WO2016037964A1

WO2016037964A1 - Improved optically active layer and method for the production thereof

Info

Publication number: WO2016037964A1
Application number: PCT/EP2015/070344
Authority: WO
Inventors: Daniel Volz
Original assignee: Cynora Gmbh
Priority date: 2014-09-08
Filing date: 2015-09-07
Publication date: 2016-03-17

Abstract

The invention relates to a method for applying a light-emitting layer (S) to the surface of a component T, consisting of applying a composition Z1 containing at least one Cu(I)-salt and a composition Z2 containing at least one non-complexed ligand, which can react with Cu(I) forming a complex, on the surface of the component T which then forms a Cu(I) complex which can emit light in the visible range of the electromagnetic spectrum at the ambient temperature from the excited singlet state S1 according to the singlet harvesting mechanism. The invention also relates to a light-emitting layer S comprising the Cu(I) complex as an emitter compound E and either non-complexed Cu(I) or a non-complexed ligand L.

Description

Improved Optically Active Layer and Method of Production

The present invention relates to a method for applying a light-emitting layer S to the surface of a component T, comprising applying a composition Z1 comprising at least one Cu (I) salt and a composition Z2 comprising at least one uncomplexed ligand L which is Cu (I) under complexing to the surface of the device T, forming a Cu (I) complex which emits light in the visible region of the electromagnetic spectrum at room temperature from the excited singlet state S1 according to the singlet harvesting mechanism can. Furthermore, the present invention comprises a light-emitting layer S comprising the Cu (I) complex as emitter compound E and either uncomplexed Cu (I) or a non-complexed ligand L.

Organo-chemical compound based optoelectronic devices, such as organic light emitting diodes (OLEDs), light emitting electrochemical cells (LECs), organic lasers, organic solar cells ( English: "organic solar cells" (OSCs) and optical sensors, are increasingly gaining practical importance, especially OLEDs and LECs are promising components in electronic devices, such as screens, but also in the lighting technology.In contrast to most inorganic-based opto Electronic devices are those devices that are based on organochemical compounds, which are often flexible and have a particularly thin layer thickness.The already available OLED screens are characterized by their high color brilliance, high contrasts and energy efficiency.The optically active materials used here (emitter or absorber Compounds) are introduced into the optically active layer (light-emitting or absorbing layer) of the corresponding opto-electronic device. For some years now, metal complexes have been increasingly used used to maximize the quantum yield. The metal-induced spin-orbit coupling results in an increased intersystem crossing rate (ISC rate), ie the change from the excited singlet to the triplet state and vice versa, and thus leads to exploiting both the singlet and triplet excitons for emission, allowing a theoretically achievable internal quantum efficiency of 100 percent.

The preparation of phosphorescent metal complexes as emitter compounds by vacuum processing has been described (see Liu ei a /., Chem. Mater., 2014, 26 (7), 2368-2373; Liu et al., J. Am. Chem. Soc 201 1, 133, 3700-3703; Schmid et al., Adv. Mater. 2014, 26, 878-885, WO 2012016074). On the other hand, DE 10 201 1017572 discloses a layer-wise application but no effective production of metal complexes having positive optical properties.

However, such phosphorescent complexes have the disadvantage that occur at higher concentrations of complexes as emitters concentration quenching effects, therefore, the quantum yield is reduced. However, such high emitter concentrations are often desirable and sometimes occur unintentionally, since self-aggregation and crystallization can occur in the optically active layer, as a result of which the concentration is greatly increased locally. In addition, the light emission is delayed by phosphorescence.

Thus, there is a need to provide methods for making optically active layers having improved properties and for applying to components.

Surprisingly, it has been found that the separate application of Cu (I) salt and one or more of this complexing ligand to the surface of a component leads to particularly positive technical properties, when a Cu (I) complex is formed, which is formed at room temperature can emit light in the visible region of the electromagnetic spectrum at the excited singlet level according to the singlet harvesting mechanism. On the one hand, self-aggregation and crystallization are reduced by the separate application of the components Cu (I) salt and ligand (s), and it is also possible to prepare poorly soluble Cu (I) complexes. On the other hand, at the same time, light is effectively emitted by fluorescence at the same time and there is clearly reduced to hardly any concentration quenching. In this case, Cu (I) salt and ligand need not necessarily be reacted in a stoichiometric ratio with each other. An excess of Cu (I) salt or ligand (s) can bring further technical advantages, such as increased stability and / or increased lifespan.

A first aspect of the present invention relates to methods for applying a light-emitting layer S on the surface of a component T, comprising the steps of: (i) providing:

(a) a composition Z1 comprising at least one complexed or uncomplexed Cu (I) salt and optionally a coordinating solvent,

(b) a composition Z2 containing at least one uncomplexed ligand L capable of reacting with Cu (I) to complex, and optionally

(c) a composition Z3 comprising at least one host molecule W which can form a matrix for the light-emitting layer S; and

(ii) applying the compositions Z1, Z2 and optionally Z3 to the surface of the component T, wherein the Cu (I) complexes with the ligand L or several of the ligands L and thereby forms a Cu (I) complex, which is at room temperature can emit light in the visible region of the electromagnetic spectrum at the excited singlet level according to the singlet harvesting mechanism. Therefore, the Cu (I) complex formed represents an emitter compound E which is capable of emitting light to the ground state (SO) by fluorescence, therefore by relaxation of an excited singlet state (such as S1), with the energy gap ΔΕ between the excited singlet state S1 and the excited triplet state T1 is so small that even at room temperature (20 ° C) energy from the excited T1 state to the overlying S1 state can be transmitted by reverse intersystem crossing (RISC). Therefore, preferably, the energy gap ΔΕ between S1 and T1 (the singlet-triplet energy splitting, AE (S1-T1)) is not greater than 3000 cm ^"1, more preferably not greater than 2500 ^{cm" 1,} more preferably not greater than 2000 cm ^{" 1.} Optionally, AE (S1-T1) is not even more than 1500 cm ^"1 or not more than 1000 cm ^{" 1} .

The process may here be application from the gas phase or from the liquid phase (also "liquid processing", "film processing" or "wet processing") .The liquid processing is also understood as an in situ procedure, and can also be referred to as "chemistry in the layer". Preferably, the compositions Z1, Z2 and optionally Z3 are not mixed together before application to the surface, but applied independently of each other, therefore not combined with each other The compositions Z1, Z2 and optionally Z3 optionally intermix or otherwise come into contact with each other Optionally, the compositions Z1, Z2 and optionally Z3 are each liquid Optionally, the compositions Z1, Z2 and optionally Z3 are each evaporable without being destroyed Alternatively, one or more of the compositions Z1, Z2 and / or optionally Z3 fl SSGIs and others to be destroyed without evaporierbar.

The inventive method also opens up new ways to develop materials. A combinatorial screening of different combinations of a series of Cu (l) salts with a series of ligands L and optionally a number of host molecules W is enabled. By using current automation processes, such as using pipetting robots, microtiter plates and optical read-out units, high-throughput screening of various Cu (I) salts and ligands L in variable Cu (I): L stoichiometries can be performed, and the result read , By adding further components, such as, for example, host molecules W or additives which, for example, optimize the viscosity, entire light-emitting layers S can be automated in this way. Furthermore, the method according to the invention also makes it possible to produce light-emitting layers S comprising sparingly soluble Cu (I) complexes which, although obtainable by conventional production methods, are not yet processable into light-emitting layers S since the application fails as a layer. Such materials are often initially dissolved in the course of the reaction, often accumulate during the synthesis after isolation in substance as insoluble substances and can not be brought back into solution in the heat after completion of crystallization.

A light-emitting layer S in the context of the present invention is to be understood in the broadest sense as any optically active layer which is capable of emitting light in an optoelectronic device under certain conditions. Accordingly, the light-emitting layer S can actually be used to generate light. But it can also be used differently, such as to absorb light and convert it into electrical energy (charge separation or current flow).

