1H).

Photoluminescence (2% in PMMA film):

λ _max =515 nm, CIE: (0.29;0.50), QY=74%

Complex fac-Em3:

A solution of mer-Em3 in butanone is mixed with hydrochloric acid and stirred under reflux overnight. The solution is concentrated, diluted with dichloromethane and washed with water. The organic phase is dried over sodium sulfate and concentrated to anhydrous state. The residue is purified by column chromatography.

Example 4

μ-dichloro dimer D1:

N-(2,6-diisopropylphenyl)-2-phenylimidazole is synthesized similarly to Example 14 of WO2006/121811.

3.50 g (11.5 mmol) of 1-(2,6-diisopropylphenyl)-2-phenyl-1H-imidazole was initially charged with 200 mL of 2-ethoxyethanol/water (ratio 3/1), Mix with 1.84 g (5.2 mmol) of iridium(III) chloride trihydrate. The reaction mixture is heated to reflux for 18 hours. After cooling, 50 ml of distilled water is added. The precipitate is filtered off, washed with distilled water and dried. This produces 3.50 g (80%) of μ-dichloro dimer D1 as a yellow powder.

¹ H NMR (CD ₂ Cl ₂ , 400 MHz):

δ = 0.95 (d, 12H), 1.18 (d, 12H), 1.27 (d, 12H), 1.34 (d, 12H), 2.80-2.91 (m, 8H), 6.08 (d, 4H), 6.24 (d, 4H), 6.39 (pt, 4H), 6.53 (pt, 4H), 6.97 (d, 4H), 7.39-7.45 (m, 8H), 7.59 (t, 4H), 7.67 (d, 4H).

Complex mer-Em7:

A suspension of 1,3-diphenylpyrazinoimidazolium iodide (0.5 g, 1.25 mmol) in anhydrous dioxane (100 ml) is mixed with molecular sieve (10 g) and silver oxide (I) (0.19 g, 0.81 mmol) And stirred overnight at room temperature. Then, a solution of chloro dimer D1 (0.52 g, 0.31 mmol) in dioxane (74 ml) is added dropwise. Thereafter, the mixture was stirred under reflux for 1 hour. The reaction mixture is cooled and filtered. The solvent is removed from the filtrate under reduced pressure, washed with methanol, and purified by column chromatography (silica gel, eluent cyclohexane/acetone=1/0.25). This gives 0.40 g of mer-Em7 as an orange powder (63%).

¹ H NMR (CD ₂ Cl ₂ , 500 MHz):

δ = 0.89 (d, 3H), 0.90 (d, 6H), 0.92 (d, 3H), 1.09 (d, 3H), 1.16 (d, 3H), 1.21 (d, 3H), 1.24 (d, 3H) , 2.13 (sept, 1H), 2.66 (m, 2H), 2.73 (sept, 1H), 6.08-6.23 (m, 5H), 6.45-6.48 (m, 3H), 6.66 (d, 1H), 6.70-6.76 (m, 3H), 6.85-6.92 (m, 2H), 6.98 (m, 4H), 7.08-7.13 (m, 2H), 7.31 (t, 2H), 7.35 (d, 1H), 7.39 (d, 1H) ), 7.50 (t, 1H), 7.55 (t, 1H), 8.21 (d, 1H), 8.41 (d, 1H), 8.80 (d, 1H).

Photoluminescence (2% in PMMA film):

λ _max =565 nm, CIE: (0.44;0.49)

Complex fac-Em7:

The complex fac-Em7 (isomer for mer-Em7) was prepared by converting a solution of mer-Em7 in 3-methoxypropionitrile to a black light blue lamp (Osram, L18W/73, λ _max =370-380 nm). After irradiation, it is obtained by purification by column chromatography.

Example 5:

Complex K1:

5.00 g (14.0 mmol) of benzimidazolium salt S1 is suspended in 80 ml of anhydrous toluene and cooled to -8°C. Then 28 ml of potassium bis(trimethylsilyl)amide (KHMDS, 0.5M in toluene, 14.0 mmol) is added within 10 minutes. After the mixture was stirred at room temperature for 1 hour, a solution of 4.70 g (7.0 mmol) of [(μ-Cl)Ir(η ⁴ -1,5-COD)] ₂ in 120 ml toluene within 15 minutes at -78°C. Drops on The reaction mixture was stirred at room temperature for 1.5 hours and then heated to reflux for 19 hours. After cooling, the precipitate is filtered off and washed with toluene. The combined toluene phases are concentrated to dryness and purified by column chromatography (silica gel, eluent methylene chloride). This produces 5.8 g (68%) of K1 as a yellow powder.

*

* ¹ H NMR (CD ₂ Cl ₂ , 500 MHz):

δ = 1.17 (m, 2H), 1.34 (m, 4H), 1.61 (m, 2H), 2.43 (m, 2H), 4.31 (m, 2H), 7.18 (m, 2H), 7.25 (m, 2H) , 7.51 (m, 6H), 7.96 (m, 4H).

Complex Em8:

A suspension of 1,3-diphenylpyrazinoimidazolium iodide (3.17 g, 7.92 mmol) in anhydrous 1,4-dioxane (140 mL) was molecular sieve (15 g) and silver oxide (I) (1.48 g, 6.34) mmol) and stirred overnight at room temperature. Then, a solution of complex K1 (1.60 g, 2.64 mmol) in anhydrous o-xylene (200 ml) is added dropwise. Thereafter, the mixture was stirred under reflux for 24 hours. The reaction mixture is cooled and filtered. The solvent was removed from the filtrate under reduced pressure, and purified by column chromatography (silica gel, eluent ethyl acetate/cyclohexane=1/2). This gives 0.80 g of Em8 (30%).

¹ H NMR (CD ₂ Cl ₂ , 500 MHz):

δ = 6.20-7.40 (very flat wide signal, 8H), 6.26 (d, 1H), 6.36-6.42 (m, 3H), 6.59 (d, 1H), 6.66 (t, 2H), 6.76-6.85 (m , 6H), 7.06-7.17 (m, 4H), 7.29 (t, 1H), 7.33 (t, 1H), 8.01 (m, 2H), 8.04 (d, 1H), 8.18 (d, 1H), 8.27 ( d, 1H), 8.31 (d, 1H), 8.70 (d, 1H), 8.77 (d, 1H).

Photoluminescence (2% in PMMA film):

λ _max =480 nm, CIE: (0.17; 0.31)

Example 6:

Complex D2:

4.29 g (18.5 mmol) of silver oxide was suspended in 9.47 g (33.1 mmol) of imidazolium iodide and 3.56 g (10.1 mmol) of iridium trichloride in 350 ml of 2-ethoxyethanol and at 120° C. in the dark. Stir for 15 hours. Then, the solvent was removed under reduced pressure, and the residue was extracted with methylene chloride. The extract is concentrated to 1/4 of its volume and mixed with methanol. The precipitated solid is filtered off and dried. This gives 1.7 g of complex D2 (31%).

¹ H NMR (CD ₂ Cl ₂ , 500 MHz):

δ = 7.59 (d, 4H), 7.17 (d, 4H), 6.99 (d, 4H), 6.73 (pt, 4H), 6.45 (pt, 4H), 6.09 (d, 4H), 3.91 (s, 12H) .

Complex Em9:

A suspension of 1,3-diphenylpyrazinoimidazolium iodide (0.59 g, 1.48 mmol) in anhydrous 1,4-dioxane (35 ml) was obtained through molecular sieve (5 g) and silver oxide (I) (0.28 g, 1.18). mmol) and stirred overnight at room temperature. Then, a suspension of complex D2 (0.40 g, 0.37 mmol) in anhydrous o-xylene (50 ml) is added. Thereafter, the mixture was stirred under reflux for 3.5 hours. The reaction mixture is cooled and filtered. The solvent was removed from the filtrate under reduced pressure, and purified by column chromatography (silica gel, eluent dichloromethane).

This is a mixture of each of the two different isomers of Em9, 0.11 g (20%, orange powder, R _F =0.39, 20/80 isomer mixture) of fraction 1 and 0.23 g (40%, yellow powder, R _F =0.31 , 40/60 isomer mixture).

Fraction 1:

MS (Maldi):

m/e=779 (M+H ⁺ )

Photoluminescence (2% in PMMA film):

λ _max =547 nm, CIE: (0.40;0.54)

Fraction 2:

MS (Maldi):

m/e=779 (M+H ⁺ )

Photoluminescence (2% in PMMA film):

λ _max =526 nm, CIE: (0.33;0.55)

Example 7:

Complex K2:

3.10 g (9.41 mmol) of 5-methoxy-1,3,4-triphenyl-4,5-dihydro-1H-[1,2,4]-triazole was reduced to 90°C under reduced pressure (10 ^-3 mbar ) For 16 hours. After cooling, the residue is taken in 120 ml anhydrous toluene and mixed with a solution of 1.38 g (2.03 mmol) μ-chloro(1,5-cyclooctadiene)iridium(I) dimer in 120 ml anhydrous toluene. . The reaction mixture is gradually heated to 50° C. and stirred at this temperature for 1 hour. After cooling, the orange-red precipitate is filtered off, washed with toluene and dried. This produces 2.68 g of K2 (70%).

¹ H NMR (CD ₂ Cl ₂ , 500 MHz):

δ = 1.19 (m, 2H), 1.29 (m, 2H), 2.14 (m, 2H), 2.26 (m, 2H), 2.77 (m, 2H), 4.95 (m, 2H), 7.25-7.44 (m, 26H), 7.82 (d, 4H).

*

*

* Complex Em10:

A suspension of 0.5 g (1.25 mmol) of 1,3-diphenylpyrazinoimidazolium iodide in anhydrous dioxane (40 mL) was mixed with 10 g of molecular sieve and 0.22 g (0.95 mmol) of silver oxide (I). Stir overnight at room temperature. Then, 0.94 g (1.01 mmol) of complex K2 is added in portions. The reaction mixture is heated under reflux overnight. After cooling, the precipitate is filtered. The filtrate is concentrated to dryness, purified by column chromatography (silica gel, eluent: cyclohexane/acetone), and washed with a small amount of methanol. This produces 0.21 g of emitter Em10 (20%).

Example 8:

Complex K3:

10.4 g (27.6 mmol) of 3-dibenzofuran-4-yl-1-methyl-3H-imidazol-1-ium in 10.4 g (27.6 mmol) of anhydrous toluene are gradually added to 55.3 mL of potassium bis(trimethylsilyl) at room temperature. Mix with amide solution (KHMDS, 0.5M in toluene, 27.6 mmol) and stir for 1 hour. Then, a solution of 4.68 g (6.9 mmol) of μ-chloro(1,5-cyclooctadiene)iridium(I) dimer in 230 ml anhydrous toluene is added dropwise. The reaction mixture is heated to reflux overnight. After cooling, the precipitate is filtered, washed with a small amount of water and extracted with ethanol. The extract was dried to give 6.8 g of K3 (53%) as an orange-red powder.

¹ H NMR (CD ₂ Cl ₂ , 500 MHz):

δ = 1.49 (m, 2H), 1.84 (m, 2H), 2.02 (m, 2H), 2.16 (m, 2H), 3.29 (m, 2H), 4.85 (m, 2H), 6.53 (s, 2H) , 6.93 (s, 2H), 7.37 (d, 2H), 7.47-7.62 (m, 8H), 8.14 (d, 2H), 8.25 (d, 2H).

Complex Em11:

Em11 is synthesized similarly to Em10.

Example 9:

Manufacturing OLED-Comparison of various emitters

The ITO substrate used as an anode in a commercially available LCD-producing detergents ^[® Deconex 20NS and 25ORGAN-ACID ^® neutralizing agent] to a first washed, then, acetone / isopropanol mixture is washed in an ultrasonic bath. To remove possible organic residues, the substrate is exposed to a continuous ozone flow in an ozone oven for an additional 25 minutes. This treatment also improves the hole injection properties of ITO. Then, the hole injection layer AJ20-1000 from Flexcore is spun from the solution.

Thereafter, the organic material specified below is applied to the substrate cleaned by vapor deposition at a rate of about 0.5-5 nm/min at about 10 ^-7 -10 ^-9 mbar. The hole conductor and exciton blocker applied to the substrate are Ir(DPBIC) ₃ with a thickness of 45 nm, and the first 35 nm is doped with MoO _x (10% for diodes with CEm and fac-Em2, and fac-Em1 In the case of diodes having 50%), the conductivity is improved.

(For the production of Ir(DPBIC) ₃ , see Ir complex 7 in application PCT/EP/04/09269).

Thereafter, a mixture of emitters (10% for CEm, 20% for fac-Em1 and fac-Em2) and compound Ma1 (90% and 80% respectively) was applied to the thickness of 40 nm by vapor deposition, the latter The compound acts as a matrix material. Subsequently, the material Ma1 (for fac-Em1) is applied by evaporation to a thickness of 5 nm or Ma5 (5 nm for Em1, 10 nm for fac-Em2) is applied as exciton and hole blocker.

