Light-emitting layer suitable for bright luminescence
11367848 · 2022-06-21
Assignee
Inventors
- Thomas Baumann (Karlsruhe, DE)
- Mathias MYDLAK (Karlsruhe, DE)
- Harald FLUGGE (Karlsruhe, DE)
- Charlotte FLECHON (Bruchsal, DE)
- Georgios Liaptsis (Mannheim, DE)
Cpc classification
H10K85/361
ELECTRICITY
H10K71/00
ELECTRICITY
H10K50/125
ELECTRICITY
H10K2101/30
ELECTRICITY
H10K85/371
ELECTRICITY
H10K2101/00
ELECTRICITY
H10K2101/40
ELECTRICITY
H10K2102/00
ELECTRICITY
H10K50/131
ELECTRICITY
Y02E10/549
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
Abstract
The present invention relates to a light-emitting layer B comprising a first emitter compound (a) having a non-exited state S0(a), a first excited singlet state S1(a) and a first excited triplet state T1(a); a second emitter compound (b) having a non-exited state S0(b), a first excited singlet state S1(b) and a first excited triplet state T1(b), wherein the energy level of S1(a) is higher than that of S1(b), the energy level of S1(b) is higher than that of T1(b) and wherein the rate of reverse intersystem crossing from T1(a) to S1(a) is higher than the rate of excitation energy transfer from S1(a) to S1(b) and/or the rate of excitation energy transfer from T1(a) to T1(b), and/or wherein the energy level of T1(b) is higher than that of T1(a). Further, the present invention also refers to an opto-electronic device comprising such light-emitting layer B and use thereof.
Claims
1. A light-emitting layer B comprising: (a) a first emitter compound (a) having a non-exited state S0(a), a first excited singlet state S1(a) and a first excited triplet state T1(a); (b) a second emitter compound (b) having a non-exited state S0(b), a first excited singlet state S1(b) and a first excited triplet state T1(b); and (c) optionally, one or more host components (c), wherein the energy level of S1(a) is higher than that of S1(b), the energy level of S1(a) is higher than that of T1(a), the energy level of S1(b) is higher than that of T1(b), and exciton energy is transferred from the first emitter compound (a) to the second emitter compound (b), wherein the rate of reverse intersystem crossing from T1(a) to S1(a) is higher than the rate of excitation energy transfer from S1(a) to S1(b), wherein the rate of reverse intersystem crossing from T1(a) to S1(a) is higher than the rate of the radiative or non-radiative transition from T1(a) to S0(a), wherein the light emitting layer B is further characterized by one or both of the following: (i) the rate of reverse intersystem crossing from T1(a) to S1(a) is higher than the rate of excitation energy transfer from T1(a) to T1(b), or (ii) the energy level of T1(b) is higher than that of T1(a), wherein energy transfer from S1(a) to S1(b) and radiative decay from S1(b) to S0(b) occur in the light-emitting layer B, wherein the energy difference ΔE.sub.ST(b) between S1(b) and T1(b) is not higher than 10000 cm.sup.−1, wherein at least one of the emitter compounds (a) and (b) is a thermally activated delayed fluorescence (TADF) emitter having an energy gap between its first excited singlet state and its first excited triplet state ΔE.sub.ST of not more than 5000 cm.sup.−1, and wherein the molar ratio of the first emitter compound (a) and the second emitter compound (b) (a):(b) is from 50:50 to 95:5, wherein emitter compounds (a) and (b) are, independently from one another, a purely organic TADF emitter or a metal complex comprising a complexed metal selected from the group consisting of Cu(I), Ag(I), Au(I) and Zn(II), wherein the energy difference ΔE.sub.LUMO(a,b) between the lowest unoccupied energy level of the first emitter compound LUMO(a) and the lowest unoccupied energy level of the second emitter compound LUMO(b) is not higher than 2 eV.
2. The light-emitting layer B according to claim 1, wherein the energy difference ΔE.sub.ST(a) between S1(a) and T1(a) is not higher than 7000 cm.sup.−1.
3. The light-emitting layer B according to claim 1, wherein the energy difference ΔE.sub.HOMO(a,b) between the highest occupied energy level of the first emitter compound HOMO(a) and the highest occupied energy level of the second emitter compound HOMO(b) is not higher than 1.8 eV.
4. The light-emitting layer B according to claim 1, wherein the energy difference ΔE.sub.LUMO(a,b) between the lowest unoccupied energy level of the first emitter compound LUMO(a) and the lowest unoccupied energy level of the second emitter compound LUMO(b) is not higher than 1.5 eV.
5. The light-emitting layer B according to claim 1, wherein the light emitting layer B is further characterized by one or more of the following selected from the rate of radiative transition from S1(b) to S0(b) differs from the transition rate from S1(a) to S1(b); the rate of reverse intersystem crossing from T1(a) to S1(a) is higher than Forster or Dexter energy transfer from T1(a) to T1(b); the rate of intersystem crossing from S1(b) to T1(b) differs from the rate of transition from S1(a) to S1(b); or the rate of the Förster resonance energy transfer from both the excited singlet and the excited triplet state of the first emitter compound S1(a) and T1(a) to the excited singlet and excited triplet state of the second emitter compound S1(b) and T1(b) is higher than the rate of the radiative transition from T1(a) to S0(a).
6. The light-emitting layer B according to claim 1, wherein the molar ratio between the first emitter compound (a) and the second emitter compound (b) (a):(b) is from 60:40 to 95:5.
7. The light-emitting layer B according to claim 1, wherein at least one of the emitter compounds (a) or (b) is either a purely organic thermally activated delayed fluorescence emitter compound or a Cu(I) complex.
8. The light-emitting layer B according to claim 1, wherein said light-emitting layer B concomitantly has a functionality selected from the group consisting of an electron transport layer, a hole blocking layer, a hole transport layer and an electron blocking layer.
9. A method of preparing a light-emitting layer B of claim 1, comprising the step of bringing the first emitter compound (a) and the second emitter compound (b) in close proximity with each other, by means of: (i) admixing the first emitter compound (a) and the second emitter compound (b) and optionally one or more host components (c) with each other, optionally in a solvent where (a), (b) and optionally (c) are dissolved in; (ii) providing a first layer comprising the first emitter compound (a) directly contacted with a second layer comprising the second emitter compound (b) and optionally one or more host components (c); (iii) providing a first layer comprising the first emitter compound (a) and optionally one or more host components (c) separated from a second layer comprising the second emitter compound (b) and optionally one or more host components (c) by a third layer that is a charge generation layer; (iv) using vacuum processing where the first emitter compound (a) and the second emitter compound (b) and optionally one or more host components (c) are co-deposited to form a mixed layer of the two emitter compounds (a) and (b); or (v) using vacuum processing where the first emitter compound (a) and the second emitter compound (b) and optionally one or more host components (c) are co-deposited to form a gradient of the two emitter compounds (a) and (b).
10. An opto-electronic device comprising a light-emitting layer B according to claim 1.
11. The opto-electronic device according to claim 10, comprising at least the layers: A) an anode layer A comprising indium tin oxide, indium zinc oxide, PbO, SnO, graphite, doped silicium, doped germanium, doped GaAs, doped polyaniline, doped polypyrrole, doped polythiophene, or a combination of two or more thereof; B) a light-emitting layer B according to claim 1; and C) a cathode layer C comprising Al, Au, Ag, Pt, Cu, Zn, Ni, Fe, Pb, In, W, Pd, LiF, Ca, Ba, Mg, or mixtures or alloys of two or more thereof.
12. The opto-electronic device according to claim 10, wherein said opto-electronic device is a device selected from the group consisting of an organic light emitting diode, a light emitting electrochemical cell, a transistor, a light-emitting transistor, an organic solar cell, and an optical sensor.
13. A method for generating light of a desired wavelength range, comprising the step of providing an opto-electronic device according to claim 10.
14. The light-emitting layer B according to claim 1, wherein: (i) both emitter compounds (a) and (b) are thermally activated delayed fluorescence emitters, (ii) emitter compound (a) is a thermally activated delayed fluorescence emitter and emitter compound (b) is a fluorescence or phosphorescence emitter, or (iii) emitter compound (a) is a phosphorescence emitter and emitter compound (b) is a thermally activated delayed fluorescence emitter.
15. The light-emitting layer B according to claim 1, wherein the energy difference ΔE.sub.ST(a) between S1(a) and T1(a) is not higher than 1500 cm.sup.−1.
16. The light-emitting layer B according to claim 1, wherein the energy difference ΔE.sub.ST(b) between S1(b) and T1(b) is not higher than 1500 cm.sup.−1.
17. The light-emitting layer B according to claim 1, wherein the energy difference ΔE.sub.HOMO(a,b) between the highest occupied energy level of the first emitter compound HOMO(a) and the highest occupied energy level of the second emitter compound HOMO(b) is not higher than 1 eV.
18. The light-emitting layer B according to claim 1, wherein the energy difference ΔE.sub.LUMO(a,b) between the lowest unoccupied energy level of the first emitter compound LUMO(a) and the lowest unoccupied energy level of the second emitter compound LUMO(b) is not higher than 1 eV.
19. The light-emitting layer B according to claim 1, wherein the light emitting layer B is further characterized by one or more of the following: the radiative transition from S1(b) to S0(b) is faster than the transition from S1(a) to S1(b); the transition from S1(a) to S1(b) is faster than the radiative transition from S1(a) to S0(a); or the intersystem crossing from S1(b) to T1(b) is faster than the transition from S1(a) to S1(b).
20. The light-emitting layer B according to claim 1, wherein at least one of the emitter compounds (a) or (b) is a Cu(I) complex of one of the following structures (I)-(III): ##STR00093## wherein L.sup.i-L.sup.iiii are each independently selected from: A) suitable organic ligands L, which may be the same or different, or B) residues of organic ligands, which may be the same or different, wherein optionally two or more of L.sup.i-L.sup.iiii may be covalently bound with another; wherein X and X′ each independently represent an inorganic ligand or an anion selected from the group consisting of Cl.sup.−, Br.sup.−, I.sup.−, SCN.sup.−, CN.sup.−, RS.sup.−, RSe.sup.−, RR′N.sup.−, RR′P.sup.− and R—C≡C.sup.−, wherein R and R′ are an organic residue independently selected from the group consisting of an unsubstituted or substituted C.sub.1-20-alkyl residue, an adamantadyl residue, an unsubstituted or substituted C.sub.7-40-alkylaryl residue, an unsubstituted or substituted C.sub.7-40-arylalkyl residue, an unsubstituted or substituted C.sub.7-40-alkylarylalkyl residue, an unsubstituted or substituted C.sub.6-14-aryl residue, an unsubstituted or substituted C.sub.2-13-heteroaryl residue, an unsubstituted or substituted C.sub.2-20-alkenyl residue (e.g., CR═CR″R′″), an unsubstituted or substituted C.sub.2-20-alkinyl residue, —OR″, and —NR″R′″, wherein R″, R′″ are defined as R any may optionally also be H.
Description
(1) The Examples, the Figures shown below and the claims further exemplify the invention.
(2)
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wherein the molecular orbitals of Ak and Gr and of Do and Gr, respectively, overlap.
EXAMPLES
(16) Examples of Specific Combinations of Emitter Compounds
(17) One general example is that energy is partly transferred from an excited S1 energy level of a high energy delayed fluorescent emitter compound (a) to the lower S1(b) and/or T1(b) energy level(s) of another emitter compound (b). Herein, compound (a) may be a blue copper-based singlet harvesting emitter. Compound (b) may be a fluorescent or a phosphorescent emitter. Compounds (a) and (b) may be mixed in a common layer or separated in two adjacent layers. Two adjacent layers may preferably be obtained by using orthogonal solvents, or cross-linkable layers, or by subsequent thermal evaporation.
Example I
(18) On an indium tin oxide (ITO) electrode, a 30 nm thick poly(3,4-ethylenedioxythiophene) polystyrene sulfonate copolymer (PEDOT:PSS) layer is deposited by spin-coating. The emitting layer consisted of a blue copper complex and a green copper complex blended together in toluene and deposited by spin coating. The electron transporting layer is a 50 nm thick 1,3,5-tri(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl (TPBi) layer. The electrodes are a lithium fluoride (LiF) layer (1 nm) and an aluminum layer (100 nm).
Example II
(19) On an indium tin oxide (ITO) electrode, a 30 nm thick poly(3,4-ethylenedioxythiophene) polystyrene sulfonate copolymer (PEDOT:PSS) layer is deposited by spin-coating. The emitting layer consisted of a blue copper complex and a green copper complex and an organic host compound blended together in toluene and deposited by spin coating. The electron transporting layer is a 50 nm thick 1,3,5-tri(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl (TPBi) layer. The electrodes are a lithium fluoride (LiF) layer (1 nm) and an aluminum layer (100 nm).
Example III
(20) On an indium tin oxide (ITO) electrode, a 30 nm thick poly(3,4-ethylenedioxythiophene) polystyrene sulfonate copolymer (PEDOT:PSS) layer is deposited by spin-coating. The emitting layer consisted of a blue copper complex and a green pure organic TADF emitter blended together in toluene and deposited by spin coating. The electron transporting layer is a 50 nm thick 1,3,5-tri(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl (TPBi) layer. The electrodes are a lithium fluoride (LiF) layer (1 nm) and an aluminum layer (100 nm).
Example IV
(21) On an indium tin oxide (ITO) electrode, a 30 nm thick poly(3,4-ethylenedioxythiophene) polystyrene sulfonate copolymer (PEDOT:PSS) layer is deposited by spin-coating. The emitting layer consisted of a blue copper complex and a green pure organic TADF emitter and an organic host compound blended together in toluene and deposited by spin coating. The electron transporting layer is a 50 nm thick 1,3,5-tri(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl (TPBi) layer. The electrodes are a lithium fluoride (LiF) layer (1 nm) and an aluminum layer (100 nm).
Example V
(22) On an indium tin oxide (ITO) electrode, a 30 nm thick poly(3,4-ethylenedioxythiophene) polystyrene sulfonate copolymer (PEDOT:PSS) layer is deposited by spin-coating. The emitting layer consisted of a blue copper complex and a green fluorescent emitter blended together in toluene and deposited by spin coating. The electron transporting layer is a 50 nm thick 1,3,5-tri(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl (TPBi) layer. The electrodes are a lithium fluoride (LiF) layer (1 nm) and an aluminum layer (100 nm).
Example VI
(23) On an indium tin oxide (ITO) electrode, a 30 nm thick poly(3,4-ethylenedioxythiophene) polystyrene sulfonate copolymer (PEDOT:PSS) layer is deposited by spin-coating. The emitting layer consisted of a blue copper complex and a green fluorescent emitter and an organic host compound blended together in toluene and deposited by spin coating. The electron transporting layer is a 50 nm thick 1,3,5-tri(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl (TPBi) layer. The electrodes are a lithium fluoride (LiF) layer (1 nm) and an aluminum layer (100 nm).
Example VII
(24) On an indium tin oxide (ITO) electrode, a 30 nm thick poly(3,4-ethylenedioxythiophene) polystyrene sulfonate copolymer (PEDOT:PSS) layer is deposited by spin-coating. The emitting layer consisted of a blue copper complex and a green phosphorescent emitter blended together in toluene and deposited by spin coating. The electron transporting layer is a 50 nm thick 1,3,5-tri(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl (TPBi) layer. The electrodes are a lithium fluoride (LiF) layer (1 nm) and an aluminum layer (100 nm).