Under a layer according to the present invention is preferably a largely planar geometry to understand. The light-emitting layer S is preferably not thicker than 1 mm, more preferably not thicker than 0.1 mm, more preferably not thicker than 10 μιτι, even more preferably not thicker than 1 μιτι, in particular not thicker than 0.1 μιτι. Likewise, the emitter compound E in the context of the present invention in the broadest sense is to be understood as any optically active compound which is able to emit light under certain conditions in an opto-electronic device. Accordingly, the emitter connection E can actually be used to generate light. But it can also be used differently, for example to absorb light and convert it into electrical energy.

To generate light or electrical energy from light, a component T comprising at least one light-emitting layer S is typically built in or on the opto-electronic device. In most cases, to generate light, the light-emitting layer S is supplied with electrical or chemical energy in the optoelectronic device, in particular electrical energy is supplied. For the supply of energy, electricity can be connected, wherein the current flow through the light-emitting layer S, the emitter compounds E contained therein excites so that so-called excitons arise that can relax under the emission of light in the ground state.

The structure of possible opto-electronic devices is known to the person skilled in the art and will also be explained below by way of example.

The component T as used herein can be broadly any technical element that supports the light-emitting layer S. The structure depends on which type of opto-electronic device the component T is provided.

A component T preferably has a (largely) planar surface onto which compositions Z1 and Z2 and optionally Z3 can be applied.

In most opto-electronic devices, the device T includes a substrate (eg, a glass or plastic plate or a metal foil) and either an anode layer A (eg, an indium-tin-oxide layer) or a cathode layer C (eg, a metal or metal oxide) a metal alloy, as exemplified by Al, Mg or Ca). The component T preferably contains a substrate and an anode layer A. If the component T is provided, for example, for an organic light-emitting diode (OLED), the component T preferably additionally contains a hole-conducting layer, for example of electron-rich heteroaromatics such as arylamines and / or carbazoles (for example tris (4-carbazoyl-9-ylphenyl) amine (TCTA)). Optionally, the component T provided for an OLED may also contain a hole injection layer (eg poly-3,4-ethylenedioxythiophene (PEDOT) and / or polystyrene sulfonate (PSS)). Further examples of the composition of the individual layers and the structure of an OLED are generally known to the person skilled in the art and explained by way of example below.

Alternatively, an OLED can also be produced in the reverse orientation. The component T may then comprise the following layers: an electron conduction layer (eg comprising an electron-deficient compound such as benzimidazoles, pyridines, triazoles, phosphine oxides and sulfones, a star-shaped heterocycle such as 1,3,5-tri (1-phenyl-1H-benzo) d] imidazol-2-yl) phenyl (TPBi)), a cathode layer C (eg of a metal or a metal alloy, such as, for example, Al, Mg or Ca) and a protective layer or substrate.

The surface of the component T, to which the compositions Z1, Z2 and optionally Z3 are applied, may be any surface of the component T. On soft surface of the component T, the compositions Z1, Z2 and optionally Z3 are applied, depends on which opto-electronic device, the component T is to be used.

When the component T is provided, for example, for an organic light-emitting diode (OLED), the surface is preferably either a hole-conducting layer (eg comprising an electron-rich heteroaromatic, such as a triarylamine and / or a carbazole, such as tris (4-carbazoyl-9-ylphenyl) amine (TCTA)) or an electron conduction layer (eg comprising an electron-deficient compound such as a benzimidazole, pyridine, triazole, phosphine oxide or sulfone or a star-shaped heterocycle such as 1, 3,5-tri (1-phenyl-1H-benzo [d ] imidazole-2- yl) phenyl (TPBi)). Particularly preferably, the surface is such a hole line layer. As electron transporter materials it is also possible optionally to use compounds as disclosed in WO 2012/130571. For example, when the device T is provided for a light emitting electrochemical cell (LEC), the surface is preferably an electrode layer (eg, a layer of indium-tin oxide or a metal or a metal alloy such as Al, Mg, or Ca). The compositions Z1, Z2 and Z3 may be solutions (hence liquid compositions) or gas phase molecular compositions in which the respective components are contained in any form (eg dissolved or co-evaporated, therefore gasified). In the printing process, such solutions may also be referred to as inks. Dispersions can also be used.

Optionally, the composition Z1 consists only or largely of one or more Cu (I) salt (s). Preferably, the Cu (I) salt (s) is / are uncomplexed. Alternatively, this Cu (l) salt is already (partially) complexed, but can be further complexed by the ligand L from composition Z2.

Alternatively, the composition Z1 contains one or more other components, such as besides the at least one salt of a non-complexed Cu (I) and at least one solvent in which the at least one salt is soluble. Particular preference is given here to those coordinating solvents in which both Z1 and Z2 and optionally Z3 are soluble. A coordinating solvent is, for example, a solvent selected from the group consisting of tetrahydrothiophene, benzonitrile, pyridine, a nitrile (eg acetonitrile), a thioether, trihydrofuran, triarylamine and toluene. It is also possible to use combinations of different solvents. Very particular preference is given to acetonitrile. The dissolved, at least one Cu (I) salt can then be applied in liquid form to the surface of the component T. A Cu (I) salt contained in the composition Z1 may be a Cu (I) salt having any anion. The salt of Cu (I) is preferably a halide salt (especially a salt with CI ^" anions), a cyanide salt (hence a salt with CN anions), a thiocyanate salt (hence a salt with SCN ^' anions), a thiolate salt ( therefore, a salt with RS ^" anions, wherein R is any organic radical having 1-40 carbon atoms, preferably an unsubstituted or substituted Ci-2o-alkyl radical, an unsubstituted or substituted C2-2o-Alkyenrest, an unsubstituted or substituted C2-2o Alkynyl, unsubstituted or substituted phenyl, unsubstituted or substituted phenyl or benzyl, unsubstituted or substituted pyridyl, unsubstituted or substituted pyrimidine, unsubstituted or substituted purine, unsubstituted or substituted indolyl, or unsubstituted or substituted naphthyl) Acetylide salt (hence a salt with RC ^ C ^" - anions, where R is any organic Is radical with 1-40 carbon atoms, preferably wherein the acetylide adjacent carbon atom carries no multiple bond, more preferably R is an unsubstituted or substituted Ci-20-alkyl radical, an unsubstituted or substituted 03-20- Alkyenrest, an unsubstituted or substituted C3- 2o-alkynyl, an unsubstituted or substituted phenyl, an unsubstituted or substituted benzyl, an unsubstituted or substituted pyridyl, an unsubstituted or substituted pyrimidine, an unsubstituted or substituted purine, an unsubstituted or substituted indolyl, or an unsubstituted or substituted naphthyl).

More preferably, the anion of the salt is selected from the group consisting of Br ^" , Cl ^" , SCN ^" and CN ^" . Even more preferably, the salt is an iodide or chloride salt. Most preferably, the salt is an iodide salt. Particularly preferred is a Cu (I) salt selected from the group consisting of: Cul, CuBr, CuCl, CuSCN and CuCN. Most preferably, the salt is Cu (copper iodide).

Optionally, the composition Z2 consists only or largely of one or more ligands L. Alternatively, the composition Z2 also contains one or more other components such as at least one solvent in which the ligand L is soluble. Each ligand L is preferably low molecular weight, therefore L preferably has a molecular weight of not more than 5 kDa, more preferably not more than 2 kDa, especially not more than 1 kDa. Often the molecular weight is not greater than 500 kDa.

Particularly preferred are those solvents in which both Z1 and Z2 and optionally Z3 are soluble, or which is miscible with a solvent in which they are soluble. Therefore, coordinating solvents are preferred, such as those selected from the group consisting of the group consisting of tetrahydrothiophene, benzonitrile, pyridine, a nitrile (e.g., acetonitrile), a thioether, trihydrofuran, triarylamine, and toluene. It is also possible to use combinations of different solvents. The dissolved, at least one ligand L can then be applied in liquid form to the surface of the component T.

The ligand L is preferably an organochemical ligand, therefore predominantly consists of carbon, nitrogen, phosphorus and hydrogen. The ligand L may be one which can form a monodentate or a bidentate Cu (I) complex with the Cu (I). Preferably, two Cu (I) are complexed in a Cu (I) complex.