The synthesis of Ma1 is described in WO2010079051, the synthesis of Ma5 is described in WO2009003898.

The emitter used for comparison in the prior art is CEm:

Then, Liq and BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) as electron transporters (50:50 for fac-Em1, 0 for CEm and fac-Em2) :100) by vapor deposition to a thickness of 40 nm for fac-Em1, a thickness of 30 nm for CEm and fac-Em2, and a 1.0 nm-thick liq layer for fac-Em1, CEm and fac- For Em2 it is applied as a 0.7 nm LiF layer and finally a 100 nm-thick Al electrode. All ingredients are glued to the glass lid in an inert nitrogen atmosphere.

To characterize the OLED, electroluminescence spectra are recorded at different currents and voltages. Moreover, the current-voltage characteristic is measured in combination with the emitted light output. The light output can be converted to metering parameters by correction using a photometer. The lifetime t _1/2 of a diode is defined as the time measured when the luminance is reduced to 50% of its initial value. The life measurement is carried out with a constant current.

For the various emitters in the OLED structures described above, the following electro-optical data is obtained:

Example 10:

Influence of matrix material (Part 1)

* The light emitting layer having the structure described in Example 9 was changed. The doping level of MoO _x is 50%. A mixture of emitter fac-Em1 (20%) and various matrix materials (80%) is applied to a thickness of 20 nm by vapor deposition. The hole/exciton blocker (5 nm) used in each case is a matrix material. The electron conductor used is a mixture of 50 nm thick BCP and liq (50:50). The electron injector used is liq (1 nm). In addition to Ma1, the following materials are used:

The synthesis of Ma2, Ma3 and Ma4 is described in WO2010079051.

Ma6 can be produced by methods known to those skilled in the art. 9-(8-Bromo-dibenzofuran-2-yl)-9H-carbazole (see WO2010079051) is n-BuLi and 2-isopropoxy-4,4,5,5-tetramethyl-1 in THF. 9-[8-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)dibenzofuran-2 by reacting with ,3,2-dioxaborolan -Yl]-9H-carbazole (similar to step 1 in Example 18), followed by reaction with 1,3-diiodobenzene by Suzuki coupling known to those skilled in the art to obtain Ma6.

The synthesis of Ma7 is described in Example 19.

For the various matrix materials in the OLED structure described above, the following electro-optical data (normalized to the value of Ma5) are obtained:

*

Example 10a:

The light emitting layer having the structure described in Example 10 was changed. The light-emitting layer used was a mixture of fac-Em1 (30%) and matrix (see table below, 70%). The hole conductor layer used is a 40 nm Ir(DPBIC) ₃ layer, the first 35 nm of which is doped with ReO ₃ (5%). The hole/exciton blocker used is a 5 nm layer of Ma7. The electron conductor used is a mixture of liq and ETM1 (50:50, 40 nm). The electron injector used was KF with a thickness of 4 nm.

ETM1 is commercially available.

The synthesis of Ma8, Ma9 and Ma10 is described in JP2006083167.

For the various matrix materials in the OLED structure described above, the following electro-optical data (normalized to the value of Ma8) are obtained:

Example 10b

The diode with emitter Em8 is structured similarly to Example 10. The hole conductor layer has a thickness of 40 nm. Em8 is doped with Ma4 at a level of 30%. The electron conductor layer used was ETM1 with a thickness of 40 nm. The electron injector used was KF (2 nm).

The diode represents the color coordinates CIE 0.19, 0.37. At 300 cd/m 2, the voltage is 3.5 V and the luminous efficiency is 11 lm/W.

Example 10c

The diode is structured similarly to Example 10a for Ma7. The emitter used is Em8 instead of fac-Em1.

The diode represents the color coordinates CIE 0.17, 0.31.

Example 10d

The diode is structured similarly to Example 10a for Ma7. The emitter used is Em8 instead of fac-Em1. The matrix changes. For the various matrix materials in the OLED structure described above, the following electro-optical data (normalized to the value of Ma10) are obtained:

Example 10e

The diode is structured similarly to Example 10a. The emitter used is fac-Em12 with a dopant concentration of 20% in matrix Ma4 (80%) instead of fac-Em1. The hole/exciton blocker is used with a thickness of 10 nm.

The diode represents the color coordinates CIE 0.19, 0.36. At 300 cd/m2, the voltage is 4.0 V and the external quantum efficiency is 13%.

Example 10f

The diode is structured similarly to Example 10a. The emitter used is fac-Em14 with a dopant concentration of 20% in matrix Ma4 (80%) instead of fac-Em1. Hole/exciton blockers are used with a thickness of 10 nm.

The diode represents the color coordinates CIE 0.20, 0.27.

*

* Example 10g

The diode is structured similarly to Example 10a. The hole conductor and exciton blocker applied to the substrate is Ir(DPBIC) ₃ with a thickness of 45 nm, and the first 35 nm is doped with MoO _x (10%) to improve conductivity. The hole/exciton blocker is applied with a thickness of 10 nm. The emitter used is fac-Em13 with a dopant concentration of 20% in matrix Ma4 (80%) instead of fac-Em1.

The diode represents the color coordinates CIE 0.14, 0.22. At 300 cd/m 2, the voltage is 3.7 V.

Example 10h

The diode is structured similarly to Example 10g. The emitter used is fac-Em13 with a dopant concentration of 20% in matrix Ma7 (80%).

The diode represents the color coordinates CIE 0.14, 0.22. At 300 cd/m2, the voltage is 3.6 V and the external quantum efficiency is 16%.

Example 11:

Influence of matrix material (Part 2)

The light emitting layer having the structure described in Example 10 was changed. A mixture of emitter fac-Em1 (20%) and one or two matrix materials is applied to a thickness of 20 nm by vapor deposition. When two matrix materials are used, the two matrix materials are used in the same ratio. The hole/exciton blocker used in each case is Ma1.

The following electro-optical data is obtained:

Ma11 is commercially available.

Example 11a:

Structure as in Example 10a. The light emitting layer used is a mixture of Ir(DPBIC) ₃ (35%), fac-Em1 (30%) and matrix (35%, see table below). The hole/exciton blocker used in each case is a matrix material.

The synthesis of Ma13 is described in WO2009008100.

The synthesis of Ma12 is described in Example 20, and the synthesis of Ma14 is described in Example 18.

For the various matrix materials in the OLED structure described above, the following electro-optical data (normalized to the value of Ma9) are obtained:

Example 11b

*Structure as in Example 10a. The light emitting layer used is a mixture of Ir(DPBIC) ₃ (45%), Em8 (10%) and matrix (45%, see table below).

For the various matrix materials in the OLED structures described above, the following electro-optical data (normalized to the value of Ma9) were obtained:

Example 11c

Structure as in Example 11a. The hole conductor and exciton blocker applied to the substrate are Ir(DPBIC) ₃ having a thickness of 40 nm, and the first 35 nm is doped with MoO _x (50%) to improve conductivity. The light emitting layer used was a mixture of Ir(DPBIC) ₃ (40%), fac-Em12 (20%) and Ma4 (40%). The electron conductor layer used is a mixture of 40 nm thick ETM1:Liq (75:25). The electron injector used was KF (2 nm).

The diode represents the color coordinates CIE 0.20, 0.40. At 300 cd/m 2, the voltage is 3.0 V and the external quantum efficiency is 13%.

Example 11d

Structure as in Example 11b. The light emitting layer used is a mixture of Ir(DPBIC) ₃ (45%), fac-Em14 (10%) and Ma4 (45%).

The diode represents the color coordinates CIE 0.26, 0.39. At 300 cd/m 2, the voltage is 3.0 V.

Example 11e

The diode is structured similarly to Example 11a. The hole conductor and exciton blocker applied to the substrate is Ir(DPBIC) ₃ with a thickness of 45 nm, and the first 35 nm is doped with MoO _x (10%) to improve conductivity. The hole/exciton blocker used was Ma7 (5 nm). The light emitting layer used is a mixture of Ir(DPBIC) ₃ (40%), fac-Em13 (30%) and Ma4 (30%).

Diodes show color coordinates CIE 0.15, 0.26. At 300 cd/m 2, the voltage is 3.4 V.

Example 11f

The diode is structured similarly to Example 11a. The hole conductor and exciton blocker applied to the substrate is Ir(DPBIC) ₃ with a thickness of 45 nm, and the first 35 nm is doped with MoO _x (10%) to improve conductivity. The hole/exciton blocker is applied with a thickness of 10 nm. The light emitting layer used is a mixture of Ir(DPBIC) ₃ (40%), fac-Em13 (30%) and Ma7 (30%).

The diode represents the color coordinates CIE 0.14, 0.25. At 300 cd/m 2, the external quantum efficiency is 15%.

Example 11 g

The diode is structured similarly to Example 11a. The light emitting layer used is a mixture of Ir(DPBIC) ₃ (40%), fac-Em13 (30%) and Ma15 (30%).

The diode represents the color coordinates CIE 0.14, 0.23. At 300 cd/m 2, the external quantum efficiency is 17%.

The synthesis of Ma15 is described in WO2010079051.

Example 11h

The diode is structured similarly to Example 11a for Ma12. Instead of Ma12, Ma16 (see synthesis at JP2009267255) is used.

The diode shows the color coordinates CIE 0.18, 0.34, and the voltage is 3.3 V at 300 cd/m 2.

Example 11i:

White light diode

Using ITO as the anode substrate is washed in an ultrasonic bath after washing in a commercially available LCD-producing detergents (Deconex 20NS ^®, and 25ORGAN-ACID ^® neutralizing agent), acetone / isopropanol mixture. To remove possible organic residues, the substrate is exposed to a continuous ozone flow in an ozone oven for an additional 25 minutes. This treatment also improves the hole injection properties of ITO. Then, the hole injection layer AJ20-1000 from FlexCore is spun from the solution.

Layered white light (Example 11ia):

After the hole injection layer, the organic material specified below is applied to the cleaned substrate at a rate of about 0.5-5 nm/min at about 10 ^-7 -10 ^-9 mbar. The hole conductor and exciton blocker applied to the substrate are Ir(DPBC) _{3 having} a thickness of 20 nm, and first, doping 10 nm with 10% MoO _x to improve conductivity.

Thereafter, a mixture of 10% emitter Red1 and 90% of compound Ma7 is applied by vapor deposition to a thickness of 6 nm, the latter compound acting as a matrix material. In a further structure 11ib, the aforementioned mixture is replaced with a mixture of 10% emitter Red1, 60% matrix Ma7 and 30% matrix Ir(DPBIC) ₃ .

Thereafter, a mixture of materials fac-Em1, Ma7 and Ir(DPBIC) ₃ is applied by vapor deposition to a layer thickness of 30 nm. The mixing ratio is 40% emitter fac-Em1, 30% matrix Ma7 and 30% secondary matrix Ir(DPBIC) ₃ . Subsequently, the material Ma7 is applied as a hole and exciton blocker with a layer thickness of 10 nm. The subsequent electron conductor layer used is a Cs ₂ CO ₃ -doped BCP layer with a 30 nm layer thickness. An aluminum cathode with a thickness of 100 nm produces a diode.

All parts are glued to the glass lid in an inert nitrogen atmosphere.

Laminated white light (Example 11ic):

After the hole injection layer, the organic material specified below is applied to the clean substrate by vapor deposition at a rate of about 0.5-5 nm/min at about 10 ^-7 -10 ^-9 mbar. The hole conductor and exciton blocker applied to the substrate is Ir(DPBIC) _{3 with} a thickness of 20 nm, and the conductivity is improved by doping the first 10 nm with 10% MoO _x .

Thereafter, a mixture of materials fac-Em1, Ma1 and Ir(DPBIC) ₃ is applied to the thickness of 20 nm by vapor deposition. The mixing ratio is 30% emitter fac-Em1, 40% matrix Ma1 and 30% matrix Ir(DPBIC) ₃ . Thereafter, a pure layer of 10 nm Ma1 is applied as exciton and hole blocker.

A further combination of 20 nm BCP doped with Cs ₂ CO ₃ and 60 nm Ir(DPBIC) ₃ doped with 10% MoO _x (at an additional structure 11id with 90 nm Ir(DPBIC) ₃ ) It acts as a charge generating layer.

Thereafter, Ir(DPBIC) ₃ as a hole conductor and an exciton blocker is applied to a 10 nm thick substrate. Thereafter, a mixture of materials Red1, NPD and Ma17 is applied to a thickness of 20 nm. The mixing ratio is 10% emitter Red1, 40% matrix NPD and 50% secondary matrix Ma17.

Thereafter, a pure layer of 10 nm BAlq is applied as exciton and hole blocker.

The subsequent electron conductor layer used is a Cs ₂ CO ₃ -doped BCP layer with a layer thickness of 50 nm. An aluminum cathode with a thickness of 100 nm produces a diode.

All parts are glued to the glass lid in an inert nitrogen atmosphere.