Example VIII
(25) On an indium tin oxide (ITO) electrode, a 30 nm thick poly(3,4-ethylenedioxythiophene) polystyrene sulfonate copolymer (PEDOT:PSS) layer is deposited by spin-coating. The emitting layer consisted of a blue phosphorescent metal complex and a green copper-complex emitter blended together in toluene and deposited by spin coating. The electron transporting layer is a 50 nm thick 1,3,5-tri(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl (TPBi) layer. The electrodes are a lithium fluoride (LiF) layer (1 nm) and an aluminum layer (100 nm).
Example IX
(26) On an indium tin oxide (ITO) electrode, a 30 nm thick poly(3,4-ethylenedioxythiophene) polystyrene sulfonate copolymer (PEDOT:PSS) layer is deposited by spin-coating. The emitting layer consisted of a blue phosphorescent metal complex and a green copper-complex emitter and an organic host compound blended together in toluene and deposited by spin coating. The electron transporting layer is a 50 nm thick 1,3,5-tri(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl (TPBi) layer. The electrodes are a lithium fluoride (LiF) layer (1 nm) and an aluminum layer (100 nm).
Examples X-XVI: Further Emitter Compounds in the Context of the Present Invention
(27) In the following Examples X-XVI, emitter compounds that could serve as emitter compound (a) and/or emitter compound (b) are provided.
(28) In general, if not otherwise defined, in the chemical structures, the following definitions may apply: N represents nitrogen; P represents phosphor; O represents oxygen; H represents hydrogen; D represents deuterium; Ph represents a phenyl residue; Me represents a methyl residue; Ar represents an unsubstituted or substituted aryl residue; M and M′ each represents a metal, in particular metal (I); Cu represents copper, in particular Cu(I); X and X′ each represents represent an anion; an alkyl residue may exemplarily be an unsubstituted or substituted methyl residue, ethyl residue, propyl residue, butyl residue, pentyl residue, hexyl residue, heptyl residue, octyl residue, nonyl residue, or decyl residue etc.; an alkylene residue may exemplarily be an unsubstituted or substituted methylene residue, ethylene residue, propylene residue, butylene residue, pentylene residue, hexylene residue, heptyl residue, octylene residue, nonylene residue, or decylene residue etc. an alkenyl residue may exemplarily be an unsubstituted or substituted methenyl residue, ethenyl residue, propenyl residue, butenyl residue, pentenyl residue, hexenyl residue, heptenyl residue, octenyl residue, nonenyl residue, or decenyl residue etc.; and an alkenylene residue may exemplarily be an unsubstituted or substituted methenylene residue, ethenylene residue, propenylene residue, butenylene residue, pentenylene residue, hexenylene residue, heptenyl residue, octenylene residue, nonenylene residue, or decenylene residue etc.
(29) Residues (in particular R, with or without further indices) that are not defined in more detail may represent any (unsubstituted or substituted organic) residue comprising not more than 40 carbon atoms. Likewise, each Z with or without further indices that is not defined in more detail may represent any divalent (unsubstituted or substituted organic) linker comprising not more than 40 carbon atoms or a bond.
(30) A ligand designated by two letters interconnected by “{circumflex over ( )}” means that the ligand is the structure between the first letter to the second letter comprising the structural elements depicted in the respective chemical structure.
Example X: Emitter Compound of Structure A
(31) Exemplarily, the first emitter compound (a) and/or the second emitter compound (b) may be a Cu(I) complex having a structure according to one of the following formulae A, A′, A″ or A′″. Examples for respective complexes are also provided in WO 2013/007707 (cf., exemplarily Examples 1-6 thereof)
(32) ##STR00003##
wherein the ligand comprising L, L′ and Z (L{circumflex over ( )}L′) is a neutral, bidentate ligand that is bound to the Cu via non-ionic groups;
wherein the ligand comprising D, [B].sub.n, N.sup.− (and Z′) (D{circumflex over ( )}N.sup.−) is bound to the Cu via an anionic group;
wherein D is a residue comprising at least one substituent D* selected from the group consisting of a bivalent carbene C*, N, O, P, S, As and Sb or consisting of D*,
wherein D* binds to Cu,
wherein D may further comprise a residue of up to 40 carbon atoms selected from the group consisting of a linear, branched or cyclic alkylene residue, a linear, branched or cyclic heteroalkylene residue, an arylene residue, a heteroarylene residue, a linear, branched or cyclic alkenylene residue, and a linear, branched or cyclic alkinylene residue, that may be each optionally substituted with one or more substituents selected from the group consisting of halogens, deuterium, linear, branched or cyclic alkyl residues, linear, branched or cyclic heteroalkyl residues, aryl residues, heteroaryl residues, linear, branched or cyclic alkenyl residues, linear, branched or cyclic alkinyl residues, and other donor or acceptor groups such as exemplarily amines, phosphines, carboxylates and esters thereof, and CF.sub.3— groups, wherein the substituents may optionally form a cyclic or anellated structure with each other and/or with residue D;
wherein N.sup.− is anionic nitrogen;
wherein Z′ is —R.sup.u—, —R.sup.u—NR.sup.u″—, —NR.sup.u″—R.sup.u—, —R.sup.u—NR.sup.u″—R.sup.u′—, —R.sup.u—SiR.sup.u″R.sup.u′″—R.sup.u′—, —R.sup.u—SiR.sup.u″R.sup.u′″—SiR.sup.u″R.sup.u′″—R.sup.u—, —R.sup.u—GeR.sup.u″R.sup.u′″—R.sup.u′—, —R.sup.u—GeR.sup.u″R.sup.u′″—, —GeR.sup.u″R.sup.u′″—R.sup.u—, —R.sup.u—O—R.sup.u′, —R.sup.u—CO—R.sup.u′, —R.sup.u—CO—O—R.sup.u′—, —R.sup.u—O—CO—O—R.sup.u′—, —R.sup.u—O—CO—R.sup.u′—, —O—R.sup.u′—, —R.sup.u—CS—R.sup.u′—, —R.sup.u—CO—S—R.sup.u′—, —R.sup.u—S—CO—R.sup.u′—, —R.sup.u—CO—NH—R.sup.u′—, —R.sup.u—NH—CO—R.sup.u′—, —R.sup.u—O—, —R.sup.u—S—R.sup.u′—, —S—R.sup.u′—, —R.sup.u—S—, —R.sup.u—SO—R.sup.u′—, —SO—R.sup.u′—, —R.sup.u—SO—, —R.sup.u—SO.sub.2—R.sup.u′—, —SO.sub.2—R.sup.u′—, or —R.sup.u—SO.sub.2—,
wherein R.sup.u and R.sup.u′ each independently from another are a residue of up to 40 carbon atoms selected from the group consisting of a linear, branched or cyclic alkylene residue, a linear, branched or cyclic heteroalkylene residue, an arylene residue, a heteroarylene residue, a linear, branched or cyclic alkenylene residue, and a linear, branched or cyclic alkinylene residue, that may be each optionally substituted with one or more substituents selected from the group consisting of halogens, deuterium, linear, branched or cyclic alkyl residues, linear, branched or cyclic heteroalkyl residues, aryl residues, heteroaryl residues, linear, branched or cyclic alkenyl residues, linear, branched or cyclic alkinyl residues, and other donor or acceptor groups such as exemplarily amines, phosphines, carboxylates and esters thereof, and CF.sub.3— groups,
wherein the substituents may optionally form a cyclic or anellated structure with each other and/or with residue D,
wherein R.sup.u″ and R.sup.u′″ each independently from another are a residue of up to 40 carbon atoms selected from the group consisting of hydrogen, halogen, —R.sup.t, —OC(O)R.sup.t, —COOH, —OR.sup.t, —NR.sup.tR.sup.t′, —SiR.sup.tR.sup.t′R.sup.t″, —GeR.sup.tR.sup.t′R.sup.t″, —SR.sup.t, —SOR.sup.t, —SO.sub.2R.sup.t and other donor or acceptor groups such as exemplarily carboxylates and esters thereof, and CF.sub.3— groups,
wherein R.sup.t, R.sup.t′ and R.sup.t″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein two or more of the residues R.sup.t, R.sup.t′, R.sup.t″, R.sup.u, R.sup.u′, R.sup.u″, and R.sup.u′″ may optionally also form anellated cyclic structures;
wherein each B is a bivalent organic linker independently from another selected from the group consisting of ═CR.sup.z—, —CR.sup.zR.sup.y—, —NR.sup.z—, —O—, —SiR.sup.zR.sup.y—, —GeR.sup.zR.sup.y—, —S—, —S(O)—, and —S(O).sub.2— or a bond,
wherein R.sup.z and R.sup.y are each independently from another selected from the group consisting of hydrogen, halogen, —OR.sup.x, —O—C(O)—R.sup.x, —NR.sup.xR.sup.x′, —SiR.sup.xR.sup.x′R.sup.x″, —GeR.sup.xR.sup.x′R.sup.x″, —SR.sup.x, —SOR.sup.x, and —SO.sub.2R.sup.x,
wherein R.sup.x, R.sup.x′ and R.sup.x″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein R.sup.x, R.sup.x′ and R.sup.x″ may optionally also form anellated cyclic structures wherein B may exemplarily be a part of a phenyl and/or substituted phenyl moiety,
wherein each B may be the same of different,
wherein there is at least one carbon atom between N and D*,
wherein one or more substituents of D and/or of N.sup.− may optionally form cyclic, aliphatic, conjugated, aromatic and/or anellated systems;
wherein T is CR.sup.w or nitrogen,
wherein R.sup.w is a residue selected from the group consisting of hydrogen, halogen, —R.sup.v, —OC(O)R.sup.v, —COOH, —OR.sup.v, —NR.sup.vR.sup.v′, —SiR.sup.vR.sup.v′R.sup.v′″, —GeR.sup.vR.sup.v′R.sup.v″, —SR.sup.v, —SOR.sup.v, —SO.sub.2R.sup.v and other donor or acceptor groups such as exemplarily carboxylates and esters thereof, and CF.sub.3— groups,
wherein R.sup.v, R.sup.v′ and R.sup.v″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, NHR.sup.v′″, NHR.sup.v′″R.sup.v″″, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein R.sup.v′″ and R.sup.v″″ are each independently from another selected from the group consisting of OH, NH.sub.2, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein two or more of R.sup.v, R.sup.v″, R.sup.v′″ and R.sup.w may optionally also form anellated cyclic structures,
wherein T may form one or more anellated cyclic structures with one or more B;
wherein n represents an integer from 1 to 9;
wherein L and L′ are each independently from another bound to the Cu,
wherein L comprises a residue L* and L′ comprises a residue L′*, wherein L* and L′* are each independently from another selected from the group consisting of a bivalent carbene C*, N, O, P, S, As and Sb and wherein each of L* and L′* binds to the Cu,
wherein L comprises one or more, preferably three, residues bound to the L*, and L′ comprises one or more, preferably three, residues bound to the L′*,
wherein the residues bound to L* and L′* are each independently a residue of up to 40 carbon atoms selected from the group consisting of a linear, branched or cyclic alkylene residue, a linear, branched or cyclic heteroalkylene residue, an arylene residue, a heteroarylene residue, a linear, branched or cyclic alkenylene residue, and a linear, branched or cyclic alkinylene residue, that may be each optionally substituted with one or more substituents selected from the group consisting of halogens, deuterium, linear, branched or cyclic alkyl residues, linear, branched or cyclic heteroalkyl residues, aryl residues, heteroaryl residues, linear, branched or cyclic alkenyl residues, linear, branched or cyclic alkinyl residues, and other donor or acceptor groups such as exemplarily amines, phosphines, carboxylates and esters thereof, and CF.sub.3— groups, wherein the substituents may optionally form a cyclic or anellated structure with each other;
wherein each one residue bound to the L* and one residue bound to the L′* may be linked by Z, in particular wherein the other residues bound to L* and L′* are aryl residues,
wherein Z is —O—, a bond, —R.sup.ub—, —R.sup.ub—NR.sup.ub″, —NR.sup.ub″—R.sup.ub—, —R.sup.ub—NR.sup.ub″—R.sup.ub′—, —R.sup.ubSiR.sup.ub″R.sup.ub′″—R.sup.ub′—, —R.sup.ub—SiR.sup.ub″R.sup.ub′″—, —SiR.sup.ub″R.sup.ub′″—R.sup.ub, —R.sup.ub—GeR.sup.ub″R.sup.ub′″—R.sup.ub′—, —R.sup.ub—GeR.sup.ub″R.sup.ub′″—, —GeR.sup.ub″R.sup.ub′″—R.sup.ub—, —R.sup.ub—O—R.sup.ub′—, —R.sup.ub—CO—R.sup.ub′—, —R.sup.ub—CO—O—R.sup.ub′—, —R.sup.ub—O—CO—O—R.sup.ub′—, —R.sup.ub—O—CO—R.sup.ub′—, —O—R.sup.ub′—, —R.sup.ub—CS—R.sup.ub′—, —R.sup.ub—CO—S—R.sup.ub′—, —R.sup.ub—S—CO—R.sup.ub′—, —R.sup.ub—CO—NH—R.sup.ub′—, —R.sup.ub—NH—CO—R.sup.ub′—, —R.sup.ub—O—, —R.sup.ub—S—R.sup.ub′—, —S—R.sup.ub′—, —R.sup.ub—S—, —R.sup.ub—SO—R.sup.ub′—, —SO—R.sup.ub′—, —R.sup.ub—SO—, —R.sup.ub—SO.sub.2R.sup.ub′, —SO.sub.2—R.sup.ub′—, —R.sup.ub—CO—NR.sup.v′″—R.sup.ub′—, —R.sup.ub—NR.sup.v′″—CO—R.sup.ub′— or —R.sup.ub—SO.sub.2— or may be missing and, gus, not linking L and L′,
wherein R.sup.ub and R.sup.ub′ are each independently from another a substituent of up to 40 carbon atoms selected from the group consisting of a linear, branched or cyclic alkylene residue, a linear, branched or cyclic heteroalkylene residue, an arylene residue, a heteroarylene residue, a linear, branched or cyclic alkenylene residue, and a linear, branched or cyclic alkinylene residue, that may be each optionally substituted with one or more substituents selected from the group consisting of halogens, deuterium, linear, branched or cyclic alkyl residues, linear, branched or cyclic heteroalkyl residues, aryl residues, heteroaryl residues, linear, branched or cyclic alkenyl residues, linear, branched or cyclic alkinyl residues, and other donor or acceptor groups such as exemplarily amines, phosphines, carboxylates and esters thereof, and CF.sub.3— groups, wherein the substituents may optionally form a cyclic or anellated structure with each other;
wherein R.sup.ub″ and R.sup.ub′″ each independently from another are a residue of up to 40 carbon atoms selected from the group consisting of hydrogen, halogen, —R.sup.t′″, —OC(O)R.sup.t′″, —COOH, —OR.sup.t′″, —NR.sup.t′″R.sup.t′″, —SiR.sup.t′″R.sup.t″″R.sup.t′″″, —GeR.sup.t′″R.sup.t″″R.sup.t′″″, —SR.sup.t′″, —SOR.sup.t′″, —SO.sub.2R.sup.t′″ and other donor or acceptor groups such as exemplarily carboxylates and esters thereof, and CF.sub.3— groups,
wherein R.sup.t′″, R.sup.t″″ and R.sup.t′″″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein the residues R.sup.t′″, R.sup.t″″, R.sup.t′″″, R.sup.ub, R.sup.ub′, R.sup.ub″, and R.sup.ub′″ may optionally form a cyclic or anellated structure with each other.
