Metal complex, semiconductor layer comprising metal complex, and organic electronic device

Abstract

The present invention relates to a metal complex, a semiconductor layer comprising said metal complex and an organic electronic device comprising at least one metal complex thereof.

Description

Technical Field

[0001] The present invention relates to a metal complex, a semiconductor layer comprising the metal complex and an organic electronic device comprising at least one metal complex thereof. Background Art

[0002] Electronic devices as self-luminous devices, such as organic light-emitting diodes (OLEDs), have wide viewing angles, excellent contrast, fast response, high brightness, excellent operating voltage characteristics, and color reproduction. A typical OLED includes an anode layer, a hole injection layer HIL, a hole transport layer HTL, an emission layer EML, an electron transport layer ETL, and a cathode layer, which are sequentially stacked on a substrate. In this regard, HIL, HTL, EML, and ETL are thin films formed of organic compounds.

[0003] When voltage is applied to the anode and cathode, holes injected from the anode move to the EML via the HIL and HTL, and electrons injected from the cathode move to the EML via the ETL. Holes and electrons recombine in the EML to generate excitons. When the excitons drop from the excited state to the ground state, light is emitted. The injection and flow of holes and electrons should be balanced so that the OLED having the above structure has a low operating voltage, excellent efficiency and / or a long life.

[0004] The performance of an organic light emitting diode may be affected by the characteristics of the hole injection layer, in particular, by the characteristics of the hole transport compound and the metal complex contained in the hole injection layer.

[0005] US 2015200374 A relates to a hole injection layer consisting of, for example, a secondary planar mononuclear transition metal complex, such as a copper 2+ complex, embedded in a hole-conducting matrix.

[0006] WO16188604 A1 relates to a composition comprising at least one hole transport material and / or one hole injection material and at least one metal complex as a p-type dopant.

[0007] ZHANG XINYU et al.: “Highly efficient near-infrared (NIR) luminescent tris-[beta]-diketonate Yb3+ complex in solution and in PMMA”, INORGANIC CHEMISTRYCOMMUNICATIONS, ELSEVIER, AMSTERDAM, NL, Vol. 70, 7 June 2016 (2016-06-07), pp. 153-156, XP029632563, ISSN: 1387-7003.

[0008] FU GUORUI et al.: “An efficient and weak efficiency-roll-offnearinfrared (NIR) polymer light-emitting diode (PLED) based on aPVKsupported Zn 2+ -Yb 3+ -containing metallopolymer”, JOURNAL OF MATERIALSCHEMISTRY C, Vol. 6, No. 15, 1 January 2018 (2018-01-01 ), pp. 4114-4121, XP093013435, GB, ISSN: 2050-7526.

[0009] ZHANG ZHAO et al.: “PMMA-supported hybrid materials doped with highly near-infrared (NIR) luminescent neutral trikis-[beta]diketonate Yb3+com”, INORGANIC CHEMISTRY COMMUNICATIONS, ELSEVIER, AMSTERDAM, NL, Vol. 52, December 20, 2014 (2014-12-20), pp. 53-55, XP029131863, ISSN: 1387-7003.

[0010] PETTINARI C et al.: “Tin(IV) and organotin(IV) derivatives of novel beta-diketones 1. DIALKYLTIN (IV) COMPLEXES OF 1-PHENYL-3-METHYL-4-R' (C=O)-PYRAZOL-5-ONE (R' = CCl3, OCH3, O-C2H5, O-1-C3H7, O-C7H7)”. O-C7H7). CRYSTAL AND MOLECULAR STRUCTURE OF TRANS-DIMETHYLBISÄ 1-PHENYL-3-METHYL-4-1-ROPOXYCARBONYL-PYRAZOLON-5-ATOÜTIN(IV))”, INORGANICA CHIMICA ACTA, ELSEVIER BV, NL, Vol. 257, 1 January 1997 (1997-01-01), pp. 37-48, XP002216369, ISSN: 0020-1693.

[0011] The performance of an organic light-emitting diode can be influenced by the properties of the semiconductor layer, in particular by the properties of the metal complex also contained in the semiconductor layer.

[0012] There is still a need to improve the performance of metal complexes suitable as semiconductor materials, semiconductor layers thereof and electronic devices, in particular to achieve improved operating voltage stability over time by improving the properties of the metal complexes contained therein.

[0013] Furthermore, there remains a need to improve the properties of metal complexes suitable for use as semiconductor materials and having improved thermal properties and / or solubility in organic solvents.

[0014] Furthermore, there remains a need to improve the performance of electronic devices by providing semiconductor layers, such as hole injection layers, with improved properties, and in particular to achieve improved operating voltages by improving the characteristics of semiconductor layers, such as hole injection layers, and electronic devices. Summary of the invention

[0015] One aspect of the present invention provides a metal complex of formula (I):

[0016] (I)

[0017] in

[0018] M is a metal ion;

[0019] n is the valence of M and is selected from 1 to 4;

[0020] L has the formula (II)

[0021] (II)

[0022] R 1 and R 2 are independently selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 Heteroaryl or substituted or unsubstituted 6-membered heteroaryl;

[0023] R 3 is selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 heteroaryl, substituted or unsubstituted 6-membered heteroaryl or CN;

[0024] in

[0025] Substituted C1 to C 12 Alkyl, substituted C6 to C 19 Aryl, substituted C2 to C 20At least one of the substituents of the heteroaryl or substituted 6-membered heteroaryl is independently selected from halogen, Cl, F, CN, partially fluorinated or perfluorinated C1 to C8 alkyl, partially fluorinated or perfluorinated C1 to C8 alkoxy;

[0026] in

[0027] R 1 , R 2 and R 3 At least one or R 1 , R 2 and R 3 The group comprises at least three atoms selected from halogen, Cl, F or N;

[0028] in

[0029] AL is an auxiliary ligand coordinated to the metal M;

[0030] m is an integer selected from 0 to 2.

[0031] According to one embodiment, there is provided a metal complex of formula (I):

[0032] (I), where

[0033] M is a metal ion, wherein M is a metal ion selected from Li(I), K(I), Rb(I), Cs(I), Ag(I), Cu(II), Zn(II), Pd(II), Ir(III), Al(III), Sc(III), Mn(III), Ru(III), In(III), Y(III), Eu(III), Fe(III), V(IV), Zr(IV), Hf(IV) and Ce(IV);

[0034] n is the valence of M and is selected from 1 to 4;

[0035] L has the formula (II)

[0036] (II)

[0037] R 1 and R 2 are independently selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 Heteroaryl or substituted or unsubstituted 6-membered heteroaryl;

[0038] R 3 is selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C19 Aryl, substituted or unsubstituted C2 to C 20 heteroaryl, substituted or unsubstituted 6-membered heteroaryl or CN;

[0039] in

[0040] Substituted C1 to C 12 Alkyl, substituted C6 to C 19 Aryl, substituted C2 to C 20 At least one of the substituents of the heteroaryl or substituted 6-membered heteroaryl is independently selected from halogen, Cl, F, CN, partially fluorinated or perfluorinated C1 to C8 alkyl, partially fluorinated or perfluorinated C1 to C8 alkoxy;

[0041] in

[0042] R 1 , R 2 and R 3 At least one or R 1 , R 2 and R 3 The group comprises at least three atoms selected from halogen, Cl, F or N;

[0043] in

[0044] AL is an auxiliary ligand coordinated to the metal M;

[0045] m is an integer selected from 0 to 2.

[0046] definition

[0047] It should be noted that throughout the application and claims, metal complexes or metal complexes of formula (I) are also referred to as compounds.

[0048] The terms "metal complex of formula (I)" and "acetylpyrazolone acid metal complex according to formula (I)" are used synonymously.

[0049] It should be noted that throughout the application and claims, unless otherwise indicated, any R 1 , R 2 , R 3 , L and M always independently of one another refer to the same part according to their definitions.

[0050] In the present specification, when no definition is provided otherwise, "substituted" refers to a substituted or unsubstituted C1 to C 12 Alkyl, partially fluorinated or fully fluorinated C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl and substituted or unsubstituted C2 to C 20The substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl and substituted or unsubstituted C2 to C 20 Substituents of the heteroaryl group are independently selected from halogen, Cl, F, CN, partially fluorinated or perfluorinated C1 to C8 alkyl, partially fluorinated or perfluorinated C1 to C8 alkoxy.

[0051] In this specification, "aryl group" and "aromatic ring" refer to a hydrocarbon group that can be generated by subtracting one hydrogen atom from the aromatic ring form in the corresponding aromatic hydrocarbon. Aromatic hydrocarbon refers to a hydrocarbon containing at least one aromatic ring or aromatic ring system. Aromatic ring or aromatic ring system refers to a planar ring or ring system of covalently bound carbon atoms, wherein the planar ring or ring system contains a delocalized electron conjugated system that satisfies Huckel's rule. Examples of aryl groups include monocyclic groups such as phenyl or tolyl, polycyclic groups such as biphenyl containing multiple aromatic rings connected by single bonds, and polycyclic groups such as naphthyl or fluorenyl containing fused rings.

[0052] Similarly, "heteroaryl" and "heteroaromatic" are to be understood, where appropriate, as radicals which are derived by formally subtracting one ring hydrogen from such a ring in metal complexes which contain at least one heterocyclic aromatic ring.

[0053] The term "non-heterocyclic" is understood to mean a ring or ring system which does not contain heteroatoms as ring members.

[0054] The term "heterocycle" is understood to mean a heterocycle comprising at least one ring comprising one or more heteroatoms. A heterocycle comprising more than one ring means that all rings contain heteroatoms or at least one ring contains heteroatoms and at least one ring contains only C atoms and no heteroatoms. A C2 heteroaryl group means that the heteroaryl ring contains two C atoms and the other atoms are heteroatoms.

[0055] Heterocycloalkyl is understood, where appropriate, in particular as a radical which is derived by formally subtracting one ring hydrogen from at least one saturated cycloalkyl ring in compounds which comprise such a ring.

[0056] The term "aryl" having at least 9 C atoms may include at least one fused aryl ring. The term "heteroaryl" having at least 9 atoms may include at least one fused heteroaryl ring fused to a heteroaryl ring or to an aryl ring.

[0057] The term "fused aryl ring" or "condensed aryl ring" is understood to mean when two aryl rings share at least two common sp 2 When carbon atoms are hybridized, they are considered fused or condensed.

[0058] The term "fused ring system" is understood to mean a ring system wherein two or more rings share at least two atoms.

[0059] The term "5-membered ring, 6-membered ring or 7-membered ring" is understood to mean a ring containing 5, 6 or 7 atoms. The atoms may be selected from C and one or more heteroatoms.

[0060] In this specification, a single bond means a direct bond.

[0061] In the present specification, when no definition is otherwise provided, "substituted" means substituted with H, deuterium, halogen, Cl, F, CN, partially fluorinated or perfluorinated C1 to C8 alkyl, partially fluorinated or perfluorinated C1 to C8 alkoxy.

[0062] In the present specification, "substituted aryl" refers to, for example, a C6 to C 19 Aryl or C6 to C 18 Aryl, wherein the substituent may be unsubstituted or substituted with one or more substituents, preferably, the substituent may be selected from H, deuterium, halogen, Cl, F, CN, partially fluorinated or perfluorinated C1 to C8 alkyl, partially fluorinated or perfluorinated C1 to C8 alkoxy.

[0063] Accordingly, in the present specification, "substituted heteroaryl" refers to being substituted by one or more substituents, which themselves may be substituted by one or more substituents, preferably the substituents may be selected from H, deuterium, halogen, Cl, F, CN, partially fluorinated or perfluorinated C1 to C8 alkyl, partially fluorinated or perfluorinated C1 to C8 alkoxy.

[0064] In the present specification, when no definition is provided otherwise, a substituted heteroaryl group having at least 2 C ring atoms may be substituted by one or more substituents. For example, a substituted C2 heteroaryl group may have 1 or 2 substituents.

[0065] Substituted aryl groups having at least 6 ring atoms may be substituted by 1, 2, 3, 4 or 5 substituents.

[0066] Substituted heteroaryl groups may contain at least 5 or 6 ring atoms. Substituted heteroaryl groups which may contain at least 5 or 6 ring atoms may be substituted by 1, 2, 3 or 4 substituents if the heteroaryl group contains one heteroatom and five C atoms, or by 1, 2 or 3 substituents if the heteroaryl group with at least 6 ring atoms contains two heteroatoms and four C atoms, or by 1 or 2 substituents if the heteroaryl group with at least 6 ring atoms contains three heteroatoms and three C atoms, wherein the substituents are bonded only to C ring atoms.

[0067] In this specification, when no definition is provided otherwise, "alkyl group" refers to a saturated aliphatic hydrocarbon group. The alkyl group can be C1 to C 12 More specifically, the alkyl group may be C1 to C 10 Alkyl groups or C1 to C6 alkyl groups. For example, C1 to C4 alkyl groups include 1 to 4 carbons in the alkyl chain and can be selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl.

[0068] Specific examples of the alkyl group may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a branched pentyl group, a hexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, and the like.

[0069] In the present specification, when no definition is provided otherwise, "substituted alkyl group" may refer to a linear, branched or cyclic substituted saturated aliphatic hydrocarbon group. The substituted alkyl group may be a linear, branched or cyclic C1 to C 12 More specifically, the substituted alkyl group may be a linear, branched or cyclic substituted C1 to C 10 Alkyl groups or linear, branched or cyclic substituted C1 to C6 alkyl groups. For example, linear, branched or cyclic substituted C1 to C4 alkyl groups include 1 to 4 carbons in the alkyl chain and can be selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and cyclohexyl. Substituents can be selected from halogen, F, Cl, CN, OCH3, OCF3.

[0070] The term "hetero" is understood to mean that in a structure that can be formed by covalently bonded carbon atoms, at least one carbon atom is replaced by another polyvalent atom. Preferably, the heteroatom is selected from B, Si, N, P, O, S; more preferably, it is selected from N, P, O, S; most preferably, N.

[0071] In the present specification, when a substituent is not named, the substituent may be H.

[0072] The term "charge neutral" means that the group L is overall charge neutral.

[0073] In the context of the present invention, "different" means that the metal complexes do not have the same chemical structure.

[0074] The terms "does not contain", "does not contain", "does not include" do not exclude impurities that may be present in the metal complex before deposition. Impurities have no technical influence on the purpose to be achieved by the present invention.

[0075] The term "sandwiched in contact" refers to a three-layer arrangement in which an intermediate layer is in direct contact with two adjacent layers.

[0076] The terms "light absorbing layer" and "light absorbing layer" are used synonymously.

[0077] The terms "light emitting layer", "light emitting layer" and "emissive layer" are used synonymously.

[0078] The terms "OLED," "organic light emitting diode," and "organic light emitting device" are used synonymously.

[0079] The terms anode, anode layer and anode electrode are used synonymously.

[0080] The term "at least two anode sublayers" is understood to mean two or more anode sublayers, for example two or three anode sublayers.

[0081] The terms cathode, cathode layer and cathode electrode are used synonymously.

[0082] The term "hole injection layer" is understood to mean a layer which improves the injection of charges from the anode layer into other layers of the electronic device or from other layers of the electronic device into the anode.

[0083] The term “hole transport layer” is understood to mean a layer which transports holes between the hole injection layer and further layers arranged between the hole injection layer and the cathode layer.

[0084] The operating voltage U is measured in volts.

[0085] In the context of this specification, the term "substantially non-luminescent" or "non-luminescent" means that the contribution of the metal complex of formula (I) or the hole injection layer comprising the metal complex of formula (I) to the visible emission spectrum from an electronic device such as an OLED or a display device is less than 10%, preferably less than 5%, relative to the visible emission spectrum. The visible emission spectrum is the emission spectrum with a wavelength of about ≥380 nm to about ≤780 nm.

[0086] In the context of the present invention, the term "sublimation" may refer to a transition from a solid to a gas phase or from a liquid to a gas phase.

[0087] In this specification, hole characteristics refer to the ability to provide an electron to form a hole when an electric field is applied, and the hole formed in the anode can be easily injected into the light-emitting layer and transported in the light-emitting layer due to the conductive characteristics according to the highest occupied molecular orbital (HOMO) energy level.

[0088] In addition, the electronic property refers to the ability to accept electrons when an electric field is applied, and according to the lowest unoccupied molecular orbital (LUMO) energy level, the electrons formed in the cathode can be easily injected into the light-emitting layer and transported in the light-emitting layer due to the conductive property.

[0089] The term "HOMO level" is understood to mean the highest occupied molecular orbital and is measured in eV (electron volts).

[0090] The term "HOMO energy level further from the vacuum energy level" is understood to mean that the absolute value of the HOMO energy level is higher than the absolute value of the HOMO energy level of the reference compound. For example, the term "further away from the vacuum energy level than the HOMO energy level of N2,N2,N2',N2',N7,N7,N7',N7'-octa(4-methoxyphenyl)-9,9'-spirobi[fluorene]-2,2',7,7'-tetramine" is understood to mean that the absolute value of the HOMO energy level of the host compound of the hole injection layer is higher than the HOMO energy level of N2,N2,N2',N2',N7,N7,N7',N7'-octa(4-methoxyphenyl)-9,9'-spirobi[fluorene]-2,2',7,7'-tetramine.

[0091] The term "absolute value" is understood to mean a value without a "-" sign. According to one embodiment of the present invention, the HOMO energy level of the host compound of the hole injection layer can be calculated by a quantum mechanical method.