To characterize the OLED, electroluminescence spectra are recorded at different currents and voltages. In addition, the current-voltage characteristic is measured in combination with the emitted light output. The light output can be converted to metering parameters by calibration using a photometer.

For two working examples of white light OLEDs, the following electro-optical data are obtained:

Example 11j: Liquid-treated light emitting layer

After washing with a commercially available detergent (Deconex 20NS ^®, and 25ORGANO-ACID ^® neutralizing agent) for producing first LCD substrate with the ITO as the anode, and in acetone / isopropanol mixture it is washed in an ultrasonic bath. To remove possible organic residues, the substrate is exposed to a continuous ozone flow in an ozone oven for an additional 25 minutes. This treatment also improves the hole injection properties of ITO. Then, the hole injection layer AJ20-1000 from FlexCore is spun from the solution.

Thereafter, a hole conductor and an exciton blocker Ir (DPBIC) ₃ are applied from the liquid phase. To this end, a solution of Ir(DPBIC) ₃ in THF is spun at a concentration of 10 mg/ml at 5,000 revolutions per minute (rpm) (spin-coating).

Thereafter, a light emitting layer consisting of emitter fac-Em1 and host Ma7 is likewise applied from the liquid phase. To this end, the solutions of fac-Em1 and Ma7 in methylene chloride are spun at a concentration of 10 mg/ml at a rate of 5,000 rpm. The weight ratio of solids between the emitter and host is 30:70.

Thereafter, the organic material mentioned below is applied to the layer already present at about 10 ^-7 -10 ^-9 mbar at a rate of about 0.5-5 nm/min under reduced pressure by vapor deposition.

First, 10 nm of pure Ma7 is applied as an exciton blocker by vapor deposition. Thereafter, the electron conductor ETM1:Liq (50:50) is applied to the layer thickness of 20 nm by vapor deposition.

Thereafter, 1 nm of CsF follows the electron injector, and 100 nm of aluminum is applied as the cathode. The parts are glued to the glass lid in an inert nitrogen atmosphere and represent the color coordinates CIE x=0.20, y=0.35.

Example 12:

Effects of the mixed electron conductor layer

For fac-Em1, the electron transport layer having the structure described in Example 9 was changed. The following electro-optical data is obtained:

Example 13:

Emitter Em12:

2,3-bis-(N-4'-methylphenylamino)pyrazine

A mixture of 2,3-dichloropyrazine (13.4 g, 90 mmol) in p-toluidine (21.2 g, 198 mmol) is stirred at 110° C. overnight. After cooling to room temperature, the mixture was taken in dichloromethane (200 mL) and extracted by shaking with a 25% sodium hydroxide solution. The combined organic phase is dried over sodium sulfate and concentrated to anhydrous state. The residue is stirred with petroleum ether, filtered off with suction and washed with cyclohexane. Yield: 15.7 g (60%).

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 2.30 (s, 6H), 6.24 (br s, 2H), 7.10 (d, 4H), 7.18 (d, 4H), 7.67 (s, 2H) .

2-ethoxy-1,3-bis(4'-methylphenyl)pyrazinoimidazoline

A mixture of 2,3-bis(N-4'-methylphenylamino)pyrazine (4.0 g, 14 mmol) in triethyl orthoformate (65 mL) is stirred at 75°C overnight. After cooling to room temperature, the mixture is filtered and the filtrate is concentrated to dryness. The residue is recrystallized from methyl tert-butyl ether. Yield: 3.3 g (70%).

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 0.99 (t, 3H), 2.32 (s, 6H), 3.24 (q, 2H), 7.16 (s, 1H), 7.21 (d, 4H), 7.42 (s, 2H), 7.85 (d, 4H).

Complex fac-Em12:

A solution of 2-ethoxy-1,3-bis(4'-methylphenyl)pyrazinoimidazoline (3.5 g, 10 mmol) in o-xylene (60 ml) was prepared with 3Å molecular sieve (6 g) and chloro (1 ,5-cyclooctadiene) iridium (I) dimer (672 mg, 1.0 mmol). The mixture is stirred at 115°C overnight. After cooling to 80° C., the residue is filtered off with suction and washed with dichloromethane. The combined filtrate was concentrated to dryness, and the residue was washed with warm isopropanol. The crude product is purified by column chromatography (silica gel, toluene→dichloromethane). Yield: 0.8 g (37%).

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 1.85 (s, 9H), 2.06 (s, 9H), 6.44 (s, 3H), 6.91 (d, 3H), 7.97 (d, 3H), 8.27 (d, 3H), 8.56 (d, 3H). The 12 protons of the non-cyclometallated tolyl ring are only identifiable as a very broad development at the aromatic site at room temperature due to the rotation of the aromatic system.

Photoluminescence (2% in PMMA film):

λ _max =485 nm, CIE: (0.18;0.36), QY=85%

Example 14:

Emitter Em13:

Pyrazine compound (a)

3,3,5,5-tetramethylcyclopentane-1,2-dione in ethanol (1.45 L) (for synthesis see T. Laitalainen, Finn. Chem. Lett. 1982, 10) (30.5 g, 188 mmol) and a mixture of ethylenediamine (15.9 mL, 235 mmol) was stirred under reflux overnight. After cooling to 45° C., manganese (IV) oxide (36.0 g, 414 mmol) and potassium hydroxide (11.6 g, 207 mmol) are added and the mixture is stirred under reflux for 5 hours. After cooling to 70° C., the mixture is filtered and the filtrate is neutralized with 10% hydrochloric acid at room temperature. The suspension is filtered and the filtrate is concentrated to dryness. The residue is column filtered with silica gel using dichloromethane. Yield: 22.7 g (69%).

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 1.33 (s, 12H), 1.98 (s, 2H), 8.30 (s, 2H).

Pyrazine compound (b)

A mixture of pyrazine compound (a) (18.1 g, 98 mmol) and water (750 mL) is mixed with potassium peroxomonosulfate (Oxone, 144 g, 234 mmol) and stirred at 50° C. overnight. The aqueous phase is extracted with dichloromethane, washed twice with water, dried over sodium sulfate and concentrated to anhydrous state. Yield: 17.0 g (84%).

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 1.51 (s, 12H), 1.97 (s, 2H), 7.78 (s, 2H).

Pyrazine compound (c)

A mixture of pyrazine compound (b) (18.3 g, 83 mmol) in phosphoryl chloride (325 mL) is stirred under reflux overnight. After cooling to room temperature, the solution is carefully added dropwise to a mixture of ice water (5 L) and dichloromethane (1.5 L). After neutralization with concentrated sodium hydroxide solution, the organic phase is removed, washed three times with water, dried over sodium sulfate and concentrated to dryness. This gives a mixture of product (about 80%) and monochlorination byproduct (about 20%), which is used without further workup. The pure product can be obtained by stirring in petroleum ether. Total yield: 19.2 g (94%).

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 1.29 (s, 12H), 1.99 (s, 2H).

Pyrazine compound (d)

A mixture of pyrazine compound (c) (5.5 g, 22 mmol) and aniline (24.6 mL, 270 mmol) in o-xylene (65 mL) is stirred at 150° C. overnight. After cooling to room temperature, the precipitate is filtered off with suction and washed with toluene. The combined filtrates are concentrated in anhydrous state in the presence of silica gel. The residue is filtered through silica gel using a mixture of cyclohexane and ethyl acetate, and the filtrate is concentrated to dryness. Yield: 6.6 g (81%).

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 1.28 (s, 12H), 1.95 (s, 2H), 6.25 (br s, 2H), 6.90-6.95 (m, 2H), 7.21-7.27 ( m, 8H).

Pyrazine compound (e)

A mixture of pyrazine compound (d) (0.50 g, 0.7 mmol) in triethyl orthoformate (3.5 mL) is mixed with ammonium iodide (0.31 g, 2.1 mmol) and stirred at 85° C. for 2 hours. After cooling to room temperature, the solid is filtered off with suction, washed with triethyl orthoformate, cold ethanol and n-heptane and dried at 65° C. in a vacuum drying cabinet. Yield: 0.16 g (46%).

¹ H NMR (d ₆ -DMSO, 500 MHz): δ = 1.41 (s, 12H), 2.19 (s, 2H), 7.74 (dd, 2H), 7.82 (dd, 4H), 8.01 (d, 4H), 10.98 (s, 1 H).

Complex fac-Em13:

A suspension of the pyrazine compound (e) (1.1 g, 2.1 mmol) in dioxane (60 ml) is mixed with 4 Å molecular sieve (11 g) and silver oxide (I) (0.5 g, 2.1 mmol) and stirred overnight at room temperature. . Then, a solution of chloro(1,5-cyclooctadiene)iridium(I) dimer (142 mg, 0.2 mmol) in o-xylene (75 ml) is added. The mixture was stirred at reflux overnight. After cooling to 80° C., the residue is filtered off with suction. The filtrate is concentrated on a rotary evaporator to a volume of about 60 ml and left overnight. The precipitate is filtered off, washed with toluene and n-hexane and dried at 85° C. in a vacuum drying cabinet. Yield: 0.3 g (57%).

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 1.15 (s, 9H), 1.35 (s, 9H), 1.46 (s, 9H), 1.59 (s, 9H), 2.11 (m _c , 6H) , 6.67 (d, 3H), 6.73 (dd, 3H), 6.79 (dd, 3H), 7.14 (dd, 3H), 8.86 (d, 3H). Twelve of the 15 protons of the non-cyclometalated phenyl ring are only identifiable as a very broad development at the aromatic site at room temperature due to the rotation of the aromatic system.

Photoluminescence (2% in PMMA film):

λ _max =474 nm, CIE: (0.14;0.24), QY=91%

Example 15:

Emitter Em14:

2,3-bis(N-4'-fluorophenylamino)pyrazine

A mixture of 2,3-dichloropyrazine (8.6 g, 58 mmol) and 4-fluoroaniline (66.3 g, 148 mmol) in o-xylene (100 mL) is stirred at 130° C. overnight and at 140° C. for 4 hours. . After cooling to room temperature, the mixture was concentrated to dryness, and the residue was taken up in dichloromethane (300 mL), water (100 mL) and ammonia (25% in water, 100 mL). The organic phase is removed, washed twice with water, dried over sodium sulfate and concentrated to dryness. The residue is stirred with petroleum ether, filtered off with suction and washed with methyl tert-butyl ether. Yield: 12.7 g (73%).

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 6.30 (br s, 2H), 7.03 (dd, 4H), 7.31 (dd, 4H), 7.72 (s, 2H).

2-ethoxy-1,3-bis(4'-fluorophenyl)pyrazinoimidazoline

A mixture of 2,3-bis(N-4'-fluorophenylamino)pyrazine (1.2 g, 4 mmol) in triethyl orthoformate (36 mL) was added with sodium sulfate (4.7 g) and 5 kV molecular sieve (4.7 g). Mix with and stir at 100° C. for 24 hours. After cooling to room temperature, the mixture is filtered through sodium sulfate and cotton wool and washed with methyl tert-butyl ether. The combined filtrates are concentrated to dryness. The residue is stirred with n-pentane and filtered off with suction. Yield: 0.6 g (42%).

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 1.01 (t, 3H), 3.26 (q, 2H), 7.08-7.16 (m, 5H), 7.46 (s, 2H), 7.98 (dd, 4H) ).

Complex fac-Em14:

A solution of 2-ethoxy-1,3-bis(4'-fluorophenyl)pyrazinoimidazoline (560 mg, 1.60 mmol) in o-xylene (60 ml) in sodium sulfate (4.7 g), 5 kV molecular sieve (4.7 g) and chloro(1,5-cyclooctadiene)iridium(I) dimer (107 mg, 0.16 mmol). The mixture is stirred at 110°C overnight. After addition of chloro(1,5-cyclooctadiene)iridium(I) dimer (107 mg, 0.16 mmol), the mixture was stirred at 110° C. for 5 hours. After cooling to 80° C., the residue is filtered off with suction and washed with dichloromethane. The combined filtrate was concentrated to anhydrous state, and the residue was purified by column chromatography (silica gel, chloroform→toluene). Yield: 133 mg (19%).

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 6.30 (dd, 3H), 6.84 (ddd, 3H), 8.09 (d, 3H), 8.36 (d, 3H), 8.71 (dd, 3H). The 12 protons of the non-cyclometalated 4-fluorophenyl ring are only identifiable as a very broad development at the aromatic site at room temperature due to the rotation of the aromatic system.