The Cu (I) complex may be homoleptic (like ligands) or heteroleptic (different ligands).

For example, a ligand L may be one as described in WO 2013/072508, WO 2013/007709, WO 2013/007710 or WO 2013/014066. These documents also describe how such a ligand L can be prepared and how a Cu (I) complex can be formed therefrom.

The ligand L may be any ligand capable of complexing the Cu (I) alone or together with other ligands. For example, a ligand L may be selected from the group consisting of: 4-Methyl-2- (diphenylphosphino) -pyridine (MePyrPHOS), 4-heptyl-2- (diphenylphosphino) -pyridine, 4-butyne-1-yl (diphenylphosphino) -pyridine

(ButinylPyrPHOS), 2-diphenylphosphino-4- (4-vinyl-phenethyl) -pyridine and poly (2-diphenylphosphino-4- (4-vinyl-phenethyl) -pyhdine) (poly-16). The ligand L is particularly preferably MePyrPHOS.

Also, a ligand may be used as illustrated in embodiments below. Particularly preferred embodiments are also shown in the experimental examples below.

Preferably, the composition Z3, if present, contains at least one host molecule W and optionally at least one solvent in which the host molecule W is soluble. Particular preference is given here to solvents in which both Z1 and Z2 and optionally Z3 are soluble. Therefore, coordinating solvents are preferred in which both Z1 and Z2 and optionally Z3 are soluble or which are miscible with a solvent in which they are soluble. Therefore, coordinating solvents are preferred such as those selected from the group consisting of: tetrahydrothiophene, benzonitrile, pyridine, acetonitrile, trihydrofuran, triarylamine and toluene. Very particular preference is given to acetonitrile. The dissolved at least one host molecule W can then be applied in liquid form to the surface of the component T.

For example, a host molecule W may have a polymeric structure. These are often particularly well used in liquid processing. A host molecule W should, ideally, perform additional tasks such as a spatial separation between the emitter compound E and dyes F to avoid undesired (quenching) quenching and triplet triplet annihilation under emission abatement, and possibly enhanced carrier injection , enable improved charge transport and an increased probability of recombination directly on the emitter compounds E. It is possible to use the host molecules W described in WO 2013/007709 or WO 2013/007710, which can also be used in an unconjugated manner, in particular for the production of LECs It is also possible to use guanidium compounds as described in WO 2012/130571 and / or polyethylene oxide (PEO).

The step (i) of providing can be done in any way. For example, the at least one Cu (I) salt and the at least one ligand L can each be used as such (for example in coevaporation) or they can be dissolved.

Alternatively, if the Cu (I) complexes are to be formed from the liquid phase, the compositions Z1, Z2 and / or optionally Z3 may also contain solvents.

The compositions Z1, Z2 and / or optionally Z3 can then optionally be commercially available. Alternatively, a ligand L, a Cu (I) salt and / or a host molecule W may then be dissolved in a suitable solvent, respectively, to obtain the respective composition.

The step (ii) applying the compositions Z1, Z2 and optionally Z3 to the surface of the component T can be carried out in any desired manner. For example, the at least one Cu (I) salt and the at least one ligand L can be co-evaporated with one another in vacuo and sublimated on the surface. Such a step may be that of Liu et al., Chem. Mater. 2014, 26 (7), 2368-2373 and Liu ei a /., J. Am. Chem. Soc. 201 1, 133, 3700-3703 or WO 2012/016074 described, with the difference that other complexes are formed in the context of the present invention and also ligand L can be used in excess.

Alternatively, the Cu (I) complexes can also be formed from the liquid phase. For example, step (ii) may then be spin coating, dropcasting, slot casting, curtain casting, a rolling process, or a printing process (eg, inkjet printing, gravure, or knife coating). Here, the compositions Z1, Z2 and / or optionally Z3 may also contain a vaporizable organic solvent, such as a solvent selected from the group consisting of: Tetrahydrofuran, dioxane, chlorobenzene, diethylene glycol diethyl ether, diethylene glycol monoethyl ether, gamma-butyrolactone, N-methylpyrollidinone, ethoxyethanol, xylene, toluene, anisole, phenetole, acetonitrile, tetrahydrothiophene, benzonitrile, pyridine, trihydrofuran, triarylamine and PGMEA (propylene glycol monoethyl ether acetate). It is also possible to use combinations of two or more solvents. Optionally, the liquid composition Z1, Z2 and / or optionally Z3 to be applied to the surface can also be admixed with agents for improving the flow properties. Such agents are well known to those skilled in the art. For example, such an agent or component may be selected from the group consisting of: polyethyloxides (polyethylene glycols), polyethylenediamines, polyacrylates (eg polymethyl methacrylate (PMMA), polyacrylic acid and their salts (superabsorbents)), substituted or unsubstituted polystyrenes (eg polyhydroxystyrene), polyvinyl alcohols , Polyesters or polyurethanes, polyvinylcarbazoles, polytriaryamines, polythiophenes and

Polyvinylidenphenylenen. Combinations of two or more agents may also be used. The application of the composition in the liquid phase produces a wet phase containing a Cu (I) complex or the composition Z, which can then be dried and / or cured by means of customary processes known in the art. By applying the compositions Z1, Z2 and optionally Z3 in the liquid phase to the surface of the component T, a wet film is formed in which Cu (I), in place of the Cu (I) contained in Z1, is present in situ (in situ). Salt and ligand (s) L of Z2 which form Cu (I) complexes which are emitter compounds E.

The Cu (I) complex formed from the one or more Cu (I) salt (s) and the one or more ligand (s) L may, in principle, take on any conceivable stoichiometry. It is preferably a complex having a stoichiometry selected from the group consisting of Cu (I) 2L ₂ , Cu (I) ₂ L ₃ , Cu (I) Li, Cu (I) I L ₂ , Cu (L) i L ₃ , Cu (I) i L ₄ , Cu (I) ₂ Li and Cu (I) ₂ L ₄ . More preferably, it is selected from the group consisting of Cu (I) ₂ L ₂ , Cu (I) ₂ L ₃ , Cu (I) Li and Cu (I) I L ₂ , in particular Cu (I) ₂ L ₂ or Cu (I) ₂ L ₃ . Here, L represents only the organochemical ligands L, the similar (homoleptic) or may be different (heteroleptic) ligands. Any inorganic ions are not included in the aforementioned stoichiometry. A complex containing two Cu (I) (eg, Cu (I) 2L ₂ or Cu (I) 2L ₃ ) may have a planar or butterfly structure, or a structure depending on the environment Conformation can change.

The Cu (I) complex preferably has one of the following structures (a), (b) or (c):

(a) (b) (c) wherein L ¹ - L "" are each independently:

A) suitable organic ligands L, which may be either the same or different, or

B) parts of organic ligands L, which may be either the same or different, where two or more of L '- L "' may be covalently linked together, such as L 'with L'", L "with L" ", L 'with L ", L"' with L '

L 'with L "" and / or L "with L'", in which case the conjugate represents an organic ligand L; and

where X and X 'are each independently of one another a suitable anionic ligand, for example an anion selected from the group consisting of CI ^" , Br ^" , I ^" , SCN ^" , CN ^" , RS ^" , RSe ^" , RR'N ^" , RR'P ^" and RC ^ C ^" are present,

wherein R and R 'are independently selected from the group consisting of a Ci-20-alkyl radical (eg, methyl, ethyl, n-propyl, iso-propyl, n-butyl or tert-butyl radical), adamantyl group, C _6- i ₄ aryl radical (such as phenyl, tolyl, napthyl, C6F ₅ radical), C2-i ₃ heteroaryl radical (eg, furyl, thienyl, pyridyl or pyrimidyl radical), _C-2- 2o alkenyl group (for example, CR = CR "R"'), C _2- 2o alkynyl radical (- C ^ CR "), -OR', and -NR "R"', where R "and R '" are defined as R and can also be H.

Preferably, the ligands L ¹ - L "" selected from mono- and bidentate phosphine and Arsanlanden and ligands having at least one N-donor atom. The ligands can be either neutral or simply negatively charged.