[0092] Beneficial Effects

[0093] Surprisingly, it was found that the electronic device according to the invention solves the problem underlying the invention by making electronic devices such as organic light emitting diodes superior to electronic devices known in the art in various aspects, in particular in terms of operating voltage.

[0094] In addition, it was found that the underlying problem of the present invention can be solved by providing a metal complex suitable for deposition by vacuum thermal evaporation under conditions suitable for mass production. In particular, the standard starting temperature of the metal complex of formula (I) of the present invention can be within a range suitable for mass production. In addition, the metal complex of formula (I) of the present invention shows improved thermal properties and / or organic solvent solubility.

[0095] The metal complex of formula (I) is non-luminescent. In the context of this specification, the term "substantially non-luminescent" or "non-luminescent" means that the contribution of the metal complex of formula (I) to the visible emission spectrum from an electronic device such as an OLED or a display device is less than 10%, preferably less than 5%, relative to the visible emission spectrum. The visible emission spectrum is the emission spectrum with a wavelength of about ≥380 nm to about ≤780 nm.

[0096] M of the metal complex of formula (I)

[0097] The term "M" represents a metal ion. According to one embodiment, M is a metal ion selected from alkali metals, alkaline earth metals, transition metals, rare earth metals or metals from Group III to Group V, preferably M is a metal ion selected from transition metals or metals from Group III to Group V; preferably M is a metal ion selected from the following: Li(I), K(I), Rb(I), Cs(I), Ag(I), Cu(II), Zn(II), Pd(II), Ir(III), Al(III), Sc(III), Mn(III), Ru(III), In(III), Y(III), Eu(III), Fe(III), V(IV), Zr(IV), Hf(IV) and Ce(IV); more preferably M is a metal ion selected from the following: Li(I), K(I), Ag(I), Cu(II), Zn(II), Al(III), Sc(III), Mn(III), Fe(III), Zr(IV) and Ce(IV); further preferably M is Cu(II) or Fe(III), and more preferably M is Cu(II); wherein the numbers in brackets represent the oxidation state.

[0098] According to one embodiment, M is a metal ion and may be selected from Cu, Fe, Mn, Al, Hf or Zr, preferably Cu(II), Fe(III), Mn(III), Al(III), Hf(IV) or Zr(IV).

[0099] According to one embodiment, M is a metal ion and may be selected from Ce, preferably Ce(IV).

[0100] The ligand L of formula (I)

[0101] The term "L" is represented by formula (II)

[0102] (II), where

[0103] R 1 and R 2 are independently selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 Heteroaryl or substituted or unsubstituted 6-membered heteroaryl;

[0104] R 3 is selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 heteroaryl, substituted or unsubstituted 6-membered heteroaryl or CN;

[0105] in

[0106] Substituted C1 to C 12 Alkyl, substituted C6 to C 19 Aryl, substituted C2 to C 20 At least one of the substituents of the heteroaryl or substituted 6-membered heteroaryl is independently selected from halogen, Cl, F, CN, partially fluorinated or perfluorinated C1 to C8 alkyl, partially fluorinated or perfluorinated C1 to C8 alkoxy;

[0107] in

[0108] R 1 , R 2 and R 3 At least one or R 1 , R 2 and R 3 The group comprises at least three atoms selected from halogen, Cl, F or N.

[0109] According to one embodiment, the ligand L in the metal complex of formula (I) may be selected from groups containing at least 11 carbon atoms and at most 20 carbon atoms or at least 12 carbon atoms and at most 19 carbon atoms.

[0110] According to one embodiment, the ligand L in the metal complex of formula (I) can be selected from a group comprising at least 11 carbon atoms and at most 20 carbon atoms, or at least 12 carbon atoms and at most 19 carbon atoms; and two oxygen atoms and at least one to four nitrogen atoms, or two oxygen atoms and two nitrogen atoms, or two oxygen atoms and three nitrogen atoms, or two oxygen atoms and four nitrogen atoms.

[0111] According to one embodiment, the ligand L in the metal complex of formula (I) can be selected from the following group, which contains at least 11 carbon atoms and at most 20 carbon atoms or at least 12 carbon atoms and at most 19 carbon atoms; and two oxygen atoms and at least one to four nitrogen atoms, or two oxygen atoms and two nitrogen atoms, or two oxygen atoms and three nitrogen atoms, or two oxygen atoms and four nitrogen atoms; and at least one or more selected from halogen, F, CN, perfluorinated C1 to C 16 Alkyl group.

[0112] According to one embodiment, the ligand L in the metal complex of formula (I) can be selected from the following group, which contains at least 11 carbon atoms and at most 20 carbon atoms or at least 12 carbon atoms and at most 19 carbon atoms; and two oxygen atoms and at least one to four nitrogen atoms, or two oxygen atoms and two nitrogen atoms, or two oxygen atoms and three nitrogen atoms, or two oxygen atoms and four nitrogen atoms; and at least one to five groups selected from halogen, F, CN, and perfluorinated C1 to C3 alkyl.

[0113] The n-valence state of M

[0114] The term "n" is the valence of M and is selected from 1 to 4, preferably n = 1, 2, 3 or 4, more preferably n = 3 or 4. Furthermore, n = 1 or 2 is preferred.

[0115] According to one embodiment, "n" is an integer selected from 2, 3 and 4, corresponding to the valence of M. According to one embodiment, "n" is an integer selected from 2 or 3, corresponding to the valence of M. According to one embodiment, "n" is selected to be 2. According to another embodiment, "n" is selected to be 4. According to another embodiment, "n" is selected to be 3. According to another embodiment, "n" is selected to be 4.

[0116] The term "m"

[0117] The term "m" is an integer selected from 0 to 2, corresponding to the oxidation number of M. According to one embodiment, "m" is an integer selected from 0 or 1. According to another embodiment, "m" is an integer selected from 1. According to another embodiment, "m" is an integer selected from 2. Preferably, "m" is an integer and may be selected from 0.

[0118] According to another embodiment, wherein n = 2 or 3; and / or m is an integer selected from 0 or 1, preferably 0.

[0119] Implementation

[0120] The metal complex of formula (I) may also be referred to as metal complex or acetylacetonate metal complex.

[0121] According to one embodiment, the molecular weight of the metal complex of formula (I) can be Mw ≥ 287 g / mol and ≤ 2000 g / mol, preferably the molecular weight is Mw ≥ 400 g / mol and ≤ 1500 g / mol, more preferably the molecular weight is Mw ≥ 580 g / mol and ≤ 1500 g / mol, further preferably the molecular weight is Mw ≥ 580 g / mol and ≤ 1400 g / mol, further preferably the molecular weight is Mw ≥ 580 g / mol and ≤ 1100 g / mol.

[0122] According to one embodiment, the metal complex of formula (I)

[0123] (I)

[0124] in

[0125] M is a metal ion;

[0126] n is the valence of M and is selected from 1 to 4;

[0127] L has the formula (II)

[0128] (II)

[0129] R 1 and R 2 are independently selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 Heteroaryl or substituted or unsubstituted 6-membered heteroaryl;

[0130] R 3 is C1 to C3 alkyl, substituted or unsubstituted C6 to C 12 Aryl, substituted or unsubstituted C3 to C9 heteroaryl or CN, preferably CH3 or CN;

[0131] in

[0132] Substituted C1 to C 12 Alkyl, substituted C6 to C 19 Aryl, substituted C2 to C 20 At least one of the substituents of the heteroaryl or substituted 6-membered heteroaryl is independently selected from halogen, Cl, F, CN, partially fluorinated or perfluorinated C1 to C8 alkyl, partially fluorinated or perfluorinated C1 to C8 alkoxy;

[0133] in

[0134] R 1 , R 2 and R 3 At least one or R 1 , R 2 and R 3 The group comprises at least three atoms selected from halogen, Cl, F or N;

[0135] in

[0136] AL is an auxiliary ligand coordinated to the metal M;

[0137] m is an integer selected from 0 to 2.

[0138] According to one embodiment, the metal complex of formula (I)

[0139] (I)

[0140] in

[0141] M is a metal ion;

[0142] n is the valence of M and is selected from 1 to 4;

[0143] L has the formula (II)

[0144] (II)

[0145] R 1 and R 2 Independently selected from substituted C6 to C 12 Aryl or substituted C3 to C9 heteroaryl;

[0146] R 3 is C1 to C3 alkyl, substituted or unsubstituted C6 to C 12 Aryl, substituted or unsubstituted C3 to C9 heteroaryl or CN, preferably CH3 or CN;

[0147] in

[0148] Substituted C6 to C 12 At least one of the substituents of the aryl or substituted C3 to C9 heteroaryl is independently selected from F, CN, partially fluorinated or perfluorinated C1 to C3 alkyl, partially fluorinated or perfluorinated C1 to C3 alkoxy;

[0149] in

[0150] R 1 , R 2 and R 3 At least one or R 1 , R 2 and R 3 The group comprises at least three atoms selected from halogen, Cl, F or N;

[0151] in

[0152] AL is an auxiliary ligand coordinated to the metal M;

[0153] m is an integer selected from 0 to 2.

[0154] According to one embodiment, the metal complex of formula (I)

[0155] (I)

[0156] in

[0157] M is a metal ion;

[0158] n is the valence of M and is selected from 1 to 4;

[0159] L has the formula (II)

[0160] (II)

[0161] R 1 and R 2 is a substituted C6 aryl group or a substituted 6-membered C4 to C5 heteroaryl group;

[0162] R 3 is C1 to C3 alkyl, substituted or unsubstituted C6 aryl, substituted or unsubstituted 6-membered C4 to C5 heteroaryl or CN, preferably CH3 or CN;

[0163] in

[0164] At least one of the substituents of the substituted C6 aryl or substituted 6-membered C4 to C5 heteroaryl is independently selected from F, CN, partially fluorinated or perfluorinated C1 to C3 alkyl, partially fluorinated or perfluorinated C1 to C3 alkoxy;

[0165] in

[0166] R 1 , R 2 and R 3 At least one or R 1 , R 2 and R 3 The group comprises at least three atoms selected from halogen, Cl, F or N;

[0167] in

[0168] AL is an auxiliary ligand coordinated to the metal M;

[0169] m is an integer selected from 0 to 2.

[0170] According to one embodiment, the metal complex of formula (I)

[0171] (I)

[0172] in

[0173] M is a metal ion;

[0174] n is the valence of M and is selected from 1 to 4;

[0175] L has the formula (II)

[0176] (II)

[0177] R 1 and R 2 is a substituted C6 aryl group or a substituted 6-membered C4 to C5 heteroaryl group;

[0178] R 3 is C1 to C3 alkyl, substituted or unsubstituted C6 aryl, substituted or unsubstituted 6-membered C4 to C5 heteroaryl or CN, preferably CH3 or CN;

[0179] in

[0180] At least one of the substituents of the substituted C6 aryl or substituted 6-membered C4 to C5 heteroaryl is independently selected from F, CN, partially fluorinated or perfluorinated C1 to C3 alkyl, partially fluorinated or perfluorinated C1 to C3 alkoxy;

[0181] in

[0182] R 1 , R 2 and R 3 At least one or R 1 , R 2 and R 3 The group comprises at least three atoms selected from halogen, Cl, F or N;

[0183] in

[0184] AL is an auxiliary ligand coordinated to the metal M;

[0185] m is an integer selected from 0 to 2; and

[0186] The metal complex of formula (I) comprises at least one or two 6-membered rings and at least one 5-membered ring.

[0187] According to one embodiment, the metal complex of formula (I):

[0188] (I)

[0189] in

[0190] M is a metal ion selected from the main group metals or transition metals, preferably selected from Cu, Fe, Mn, Al, Hf, Zr;

[0191] n is the valence of M and is selected from 2 or 3;

[0192] L has the formula (II)

[0193] (II)

[0194] R1 and R 2 are independently selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 Heteroaryl or substituted or unsubstituted 6-membered heteroaryl;

[0195] R 3 is selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 heteroaryl, substituted or unsubstituted 6-membered heteroaryl or CN;

[0196] in

[0197] Substituted C1 to C 12 Alkyl, substituted C6 to C 19 Aryl, substituted C2 to C 20 At least one of the substituents of the heteroaryl or substituted 6-membered heteroaryl is independently selected from halogen, Cl, F, CN, partially fluorinated or perfluorinated C1 to C8 alkyl, partially fluorinated or perfluorinated C1 to C8 alkoxy;

[0198] in

[0199] R 1 , R 2 and R 3 At least one or R 1 , R 2 and R 3 The group comprises at least three atoms selected from halogen, Cl, F or N;

[0200] in

[0201] By R 1 , R 2 and R 3 The group also includes:

[0202] - at least two moieties selected from CF3 or CN; or

[0203] - at least one moiety selected from CF3 or CN and a substituted or unsubstituted 6-membered heteroaryl group; or

[0204] -R 3 It is CN;

[0205] AL is an auxiliary ligand coordinated to the metal M;

[0206] m is an integer selected from 0 to 2.

[0207] According to one embodiment, the metal complex of formula (I):

[0208] (I)

[0209] in

[0210] M is Ce ion;

[0211] n is the valence of M and is 4;

[0212] L has the formula (II)

[0213] (II)

[0214] R 1 and R 2 are independently selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 Heteroaryl or substituted or unsubstituted 6-membered heteroaryl;

[0215] R 3 is selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 heteroaryl, substituted or unsubstituted 6-membered heteroaryl or CN;

[0216] in

[0217] The substituted C1 to C 12 Alkyl, substituted C6 to C 19 Aryl, substituted C2 to C 20 At least one of the substituents of the heteroaryl or substituted 6-membered heteroaryl is independently selected from halogen, Cl, F, CN, partially fluorinated or perfluorinated C1 to C8 alkyl, partially fluorinated or perfluorinated C1 to C8 alkoxy;

[0218] in

[0219] R 1 , R 2 and R 3 At least one or R 1 , R 2 and R 3 The group comprises at least three atoms selected from halogen, Cl, F or N;

[0220] AL is an auxiliary ligand coordinated to the metal M;

[0221] m is an integer selected from 0 to 2.

[0222] According to one embodiment, the metal complex of formula (I):

[0223] (I)

[0224] in

[0225] M is a metal ion;

[0226] n is the valence of M and is selected from 1 to 4;

[0227] L has the formula (II)

[0228] (II)

[0229] R 1 and R 2 are independently selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C3 containing at least one substituted or unsubstituted 6-membered heteroaryl group 20 heteroaryl;

[0230] R 3 Selected from partially fluorinated or perfluorinated C1 to C4 alkyl or CN;

[0231] in

[0232] Substituted C1 to C 12 Alkyl, substituted C6 to C 19 Aryl, substituted C2 to C 20 At least one of the substituents of the heteroaryl or substituted 6-membered heteroaryl is independently selected from halogen, Cl, F, CN, partially fluorinated or perfluorinated C1 to C8 alkyl, partially fluorinated or perfluorinated C1 to C8 alkoxy;

[0233] in

[0234] AL is an auxiliary ligand coordinated to the metal M;

[0235] m is an integer selected from 0 to 2.

[0236] According to one embodiment, the metal complex of formula (I):

[0237] (I)

[0238] in

[0239] M is a metal ion;

[0240] n is the valence of M and is selected from 1 to 4;

[0241] L has the formula (II)

[0242] (II)

[0243] R 1 and R 2 are independently selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 Heteroaryl, substituted or unsubstituted 6-membered heteroaryl;

[0244] R 3 is selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 heteroaryl, substituted or unsubstituted 6-membered heteroaryl or CN;

[0245] in

[0246] Substituted C1 to C 12 Alkyl, substituted C6 to C 19 Aryl, substituted C2 to C 20 At least one of the substituents of the heteroaryl or substituted 6-membered heteroaryl is independently selected from halogen, Cl, F, CN, partially fluorinated or perfluorinated C1 to C8 alkyl, partially fluorinated or perfluorinated C1 to C8 alkoxy;

[0247] in

[0248] R 1 , R 2 and R 3 At least one or R 1 , R 2 and R 3 The group includes substituted or unsubstituted C2 to C 20 heteroaryl;

[0249] in

[0250] AL is an auxiliary ligand coordinated to the metal M;

[0251] m is an integer selected from 0 to 2.

[0252] According to one embodiment of the metal complex of formula (I), at least one R 1 or R 3 , or R 1 and R 3 selected from substituted C2 to C 20The heteroaryl group, wherein the C2 to C 20 The heteroaryl group is selected from pyridyl, pyrimidinyl, pyrazinyl, triazinyl.

[0253] According to one embodiment of the metal complex of formula (I), wherein R 1 is selected from unsubstituted or substituted phenyl, substituted pyridyl, substituted pyrimidyl, substituted pyrazinyl, substituted triazinyl, wherein the substituent of the substituted phenyl, substituted pyridyl, substituted pyrimidyl, substituted pyrazinyl or substituted triazinyl is selected from CN, CF3, C2F5, C3F7 or C4F9.

[0254] According to one embodiment of the metal complex of formula (I), wherein R 1 Selected from unsubstituted or substituted phenyl, substituted pyridyl, substituted pyrimidyl, substituted pyrazinyl, substituted triazinyl, wherein at least two or three of the substituents of the substituted phenyl, substituted pyridyl, substituted pyrimidyl, substituted pyrazinyl or substituted triazinyl are selected from CN, CF3, C2F5, C3F7 or C4F9.