Photoluminescence (2% in PMMA film):

λ _max =458 nm, CIE: (0.17;0.17), QY=58%

Example 16:

*

*

* Emitter Em15

2-ethoxy-1,3-diphenyl-2,3-dihydro-1H-imidazo[4,5-b]pyrazine

15.30 g (58.3 mmol) of 2,3-bis(N-phenylamino)pyrazine, 68.00 g of sodium sulfate and 68.00 g of molecular sieve (4A) in 270 ml of triethyl orthoformate at 45 DEG C for 45 hours do. After cooling, the solid is filtered off and washed with methyl tert-butyl ether. The solvent is removed from the filtrate under reduced pressure. The resulting reddish-brown oil is repeatedly stirred with a small amount of n-heptane and dried again under reduced pressure. The residue is purified by column chromatography (silica gel, eluent: 4/1 cyclohexane/acetone). This produces 11.39 g (61%) of 2-ethoxy-1,3-diphenyl-2,3-dihydro-1H-imidazo[4,5-b]pyrazine.

¹ H NMR (DMSO-D ₆ , 500 MHz): δ = 0.88 (t, 3H), 3.17 (q, 2H), 7.16-7.20 (m, 2H), 7.45-7.48 (m, 4H), 7.52 (s , 2H), 7.76 (s, 1H), 8.04-8.06 (m, 4H).

Complex Em15

1.85 g (4.90 mmol) of dichloro(1,5-cyclooctadiene) platinum (II) at room temperature 1.85 g (5.82 mmol) of 2-ethoxy-1,3-diphenyl-2 in 60 ml of butanone ,3-dihydro-1H-imidazo[4,5-b]pyrazine. The suspension is heated under reflux for 4 hours. Thereafter, 1.64 g (7.84 mmol) of silver(I) acetylacetonate is added at room temperature. Thereafter, the mixture is heated under reflux overnight. After cooling, the suspension is filtered. The solvent was removed from the filtrate under reduced pressure, and purified by column chromatography (silica gel, eluent: methylene chloride). This gives 0.24 g of Em15 (9%).

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ =1.36 (s, 3H), 2.02 (s, 3H), 5.36 (s, 1H), 7.07 (dt, 1H), 7.17 (dt, 1H), 7.57-7.65 (m, 5H), 7.81 (dd, 1H), 8.20 (dd, 1H), 8.30 (d, 1H), 8.43 (d, 1H).

Photoluminescence (2% in PMMA film):

λ _max =484 nm, CIE: (0.22;0.34)

Example 17:

Emitter Em16

Complex K4

A solution of 0.63 g (0.94 mmol) of bis(1,5-cyclooctadiene)diiridium(I) chloride in 50 ml of anhydrous toluene was added to 2-0 of 0.60 g (1.88 mmol) in 30 ml of anhydrous toluene at room temperature. To the solution of methoxy-1,3-diphenyl-2,3-dihydro-1H-imidazo[4,5-b]pyrazine is added dropwise. The mixture is stirred at 60°C for 30 minutes and at 90°C for 24 hours. After cooling, the solvent is removed under reduced pressure, and the residue is purified by column chromatography (silica gel, eluent: 100/1 methylene chloride/methanol). This produces 0.85 g (75%) of K4.

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 1.32-1.38 (m, 2H), 1.44-1.52 (m, 2H), 1.53-1.59 (m, 2H), 1.73-1.81 (m, 2H) , 2.55-2.59 (m, 2H), 4.60-4.62 (m, 2H), 7.58-7.65 (m, 6H), 8.13-8.15 (m, 4H), 8.29 (s, 2H).

Complex Em16:

0.75 g (2.09 mmol) of N,N'-diphenylbenzimidazolium tetrafluoroborate (synthesis similar to WO2005/019373) in 30 mL of anhydrous toluene at 4.20 mL (2.10 mmol) of 0.5 mol toluene at 0°C Mix with a solution of sex potassium hexamethyldisilylamide (KHMDS). Allow the mixture to thaw to room temperature and stir for 1 hour. Then a solution of 0.61 g (0.99 mmol) K4 in 150 ml anhydrous toluene is added dropwise and the mixture is stirred for an additional 30 minutes. Then the mixture is heated to reflux for 1 hour. After cooling, the reaction mixture is filtered. The solvent was removed from the filtrate under reduced pressure, and purified by column chromatography (silica gel, eluent: cyclohexane/acetone=4/1). This gives 0.30 g of Em16 (30% yield).

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 6.10-7.20 (very flat wide signal, 4H), 6.19 (br.d, 1H), 6.22-6.25 (m, 2H), 6.37-6.50 ( m, 5H), 6.61 (br. d, 2H), 6.67 (br. d, 1H), 6.72-6.81 (m, 6H), 7.02-7.17 (m, 5H), 7.27-7.34 (m, 4H), 7.95 (d, 1H), 8.00-8.02 (m, 2H), 8.14 (d, 1H), 8.18 (d, 1H), 8.26 (d, 1H), 8.71 (d, 1H).

Photoluminescence (2% in PMMA film):

λ _max =489 nm, CIE: (0.19;0.38), 98% QY

Example 18:

Preparation of 2,8-di(dibenzofuran-2-yl)dibenzofuran, Ma14

Step 1:

10.4 g (42.09 mmol) of 2-bromodibenzofuran (prepared by J. Med. Chem 52(7), 1799-1802, 2009) equipped with a magnetic stirrer, thermometer, diaphragm and nitrogen blanketing Weigh in a 1 ℓ 3 neck round bottom flask that has been heated. 300 ml of THF (made anhydrous on sodium) is added, and the clear colorless solution is cooled to -78°C with stirring under argon atmosphere. Within 30 minutes, 17.1 ml (46.3 mmol) of a 2.7 M butyl lithium solution in hexane is added dropwise while maintaining the internal temperature at <73°C. Then, it is stirred for an additional 30 minutes at this temperature. Thereafter, 8.61 g (46.3 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane were added to the yellow suspension and the internal temperature was maintained at <73°C within 40 minutes. Drop while keeping. Stir at this temperature for an additional 60 minutes. The reaction mixture was allowed to warm to room temperature, a clear yellow solution was poured into 200 ml of pH 7 buffer, and 23 ml of 2N HCl was added. The solvent was concentrated on a rotary evaporator, and the aqueous phase was extracted three times with 250 ml of EtOAc. The combined organic phase is washed once with 100 ml of saturated NaCl solution, dried over magnesium sulfate, filtered and concentrated. This produced 12.95 g of a white solid, which was mixed with 50 ml of MeOH and heated to reflux. The formed clear solution is cooled to room temperature while stirring, and then cooled to 0°C. The suspension formed is filtered off, and the residue is washed twice with 10 ml of ice-cold MeOH and dried overnight in a vacuum drying cabinet at 50°C/120T. This produces 8.97 g (71.6% theoretical) of 2-dibenzofuran-2-yl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane with a purity of 98.3%. NMR and MS data are consistent with the proposed structure.

Step 2:

4.09 g (9.73 mmol) of 2,8-diiododibenzofuran (prepared by J. Amer. Chem. Soc . 124(40), 11900-11907, 2002), 6.30 g (21.04 mmol) ) 2-Dibenzofuran-2-yl-4,4,5,5-tetramethyl-1,3,2-dioxaborolan, 6.86 g (49.67 mmol) of potassium carbonate, 180 mL toluene, 79 Ml EtOH and 37 ml H ₂ O ₂ are initially added to a 500 ml 3-neck flask equipped with a magnetic stirrer, thermometer, reflux condenser and nitrogen blanketing, empty the apparatus and fill 4 times with argon. Then, 1.58 g (1.36 mmol) of tetrakis(triphenylphosphine)palladium is added, the device is emptied and filled with argon 4 times. Thereafter, the reaction mixture was heated to reflux with vigorous stirring for 4 hours, then diluted with 200 ml of toluene and cooled to room temperature. The phases are separated, and the organic phase is washed twice with 150 ml of water, dried over magnesium sulfate, filtered and concentrated. This gives 5.72 g of a brown solid. Purification by flash chromatography using hexane/toluene=5:2 as eluent gives 1.20 g of 2,8-di(dibenzofuran-2-yl)dibenzofuran as a white solid with a purity of 99.3%. NMR and MS data are consistent with the proposed structure.

Example 19

Manufacturing of Ma7

Ni(COD) ₂ (9.03 g, 32.8 mmol), 1,5-cyclooctadiene (3.55 g, 32.8 mmol) and 2,2'-bipyridine (5.12 g, 32.8 mmol) in a Schlenk flask ( Glove box) in anhydrous DMF (140 mL). The mixture is stirred at 80° C. for 30 minutes. A solution of 9-(8-bromo-dibenzofuran-2-yl)-9H-carbazole (11.75 g, 11.8 mmol) in anhydrous toluene (380 mL) is added gradually. After stirring at 80° C. under argon for 24 hours, the mixture was cooled to room temperature, added to MeOH/HCl (1:1, 2,000 mL) and stirred for 1 hour. The organic phase is extracted with toluene, dried over Na ₂ SO ₄ and concentrated. Ma7 (9.14 g, 87%) is produced by LC (SiO ₂ ; cyclohexane/CH ₂ Cl ₂ ; 4/1).

¹ H NMR (400 MHz, CD ₂ Cl ₂ ): 8.25 (2H, d, J=2Hz), 8.19 (2H, d, J=2Hz), 8.15 (4H, d, J=8Hz), 7.88 (1H, d, J=2Hz), 7.83 (1H, d, J=2Hz), 7.77 (4H, AB, J=8Hz), 7.65 (1H, d, J=2Hz), 7.62 (1H, d, J=2Hz) , 7.43-7.38 (8H, m), 7.31-7.24 (4H, m).

Example 20

Preparation of Ma12

Step 1:

t-BuLi (1.7M in pentane) (46.8 mL, 79.4 mmol) was added dropwise a solution of diphenyl ether (6 mL, 37.8 mmol) in dry THF (82 mL) under argon at -30°C. After the mixture was stirred at -30°C for 5.5 hours, phenylsilane (4.64 g, 41.6 mmol) was added. The mixture was stirred at -30°C for an additional hour, then warmed to room temperature overnight. Acidified ice (H ₂ SO ₄ ) is added, the organic phase is extracted with CH ₂ Cl ₂ , dried over Na ₂ SO ₄ , filtered, and concentrated. Recrystallization from MeHO gives 10-phenylphenoxacillin (49%).

¹ H NMR (CD ₂ Cl ₂ , 400 MHz): 7.57 (2H, dd, J=8.0 Hz, J=1.6 Hz), 7.48-7.35 (7H, m), 7.23 (2H, d, J=8.4 Hz) , 7.11 (2H, AB, J=7.2 Hz, J=0.8 Hz), 5.50 (1H, s).

Step 2:

9-(8-Bromodibenzofuran-2-yl)-9H-carbazole (1.24 g, 3 mmol) in diethyl ether (60 mL) n-BuLi (1.6M in hexane) (2.44 mL, 3.9 mmol) ) Solution is gradually added under Ar at 0°C. After stirring at 0°C for 20 minutes, a solution of 10-phenylphenoxacillin (0.99 g, 3.6 mmol) in diethyl ether (10 mL) is added at 0°C. The mixture was allowed to warm to room temperature while stirring overnight. Saturated NH ₄ Cl solution is added, and the organic phase is extracted with diethyl ether, dried over Na ₂ SO ₄ , filtered, and concentrated. 9-(8-(10-phenyl-10H-dibenzo[b,e][1,4]oxacillin-10-yl)dibenzo[b,d]furan- by recrystallization from cyclohexane/CH ₂ Cl ₂ 2-Day)-9H-carbazole (0.92 g) is obtained in 51% yield.

¹ H NMR (CD ₂ Cl ₂ , 400 MHz): 8.16 (1H, s), 8.14 (2H, d, J=8.0 Hz), 8.03 (1H, d, J=2.0 Hz), 7.78 (1H, d, J=8.4 Hz), 7.72 (1H, d, J=8.0 Hz), 7.65 (1H, d, J=8.4 Hz), 7.62-7.58 (5H, m), 7.46 (2H, t, J=7.4 Hz, J=2.0 Hz), 7.40-7.33 (7H, m), 7.33-7.24 (4H, m), 7.13 (2H, t, J=7.2 Hz). ¹³ C NMR (CD ₂ Cl ₂ , 125 MHz): 110.0, 112.3, 113.3, 116.4, 118.6, 120.3, 120.5, 120.6, 123.4, 123.6, 124.4, 125.7, 126.4, 127.3, 128.6, 128.8, 129.3, 130.5, 132.2 , 133.3, 134.3, 135.7, 136.2, 141.2, 155.6, 158.8, 160.8.