Particularly preferred embodiments for ligands and complexes are shown below as examples.

The ligands can either be monodentate ligands or be interconnected and form polydentate, especially bidentate, ligands. The structures therefore contain either four monodentate ligands or two bidentate ligands or a bidentate and two monodentate ligands or a tridentate and a monodentate ligand or a tetradentate ligand.

If the preparation of the Cu (I) complex is carried out by liquid processing, optionally a further step (iii) of drying and / or curing the coating S obtained by the application on the surface of the component T can follow the method described above. This step (iii) can in principle be arbitrary. The drying may optionally be carried out under reduced pressure and / or under elevated temperature. For example, the drying can be carried out at atmospheric pressure and 50 ° C. Alternatively, the drying can be carried out at atmospheric pressure and a temperature of 50-60 ° C, in particular 60 ° C. The curing may be accompanied by a polymerization, such as an acrylic resin, in which the compounds are embedded. By the step of drying, the wet film is transferred into a dry film. Optionally, in this case also the ligand L can be chemically bound covalently or noncovalently with one or more host molecules, as described, for example, in WO 2013/007709 and WO 2013/007710. A method is preferred in which the following steps are used to apply a light-emitting layer S on the surface of a component T:

Deploy from:

(a) a composition Z1 of a non-complexed Cu (I) salt,

(b) a composition Z2 of a non-complexed organochemical ligand L capable of complexing Cu (I), and optionally

(c) a composition Z3 of a host molecule W which can form a matrix for the light-emitting layer S;

Applying the solutions Z1, Z2 and optionally Z3 to the hole-line layer of the component T; and optional

Drying the layer S obtained by the application on the hole-line layer of the component T.

As stated above, according to the present invention, the Cu (I) complex formed is one which can emit light in the visible spectrum of light (hence in the wavelength range of 350 to 950 nm, especially 400 to 800 nm) according to the singlet harvesting mechanism ,

In a preferred embodiment, the Cu (I) complex in the powder or film state has a photoluminescence quantum efficiency of at least 50%. More preferably, the Cu (I) complex in the powder or film state has a photoluminescence quantum efficiency of at least 60% or at least 70%.

According to a preferred embodiment, the Cu (I) complex has a singlet-triplet energy splitting AE (S1-T1) of not more than 3000 cm ^-1 _, preferably not more than 2500 cm ^-1, and more preferably not more than 2000 cm ^" ¹ on. Optional AE (S1-T1) is even no more than 1500 cm ^"1, or not more than 1000 ^{cm" 1.} The application of the compositions to the surface of the component T according to step (ii) of the method according to the invention can be carried out as desired.

According to a preferred embodiment, the compositions Z1 and Z2 are applied simultaneously to the surface of the component T.

According to the invention, they are then applied simultaneously as two separate compositions (such as Z1 and Z2 in the gas phase or Z1 or Z2 containing separate solutions) on the surface of the component T, wherein the composition preferably mix on the surface itself or otherwise come into contact.

Alternatively, the compositions Z1 and Z2 can also be successively applied to the surface of the component T. Optionally, first Z1 can then Z2 be applied to the surface of the component T or first Z2 then Z3 be applied to the surface of the component T. This can be achieved, for example, by a printing method in which first Z1, then Z2 are printed on the same position of the surface of the component T. Alternatively, for example, can be achieved by a printing method in which first Z2, then Z1 are printed on the same position of the surface of the component T. Thus, for example, Z1 can first be applied in the liquid phase and, while Z1 is still liquid, Z2 can be added in the liquid phase, so that the liquids can mix in situ. Alternatively, for example, Z2 can first be applied in the liquid phase and, while Z2 is still liquid, Z1 can be added in the liquid phase, so that the liquids can mix in situ. Alternatively, for example, Z1 may first be applied in the liquid phase, then dried in situ, and then Z2 added in the liquid phase to the dried Z1. Alternatively, for example, Z2 may first be applied in the liquid phase, then dried in situ, and then Z1 added in the liquid phase to the dried Z2.

The stoichiometry between Cu (l) and ligand (s) L may optionally be chosen so that when the compositions Z1 and Z2 (almost) the entire Cu (l) and the entire ligand L in Cu (l) complexes is complexed.

However, a deviation from this stoichiometry is preferred so that uncomplexed Cu (I) or non-complexed ligand L is present in the light-emitting layer S obtained by the method.

The presence of uncomplexed Cu (I) or uncomplexed ligand L in the light-emitting layer S may allow so-called self-healing of such a layer. For example, a loss of Cu (I) from the Cu (I) complex can be counterbalanced by uncomplexed Cu (I).

According to a preferred embodiment, the compositions Z1 and Z2 are chosen such that an excess of at least 0.1 mol%, preferably at least 0.5 mol%, more preferably at least 1 mol%, in particular at least 5 mol% of Cu (L) is applied to ligand L on the surface of the component T.

It will be immediately understood that an excess as used herein represents the corresponding excess of one component over the other component in the applied and obtained light-emitting layer S.

It can thereby be achieved that uncomplexed Cu (I) is present in the light-emitting layer S obtained.

Due to the hole-conducting properties of Cu (I) salts (in particular of copper halides such as Cul, CuCl or CuBr), an excess of these can contribute to an increase in the conductivity.

According to an alternative embodiment, the compositions Z1 and Z2 are chosen such that an excess of at least 1 mol%, preferably at least 5 mol%, more preferably at least 10 mol%, in particular at least 20 mol% of ligand L to Cu (l) is applied to the surface of the component T.

As a result, it is possible to obtain non-complexed ligand L in the resulting light-emitting layer S.

Due to the structure-stabilizing properties of the uncomplexed ligands L, an excess thereof can contribute to an improvement in the molecular structure of the light-emitting layer S.

Alternatively, a stoichiometry can be selected which achieves (almost) complete complexation of the Cu (I) and of the ligand (s) L, and thus (almost) no uncomplexed Cu (I) and (almost) no uncomplexed ligand L is present in the obtained light-emitting layer S.

As stated above, the step (ii) of applying the compositions Z1, Z2 and optionally Z3 to the surface of the component T may be carried out by any method. For example, co-evaporation followed by vacuum sublimation, spin coating, dropcasting, slot casting, curtain casting, rolling or printing processes (e.g., inkjet printing) may be employed.

According to a preferred embodiment, the step (ii) of applying the compositions Z1, Z2 and optionally Z3 to the surface of the component T is carried out by coevaporation in vacuo and subsequent sublimation from the gas phase or by spin coating in the liquid phase.

As already described above, the method according to the invention can be used to produce a light-emitting layer S. This has different properties than light-emitting layers S, in which pre-prepared Cu (l) complexes are processed. Therefore, another aspect of the invention relates to a light-emitting layer S preparable (or manufactured) by a method according to the present invention. A light-emitting layer S is preferably an organochemical light-emitting layer S which consists predominantly of organic materials, ie of hydrocarbon compounds, where the hydrocarbon compounds may be substituted by heteroatoms such as nitrogen, phosphorus, oxygen and / or halogens. At least one of the hydrocarbon compounds represents a ligand L in the context of the invention. The light-emitting layer S preferably contains a Cu (I) complex of Cu (I) and at least one ligand L, and at least one host compound W, and optionally non-complexed Cu (l) salt or ligands L. Optionally, the light-emitting layer S can also fluorescent polymers (eg Superyellow (SY)), photoluminescent nanoparticles (such as silicon), quantum dots, cadmium selenide and / or exciplexes ( Optional complexes diluted with host molecules ("hosts") If the uncomplexed Cu (I) salt or ligand L is present, the light-emitting layer S can, as described above, have very particularly positive properties exhibit.

Therefore, the present invention also includes a light-emitting layer S containing:

(a) an emitter compound E which is a Cu (I) complex of one or more ligands L and one or more Cu (I); and

(b) either a portion of uncomplexed Cu (I) salt capable of being complexed by the ligand L or a portion of uncomplexed ligand L capable of supporting the Cu ( l) to complex.