(33) In a preferred embodiment, N′ together with Z′ of formula A, A′, A″ or A′″ represents an anion of an unsaturated or saturated N-heterocyclic moiety of 5 to 14 ring atoms that is obtained from N-deprotonating a residue selected from the group consisting of purinyl, pyrryl, indyl, carbazolyl, triazolyl, benzotriazolyl, pyrazolyl, benzopyrazolyl, imidazolyl, benzimidazolyl, and tetrazolyl, that may optionally be substituted further.
(34) Alternatively, also two or more Z may link L and L′.
(35) As can be seen from above, Z may also be also missing. Then, L and L′ are both each binding to the but are not linked directly with another.
(36) In a preferred embodiment, the residue D of the ligand comprising D, [B].sub.n, N.sup.− (and Z′) (D{circumflex over ( )}N.sup.−) of formula A, A′, A″ or A′″ is selected from the group consisting of (wherein the ligand does not comprise more than 20 carbon atoms):
(37) (i) a carbene C* that is a part of a carbene ligand selected from the group consisting of:
(38) ##STR00004##
wherein the two dots “:” represent a bivalent carbene that is coordinated with the Cu, and wherein the carbene ligand is conjugated to B via one of the binding sites indicated by #,
wherein the other binding site indicated by # represents the binding site to the residue selected from the group consisting of hydrogen, deuterium, nitrogen, —OR.sup.s, —O—C(O)—R.sup.s, —NR.sup.sR.sup.s′, —SiR.sup.sR.sup.s′R.sup.s″, —GeR.sup.sR.sup.s′R.sup.s″, —SR.sup.s, —SOR.sup.s and —SO.sub.2R.sup.s,
wherein R is each independently from another selected from the group consisting of hydrogen, deuterium, hydroxyl, OH, NH.sub.2, —R.sup.s, —OR.sup.s, —O—C(O)—R.sup.s, —NR.sup.sR.sup.s′, —SiR.sup.sR.sup.s′R.sup.s″, —GeR.sup.sR.sup.s′R.sup.s″, —SR.sup.s, —SOR.sup.s and —SO.sub.2R.sup.s,
wherein R.sup.s, R.sup.s′ and R.sup.s″ are each independently from another selected from the group consisting of hydrogen, deuterium, OH, NH.sub.2, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein two or more of the residues R, R.sup.s, R.sup.s′ and R.sup.s″ may also form anellated cyclic structures with each other;
wherein Y is nitrogen or CR.sup.r,
wherein R.sup.r is a residue selected from the group consisting of hydrogen, deuterium, halogen, —R.sup.q, —OC(O)R.sup.q, —COOH, —OR.sup.q, —NR.sup.qR.sup.q′, —SiR.sup.qR.sup.q′R.sup.q″, —GeR.sup.qR.sup.q′R.sup.q″, —SR.sup.q, —SOR.sup.q, —SO.sub.2R.sup.q and other donor or acceptor groups such as exemplarily carboxylates and esters thereof, and CF.sub.3— groups,
wherein R.sup.q, R.sup.q′ and R.sup.q″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, NR.sup.sR.sup.s′, NHR.sup.s, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein two or more of the residues R.sup.q, R.sup.q′, R.sup.q″ and R.sup.r may optionally form anellated cyclic structures; and
wherein z represent an integer of 1, 2, 3 or 4;
(ii) an unsaturated or aromatic N-heterocyclic moiety of 4 to 8 ring atoms, wherein the Cu is coordinated via a nitrogen atom of the N-heterocyclic moiety, selected from the group consisting of pyridyl, pyrimidyl, pyridazyl, pyrazyl, pyranyl, cumaryl, pteridyl, thiophenyl, benzothiophenyl, furyl, benzofuryl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, thienothienyl, dithiaindacenyl, chinolyl, isochinolyl, chinoxalyl, acridyl, azanaphthyl, phenanthrolyl, triazinyl, thienyl, thiadiazolyl, isoxazolyl, isothiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1,2,4-oxadiazolyl, 1,2,4-thiadiazolyl, tetrazolyl, 1,2,3,4-oxatriazolyl and 1,2,3,4-thiatriazolyl, that may optionally be further substituted and/or anellated, and an N-heterocyclic moiety selected from the group consisting of:
(39) ##STR00005##
wherein the moiety is conjugated to B at the site indicated by #, and * represents the atom that form a complex binding to Cu,
wherein Z.sub.1, Z.sub.2, Z.sub.3 and Z.sub.4 are each independently from another CR.sup.l or nitrogen,
wherein R.sup.l a residue selected from the group consisting of hydrogen, deuterium, halogen, —R.sup.k, —OC(O)R.sup.k, —COOH, —OR.sup.k, —NR.sup.kR.sup.k′, —SiR.sup.kR.sup.k′R.sup.k″, —GeR.sup.kR.sup.k′R.sup.k″, —SR.sup.k, —SOR.sup.k, —SO.sub.2R.sup.k and other donor or acceptor groups such as exemplarily carboxylates and esters thereof, and CF.sub.3— groups,
wherein R.sup.k, R.sup.k′ and R.sup.k″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, NR.sup.sR.sup.s′, NHR.sup.s, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein two or more of the residues R.sup.k, R.sup.k′, R.sup.k″ and R.sup.l may optionally form anellated cyclic structures,
wherein Y may be defined as above;
(iii) a phosphanyl, arsenyl or antimonyl moiety of the structure -ER.sup.iR.sup.j,
wherein E is selected from the group consisting of P, As and Sb, that coordinate to the Cu,
wherein R.sup.i and R.sup.j are each independently from another selected from the group consisting of hydrogen, deuterium, halogen, —R.sup.k, —OC(O)R.sup.k, —COOH, —OR.sup.k, —NR.sup.kR.sup.k′, —SiR.sup.kR.sup.k′R.sup.k″, —GeR.sup.kR.sup.k′R.sup.k″, —SR.sup.k, —SOR.sup.k, —SO.sub.2R.sup.k and other donor or acceptor groups such as exemplarily carboxylates and esters thereof, and CF.sub.3— groups,
wherein R.sup.k, R.sup.k′ and R.sup.k″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, NR.sup.sR.sup.s′, NHR.sup.s, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein two or more of the residues R.sup.k, R.sup.k′, R.sup.k″, R.sup.i and R.sup.j may optionally form anellated cyclic structures.
(40) In a preferred embodiment, the carbene C* of the ligand comprising D, [B].sub.n and N.sup.− of formula A, A′, A″ or A′″ forms part of a moiety having one of the following structures:
(41) ##STR00006##
wherein the two dots “:” represent a bivalent carbene that is coordinated with the Cu, and
wherein the carbene ligand is conjugated to B via one of the binding sites indicated by #,
wherein the other binding site indicated by # represents the binding site to the residue selected from the group consisting of hydrogen, nitrogen, OR.sup.g, —O—C(O)—R.sup.g, —NR.sup.gR.sup.g′, —SiR.sup.gR.sup.g′R.sup.g″, —GeR.sup.gR.sup.g′R.sup.g″, —SR.sup.g, —SOR.sup.g and —SO.sub.2R.sup.g,
wherein R is each independently from another selected from the group consisting of hydrogen, deuterium, nitrogen, —R.sup.g, —OR.sup.g, —O—C(O)—R.sup.g, —NR.sup.gR.sup.g′, —SiR.sup.gR.sup.g′R.sup.g″, —GeR.sup.gR.sup.g′R.sup.g″, —SR.sup.g, —SOR.sup.g and —SO.sub.2R.sup.g,
wherein R.sup.g, R.sup.g′ and R.sup.g″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, NR.sup.sR.sup.s′, NHR.sup.s, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein two or more of the residues R, R.sup.g, R.sup.g′ and R.sup.g″ may also form anellated cyclic structures with each other;
wherein Y is nitrogen or CR.sup.f,
wherein R.sup.f is a residue selected from the group consisting of hydrogen, deuterium, halogen, —R.sup.e, —OC(O)R.sup.e, —COOH, —OR.sup.e, —NR.sup.eR.sup.e′, —SiR.sup.eR.sup.e′R.sup.e″, —GeR.sup.eR.sup.e′R.sup.e″, —SR.sup.e, —SOR.sup.e, —SO.sub.2R.sup.e and other donor or acceptor groups such as exemplarily carboxylates and esters thereof, and CF.sub.3— groups,
wherein R.sup.e, R.sup.e′ and R.sup.e″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, NR.sup.sR.sup.s′, NHR.sup.s, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein two or more of the residues R.sup.e, R.sup.e′, R.sup.e″ and R.sup.f may optionally form anellated cyclic structures; and
wherein z represent an integer of 1, 2, 3 or 4.
(42) In a preferred embodiment, the ligand L{circumflex over ( )}L′ is a bidentate ligand of the form L-G-L′,
(43) wherein G is a substituted or unsubstituted C.sub.1-9-alkylene, C.sub.2-8-alkenylene, C.sub.2-8-alkinylene or arylene moiety, —R.sup.d—NR.sup.d″—, —NR.sup.d″—R.sup.d—, —R.sup.d—NR.sup.d″—R.sup.d′—, —R.sup.d—SiR.sup.d″R.sup.d′″—R.sup.d′—, —R.sup.d—SiR.sup.d″R.sup.d′″—, —SiR.sup.d″R.sup.d′″—, —R.sup.d—GeR.sup.d″R.sup.d′″—R.sup.d′—, —R.sup.d—GeR.sup.d″R.sup.d′″—, —GeR.sup.d″R.sup.d′″—, R.sup.d—, R.sup.d—O—R.sup.d′—, —R.sup.d—CO—R.sup.d′—, —R.sup.d—CO—O—R.sup.d′—, —R.sup.d—O—CO—O—R.sup.d′—, —R.sup.d—O—CO—R.sup.d′—, —O—R.sup.d′—, —R.sup.d—CS—R.sup.d′—, —R.sup.d—CO—S—R.sup.d′—, —R.sup.d—S—CO—R.sup.d′—, —R.sup.d—CO—NH—R.sup.d′—, —R.sup.d—NH—CO—R.sup.d′—, —R.sup.d—O—, —R.sup.d—S—R.sup.d′—, —S—R.sup.d′—, —R.sup.d—S—, —R.sup.d—SO—R.sup.d′—, —SO—R.sup.d′—, —R.sup.d—SO—, —R.sup.dSO.sub.2—R.sup.d′—, —SO.sub.2—R.sup.d′—, or —R.sup.d—SO.sub.2—,
wherein R.sup.d and R.sup.d′ are each independently from another a residue of up to 20 carbon atoms selected from the group consisting of a linear, branched or cyclic alkylene residue, a linear, branched or cyclic heteroalkylene residue, an arylene residue, a heteroarylene residue, a linear, branched or cyclic alkenylene residue, and a linear, branched or cyclic alkinylene residue, that may be each optionally substituted with one or more substituents selected from the group consisting of halogens, deuterium, linear, branched or cyclic alkyl residues, linear, branched or cyclic heteroalkyl residues, aryl residues, heteroaryl residues, linear, branched or cyclic alkenyl residues, linear, branched or cyclic alkinyl residues, and other donor or acceptor groups such as exemplarily amines, phosphines, carboxylates and esters thereof, and CF.sub.3— groups,
wherein the substituents may optionally form a cyclic and/or anellated structure with each other and/or with one or both of the residues L and/or L′;
wherein R.sup.d″ and R.sup.d′″ are each independently from another a residue of up to 20 carbon atoms selected from the group consisting of hydrogen, halogen, —R.sup.c, —OC(O)R.sup.c, —COOH, —OR.sup.c, —NR.sup.cR.sup.c′, —SiR.sup.cR.sup.c′R.sup.c″, —GeR.sup.cR.sup.c′R.sup.c″, —SR.sup.c, —SOR.sup.c, —SO.sub.2R.sup.c and other donor or acceptor groups such as exemplarily carboxylates and esters thereof, and CF.sub.3— groups,
wherein R.sup.c, R.sup.c′ and R.sup.c″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, NR.sup.sR.sup.s′, NHR.sup.s, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein two or more of the residues R.sup.c, R.sup.c′, R.sup.c″, R.sup.d, R.sup.d′, R.sup.d″, and R.sup.d′″ may optionally form anellated cyclic structures;
wherein L and L′ are substituents that may be the same of different from another and are independently from another selected from the group consisting of (wherein the ligand does not comprise more than 20 carbon atoms): (i) the fragment X.sup.b or an unsaturated or aromatic N-heterocyclic moiety of 4 to 8 ring atoms selected from the group consisting of pyridyl, pyrimidyl, pyridazyl, pyrazyl, pyranyl, cumaryl, pteridyl, thiophenyl, benzothiophenyl, furyl, benzofuryl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, thienothienyl, dithiaindacenyl, chinolyl, isochinolyl, chinoxalyl, acridyl, azanaphthyl, phenanthrolyl, triazinyl, thienyl, thiadiazolyl, isoxazolyl, isothiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1,2,4-oxadiazolyl, 1,2,4-thiadiazolyl, tetrazolyl, 1,2,3,4-oxatriazolyl and 1,2,3,4-thiatriazolyl, that may optionally be further substituted and/or anellated,
wherein the Cu is coordinated via a nitrogen atom of the fragment X.sup.b or a nitrogen atom of the N-heterocyclic moiety,
wherein the fragment X.sup.b is selected from the group consisting of:
(44) ##STR00007##
wherein the moiety is conjugated to G at the site indicated by # and * represents the atom that forms a complex binding to Cu,
wherein Z.sub.1, Z.sub.2, Z.sub.3 and Z.sub.4 are each independently from another CR.sup.az or nitrogen,
wherein R.sup.az a residue selected from the group consisting of hydrogen, halogen, —R.sup.ay, —OC(O)R.sup.ay, —COOH, —OR.sup.ay, —NR.sup.ayR.sup.ay′, —SiR.sup.ayR.sup.ay′R.sup.ay″, —GeR.sup.ayR.sup.ay′R.sup.ay″, —SR.sup.ay, —SOR.sup.ay, —SO.sub.2R.sup.ay and other donor or acceptor groups such as exemplarily carboxylates and esters thereof, and CF.sub.3— groups,
wherein R.sup.ay, R.sup.ay′ and R.sup.ay″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, NR.sup.sR.sup.s′, NHR.sup.s, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein two or more of the residues R.sup.ay, R.sup.ay′, R.sup.ay″, and R.sup.az may optionally form anellated cyclic structures; (ii) a phosphanyl, arsenyl or antimonyl moiety in the form of -ER.sup.iR.sup.j as defined above; and/or (iii) a group D comprising the C* selected from the group consisting of:
(45) ##STR00008##
wherein the two dots “:” represent a bivalent carbene that is coordinated with the Cu, and
wherein the carbene ligand is conjugated to B via one of the binding sites indicated by #,
wherein the other binding site indicated by # represents the binding site to the residue selected from the group consisting of hydrogen, nitrogen, OR.sup.g, —O—C(O)—R.sup.g, —NR.sup.gR.sup.g′, —SiR.sup.gR.sup.g′R.sup.g″, —GeR.sup.gR.sup.g′R.sup.g″, —SR.sup.g, —SOR.sup.g and —SO.sub.2R.sup.g, and
wherein two or more of the residues R, R.sup.g, R.sup.g′, R.sup.g″, Y and Z are defined as above.