Example 21

Synthesis of Red1

a) 3-isobutylphenanthro[9,10-b]pyrazine proceeds from 32.2 g (0.14 mol) of dibenzo-[f,h]quinoxaline according to Example 9c of patent application WO2009/100991 in heptane It is produced using 90 ml (0.15 mol) of a 1.7 M solution of isobutyl lithium and 50 g of manganese (IV) oxide. The crude product is filtered hot through silica gel and the filtrate is concentrated under reduced pressure. The resulting solid is stirred overnight in ethanol for an additional 18 hours. Filtration and washing with ethanol gave the product as a light beige solid (yield: 8.7 g, 31%).

b) 8.0 ml (28 mmol) of 3-isobutylphenanthro[9,10-b]pyrazine and 4.82 g (13.2 mmol) of iridium(III) chloride hydrate (53.01% iridium content) are initially 100 ml at room temperature 2-ethoxyethanol. The gray-black suspension is stirred at 123° C. over 24 hours. The resulting red suspension is filtered, and the solid is washed with ethanol, then further dried under reduced pressure. Product 21a was obtained as a red powder (yield: 10.1 g, 95%).

c) 4.95 g (3.1 mmol) of product 21a and 3.3 g (3.1 mmol) of sodium carbonate are initially added to 40 mL of 2-ethoxyethanol and 20 mL of N,N-dimethylformamide. The red suspension is mixed with 2.5 g (24.8 mmol) of acetylacetone, then stirred at 121° C. over 70 minutes. The resulting dark red suspension is filtered, and the solid is stirred once with ethanol and twice with water and washed with hexane. The product is obtained as a red powder (yield: 4.3 g, 81%).

¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.15 (t, 12H), 1.86 (s, 6H), 2.40-2.50 (m, 2H), 3.10-3.15 (m, 4H), 5.35 (s, 1H) ), 6.45 (d, 2H), 7.04 (6, 2H), 7.73-7.82 (m, 4H), 7.93 (d, 2H), 8.56 (d, 2H), 8.67 (s, 2H), 9.33 (d, 2H).

Example 22:

Emitter Em17

(2-Chloropyridin-3-yl)isopropylamine:

12.5 ml (9.7 g, 167.0 mmol) acetone and 75 ml glacial acetic acid are added to a solution of 8.0 g (62.2 mmol) 3-amino-2-chloropyridine in 150 ml anhydrous dichloromethane. At 0°C, 6.5 ml (5.2 g, 68.4 mmol) of borane-dimethyl sulfide complex are added. After gas evolution has ended, the mixture is thawed to room temperature and stirred further overnight. The pH is then adjusted to 8 by adding 25% ammonia solution. 50 ml of water are added. The aqueous phase is extracted three times with 50 ml of dichloromethane each time. The combined organic phase is dried over sodium sulfate and the solvent is removed. This gives 10.5 g (99%) of yellow oil.

¹ H NMR (DMSO-D ₆ , 500 MHz): δ = 1.18 (d, 6H), 3.64 (sept, 1H), 4.96 (d, 1H), 7.07 (d, 1H), 7.17 (dd, 1H), 7.57 (dd, 1 H).

2-N-phenylamino-3-N-isopropylaminopyridine:

10.5 g (61.5 mmol) of (2-chloropyridin-3-yl)isopropylamine is mixed with 5.84 g (62.5 mmol) of aniline, and the mixture is stirred at 184° C. for 16 hours. After cooling to room temperature, 50 ml of water is added. The mixture was stirred for 1 hour and adjusted to pH=11 with NaOH aqueous solution. The mixture is extracted three times with 50 ml of dichloromethane each time. The combined organic phase is dried over sodium sulfate and the solvent is removed under reduced pressure. The residue is purified by column chromatography (silica gel, eluent: cyclohexane/ethyl acetate=5/1). This gives 7.5 g (53%) of a light brown solid.

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 1.21 (d, 6H), 3.23 (s br, 1H), 3.57 (sept, 1H), 6.26 (s br, 1H), 6.83 (dd, 1H) ), 6.92-6.99 (m, 2H), 7.25-7.29 (m, 4H), 7.70 (dd, 1H).

1-phenyl-3-isopropylpyridinoimidazolium iodide:

7.3 g (32.1 mmol) of 2-N-phenylamino-3-N-isopropylaminopyridine are dissolved in 30 ml of triethyl orthoformate and 4.8 g (33.1 mmol) of ammonium iodide are added. The reaction mixture was stirred at 82°C overnight. After cooling, the formed pale yellow solid is filtered off, washed with 3x15 ml petroleum ether and 3x30 ml dichloromethane, and dried. This produces 10.2 g (86%) of the imidazolium salt.

¹ H NMR (DMSO-D ₆ , 500 MHz): δ = 1.72 (d, 6H), 5.19 (sept, 1H), 7.67-7.70 (m, 1H), 7.73-7.76 (m, 2H), 7.86-7.88 (m, 1H), 7.95-7.97 (m, 2H), 8.81-8.82 (m, 2H), 10.43 (s, 1H).

Complex K5

3.00 g (8.21 mmol) of 1-phenyl-3-isopropylpyridinoimidazolium iodide is suspended in 45 ml of anhydrous toluene. 16.42 mL of a 0.5 mol KHMDS solution in toluene (8.21 mmol) is added at -8°C. The mixture is thawed to room temperature and stirred for 1 hour. Then, the red suspension is added to 2.76 g (4.11 mmol) of a solution of bis(1,5-cyclooctadiene)diiridium(I) chloride in 75 ml of anhydrous toluene at -78°C. The mixture is then heated at room temperature for 1.5 hours and under reflux for 1 hour. After cooling, the reaction mixture is filtered. The solvent was removed from the filtrate under reduced pressure, and purified by column chromatography (silica gel, eluent: methylene chloride). This produces 3.70 g (68%) of complex K5 as a yellow powder.

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 1.02-1.08 (m, 1H), 1.16-1.21 (m, 1H), 1.37-1.42 (m, 1H), 1.59-1.72 (m, 3H) , 1.76 (dd, 6H), 2.07-2.18 (m, 2H), 2.51-2.55 (m, 1H), 3.15-3.18 (m, 1H), 4.65-4.69 (m, 1H), 4.87-4.91 (m, 1H), 6.06 (sept, 1H), 7.23 (dd, 1H), 7.49-7.56 (m, 3H), 7.85 (dd, 1H), 8.04-8.06 (m, 2H), 8.22 (dd, 1H).

Complex Em17:

A solution of 0.90 g (2.83 mmol) of 2-ethoxy-1,3-diphenyl-2,3-dihydro-1H-imidazo[4,5-b]pyrazine in 50 ml anhydrous o-xylene is continuously Mix with a solution of 0.86 g (1.29 mmol) K5 in 10 g of molecular sieve and 75 ml of anhydrous o-xylene at room temperature. The mixture is stirred at 115°C for 22 hours. After cooling, it is filtered. The solvent was removed from the filtrate under reduced pressure, and purified by column chromatography (silica gel, eluent: cyclohexane/acetone=4/1). This gives 0.53 g (42%) of Em17 as a yellow powder.

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 0.62 (d, 3H), 1.06 (d, 3H), 4.28 (sept, 1H), 6.35-7.53 (very flat broad signal, 8H, 2 Ortho- and meta-H of non-cyclometalated phenyl rings), 6.52 (dd, 1H), 6.59 (dd, 1H), 6.64 (dd, 1H), 6.72-6.77 (m, 3H), 6.81 (dt , 1H), 6.97-7.01 (m, 1H), 7.05-7.08 (m, 2H), 7.14 (dt, 1H), 7.19 (dt, 1H), 7.41 (dd, 1H), 8.07 (d, 1H), 8.12 (d, 1H), 8.34 (dd, 2H), 8.37 (dd, 1H), 8.69 (dd, 1H), 8.80 (dd, 1H), 8.95 (dd, 1H).

Photoluminescence (2% in PMMA film):

λ _max =484 nm, CIE: (0.17;0.34), 95% QY

Example 23:

Complex Em18:

1.06 g (2.98 mmol) 2-ethoxy-1,3-bis(4-fluorophenyl)-2,3-dihydro-1H-imidazo[4,5-b]pyrazine (2-ethoxy- 1,3-bis-(4'-fluorophenyl)pyrazinoimidazoline) was added to 1.00 g (1.49 mmol) of [(μ-Cl)Ir(η ⁴ -1,5-) in 100 ml of o-xylene. COD)] ₂ . Thereafter, the resulting solution was stirred at 65° C. for 20 hours. After adding 1.80 g (5.66 mmol) of 2-ethoxy-1,3-diphenyl-2,3-dihydro-1H-imidazo[4,5-b]pyrazine, the reaction mixture is added at 95°C. Stir for 48 hours. After cooling, the precipitate is filtered off and washed with o-xylene and cyclohexane. The combined organic phase is concentrated to anhydrous state and purified by column chromatography (silica gel, eluent ethyl acetate/cyclohexane=1/4). This produces 0.30 g (20%) of Em18 as a yellow powder.

¹ H NMR (CD ₂ Cl ₂ , 500 MHz):

δ = 6.20-6.90 (very flat wide signal, 8H), 6.28 (dd, 1H), 6.65 (ddd, 3H), 6.59 (d, 1H), 6.80-6.86 (m, 6H), 7.14-7.19 (m , 2H), 8.05 (d, 1H), 8.07 (dd, 2H), 8.32 (d, 1H), 8.35 (t, 2H), 8.72 (dd, 1H), 8.76 (dd, 2H).

Photoluminescence (2% in PMMA film):

λ _max =466 nm, CIE: (0.15;0.19); QY=95%

Example 24:

Complex Em19:

0.47 g (1.49 mmol) of 2-ethoxy-1,3-diphenyl-2,3-dihydro-1H-imidazo[4,5-b]pyrazine is 0.50 g (0.74 in 50 ml o-xylene) mmol) to the solution of [(μ-Cl)Ir(η ⁴ -1,5-COD)] ₂ . Thereafter, the resulting solution was stirred at 60°C for 22 hours. After adding 1.04 g (2.94 mmol) of 2-ethoxy-1,3-bis(4-fluorophenyl)-2,3-dihydro-1H-imidazo[4,5-b]pyrazine, the reaction The mixture is stirred at 95° C. for an additional 48 hours. After cooling, the reaction mixture is concentrated to dryness. The solid residue is dissolved in dichloromethane/cyclohexane and filtered through celite. The filtrate is concentrated to dryness, and the residue is purified by column chromatography (silica gel, eluent ethyl acetate/cyclohexane=1/4). This gives 0.17 g (11%) of Em19 as a yellow powder.

¹ H NMR (CD ₂ Cl ₂ , 500 MHz):

δ = 6.20-6.90 (very flat wide signal, 8H), 6.31 (ddd, 3H), 6.68 (dd, 2H), 6.83-6.88 (m, 4H), 7.21 (dt, 1H), 8.10 (dd, 2H ), 8.12 (d, 1H), 8.37 (t, 2H), 8.40 (d, 1H), 8.71-8.75 (m, 2H), 8.79 (dd, 1H).

Photoluminescence (2% in PMMA film):

λ _max =461 nm, CIE: (0.15;0.16); QY=90%

Example 25:

Emitter Em20

Pyrazine compound (f)

10.5 g (29.3 mmol) of pyrazine compound (d) and 15.0 g of molecular sieve (5A) are heated to 120° C. in 230 ml of triethyl orthoformate for 48 hours. After cooling, the solid is filtered and the solvent is removed from the filtrate under reduced pressure. The obtained brown oil was purified by column chromatography (silica gel, eluent: cyclohexane/ethyl acetate=9/1). The resulting fractions are combined and recrystallized from methyl tert-butyl ether. This gives 4.63 g (38%) of the pyrazine compound (f).

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 1.06 (t, 3H), 1.33 (s, 6H), 1.34 (s, 6H), 1.98 (s, 2H), 3.32 (q, 2H), 7.12-7.16 (m, 2H), 7.21 (s, 1H), 7.40-7.47 (m, 4H), 8.11-8.16 (m, 4H).

Complex Em20:

A solution of 1.9 g (1.8 mmol) pyrazine compound (f) in 200 ml o-xylene (anhydrous) was initially added with 20 g molecular sieve, and 1.26 g (0.8) in 150 ml o-xylene (anhydrous). mmol) of the complex K1 is added. Thereafter, the reaction mixture was stirred at 115° C. for 18 hours. After cooling, the reaction mixture is filtered. The filtrate was concentrated to dryness, purified by column chromatography (silica gel, eluent cyclohexane/acetone=4/1), and recrystallized from methylene chloride/methanol. Then, it is further purified by column chromatography (silica gel, eluent cyclohexane/acetone=10/1). This produces 0.75 g (30%) of Em20 as a pale yellow powder.

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 1.13 (d, 6H), 1.36 (d, 6H), 1.45 (d, 6H), 1.58 (d, 6H), 2.03-2.16 (m, 4H ), 6.18-6.43 (m, 5H), 6.44-6.97 (m, broad, 15H), 6.98-7.22 (m, 6H), 7.32 (t, 1H), 7.99 (d, 1H), 8.17 (d, 1H) ), 8.78 (d, 1H), 8.90 (d, 1H).