Such a light-emitting layer S is preferably produced in accordance with the method according to the invention. In order to further modify the color and / or the emission spectrum of the emitted light or to modify the absorption spectrum, the light-emitting layer S may optionally additionally contain a dye F. According to a preferred embodiment, the light-emitting layer S additionally contains a dye F. Preferably, a dye F is not a Cu (I) complex according to the present invention.

Any desired dye F or else a dye combination can be used here. The dye F can also be a fluorescent and / or phosphorescent dye F, which can shift the emission and / or absorption spectrum of the light-emitting layer S. Optionally, diphoton effects can also be used, therefore absorbing two photons with half the energy of the absorption maximum. By a fluorescent and / or phosphorescent dye F usually a bathochromic effect is achieved (for example by heat loss). However, a hypsochromic effect can also be achieved (for example by diphoton effects).

In addition, particularly when the optoelectronic device is an LEC, the light emitting layer S may contain an ionic liquid or a combination of two or more ionic liquids. For example, such an ionic liquid or combination of two or more ionic liquids may be selected from the group consisting of:

Methyl imidazolium hexafluorophosphates (eg 1-alkyl-3-methylimidazolium hexafluorophosphates such as, for example, 1-methyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-propyl-3-methylimide dzolium hexafluorophosphate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-benzyl-3-methylimidazolinium hexafluorophosphate), dimethylimidazolium hexa-fluorophosphates (eg, 1-alkyl-2,3-dimethylimidazolium hexafluorophosphates such as 1-butyl-2,3 dimethyl imidazolium hexafluorophosphate), 3-methylimidazolium hexafluorophosphates (eg 1-alkyl-methyl-imidazolium hexafluorophosphate) Phosphates such as 1-methyl-3-methyl-inazolinohexafluorophosphate, 1-ethyl-3-methyl-inazolinohexafluorophosphate, 1-propyl-3-methylimidazolinohexa-fluorophosphate, 1-butyl-3-methylimidazolinohexafluorophosphate, 1-pentyl-3 methyl imidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolinohexafluorophosphate), 1-butyl-1 - (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl ) -imidazolinohexafluorophosphate, 1-methyl-3- (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-octyl) -innidazolinohexafluoro-phosphate, 1-methyl- 3-octylimidazolinohexafluorophosphate, methylimidazolium tetrafluoroborates (eg 1,3-dimethylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazole tetrafluoroborate, 1-propyl-3-methyl-innidazolene tetrafluoroborate, 1-butyl-3-methyl-innidazolene tetrafluoroborate ), 1-butyl-2,3-dimethyl-imidazolene tetrafluoro-borate, 1-hexyl-3-methyl-imidazolium tetrafluoroborate, 1-methyl-3-octyl-imidazolium-tetrafluoroborate, methylimidazolium trifluoronnethane esulfonates (eg, 1-methyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methyl-innidazolino-n-fluoro-methanesulfonate, 1-propyl-3-methyl-imidazolium-t-fluoromethanesulfonate, 1-butyl-3-methyl-imidazolium-n-fluoronethanesulfonate), 1, 2 3-trin-ethyl-imidazolium trifluoro-methanesulfonate, 1-ethyl-3-methyl-innidazolino-bis (pentafluoroethylsulfonyl) -amide, 1-butyl-3-methylimidazolino-bis (trifluoromethylsulfonyl) -amide, 1-butyl-3-methyl-naphthol-zoluenedithethanesulfonate, tetrabutyl-ammonium-bis-trifluoromethanesulfonimidat, tetrabutyl ammoniummethanesulfonat, tetrabutyl amnnoniunn nonafluorobutane-sulfonate, tetrabutyl amnnoniunnheptadecafluorooetanesulfonat, tetrahexyl-ammoniunn tetrafluoroborate, tetrabutyl amnnoniunntrifluoronnethanesulfonat, tetrabutyl amnnoniunnbenzoate, tetrabutyl ammonium halides (eg, tetrabutylammonium amnnoniunnchlond, tetrabutyl amnnoniunnbronnid) 1-Benzyl-3-methyl-imidazolene tetrafluoroborate, trihexyl-tetradecylphosphonium hexafluorophosphate, Tetrabu tyl-phosphonium methanesulfonates, tetrabutyl-phosphonium tetrafluoroborate, tetrabutylphosphonium bromide, 1-butyl-3-methylpyndinium bis (trifluoromethylsulfonyl) imide, 1-butyl-4-methylpyridinium hexafluorophosphate, 1-butyl-4-methylpyridinium tetrafluoroborate, sodium tetraphenylborate, Tetrabutyl-aminononetetra-phenylborate, sodium tetrakis (1-imidazolyl) borate and Cäsiumtetraphenylborat. Additionally or alternatively, the light-emitting layer S may contain one or more electrolytes, such as KCF3SO3. The stoichiometry between Cu (I) and ligand (s) L in the light-emitting layer can be optionally chosen so that all the Cu (I) and the entire ligand L are complexed in Cu (I) complexes.

However, as stated above, a deviation from this stoichiometry is preferred so that uncomplexed Cu (I) or non-complexed ligand L is present in the light-emitting layer S. The presence of uncomplexed Cu (I) or uncomplexed ligand L in the light-emitting layer S may enable self-healing of such. For example, a loss of Cu (I) from the Cu (I) complex can be compensated by uncomplexed Cu (I).

According to a preferred embodiment, in the light-emitting layer S at least 0.1 mol%, preferably at least 0.5 mol%, more preferably at least 1 mol%, in particular at least 5 mol% of the total Cu (l) as non- complexed Cu (I).

According to an alternative preferred embodiment, at least 1 mol%, preferably at least 5 mol%, more preferably at least 10 mol%, in particular at least 20 mol% of the total ligand L is present in the light-emitting layer S as uncomplexed ligand L.

This can cause each of the advantageous technical effects described above. As described above, such a light-emitting layer S is usually incorporated in an opto-electronic device to generate light. Therefore, another aspect of the invention relates to an opto-electronic device including a light-emitting layer S according to the present invention. An optoelectronic device according to the invention is preferably an organochemical optoelectronic device in which the light emitting layer S consists at least predominantly of organic materials. These may consist of hydrocarbon compounds, wherein the hydrocarbon compounds may be substituted with heteroatoms such as nitrogen, phosphorus, oxygen and / or halogens.

The light-emitting layer S is to be understood in the broadest sense as described above. Therefore, the light-emitting layer S, as described above, a Cu (l) complex of at least one Cu (l) salt and at least one ligand L as the emitter compound E, and optionally one or more host molecules W. The proportion of Cu (l ) Complex in the light-emitting layer S may be 0.1 to 100%. Accordingly, the light-emitting layer S may consist entirely or largely of the Cu (I) complex or else the Cu (I) complex only as a small or large proportion in addition to other compounds (such as one or more unbound salt (s) of the Cu ( l) and / or other metals, one or more unbound ligands L or one or more host molecules W). In many optoelectronic devices, such as LECs, the proportion of Cu (I) complex in the light-emitting layer S is preferably more than 30% by weight, more than 40% by weight, more than 50% by weight. %, more than 60 wt .-%, more than 70 wt .-%, more than 80 wt .-% or more than 90 wt .-%.

The opto-electronic device may be opaque, semi-transparent or (substantially) transparent. The optoelectronic device can be any optoelectronic device that includes a light emitting layer S according to the invention. According to a preferred embodiment, the optoelectronic device is an organic light emitting diode (OLED), an organic laser, an organic solar cell (OSC) or an optical sensor. The optoelectronic device is particularly preferably an organic light-emitting diode (OLED) or an organic solar cell (OSC). An organic solar cell (OSC) may also be referred to as an organochemical photovoltaic device (OPV).