[0255] According to one embodiment of the metal complex of formula (I), wherein R 2 is selected from substituted pyridyl, substituted pyrimidinyl, substituted pyrazinyl, substituted triazinyl, CF3, C2F5, C3F7 or C4F9, wherein the substituent of the substituted pyridyl, substituted pyrimidinyl, substituted pyrazinyl or substituted triazinyl is selected from CF3, C2F5, C3F7 or C4F9.

[0256] According to one embodiment of the metal complex of formula (I), wherein R 2 is selected from substituted pyridyl, substituted pyrimidinyl, substituted pyrazinyl, substituted triazinyl, CF3, C2F5, C3F7 or C4F9, wherein at least two or three of the substituents of the substituted pyridyl, substituted pyrimidinyl, substituted pyrazinyl or substituted triazinyl are selected from CF3, C2F5, C3F7 or C4F9.

[0257] According to one embodiment of the metal complex of formula (I), wherein R 2 Selected from CF3, C2F5, C3F7 or C4F9.

[0258] According to one embodiment of the metal complex of formula (I), wherein R 3 Selected from unsubstituted or substituted phenyl, CH3 or CN, wherein the substituent of the substituted phenyl is selected from CN, CF3, C2F5, C3F7 or C4F9, preferably CF3.

[0259] According to one embodiment of the metal complex of formula (I), wherein R 1 , R 2 and R 3 At least one or R 1 , R 2 and R 3 The group comprises at least three atoms selected from halogen, Cl, F or N.

[0260] According to one embodiment of the metal complex of formula (I), wherein R 1 and R 2 are independently selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C3 containing at least one substituted or unsubstituted 6-membered heteroaryl group 20 heteroaryl; and R 3 Selected from partially fluorinated or perfluorinated C1 to C4 alkyl or CN, preferably CF3.

[0261] According to one embodiment of the metal complex of formula (I), wherein R 1 , R 2 and R 3 The group consisting of at least two moieties selected from CF3 or CN; or wherein R 1 , R 2 and R 3 The group consisting of at least one moiety selected from CF3 or CN and a substituted or unsubstituted 6-membered heteroaryl group; or R 3 For CN.

[0262] According to one embodiment of the metal complex of formula (I), wherein R 1 , R 2 and R 3 At least one of the group consisting of is selected from CN, CH3, CF3, C2F5, C3F7 or C4F9, preferably CN, CH3, CF3, C2F5 or C3F7; more preferably CN, CH3 or CF3.

[0263] According to one embodiment of the metal complex of formula (I), the metal complex of formula (I) comprises at least one CF3 group, preferably at least two CF3 groups, more preferably at least three CF3 groups, and further preferably at least four CF3 groups, or at least two CF3 groups and at least one C2F5, or at least two CF3 groups and at least one group selected from CN, F or CH3.

[0264] According to one embodiment of the metal complex of formula (I), at least one R 1 and / or R 2Selected from substituted C6 to C 19 Aryl or substituted C3 to C 20 The heteroaryl group, wherein the substituted C6 to C 19 Aryl or substituted C3 to C 20 At least one substituent of the heteroaryl group is selected from CN or a partially or fully fluorinated C1 to C 12 Alkyl, preferably partially fluorinated or fully fluorinated C1 to C4 alkyl.

[0265] According to one embodiment of the metal complex of formula (I), at least one R 1 and / or R 2 Selected from substituted C6 to C 19 Aryl or substituted C3 to C 20 The heteroaryl group, wherein the substituted C6 to C 19 Aryl or substituted C3 to C 20 At least two substituents of the heteroaryl group are selected from CN or a partially or fully fluorinated C1 to C 12 Alkyl, preferably partially fluorinated or fully fluorinated C1 to C4 alkyl.

[0266] According to one embodiment of the metal complex of formula (I), the metal complex of formula (I) comprises at least one CF3 group, preferably at least two CF3 groups, more preferably at least three CF3 groups, and further preferably at least four CF3 groups, or at least two CF3 groups and at least one C2F5, or at least two CF3 groups and at least one group selected from CN, F or CH3.

[0267] According to one embodiment of the metal complex of formula (I), at least one R 1 and / or R 2 selected from substituted C3 to C 20 A heteroaryl group, wherein

[0268] - the substituted heteroaryl group contains at least 2 to 6 N atoms, preferably 3 to 5 N atoms, more preferably 2 N atoms; and / or

[0269] - The heteroaryl group of the substituted heteroaryl group is a six-membered ring containing 1, 2 or 3 heteroatoms, wherein the heteroatom is preferably N.

[0270] According to one embodiment of the metal complex of formula (I), at least one R 1 and / or R 2 selected from substituted C3 to C 20 A heteroaryl group, wherein

[0271] - the substituted heteroaryl group contains at least 2 to 6 N atoms, preferably 3 to 5 N atoms, more preferably 2 N atoms; and / or

[0272] - The heteroaryl group of the substituted heteroaryl group is a six-membered ring containing 1, 2 or 3 heteroatoms, wherein the heteroatom is preferably N.

[0273] According to one embodiment, at least one R 1 and / or R 2 Selected from substituted C3 to C 20 A heteroaryl group, wherein the heteroaryl group is selected from pyridyl, pyrimidinyl, pyrazinyl or triazinyl.

[0274] According to one embodiment, at least one R 1 and / or R 2 Selected from substituted C3 to C 20 A heteroaryl group wherein the C3 to C 20 The heteroaryl group is selected from pyridyl, pyrimidinyl, pyrazinyl, triazinyl.

[0275] According to one embodiment, at least one R 1 and / or R 2 Selected from substituted C3 to C 20 A heteroaryl group, wherein at least one substituent of the substituted heteroaryl group is selected from halogen, F, Cl, CN, partially fluorinated or fully fluorinated C1 to C6 alkyl, preferably selected from halogen, F, Cl, CN, partially fluorinated or fully fluorinated C1 to C6 alkyl, more preferably selected from halogen, F, Cl, CN, partially fluorinated or fully fluorinated C1 to C4 alkyl; more preferably selected from F, CN, partially fluorinated or fully fluorinated C1 to C6 alkyl; also preferably F, CN, partially fluorinated or fully fluorinated C1 to C6 alkyl, also preferably halogen, F, Cl, CN, partially fluorinated or fully fluorinated C1 to C4 alkyl; more preferably selected from at least one CN, at least one CF3 group and / or at least two F atoms.

[0276] According to one embodiment, at least one R 1 and / or R 2 Selected from substituted C3 to C 20 A heteroaryl group wherein at least one substituent is selected from halogen, F, Cl, CN, partially fluorinated or fully fluorinated C1 to C6 alkyl, and one R 1 and / or R 2 is selected from substituted or unsubstituted C1 to C 12 Alkyl, wherein the at least one substituent is selected from halogen, F, Cl, CN, partially fluorinated or fully fluorinated C1 to C6 alkyl.

[0277] According to one embodiment, one of the R 1 Selected from substituted C3 to C 20 A heteroaryl group wherein at least one, two or three substituents are selected from a CF3 group.

[0278] According to one embodiment, wherein R 2 Selected from substituted C3 to C 20 A heteroaryl group wherein at least one, two or three substituents are selected from CF3 groups and / or CN groups.

[0279] According to one embodiment, wherein R 1 Selected from substituted C6 to C 19 An aryl group wherein at least one, two or three substituents are selected from a CF3 group.

[0280] According to one embodiment, wherein R 2 Selected from substituted C6 to C 19 Aryl groups, wherein at least one, two or three substituents are selected from CF3 groups and / or CN groups.

[0281] According to one embodiment, wherein R 1 is selected from substituted pyridine groups, wherein at least one, two or three substituents are selected from CF3 groups.

[0282] According to one embodiment, wherein R 2 is selected from substituted pyridine groups, wherein at least one, two or three substituents are selected from CF3 groups and / or CN groups.

[0283] According to one embodiment, wherein R 1 is selected from substituted phenyl groups, wherein at least one, two or three substituents are selected from CF3 groups.

[0284] According to one embodiment, wherein R 2 is selected from substituted phenyl groups, wherein at least one, two or three substituents are selected from CF3 groups and / or CN groups.

[0285] According to one embodiment, wherein R 1 is selected from substituted phenyl groups, wherein at least one, two or three substituents are selected from CF3 groups; and wherein R 3 is selected from substituted phenyl groups, wherein at least one, two or three substituents are selected from CF3 groups and / or CN groups.

[0286] According to one embodiment, wherein R 1 and / or R 2 cannot be selected from substituted or unsubstituted C6 to C 19 an aryl group or a substituted or unsubstituted C6 to C18 Aryl group.

[0287] According to one embodiment, wherein R 1 and R 2 It cannot be selected from unsubstituted aryl and / or unsubstituted heteroaryl groups.

[0288] According to one embodiment, formula (I) cannot contain unsubstituted aryl and / or unsubstituted heteroaryl groups.

[0289] According to one embodiment, formula (I) cannot contain substituted aryl groups.

[0290] According to one embodiment, formula (I) cannot contain substituted heteroaryl groups.

[0291] According to one embodiment, wherein R of formula (I) 1 , R 2 and R 3 At least one of the group consisting of substituted or unsubstituted C6 to C 19 Aryl or a substituted C2 to C 20 A heteroaryl group, and is selected from the following formula D1 to formula D71:

[0292] (D1), (D2), (D3), (D4), (D5), (D6), (D7), (D8), (D9), (D10), (D11), (D12), (D13), (D14), (D15), (D16), (D17), (D18), (D19), (D20), (D21), (D22), (D23), (D24), (D25), (D26), (D27), (D28), (D29), (D30), (D31), (D32), (D33), (D34), (D35), (D36), (D37), (D38), (D39), (D40), (D41), (D42), (D43), (D44), (D45), (D46), (D47), (D48), (D49), (D50), (D51), (D52), (D53), (D54), (D56), (D57), (D58), (D59), (D60), (D61), (D62), (D63), (D64), (D65), (D67), (D68), (D69), (D70), (D71), where “*” indicates the binding position.

[0293] According to one embodiment of formula (I), the ligand L is selected from the following formula E1 to formula E212:

[0294] (E1), (E2), (E3), (E4), (E5), (E6), (E7), (E8), (E9), (E10), (E11), (E12), (E13), (E14), (E15), (E16), (E17), (E18), (E19), (E20), (E21), (E22), (E23), (E24), (E25), (E26), (E27), (E28), (E29), (E30), (E31), (E32), (E33), (E34), (E35), (E36), (E37), (E38), (E39), (E40), (E41), (E42), (E43), (E44), (E45), (E46), (E47), (E48), (E49), (E50), (E51), (E52), (E53), (E54), (E55), (E56), (E57), (E58),<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E59)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E60)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E61)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E62)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E63)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E64)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E65)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E66)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E67)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E68)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E69)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E70)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E71)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E72)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E73)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E74)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E75)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E76)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E77),<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E78)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E79)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E80)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E81)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E82)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E83)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E84)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E85)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E86)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E87)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E88)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E89)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E90)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E91)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E92)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E93)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E94)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E95)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E96)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E97)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E98)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E99)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E100)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E101)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E102)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E103)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E104)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E105)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E106)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E107)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E108)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E109)<h2 style=";text-align:left;direction:ltr"> (E110), (E111), (E112), (E113), (E114), (E115), (E116), (E117), (E118), (E119), (E120), (E121), (E122), (E123), (E124), (E125), (E126), (E127), (E128), (E129), (E130), (E131), (E132), (E133), (E134), (E135), (E136), (E137), (E138), (E139), (E140), (E141), (E142), (E143), (E144), (E145), (E146), (E147), (E148), (E149), (E150), (E151), (E152), (E153), (E154), (E155), (E156), (E157), (E158), (E159), (E160), (E161), (E162), (E163), (E164), (E165), (E166), (E167), (E168), (E169), (E170), (E171), (E172), (E173), (E174), (E175), (E176), (E177), (E178), (E179), (E180), (E181), (E182), (E183), (E184), (E185), (E186), (E187), (E188), (E189), (E190), (E191), (E192), (E193), (E194), (E195), (E196), (E197), (E198), (E199), (E200), (E201), (E202), (E203), (E204), (E205), (E206), (E207), (E208), (E209), (E210), (E211), (E212).

[0295] According to one embodiment of the present invention, M is selected from Cu(II), Fe(III), Ag(I), Al(III), Ir(III), In(III), Mn(III), Ru(III) or Ce(IV), wherein the numbers in brackets represent the oxidation state, and L is selected from Formula E1 to Formula E212.

[0296] According to one embodiment of the present invention, M is selected from Cu(II), Fe(III), In(III), Mn(III), Ru(III) or Ce(IV), wherein the numbers in brackets represent the oxidation state, and L is selected from Formula E1 to Formula E212.

[0297] According to one embodiment of the present invention, M is selected from Cu(II) or Fe(III), wherein the numbers in brackets represent the oxidation state, and L is selected from Formula E1 to Formula E212.

[0298] Table 1 shows acetylpyrazolone acid metal complexes MC1 to MC60 according to formula (I) which can be appropriately used according to the present invention and comparative compounds CC1 to CC5 used in comparative examples.

[0299] Table 1 Acetylpyrazolone acid metal complex according to formula (I)

[0300]

[0301] According to one embodiment of formula (I), wherein AL is selected from H2O, C2 to C 40 Monodentate or polydentate ethers and C2 to C 40 Thioether, C2 to C 40 Amines, C2 to C 40 Phosphine, C2 to C 20 Alkyl nitrile or C2 to C 40Aryl nitrile, or a compound according to formula (III);

[0302] (III), where

[0303] R 6 and R 7 Independently selected from C1 to C 20 Alkyl, C1 to C 20 Heteroalkyl, C6 to C 20 Aryl, heteroaryl having 5 to 20 ring atoms, halogenated or perhalogenated C1 to C 20 Alkyl, halogenated or perhalogenated C1 to C 20 Heteroalkyl, halogenated or perhalogenated C6 to C 20 aryl, halogenated or perhalogenated heteroaryl having 5 to 20 ring atoms, or at least one R 6 and R 7 bridged to form a 5- to 20-membered ring, or two R 6 and / or two R 7 bridged to form a 5 to 40 membered ring or to form a ring containing unsubstituted or C1 to C 12 The 5- to 40-membered ring of the substituted phenanthroline.

[0304] Semiconductor Materials

[0305] According to another aspect, the semiconductor material comprises at least one compound of formula (I) according to the present invention.

[0306] According to one embodiment, the semiconductor material further comprises at least one covalent matrix compound or at least one substantially covalent matrix compound.

[0307] According to another aspect, the semiconductor material comprises at least one compound of formula (I) according to the invention and additionally at least one covalent matrix compound or at least one essentially covalent matrix compound.

[0308] Essentially covalent matrix compound / covalent matrix compound

[0309] The substantially covalent matrix compound, also referred to as a matrix compound, may be an organic aromatic matrix compound comprising organic aromatic covalently bonded carbon atoms. The substantially covalent matrix compound may be an organic compound consisting essentially of covalently bonded C, H, O, N, S, and may optionally further comprise covalently bonded B, P or Si. The substantially covalent matrix compound may be an organic aromatic covalently bonded compound free of metal atoms, the skeleton atoms of which may mostly be selected from C, O, S, N, preferably from C, O and N, wherein the atoms are mostly C atoms. Alternatively, the covalent matrix compound may be free of metal atoms and the skeleton atoms of which may mostly be selected from C and N, preferably the covalent matrix compound may be free of metal atoms and the skeleton atoms of which may mostly be selected from C, and a minority of the skeleton atoms may be N.

[0310] According to one embodiment, the molecular weight Mw of the substantially covalent matrix compound may be ≥400 g / mol and ≤2000 g / mol, preferably the molecular weight Mw is ≥450 g / mol and ≤1500 g / mol, more preferably the molecular weight Mw is ≥500 g / mol and ≤1000 g / mol, further preferably the molecular weight Mw is ≥550 g / mol and ≤900 g / mol, further preferably the molecular weight Mw is ≥600 g / mol and ≤800 g / mol.

[0311] In one embodiment, the HOMO energy level of the substantially covalent host compound may be more negative than the HOMO energy level of N2,N2,N2',N2',N7,N7,N7',N7'-octa(4-methoxyphenyl)-9,9'-spirobi[fluorene]-2,2',7,7'-tetraamine (CAS 207739-72-8) when measured under the same conditions.

[0312] In one embodiment of the present invention, the substantially covalent matrix compound may be free of alkoxy groups.

[0313] Preferably, the substantially covalent matrix compound comprises at least one arylamine moiety, or a diarylamine moiety, or a triarylamine moiety.

[0314] Preferably, the substantially covalent matrix compound does not contain TPD or NPB.