(46) In a preferred embodiment, a Cu(I) complex of formula A, A′, A″ or A′″ has one of the following structures:
(47) ##STR00009## ##STR00010##
wherein Z.sup.1, Z.sup.2, Z.sup.3, Z.sup.4, Z.sup.5, Z.sup.6 and Z.sup.7 are each independently from another nitrogen or CR.sup.r,
wherein R.sup.r is a residue selected from the group consisting of hydrogen, deuterium, halogen, —R.sup.q, —OC(O)R.sup.q, —COOH, —OR.sup.q, —NR.sup.qR.sup.q″, —SiR.sup.qR.sup.q′R.sup.q″, —GeR.sup.qR.sup.q′R.sup.q″, —SR.sup.q, —SOR.sup.q, —SO.sub.2R.sup.q and other donor or acceptor groups such as exemplarily carboxylates and esters thereof, and CF.sub.3— groups,
wherein R.sup.q, R.sup.q′ and R.sup.q″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, NR.sup.sR.sup.s′, NHR.sup.s, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue;
wherein Z is defined as above, i.e. is a divalent group as laid out in the context of a structure of formula A, A′, A″ or A′″ above or is a bond;
wherein Y* is selected from the group consisting of O, S and NR.sup.r, wherein R.sup.r is defined as above;
wherein C*, L and L′ are each independently from another are defined as laid out in the context of a structure of formula A, A′, A″ or A′″ above;
wherein Q is selected from the group consisting of a substituted or unsubstituted C.sub.1-9-alkylene residue, C.sub.2-8-alkenylene residue, C.sub.2-8-alkinylene residue, arylene residue, —R.sup.a—NR.sup.a″—, —NR.sup.a″—R.sup.a—, —R.sup.a—NR.sup.a″—R.sup.a′—, —R.sup.a—SiR.sup.a″R.sup.a′″—R.sup.a′—, —R.sup.a—SiR.sup.a″R.sup.a′″—, —SiR.sup.a″R.sup.a′″—R.sup.a—, —R.sup.a—O—R.sup.a′—, —R.sup.a—CO—R.sup.a′—, —R.sup.a—CO—O—R.sup.a′—, —R.sup.a—O—CO—O—R.sup.a′—, —R.sup.a—O—CO—R.sup.a′—, —O—R.sup.a′—, —R.sup.a—CS—R.sup.a′—, —R.sup.a—CO—S—R.sup.a′—, —R.sup.a—S—CO—R.sup.a′—, —R.sup.a—CO—NH—R.sup.a′—, —R.sup.a—NH—CO—R.sup.a′—, —R.sup.a—O—, —R—S—R.sup.a′—, —S—R.sup.a′—, —R.sup.a—S—, —R—SO—R.sup.a′, —SO—R.sup.a′—, —R.sup.a—SO—, —R.sup.a—SO.sub.2—R.sup.a′—, —SO.sub.2—R.sup.a′—, and —R.sup.a—SO.sub.2—,
wherein R.sup.a and R.sup.a′ each independently from another are each a residue of up to 20 carbon atoms selected from the group consisting of a linear, branched or cyclic alkylene residue, a linear, branched or cyclic heteroalkylene residue, an arylene residue, a heteroarylene residue, a linear, branched or cyclic alkenylene residue, and a linear, branched or cyclic alkinylene residue, that may be each optionally substituted with one or more substituents selected from the group consisting of halogens, deuterium, linear, branched or cyclic alkyl residues, linear, branched or cyclic heteroalkyl residues, aryl residues, heteroaryl residues, linear, branched or cyclic alkenyl residues, linear, branched or cyclic alkinyl residues, and other donor or acceptor groups such as exemplarily amines, phosphines, carboxylates and esters thereof, and CF.sub.3— groups, wherein the substituents may optionally form a cyclic or anellated structure with each other;
wherein R.sup.a″ and R.sup.a′″ each independently from another are a residue of up to 20 carbon atoms selected from the group consisting of hydrogen, halogen, -deuterium, R.sup.c, —OC(O)R.sup.c, —COOH, —OR.sup.c, —NR.sup.cR.sup.c′, —SiR.sup.cR.sup.c′R.sup.c″ —SR.sup.c, —SOR.sup.c, —SO.sub.2R.sup.c and other donor or acceptor groups such as exemplarily carboxylates and esters thereof, and CF.sub.3— groups,
wherein R.sup.c, R.sup.c′ and R.sup.c″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, NHR.sup.1, NR.sup.1R.sup.1′, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein two or more of the residues R.sup.c, R.sup.c′, R.sup.c″, R.sup.a, R.sup.a′, R.sup.a″, and R.sup.a′″ may optionally also form anellated cyclic structures;
wherein E is selected from the group consisting of P, As and Sb;
wherein each F is a bivalent organic linker independently from another selected from the group consisting of ═CR.sup.z—, —CR.sup.zR.sup.y—, —NR.sup.z—, —O—, —SiR.sup.zR.sup.y—, —GeR.sup.zR.sup.y—, —S—, —S(O)—, and —S(O).sub.2— or a bond,
wherein R.sup.z and R.sup.y are each independently from another selected from the group consisting of hydrogen, halogen, —OR.sup.x, —O—C(O)—R.sup.x, —NR.sup.xR.sup.x′, —SiR.sup.xR.sup.x′R.sup.x″, —GeR.sup.xR.sup.x′R.sup.x″, —SR.sup.x, —SOR.sup.x, and —SO.sub.2R,
wherein R.sup.x, R.sup.x′ and R.sup.x″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein R.sup.x, R.sup.x′ and R.sup.x″ may optionally also form anellated cyclic structures wherein F may exemplarily be a part of a phenyl and/or substituted phenyl moiety,
wherein each F may be the same of different;
wherein the residues A, R*, R**, R*** and R**** are each independently from another are any organic moiety comprising not more than 40 carbon atoms, preferably wherein each of said residues is each independently from another selected from the group consisting of H, OH, NH.sub.2, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue; and
wherein n represents an integer from 1 to 9.
(48) In a more preferred embodiment, a Cu(I) complex of formula A, A′, A″ or A′″ may have one of the aforementioned structures, wherein Z is
(49) ##STR00011##
wherein # represents the binding sites to the rest of the structure of the Cu(I) complex of formula A, A′, A″ or A′″, e.g., to N, P, L or L′.
(50) In an even more preferred embodiment, a Cu(I) complex of formula A, A′, A″ or A′″ may have one of the following structures:
(51) ##STR00012## ##STR00013##
wherein Z, L and L′ are each independently defined as above.
(52) Particularly preferably, a Cu(I) complex of a structure of formula A, A′, A″ or A′″ may be one of the following:
(53) ##STR00014## ##STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022## ##STR00023## ##STR00024## ##STR00025## ##STR00026## ##STR00027## ##STR00028## ##STR00029## ##STR00030## ##STR00031## ##STR00032## ##STR00033## ##STR00034## ##STR00035##
(54) Further preferred examples for the ligand ligand comprising D, [B].sub.n, N.sup.− (and Z′) (D{circumflex over ( )}N.sup.−) according to formula A, A′, A″ or A′″ are the following:
(55) ##STR00036## ##STR00037##
wherein R is defined as above, in particular wherein each R is independently from another selected from the group consisting of H, OH, NH.sub.2, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue; and
wherein Z.sup.1-Z.sup.4 are defined as in the context of formula A-A′″ above.
(56) Further preferred examples for the ligand comprising L, L′ and Z (L{circumflex over ( )}L′) according to formula A, A′, A″ or A′″ are the following:
(57) ##STR00038## ##STR00039## ##STR00040## ##STR00041## ##STR00042## ##STR00043##
wherein each R is independently from another selected from the group consisting of H, OH, NH.sub.2, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue; and
wherein the two dots “:” represent a bivalent carbene that may be coordinated with the Cu.
Example XI: Emitter Compound of Structure B
(58) Exemplarily, the first emitter compound (a) and/or the second emitter compound (b) may be a Cu(I) complex having a structure according to the following formula B. Examples for respective complexes are also provided in WO 2013/007707 (cf., formulae I and A thereof) and in WO 2010/031485 (cf., exemplarily formulae II, IV and VI-IX thereof).
(59) ##STR00044##
wherein the ligand comprising L, L′ and Z (L{circumflex over ( )}L′) is a neutral, bidentate ligand that is bound to the Cu via non-ionic groups;
wherein the ligand comprising the cyclic moieties A and A′ and the linking moiety Z′ (N{circumflex over ( )}N) may optionally be bound to the Cu via anionic moieties, wherein the ligand N{circumflex over ( )}N may then neutralize the positive charge of the Cu(I);
wherein the cyclic moieties A and A′ bear one of the following structures:
(60) ##STR00045##
wherein Z.sub.1, Z.sub.2 and Z.sub.3 are each independently from another nitrogen or CR,
wherein each R is independently selected from the group consisting of —H, -D, —F, —Cl, —Br, —I, —CN, —NO.sub.2, —SO, —SO.sub.2, ═O, ═S, —R.sup.a—NR.sup.1R.sup.2, —NR.sup.1R.sup.2, —R.sup.a—C(═O)R.sup.1, —C(═O)R.sup.1, —R.sup.a—SiR.sup.1R.sup.2R.sup.3, —SiR.sup.1R.sup.2R.sup.3, —R.sup.a—GeR.sup.1R.sup.2R.sup.3, —GeR.sup.1R.sup.2R.sup.3, —R.sup.a—SeR.sup.1R.sup.2R.sup.3, —SeR.sup.1R.sup.2R.sup.3, —R.sup.a—R.sup.1C═CR.sup.2R.sup.3, R.sup.1C═CR.sup.2R.sup.3, —R.sup.a—C≡C—R.sup.1, —C≡C—R.sup.1, —R.sup.a—C═O, —R.sup.a—C═S, —R.sup.a—C═Se, —R.sup.a—C═NR.sup.1, —C═O, —C═S, —C═Se, —C═NR.sup.1, —R.sup.a—C—N═R.sup.1, —C—N═R.sup.1, —R.sup.a—POR.sup.1R.sup.2R.sup.3, —R.sup.a—N═R′, —CO—NH—R.sup.1, —R.sup.a—CO—NH—R.sup.1, —NH—CO—R.sup.1, —R.sup.a—NH—CO—R.sup.1,
wherein R.sup.1, R.sup.2 and R.sup.3 each independently from another are selected from the group consisting of H, D, F, I, Br, Cl, CN, an aliphatic hydrocarbon of 1 to 20 carbon atoms, an aromatic or heteroaromatic moiety of 5 to 30 atoms in the (hetero)aromatic ring, wherein one or more hydrogens may optionally be substituted by D, F, Cl, Br, I or CN,
wherein R.sup.4 is selected from the group consisting of an aliphatic hydrocarbon of 1 to 20 carbon atoms, wherein one or more hydrogens may optionally be substituted by D, F, Cl, Br, I or CN and/or that may be substituted by on e or more aromatic or heteroaromatic rings.