An optical sensor may, for example, be an optical sensor which measures the light intensity. Also, the optical sensor may optionally determine the light intensity of light of a particular wavelength range. An optical sensor may also be part of an array of optical sensors (hence an array), as used, for example, as an image sensor in a digital camera. Even if the optoelectronic device is an organic light emitting diode (OLED), a light emitting electrochemical cell (LEC), an organic solar cell (OSC) or an optical sensor, the optoelectronic device can optionally also be designed as a thin layer, the total not thicker than 5 mm, not thicker than 2 mm, not thicker than 1 mm, not thicker than 0.5 mm, not thicker than 0.25 mm, not thicker than 100 μιτι or not thicker than 10 μιτι. The optoelectronic device may also have a thickness in the range of 8-9 μιτι, 7-8 μιτι, 6-7 [im, 5-6 [im, 4-5 [im, 3-4 [im, 2-3 im, 1 -2 [im or less than 1 [im. According to a particularly preferred embodiment, the optoelectronic device is an organic light emitting diode (OLED). OLEDs are known to be composed of several layers. Mostly, an anode layer A is on a substrate. The substrate may be made of any material or combination of materials. Glass plates are most commonly used. Alternatively, however, thin metal foils (for example copper, gold, silver or aluminum foils) or plastics can also be used, which allows greater flexibility of the OLED. In anode layer A, transparent materials are often used as anode materials. Since at least one of the electrodes must be transparent in order to be able to decouple the light generated in the OLED, either the anode layer A or the cathode layer C must be largely, preferably (almost) completely transparent to the light to be coupled out. Anode layer A usually consists to a large part or (almost) completely of one or more (largely) transparent conductive oxides ("transparent conductive oxides", TCOs) Such an anode layer A can be, for example, indium tin oxide, aluminum zinc Oxide, fluorine-tin oxide, indium-zinc oxide, PbO, SnO, zirconium oxide, molybdenum oxide, vanadium oxide, tungsten oxide, graphite, doped Si, doped Ge, doped GaAs, doped polyaniline, doped polypyrrole and / or doped polythiophene. The anode layer A can also be composed of one or more of the abovementioned materials, more preferably the anode consists of indium-tin-oxide (ITO) (usually (InO) o, 9 (SnO 2) o, i).

The roughness of the transparent, conductive oxides used in the anode layer A can be compensated for by the use of an additional hole injection layer (HIL) Furthermore, the hole injection layer can facilitate the injection of positive quasi charge carriers by preventing the transfer of the carrier from the transparent, Poly-3,4-ethylenedioxythiophene (PEDOT), polystyrene sulfonate (PSS), MoO ₂ , V ₂ O ₅ or Cul, especially a mixture of PEDOT and PSS, can be used in the hole injection layer can also prevent the diffusion of metals from the anode layer A in the transition in the hole line layer.

On the anode layer A or hole injection layer, a hole transport layer (HTL) is typically arranged, in which case any hole conductor can be used, for example electron-rich heteroaromatics such as triarylamines or carbazoles can be used as hole conductors Function and bridge the energy barrier to the light emitting layer S (emitter layer, English, "layer", EML, or "light emitting layer", LEL) Hole conduction layer may also be referred to as an electron blocking layer (EBL) Preferably, the hole conductors have high triplet energies For example, the hole conduction layer as a hole conductor may be a star-shaped heterocycle such as tris (4-carbazoyl-9-ylphenyl) amine (TCTA).

As a rule, the light-emitting layer S, which in the context of the present invention contains at least one Cu (I) complex of at least one Cu (I) salt and at least one ligand L, is applied to the hole-conducting layer. Optionally, the light-emitting layer S can also consist of this Cu (I) complex. The composition of a light-emitting layer S will be described in detail above.

Finally, an electron transport layer (ETL) can be applied to the light-emitting layer S. Any electron conductor can be used here, for example electron-deficient compounds such as benzimidazoles, pyridines, triazoles, oxadiazoles (for example 1, 3, For example, the electron conduction layer may be a star-shaped heterocycle as an electron conductor, such as 1,3,5-tri (1-phenyl-1H-benzo [d] imidazol-2-yl) phenyl (TPBi). The electron transport layer can be used for energetic leveling between cathode layer C and light-emitting layer S. On the electron conduction layer, typically a cathode layer C is applied, which may consist of a metal or a metal alloy, for example Al, Au, Ag , Pt, Cu, Zn, Ni, Fe, Pb, In, W, Pd and / or Mi shingles or alloys of two or more of these metals. For practical reasons, the cathode layer C may consist of largely optically nontransparent metals, such as Mg, Ca or Al. Alternatively, the cathode layer C may also contain graphite and / or carbon nanotubes (CNTs) In these cases of an intransparent cathode layer C, the anode layer A should be as transparent as possible. Also, the cathode layer C may also consist largely of semitransparent materials such as nanoscale silver wires. The cathode layer can be vapor-deposited, for example, in a high vacuum.

As a protective layer and to reduce the injection barrier for electrons, a thin protective layer may optionally be applied between the cathode layer C and the ETL. This may for example contain lithium fluoride, cesium fluoride and / or silver and may optionally be applied by vapor deposition.

OLEDs can also be produced, for example, as illuminated foils, as luminous labels in smart packaging or as innovative design elements, and can also be used in cell recognition and analysis.

An OLED preferably comprises at least the following layers:

A) an anode layer A, preferably comprising indium tin oxide, indium zinc oxide, PbO, SnO, graphite, doped Si, doped Ge, doped GaAs, doped polyaniline, doped polypyrrole and / or doped polythiophene; S) a light-emitting layer S according to the present invention; and

C) a cathode layer C, preferably comprising Al, Ca, Au, Ag, Pt, Cu, Zn, Ni, Fe, Pb, In, W, Pd and / or mixtures or alloys of two or more of these metals,

preferably wherein S) is arranged between A) and C).

More preferably, an OLED comprises at least the following layers:

A) an anode layer A, in particular one comprising indium tin oxide;

HTL) a hole line layer;

S) a light-emitting layer S according to the present invention;

ETL) an electron conduction layer; and

C) a cathode layer C, preferably comprising Al, Ca and / or Mg. preferably in the arrangement A) - HTL) - S) - ETL) - C), wherein the layers either directly adjoin or still one or more layer (s) may be therebetween.

Further preferred examples are shown in the experimental part.

In the OLED, the electrons (hence negative charge carriers) migrate in operation from the cathode towards the anode, which provides the holes (hence positive quasi charge carriers).

Holes and electrons meet in the ideal case in the light-emitting layer S, which is why it can also be referred to as a recombination layer. Clashing electrons and holes form a bound state (exciton). From an exciton, by energy transfer, a Cu (I) complex serving as an emitter compound as described herein can be excited. This Cu (I) complex can relax to the ground state and thereby emit a photon. The color of the emitted light depends on the energy gap (ΔΕ) between the excited and the ground state and can be varied by variation of the Cu (I) complex or of the ligand (L).

When the optoelectronic device according to the invention is an organic solar cell (OSC), it is preferred that the device comprises the Cu (I) complex of Cu (I) and L according to the invention as constituent of an absorber layer on Cu (I) complex in the absorber layer is preferably between 30 and 100 wt .-%. As with OLEDs, two electrodes are also provided for OSCs. Between these, the absorber layer is arranged, in which the Cu (I) complex described in the present application is used.

The above-described Cu (I) complex can emit light, therefore serving as emitter compound E. By varying the ligand (s) L and / or Cu (I), the ΔΕ distance between the first excited triplet state T1 and the singlet ground state SO and the first excited singlet state S1 and the singlet ground state SO can be varied so that it is possible to vary the wavelength of the emitted light. In particular, with Cu (I) complexes which have a mono- or bidentate ligand L, excellent results have been achieved in this regard.

If the opto-electronic device is an OSC, it may be a single-layer or multi-layer OSC. For example, a single-layer OSC can have the following layers:

A) a first electrode layer to a large extent or (almost) completely consisting of one or more (largely) transparent conductive oxides ("transparent conductive oxides", TCOs), for example indium tin oxide, aluminum zinc oxide, fluorine tin oxide,

Indium zinc oxide, PbO, SnO, graphite, doped Si, doped Ge, doped GaAs, doped polyaniline, doped polypyrrole and / or doped polythiophene, in particular indium tin oxide (ITO) (eg (lnOs) o, 9 ( SnO2) o, i);

B) an absorber layer S (corresponding to the light-emitting layer S in OLEDs) containing at least one Cu (I) complex of at least one

Cu (I) salt and at least one ligand contains L; and

C) a second electrode layer of a metal or a metal alloy, such as Al, Au, Ag, Pt, Cu, Zn, Ni, Fe, Pb, In, W, Pd and / or mixtures or alloys of two or more of these metals, Carbon nanotubes (CNTs) and / or nanoscale silver wires, in particular Mg, Ca or Al,

wherein the single-layer OSC is typically applied to one substrate (such as the first electrode layer) and protected on the other outside with a protective layer.