[0315] The compound of formula (IV) or the compound of formula (V)

[0316] According to the present invention, the substantially covalent matrix compound or covalent matrix compound (also referred to herein as a matrix compound) may comprise at least one arylamine compound, diarylamine compound, triarylamine compound, a compound of formula (IV) or a compound of formula (V):

[0317] (IV), (V),

[0318] in:

[0319] T 1 , T 2 , T 3 , T 4 and T 5 independently selected from a single bond, a phenylene group, a biphenylene group, a terphenylene group or a naphthalene group, preferably a single bond or a phenylene group;

[0320] T 6 is a phenyl subunit, a biphenyl subunit, a terphenyl subunit or a naphthalene subunit;

[0321] Ar 1 ,Ar 2 ,Ar 3 ,Ar 4 and Ar 5 independently selected from substituted or unsubstituted C6 to C 20 Aryl, or substituted or unsubstituted C3 to C 20 Heteroarylidene, substituted or unsubstituted biphenylidene, substituted or unsubstituted fluorene, substituted 9-fluorene, substituted 9,9-fluorene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthrene, substituted or unsubstituted pyrene, substituted or unsubstituted perylene, substituted or unsubstituted terphenylidene, substituted or unsubstituted tetracene, substituted or unsubstituted benzanthracene, substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted xanthene, substituted or unsubstituted carbazole, substituted 9-phenylcarbazole, substituted or unsubstituted azepane, substituted or unsubstituted dibenzo[b,f]azepane, substituted or unsubstituted 9,9'- Spirobi[fluorene], substituted or unsubstituted spiro[fluorene-9,9'-xanthene], or a substituted or unsubstituted aromatic fused ring system comprising at least three substituted or unsubstituted aromatic rings selected from substituted or unsubstituted non-heterocyclic, substituted or unsubstituted hetero 5-membered rings, substituted or unsubstituted 6-membered rings and / or substituted or unsubstituted 7-membered rings, substituted or unsubstituted fluorene, or a fused ring system comprising 2 to 6 substituted or unsubstituted 5- to 7-membered rings, and the rings are selected from (i) heterocyclic unsaturated 5- to 7-membered rings, (ii) aromatic heterocyclic 5- to 6-membered rings, (iii) non-heterocyclic unsaturated 5- to 7-membered rings, (iv) aromatic non-heterocyclic 6-membered rings;

[0322] in

[0323] Ar 1 ,Ar 2 ,Ar 3 ,Ar 4 and Ar 5The substituents are selected from H, D, F, C(-O)R 2 、CN、Si(R 2 )3. P(-O)(R 2 2. OR 2 、S(-O)R 2 、S(-O)2R 2 , substituted or unsubstituted straight-chain alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted branched-chain alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cyclic alkyl groups having 3 to 20 carbon atoms, substituted or unsubstituted alkenyl or alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aromatic ring systems having 6 to 40 aromatic ring atoms, and substituted or unsubstituted heteroaromatic ring systems having 5 to 40 aromatic ring atoms, unsubstituted C6 to C 18 Aryl, unsubstituted C3 to C 18 heteroaryl, a fused ring system comprising 2 to 6 unsubstituted 5- to 7-membered rings, and the rings are selected from heterocyclic unsaturated 5- to 7-membered rings, aromatic heterocyclic 5- to 6-membered rings, non-heterocyclic unsaturated 5- to 7-membered rings and aromatic non-heterocyclic 6-membered rings,

[0324] Where R 2 The alkyl radical may be selected from H, D, a linear alkyl radical having 1 to 6 carbon atoms, a branched alkyl radical having 1 to 6 carbon atoms, a cyclic alkyl radical having 3 to 6 carbon atoms, an alkenyl or alkynyl radical having 2 to 6 carbon atoms, a C6 to C 18 Aryl or C3 to C 18 Heteroaryl.

[0325] According to one embodiment of the electronic device, wherein the substantially covalent matrix compound comprises a compound of formula (IV) or formula (V):

[0326] (IV), (V),

[0327] in

[0328] T 1 , T 2 , T 3 , T 4 and T 5 can be independently selected from a single bond, a phenylene group, a biphenylene group, a terphenylene group or a naphthalene group, preferably a single bond or a phenylene group;

[0329] T 6 is a phenyl subunit, a biphenyl subunit, a terphenyl subunit or a naphthalene subunit;

[0330] Ar 1 ,Ar 2 ,Ar 3,Ar 4 and Ar 5 may be independently selected from substituted or unsubstituted C6 to C 20 Aryl, or substituted or unsubstituted C3 to C 20 Heteroarylidene, substituted or unsubstituted biphenylidene, substituted or unsubstituted fluorene, substituted 9-fluorene, substituted 9,9-fluorene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthrene, substituted or unsubstituted pyrene, substituted or unsubstituted perylene, substituted or unsubstituted terphenylidene, substituted or unsubstituted tetracene, substituted or unsubstituted benzanthracene, substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted xanthene, substituted or unsubstituted carbazole, substituted 9-phenylcarbazole, substituted or unsubstituted azepane, substituted or unsubstituted dibenzo[b,f]azepane, substituted or unsubstituted 9,9'- Spirobi[fluorene], substituted or unsubstituted spiro[fluorene-9,9'-xanthene], or a substituted or unsubstituted aromatic fused ring system comprising at least three substituted or unsubstituted aromatic rings selected from substituted or unsubstituted non-heterocyclic, substituted or unsubstituted hetero 5-membered rings, substituted or unsubstituted 6-membered rings and / or substituted or unsubstituted 7-membered rings, substituted or unsubstituted fluorene, or a fused ring system comprising 2 to 6 substituted or unsubstituted 5- to 7-membered rings, and the rings are selected from (i) heterocyclic unsaturated 5- to 7-membered rings, (ii) aromatic heterocyclic 5- to 6-membered rings, (iii) non-heterocyclic unsaturated 5- to 7-membered rings, (iv) aromatic non-heterocyclic 6-membered rings;

[0331] Among them, Ar 1 ,Ar 2 ,Ar 3 ,Ar 4 and Ar 5 The substituents are selected, identically or differently, from H, straight-chain alkyl groups having 1 to 20 carbon atoms, branched-chain alkyl groups having 1 to 20 carbon atoms, cyclic alkyl groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, C6 to C 18 Aryl, C3 to C 18 Heteroaryl, a fused ring system comprising 2 to 6 unsubstituted 5 to 7 membered rings, and the rings are selected from heterocyclic unsaturated 5 to 7 membered rings, aromatic heterocyclic 5 to 6 membered rings, non-heterocyclic unsaturated 5 to 7 membered rings and aromatic non-heterocyclic 6 membered rings.

[0332] Preferably, Ar 1 ,Ar 2 ,Ar 3 ,Ar 4 and Ar 5The substituents are selected, identically or differently, from H, straight-chain alkyl groups having 1 to 6 carbon atoms, branched-chain alkyl groups having 1 to 6 carbon atoms, cyclic alkyl groups having 3 to 6 carbon atoms, alkenyl or alkynyl groups having 2 to 6 carbon atoms, C6 to C 18 Aryl, C3 to C 18 heteroaryl, a fused ring system comprising 2 to 4 unsubstituted 5- to 7-membered rings, and the rings are selected from heterocyclic unsaturated 5- to 7-membered rings, aromatic heterocyclic 5- to 6-membered rings, non-heterocyclic unsaturated 5- to 7-membered rings and aromatic non-heterocyclic 6-membered rings; more preferably, the substituents are selected, identically or differently, from H, straight-chain alkyl groups having 1 to 4 carbon atoms, branched-chain alkyl groups having 1 to 4 carbon atoms, cyclic alkyl groups having 3 to 4 carbon atoms and / or phenyl groups.

[0333] Thus, the compound of formula (IV) or formula (V) may have a standard starting temperature suitable for mass production.

[0334] According to one embodiment of the electronic device, wherein the substantially covalent matrix compound comprises a compound of formula (IV) or formula (V):

[0335] (IV), (V),

[0336] in

[0337] T 1 , T 2 , T 3 , T 4 and T 5 can be independently selected from a single bond, a phenylene group, a biphenylene group, a terphenylene group or a naphthalene group, preferably a single bond or a phenylene group;

[0338] T 6 is a phenyl subunit, a biphenyl subunit, a terphenyl subunit or a naphthalene subunit;

[0339] Ar 1 ,Ar 2 ,Ar 3 ,Ar 4 and Ar 5 can be independently selected from unsubstituted C6 to C 20 Aryl, or unsubstituted C3 to C 20Heteroarylidene, unsubstituted biphenylidene, unsubstituted fluorene, substituted 9-fluorene, substituted 9,9-fluorene, unsubstituted naphthalene, unsubstituted anthracene, unsubstituted phenanthrene, unsubstituted pyrene, unsubstituted perylene, unsubstituted terphenylidene, unsubstituted tetracene, unsubstituted benzanthracene, unsubstituted dibenzofuran, unsubstituted dibenzothiophene, unsubstituted xanthene, unsubstituted carbazole, substituted 9-phenylcarbazole, unsubstituted azepane, unsubstituted dibenzo[b,f]azepane, unsubstituted 9,9'-spirobi[fluorene], unsubstituted spiro[fluorene- 9,9'-xanthene], or an unsubstituted aromatic fused ring system comprising at least three unsubstituted aromatic rings, the unsubstituted aromatic rings being selected from unsubstituted non-heterocyclic, unsubstituted hetero 5-membered rings, unsubstituted 6-membered rings and / or unsubstituted 7-membered rings, unsubstituted fluorene, or a fused ring system comprising 2 to 6 unsubstituted 5- to 7-membered rings, and the rings are selected from (i) heterocyclic unsaturated 5- to 7-membered rings, (ii) aromatic heterocyclic 5- to 6-membered rings, (iii) non-heterocyclic unsaturated 5- to 7-membered rings, and (iv) aromatic non-heterocyclic 6-membered rings.

[0340] According to one embodiment of the electronic device, wherein the substantially covalent matrix compound comprises a compound of formula (IV) or formula (V):

[0341] (IV), (V),

[0342] in

[0343] T 1 , T 2 , T 3 , T 4 and T 5 can be independently selected from a single bond, a phenylene group, a biphenylene group, a terphenylene group or a naphthalene group, preferably a single bond or a phenylene group;

[0344] T 6 is a phenyl subunit, a biphenyl subunit, a terphenyl subunit or a naphthalene subunit;

[0345] Ar 1 ,Ar 2 ,Ar 3 ,Ar 4 and Ar 5 can be independently selected from unsubstituted C6 to C 20 Aryl, or unsubstituted C3 to C 20heteroarylidene, unsubstituted biphenylidene, unsubstituted fluorene, substituted 9-fluorene, substituted 9,9-fluorene, unsubstituted naphthalene, unsubstituted anthracene, unsubstituted phenanthrene, unsubstituted pyrene, unsubstituted perylene, unsubstituted terphenylidene, unsubstituted tetracene, unsubstituted benzanthracene, unsubstituted dibenzofuran, unsubstituted dibenzothiophene, unsubstituted xanthene, unsubstituted carbazole, substituted 9-phenylcarbazole, unsubstituted azepane, unsubstituted dibenzo[b,f]azepane, unsubstituted 9,9'-spirobi[fluorene], unsubstituted spiro[fluorene-9,9'-xanthene].

[0346] Thus, the compound of formula (IV) or formula (V) may have a standard starting temperature suitable for mass production.

[0347] According to one embodiment, wherein T 1 , T 2 , T 3 , T 4 and T 5 can be independently selected from a single bond, a phenyl group, a biphenyl group or a terphenyl group. According to one embodiment, wherein T 1 , T 2 , T 3 , T 4 and T 5 can be independently selected from a phenyl subunit, a biphenyl subunit or a terphenyl subunit, and T 1 , T 2 , T 3 , T 4 and T 5 is a single bond. According to one embodiment, wherein T 1 , T 2 , T 3 , T 4 and T 5 may be independently selected from a phenylene group or a biphenylene group, and T 1 , T 2 , T 3 , T 4 and T 5 is a single bond. According to one embodiment, wherein T 1 , T 2 , T 3 , T 4 and T 5 may be independently selected from a phenylene group or a biphenylene group, and T 1 , T 2 , T 3 , T 4 and T 5 Two of them are single bonds.

[0348] According to one embodiment, wherein T1 , T 2 and T 3 may be independently selected from phenylene groups, and T 1 , T 2 and T 3 is a single bond. According to one embodiment, wherein T 1 , T 2 and T 3 may be independently selected from phenylene groups, and T 1 , T 2 and T 3 Two of them are single bonds.

[0349] According to one embodiment, wherein T 6 It can be a phenyl subunit, a biphenyl subunit, or a terphenyl subunit. According to one embodiment, wherein T 6 According to one embodiment, wherein T 6 It can be a biphenyl subunit. According to one embodiment, wherein T 6 It may be a terphenyl subunit.

[0350] According to one embodiment, wherein Ar 1 ,Ar 2 ,Ar 3 ,Ar 4 and Ar 5 Can be independently selected from B1 to B16:

[0351] (B1), (B2), (B3), (B4), (B5), (B6), (B7), (B8), (B9), (B10), (B11), (B12), (B13), (B14), (B15), (B16),

[0352] The asterisk "*" indicates the binding position.

[0353] According to one embodiment, wherein Ar 1 ,Ar 2 ,Ar 3 ,Ar 4 and Ar5 Can be independently selected from B1 to B15; or selected from B1 to B10 and B13 to B15.

[0354] According to one embodiment, wherein Ar 1 ,Ar 2 ,Ar 3 ,Ar 4 and Ar 5 Can be independently selected from B1, B2, B5, B7, B9, B10, B13 to B16.

[0355] When Ar is selected within this range 1 ,Ar 2 ,Ar 3 ,Ar 4 and Ar 5 When the standard starting temperature is in a range that is particularly suitable for mass production.

[0356] The “host compound of formula (IV) or formula (V)” may also be referred to as a “hole transport compound”.

[0357] According to one embodiment, the compound of formula (IV) or formula (V) may contain at least ≥1 to ≤6 substituted or unsubstituted aromatic fused ring systems containing heteroaromatic rings.

[0358] According to one embodiment, the compound of formula (IV) or formula (V) may contain at least ≥1 to ≤6 substituted or unsubstituted aromatic fused ring systems containing heteroaromatic rings and at least ≥1 to ≤3 substituted or unsubstituted heterocyclic unsaturated 5 to 7 membered rings, preferably ≥2 to ≤5 substituted or unsubstituted aromatic fused ring systems containing heteroaromatic rings.

[0359] According to one embodiment, the compound of formula (IV) or formula (V) may contain at least ≥1 to ≤6 substituted or unsubstituted aromatic fused ring systems containing heteroaromatic rings and at least ≥1 to ≤3 substituted or unsubstituted heterocyclic unsaturated 5 to 7 membered rings, preferably ≥2 to ≤5 substituted or unsubstituted aromatic fused ring systems containing heteroaromatic rings and at least ≥1 to ≤3 substituted or unsubstituted heterocyclic unsaturated 5 to 7 membered rings, more preferably 3 or 4 substituted or unsubstituted aromatic fused ring systems containing heteroaromatic rings and optionally at least ≥1 to ≤3 substituted or unsubstituted heterocyclic unsaturated 5 to 7 membered rings, and it is also preferred that the aromatic fused ring system containing heteroaromatic rings is unsubstituted and optionally at least ≥1 to ≤3 unsubstituted heterocyclic unsaturated 5 to 7 membered rings.

[0360] According to one embodiment, the compound of formula (IV) or formula (V) may contain at least ≥1 to ≤6 substituted or unsubstituted aromatic fused ring systems, preferably ≥2 to ≤5 substituted or unsubstituted aromatic fused ring systems, and more preferably 3 or 4 substituted or unsubstituted aromatic fused ring systems.

[0361] According to one embodiment, the compound of formula (IV) or formula (V) may contain at least ≥1 to ≤6 substituted or unsubstituted aromatic fused ring systems, preferably ≥2 to ≤5 substituted or unsubstituted aromatic fused ring systems, more preferably 3 or 4 substituted or unsubstituted aromatic fused ring systems, wherein the aromatic fused ring system contains a substituted or unsubstituted heteroaromatic ring.

[0362] According to one embodiment, the compound of formula (IV) or formula (V) may contain at least ≥1 to ≤3 or 2 substituted or unsubstituted heterocyclic unsaturated 5- to 7-membered rings.

[0363] According to one embodiment, the compound of formula (IV) or formula (V) may contain at least ≥1 to ≤3 or 2 substituted or unsubstituted heterocyclic unsaturated 7-membered rings.

[0364] According to one embodiment, the substituted or unsubstituted aromatic fused ring system of the compound of formula (IV) or formula (V) may contain at least ≥1 to ≤3 or 2 substituted or unsubstituted heterocyclic unsaturated 5- to 7-membered rings.

[0365] According to one embodiment, the substituted or unsubstituted aromatic fused ring system of the host compound of formula (IV) or (V) may contain at least ≥1 to ≤3 or 2 substituted or unsubstituted heterocyclic unsaturated 7-membered rings.

[0366] According to one embodiment, the compound of formula (IV) or formula (V) may contain at least ≥1 to ≤6 substituted or unsubstituted aromatic fused ring systems, preferably ≥2 to ≤5 substituted or unsubstituted aromatic fused ring systems, more preferably 3 or 4 substituted or unsubstituted aromatic fused ring systems, and wherein the aromatic fused ring system contains a substituted or unsubstituted heterocyclic unsaturated 5 to 7 membered ring.

[0367] According to one embodiment, the compound of formula (IV) or formula (V) may contain at least ≥1 to ≤6 substituted or unsubstituted aromatic fused ring systems, preferably ≥2 to ≤5 substituted or unsubstituted aromatic fused ring systems, more preferably 3 or 4 substituted or unsubstituted aromatic fused ring systems, wherein the aromatic fused ring system contains a substituted or unsubstituted heteroaromatic ring, and wherein the aromatic fused ring system contains a substituted or unsubstituted heterocyclic unsaturated 5 to 7 membered ring.