wherein R.sup.a is selected from the group consisting of a substituted or unsubstituted C.sub.1-9-alkylene residue, C.sub.2-8-alkenylene residue, C.sub.2-8-alkinylene residue or arylene moiety, —R.sup.a′—NR.sup.a′″—, —NR.sup.a′″R.sup.a′—, —R.sup.a′—NR.sup.a′″R.sup.a″—, —R.sup.a′—SiR.sup.a′″R.sup.a″″R.sup.a″—, —R.sup.a′—SiR.sup.a′″R.sup.a″″—, —SiR.sup.a′″R.sup.a″″—R.sup.a′—, —R.sup.a′—O—R.sup.a″—, —R.sup.a′—CO—R.sup.a″—, —R.sup.a′—CO—O—R.sup.a″—, —R.sup.a′—O—CO—O—R.sup.a″—, —R.sup.a′—O—CO—R.sup.a″—, —O—R.sup.a″—, —R.sup.a′—CS—R.sup.a″—, —R.sup.a′—CO—S—R.sup.a″—, —R.sup.a′—S—CO—R.sup.a″—, —R.sup.a′—CO—NH—R.sup.a″—, —R.sup.a′—NH—CO—R.sup.a″—, —R.sup.a′—O—, —R.sup.a′—S—R.sup.a″—, —S—R.sup.a″—, —R.sup.a′—S—, —R.sup.a′—SO—R.sup.a″—, —SO—R.sup.a″—, —R.sup.a′—SO—, —R.sup.a′—SO.sub.2—R.sup.a″—, —SO.sub.2—R.sup.a″—, and —R.sup.a′—SO.sub.2—,
wherein R.sup.a′ and R.sup.a″ each independently from another are each a residue of up to 20 carbon atoms selected from the group consisting of a linear, branched or cyclic alkylene residue, a linear, branched or cyclic heteroalkylene residue, an arylene residue, a heteroarylene residue, a linear, branched or cyclic alkenylene residue, and a linear, branched or cyclic alkinylene residue, that may be each optionally substituted with one or more substituents selected from the group consisting of halogens, deuterium, linear, branched or cyclic alkyl residues, linear, branched or cyclic heteroalkyl residues, aryl residues, heteroaryl residues, linear, branched or cyclic alkenyl residues, linear, branched or cyclic alkinyl residues, and other donor or acceptor groups such as exemplarily amines, phosphines, carboxylates and esters thereof, and CF.sub.3— groups,
wherein the substituents may optionally form a cyclic or anellated structure with each other and/or with residue Z′;
wherein R.sup.a′″ and R.sup.a″″ each independently from another are a residue of up to 20 carbon atoms selected from the group consisting of hydrogen, halogen, —R.sup.c, —OC(O)R.sup.c, —COOH, —OR.sup.c, —NR.sup.cR.sup.c′, —SiR.sup.cR.sup.c′R.sup.c″ —SR.sup.c, —SOR.sup.c, —SO.sub.2R.sup.c and other donor or acceptor groups such as exemplarily carboxylates and esters thereof, and CF.sub.3— groups,
wherein R.sup.c, R.sup.c′ and R.sup.c″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, NHR.sup.a′″, NR.sup.a′″R.sup.a″″, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein two or more of the residues R.sup.c, R.sup.c′, R.sup.c″, R.sup.a′, R.sup.a″, R.sup.a′″, and R.sup.a″″ may optionally also form anellated cyclic structures;
wherein two or more adjacent substituents may form a mono-, di-, tri- or polycyclic aliphatic, aromatic or heteroaromatic cyclic moiety; and
wherein Y is O, S or NR, wherein R is defined as above;
wherein Z′ is BR.sup.1R.sup.2, wherein R.sup.1 and R.sup.2 are defined as above and B is a boron atom, in particular wherein Z′ is selected from the group consisting of H.sub.2B, BPh.sub.2, B(CH.sub.3).sub.2, and B(NR.sup.1R.sup.2).sub.2, wherein Ph is a phenyl residue,
wherein “*” indicates the atom complexed with the Cu and # indicates the atom binding to Z′, the two dots “:” represent a bivalent carbene that is coordinated with the Cu, and wherein the carbene ligand is conjugated to Z via one of the binding sites indicated by #;
wherein L and L′ may be defined as in the context of formula A above;
wherein Z may be defined as in the context of formula A above and/or is —R.sup.ub— —R.sup.ub—NR.sup.ub″—, —NR.sup.ub″—R.sup.ub—, —R.sup.ub—NR.sup.ub″—R.sup.ub′—, —R.sup.ub—SiR.sup.ub″R.sup.ub′″—R.sup.ub′—, —R.sup.ub—SiR.sup.ub″R.sup.ub′″—, —SiR.sup.ub″R.sup.ub′″—R.sup.ub—, —R.sup.ub—O—R.sup.ub′—, —R.sup.ub—CO—R.sup.ub′—, —R.sup.ub—CO—O—R.sup.ub′—, —R.sup.ub—O—CO—O—R.sup.ub′—, —R.sup.ub—O—CO—R.sup.ub′—, —O—R.sup.ub′—, —R.sup.ub—CS—R.sup.ub′—, —R.sup.ub—CO—S—R.sup.ub′—, —R.sup.ub—S—CO—R.sup.ub′—, —R.sup.ub—CO—NH—R.sup.ub′—, —R.sup.ub—NH—CO—R.sup.ub′—, —R.sup.ub—O—, —R.sup.ub—S—R.sup.ub′—, —S—R.sup.ub′—, —R.sup.ub—S—, —R.sup.ub—SO—R.sup.ub′—, —SO—R.sup.ub′—, —R.sup.ub—SO—, —R.sup.ub—SO.sub.2—R.sup.ub′—, —SO.sub.2—R.sup.ub′ or —R.sup.ub—SO.sub.2—,
wherein R.sup.ub and R.sup.ub′ each independently from another are each a residue of up to 20 carbon atoms selected from the group consisting of a linear, branched or cyclic alkylene residue, a linear, branched or cyclic heteroalkylene residue, an arylene residue, a heteroarylene residue, a linear, branched or cyclic alkenylene residue, and a linear, branched or cyclic alkinylene residue, that may be each optionally substituted with one or more substituents selected from the group consisting of halogens, deuterium, linear, branched or cyclic alkyl residues, linear, branched or cyclic heteroalkyl residues, aryl residues, heteroaryl residues, linear, branched or cyclic alkenyl residues, linear, branched or cyclic alkinyl residues, and other donor or acceptor groups such as exemplarily amines, phosphines, carboxylates and esters thereof, and CF.sub.3— groups,
wherein the substituents may optionally form a cyclic or anellated structure with each other and/or with residue Z;
wherein R.sup.ub″ and R.sup.ub′″ each independently from another are a residue of up to 20 carbon atoms selected from the group consisting of hydrogen, halogen, —R.sup.t′″, —OC(O)R.sup.t′″, —COOH, —OR.sup.t′″, —NR.sup.t′″R.sup.t″″, —SiR.sup.t′″R.sup.t″″R.sup.t′″″ —SR.sup.t′″, —SOR.sup.t′″, —SO.sub.2R.sup.t′″ and other donor or acceptor groups such as exemplarily carboxylates and esters thereof, and CF.sub.3— groups,
wherein R.sup.t′″, R.sup.t″″ and R.sup.t′″″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, NHR.sup.a′″, NR.sup.a′″R.sup.a″″, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein two or more of the residues R.sup.t′″, R.sup.t″″, R.sup.t′″″, R.sup.ub, R.sup.ub′, R.sup.ub″, and R.sup.ub′″ may optionally also form anellated cyclic structures.
(61) The following structures provide examples of the ligand N{circumflex over ( )}N:
(62) ##STR00046##
wherein Me is a methyl residue and Ph is a phenyl residue.
(63) In a preferred embodiment, a Cu(I) complex of a structure of formula B may have one of the following structures:
(64) ##STR00047## ##STR00048## ##STR00049## ##STR00050## ##STR00051## ##STR00052## ##STR00053## ##STR00054##
wherein each Z independently from another is selected from CR′ und N;
wherein Y is selected from the groups consisting of S, O und NR′; and
wherein each R′ is independently selected from the group consisting of —H, -D, —F, —Cl, —Br, —I, —CN, —NO.sub.2, —SO, —SO.sub.2, ═O, ═S, —R.sup.a—NR.sup.1R.sup.2, —NR.sup.1R.sup.2, —R.sup.a—C(═O)R.sup.1, —C(═O)R.sup.1, —R.sup.a—SiR.sup.1R.sup.2R.sup.3, —SiR.sup.1R.sup.2R.sup.3, —R.sup.a—GeR.sup.1R.sup.2R.sup.3, —GeR.sup.1R.sup.2R.sup.3, —R.sup.a—SeR.sup.1R.sup.2R.sup.3, —SeR.sup.1R.sup.2R.sup.3, —R.sup.a—R.sup.1C═CR.sup.2R.sup.3, R.sup.1C═CR.sup.2R.sup.3, —R.sup.a—C≡C—R.sup.1, —C≡C—R.sup.1, —R.sup.a—C═O, —R.sup.a—C═S, —R.sup.a—C═Se, —R.sup.a—C═NR.sup.1, —C═O, —C═S, —C═Se, —C═NR.sup.1, —R.sup.a—C—N═R.sup.1, —C—N═R.sup.1, —R.sup.a—POR.sup.1R.sup.2R.sup.3, —R.sup.a—N═R.sup.1, —CO—NH—R.sup.1, —R.sup.a—CO—NH—R.sup.1, —NH—CO—R.sup.1, —R.sup.a—NH—CO—R.sup.1, wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.a are each independently from another defined as laid out in the context of a Cu(I) complex of a structure formula B as laid out above; and
wherein each R is independently from another selected from the group consisting of H, methyl or phenyl.
(65) Particularly preferred examples of Cu(I) complexes of a structure of formula B are selected from the group consisting of:
(66) ##STR00055## ##STR00056## ##STR00057## ##STR00058## ##STR00059## ##STR00060## ##STR00061## ##STR00062##
wherein each R is independently from another H, methyl or phenyl.
Example XII: Emitter Compound of Structure C
(67) Exemplarily, the first emitter compound (a) and/or the second emitter compound (b) may be a metal(I) complex having a structure according to the following formula C. Examples for respective complexes are also provided in WO 2014/102079 (cf., exemplarily formulae A and I-IX thereof).
(68) ##STR00063##
wherein M and M′ are each independently from another selected from the group consisting of Cu, Ag and Au, in particular are both Cu;
wherein X and X′ are both independently from another selected from the group consisting of Cl, Br, I, CN, OCN, SCN, alkinyl and N.sub.3;
wherein the ligand comprising E, Y, Z, Q and D (E∩D) and the ligand comprising E′, Y′, Z′, Q′ and D′ (E′∩D′) are each a bidentate ligand,
wherein E and E′ each independently from another are RR′E* wherein E* is N, P, As or Sb,
wherein N is or is not an imine nitrogen atom or a part of an N-heterocyclic ring, or E and E′ each independently from another are RE* wherein E* is a divaltent carbene C*, O or S,
wherein R and R′ each independently from another are a residue of up to 20 carbon atoms selected from the group consisting of hydrogen, deuterium, halogen, —R.sup.1, —OC(O)R.sup.1, —COOH, —OR.sup.1, —NR.sup.1R.sup.1′, —SiR.sup.1R.sup.1′R.sup.1″ —SR.sup.1, —SOR.sup.1, —SO.sub.2R.sup.1 and other donor or acceptor groups such as exemplarily carboxylates and esters thereof, and CF.sub.3— groups,
wherein R.sup.1, R.sup.1′ and R.sup.1″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, NHR.sup.x, NR.sup.xR.sup.y a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein R.sup.x and R.sup.y are each independently from another selected from the group consisting of a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein two or more of the residues R.sup.1, R.sup.1′, R.sup.1″, R, and R′ may optionally also form anellated cyclic structures,
wherein D and D′ each independently from another are R″R′″D* wherein D* is N, P, As or Sb, wherein N is or is not an imine nitrogen atom or a part of an N-heterocyclic ring, or D and D′ each independently from another are R″D* wherein D* is a divaltent carbene C*, O or S,
wherein R″ and R′″ each independently from another are a residue of up to 20 carbon atoms selected from the group consisting of hydrogen, deuterium, halogen, —R.sup.2, —OC(O)R.sup.2, —COOH, —OR.sup.2, —NR.sup.2R.sup.2′, —SiR.sup.2R.sup.2′R.sup.2″—SR.sup.2, —SOR.sup.2, —SO.sub.2R.sup.2 and other donor or acceptor groups such as exemplarily carboxylates and esters thereof, and CF.sub.3— groups,
wherein R.sup.2, R.sup.2′ and R.sup.2″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, NHR.sup.1, NR.sup.1R.sup.1′, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein two or more of the residues R.sup.2, R.sup.2′, R.sup.2″, R″, and R′″ may optionally also form anellated cyclic structures,
wherein D and E may be the same or different from another;
wherein Q, Y, Z, Q′, Y′ and Z′ are each independently from another selected from the group consisting of a substituted or unsubstituted C.sub.1-9-alkylene residue, C.sub.2-8-alkenylene residue, C.sub.2-8-alkinylene residue, arylene residue, —R.sup.a—NR.sup.a″—, —NR.sup.a″—R.sup.a—, —R.sup.a—NR.sup.a″—R.sup.a′—, —R.sup.a—SiR.sup.a″R.sup.a′″—R.sup.a—, —R.sup.a—SiR.sup.a″R.sup.a′″, —SiR.sup.a″R.sup.a′″—R.sup.a—, —R.sup.a—O—R.sup.a′—, —R.sup.a—CO—R.sup.a′—, —R.sup.a—CO—O—R.sup.a′—, —R.sup.a—O—CO—O—R.sup.a′—, —R.sup.a—O—CO—R.sup.a′—, —O—R.sup.a′—, —R.sup.a—CS—R.sup.a′—, —R.sup.a—CO—S—R.sup.a′—, —R.sup.a—S—CO—R.sup.a′—, —R.sup.a—CO—NH—R.sup.a′—, —R.sup.a—NH—CO—R.sup.a′—, —R.sup.a—O—, —R.sup.a—S—R.sup.a′—, —S—R.sup.a′—, —R.sup.a—S—, —R.sup.a—SO—R.sup.a′—, —SO—R.sup.a′—, —R.sup.a—SO—, —R.sup.a—SO.sub.2—R.sup.a′—, —SO.sub.2—R.sup.a′—, and —R.sup.a—SO.sub.2—,
wherein R.sup.a and R.sup.a′ each independently from another are each a residue of up to 20 carbon atoms selected from the group consisting of a linear, branched or cyclic alkylene residue, a linear, branched or cyclic heteroalkylene residue, an arylene residue, a heteroarylene residue, a linear, branched or cyclic alkenylene residue, and a linear, branched or cyclic alkinylene residue, that may be each optionally substituted with one or more substituents selected from the group consisting of halogens, deuterium, linear, branched or cyclic alkyl residues, linear, branched or cyclic heteroalkyl residues, aryl residues, heteroaryl residues, linear, branched or cyclic alkenyl residues, linear, branched or cyclic alkinyl residues, and other donor or acceptor groups such as exemplarily amines, phosphines, carboxylates and esters thereof, and CF.sub.3— groups, wherein the substituents may optionally form a cyclic or anellated structure with each other;
wherein R.sup.a″ and R.sup.a′″ each independently from another are a residue of up to 20 carbon atoms selected from the group consisting of hydrogen, halogen, -deuterium, R.sup.c, —OC(O)R.sup.c, —COOH, —OR.sup.c, —NR.sup.cR.sup.c′, —SiR.sup.cR.sup.c′R.sup.c″ —SR.sup.c, —SOR.sup.c, —SO.sub.2R.sup.c and other donor or acceptor groups such as exemplarily carboxylates and esters thereof, and CF.sub.3— groups,
wherein R.sup.c, R.sup.c′ and R.sup.c″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, NHR.sup.1, NR.sup.1R.sup.1′, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein two or more of the residues R.sup.c, R.sup.c′, R.sup.c″, R.sup.a, R.sup.a′, R.sup.a″, and R.sup.a′″ may optionally also form anellated cyclic structures.
(69) Optionally, both bidentate ligands E∩D and E′∩D′ may also conjugated with another via a linker (e.g., a C.sub.1-10-alkylene moiety) resulting in a tetravalent ligand.
(70) Optionally, an improvement of the metal complex may be achieved in that at least one of the ligands E∩D and E′∩D′ bears a suitable substituent.
(71) In a preferred embodiment, a metal(I) complex according to formula C may have one of the following structures:
(72) ##STR00064##
wherein X and X′ are both independently from another selected from the group consisting of Cl, Br, I, CN, OCN, SCN, alkinyl and N.sub.3;
wherein M and M′ are each independently from another selected from the group consisting of Cu, Ag and Au, preferably Cu and Ag, in particular are both Cu;
wherein each E** is selected from the group consisting of P, As and Sb;
wherein C* is a divalent carbene;
wherein each Q, Y and Z each independently from another are defined as laid out in the context of a structure of formula C above;
wherein each of G, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 each independently from another are a residue of up to 20 carbon atoms selected from the group consisting of hydrogen, halogen, deuterium, R.sup.c, —OC(O)R.sup.c, —COOH, —OR.sup.c, —NR.sup.cR.sup.c′, —SiR.sup.cR.sup.c′R.sup.c″ —SR.sup.c, —SOR.sup.c, —SO.sub.2R.sup.c and other donor or acceptor groups such as exemplarily carboxylates and esters thereof, and CF.sub.3— groups, wherein R.sup.c, R.sup.c′ and R.sup.c″ are each independently from another defined as laid out in the context of a structure of formula C above; and
(73) Herein, preferably the parts of the structure consisting of Y—C*-G may be independently from another selected from the group consisting of
(74) ##STR00065##
wherein the two dots “:” represent a bivalent carbene that may be coordinated with the metal (e.g., Cu);
wherein # represents the binding sites to Y and Z, respectively,
wherein T is selected from the group consisting of CRR′, NR and SR; and
wherein R may be defined as laid out in the context of a structure of formula C above; and
wherein z represent an integer of 1, 2, 3 or 4.
(75) In a more preferred embodiment, a metal(I) complex according to formula C may have one of the following structures:
(76) ##STR00066##
wherein X, X′, M, M′, C*, G, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, Q, Y and Z are each independently from another are defined as laid out in the context of a structure of formula C above.
(77) Highly preferably, a metal(I) complex of formula is a Cu(I) complex, in particular a Cu(I) complex having one of the following structures:
(78) ##STR00067## ##STR00068## ##STR00069##
wherein each X is independently from another selected from Cl, Br and I, in particular wherein both X are each I; and
wherein Me in methyl and Ph is phenyl.