Photoluminescence (2% in PMMA film):

λ _max =479 nm, CIE: (0.14; 0.29), 95% QY

Example 26:

Emitter Em21

2,3-di(N-phenylamino)pyridine:

A suspension of 2,3-diaminopyridine (8.9 g, 9 mmol) and iodobenzene (17.8 mL, 18 mmol) in dioxane (270 mL) is tris(dibenzylideneacetone)dipalladium (838 mg, 0.1 mmol) ), 9,9-dimethyl-4,5-bis(diphenylphosphine)xanthene (1.4 g, 0.3 mmol), sodium tert-butoxide (15.4 g, 18 mmol) and water (2.3 g). . The mixture is stirred under reflux overnight. After cooling to room temperature, the precipitate is filtered off with suction and washed with dichloromethane. The combined filtrates were concentrated to dryness, the residue was dissolved in dichloromethane (125 mL) and cyclohexane (150 mL) and column filtered. The product fractions are concentrated and the precipitated product is filtered. Yield: 14.2 g (67%).

¹ H NMR (CD ₂ Cl ₂ , 500 MHz, 0698403439): δ = 5.19 (br s, 1H), 6.71-6.76 (m, 3H), 6.84 (dd, 1H), 6.89-6.96 (m, 2H), 7.19 (dd, 2H), 7.23 (dd, 2H), 7.39 (d, 1H), 7.51 (d, 2H), 8.02 (d, 1H).

2,3-di(N-phenylamino)pyridine hydrochloride

A suspension of 2,3-di(N-phenylamino)pyridine (14.2 g, 54 mmol) in hydrochloric acid (200 mL) is stirred overnight at room temperature. The mixture is concentrated to dryness. Yield: 14.0 g (87%).

¹ H NMR (d ₆ -DMSO, 500 MHz, 0698403873): δ = 6.94-7.00 (m, 2H), 7.17 (d, 2H), 7.30 (m _c , 3H), 7.40-7.51 (m, 5H), 7.74 (dd, 1 H). NH protons are not detectable.

1,3-diphenyl-4-azabenzimidazolium chloride:

A mixture of 2,3-di(N-phenylamino)pyridine hydrochloride (14.0 g, 47 mmol) in triethyl orthoformate (160 mL) is stirred at 105°C overnight. After cooling to room temperature, the solid is filtered off with suction and washed with triethyl orthoformate. Yield: 10.3 g (71%).

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 7.55-7.73 (m, 7H), 8.08 (dd, 2H), 8.19 (dd, 1H), 8.33 (dd, 2H), 8.80 (dd, 1H) ), 12.24 (s, 1H).

Complex Em21

0.65 g of 1,3-diphenyl-4-azabenzimidazolium chloride (2.1 mmol) is suspended in 100 ml of anhydrous toluene and cooled to 0°C. Then, 4.2 ml of potassium bis(trimethylsilyl)amide (KHMDS, 0.5M in toluene, 2.1 mmol) is added gradually. After the mixture was stirred at room temperature for 1 hour, a solution of 0.61 g K4 (1.0 mmol) in 100 ml anhydrous toluene was added. The mixture is stirred at room temperature for 1 hour and then heated to reflux for 18 hours. After the mixture is cooled, it is concentrated to dryness. The residue is purified by column chromatography (silica gel, eluent: cyclohexane/acetone=4/1). This produces 0.13 g (13%) of Em21 as a pale yellow powder.

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 6.23-6.32 (m, 3H), 6.38 (t, 1H), 6.40-6.85 (m, 17H), 7.00-7.05 (m, 2H), 7.10 -7.16 (m, 3H), 7.32 (t, 2H), 8.01 (d, 1H), 8.28 (d, 1H), 8.39 (dt, 2H), 8.72 (d, 1H), 8.94 (d, 1H), 8.98 (d, 1 H).

Photoluminescence (2% in PMMA film):

λ _max =480 nm, CIE: (0.17; 0.30), 95% QY

Example 27:

Emitter Em22

2.30 g (6.4 mmol) of iodide 1-(4-cyanophenyl)-3-methylbenzimidazolium in 200 ml of 1,4-dioxane (anhydrous, ultra-dry) (see WO2006/056418 for manufacture) The solution of is mixed with 1.11 g (4.8 mmol) of silver (I) oxide and 20 g of molecular sieve, and stirred at room temperature overnight. Then a solution of 1.29 g (2.1 mmol) of complex K4 in 200 ml of anhydrous o-xylene is added and the mixture is stirred at 110° C. for 22 hours. After cooling, the reaction mixture is filtered. The solvent was removed from the filtrate under reduced pressure, and then separated by column chromatography (silica gel, eluent: cyclohexane/acetone=2/1). This produced 0.61 g (31%) of Em22 isomer 1 (RF=0.31), 0.45 g (23%) of Em22 isomer 2 (RF=0.25) and 0.25 g (13%) of Em22 isomer 3 (RF=0.20). Each of them is recrystallized from methylene chloride/methanol one more time.

Em22 isomer 1:

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 2.78 (s, 3H), 3.15 (s, 3H), 6.31 (d, very broad, 2H), 6.53 (d, 1H), 6.68 (t, 1H), 6.77 (t, 1H), 6.92 (d, 1H), 7.11-7.16 (m, 2H), 7.23-7.52 (m, 10H), 7.88 (d, 1H), 7.91 (d, 1H), 7.99 (d, 1H), 8.11 (d, 1H), 8.18 (d, 1H), 8.41 (d, 1H), 8.76 (d, 1H).

Photoluminescence (2% in PMMA film):

λ _max =484 nm, CIE: (0.19; 0.33), 87% QY

Em22 isomer 2:

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 3.20 (s, 3H), 3.37 (s, 3H), 5.67-6.92 (very flat wide signal, 2H), 6.51 (d, 1H), 6.70 -6.77 (m, 2H), 6.97-7.00 (m, 1H), 7.06-7.12 (m, 3H), 7.20-7.47 (m, 10 H), 7.90 (d, 1H), 8.06 (t, 2H), 8.24 (d, 1H), 8.45 (d, 1H), 8.80 (d, 1H).

Photoluminescence (2% in PMMA film):

λ _max =494 nm, CIE: (0.22; 0.41), 87% QY

Em22 isomer 3:

¹ H NMR (CD ₂ Cl ₂ , 500 MHz): δ = 2.75 (s, 3H), 3.56 (s, 3H), 6.02-7.26 (very flat wide signal, 4H), 6.48 (dd, 1H), 6.68 (d, 1H), 6.69-6.73 (m, 1H), 6.78 (dt, 1H), 6.86 (d, 1H), 6.90 (d, broad, 1H), 7.14 (dt, 1H), 7.24 (dt, 1H) ), 7.30-7.39 (m, 5H), 7.49 (dd, 1H), 7.87 (d, 1H), 7.94 (d, 1H), 8.03 (d, 1H), 8.08 (d, 1H), 8.17 (d, 1H), 8.41 (d, 1H), 8.79 (dd, 1H).

Photoluminescence (2% in PMMA film):

λ _max =468 nm, CIE: (0.16; 0.21), 90% QY

Example 28

Preparation of doped OLED

After washing with first LCD for producing commercially available detergent (Deconex 20NS ^®, and 25ORGAN-ACID ^® neutralizer) an ITO substrate was used as the anode, and in acetone / isopropanol mixture is washed in an ultrasonic bath. To remove possible organic residues, the substrate is exposed to a continuous ozone flow in an ozone oven for an additional 25 minutes. This treatment also improves the hole injection properties of ITO. Then, the hole injection layer AJ20-1000 from FlexCore is spun from the solution.

Example 28a:

After the hole injection layer, the organic material specified below is applied at about 10 ^-7 -10 ^-9 mbar to the cleaned substrate at a rate of about 0.5-5 nm/min. The hole conductor applied by vapor deposition is a mixture of Ir(DPBIC) ₃ and 20 nm of 4% p-dopant F6-TNAP. The exciton blocker applied to the substrate is Ir(DPBIC) _{3 with a} thickness of 10 nm.

(For the production of Ir(DPBIC) ₃ see Ir complex (7) in application WO 2005/019373 A2).

Thereafter, a mixture with a thickness of 30 nm of 30% emitter fac-Em1, 60% of compound Ma7 and 10% of compound Ir(DPBIC) ₃ was applied as an emissive layer by vapor deposition, the latter two compounds being a matrix material Acts as

The subsequent electronic conductor layer used is an ETM2 layer doped with 8% W(hpp) ₄ (see EP1786050) with a layer thickness of 25 nm (see compound number 28 in EP1097981).

An aluminum cathode with a thickness of 100 nm produces a diode.

All parts are encapsulated in a glass lid in an inert nitrogen atmosphere.

Example 28b:

The OLED from Example 28b has the same structure as the OLED from Example 28a, except that the emissive layer consists of 30% Em8 and 70% matrix material Ma7.

To characterize the OLED, electroluminescence spectra are recorded at different currents and voltages. In addition, the current-voltage characteristic is measured in combination with the emitted light output. The light output can be converted to metering parameters by calibration using a photometer.

For two working examples of doped OLED, the following electro-optical data is obtained:

Example 29

Diode using various emitters

After washing with first LCD for producing commercially available detergent (Deconex 20NS ^®, and 25ORGAN-ACID ^® neutralizer) an ITO substrate was used as the anode, and in acetone / isopropanol mixture is washed in an ultrasonic bath. To remove possible organic residues, the substrate is exposed to a continuous ozone flow in an ozone oven for an additional 25 minutes. This treatment also improves the hole injection properties of ITO. Next, a 40 nm-thick hole injection layer AJ20-1000 from FlexCore was spun from the solution.

Thereafter, the organic material specified below is applied to the clean substrate at a rate of about 0.5-5 nm/min by deposition at about 10 ^-7 -10 ^-9 mbar.

The applied hole conductor and exciton blocker are Ir (DPBIC) _{3 with a} thickness of 20 nm, and the first 15 nm is doped with 5% ReO ₃ . Thereafter, a 20 nm-thick light emitting layer composed of an emitter and two matrix materials is applied by vapor deposition. Thereafter, a 5 nm-thick layer of exciton and hole blocker is applied. Then, a mixture of 50% Liq and 50% ETM1 as an electron transport layer is applied to a thickness of 40 nm. Finally, a 4 nm-thick layer of KF and a 100 nm-thick Al electrode are applied by vapor deposition.

Example 29a

The diode is structured with a light emitting layer consisting of 10% emitter Em16 and 45% matrix materials Ir (DPBIC) ₃ and Ma13, respectively, as described above. The exciton and hole blocker used was Ma13.

The diode represents the color coordinates CIE 0.20, 0.43. At 300 cd/m 2, the voltage is 3.6 V and the external quantum efficiency is 17.7%.

Example 29b

The diode is structured with a light emitting layer consisting of 10% emitter Em16 and 45% matrix materials Ir (DPBIC) ₃ and Ma7, respectively, as described above. The exciton and hole blocker used was Ma7.

The diode represents the color coordinates CIE 0.19, 0.43. At 300 cd/m 2, the voltage is 3.6 V and the external quantum efficiency is 14.7%.

Example 29c

The diode is structured with a light emitting layer consisting of 10% emitter Em17 and 45% matrix materials Ir (DPBIC) ₃ and Ma13, respectively, as described above. The exciton and hole blocker used was Ma13.

The diode represents the color coordinates CIE 0.20, 0.44. At 300 cd/m 2, the luminous efficiency is 45.5 lm/W and the external quantum efficiency is 19.6%.

Example 29d

The diode is constructed with a light emitting layer consisting of 10% emitter Em17 and 45% matrix materials Ir (DPBIC) ₃ and Ma7, respectively, as described above. The exciton and hole blocker used was Ma7.

The diodes represent color coordinates CIE 0.18, 0.39. At 300 cd/m 2, the voltage is 3.8 V and the luminous efficiency is 40.4 lm/W.

Example 29e

The diode is structured as a light emitting layer consisting of 10% emitter Em20 and 45% matrix materials Ir (DPBIC) ₃ and Ma7, respectively, as described above. The exciton and hole blocker used was Ma7.

Diodes show color coordinates CIE 0.15, 0.29. At 300 cd/m 2, the voltage is 3.6 V and the external quantum efficiency is 19.9%.

Example 29f

The diode is structured as a light emitting layer consisting of 10% emitter Em20 and 45% matrix materials Ir (DPBIC) ₃ and Ma13, respectively, as described above. The exciton and hole blocker used was Ma13.

Diodes have color coordinates CIE 0.15, 0.29. At 300 cd/m 2, the voltage is 3.3 V and the external quantum efficiency is 19.0%.

Example 30

Homojunction OLED

Example 30a

After washing with first LCD for producing commercially available detergent (Deconex 20NS ^®, and 25ORGAN-ACID ^® neutralizer) an ITO substrate was used as the anode, and in acetone / isopropanol mixture is washed in an ultrasonic bath. To remove possible organic residues, the substrate is exposed to a continuous ozone flow in an ozone oven for an additional 25 minutes. This treatment also improves the hole injection properties of ITO. Then, a 40 nm-thick hole injection layer AJ20-1000 from FlexCore was spun from the solution.

Thereafter, the organic material specified below is applied to the clean substrate at a rate of about 0.5-5 nm/min by deposition at about 10 ^-7 -10 ^-9 mbar.