A multilayer OSC can be constructed in accordance with an OLED, wherein the layer S in the OSC is referred to as the absorber layer S, but otherwise the light-emitting layer S can correspond to an OLED and thus is also able to emit light under suitable conditions.

An optoelectronic device according to the invention can also be used to emit light. Accordingly, another aspect of the invention includes a method of producing light of a particular wavelength, comprising the step of providing an opto-electronic device according to the present invention.

For example, the wavelength of the emitted light can also be adjusted to short-wave emission, so that blue light is emitted. Accordingly, the present invention also includes a method of producing blue, green, yellow, orange or red emission.

By way of example, therefore, light in the range of 400-800 nm may be emitted, such as in the range of 400-500 nm, 450-550 nm, 500-600 nm, 550-650 nm, 600-700 nm, 650 -750 nm and / or 700-800 nm.

If the optoelectronic device according to the present invention is an OLED, it can also be used, for example, as a large-area light source, as a luminous wallpaper, a luminous window, a luminescent label, a luminescent poster or a flexible screen.

If the opto-electronic device according to the present invention is an OSC, it can also be used, for example, as a roll-up solar cell (for mobile applications such as smartphones, laptops, tablets, etc.), as an architectural element (eg wall or roof cladding element) or as Component in the traffic engineering area (eg in the automotive, aircraft, train, and / or ship area) are used. Such products, which contain the opto-electronic device according to the invention, are the subject of the present invention.

A further aspect of the invention relates to a process according to the present invention in which a Cu (I) complex is formed, which has a structure according to one of the following formulas A or A 'and in analogy to the complexes described above, in a light-emitting Layer S, can be used in an optoelectronic device and a method of generating light as described herein. Examples of corresponding complexes are also given in WO 2013/007707 (see, for example, Examples 1 -6 thereof). According to formulas A and A ', the complexes described herein can be used to form complexes which emit singlet harvesting mechanism (and TADF, thermally activated delayed fluorescence). For this reason, when these complexes are used as emitters in OLEDs, particularly high quantum efficiencies and brightnesses can be achieved, even if the doping concentrations in the emission layer are higher than 5 percent by weight. Since the compounds of the formula A or A 'generally have high glass transition temperatures, they are furthermore also suitable for use as a pure layer without the use of a matrix material. Thus, in a preferred embodiment, the emissive layer contains exclusively the compound according to formula A or A ', i. in a concentration of 100%, and thus no further matrix material.

Formula A Formula A ', in which the L, L 'and Z-containing ligand (Ι_ ^Λ Ι_') is a neutral, bidentate ligand bound to the Cu via non-ionic groups; in which the D, [B] _n and N ^" comprehensive ligand (D ^A N ^~ ) is bound via an anionic group to the Cu, wherein D is a radical having at least one substituent D ^* selected from the group consisting of a divalent carbene C ^* , N, O, P, S, As and Sb or consists of D ^* ,

where D ^* binds to Cu,

wherein D furthermore has a radical having up to 40 carbon atoms selected from the group consisting of a linear, branched or cyclic alkylene radical, a linear, branched or cyclic heteroalkylene radical, an arylene radical, a heteroaryl radical, a linear, branched or cyclic alkenylene radical and a linear, branched or cyclic alkynylene radical, each optionally containing one or more of the substituents selected from the group consisting of halogens, deuterium, linear, branched or cyclic alkyl radicals, linear, branched or cyclic heteroalkyl radicals, aryl radicals, heteroaryl radicals, linear, branched or cyclic alkenyl radicals , linear, branched or cyclic alkynyl radicals and other donor and acceptor groups such as, for example, amines, phosphines, carboxylates and their esters, and CF ₃ groups, where the substituents with one another and / or with the radical D are optional form a cyclized and / or fused structure; wherein N ^{"is an} anionic nitrogen in which Z 'is R ^u -, -R ^U -NR ^U" , -NR ^{U "} -R ^U -, -R ^U -NR ^U" -R ^U -, -R ^u -SiR ^{u "} R ^u" R ^u -, -R ^u -SiR ^{u "} R ^u" -, -SiR ^{u "} R ^u" -, -R ^u -GeR ^{u "} R ^u" R ^u -, -R ^u -GeR ^{u "} R ^u" -, -GeR ^u R ^u -, R ^u -, -R ^u -OR ^u -, -R ^u - CO-R ^u -, -R ^u -CO-OR ^u -, - R ^u -O-CO-OR ^u -, -R ^u -O-CO-R ^u -, -OR ^u -, -R ^-CS-U R ^U -, -R ^u - CO-SR ^u -, -R ^u -S-CO-R ^u -, -R ^u -CO-NH-R ^u -, -R ^u -NH-CO-R ^u -, -R ^u -O-, -R ^u -SR ^u -, - S- R ^u -, -R ^u -S-, -R ^u -SO-R ^u -, -SO-R ^u -, -R ^u -SO-, -R ^u -SO ₂ -R ^u -, -SO ₂ - R ^u - or -R ^u -SO ₂ -, wherein R ^u and R ^u are each independently a radical having up to 40 carbon atoms, selected from the group consisting of a linear, branched or cyclic alkylene radical, a linear, branched or cyclic heteroalkylene radical, an arylene radical, a heteroaryl radical, a linear, branched or cyclic alkenylene radical and a linear, branched or cyclic alkynylene radical,

each optionally with one or more of the substituents selected from the group consisting of halogens, deuterium, linear, branched or cyclic alkyl, linear, branched or cyclic heteroalkyl, aryl, heteroaryl, linear, branched or cyclic alkenyl, linear, branched or cyclic alkynyl and other donor and acceptor groups, such as, for example, amines, phosphines, carboxylates and their esters and CF ₃ groups, where the substituents with one another and / or with the radical D can optionally form a cyclized and / or fused-on structure,

wherein R ^u and R ^u are each independently a radical of up to 40 carbon atoms, independently selected from the group consisting of hydrogen, halogen, -R ', -ΟΟ (Ο) ^, -COOH, -OR', -NR 'R'^', - SiR'R' R *, -GeR'R'R '^",-SR', -SOR ', -SO ₂ R' and other donor and acceptor groups, such as carboxylates and their esters and CF ₃ groups, wherein R ', R * and R ^{r are} independently selected from the group consisting of H, OH, NH ₂ , a halogen, a substituted or unsubstituted, linear, branched or cyclic Ci _-2 o- alkyl, Ci _-2 o- heteroalkyl, C _2-2 o alkenyl, Ci-io-Heteroalkenylrest and a substituted or unsubstituted C6-aryl _-2 o, C _5-2 o-heteroaryl, C _7- 32-arylalkyl, C6-3i-heteroarylalkyl, Cs-33-Alkylarylalkylrest and a C ₇ 3 ₂ -Heteroalkylarylalkylrest, where the radicals R ', R ^f , R ^r , R ^u , R ^u' , R ^{u "} and R ^u" can optionally also lead to fused ring systems; wherein each B is a divalent organic bridge independently selected from the group consisting of = CR ^Z -, -CR ^z R ^y -, -NR ^Z -, -O-, -SiR ^z R ^y -, - GeR ^z R ^y - , -S-, -S (O) - and -S (O) ₂ - or a bond, wherein R ^z and R ^{y are} independently selected from the group consisting of hydrogen, halogen -OR ^x , -OC (O ) R ^x , -NR ^X R ^X , -SiR ^x R ^x R ^{x "} , GeR ^x R ^x R ^x , -SR ^X , -SOR ^x and -SO ₂ R ^x , where R ^x , R ^x and R ^are independently selected from H, OH, NH ₂ , a halogen, a substituted or unsubstituted, linear, branched or cyclic C 20-alkyl, C 20-heteroalkyl, C 2-30 alkenyl, CMO Heteroalkenylrest and a substituted or unsubstituted C6-2o-aryl, C _5- 2O heteroaryl, C ₇ 32 arylalkyl, C6-3i-heteroarylalkyl, C8-33-Alkylarylalkylrest and a C _7- 32-Heteroalkylarylalkylrest, wherein the radicals R ^x , R ^y and R ^{z may} optionally also lead to fused ring systems, wherein B is exemplified May be part of a phenyl and / or substituted phenyl moiety,