[0368] According to one embodiment, the compound of formula (IV) or formula (V) may contain at least ≥1 to ≤6 substituted or unsubstituted aromatic fused ring systems, preferably ≥2 to ≤5 substituted or unsubstituted aromatic fused ring systems, more preferably 3 or 4 substituted or unsubstituted aromatic fused ring systems, and wherein the aromatic fused ring system contains at least ≥1 to ≤3 or 2 substituted or unsubstituted heterocyclic unsaturated 5 to 7 membered rings.

[0369] According to one embodiment, the matrix compound of formula (IV) or formula (V) may contain at least ≥1 to ≤6 substituted or unsubstituted aromatic fused ring systems, preferably ≥2 to ≤5 substituted or unsubstituted aromatic fused ring systems, more preferably 3 or 4 substituted or unsubstituted aromatic fused ring systems, wherein the aromatic fused ring system contains a substituted or unsubstituted heteroaromatic ring, and wherein the aromatic fused ring system contains at least ≥1 to ≤3 or 2 substituted or unsubstituted heterocyclic unsaturated 5 to 7 membered rings.

[0370] According to one embodiment, the compound of formula (IV) or formula (V) may comprise:

[0371] - a substituted or unsubstituted aromatic fused ring system having at least ≥2 to ≤6, preferably ≥3 to ≤5, or 4 fused aromatic rings selected from substituted or unsubstituted non-heteroaromatic rings, substituted or unsubstituted hetero 5-membered rings, substituted or unsubstituted 6-membered rings and / or substituted or unsubstituted heterocyclic unsaturated 5- to 7-membered rings; or

[0372] - an unsubstituted aromatic fused ring system having at least ≥2 to ≤6, preferably ≥3 to ≤5, or 4 fused aromatic rings selected from unsubstituted non-heteroaromatic rings, unsubstituted hetero 5-membered rings, unsubstituted 6-membered rings and / or unsubstituted heterocyclic unsaturated 5 to 7-membered rings.

[0373] It should be noted here that the wording "aromatic fused ring system" may include at least one aromatic ring and at least one substituted or unsubstituted unsaturated 5 to 7 membered ring. It should be noted here that the substituted or unsubstituted unsaturated 5 to 7 membered ring may not be an aromatic ring.

[0374] According to one embodiment, the compound of formula (IV) or formula (V) may contain at least ≥1 to ≤6, preferably ≥2 to ≤5, or more preferably 3 or 4 substituted or unsubstituted aromatic fused ring systems having:

[0375] - at least one unsaturated 5-membered ring, and / or

[0376] - at least one unsaturated 6-membered ring, and / or

[0377] - at least one unsaturated 7-membered ring; wherein preferably at least one unsaturated 5-membered ring and / or at least one unsaturated 7-membered ring contains at least 1 to 3, preferably 1, heteroatom.

[0378] According to one embodiment, the compound of formula (IV) or formula (V) may contain at least ≥1 to ≤6, preferably ≥2 to ≤5, or more preferably 3 or 4 substituted or unsubstituted aromatic fused ring systems having:

[0379] - at least one aromatic 5-membered ring, and / or

[0380] - at least one aromatic 6-membered ring, and / or

[0381] - at least one aromatic 7-membered ring; wherein preferably at least one aromatic 5-membered ring and / or at least one aromatic 7-membered ring contains at least 1 to 3, preferably 1, heteroatom;

[0382] The substituted or unsubstituted aromatic fused ring system contains at least ≥1 to ≤3 or 2 substituted or unsubstituted heterocyclic unsaturated 5 to 7 membered rings.

[0383] According to one embodiment, the compound of formula (IV) or formula (V) may comprise:

[0384] - at least ≥6 to ≤12, preferably ≥7 to ≤11, more preferably ≥8 to ≤10 or 9 aromatic rings; and / or

[0385] - at least ≥4 to ≤11, preferably ≥5 to ≤10, more preferably ≥6 to ≤9 or more preferably 7 or 8 non-heteroaromatic rings, preferably the non-heteroaromatic rings are aromatic C6 rings; and / or

[0386] - at least ≥1 to ≤4, preferably 2 or 3, aromatic 5-membered rings, preferably heteroaromatic 5-membered rings; and / or

[0387] - at least 1 or 2 heterocyclic unsaturated 5- to 7-membered rings, preferably at least 1 or 2 heterocyclic unsaturated 7-membered rings;

[0388] - at least ≥6 to ≤12, preferably ≥7 to ≤11, more preferably ≥8 to ≤10 or 9 aromatic rings, wherein

[0389] At least ≥4 to ≤11, preferably ≥5 to ≤10, more preferably ≥6 to ≤9 or more preferably 7 or 8 are non-heteroaromatic rings, and

[0390] At least ≥1 to ≤4, preferably 2 or 3, of the aromatic rings are heteroaromatic rings, wherein the total number of non-heteroaromatic rings and heteroaromatic rings does not exceed 12 aromatic rings; and / or

[0391] - at least ≥6 to ≤12, preferably ≥7 to ≤11, more preferably ≥8 to ≤10 or 9 aromatic rings; wherein

[0392] At least ≥4 to ≤11, preferably ≥5 to ≤10, more preferably ≥6 to ≤9 or more preferably 7 or 8 are non-heteroaromatic rings, and

[0393] at least ≥1 to ≤4, preferably 2 or 3, of the aromatic rings are heteroaromatic rings, wherein the total number of non-heteroaromatic rings and heteroaromatic rings does not exceed 12 aromatic rings; and

[0394] The hole transport compound or the hole transport compound according to formula (I) comprises at least ≥1 to ≤4, preferably 2 or 3, aromatic 5-membered rings, preferably heteroaromatic 5-membered rings, and / or

[0395] The hole transport compound or the hole transport compound according to formula (I) comprises at least 1 or 2 heterocyclic unsaturated 5- to 7-membered rings, preferably at least 1 or 2 heterocyclic unsaturated 7-membered rings.

[0396] According to one embodiment, the compound of formula (IV) or formula (V) may contain a heteroatom, and the heteroatom may be selected from O, S, N, B or P, preferably the heteroatom may be selected from O, S or N.

[0397] According to one embodiment, the matrix compound of formula (IV) or formula (V) may contain at least ≥1 to ≤6, preferably ≥2 to ≤5, or more preferably 3 or 4 substituted or unsubstituted aromatic fused ring systems having:

[0398] - at least one aromatic 5-membered ring, and / or

[0399] - at least one aromatic 6-membered ring, and / or

[0400] - at least one aromatic 7-membered ring; wherein preferably at least one aromatic 5-membered ring and / or at least one aromatic 7-membered ring contains at least 1 to 3, preferably 1, heteroatom;

[0401] wherein the substituted or unsubstituted aromatic fused ring system optionally contains at least ≥1 to ≤3 or 2 substituted or unsubstituted heterocyclic unsaturated 5 to 7 membered rings; and wherein the substituted or unsubstituted aromatic fused ring system contains heteroatoms, which may be selected from O, S, N, B, P or Si, preferably the heteroatoms may be selected from O, S or N.

[0402] According to one embodiment, the compound of formula (IV) or formula (V) may contain no heteroatoms that are not part of an aromatic ring and / or part of an unsaturated 7-membered ring, preferably the hole transport compound or the hole transport compound according to formula (I) may contain no N atoms other than N atoms that are part of an aromatic ring or that are part of an unsaturated 7-membered ring.

[0403] According to one embodiment, the substantially covalent matrix compound comprises at least one naphthyl group, carbazole group, dibenzofuran group, dibenzothiophene group and / or substituted fluorenyl group, wherein the substituents are independently selected from methyl, phenyl or fluorenyl.

[0404] According to one embodiment of the present invention, the compound of formula (IV) or formula (V) is selected from K1 to K16:

[0405] (K1), (K2), (K3), (K4), (K5), (K6), (K7), (K8), (K9), (K10), (K11), (K12), (K13), (K14), (K15), and (K16).

[0406] The substantially covalent matrix compound may be free of HTM014, HTM081, HTM163, HTM222, EL-301, HTM226, HTM355, HTM133, HTM334, HTM604 and EL-22T. The abbreviations represent the names of manufacturers, such as Merck KGaA or Jiguang Technology Co., Ltd.

[0407] Hole injection layer

[0408] A hole injection layer (HIL) may be formed on the anode layer by vacuum deposition, spin coating, printing, casting, slot die coating, Langmuir-Blodgett (LB) deposition, etc. When the HIL is formed using vacuum deposition, the deposition conditions may vary depending on the hole transport compound used to form the HIL and the desired structure and thermal properties of the HIL. However, in general, the conditions for vacuum deposition may include a deposition temperature of 100° C. to 350° C., a ... -8 Support up to 10-3 Torr pressure (1 Torr equals 133.322 Pa) and a deposition rate of 0.1 nm / s to 10 nm / s.

[0409] When the HIL is formed using spin coating or printing, the coating conditions may vary depending on the hole transport compound used to form the HIL and the desired structure and thermal properties of the HIL. For example, the coating conditions may include a coating speed of about 2000 rpm to about 5000 rpm and a heat treatment temperature of about 80° C. to about 200° C. After coating, heat treatment is performed to remove the solvent.

[0410] The HIL may be formed from a metal complex according to formula (I).

[0411] The thickness of the HIL may be in a range of about 1 nm to about 15 nm, for example, about 2 nm to about 15 nm or about 2 nm to about 12 nm.

[0412] When the thickness of the HIL is within this range, the HIL may have excellent hole injection characteristics without substantially deteriorating driving voltage.

[0413] According to one embodiment of the present invention, the hole injection layer may include:

[0414] - at least about ≥0.5 wt. % to about ≤30 wt. %, preferably about ≥0.5 wt. % to about ≤20 wt. %, more preferably about ≥15 wt. % to about ≤1 wt. % of a metal complex according to formula (I), and

[0415] - at least about ≥70 wt. % to about ≤99.5 wt. %, preferably about ≥80 wt. % to about ≤99.5 wt. %, more preferably about ≥85 wt. % to about ≤99 wt. % of a substantially covalent matrix compound; preferably the wt. % of the metal complex according to formula (I) is lower than the wt. % of the substantially covalent matrix compound; wherein the wt. % of the components is based on the total weight of the hole injection layer.

[0416] Preferably, the hole injection layer may not contain ionic liquids, metal phthalocyanines, CuPc, HAT-CN, pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile, F4TCNQ, metal fluorides and / or metal oxides, wherein the metal in the metal oxide is selected from Re and / or Mo. Thus, the hole injection layer can be deposited under conditions suitable for mass production.

[0417] According to an embodiment of the electronic device, the hole injection layer is non-emissive.

[0418] It is to be understood that the hole injection layer is not part of the anode layer.

[0419] Hole transport layer / hole injection layer

[0420] According to another embodiment, the organic electronic device further comprises a hole transport layer, wherein the hole transport layer is arranged between the hole injection layer and the at least one light emitting layer.

[0421] In one embodiment of the invention, the hole injection layer comprises a substantially covalent matrix compound.

[0422] In one embodiment of the invention, the hole transport layer comprises a substantially covalent host compound.

[0423] In one embodiment of the invention, the hole transport layer comprises a substantially covalent matrix compound, wherein the substantially covalent matrix compound in the hole injection layer and the hole transport layer is selected to be identical.

[0424] Preferably, the matrix compound of the hole injection layer is free of metals and / or ionic bonds.

[0425] Other layers

[0426] According to the present invention, in addition to the layers already mentioned above, the electronic device may also include other layers. Exemplary embodiments of the corresponding layers are described below:

[0427] Base

[0428] The substrate can be any substrate commonly used in the manufacture of electronic devices such as organic light emitting diodes. If light is to be emitted through the substrate, the substrate should be a transparent or translucent material, such as a glass substrate or a transparent plastic substrate. If light is to be emitted through the top surface, the substrate can be both a transparent material and an opaque material, such as a glass substrate, a plastic substrate, a metal substrate, a silicon substrate, or a transistor backplane. Preferably, the substrate is a silicon substrate or a transistor backplane.

[0429] Anode layer

[0430] The anode layer is also referred to as the anode electrode and can be formed by depositing or sputtering a material for forming the anode layer. The material for forming the anode layer can be a high work function material, thereby promoting hole injection. The anode layer can be a transparent electrode or a reflective electrode. Transparent conductive oxides such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), aluminum zinc oxide (AlZO) and zinc oxide (ZnO) can be used to form the anode layer. Metals, typically silver (Ag), gold (Au), or metal alloys can also be used to form the anode layer.

[0431] The anode layer may comprise two or more anode sublayers.

[0432] According to one embodiment, the anode layer comprises a first anode sublayer and a second anode sublayer, wherein the first anode sublayer is arranged closer to the substrate and the second anode sublayer is arranged closer to the cathode layer.

[0433] According to one embodiment, the anode layer may include a first anode sublayer including or consisting of Ag or Au and a second anode sublayer including or consisting of a transparent conductive oxide.

[0434] According to one embodiment, the anode layer includes a first anode sublayer, a second anode sublayer and a third anode sublayer, wherein the first anode sublayer is arranged closer to the substrate, the second anode sublayer is arranged closer to the cathode layer, and the third anode sublayer is arranged between the substrate and the first anode sublayer.

[0435] According to one embodiment, the anode layer may include a first anode sublayer comprising Ag or Au or consisting thereof, a second anode sublayer comprising a transparent conductive oxide or consisting thereof, and an optional third anode sublayer comprising a transparent conductive oxide or consisting thereof. Preferably, the first anode sublayer may comprise Ag or consist thereof, the second anode sublayer may comprise ITO or IZO or consist thereof, and the third anode sublayer may comprise ITO or IZO or consist thereof.

[0436] Preferably, the first anode sublayer may contain or consist of Ag, the second anode sublayer may contain or consist of ITO, and the third anode sublayer may contain or consist of ITO.

[0437] Preferably, the transparent conductive oxide in the second anode sublayer and the third anode sublayer may be selected to be the same.

[0438] According to one embodiment, the anode layer may include a first anode sublayer including Ag or Au and having a thickness of 100 nm to 150 nm, a second anode sublayer including or consisting of a transparent conductive oxide and having a thickness of 3 nm to 20 nm, and a third anode sublayer including or consisting of a transparent conductive oxide and having a thickness of 3 nm to 20 nm.

[0439] Hole transport layer

[0440] According to one embodiment of the electronic device, the electronic device further comprises a hole transport layer, wherein the hole transport layer is arranged between the hole injection layer and the at least one first light emitting layer.

[0441] The hole transport layer may comprise a substantially covalent matrix compound. According to one embodiment, the substantially covalent matrix compound of the hole transport layer may be selected from at least one organic compound. The substantially covalent matrix may consist essentially of covalently bound C, H, O, N, S, optionally further comprising covalently bound B, P, As and / or Se.

[0442] According to one embodiment of the electronic device, the hole transport layer comprises a substantially covalent matrix compound, wherein the substantially covalent matrix compound of the hole transport layer can be selected from organic compounds consisting essentially of covalently bound C, H, O, N, S, optionally further comprising covalently bound B, P, As and / or Se.

[0443] According to one embodiment, the molecular weight Mw of the substantially covalent matrix compound of the hole transport layer can be ≥400 g / mol and ≤2000 g / mol, preferably the molecular weight Mw is ≥450 g / mol and ≤1500 g / mol, more preferably the molecular weight Mw is ≥500 g / mol and ≤1000 g / mol, further preferably the molecular weight Mw is ≥550 g / mol and ≤900 g / mol, and further preferably the molecular weight Mw is ≥600 g / mol and ≤800 g / mol.

[0444] Preferably, the substantially covalent matrix compound of the hole injection layer and the substantially covalent matrix compound of the hole transport layer are chosen to be identical.

[0445] According to an embodiment of the electronic device, wherein the hole transport layer of the electronic device comprises a substantially covalent matrix compound, preferably the substantially covalent matrix compounds in the hole injection layer and the hole transport layer are chosen to be identical.

[0446] A hole transport layer (HTL) may be formed on the HIL by vacuum deposition, spin coating, slot die coating, printing, casting, Langmuir-Blodgett (LB) deposition, etc. When the HTL is formed by vacuum deposition or spin coating, the conditions for deposition and coating may be similar to those for forming the HIL. However, the conditions for vacuum or solution deposition may vary depending on the hole transport compound used to form the HTL.

[0447] The thickness of the HTL may be in the range of about 5 nm to about 250 nm, preferably about 10 nm to about 200 nm, more preferably about 20 nm to about 190 nm, more preferably about 40 nm to about 180 nm, more preferably about 60 nm to about 170 nm, more preferably about 80 nm to about 200 nm, more preferably about 100 nm to about 180 nm, more preferably about 110 nm to about 140 nm.

[0448] When the thickness of the HTL is within this range, the HTL may have excellent hole transport characteristics without substantially deteriorating driving voltage.

[0449] Electron blocking layer

[0450] The function of the electron blocking layer (EBL) is to prevent electrons from being transferred from the light-emitting layer to the hole transport layer, thereby confining the electrons in the light-emitting layer. This can improve efficiency, operating voltage and / or lifetime. Typically, the electron blocking layer comprises a triarylamine compound.

[0451] If the electron blocking layer has a high triplet energy level it can also be described as a triplet controlling layer.

[0452] If a phosphorescent green or blue light-emitting layer is used, the function of the triplet control layer is to reduce triplet quenching. Thus, a higher luminous efficiency of the phosphorescent light-emitting layer can be achieved. The triplet control layer can be selected from triarylamine compounds having a triplet energy level higher than the triplet energy level of the phosphorescent emitter in the adjacent light-emitting layer.