The applied hole conductor and exciton blocker are Ma4 having a thickness of 20 nm, and the first 15 nm is doped with 5% ReO ₃ . Thereafter, a 20 nm-thick light emitting layer consisting of 10% fac-Em1, 35% Ir (DPBIC) ₃ and 55% Ma4 is applied by vapor deposition. Thereafter, a 5 nm-thick layer of Ma4 of exciton and hole blocker is applied. Then, a mixture of 50% Liq and 50% Ma4 as the electron transport layer is applied to a thickness of 40 nm. Finally, a 4 nm-thick layer of KF and a 100 nm-thick Al electrode are applied by vapor deposition.

The diode represents the color coordinates CIE 0.15, 0.25. At 300 cd/m 2, the external quantum efficiency is 18.7%.

*

* Example 30b

The diode was structured similarly to Example 30a, except that the light emitting layer consisted of 30% fac-Em1, 35% Ir (DPBIC) ₃ and 35% Ma4.

The diode represents the color coordinates CIE 0.16, 0.31. At 300 cd/m 2, the external quantum efficiency is 16.2%.

* Example 30c

The diode is structured similarly to Example 30a, except that Ma4 is replaced by Ma7 in a specific layer, and the light emitting layer is composed of 10% fac-Em1, 45% Ir (DPBIC) ₃ and 45% Ma7.

The diode represents the CIE color coordinates 0.16, 0.28. At 300 cd/m 2, the external quantum efficiency is 11.9%.

Example 30d

The diode is structured similarly to Example 30a, except that Ma4 is replaced by Ma7 in a specific layer, and the light emitting layer consists of 30% fac-Em1, 35% Ir (DPBIC) ₃ and 35% Ma7.

Diodes show CIE color coordinates 0.18, 0.34. At 300 cd/m 2, the external quantum efficiency is 16.3%.

Example 31

Synthesis of ETM3

Step 1

To a 250 ml three neck round bottom flask equipped with a magnetic stirrer, thermometer, dropping funnel, reflux condenser and nitrogen blanketing, 150 ml of methanol is initially added, and 3.8 g of potassium hydroxide (≥85%) is added. The mixture is stirred at room temperature until a clear colorless solution is formed. Then, it was allowed to cool to 0° C. using an ice bath, and 14.3 g (56.7 mmol) of 1-(8-acetyldibenzofuran-2-yl)ethanone (MJ Bruce, Perkin Transactions I , 1789 (1995 )). After the suspension was stirred at 0° C. for 1 hour, 17.3 ml (170 mmol) of benzaldehyde was added dropwise within 3 minutes. Thereafter, the reaction mixture was allowed to warm to room temperature and stirred for 14 hours. The fine beige-yellow suspension is filtered and the residue is washed with 50 ml of ethanol. The crude product is suspended in 150 ml of ethanol and stirred for 30 minutes under reflux. Then it was cooled to room temperature, then cooled to 0° C., filtered, washed twice with 10 ml of ice cold ethanol, and the residue dried at 50° C./150 mbar overnight. This gives 21.6 g (88.9% theoretical) 3-phenyl-1-{8-(3-phenylacryloyl)]-dibenzofuran-2-yl}propenone as pale beige crystals.

¹ H NMR (CDCl ₃ , 300 MHz):

8.67 (s, 2H), 8.25 (d, J=7 Hz, 2H), 7.89 (s, J=12 Hz, 2H), 7.8-7.65 (m, 8H), 7.55-7.4 (m, 6H).

Stage 2

To a 100 ml 3-neck round bottom flask equipped with a magnetic stirrer, thermometer, reflux condenser and nitrogen blanketing, 60 ml of methanol was initially added and cooled to 0° C. using an ice bath while stirring. Thereafter, 15.7 g (240 mmol) of potassium tert-butoxide are added in several portions within 10 minutes. After initially adding 90 ml of methanol to a 500 ml 3-neck round bottom flask equipped with a magnetic stirrer, thermometer, dropping funnel, reflux condenser and nitrogen blanketing, 8.6 g (20 mmol) of 3-phenyl-1-{8 -(3-phenylacryloyl)]dibenzofuran-2-yl}propenone and 41.8 g (80 mmol) benzamidine hydrochloride (30% in methanol) are added with stirring. After the beige suspension is heated to reflux, a pre-produced potassium tert-butoxide solution is added dropwise within 20 minutes. The beige-brown suspension is stirred under reflux overnight. Then, after cooling to room temperature, 150 ml of water was added dropwise, and the mixture was stirred for 4 hours. A suspension is formed, which is filtered. The residue was suspended in 200 ml of water and heated to reflux for 2 hours. Thereafter, the mixture was cooled to room temperature, filtered, and the residue was washed with 50 ml of water, and then dried at 60°C/150 mbar overnight. This gives 10.9 g of 2,8-bis(2,4-diphenyl-1,4-dihydropyrimidinyl)dibenzofuran (85.8% theoretical) as yellow crystals. The crude product used is used without further purification.

Step 3

Initially 10.9 g (17 mmol) of crude 2,8-bis (2,4) in 100 ml o-dichlorobenzene in a 500 ml three neck round bottom flask equipped with a magnetic stirrer, thermometer, reflux condenser and nitrogen blanketing -Diphenyl-1,4-dihydropyrimidinyl)dibenzofuran is added and heated to 60 DEG C while stirring. Thereafter, 19.1 g (78 mmol) of chloranyl is added, and the dark reaction mixture is heated to reflux for 14 hours. Then, 160 ml of MeOH is added, and the mixture is stirred under reflux for 15 minutes. Then, it was cooled to 0° C. with an ice bath, the dark brown suspension was filtered, and the residue was washed three times with 50 ml of MeOH each time and twice with 50 ml of water each time. After drying at 60° C./125 mbar overnight, 18.0 g of brown crystals are obtained. The crude product was suspended in 100 ml of MeOH under reflux for 1 hour, then cooled to 0°C, washed twice with 20 ml of MeOH each time, and dried at 60°C/125 mbar. This gives 16.4 g of brown crystals. 5.7 g of this material was suspended in 50 ml of EtOH under reflux for 30 minutes, then cooled to 0°C, washed twice with 20 ml of EtOH each time, and dried at 60°C/125 mbar. This gives 5.0 g of brown crystals. This crude product is slurried in 190 ml toluene and stirred for 30 minutes under reflux. Thereafter, it was cooled to 0°C with an ice bath, the suspension was filtered, and the residue was washed three times with 20 ml of toluene each time. After drying at 60° C./125 mbar overnight, 3.0 g (81% theoretical) of the desired product are obtained as white-beige crystals.

HPLC-MS: purity 99.5%, [M+1]=629.5 m/z.

¹ H NMR (CDCl ₃ , 300 MHz):

8.97 (s, 2H), 8.73 (d, J=9 Hz, 4H), 8,43 (d, J=10 Hz, 2H), 8.42-8.28 (m, 4H), 8.11 (s, 2H), 7.73 (d , J=9Hz, 2H) 7.60-7.35 (m, 12H)

Example 32

First, the ITO substrate used as the anode was treated as in Example 30a, and a 40 nm-thick hole injection layer AJ20-1000 from FlexCore was provided as described above.

Thereafter, the organic materials specified below are applied to the clean substrate at a rate of about 0.5-5 nm/min by deposition at about 10 ^-7 -10 ^-9 mbar:

Example 32a

The applied hole conductor and exciton blocker are Ir (DPBIC) _{3 with a} thickness of 20 nm, and the first 15 nm is doped with 5% ReO ₃ . Thereafter, a 20 nm-thick light emitting layer consisting of 10% fac-Em1, 45% Ir (DPBIC) ₃ and 45% Ma13 is applied by vapor deposition. Thereafter, a 5 nm-thick layer Ma13 of exciton and hole blocker is applied. Then, a mixture of 50% Liq and 50% ETM3 as an electron transport layer is applied to a thickness of 40 nm. Finally, a 4 nm-thick layer of KF and a 100 nm-thick Al electrode are applied by vapor deposition.

Diodes show CIE color coordinates 0.16, 0.27. At 300 cd/m 2, the external quantum efficiency is 13.7%.

Example 32b

Diodes, except that the electron transport layer is made of pure ETM3. Structure as described in Example 32a.

Diodes show CIE color coordinates 0.16, 0.27. At 300 cd/m 2, the voltage is 3.4 V.

Example 32c

The diode was structured as described in Example 32a, except that the light emitting layer consisted of 30% fac-Em1, 35% Ir (DPBIC) ₃ and 35% Ma13.

Diodes show CIE color coordinates 0.17, 0.32. At 300 cd/m 2, the voltage is 3.4 V.

Example 32d

The diode is structured as described in Example 32c, except that the electron transport layer is made of pure ETM3.

The diode represents the CIE color coordinates 0.17, 0.31. At 300 cd/m 2, the external quantum efficiency is 14.2%.

Example 33

Synthesis of ETM4

Step 1

1.09 in a mixture of initially 1.8 ml ethanol and 50 ml 1,4-dioxane in a 100 ml 3 neck round bottom flask equipped with a magnetic stirrer, thermometer, reflux condenser, gas inlet tube, nitrogen blanketing and gas scrubbing bottle. g (5.0 mmol) of dibenzofuran-2,8-dicarbonitrile (produced by S. Wang, Eur.J. Med. Chem . 34, 215 (1999)) was added and EtOH/CO After cooling to 0° C. with a ₂ bath, HCl gas is added until saturated. The flask is then sealed, and the white suspension is warmed to room temperature and stirred for 48 hours. Thereafter, anhydrous N ₂ is blown into the suspension until HCl can no longer be detected in any exhaust gas. 25 ml of t-butyl methyl ether is added and the yellowish suspension is filtered. The residue was washed twice with 25 ml of t-butyl methyl ether each time, then suspended in 40 ml of 2M NH _{3 in} ethanol and stirred at 60° C. for 18 hours. The suspension is then cooled and anhydrous N ₂ is blown into the suspension until NH ₃ can no longer be detected in any exhaust gas. Thereafter, it was cooled with an ice bath and HCl gas was added again until it became saturated. Thereafter, anhydrous N ₂ was blown again, the beige suspension was filtered, and washed with a portion of a total of 25 ml of ice-cold EtOH. The residue is dried overnight at 50°C/125 mbar. This produces 1.71 g (99.2% theoretical) of dibenzofuran-2,8-bisamidine hydrochloride as beige crystals.

¹ H NMR (DMSO, 300 MHz):

8.90-8.75 (m, 2H), 8.25-8.00 (m, 4H)

Stage 2

To a 100 ml 3-neck round bottom flask equipped with a magnetic stirrer, thermometer, reflux condenser, and nitrogen blanketing, 40 ml of methanol was initially added and cooled to 0°C with an ice bath while stirring. Thereafter, 2.85 g (25.4 mmol) of potassium tert-butoxide are added in portions within 10 minutes. In a 250 ml three neck round bottom flask equipped with a magnetic stirrer, thermometer, dropping funnel, reflux condenser and nitrogen blanketing, initially 60 ml methanol followed by 1.7 g dibenzofuran-2,8-bisamidine hydrochloride and 4.08 g (19 mmol) of benzylidene acetophenone is added with stirring. After the beige suspension is heated to reflux, a pre-produced potassium tert-butoxide solution is added dropwise within 5 minutes. The beige suspension is stirred under reflux overnight. Thereafter, the mixture was cooled to 0° C., filtered, and the residue was washed with 15 mL of ice-cold MeOH, washed 3 times with 60 mL of water, and dried at 60° C./150 mbar overnight. This gives 1.59 g of 2,8-bis(4,6-diphenyl-1,4-dihydropyrimidinyl)dibenzofuran (39.6% theoretical) as yellow crystals. The crude product is used without further purification.

Step 3

Initially in a 100 ml three neck round bottom flask equipped with a magnetic stirrer, thermometer, reflux condenser and nitrogen blanketing, 1.59 g (2.45 mmol) of 2,8-di (4,6-di) in 15 ml o-dichlorobenzene initially Phenyl-1,4-dihydropyrimidinyl)dibenzofuran is added. After the mixture was heated to 50° C. with stirring, 2.41 g (9.80 mmol) of chloranyl was added. After the beige-brown suspension was heated to reflux for 4 hours, 30 ml of MeOH was added dropwise followed by 1 g of NaOH dissolved in 5 ml of water. The dark brown suspension is stirred under reflux for 30 minutes, then cooled to 0° C. with an ice bath and filtered. The residue is washed 3 times with 20 ml of MeOH and 5 times with 20 ml of hot water. The beige solid was suspended in 50 ml of toluene and refluxed with stirring for 30 minutes. Then cooled to an internal temperature of 60° C., filtered, and the residue washed twice with 10 ml of toluene and dried overnight at 60° C./125 mbar. This produces 0.85 g (55.2% theoretical) of the desired product as white crystals.

HPLC-MS: purity 99.3%, [M+1]=629.5 m/z.