Example XIII: Emitter Compound of Structure D
(79) Exemplarily, the first emitter compound (a) and/or the second emitter compound (b) may be a metal(I) complex having a structure according to the following formula D. Examples for respective complexes are also provided in European patent application No. 14164815.
(80) ##STR00070##
wherein G1 and G2 are cyclic organic structures comprising not more than 20, preferably not more than 10 carbon atoms each;
wherein M and M′ are each independently from another selected from the group consisting of Cu, Ag and Au, in particular are both Cu;
wherein X and X′ are both independently from another selected from the group consisting of Cl, Br, I, CN, OCN, SCN, alkinyl and N.sub.3, in particular are each a halogenide, in particular a halogenide selected from Cl, Br, and I, or are a pseudohalogenide,
wherein E′ and E″ are each independently from another selected from the group consisting of P, As and Sb;
wherein R, R′, R″ and R′″ are each independently from another selected from the group consisting of optionally substituted alkyl, aryl, heteroaryl and alkoxy residues of up to 20 carbon atoms;
wherein N is nitrogen;
wherein Y and Y′ of the cyclic systems G1 and G2 are each independently from another selected from the group consisting of a substituted or unsubstituted C.sub.1-9-alkylene residue, C.sub.2-8-alkenylene residue, C.sub.2-8-alkinylene residue, arylene residue, —R.sup.a—NR.sup.a″—, —NR.sup.a″—R.sup.a—, —R.sup.a—NR.sup.a″—R.sup.a′—, —R.sup.a—SiR.sup.a″R.sup.a′″—R.sup.a′—, —R.sup.a—SiR.sup.a″R.sup.a′″—, —SiR.sup.a″R.sup.a′″—R.sup.a—, —R.sup.a—O—R.sup.a′—, —R.sup.a—CO—R.sup.a′—, —R.sup.a—CO—O—R.sup.a′—, —R.sup.a—O—CO—O—R.sup.a′—, —R.sup.a—O—CO—R.sup.a′—, —O—R.sup.a′—, —R.sup.a—CS—R.sup.a′—, —R.sup.a—CO—S—R.sup.a′—, —R—S—CO—R.sup.a′—, —R.sup.a—CO—NH—R.sup.a′—, —R.sup.a—NH—CO—R.sup.a′—, —R.sup.a—O—, —R.sup.a—S—R.sup.a′—, —S—R.sup.a′—, —R.sup.a—S—, —R.sup.a—SO—R.sup.a′—, —SO—R.sup.a′—, —R.sup.a—SO—, —R.sup.a—SO.sub.2—R.sup.a′—, —SO.sub.2—R.sup.a′—, and —R.sup.a—SO.sub.2—,
wherein R.sup.a and R.sup.a′ each independently from another are each a residue of up to 20 carbon atoms selected from the group consisting of a linear, branched or cyclic alkylene residue, a linear, branched or cyclic heteroalkylene residue, an arylene residue, a heteroarylene residue, a linear, branched or cyclic alkenylene residue, and a linear, branched or cyclic alkinylene residue, that may be each optionally substituted with one or more substituents selected from the group consisting of halogens, deuterium, linear, branched or cyclic alkyl residues, linear, branched or cyclic heteroalkyl residues, aryl residues, heteroaryl residues, linear, branched or cyclic alkenyl residues, linear, branched or cyclic alkinyl residues, and other donor or acceptor groups such as exemplarily amines, phosphines, carboxylates and esters thereof, and CF.sub.3— groups, wherein the substituents may optionally form a cyclic or anellated structure with each other;
wherein R.sup.a″ and R.sup.a′″ each independently from another are a residue of up to 20 carbon atoms selected from the group consisting of hydrogen, halogen, deuterium, —R.sup.c, —OC(O)R.sup.c, —COOH, —OR.sup.c, —NR.sup.cR.sup.c′, —SiR.sup.cR.sup.c′R.sup.c″ —SR.sup.c, —SOR.sup.c, —SO.sub.2R.sup.c and other donor or acceptor groups such as exemplarily carboxylates and esters thereof, and CF.sub.3— groups,
wherein R.sup.c, R.sup.c′ and R.sup.c″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, NHR.sup.x, NR.sup.xR.sup.y, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein R.sup.x and R.sup.y are each independently from another selected from the group consisting of a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein two or more of the residues R.sup.c, R.sup.c′, R.sup.c″, R.sup.a, R.sup.a′, R.sup.a″, and R.sup.a′″ may optionally also form anellated cyclic structures,
wherein B and B′ are each independently from another a linker of a chain length of at least 2 and not more than 17 atoms,
wherein the moieties thereof may be CH.sub.2—, —CHR.sup.1—, —CR.sup.1R.sup.2—, —SiR.sup.1R.sup.2—, —GeR.sup.1R.sup.2—, —O—, —S—, —Se—, —NR.sup.1—, —PR.sup.1—, and/or —AsR.sup.1—,
wherein R.sup.1 and R.sup.2 are each independently from another a residue selected from the group consisting of an alkyl moiety, aryl moiety, heteroaryl moiety, —OR.sup.3, —SR.sup.3, —SeR.sup.3 of each up to 20 carbon atoms, —H and -D,
wherein R.sup.3 is an alkyl moiety, aryl moiety, heteroaryl moiety, —OR.sup.3, —SR.sup.3, —SeR.sup.3 of each up to 20 carbon atoms, —H and -D.
(81) Preferably, the cyclic systems G1 and G2 each comprise five or six ring atoms in a heteroaromatic cycle which may optionally be substituted with further residues such as R, R′; R″, R′″, R.sup.a″ and/or R.sup.a′″ or anellated with further aromatic cyclic structures.
(82) In a preferred embodiment, a metal(I) complex of a structure of formula D is a Cu(I) complex, in particular a Cu(I) complex having one of the following structures:
(83) ##STR00071##
wherein each B is independently from another defined as in the context of a structure of formula D;
wherein X is selected from the group consisting of Cl, Br, I, CN, OCN, SCN, alkinyl and N.sub.3, in particular are each a halogenide, in particular a halogenide selected from Cl, Br, and I, or are a pseudohalogenide,
wherein each Y is independently from another selected from the group consisting of NR.sup.a″, O and S;
wherein each Z is independently from another selected from the group consisting of CR.sup.a″ and N;
wherein each R and R.sup.a″ is independently from another defined as laid out in the context of R.sup.a″ relating to a structure of formula D above.
(84) In a particularly preferred embodiment, a metal(I) compound of a structure of formula D is a Cu(I) complex selected from one of the following structures:
(85) ##STR00072## ##STR00073## ##STR00074##
wherein each X is independently from another selected from Cl, Br and I, in particular wherein both X are each I.
Example XIV: Emitter Compound of Structure E
(86) Exemplarily, the first emitter compound (a) and/or the second emitter compound (b) may be a metal(I) complex having a structure according to the following formula E. Examples for respective complexes are also provided in WO 2013/014066 (cf., exemplarily formula IV thereof).
(87) ##STR00075##
wherein M and M′ are each independently from another selected from the group consisting of Cu, Ag and Au, in particular are both Cu;
wherein X and X′ are each independently selected from the group consisting of Cl, Br, I, CN, OCN, SCN, C.sub.1-10-alkinyl and N.sub.3;
wherein the ligand comprising E, Y, Z, and D (E∩D) and the ligand comprising E′, Y′, Z′, and D′ (E′∩D′) are each a bidentate ligand,
wherein E and E′ each independently from another are RR′E* wherein E* is N, P, As or Sb,
wherein N is or is not an imine nitrogen atom or a part of an N-heterocyclic ring, or E and E′ each independently from another are RE* wherein E* is a divaltent carbene C*, O or S,
wherein R and R′ each independently from another are a residue of up to 20 carbon atoms selected from the group consisting of hydrogen, deuterium, halogen, —R.sup.1, —OC(O)R.sup.1, —COOH, —OR.sup.1, —NR.sup.1R.sup.1′, —SiR.sup.1R.sup.1′R.sup.1″ —SR.sup.1, —SOR.sup.1, —SO.sub.2R.sup.1 and other donor or acceptor groups such as exemplarily carboxylates and esters thereof, and CF.sub.3— groups,
wherein R.sup.1, R.sup.1′ and R.sup.1″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, NHR.sup.x, NR.sup.xR.sup.y, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein R.sup.x and R.sup.y are each independently from another selected from the group consisting of a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein two or more of the residues R.sup.1, R.sup.1′, R.sup.1″, R, and R′ may optionally also form anellated cyclic structures,
wherein D and D′ each independently from another are R″R′″D* wherein D* is N, P, As or Sb, wherein N is or is not an imine nitrogen atom or a part of an N-heterocyclic ring, or D and D′ each independently from another are R″D* wherein D* is a divaltent carbene C*, O or S,
wherein R″ and R′″ each independently from another are selected from the group consisting of hydrogen, deuterium, halogen, —R.sup.2, —OC(O)R.sup.2, —COOH, —OR.sup.2, —NR.sup.2R.sup.2′, —SiR.sup.2R.sup.2′R.sup.2″ —SR.sup.2, —SOR.sup.2, —SO.sub.2R.sup.2 and other donor or acceptor groups such as exemplarily carboxylates and esters thereof, and CF.sub.3— groups,
wherein R.sup.2, R.sup.2′ and R.sup.2″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, NHR.sup.x, NR.sup.xR.sup.y, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein two or more of the residues R.sup.2, R.sup.2′, R.sup.2″, R″, and R′″ may optionally also form anellated cyclic structures,
wherein D and E may be the same or different from another;
wherein Y, Z, Y′ and Z′ are each independently from another selected from the group consisting of a substituted or unsubstituted C.sub.1-9-alkylene residue, C.sub.2-8-alkenylene residue, C.sub.2-8-alkinylene residue, arylene residue, —R.sup.a—NR.sup.a″—, —NR.sup.a″—R.sup.a—, —R.sup.a—NR.sup.a″—R.sup.a′—, —R.sup.a—SiR.sup.a″R.sup.a′″—R.sup.a′—, —R.sup.a—SiR.sup.a″R.sup.a′″—, —SiR.sup.a″R.sup.a′″—R.sup.a—, —R.sup.a—O—R.sup.a′—, —R.sup.a—CO—R.sup.a′—, —R.sup.a—CO—O—R.sup.a′—, —R.sup.a—O—CO—O—R.sup.a′—, —R.sup.a—O—CO—R.sup.a′—, —O—R.sup.a′—, —R.sup.a—CS—R.sup.a′—, —R.sup.a—CO—S—R.sup.a′—, —R.sup.a—S—CO—R.sup.a′—, —R.sup.a—CO—NH—R.sup.a′—, —R.sup.a—NH—CO—R.sup.a′, —R.sup.a—CO—NR.sup.x—R.sup.a′—, —R.sup.a—NR.sup.x—CO—R.sup.a′—, —R.sup.a—O—, —R.sup.a—S—R.sup.a′—, —S—R.sup.a′—, —R.sup.a—S—, —R.sup.a—SO—R.sup.a′—, —SO—R.sup.a′, —R.sup.a—SO—, —R.sup.a—SO.sub.2—R.sup.a′—, —SO.sub.2—R.sup.a′—, and —R.sup.a—SO.sub.2—,
wherein R.sup.a and R.sup.a′ each independently from another are each a residue of up to 20 carbon atoms selected from the group consisting of a linear, branched or cyclic alkylene residue, a linear, branched or cyclic heteroalkylene residue, an arylene residue, a heteroarylene residue, a linear, branched or cyclic alkenylene residue, and a linear, branched or cyclic alkinylene residue, that may be each optionally substituted with one or more substituents selected from the group consisting of halogens, deuterium, linear, branched or cyclic alkyl residues, linear, branched or cyclic heteroalkyl residues, aryl residues, heteroaryl residues, linear, branched or cyclic alkenyl residues, linear, branched or cyclic alkinyl residues, and other donor or acceptor groups such as exemplarily amines, phosphines, carboxylates and esters thereof, and CF.sub.3— groups, wherein the substituents may optionally form a cyclic or anellated structure with each other;
wherein R.sup.a″ and R.sup.a′″ each independently from another are a residue of up to 20 carbon atoms selected from the group consisting of hydrogen, deuterium, halogen, —R.sup.c, —OC(O)R.sup.c, —COOH, —OR.sup.c, —NR.sup.cR.sup.c′, —SiR.sup.cR.sup.c′R.sup.c″ —SR.sup.c, —SOR.sup.c, —SO.sub.2R.sup.c and other donor or acceptor groups such as exemplarily carboxylates and esters thereof, and CF.sub.3— groups,
wherein R.sup.c, R.sup.c′ and R.sup.c″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, NHR.sup.x, NR.sup.xR.sup.y, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein two or more of the residues R.sup.c, R.sup.c′, R.sup.c″, R.sup.a, R.sup.a′, R.sup.a″, and R.sup.a′″ may optionally also form anellated cyclic structures.
(88) Optionally, both bidentate ligands E∩D and E′∩D′ may also conjugated with another via a linker (e.g., a C.sub.1-10-alkylene moiety) resulting in a tetravalent ligand.
(89) Optionally, an improvement of the metal complex may be achieved in that at least one of the ligands E∩D and E′∩D′ bears a suitable substituent.
(90) In a preferred embodiment, a metal(I) complex of a structure of formula E is a Cu(I) complex, in particular a Cu(I) complex having the following structure:
(91) ##STR00076##
wherein Z, Z′, Y, Y′, E, E′, M, M′, X and X′ are defined as in the context of a structure of formula E above, preferably wherein E and E′ are each independently from another selected from the group consisting of O, As and Sb; and
wherein R.sup.1, R.sup.2, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 each independently from another are a residue of up to 20 carbon atoms, preferably a residue selected from the group consisting of hydrogen, deuterium, halogen, —R.sup.c, —OC(O)R.sup.c, —COOH, —OR.sup.c, —NR.sup.cR.sup.c′, —SiR.sup.cR.sup.c′R.sup.c″ —SR.sup.c, —SOR.sup.c, —SO.sub.2R.sup.c and other donor or acceptor groups such as exemplarily carboxylates and esters thereof, and CF.sub.3— groups, wherein R.sup.c, R.sup.c′ and R.sup.c″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, NHR.sup.x, NR.sup.xR.sup.y, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue.
(92) In a more preferred embodiment, a metal(I) complex of a structure of formula E is a Cu(I) complex having the following structure:
(93) ##STR00077##
wherein each X is independently from another selected from Cl, Br and I, in particular wherein both X are each I; and
wherein R.sup.1, R.sup.2, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 each independently from another are a residue of up to 20 carbon atoms, preferably a residue selected from the group consisting of hydrogen, deuterium, halogen, —R.sup.c, —OC(O)R.sup.c, —COOH, —OR.sup.c, —NR.sup.cR.sup.c′, —SiR.sup.cR.sup.c′R.sup.c″ —SR.sup.c, —SOR.sup.c, —SO.sub.2R.sup.c and other donor or acceptor groups such as exemplarily carboxylates and esters thereof, and CF.sub.3— groups, wherein R.sup.c, R.sup.c′ and R.sup.c″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, NHR.sup.x, NR.sup.xR.sup.y, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue.