[0453] The thickness of the electron blocking layer can be selected between 2 nm and 20 nm.

[0454] Photoactive Layer (PAL)

[0455] The photoactive layer converts current into photons or converts photons into current. The PAL can be formed on the HTL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. When the PAL is formed using vacuum deposition or spin coating, the conditions for deposition and coating may be similar to those for forming the HIL. However, the conditions for deposition and coating may vary depending on the compound used to form the PAL. The photoactive layer may not contain a metal complex according to formula (I). The photoactive layer may be a light-emitting layer or a light-absorbing layer.

[0456] Emitting Layer (EML)

[0457] At least one first light emitting layer (EML), also referred to as a first light emitting layer, may be formed on the HTL or EBL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. When the EML is formed using vacuum deposition or spin coating, the conditions for deposition and coating may be similar to those for forming the HIL. However, the conditions for deposition and coating may vary depending on the compound used to form the EML.

[0458] According to the present invention, preferably the electronic device comprises one light-emitting layer, referred to as the “first light-emitting layer.” However, the electronic device optionally comprises two light-emitting layers, wherein the first layer is designated as the first light-emitting layer and the second layer is designated as the second light-emitting layer.

[0459] At least one light-emitting layer (also referred to as the first light-emitting layer) may be free of the host compound of the hole injection layer.

[0460] At least one light-emitting layer may not comprise a metal complex according to formula (I).

[0461] At least one light-emitting layer (EML) may be formed by a combination of a host and a light-emitting dopant. Examples of the host are Alq3, 4,4'-N,N'-dicarbazole-biphenyl (HTC-10), poly(n-vinylcarbazole) (PVK), 9,10-di(naphthalene-2-yl)anthracene (ADN), 4,4',4''-tri(carbazole-9-yl)-triphenylamine (TCTA), 1,3,5-tri(N-phenylbenzimidazol-2-yl)benzene (TPBI), 3-tert-butyl-9,10-di-2-naphthylanthracene (TBADN), distyrylarene (DSA), and bis(2-(2-hydroxyphenyl)benzothiazole)zinc (Zn(BTZ)2).

[0462] The emitter dopant may be a phosphorescent or fluorescent emitter. Phosphorescent emitters and emitters that emit light via a thermally activated delayed fluorescence (TADF) mechanism may be preferred due to their higher efficiency. The emitter may be a small molecule or a polymer.

[0463] Examples of red emitter dopants are PtOEP, Ir(piq)3 and Btp2Ir(acac), but are not limited thereto. These compounds are phosphorescent emitters; however, fluorescent red emitter dopants may also be used.

[0464] Examples of phosphorescent green emitter dopants are Ir(ppy)3 (ppy=phenylpyridine), Ir(ppy)2(acac), Ir(mpyp)3.

[0465] Examples of phosphorescent blue emitter dopants are F2Irpic, (F2ppy)2Ir(tmd) and Ir(dfppz)3 and trifluorene. 4,4'-bis(4-diphenylaminophenylvinyl)biphenyl (DPAVBi), 2,5,8,11-tetra-tert-butylperylene (TBPe) are examples of fluorescent blue emitter dopants.

[0466] The amount of the luminophore dopant may be in the range of about 0.01 to about 50 parts by weight relative to 100 parts by weight of the host. Alternatively, at least one luminescent layer may be composed of a luminescent polymer. The thickness of the EML may be about 10 nm to about 100 nm, for example, about 20 nm to about 60 nm. When the thickness of the EML is within this range, the EML may have excellent luminescence without causing substantial damage to the driving voltage.

[0467] Hole Blocking Layer (HBL)

[0468] A hole blocking layer (HBL) may be formed on the EML to prevent holes from diffusing into the ETL by using vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. When the EML includes a phosphorescent emitter dopant, the HBL may also have a triplet exciton blocking function.

[0469] HBL may also be called auxiliary ETL or a-ETL.

[0470] When vacuum deposition or spin coating is used to form the HBL, the conditions for deposition and coating may be similar to those for forming the HIL. However, the conditions for deposition and coating may vary with the compound used to form the HBL. Any compound commonly used to form the HBL may be used. Examples of compounds used to form the HBL include oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, and triazine derivatives.

[0471] The thickness of the HBL may be in the range of about 5 nm to about 100 nm, for example, about 10 nm to about 30 nm. When the thickness of the HBL is within this range, the HBL may have excellent hole blocking properties without substantially deteriorating driving voltage.

[0472] Electron Transport Layer (ETL)

[0473] The electronic device according to the present invention may further include an electron transport layer (ETL).

[0474] According to another embodiment of the present invention, the electron transport layer may further include an azine compound, preferably a triazine compound.

[0475] In one embodiment, the electron transport layer may further comprise a dopant selected from alkali metal organic complexes, preferably LiQ.

[0476] The thickness of the ETL may be in the range of about 15 nm to about 50 nm, for example, in the range of about 20 nm to about 40 nm. When the thickness of the ETL is within this range, the ETL may have satisfactory electron injection performance without substantially deteriorating driving voltage.

[0477] According to another embodiment of the present invention, the electronic device may further comprise a hole blocking layer and an electron transport layer, wherein the hole blocking layer and the electron transport layer comprise an azine compound. Preferably, the azine compound is a triazine compound.

[0478] Electron injection layer (EIL)

[0479] An optional EIL that can facilitate electron injection from the cathode can be formed on the ETL, preferably directly on the electron transport layer. Examples of materials for forming the EIL include 8-hydroxyquinoline lithium (LiQ), LiF, NaCl, CsF, Li2O, BaO, Ca, Ba, Yb, Mg known in the art. The deposition and coating conditions for forming the EIL are similar to those for forming the HIL, but the deposition and coating conditions may vary depending on the material used to form the EIL.

[0480] The thickness of the EIL may be in the range of about 0.1 nm to about 10 nm, for example, in the range of about 0.5 nm to about 9 nm. When the thickness of the EIL is within this range, the EIL may have satisfactory electron injection performance without substantially deteriorating driving voltage.

[0481] Cathode layer

[0482] A cathode layer is formed on the ETL or the optional EIL. The cathode layer may be formed of a metal, an alloy, a conductive compound, or a mixture thereof. The cathode layer may have a low work function. For example, the cathode layer may be formed of lithium (Li), magnesium (Mg), aluminum (Al), aluminum (Al)-lithium (Li), calcium (Ca), barium (Ba), ytterbium (Yb), magnesium (Mg)-indium (In), magnesium (Mg)-silver (Ag), etc. Alternatively, the cathode layer may be formed of a transparent conductive oxide such as ITO or IZO.

[0483] The thickness of the cathode layer may be in the range of about 5 nm to about 1000 nm, for example, in the range of about 10 nm to about 100 nm. When the thickness of the cathode layer is in the range of about 5 nm to about 50 nm, the cathode layer may be transparent or translucent even if it is formed of a metal or a metal alloy.

[0484] It is to be understood that the cathode layer is not part of the electron injection layer or the electron transport layer.

[0485] Organic Electronic Devices

[0486] According to another aspect of the present invention, an organic electronic device is provided, wherein the organic electronic device comprises a compound of formula (I).

[0487] According to one embodiment of the present invention, the organic electronic device is selected from a light emitting device, a thin film transistor, a battery, a display device or a photovoltaic cell, preferably a light emitting device, and preferably the electronic device is part of a display device or a lighting device.

[0488] According to one embodiment, the organic electronic device comprises semiconductor materials, wherein at least one semiconductor material comprises the metal complex of the formula (I).

[0489] According to one embodiment, the organic electronic device comprising the metal complex according to formula (I) of the present invention is a light-emitting device, a thin film transistor, a battery, a display device or a photovoltaic device, preferably a light-emitting device, preferably the electronic device is part of a display device or a lighting device.

[0490] According to one embodiment, the organic electronic device comprises a semiconductor material, wherein at least one semiconductor material comprises a metal complex of formula (I), and wherein the organic electronic device is a light-emitting device, a thin-film transistor, a battery, a display device or a photovoltaic device, preferably a light-emitting device, preferably the electronic device is part of a display device or a lighting device.

[0491] According to one embodiment, the organic electronic device comprises a first electrode layer, a second electrode layer, at least one photoactive layer and a semiconductor layer, wherein the semiconductor layer is arranged between the first electrode layer and the at least one photoactive layer, and the semiconductor layer comprises a metal complex of formula (I)

[0492] (I)

[0493] in

[0494] M is a metal ion;

[0495] n is the valence of M and is selected from 1 to 4;

[0496] L has the formula (II)

[0497] (II)

[0498] R 1 and R 2 are independently selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 Heteroaryl or substituted or unsubstituted 6-membered heteroaryl;

[0499] R 3 is selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 heteroaryl, substituted or unsubstituted 6-membered heteroaryl or CN;

[0500] in

[0501] Substituted C1 to C 12 Alkyl, substituted C6 to C 19 Aryl, substituted C2 to C 20At least one of the substituents of the heteroaryl or substituted 6-membered heteroaryl is independently selected from halogen, Cl, F, CN, partially fluorinated or perfluorinated C1 to C8 alkyl, partially fluorinated or perfluorinated C1 to C8 alkoxy;

[0502] in

[0503] R 1 , R 2 and R 3 At least one or R 1 , R 2 and R 3 The group comprises at least three atoms selected from halogen, Cl, F or N;

[0504] AL is an auxiliary ligand coordinated to the metal M;

[0505] m is an integer selected from 0 to 2.

[0506] Other embodiments of the metal complexes of formula (I) are described throughout the specification and references are fully incorporated herein.

[0507] Manufacturing method

[0508] According to another aspect, there is provided a method of manufacturing an electronic device, the method using:

[0509] - at least one deposition source, preferably two deposition sources, more preferably at least three deposition sources.

[0510] Suitable deposition methods may include:

[0511] - Deposition by vacuum thermal evaporation;

[0512] - deposition by solution processing, preferably selected from spin coating, printing, casting; and / or

[0513] - Slot die coating.

[0514] According to various embodiments, there is provided a method, the method using:

[0515] - a first deposition source for releasing the matrix compound, and

[0516] - A second deposition source for releasing a metal complex according to formula (I) (also referred to as metal complex).

[0517] The method comprises the step of forming a hole injection layer; wherein for the electronic device:

[0518] - Forming a hole injection layer by releasing a matrix compound according to the invention from a first deposition source and a metal complex according to formula (I) (also referred to as metal complex) from a second deposition source.

[0519] Ink preparation

[0520] According to another aspect of the present invention, there is provided an ink formulation, wherein the ink formulation comprises at least one compound of formula (I).

[0521] According to one embodiment, the ink formulation comprises a solvent. The solvent of the ink formulation may be selected from anisole and / or benzonitrile, preferably a mixture of anisole and benzonitrile.

[0522] According to one embodiment, the mixture of anisole and benzonitrile is 5:1 to 1:5, 4:1 to 1:4, 3:1 to 1:3, 2:1 to 1:2 or 1:1; preferably, it is a 5:1 mixture of anisole and benzonitrile.

[0523] The embodiments are described in more detail below with reference to examples. However, the present disclosure is not limited to the following examples. Reference will now be made in detail to the exemplary aspects. BRIEF DESCRIPTION OF THE DRAWINGS

[0524] In the described embodiments, the components mentioned above and claimed and to be used according to the invention do not have any special exceptions in terms of their size, shape, material selection and technical principles, so the selection criteria known in the relevant field can be applied without restriction.

[0525] Other details, features and advantages of the objects of the present invention are disclosed in the dependent claims and the following descriptions of the drawings, which illustrate preferred embodiments according to the present invention in an exemplary manner. However, any embodiment may not necessarily represent the full scope of the present invention, so reference is made to the claims and this article to interpret the scope of the present invention. It should be understood that the above general description and the following detailed description are only exemplary and illustrative, and are intended to further illustrate the present invention claimed.

[0526] Figure 1 is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention;

[0527] Figure 2 is a schematic cross-sectional view of an organic light emitting diode (OLED) according to an exemplary embodiment of the present invention;

[0528] Figure 3 is a schematic cross-sectional view of an organic light emitting diode (OLED) according to an exemplary embodiment of the present invention.

[0529] Figure 4 is a schematic cross-sectional view of an organic light emitting diode (OLED) according to an exemplary embodiment of the present invention;

[0530] Figure 5 is a schematic cross-sectional view of an organic light emitting diode (OLED) according to an exemplary embodiment of the present invention.

[0531] Figure 6 is a schematic cross-sectional view of an organic light emitting diode (OLED) according to an exemplary embodiment of the present invention.

[0532] Figure 1 1 is a schematic cross-sectional view of an organic electronic device 101 according to an exemplary embodiment of the present invention. The organic electronic device 101 includes a substrate (110), an anode layer (120), a hole injection layer (130) comprising a metal complex according to formula (I), a photoactive layer (PAL) (151) and a cathode layer (190).

[0533] Figure 2 1 is a schematic cross-sectional view of an organic light emitting diode (OLED) 100 according to an exemplary embodiment of the present invention. The OLED 100 includes a substrate (110), an anode layer (120), a hole injection layer (130) including a metal complex according to formula (I), an emission layer (EML) (150), and a cathode layer (190).

[0534] Figure 3 1 is a schematic cross-sectional view of an organic light emitting diode (OLED) 100 according to an exemplary embodiment of the present invention. The OLED 100 includes a substrate (110), an anode layer (120), a hole injection layer (130) including a metal complex according to formula (I), a hole transport layer (HTL) (140), an emission layer (EML) (150), an electron transport layer (ETL) (160), and a cathode layer (190).

[0535] Figure 4 1 is a schematic cross-sectional view of an organic light emitting diode (OLED) 100 according to an exemplary embodiment of the present invention. The OLED 100 includes a substrate (110), an anode layer (120), a hole injection layer (130) comprising a metal complex according to formula (I), a hole transport layer (HTL) (140), an electron blocking layer (EBL) (145), an emission layer (EML) (150), a hole blocking layer (HBL) (155), an electron transport layer (ETL) (160), an optional electron injection layer (EIL) (180) and a cathode layer (190).

[0536] Figure 51 is a schematic cross-sectional view of an organic light emitting diode (OLED) 100 according to an exemplary embodiment of the present invention. The OLED 100 includes a substrate (110), an anode layer (120) including a first anode sublayer (121) and a second anode sublayer (122), a hole injection layer (130) including a metal complex according to formula (I), a hole transport layer (HTL) (140), an electron blocking layer (EBL) (145), an emission layer (EML) (150), a hole blocking layer (HBL) (155), an electron transport layer (ETL) (160), and a cathode layer (190).

[0537] Figure 6 1 is a schematic cross-sectional view of an organic light emitting diode (OLED) 100 according to an exemplary embodiment of the present invention. The OLED 100 includes a substrate (110), an anode layer (120) including a first anode sublayer (121), a second anode sublayer (122) and a third anode sublayer (123), a hole injection layer (130) including a metal complex according to formula (I), a hole transport layer (HTL) (140), an electron blocking layer (EBL) (145), an emission layer (EML) (150), a hole blocking layer (HBL) (155), an electron transport layer (ETL) (160) and a cathode layer (190). The layers are arranged in the order mentioned above.

[0538] In the above description, the method for manufacturing an organic electronic device 101 of the present invention, for example, starts from a substrate (110) on which an anode layer (120) is formed, and a hole injection layer (130) comprising a metal complex according to formula (I), a photoactive layer (151) and a cathode electrode 190 are formed on the anode layer (120) in the following order or in the reverse order.

[0539] In the above description, the method for manufacturing an OLED of the present invention starts from a substrate (110) on which an anode layer (120) is formed, and a hole injection layer (130) comprising a metal complex according to formula (I), an optional hole transport layer (140), an optional electron blocking layer (145), a light-emitting layer (150), an optional hole blocking layer (155), an optional electron transport layer (160), an optional electron injection layer (180) and a cathode electrode 190 are formed on the anode layer (120) in the following order or in the reverse order.

[0540] The semiconductor layer (130) comprising the metal complex according to formula (I) may be a hole injection layer.

[0541] Despite Figure 1 , Figure 2 , Figure 3 , Figure 4, Figure 5 and Figure 6 Although not shown in the drawings, a capping layer and / or a sealing layer may be further formed on the cathode electrode 190 to seal the OLED 100. In addition, various other modifications may be applied thereto.

[0542] Hereinafter, one or more exemplary embodiments of the present invention will be described in detail with reference to the following examples. However, these examples are not intended to limit the purpose and scope of one or more exemplary embodiments of the present invention.

[0543] General Methods for Preparing Ink Formulations

[0544] To prepare the ink formulation, weigh the compound into a vial. Then, add the solvent. Stir the mixture for 10 minutes. Transfer the ink to an inert atmosphere. Add an aliquot of the benzonitrile solution to the anisole solution to obtain a solution with a ratio of anisole to benzonitrile solution of 5:1. Stir the resulting solution at room temperature for at least another 10 minutes. The resulting ink formulation has a solids content of 4% by weight.

[0545] Dipole moment

[0546] Dipole moment of a molecule containing N atoms Given by:

[0547]

[0548] in and is the partial charge and position of atom i in the molecule.

[0549] The dipole moments were determined by density functional theory (DFT) method.