¹ H NMR (CDCl ₃ , 300 MHz):

9.41 (s, 2H), 8.89 (d, J=9 Hz, 2H), 8.35-8.20 (m, 8H), 7.98 (s, 2H), 7.68 (d, J=9 Hz, 2H) 7.70-7.45 (m, 12H)

Claims (6)

Method of using a metal-carbene complex of formula (I) as an emitter, matrix material, charge transport material, and/or charge blocker in an OLED:
<Formula I>

In the above formula,
M, n, Y, A ² , A ³ , A ⁴ , A ⁵ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , K, L, m and o are each as defined below:
M is Ir or Pt,
n is an integer selected from 1, 2 and 3,
Y is NR ¹ , O, S or C(R ¹⁰ ) ₂ ,
A ² , A ³ , A ⁴ , A ⁵ are each independently N or C, where two A are nitrogen atoms, and one or more carbon atoms are present between two nitrogen atoms in the ring,
R ¹ is optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having a linear or branched alkyl radical having 1 to 20 carbon atoms; A cycloalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A substituted or unsubstituted aryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 6 to 30 carbon atoms; And optionally substituted with one or more heteroatoms, optionally having one or more functional groups, and having a total of 5 to 18 carbon atoms and/or heteroatoms, substituted or unsubstituted heteroaryl radicals,
R ² , R ³ , R ⁴ , R ⁵ are each a free electron pair when A ² , A ³ , A ⁴ and/or A ⁵ is N, or A ² , A ³ , A ⁴ and/or A ⁵ is In the case of C, each independently hydrogen; A linear or branched alkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups and having 1 to 20 carbon atoms; A cycloalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A substituted or unsubstituted aryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 6 to 30 carbon atoms; A substituted or unsubstituted heteroaryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having a total of 5 to 18 carbon atoms and/or heteroatoms; And groups having donor or acceptor action, or
R ³ and R ⁴ together with A ³ and A ⁴ are optionally interrupted by one or more additional heteroatoms and form an optionally substituted unsaturated ring having a total of 5 to 18 carbon atoms and/or heteroatoms,
R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently hydrogen; A linear or branched alkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups and having 1 to 20 carbon atoms; A cycloalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A cycloheteroalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A substituted or unsubstituted aryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 6 to 30 carbon atoms; A substituted or unsubstituted heteroaryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having a total of 5 to 18 carbon atoms and/or heteroatoms; And groups having donor or acceptor action, or
R ⁶ and R ⁷ , R ⁷ and R ⁸ or R ⁸ and R ⁹ are optionally interrupted by one or more heteroatoms together with the carbon atom to which they are attached and saturated with a total of 5 to 18 carbon atoms and/or heteroatoms, Form an unsaturated or aromatic, optionally substituted ring, and/or
When A ⁵ is C, R ⁵ and R ⁶ together optionally include heteroatoms, aromatic units, heteroaromatic units and/or functional groups and have a total of 1 to 30 carbon atoms and/or heteroatoms, wherein carbon atoms and / Or a substituted or unsubstituted, 5- to 8-membered ring containing heteroatoms optionally forms a saturated or unsaturated, linear or branched bridge,
R ¹⁰ is independently optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having a linear or branched alkyl radical having 1 to 20 carbon atoms; A cycloalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A substituted or unsubstituted aryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 6 to 30 carbon atoms; And optionally substituted with one or more heteroatoms, optionally having one or more functional groups, and having a total of 5 to 18 carbon atoms and/or heteroatoms, substituted or unsubstituted heteroaryl radicals,
K is an uncharged monodentate ligand or bidentate ligand,
L is a monovalent or divalent anionic ligand, which may be a monodentate ligand or a bidentate ligand,
m is 0, 1 or 2, where m is 2, the K ligands can be the same or different,
o is 0, 1 or 2, where o is 2, the L ligands may be the same or different. According to claim 1,
M, n, Y, A ² , A ³ , A ⁴ , A ⁵ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , L, m and o Are each defined as follows:
M is Ir,
n is 1, 2 or 3,
Y is NR ¹ ,
A ² , A ³ , A ⁴ , A ⁵ are each independently N or C, where two A are nitrogen atoms, and one or more carbon atoms are present between two nitrogen atoms in the ring,
R ¹ is a linear or branched alkyl radical having 1 to 6 carbon atoms; A substituted or unsubstituted aryl radical having 6 to 30 carbon atoms; And a substituted or unsubstituted heteroaryl radical having a total of 5 to 18 carbon atoms and/or heteroatoms,
R ² , R ³ , R ⁴ , R ⁵ are each a free electron pair when A ² , A ³ , A ⁴ and/or A ⁵ is N, or A ² , A ³ , A ⁴ and/or A ⁵ is In the case of C, each independently hydrogen; Linear or branched alkyl radicals having 1 to 6 carbon atoms; A substituted or unsubstituted aryl radical having 6 to 30 carbon atoms; And a substituted or unsubstituted heteroaryl radical having a total of 5 to 18 carbon atoms and/or heteroatoms, or
R ³ and R ⁴ together with A ³ and A ⁴ are optionally interrupted by one or more additional heteroatoms and form an optionally substituted unsaturated ring having a total of 5 to 18 carbon atoms and/or heteroatoms,
R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently hydrogen; A linear or branched alkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups and having 1 to 20 carbon atoms; A substituted or unsubstituted aryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 6 to 30 carbon atoms; And optionally substituted with one or more heteroatoms, optionally having one or more functional groups, and having a total of 5 to 18 carbon atoms and/or heteroatoms, substituted or unsubstituted heteroaryl radicals,
L is a monovalent anionic bidentate ligand,
m is 0,
o is 0, 1 or 2. The method according to claim 1 or 2,
M, n, Y, A ² , A ³ , A ⁴ , A ⁵ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , L, m and o Are each defined as follows:
M is Ir,
n is 2 or 3,
Y is NR ¹ ,
A ² and A ³ , A ⁴ and A ⁵ to A ² and A ⁵ are each N and A ³ and A ⁴ are each C, or
A ² and A ⁴ are each N and A ³ and A ⁵ are each C, or
A ³ and A ⁵ are each N and A ² and A ⁴ are each C,
R ¹ is a linear or branched alkyl radical having 1 to 6 carbon atoms; Substituted or unsubstituted phenyl radical; And a substituted or unsubstituted heteroaryl radical having a total of 6 to 18 carbon atoms and/or heteroatoms,
R ² , R ³ , R ⁴ , R ⁵ are each a free electron pair when A ² , A ³ , A ⁴ and/or A ⁵ is N, or A ² , A ³ , A ⁴ and/or A ⁵ Is a C each independently selected from the group consisting of hydrogen, a linear or branched alkyl radical having 1 to 6 carbon atoms, and a substituted or unsubstituted phenyl radical, or
R ³ and R ⁴ together with A ³ and A ⁴ form an optionally substituted, monounsaturated ring having a total of 5 to 7 carbon atoms,
R ⁶ , R ⁷ , R ⁸ , R ⁹ are each independently hydrogen, a linear or branched alkyl radical having 1 to 20 carbon atoms, and an o,o'-dialkylated aryl radical having 6 to 30 carbon atoms. Is selected from,
L is a monovalent anionic bidentate ligand,
m is 0,
o is 0 or 1. The method of claim 1 or 2, wherein L in formula I is a carbene ligand of formula II:
<Formula II>

In the above formula,
A ⁶ and A ⁷ are each independently C or N,
R ¹¹ is optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and a linear or branched alkyl radical having 1 to 20 carbon atoms; A cycloalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A cycloheteroalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A substituted or unsubstituted aryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 6 to 30 carbon atoms; And optionally substituted with one or more heteroatoms, optionally having one or more functional groups, and having a total of 5 to 18 carbon atoms and/or heteroatoms, substituted or unsubstituted heteroaryl radicals,
R ¹² and R ¹³ are each independently, when A is N, a free electron pair, or hydrogen when A is C; A linear or branched alkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups and having 1 to 20 carbon atoms; A cycloalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A cycloheteroalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A substituted or unsubstituted aryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 6 to 30 carbon atoms; A substituted or unsubstituted heteroaryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having a total of 5 to 18 carbon atoms and/or heteroatoms; And groups having donor or acceptor action,
R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently hydrogen; A linear or branched alkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups and having 1 to 20 carbon atoms; A cycloalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A cycloheteroalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A substituted or unsubstituted aryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 6 to 30 carbon atoms; A substituted or unsubstituted heteroaryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having a total of 5 to 18 carbon atoms and/or heteroatoms; And groups having donor or acceptor action, or
R ¹² and R ¹³ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ or R ¹⁶ and R ¹⁷ are arbitrarily interposed with one or more heteroatoms together with the A or carbon atom to which they are attached, and a total of 5 to 18 carbon atoms And/or form an unsaturated or aromatic, optionally substituted ring with heteroatoms, and/or
When A ⁶ is C, R ¹³ and R ¹⁴ together optionally include heteroatoms, aromatic units, heteroaromatic units and/or functional groups and have a total of 1 to 30 carbon atoms and/or heteroatoms, wherein carbon atoms and / Or a substituted or unsubstituted, 5- to 8-membered ring containing heteroatoms, optionally fused to form a saturated or unsaturated, linear or branched bridge. The method of claim 1 or 2, wherein L in formula I is a heterocyclic bicarbene ligand of formula III:
<Formula III>

Each of the symbols in the ligand of Formula III is as defined below:
D are each independently CR ¹⁸ or N;
W is C or N;
E are each independently CR ¹⁹ , N or NR ²⁰ ;
G is CR ²¹ , N, NR ²² , S or O;
R ¹⁸ , R ¹⁹ and R ²¹ are each independently hydrogen; A linear or branched alkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups and having 1 to 20 carbon atoms; A cycloalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A cycloheteroalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A substituted or unsubstituted aryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 6 to 30 carbon atoms; And a substituted or unsubstituted heteroaryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having a total of 5 to 18 carbon atoms and/or heteroatoms; And groups having donor or acceptor action, or
In each case the two R ¹⁸ , R ¹⁹ and R ²¹ radicals are optionally interrupted by one or more heteroatoms together with the carbon atom to which they are attached, and are saturated, unsaturated or having a total of 5 to 18 carbon atoms and/or heteroatoms. Form an aromatic, optionally substituted ring,
R ²⁰ , R ²² are each independently optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having a linear or branched alkyl radical having 1 to 20 carbon atoms; A cycloalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A cycloheteroalkyl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 3 to 20 carbon atoms; A substituted or unsubstituted aryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having 6 to 30 carbon atoms; A substituted or unsubstituted heteroaryl radical optionally interrupted by one or more heteroatoms, optionally having one or more functional groups, and having a total of 5 to 18 carbon atoms and/or heteroatoms; And groups having donor or acceptor action,
Where the solid line curve is any bridge between one of the D groups and the G group; Here, the crosslinking may be defined as alkylene, arylene, heteroarylene, alkynylene, alkenylene, O, S, SiR ²⁴ R ²⁵ and (CR ²⁶ R ²⁷ ) _d , wherein at least one non-adjacent (CR ²⁶ R ²⁷ ) group may be substituted with O, S, SiR ²⁴ R ²⁵ , wherein
d is 2 to 10;
R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ are each independently H, alkyl, aryl, heteroaryl, alkenyl or alkynyl. A method of using at least one compound of formula (X) below and at least one metal-carbene complex as defined in claim 1 or 2 in an OLED:
<Formula X>

In the above formula,
T is NR ⁵⁷ , S, O or PR ⁵⁷ ;
R ⁵⁷ is aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl;
Q'is -NR ⁵⁸ R ⁵⁹ , -P(O)R ⁶⁰ R ⁶¹ , -PR ⁶² R ⁶³ , -S(O) ₂ R ⁶⁴ , -S(O)R ⁶⁵ , -SR ⁶⁶ or -OR ⁶⁷ ,
R ⁵⁵ and R ⁵⁶ are each independently alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, SiR ⁷⁰ R ⁷¹ R ⁷² , Q'group, or a group having donor or acceptor action;
a" is 0, 1, 2, 3 or 4;
b'is 0, 1, 2 or 3;
R ⁵⁸ , R ⁵⁹ , together with the nitrogen atom, have 3 to 10 ring atoms and are substituted with one or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and groups having donor or acceptor action Form a cyclic radical which may or may not be unsubstituted and/or fused with one or more additional cyclic radicals having 3 to 10 ring atoms, wherein the fused radicals are alkyl, cycloalkyl, heterocyclo Substituted or unsubstituted with one or more substituents selected from alkyl, aryl, heteroaryl, and groups having donor or acceptor action;
R ⁷⁰ , R ⁷¹ , R ⁷² , R ⁶⁰ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ are each independently aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl , or
The two units of formula (X) are crosslinked to each other by linear or branched, saturated or unsaturated crosslinks, by bonds or by O, optionally interrupted by one or more heteroatoms.

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