(94) In a particularly preferred embodiment, a metal(I) complex of a structure of formula E is a Cu(I) complex having one the following structures:
(95) ##STR00078##
wherein each X is independently from another selected from Cl, Br and I, in particular wherein both X are each I.
Example XV: Emitter Compound of Structure F
(96) Exemplarily, the first emitter compound (a) and/or the second emitter compound (b) may be a Cu(I) complex having a structure according to the following formula F. Examples for respective complexes are also provided in WO 2013/017675 (cf., exemplarily formula A thereof).
(97) ##STR00079##
wherein X and X′ are each independently selected from the group consisting of Cl, Br, I, CN, OCN, SCN, C.sub.1-10-alkinyl and N.sub.3;
wherein P is phosphor and N is nitrogen;
wherein Z and Z′ are each independently from another a covalent linkage comprising at least two carbon and/or nitrogen atoms,
wherein the ligand comprising P, Z and N (P∩N) and the ligand comprising P, Z′ and N (P∩N′) are each a phosphane ligand substituted by an N-heterocycle bearing a structure according to formula G:
(98) ##STR00080##
wherein P is phosphor and N is nitrogen;
wherein E is a carbon or nitrogen atom;
wherein E′ is a carbon or nitrogen atom that is not bound to hydrogen;
wherein the dashed line represents a single or double bond;
wherein R is an optionally substituted, optionally branched C.sub.1-20-alkyl residue, preferably a C.sub.6-20-alkyl residue, or an optionally alkylated C.sub.6-20-aryl residue, in particular phenyl, wherein a substitution herein is a substitution with one or more halogens (e.g., F, Cl, Br and/or I), silane groups, ether groups or optionally substituted alkyl, alkenyl and/or alkinyl residues.
wherein R′ and R″ are each independently from another selected from the group consisting of alkyl residues, in particular C.sub.6-20-alkyl residues that may also be branched or cyclic, and aryl or heteroaryl residues that may optionally be substituted with alkyl residues, halogens (e.g., F, Cl, Br and/or I), silane groups or ether groups,
wherein R′ and R″ may be each directly bound to the phosphor atom of the phosphane ligand;
wherein R′″ is selected from the group consisting of alkyl residues, in particular C.sub.6-20-alkyl residues that may also be branched or cyclic, and aryl or heteroaryl residues that may optionally be substituted with alkyl residues, halogens (e.g., F, Cl, Br and/or I), silane groups or ether groups,
wherein R′″ may form an aliphatic or aromatic heterocyclic structure together with Z;
wherein Z, Z′ and Z.sup.x are each independently from another selected from the group consisting of substituted or unsubstituted linear, branched or cyclic C.sub.1-9-alkylene, C.sub.2-8-alkenylene or C.sub.2-8-alkinylene residue, an arylene residue, —R.sup.a—NR.sup.a″—, —NR.sup.a″—R.sup.a—, —R.sup.a—NR.sup.a″—R.sup.a′—, —R.sup.a—SiR.sup.a″R.sup.a′″—R.sup.a′—, —R.sup.a—SiR.sup.a″R.sup.a″—, —SiR.sup.a″R.sup.a′″—R.sup.a—, —R.sup.a—O—R.sup.a′—, —R.sup.a—CO—R.sup.a′—, —R.sup.a—CO—O—R.sup.a′—, —R.sup.a—O—CO—O—R.sup.a′—, —R.sup.a—O—CO—R.sup.a′—, —O—R.sup.a′—, —R.sup.a—CS—R.sup.a′—, —R.sup.a—CO—S—R.sup.a′—, —R.sup.a—S—CO—R.sup.a′—, —R.sup.a—CO—NH—R.sup.a′—, —R.sup.a—NH—CO—R.sup.a′—, —R.sup.a—CO—NR.sup.a″—R.sup.a′—, —R.sup.a—NR.sup.a″—CO—R.sup.a′—, —R.sup.a—O—, —R.sup.a—S—R.sup.a′—, —S—R.sup.a′—, —R.sup.a—S—, —R.sup.a—SO—R.sup.a′—, —SO—R.sup.a′—, —R.sup.a—SO—, —R.sup.a—SO.sub.2—R.sup.a′—, —SO.sub.2—R.sup.a′, and —R.sup.a—SO.sub.2—,
wherein R.sup.a and R.sup.a′ each independently from another are each a residue of up to 20 carbon atoms selected from the group consisting of a linear, branched or cyclic alkylene residue, a linear, branched or cyclic heteroalkylene residue, an arylene residue, a heteroarylene residue, a linear, branched or cyclic alkenylene residue, and a linear, branched or cyclic alkinylene residue, that may be each optionally substituted with one or more substituents selected from the group consisting of halogens, deuterium, linear, branched or cyclic alkyl residues, linear, branched or cyclic heteroalkyl residues, aryl residues, heteroaryl residues, linear, branched or cyclic alkenyl residues, linear, branched or cyclic alkinyl residues, and other donor or acceptor groups such as exemplarily amines, phosphines, carboxylates and esters thereof, and CF.sub.3— groups, wherein the substituents may optionally form a cyclic or anellated structure with each other;
wherein R.sup.a″ and R.sup.a′″ each independently from another are a residue of up to 20 carbon atoms selected from the group consisting of hydrogen, deuterium, halogen, —R.sup.c, —OC(O)R.sup.c, —COOH, —OR.sup.c, —NR.sup.cR.sup.c′, —SiR.sup.cR.sup.c′R.sup.c″ —SR.sup.c, —SOR.sup.c, —SO.sub.2R.sup.c and other donor or acceptor groups such as exemplarily carboxylates and esters thereof, and CF.sub.3— groups,
wherein R.sup.c, R.sup.c′ and R.sup.c″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, NHR.sup.x, NR.sup.xR.sup.y, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein R.sup.x and R.sup.y are each independently from another selected from the group consisting of a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein two or more of the residues R.sup.c, R.sup.c′, R.sup.c″, R.sup.a, R.sup.a′, R.sup.a″, and R.sup.a′″ may optionally also form anellated cyclic structures.
(99) In a preferred embodiment, a Cu(I) complex of a structure of formula F has one the following structures:
(100) ##STR00081##
wherein each of Z.sup.1, Z.sup.2, Z.sup.3, Z.sup.4, Z.sup.5 and Z.sup.6 is independently from another CR or N;
wherein each Y is independently from another selected from the group consisting of O, S und NR;
wherein each R is independently from another defined as laid out in the context of a structure of formula F above; and
wherein each X is selected from the group consisting of Cl, Br, I, CN, OCN, SCN, C.sub.1-10-alkinyl and N.sub.3.
(101) In a particularly preferred embodiment, a Cu(I) complex of a structure of formula F has one the following structures:
(102) ##STR00082##
wherein each X is independently from another selected from Cl, Br and I, in particular wherein both X are each I; and
Example XVI: Emitter Compound of Structure H
(103) Exemplarily, the first emitter compound (a) and/or the second emitter compound (b) may be a Cu(I) complex having a structure according to the following formula H. Examples for respective complexes are also provided in WO 2013/072508 (cf., exemplarily formula A thereof), WO 2010/149748 (cf., exemplarily formula A thereof) and WO 2013/001086 ((cf., exemplarily formula A thereof).
(104) ##STR00083##
wherein X and X* are each independently selected from the group consisting of Cl, Br, I, CN, OCN, SCN, C.sub.1-10-alkinyl and N.sub.3;
wherein N* is a nitrogen that binds to the Cu;
wherein E is RR′E*, wherein E* is N, P, As or Sb, wherein N is or is not an imine nitrogen atom or a part of an N-heterocyclic ring, or E is RE* wherein E* is a divaltent carbene C*, O or S,
wherein R and R′ each independently from another are a residue of up to 20 carbon atoms selected from the group consisting of hydrogen, deuterium, halogen, —R.sup.1, —OC(O)R.sup.1, —COOH, —OR.sup.1, —NR.sup.1R.sup.1′, —SiR.sup.1R.sup.1′R.sup.1″ —SR.sup.1, —SOR.sup.1, —SO.sub.2R.sup.1 and other donor or acceptor groups such as exemplarily carboxylates and esters thereof, and CF.sub.3— groups,
wherein R.sup.1, R.sup.1′ and R.sup.1″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, NHR.sup.x, NR.sup.xR.sup.y a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein R.sup.x and R.sup.y are each independently from another selected from the group consisting of a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein two or more of the residues R.sup.1, R.sup.1′, R.sup.1″, R, and R′ may optionally also form anellated cyclic structures,
wherein E is E*RR′, wherein E* represents N, P, As or Sb, wherein N may or may not represent an imine nitrogen atom or part of an N-heteroaromatic ring, or wherein E is RE*,
wherein E* represents divalent carbene C*, O or S,
wherein R and R′ each independently from another are selected from the group consisting of hydrogen, halogen, deuterium, —R.sup.1, —OC(O)R.sup.1, —COOH, —OR.sup.1, —NR.sup.1R.sup.1′, —SiR.sup.1R.sup.1′R.sup.1″ —SR.sup.1, —SOR.sup.1, —SO.sub.2R.sup.1 and further donor and acceptor moieties such as, e.g., carboxylates and esters thereof and CF.sub.3 residues,
wherein R.sup.1, R.sup.1′ und R.sup.1″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, NHR.sup.x, NR.sup.xR.sup.y, a halogen, a substituted or unsubstituted, linear, branched or cyclic C.sub.1-20-alkyl, C.sub.1-20-heteroalkyl, C.sub.2-20-alkenyl or C.sub.1-10-heteroalkenyl residue, and a substituted or unsubstituted C.sub.6-20-aryl, C.sub.5-20-heteroaryl, C.sub.7-32-arylalkyl, C.sub.6-31-heteroarylalkyl or C.sub.8-33-alkylarylalkyl residue and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein R.sup.x and R.sup.y are each independently from another selected from the group consisting of a substituted or unsubstituted, linear, branched or cyclic C.sub.1-20-alkyl, C.sub.1-20-heteroalkyl, C.sub.2-20-alkenyl or C.sub.1-10-heteroalkenyl residue, and a substituted or unsubstituted C.sub.6-20-aryl, C.sub.5-20-heteroaryl, C.sub.7-32-arylalkyl, C.sub.6-31-heteroarylalkyl or C.sub.8-33-alkylarylalkyl residue and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein the residues R.sup.1, R.sup.1′, R.sup.1″ und R und R′ may optionally form anellated cyclic structures;
wherein Z is a covalently bound linker comprising at least two carbon and/or nitrogen atoms or may be missing;
wherein the ligands L and L′ are each independently from another an organic ligand comprising 1 to 20 carbon atoms, preferably comprising one or more of the moieties selected from the group consisting of OC(O)R.sup.c, —COOH, —OR.sup.c, —NR.sup.cR.sup.c′, —SiR.sup.cR.sup.c′R.sup.c″ —SR.sup.c, —SOR.sup.c, —SO.sub.2R.sup.c and further donor or acceptor groups such as exemplarily carboxylates and esters thereof, CF.sub.3— groups, and moieties comprising phosphor, arsenic or antimony,
wherein R.sup.c, R.sup.c′ and R.sup.c″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, NHR.sup.a″, NR.sup.a″R.sup.a′″, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein two or more of the residues R.sup.c, R.sup.c′, R.sup.c″, R.sup.d, R.sup.d′, R.sup.d″, and R.sup.d′″ may optionally also form anellated cyclic structures, wherein L and L′ may also be conjugated with another and may be defined as above in the context of formula A and/or may be defined as below in the context of formula K,
wherein the ligand comprising N*, Z and E (E∩N*) may be a bidentate ligand having a structure according to formula K:
(105) ##STR00084##
wherein Y is a carbon or nitrogen atom;
wherein Y′ is a carbon or nitrogen atom that is conjugated to a hydrogen atom;
wherein E* is selected from the group consisting of P, N, As, Sb, a divalent carbene C*, O and S;
wherein the dashed line represents a single or double bond;
wherein N is nitrogen comprised in an imine moiety that forms part of a heteroaromatic moiety comprising N, Y, Y′ and Z.sup.x,
wherein the heteroaromatic moiety is preferably selected from the group consisting of pyridyl, pyrimidyl, pyridazinyl, triazinyl, oxazolyl, thiazolyl, imidazolyl, that may optionally also be substituted (e.g. with one or more of the aforementioned) and/or may be anellated with another moiety of the complex;
wherein R.sup.u and R.sup.v are each independently from another selected from the group consisting of alkyl residues, in particular C.sub.6-20-alkyl residues that may also be branched or cyclic, and aryl or heteroaryl residues that may optionally be substituted with alkyl residues, halogens (e.g., F, Cl, Br and/or I), silane groups or ether groups;
wherein Z and Z.sup.x are each independently from another selected from the group consisting of a substituted or unsubstituted C.sub.1-9-alkylene, C.sub.2-8-alkenylene, C.sub.2-8-alkinylene or arylene residue, —R.sup.a—NR.sup.a″—, —NR.sup.a″—R.sup.a—, —R.sup.a—NR.sup.a″—R.sup.a′—, —R.sup.a—SR.sup.a″R.sup.a′″—R.sup.a′—, —R.sup.a—SiR.sup.a″R.sup.a′″—, —SiR.sup.a″R.sup.a′″—R.sup.a—, —R.sup.a—O—R.sup.a′—, —R.sup.a—CO—R.sup.a′—, —R.sup.a—CO—O—R.sup.a′—, —R.sup.a—O—CO—O—R.sup.a′—, —R.sup.a—O—CO—R.sup.a′—, —O—R.sup.a′—, —R.sup.a—CS—R.sup.a′—, —R.sup.a—CO—S—R.sup.a′—, —R.sup.a—S—CO—R.sup.a′—, —R.sup.a—CO—NH—R.sup.a′—, —R.sup.a—NH—CO—R.sup.a′—, —R.sup.a—O—, —R.sup.a—S—R.sup.a′—, —S—R.sup.a′—, —R.sup.a—S—, —R.sup.a—SO—R.sup.a′—, —SO—R.sup.a′—, —R.sup.a—SO—, —R.sup.a—SO.sub.2—R.sup.a′—, —SO.sub.2—R.sup.a′— and —R.sup.a—SO.sub.2—,
wherein R.sup.a and R.sup.a′ each independently from another are each a residue of up to 20 carbon atoms selected from the group consisting of a linear, branched or cyclic alkylene residue, a linear, branched or cyclic heteroalkylene residue, an arylene residue, a heteroarylene residue, a linear, branched or cyclic alkenylene residue, and a linear, branched or cyclic alkinylene residue, that may be each optionally substituted with one or more substituents selected from the group consisting of halogens, deuterium, linear, branched or cyclic alkyl residues, linear, branched or cyclic heteroalkyl residues, aryl residues, heteroaryl residues, linear, branched or cyclic alkenyl residues, linear, branched or cyclic alkinyl residues, and other donor or acceptor groups such as exemplarily amines, phosphines, carboxylates and esters thereof, and CF.sub.3— groups, wherein the substituents may optionally form a cyclic or anellated structure with each other;
wherein R.sup.a″ and R.sup.a′″ each independently from another are a residue of up to 20 carbon atoms selected from the group consisting of hydrogen, deuterium, halogen, —R.sup.c, —OC(O)R.sup.c, —COOH, —OR.sup.c, —NR.sup.cR.sup.c′, —SiR.sup.cR.sup.c′R.sup.c″ —SR.sup.c, —SOR.sup.c, —SO.sub.2R.sup.c and other donor or acceptor groups such as exemplarily carboxylates and esters thereof, and CF.sub.3— groups,
wherein R.sup.c, R.sup.c′ and R.sup.c″ are each independently from another selected from the group consisting of H, OH, NH.sub.2, NHR.sup.x, NR.sup.xR.sup.y, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein R.sup.x and R.sup.y are each independently from another selected from the group consisting of a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue,
wherein two or more of the residues R.sup.c, R.sup.c′, R.sup.c″, R.sup.a, R.sup.a′, R.sup.a″, and R.sup.a′″ may optionally also form anellated cyclic structures.