[0550] As implemented in the program packages ORCA V5.0.3 (Max Planck Institute fuer Kohlenforschung, Kaiser Wilhelm Platz 1, 45470, Muelheim / Ruhr, Germany) and WEASEL 1.9.2 (FAccTs GmbH, Rolandstrasse 67, 50677 Köln, Germany), the geometric properties of the molecular structures were optimized using the GGA functional BP86 with the Def2-SVP basis set, with solvent effects introduced by the conductor-like polarized continuum model (CPCM) and the solvent acetonitrile (CPCM (acetonitrile)). If more than one conformation was feasible, the conformation with the lowest total energy was selected to determine the bond lengths of the molecule. The structures of all molecules were optimized without symmetry or internal coordinate constraints and verified as true minima by the absence of negative eigenvalues ​​in the resonance frequency analysis.

[0551] I. Geometry optimization, for elements starting from atomic number 21, using the BP86 functional with the def2-SVP basis set and SDD ECP.

[0552] II. Frequency calculations, for elements starting from atomic number 21, using the BP86 functional with the def2-SVP basis set and SDD ECP.

[0553] III. Single-point DFT calculations using the (Gaussian)-B3LYP functional with the ZORA-def2-TZVP basis set and the auxiliary basis set SARC / J.

[0554] The calculations consider Cu(II) with charge 0 and multiplicity 2, Fe(III) with charge 0 and multiplicity 6 (high spin), temperature 298.15 K, and pressure 1.0 atm. For all calculations, solvent effects are introduced by using the conductor-like polarizable continuum model (CPCM) with acetonitrile as solvent.

[0555] Programs: WEASEL (version 1.9.2) and ORCA (5.0.3-f.1), Visualization: Chemcraft.

[0556] Calculated HOMO and LUMO of the metal complex of formula (I)

[0557] HOMO and LUMO were calculated using the program packages ORCA V5.0.3 (Max Planck Institute fuer Kohlenforschung, Kaiser Wilhelm Platz 1, 45470, Muelheim / Ruhr, Germany) and WEASEL 1.9.2 (FAccTs GmbH, Rolandstrasse 67, 50677 Köln, Germany). The optimized geometric properties of the molecular structures as well as the HOMO and LUMO energy levels were determined using the hybrid functional (Gaussian)-B3LYP with the ZORA-Def2-TZVP basis set, where solvent effects were introduced by the conductor-like polarized continuum model (CPCM) and the solvent acetonitrile. If more than one conformation was feasible, the conformation with the lowest total energy was selected. The structures of all molecules were optimized without symmetry or internal constraints and verified as true minima by the absence of negative eigenvalues ​​in the resonance frequency analysis.

[0558] LUMO reference value: see Table 1

[0559] Experimental data

[0560] Synthesis example

[0561] The compounds of formula (I) may be prepared by known methods or as described below.

[0562] Synthesis of Tris((3-methyl-1-phenyl-4-(2,2,2-trifluoroacetyl)-1H-pyrazol-5-yl)oxy)iron(MC7)

[0563]

[0564] At ice bath temperature, to 12.8 g (47.4 mmol) ligand and 3.98 g (47.4 mmol) NaHCO in 120 ml methanol, add 2.56 g (15.8 mmol) FeCl in 15 ml water. Stir the mixture overnight, filter the suspension, and wash the product with a small amount of water-methanol. Dry to obtain 12.4 g (91%) desired product.

[0565] Synthesis of Bis((3-methyl-1-phenyl-4-(2,2,2-trifluoroacetyl)-1H-pyrazol-5-yl)oxy)copper(MC6)

[0566]

[0567] To a solution of 2.5 g (9.25 mmol) of the ligand in 50 ml of ethanol was added 0.92 g (4.63 mmol) of copper(II) acetate and the mixture was stirred overnight. The resulting green suspension was filtered off and the solid was dried in vacuo to give 2.3 g (83%) of a light green-yellow powder.

[0568] Synthesis of Tetrakis((3-methyl-1-phenyl-4-(2,2,2-trifluoroacetyl)-1H-pyrazol-5-yl)oxy)cerium(MC9)

[0569]

[0570] 3.76 g (13.92 mmol) of ligand and 1.07 g of ammonium acetate (13.92 mmol) were dissolved in 50 ml of acetic acid. 2.86 g (5.22 mmol) of cerium ammonium nitrate was dissolved in 30 ml of water and added dropwise to the ligand. After 30 minutes, the resulting precipitate was filtered off and dried overnight in vacuo at 100°C to give 2.63 g (62%) of a black solid.

[0571] Synthesis of 1-(1-(3,5-bis(trifluoromethyl)phenyl)-5-hydroxy-3-methyl-1H-pyrazol-4-yl)-2,2,2-trifluoroethan-1-one

[0572] Step 1. 1-(3,5-bis(trifluoromethyl)phenyl)-3-methyl-1H-pyrazol-5-ol

[0573]

[0574] 4.0 g (16.38 mmol) of 3,5-bis(trifluoromethyl)phenylhydrazine was dissolved in 60 ml of ethanol and 1.9 g (16.38 mmol) of methyl acetoacetate solution was added dropwise. The reaction was heated to reflux for 4 hours. After removing the solvent, the residue was subjected to vacuum ball-to-ball distillation. The residue was further purified by flash chromatography and sublimation using ethyl acetate / hexane to obtain 2.33 g (46%) of a slightly yellow crystalline solid.

[0575] Step 2. 1-(1-(3,5-bis(trifluoromethyl)phenyl)-5-hydroxy-3-methyl-1H-pyrazol-4-yl)-2,2,2-trifluoroethan-1-one

[0576]

[0577] 1.38 g (14.38 mmol) of sodium tert-butyrate and 1.1 g (8.63 mmol) of methyl trifluoroacetate were dissolved in 10 ml of anhydrous ether and cooled in an ice bath. A solution of 2.23 g (7.19 mmol) of 1-(3,5-bis(trifluoromethyl)phenyl)-3-methyl-1H-pyrazole-5-ol in 15 ml of ether was added dropwise. The mixture was stirred at room temperature overnight. After drying over magnesium sulfate, the solvent was removed and the crude product was sublimed to give 2.1 g (72%) of a reddish solid.

[0578] Synthesis of Bis((1-(3,5-bis(trifluoromethyl)phenyl)-3-methyl-4-(2,2,2-trifluoroacetyl)-1H-pyrazol-5-yl)oxy)copper(MC56)

[0579]

[0580] 2.0 g (4.92 mmol) of the ligand was dissolved in 20 ml of ethanol and 0.49 g (2.46 mmol) of copper(II) acetate was added. The mixture was stirred at room temperature overnight, cooled in an ice bath and the precipitate was filtered off, washed with ethanol and dried in vacuo at 70°C to give 1.95 g (91%) of a light green powder.

[0581] Other compounds according to the invention may be prepared by the methods described above or by methods known in the art.

[0582] Other compounds according to the invention may be prepared by the methods described above or by methods known in the art.

[0583] General procedure for manufacturing OLED

[0584] General procedure for making an organic electronic device comprising a semiconductor layer comprising a metal complex and a matrix compound, The semiconductor layer is deposited in a vacuum.

[0585] For Inventive Examples 1-1 to Inventive Examples 1-26 and Comparative Example 1-1 in Table 3, a glass substrate having an anode layer including a first anode sublayer of 120 nm Ag, a second anode sublayer of 8 nm ITO, and a third anode sublayer of 10 nm ITO was cut into a size of 50 mm×50 mm×0.7 mm, ultrasonically cleaned with water for 60 minutes, and then ultrasonically cleaned with isopropyl alcohol for 20 minutes. The liquid film was removed in a nitrogen stream, and then plasma treatment was performed to prepare an anode layer. The plasma treatment was performed in an atmosphere containing 97.6 volume % nitrogen and 2.4 volume % oxygen.

[0586] Then, the metal complex and the matrix compound are vacuum co-deposited on the anode layer to form a hole injection layer (HIL) with a thickness of 10 nm. The composition of the hole injection layer can be seen in Table 3. The chemical formula of the metal complex can be seen in Table 1.

[0587] Then, a matrix compound was vacuum deposited on the HIL to form a HTL with a thickness of 123 nm. The compound of formula (II) in the HTL was selected to be the same as the matrix compound in the HIL. The matrix compound can be seen in Table 3.

[0588] Then, N-(4-(dibenzo[b,d]furan-4-yl)phenyl)-N-(4-(9-phenyl-9H-fluoren-9-yl)phenyl)-[1,1′-biphenyl]-4-amine (CAS 1824678-59-2) was vacuum deposited on the HTL to form an electron blocking layer (EBL) with a thickness of 5 nm.

[0589] Then, 97 vol % of H09 as an EML host and 3 vol % of BD200 (Sun Fine Chemicals, Korea) as a fluorescent blue emitter dopant were deposited on the EBL to form a blue light-emitting first emission layer (EML) with a thickness of 20 nm.

[0590] Then, a hole blocking layer having a thickness of 5 nm was formed by depositing 2-(3′-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1′-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine on the light emitting layer EML.

[0591] Then, an electron transport layer having a thickness of 31 nm was formed on the hole blocking layer by depositing 50 wt % of 4′-(4-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)naphthalen-1-yl)-[1,1′-biphenyl]-4-carbonitrile and 50 wt % of LiQ.

[0592] Then, at 10 -7 Ag:Mg (90:10 vol %) was evaporated at a rate of 0.01 Å / s to 1 Å / s at 100 mbar to form a cathode layer with a thickness of 13 nm on the electron transport layer.

[0593] Then, K1 was deposited on the cathode layer to form a capping layer with a thickness of 75 nm.

[0594] The OLED stack is protected from environmental conditions by encapsulating the device with a glass slide, thereby forming a cavity that includes getter material for further protection.

[0595] In order to evaluate the performance of the inventive examples compared to the prior art, the current efficiency was measured at 20°C. The current-voltage characteristic line was determined by providing a voltage (in V) and measuring the current (in mA) flowing through the device under test using a Keithley 2635 source measurement unit. The voltage applied to the device varied in steps of 0.1 V in the range between 0 V and 10 V. Similarly, the luminous density (in cd / m2) was measured for each voltage value using an Instrument Systems CAS-140CT array spectrometer (calibrated by Deutsche Akkreditierungsstelle (DAkkS)). 2 The luminous density-voltage characteristic line and CIE coordinates are determined by interpolating the luminous density-voltage characteristic line and the current-voltage characteristic line respectively. 2 cd / A efficiency under .

[0596] In bottom-emitting devices, the emission is primarily Lambertian and is quantified as a percentage of the external quantum efficiency (EQE). The emission is through the anode layer. To determine the efficiency EQE (in %), a calibrated photodiode is used at 10 mA / cm 2 The light output of the device was measured.

[0597] In a top-emitting device, the light emission is forward through the cathode layer, which is non-Lambertian and also highly dependent on the microcavity. Therefore, the efficiency EQE will be higher compared to a bottom-emitting device. To determine the efficiency EQE (in %), a calibrated photodiode was used at 10 mA / cm 2 The light output of the device was measured.

[0598] At ambient conditions (20°C) and 30 mA / cm 2 The device lifetime LT was measured using a Keithley 2400 source meter and recorded in hours.

[0599] The brightness of the device is measured using a calibrated photodiode. The lifetime LT is defined as the time until the brightness of the device drops to 97% of its initial value.

[0600] To determine the time-dependent voltage stability U(100h)-(1h), a 30 mA / cm 2 The operating voltage is measured after 1 hour and 100 hours, and the voltage stability over the period from 1 hour to 100 hours is calculated. A low U(100h)-(1h) value indicates a low increase in the operating voltage over time, which improves voltage stability.

[0601] The conductivity was determined by the transmission line method. Voltages from -5 V to +5 V were applied in steps of 0.5 V to a transmission line covered with a homogeneous layer of the investigated material of uniform thickness. The current was measured using a Keithley SM2635 source measure unit. The conductivity was calculated using the known transmission line geometry and the deposited layer thickness.

[0602] General Methods for Preparing Ink Formulations

[0603] To prepare the ink formulation, weigh the compound into a vial. Then, add the solvent. Stir the mixture for 10 minutes. Transfer the ink to an inert atmosphere. Add an aliquot of the benzonitrile solution to the anisole solution to obtain a solution with a ratio of anisole to benzonitrile solution of 5:1. Stir the resulting solution at room temperature for at least another 10 minutes. The resulting ink formulation has a solids content of 4% by weight.

[0604] Ink formulation of Inventive Example 2-1

[0605] The ink formulation of Example 2-3 had the following composition: 4 wt% K1 in anisole:benzonitrile (5:1). To prepare the ink, a solution of 166 mg K1 in 3.3 ml anisole was prepared as described above. 0.7 ml benzonitrile was added to the anisole solution as described above and stirred.

[0606] Ink formulation of Inventive Example 2-1

[0607] The ink formulation of Example 2-1 has the following composition: anisole:benzonitrile (5:1) containing 4 wt% MC-9:K1. To prepare the ink, a solution of 12.6 mg (1 mol%, 1.78 wt%) MC9 in 3 ml benzonitrile and a solution of 163 mg K1 in 3.3 ml anisole were prepared as described above. 0.7 ml of the benzonitrile solution was added to the anisole solution as described above and stirred.

[0608] Ink formulation of Inventive Example 2-3

[0609] The ink formulation of Example 2-2 has the following composition: anisole:benzonitrile (5:1) containing 4 wt% MC-2:K1. To prepare the ink, a solution of 24 mg (1 mol%, 5.25 wt%) MC9 in 2 ml benzonitrile and a solution of 158 mg K1 in 3.3 ml anisole were prepared as described above. 0.7 ml of the benzonitrile solution was added to the anisole solution as described above and stirred.

[0610] A general procedure for making an electronic device comprising a semiconductor layer comprising a metal complex and a matrix compound, wherein The semiconductor layer is deposited from solution

[0611] For the conductivity device, see Example 2-1, Example 2-2 and Example 2-3 in Table 4, a 15 Ω / cm 2 A glass substrate (available from Corning) was ultrasonically cleaned with isopropyl alcohol for 5 minutes, then ultrasonically cleaned with pure water for 5 minutes, and dried at elevated temperatures.

[0612] To form the organic layer, the substrate was placed on a spin coater with the ITO side facing up and fixed with vacuum. 4 ml of the ink formulation was applied to the substrate using a syringe with a filter (PTFE, 0.2 μm). The spin coating parameters were 650 rpm (3 seconds from zero to maximum speed) for 30 seconds. The resulting film was dried on a hot plate at 60°C for 1 minute. The next step was to clean the substrate around the working area (to ensure good encapsulation before measurement). Bake on a hot plate at 100°C for another 10 minutes. The composition of the organic layer can be seen in Table 4. The chemical formula of the metal complex can be seen in Table 1.

[0613] Then, the substrate was transferred to another inert glove box for encapsulation.

[0614] Then, biphenyl-4-yl(9,9-diphenyl-9H-fluorene-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine was vacuum deposited on the HIL to form a first HTL with a thickness of 89 nm.

[0615] Technical Effects of the Invention

[0616] The calculated LUMO (in electron volts) of the metal complexes of formula (I) are shown in Table 1. Where more than one spin state is possible, the spin state is indicated in parentheses. As can be seen in Table 1, the LUMO energies are within a range suitable for organic electronic devices.

[0617] The calculated LUMO (in electron volts) of the comparative metal complexes CC1 to CC5 are also shown in Table 1. The same method as for the metal complexes of formula (I) was used. As can be seen in Table 1, the LUMO energies of the known acetylpyrazolone acid salt compounds CC1 to CC3 are closer to the vacuum level than the LUMO energies of the acetylpyrazolone acid salt compounds of the present invention.

[0618] Without being bound by theory, LUMO energies further away from the vacuum level are beneficial for improving the performance of organic electronic devices.

[0619] Table 2 shows data of top-emitting organic electronic devices fabricated by vacuum co-deposition of metal complexes and host compounds.

[0620] In Comparative Example 1-1, a metal complex known in the art was tested at 10 wt %.

[0621] As can be seen in Table 2, in Comparative Example 1-1, the operating voltage is 3.75 V, the external quantum efficiency EQE is 14.5%, and the voltage stability over time is 1.988 V.

[0622] In Inventive Example 1-1, the semiconductor layer comprises the compound MC6 of formula (I). MC6 is a metal complex of formula (I). As shown in Table 2, the operating voltage is improved to 3.71 V, the cd / A efficiency is 6.5 cd / A, the EQE is 14.4%, and the operating voltage stability over time is improved to 0.184 V.

[0623] In Inventive Example 1-2, the semiconductor layer contains 15 volume % of MC6. As can be seen in Table 2, the operating voltage, cd / A efficiency, EQE, and voltage stability over time are further improved.

[0624] In Inventive Examples 1-3 to 1-5, the semiconductor layer comprises the metal complex MC7 of formula (I). As shown in Table 2, the operating voltage, cd / A efficiency, EQE, lifespan and / or operating voltage stability over time are improved relative to Comparative Example 1-1.

[0625] In Inventive Examples 1-6 to 1-17 and Inventive Examples 1-22 to 1-26, the semiconductor layer comprises a metal complex of formula (I) and various host compounds, wherein the HOMO of the host compound is further away from the vacuum level than that of Comparative Example 1 and Inventive Examples 1-1 to 1-5. As can be seen in Table 2, the operating voltage, cd / A efficiency, EQE, lifespan and / or operating voltage stability over time are improved relative to Comparative Example 1-1.

[0626] Compared with another prior art metal complex CC5 used as a p-type dopant in Comparative Examples 1-2 to 1-8, an improvement in the performance of the organic electronic device of the present invention can also be observed.