(106) Preferably, the heteroaromatic moiety comprises N, Y, Y′ and Z.sup.x is selected from the group consisting of pyridyl, pyrimidyl, pyridazinyl, triazinyl, oxazolyl, thiazolyl, imidazolyl, that may optionally also be substituted and/or anellated with another moiety of the complex.
(107) Preferably, the ligands L and L′ according to formula H are monodentate ligands of up to 42 carbon atoms.
(108) Preferably, E is selected from the group consisting of P, As, and Sb.
(109) In a preferred embodiment, a Cu(I) complex of a structure of formula H has one the following structures:
(110) ##STR00085##
wherein each X is selected from the group consisting of Cl, Br, I, CN, OCN, SCN, C.sub.1-10-alkinyl and N.sub.3;
wherein Y.sup.1 is selected from the group consisting of O, S und NR;
wherein Y* is O or S;
wherein each of Z.sup.1, Z.sup.2 and Z.sup.3 is independently from another CR or N;
wherein Z* is CH or N;
wherein each R is independently from another selected from the group consisting of H, OH, NH.sub.2, NHR.sup.x, NR.sup.xR.sup.y, a halogen, a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue, wherein R.sup.x and R.sup.y are each independently from another selected from the group consisting of a substituted or unsubstituted linear, branched or cyclic C.sub.1-20-alkyl residue, C.sub.1-20-heteroalkyl residue, C.sub.2-20-alkenyl residue, C.sub.1-10-heteroalkenyl residue and a substituted or unsubstituted C.sub.6-20-aryl residue, C.sub.5-20-heteroaryl residue, C.sub.7-32-arylalkyl residue, C.sub.6-31-heteroarylalkyl residue, C.sub.8-33-alkylarylalkyl residue, and a C.sub.7-32-heteroalkylarylalkyl residue; and
wherein Z is defined as in the context of a structure of formula H above.
(111) Particularly preferably, herein a ligand comprising R.sub.2P—Z—PR.sub.2 has the following structure:
(112) ##STR00086## ##STR00087## ##STR00088##
wherein the two dots “:” represent a bivalent carbene that may coordinate the metal, in particular Cu(I); and
wherein R is defined as above.
(113) Exemplarily, the first emitter compound (a) and/or the second emitter compound (b) and/or the host may be a metal complex having a structure according to the following formula N:
(114) ##STR00089##
wherein M is a metal, preferably Al, Zn, Cu, Ag, Au, Ir, and Pt;
wherein Y.sup.1, Y.sup.2 and Z form a bidentate ligand;
wherein Y.sup.1 and Y.sup.2 are each independently from another selected from the group consisting of, N, O, P, and S;
wherein Z may be any divalent organic linker, in particular wherein Z is defined as in the context of any of formulas A, B, F and/or H above;
wherein L is an ancillary ligand, in particular such as defined in the context of any of formula H above; and
wherein each of n and m is independently from another an integer from 0 to the maximum number of ligands that may be bound to the metal M, wherein the sum of m and n is an integer from 1 to the maximum number of ligands that may be bound to the metal M.
(115) Exemplarily, the metal complex is selected from any one of the following structures according to formula N′ or N″:
(116) ##STR00090##
wherein is oxygen, N is nitrogen, Al is aluminum and Zn is zink; and
wherein the other residues Z, L and m are defined as above.
(117) Alternatively, the bidentate ligand comprising Y.sup.1, Y.sup.2 and Z may also be a carbene ligand.
(118) Exemplarily, the first emitter compound (a) and/or the second emitter compound (b) may be a purely organic thermally activated delayed fluorescence (TADF) emitter compound having one of the following structures O1-9:
(119) ##STR00091## ##STR00092##
wherein X represents a direct bond or a divalent organic linkage comprising or consisting of a residue selected from the group consisting of a substituted or unsubstituted C.sub.1-9-alkylene, C.sub.2-8-alkenylene, C.sub.2-8-alkinylene or arylene residue (e.g., substituted or unsubstituted phenylenes residue), —CRR′, —C═CRR′, —C═NR, —NR—, —O—, —SiR.sup.a—, —S—, —S(O)—, and —S(O).sub.2—, or a combination of two or more thereof;
wherein Y represents NR, O, or S;
wherein Ar is a substituted or unsubstituted aryl or heteroaryl group selected from the group consisting of aromatic and heteroaromatic rings of 5 to 24 aromatic ring atoms that may be optionally substituted, e.g., by one or more residue(s) R,
preferably Ar is selected from the group consisting of benzyl, phenyl ortho-, meta- or para-biphenyl, ortho-, meta-, para- or branched terphenyl, ortho-, meta-, para- or branched quaterphenyl, 1-naphtyl, 2-naphtyl, pyrrol, furanyl, thiophenyl, indolyl, benzofuranyl, benzothiophenyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, anthracenyl, phenanthrenyl, pyrenyl, benzanthracenyl and combinations of two or more thereof, that may optionally be substituted, e.g., by one or more residue(s) R, in particular wherein Ar is phenyl or benzyl;
wherein R and R′ each independently from another may be the same of different and are selected from the group consisting of hydrogen, deuterium, —F, —Cl, —Br, —I, —NR.sup.aR.sup.b, —CN, —CF.sub.3, —NO.sub.2, —OH, —COOH, —COOR.sup.a, —CO(NR.sup.a)(NR.sup.b), —SiR.sup.aR.sup.bR.sup.c, —B(OR.sup.a)(OR.sup.b), —CO—R.sup.a, —POR.sup.aR.sup.b, —O—POR.sup.aR.sup.b, —SO—R.sup.a, —SO.sub.2R.sup.a, —OSO.sub.2R.sup.a, a linear alkyl, alkoxy or thioalkoxy residue of 1 to 40 carbon atoms, a linear alkenyl or alkinyl residue of 2 to 40 carbon atoms, a branched or cyclic alkyl, alkoxy, thioalkoxy, alkenyl or alkinyl residue of 3 to 40 carbon atoms, an aromatic or heteroaromatic ring of 5 to 60 aromatic ring atoms, an aryloxy or heteroaryloxy residue of 5 to 60 aromatic ring atoms, a diarylamino, diheteroarylamino or arylheteroarylamino residue of 10 to 40 aromatic ring atoms, that may be each optionally substituted, e.g., by one or more residue(s) R.sup.a,
wherein two or more adjacent CH.sub.2 moieties may be optionally replaced by —R.sup.aC═CR.sup.b—, —C≡C—, —SiR.sup.aR.sup.b—, —GeR.sup.aR.sup.b—, —SnR.sup.aR.sup.b—, —CO—, —CS—, —CSe—, —CNR.sup.a—, —POR.sup.a—, —O—(PO)R.sup.a—O—, —SO—, SO.sub.2, —NR.sup.a—, —O—, —S— or —CONR.sup.a— and wherein one or more hydrogens may optionally be substituted by deuterium, F, Cl, Br, I, CN, CF.sub.3 or NO.sub.2, and/or wherein two or more of the aforementioned R may optionally form with another a mono-, bi- or polycyclic aliphatic or aromatic cyclic system;
wherein R.sup.a, R.sup.b and R.sup.c are each independently from another selected from the group consisting of hydrogen, deuterium, —F, —Cl, —Br, —I, —NR.sup.dR.sup.e, —CN, —CF.sub.3, —NO.sub.2, —OH, —COOH, —COOR.sup.e, —CO(NR.sup.d)(NR.sup.e), —SiR.sup.dR.sup.eR.sup.f, —B(OR.sup.d)(OR.sup.e), —CO—R.sup.a, —POR.sup.dR.sup.e, —O—POR.sup.dR.sup.e, —SO—R.sup.d, —SO.sub.2R.sup.d, —OSO.sub.2R.sup.d, a linear alkyl, alkoxy or thioalkoxy residue of 1 to 40 carbon atoms, a linear alkenyl or alkinyl residue of 2 to 40 carbon atoms, a branched or cyclic alkyl, alkoxy, thioalkoxy, alkenyl or alkinyl residue of 3 to 40 carbon atoms, an aromatic or heteroaromatic ring of 5 to 60 aromatic ring atoms, an aryloxy or heteroaryloxy residue of 5 to 60 aromatic ring atoms, a diarylamino, diheteroarylamino or arylheteroarylamino residue of 10 to 40 aromatic ring atoms,
that may be each optionally substituted, e.g., by one or more residue(s) R.sup.d,
wherein two or more adjacent CH.sub.2 moieties may be optionally replaced by —R.sup.dC═CR.sup.e—, —C≡C—, —SiR.sup.dR.sup.e—, —GeR.sup.dR.sup.e—, —SnR.sup.dR.sup.e—, —CO—, —CS—, —CSe—, —CNR.sup.d—, —POR.sup.d—, —O—(PO)R.sup.d—O—, —SO—, SO.sub.2, —NR.sup.d—, —O—, —S— or —CONR.sup.d— and wherein one or more hydrogens may optionally be substituted by deuterium, F, Cl, Br, I, CN, CF.sub.3 or NO.sub.2, or
wherein two or more of the aforementioned R may optionally form with another a mono-, bi- or polycyclic aliphatic or aromatic cyclic system;
wherein R.sup.d, R.sup.e and R.sup.f are each independently from another selected from the group consisting of hydrogen, deuterium, F, CF.sub.3, and an aliphatic, aromatic and/or heteroaromatic residue of 1 to 20 carbon atoms, wherein optionally one or more hydrogen atoms may be substituted by F or CF.sub.3,
wherein two or more of R.sup.d, R.sup.e, R.sup.f and/or its substituents may form a mono-, bi-, or polycyclic aliphatic cyclic system.
Example XVII: Preferred Compounds as Emitter Compound (a)
(120) Particularly preferably, an emitter compound (a) is a Cu(I) complex having a structure selected from the group consisting of structures A, B, C, D, E, F and H as laid out above.
(121) Alternatively, an emitter compound (a) may also be a TADF emitter having a structure of any one of structures O1-O9 as depicted above.
(122) Alternatively, an emitter compound (a) may also be a phosphorescence emitter as known in the art.
Example XVIII: Preferred Compounds as Emitter Compound (b)
(123) Particularly preferably, an emitter compound (b) is a Cu(I) complex having a structure selected from the group consisting of structures A, C, E and H as laid out above, a TADF emitter having a structure of any one of structures O1-O9 as depicted above or a fluorescence emitter as known in the art.
(124) Alternatively, an emitter compound (b) may also be a phosphorescence emitter as known in the art.
Example XIX: Combinations of an Emitter Compound (a) with an Emitter Compound (b)
(125) Particularly preferred is a combination of emitter compounds (a) and (b) wherein (i) emitter compound (a) is a Cu(I) complex (e.g., having a structure selected from the group consisting of A, B, C, D, E, F and H) and emitter compound (b) is a Cu(I) complex (e.g., having a structure selected from the group consisting of A, C, E and H); (ii) emitter compound (a) is a Cu(I) complex (e.g., having a structure selected from the group consisting of A, B, C, D, E, F and H) and emitter compound (b) is an organic TADF emitter (e.g., having a structure of any one of structures O1-O9); or (iii) emitter compound (a) is a Cu(I) complex (e.g., having a structure selected from the group consisting of A, B, C, D, E, F and H) and emitter compound (b) is a fluorescence emitter as known in the art.
(126) Alternatively, a combination of emitter compounds (a) and (b) is such wherein (i) emitter compound (a) is an organic TADF emitter (e.g., having a structure of any one of structures O1-O9) and emitter compound (b) is a Cu(I) complex (e.g., having a structure selected from the group consisting of A, C, E and H); (ii) emitter compound (a) is an organic TADF emitter (e.g., having a structure of any one of structures O1-O9) and emitter compound (b) is an organic TADF emitter (e.g., having a structure of any one of structures O1-O9); or (iii) emitter compound (a) is an organic TADF emitter (e.g., having a structure of any one of structures O1-O9) and emitter compound (b) is a fluorescence emitter as known in the art.
(127) Alternatively, a combination of emitter compounds (a) and (b) is such wherein (i) emitter compound (a) is a Cu(I) complex (e.g., having a structure selected from the group consisting of A, B, C, D, E, F and H) and emitter compound (b) is phosphorescence emitter; (ii) emitter compound (a) is an organic TADF emitter (e.g., having a structure of any one of structures O1-O9) and emitter compound (b) is phosphorescence emitter; (iii) emitter compound (a) is phosphorescence emitter and emitter compound (b) is a Cu(I) complex (e.g., having a structure selected from the group consisting of A, C, E and H); or (iii) emitter compound (a) is phosphorescence emitter and emitter compound (b) is an organic TADF emitter (e.g., having a structure of any one of structures O1-O9)
Example XX: Combinations of an Emitter Compound (a) with an Emitter Compound (b) with Respect to their Emission Properties
(128) Particularly preferred combinations are such wherein: (i) a blue light-emitting Cu(I) complex is combined with another blue light-emitting emitter, wherein the emission and/or excitation maximum (Δλ) differs by at least 20 nm; (ii) a blue light-emitting Cu(I) complex is combined with a green light-emitting emitter, wherein the emission and/or excitation maximum (Δλ) differs by at least 30 nm; (iii) a blue light-emitting Cu(I) complex is combined with a red light-emitting emitter, wherein the emission and/or excitation maximum (Δλ) differs by at least 100 nm; (iv) a green light-emitting Cu(I) complex is combined with another green light-emitting emitter, wherein the emission and/or excitation maximum (Δλ) differs by at least 20 nm; (v) a green light-emitting Cu(I) complex is combined with a red light-emitting emitter, wherein the emission and/or excitation maximum (Δλ) differs by at least 50 nm; or (vi) a red light-emitting Cu(I) complex is combined with another red light-emitting emitter with a higher emission and/or excitation maximum.
(129) Accordingly, the emission and/or excitation maximum of emitter compound (a) preferably differs at least by 20 nm from the emission and/or excitation maximum of emitter compound (b).
REFERENCES
(130) European patent application No. 14164815
(131) WO 2010/031485
(132) WO 2010/149748
(133) WO 2011/161417
(134) WO 2012/016074
(135) WO 2012/130571
(136) WO 2013/001086
(137) WO 2013/007707
(138) WO 2013/007709
(139) WO 2013/007710
(140) WO 2013/014066
(141) WO 2013/017675
(142) WO 2013/072508
(143) WO 2014/102079
(144) US 2012/0217869
(145) US 2014/0077172