[0627] In Inventive Examples 1-18 to Inventive Examples 1-21, the semiconductor layer is composed of a metal complex of formula (I). As shown in Table 2, the operating voltage, cd / A efficiency, EQE, lifespan and / or operating voltage stability over time are improved relative to Comparative Examples 1-1 to Comparative Examples 1-8.

[0628] In Table 3 are shown data for organic electronic conductivity devices fabricated by co-deposition of a compound of formula (I) and a matrix compound from solution.

[0629] As can be seen in Table 3, the conductivity of the material doped with the compound MC9 of the present invention is significantly increased compared to the undoped host compound.

[0630] Low operating voltage, high efficiency, long lifetime and / or improved operating voltage stability over time are very important for the performance and long-term stability of organic electronic devices.

[0631] Table 2: Performance of an organic electroluminescent device comprising a semiconductor layer comprising a metal complex of Formula 1

[0632]

[0633] 1) na = not applicable

[0634] Table 3: Conductivity of p-doped materials prepared by deposition from solution

[0635]

[0636] The specific combination of elements and features in the embodiments described in detail above is exemplary only; it is also explicitly contemplated to interchange and replace these teachings with other teachings in this application and the patents / applications incorporated by reference. As will be appreciated by those skilled in the art, those of ordinary skill in the art will be able to think of changes, modifications and other implementations of the contents described herein without departing from the spirit and scope of the claimed invention. Therefore, the above description is only by way of example and is not intended to be limiting. In the claims, the wording "comprising" does not exclude other elements or steps, and the indefinite article "one" or "an" does not exclude multiple. The fact that specific measures are described in mutually different dependent claims does not mean that a combination of these measures cannot be used to advantage. The scope of the present invention is defined by the following claims and their equivalents. In addition, the figure marks used in the specification and claims do not limit the scope of the claimed invention.

Claims

1. A metal complex of formula (I) (I)， in M is a metal ion; n is the valence of M and is selected from 1 to 4; L has the formula (II) (II), R 1 and R 2 are independently selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 Heteroaryl or substituted or unsubstituted 6-membered heteroaryl; R 3 is selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 heteroaryl, substituted or unsubstituted 6-membered heteroaryl or CN; in Substituted C1 to C 12 Alkyl, substituted C6 to C 19 Aryl, substituted C2 to C 20 At least one of the substituents of the heteroaryl or substituted 6-membered heteroaryl is independently selected from halogen, Cl, F, CN, partially fluorinated or perfluorinated C1 to C8 alkyl, partially fluorinated or perfluorinated C1 to C8 alkoxy; in R 1 , R 2 and R 3 At least one or R 1 , R 2 and R 3 The group comprises at least three atoms selected from halogen, Cl, F or N; in AL is an auxiliary ligand coordinated to the metal M; m is an integer selected from 0 to 2.

2. The metal complex of formula (I) according to claim 1, wherein M is a metal ion; wherein M is a metal ion selected from Li(I), K(I), Rb(I), Cs(I), Ag(I), Cu(II), Zn(II), Pd(II), Ir(III), Al(III), Sc(III), Mn(III), Ru(III), In(III), Y(III), Eu(III), Fe(III), V(IV), Zr(IV), Hf(IV) and Ce(IV); n is the valence of M and is selected from 1 to 4; L has the formula (II) (II), R 1 and R 2 are independently selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 Heteroaryl or substituted or unsubstituted 6-membered heteroaryl; R 3 is selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 heteroaryl, substituted or unsubstituted 6-membered heteroaryl or CN; in Substituted C1 to C 12 Alkyl, substituted C6 to C 19 Aryl, substituted C2 to C 20 At least one of the substituents of the heteroaryl or substituted 6-membered heteroaryl is independently selected from halogen, Cl, F, CN, partially fluorinated or perfluorinated C1 to C8 alkyl, partially fluorinated or perfluorinated C1 to C8 alkoxy; in R 1 , R 2 and R 3 At least one or R 1 , R 2 and R 3 The group comprises at least three atoms selected from halogen, Cl, F or N; in AL is an auxiliary ligand coordinated to the metal M; m is an integer selected from 0 to 2.

3. The metal complex of formula (I) according to claim 1 or 2, wherein R 1 , R 2 and R 3 At least one or R 1 , R 2 and R 3 The group comprises at least three atoms selected from halogen, Cl, F or N.

4. The metal complex of formula (I) according to claims 1 to 3, wherein R 1 and R 2 are independently selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C3 containing at least one substituted or unsubstituted 6-membered heteroaryl group 20 heteroaryl; R 3 Selected from partially fluorinated or perfluorinated C1 to C4 alkyl or CN.

5. The metal complex of formula (I) according to claim 1, wherein R 1 , R 2 and R 3 The group consists of: - at least two moieties selected from CF3 or CN; or - at least one moiety selected from CF3 or CN and a substituted or unsubstituted 6-membered heteroaryl group; or -R 3 For CN.

6. The metal complex of formula (I) according to claim 1, wherein R 1 , R 2 and R 3 At least one of the group consisting of is selected from CN, CH3, CF3, C2F5, C3F7 or C4F9, preferably CN, CH3, CF3, C2F5 or C3F7; more preferably CN, CH3 or CF3.

7. A metal complex of formula (I) according to claims 1 to 6, wherein the metal complex of formula (I) comprises at least one CF3 group, preferably at least two CF3 groups, more preferably at least three CF3 groups, in addition preferably at least four CF3 groups, or at least two CF3 groups and at least one C2F5, or at least two CF3 groups and at least one group selected from CN, F or CH3.

8. The metal complex of formula (I) according to claim 1, wherein R 1 , R 2 and R 3 At least one of the group consisting of substituted or unsubstituted C6 to C 19 Aryl or a substituted C2 to C 20 A heteroaryl group, and is selected from the following formula D1 to formula D71: <h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (D1)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (D2)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (D3) (D4), (D5), (D6), (D7), (D8), (D9), (D10), (D11), (D12), (D13), (D14), (D15), (D16), (D17), (D18), (D19), (D20), (D21), (D22), (D23), (D24), (D25), (D26), (D27), (D28), (D29), (D30), <h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (D31)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (D32)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (D33) <h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (D34)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (D35)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (D36) <h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (D37)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (D38)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (D39) (D40), (D41), (D42), (D43), (D44), (D45), (D46), (D47), (D48), (D49), (D50), (D51), (D52), (D53), (D54), <h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (D56)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (D57)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (D58) (D59), (D60), (D61), (D62), (D63), (D64), (D65), (D67), (D68), (D69), (D70), (D71), where "*" indicates the binding position.

9. The metal complex of formula (I) according to claim 1 to 8, wherein M is a metal ion selected from alkali metals, alkaline earth metals, transition metals, rare earth metals or metals of Group III to Group V, preferably M is a metal ion selected from transition metals or metals of Group III to Group V; preferably M is a metal ion selected from the following: Li(I), K(I), Rb(I), Cs(I), Ag(I), Cu(II), Zn(II), Pd(II), Ir(III), Al(III), Sc(III), Mn(III), Ru(III), I n(III), Y(III), Eu(III), Fe(III), V(IV), Zr(IV), Hf(IV) and Ce(IV); more preferably, M is a metal ion selected from the following: Li(I), K(I), Ag(I), Cu(II), Zn(II), Al(III), Sc(III), Mn(III), Fe(III), Zr(IV) and Ce(IV); further preferably, M is Cu(II) or Fe(III), and more preferably, M is Cu(II); wherein the numbers in brackets represent the oxidation state.

10. The metal complex of formula (I) according to claims 1 to 9, wherein the ligand L is selected from the following formula E1 to formula E212: <h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E1),<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E2), (E3), (E4), (E5), (E6), (E7), (E8), (E9), (E10), (E11), (E12), (E13), (E14), (E15), (E16), (E17), (E18), (E19), (E20), (E21), (E22), (E23), (E24), (E25), (E26), <h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E27)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E28)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E29)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E30) (E31), (E32), (E33), (E34), (E35), (E36), (E37), (E38), (E39), (E40), (E41), (E42), (E43), (E44), (E45), (E46), (E47), (E48), (E49), (E50), (E51), (E52), (E53), (E54), <h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E55)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E56)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E57)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E58)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E59)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E60)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E61)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E62)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E63)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E64)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E65)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E66)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E67)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E68)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E69)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E70)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E71)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E72)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E73)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E74) <h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E75)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E76)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E77),<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E78) <h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E79)<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> (E80) (E81), (E82), (E83), (E84), (E85), (E86), (E87), (E88), (E89), (E90), (E91), (E92), (E93), (E94), (E95), (E96), (E97), (E98), (E99), (E100), (E101), (E102), (E103), (E104), (E105), (E106), (E107), (E108), (E109), (E110), (E111), (E112), (E113), (E114), (E115), (E116), (E117), (E118), (E119), (E120), (E121), (E122), (E123), (E124), (E125), (E126), (E127), (E128), (E129), (E130), (E131), (E132), (E133), (E134), (E135), (E136), (E137), (E138), (E139), (E140), (E141), (E142), (E143), (E144), (E145), (E146), (E147), (E148), (E149), (E150), (E151), (E152), (E153), (E154), (E155), (E156), (E157), (E158), (E159), (E160), (E161), (E162), (E163), (E164), (E165), (E166), (E167), (E168), (E169), (E170), (E171), (E172), (E173), (E174), (E175), (E176), (E177), (E178), (E179), (E180), (E181), (E182), (E183), (E184), (E185), (E186), (E187), (E188), (E189), (E190), (E191), (E192), (E193), (E194), (E195), (E196), (E197), (E198), (E199), (E200), (E201), (E202), (E203), (E204), (E205), (E206), (E207), (E208), (E209), (E210), (E211), (E212)。 11. The metal complex of formula (I) according to claims 1 to 10, wherein AL is selected from H2O, C2 to C 40 Monodentate or polydentate ethers and C2 to C 40 Thioether, C2 to C 40 Amines, C2 to C 40 Phosphine, C2 to C 20 Alkyl nitrile or C2 to C 40 Aryl nitrile, or a compound according to formula (III): (III), where R 6 and R 7 Independently selected from C1 to C 20 Alkyl, C1 to C 20 Heteroalkyl, C6 to C 20 Aryl, heteroaryl having 5 to 20 ring atoms, halogenated or perhalogenated C1 to C 20 Alkyl, halogenated or perhalogenated C1 to C 20 Heteroalkyl, halogenated or perhalogenated C6 to C 20 aryl, halogenated or perhalogenated heteroaryl having 5 to 20 ring atoms, or at least one R 6 and R 7 Bridged to form a 5- to 20-membered ring, or two R 6 and / or two R 7 bridged to form a 5 to 40 membered ring or to form a ring containing unsubstituted or C1 to C 12 The 5- to 40-membered ring of the substituted phenanthroline.

12. The metal complex of formula (I) according to any one of claims 1 to 11, wherein - n = 2 or 3; and / or - m is an integer selected from 0 or 1, preferably 0.

13. The metal complex of formula (I) according to any one of claims 1 to 12, wherein at least one R 1 or R 3 or R 1 and R 3 selected from substituted C2 to C 20 A heteroaryl group, wherein the C2 to C 20 The heteroaryl group is selected from pyridyl, pyrimidinyl, pyrazinyl, triazinyl.

14. The metal complex of formula (I) according to claims 1 to 13: (I)， in M is a metal ion selected from the main group metals or transition metals, preferably Cu, Fe, Mn, Al, Hf, Zr; n is the valence of M and is selected from 2 or 3; L has the formula (II) (II), R 1 and R 2 are independently selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 Heteroaryl or substituted or unsubstituted 6-membered heteroaryl; R 3 is selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 heteroaryl, substituted or unsubstituted 6-membered heteroaryl or CN; in Substituted C1 to C 12 Alkyl, substituted C6 to C 19 Aryl, substituted C2 to C 20 At least one of the substituents of the heteroaryl or substituted 6-membered heteroaryl is independently selected from halogen, Cl, F, CN, partially fluorinated or perfluorinated C1 to C8 alkyl, partially fluorinated or perfluorinated C1 to C8 alkoxy; in R 1 , R 2 and R 3 At least one or R 1 , R 2 and R 3 The group comprises at least three atoms selected from halogen, Cl, F or N; in By R 1 , R 2 and R 3 The group also includes: - at least two moieties selected from CF3 or CN; or - at least one moiety selected from CF3 or CN and a substituted or unsubstituted 6-membered heteroaryl group; or -R 3 It is CN; AL is an auxiliary ligand coordinated to the metal M; m is an integer selected from 0 to 2.

15. The metal complex of formula (I) according to claims 1 to 14: (I)， in M is Ce ion; n is the valence of M and is 4; L has the formula (II) (II), R 1 and R 2 are independently selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 Heteroaryl or substituted or unsubstituted 6-membered heteroaryl; R 3 is selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 heteroaryl, substituted or unsubstituted 6-membered heteroaryl or CN; in Substituted C1 to C 12 Alkyl, substituted C6 to C 19 Aryl, substituted C2 to C 20 At least one of the substituents of the heteroaryl or substituted 6-membered heteroaryl is independently selected from halogen, Cl, F, CN, partially fluorinated or perfluorinated C1 to C8 alkyl, partially fluorinated or perfluorinated C1 to C8 alkoxy; in R 1 , R 2 and R 3 At least one or R 1 , R 2 and R 3 The group comprises at least three atoms selected from halogen, Cl, F or N; AL is an auxiliary ligand coordinated to the metal M; m is an integer selected from 0 to 2.

16. The metal complex of formula (I) according to claims 1 to 15: (I)， in M is a metal ion; n is the valence of M and is selected from 1 to 4; L has the formula (II) (II), R 1 and R 2 are independently selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C3 containing at least one substituted or unsubstituted 6-membered heteroaryl group 20 heteroaryl; R 3 Selected from partially fluorinated or perfluorinated C1 to C4 alkyl or CN; in Substituted C1 to C 12 Alkyl, substituted C6 to C 19 Aryl, substituted C2 to C 20 At least one of the substituents of the heteroaryl or substituted 6-membered heteroaryl is independently selected from halogen, Cl, F, CN, partially fluorinated or perfluorinated C1 to C8 alkyl, partially fluorinated or perfluorinated C1 to C8 alkoxy; in AL is an auxiliary ligand coordinated to the metal M; m is an integer selected from 0 to 2.

17. The metal complex of formula (I) according to claims 1 to 16: (I)， in M is a metal ion; n is the valence of M and is selected from 1 to 4; L has the formula (II) (II), R 1 and R 2 are independently selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 Heteroaryl, substituted or unsubstituted 6-membered heteroaryl; R 3 is selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 heteroaryl, substituted or unsubstituted 6-membered heteroaryl or CN; in Substituted C1 to C 12 Alkyl, substituted C6 to C 19 Aryl, substituted C2 to C 20 At least one of the substituents of the heteroaryl or substituted 6-membered heteroaryl is independently selected from halogen, Cl, F, CN, partially fluorinated or perfluorinated C1 to C8 alkyl, partially fluorinated or perfluorinated C1 to C8 alkoxy; in R 1 , R 2 and R 3 At least one or R 1 , R 2 and R 3 The group includes substituted or unsubstituted C2 to C 20 heteroaryl; in AL is an auxiliary ligand coordinated to the metal M; m is an integer selected from 0 to 2.

18. A semiconductor material comprising at least one metal complex of formula (I) according to any one of the preceding claims 1 to 17.

19. Semiconductor material according to claim 18, wherein the semiconductor material additionally comprises at least one covalent matrix compound, preferably at least one substantially covalent matrix compound.

20. An organic electronic device, comprising a first electrode layer, a second electrode layer, at least one photoactive layer and a semiconductor layer, wherein the semiconductor layer is arranged between the first electrode layer and the at least one photoactive layer, and the semiconductor layer comprises a metal complex of formula (I) (I)， in M is a metal ion; n is the valence of M and is selected from 1 to 4; L has the formula (II) (II), R 1 and R 2 are independently selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 Heteroaryl or substituted or unsubstituted 6-membered heteroaryl; R 3 is selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 heteroaryl, substituted or unsubstituted 6-membered heteroaryl or CN; in Substituted C1 to C 12 Alkyl, substituted C6 to C 19 Aryl, substituted C2 to C 20 At least one of the substituents of the heteroaryl or substituted 6-membered heteroaryl is independently selected from halogen, Cl, F, CN, partially fluorinated or perfluorinated C1 to C8 alkyl, partially fluorinated or perfluorinated C1 to C8 alkoxy; in R 1 , R 2 and R 3 At least one or R 1 , R 2 and R 3 The group comprises at least three atoms selected from halogen, Cl, F or N; AL is an auxiliary ligand coordinated to the metal M; m is an integer selected from 0 to 2.

21. The organic electronic device according to claim 20, wherein the semiconductor layer comprises a metal complex of formula (I) according to claims 1 to 17.

22. The organic electronic device according to claim 20 or 21, wherein the organic electronic device is preferably a light-emitting device, a thin film transistor, a battery, a display device or a photovoltaic device, preferably a light-emitting device, and preferably the electronic device is part of a display device or a lighting device.

23. An organic electronic device comprising a metal complex of formula (I) according to claims 1 to 17, wherein the organic electronic device is preferably a light-emitting device, a thin film transistor, a battery, a display device or a photovoltaic device, preferably a light-emitting device, preferably the electronic device is part of a display device or a lighting device.

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