where several Bs may be the same or different,

wherein at least one carbon atom is between N ^" and D *, wherein one or more substituents of D and / or N ^" with B may optionally form cyclic, aliphatic, conjugated, aromatic and / or fused systems;

where T is CR ^W or nitrogen,

wherein R ^{w is} a radical selected from the group consisting of hydrogen, halogen, -R ^v , -OC (O) R ^v , -COOH, -OR ^v , -NR ^V R ^V , -SiR ^v R ^v R ^{v "} , -GeR ^v R ^v R ^v , -SR ^V , - SOR ^v , -SO2R ^v and other donor and acceptor groups, such as carboxylates and their esters and CF ₃ groups, wherein R ^v , R ^v and R ^{v are} independently selected from the group consisting of H, OH, NH ₂ , NHR ^{V "} , NHR ^{V '} R ^V"" , a halogen, a substituted or unsubstituted, linear, branched or cyclic Ci-2o-alkyl, Ci-20-heteroalkyl, C2-2o alkenyl, Ci-io-heteroalkenyl and a substituted or unsubstituted C6-2o-aryl, C _5- 2o-heteroaryl, C _7- 32-arylalkyl, C6-3i-heteroarylalkyl, C8-33-Alkylarylalkylrest and a C _7- 32 Heteroalkylarylalkylrest. wherein R ^v and R ^v are independently selected from each other from the group consisting of OH, NH _2, halogen, a substituted or unsubstituted, linear, branched or cyclic Ci-20-alkyl, Ci-2o heteroalkyl, C2-2o alkenyl, Ci-io-heteroalkenyl and a substituted or unsubstituted C6-2o-aryl, C _{5 -} 2o-heteroaryl, C ₇ 32 arylalkyl, C6-3i-heteroarylalkyl, Cs-33-Alkylarylalkylrest and a C _7- 32-Heteroalkylarylalkylrest wherein two or more of the radicals. R ^v , R ^v , R ^v and R ^{w may} optionally also form one or more fused ring systems, where T may optionally form one or more ring systems with one or more B; where n is the integers from 1 to 9; each of L and L 'is independently a substituent attached to the Cu, wherein L contains a substituent L ^* and L' contains a substituent L ' ^* , wherein L ^* and L' ^{* are} independently selected from the group consisting of a divalent carbene C ^* , N, O, P, S, As and Sb and L ^* and L ' ^* each form a bond to the Cu, wherein L contains one or more, preferably three, substituents attached to L ^* and wherein L 'contains one or more, preferably three, substituents attached to L ^* ', those attached to L ^* and L ' ^* Substituents independently of one another are each a substituent having up to 40 carbon atoms, selected from the group consisting of a linear, branched or cyclic alkylene radical, a linear, branched or cyclic heteroalkylene radical, an arylene radical, a heteroaryl radical, a linear, branched or cyclic alkenylene radical and a linear, branched or cyclic alkynylene radical, each optionally containing one or more of the substituents selected from the group consisting of halogens, deuterium, linear, branched or cyclic alkyl radicals, linear, branched or cyclic heteroalkyl radicals, aryl radicals, heteroaryl radicals, linear, branched or cyclic alkenyl radicals , linear, branched or cyclic Alkynyl radicals and other donor and acceptor groups such as amines, phosphines, carboxylates and their esters and CF ₃ groups, where the substituents may optionally form a cyclized and / or fused-together structure with one each being attached to L ^* bonded substituent and a substituent attached to L ' ^* can be linked together via Z, in particular wherein the other substituents bonded to L ^* and L' ^{* are} each aryl radicals in which Z is -O-, a bond, -R ^ub - -R ^ub -NR ^ub -, -NR ^{ub "-R} ^ub -, -R ^ub -NR ^ub -R ^ub -, -R ^ub - SiR ^ub" R ^{ub "-R} ^ub -, -R ^ub ^{ub -SiR"} R ^{ub "} -, -SiR ^ub" R ^{ub "} ^-Rub- , -R ^ub -GeR ^ub" R ^{ub "} ^-Rub- , -R ^ub - ^Rubber" R ^{ub "} -, -GeR ^ub" R ^{ub "} - R ^ub , R ^ub -OR ^ub , R ^ub -CO-R ^ub , ^-Rub -CO-OR ^ub , R ^-ub -O-CO-OR ^ub , -R ^ub -O- CO-R- ^sub- , -OR ^{ub '} , ^-Rub-CS - ^Rub- , ^-Rub -CO- ^SRub- , ^-Rub -S-CO- ^Rub- , ^-Rub -CO-NH ^-Rub- , ^-Rub -NH-CO- ^Rub- , ^-Rub -CO-NR ^{v "} ^-Rub- , ^-Rub -N R ^{v "} -CO-R ^ub -, R ^ub -O-, -R ^ub -SR ^ub -, -SR ^{ub '} , -R ^ub -S-, -R ^ub -SO-R ^ub -, -SO- R ^{ub '} , -R ^ub -SO-, -R ^ub -SO ₂ - R ^ub -, -SO ₂ -R ^ub' or -R ^ub -SO ₂ - is absent or Z and thus no bond between L and L ' is present, wherein R ^ub and R ^ub are each independently a radical of up to 40 carbon atoms selected from the group consisting of a linear, branched or cyclic alkylene radical, a linear, branched or cyclic heteroalkylene radical, an arylene radical, a heteroarylene radical, a linear, branched one or cyclic alkenylene radical and a linear, branched or cyclic alkynylene radical,

each optionally with one or more of the substituents selected from the group consisting of halogens, deuterium, linear, branched or cyclic alkyl, linear, branched or cyclic heteroalkyl, aryl, heteroaryl, linear, branched or cyclic alkenyl, linear, branched or cyclic alkynyl and other donor and acceptor groups, such as, for example, amines, phosphines, carboxylates and their esters and CF ₃ groups, where the substituents can optionally form a cyclized and / or fused-together structure with one another, where R ^{ub "} and R ^{ub "independently} represent a radical having up to 40 carbon atoms are independently selected from the group consisting of hydrogen, halogen, -R ^r, -OC (O) R ^r, -COOH, -OR ^r, -NR * ^'R' ^"" , - SiFfFf ^' R', -GeR ^r, R ^{r "} R ^t -SR '^" , -SOR ^r , -S0 ₂ R ^r and other donor and acceptor groups such as Carboxyla and their esters and CF ₃ - groups, wherein R ^r , R ^r and R * are independently selected from the group consisting of H, OH, NH ₂ , a halogen, a substituted or unsubstituted, linear, branched or cyclic Ci -20-alkyl, Ci-2o heteroalkyl, C2-2o alkenyl, Ci-io-heteroalkenyl and a substituted or unsubstituted C6-2o-aryl, C _5- 2o-heteroaryl, C _7- 32 arylalkyl, C6-3i-heteroarylalkyl, Cs-33-Alkylarylalkylrest and a C _7- 32-Heteroalkylarylalkylrest, where the radicals R ^r, R ^''', R *, R ^ub, ^{ub R',} R ^{ub "and} R ^{ub "may} optionally lead to fused ring systems. Z may also be absent, so that L and L 'are each independently bound to the Cu.

Alternatively, two or more Z L and L 'may connect to each other.

In one embodiment, N ^" together with Z 'of the formula A or A' forms an anion of an unsaturated or aromatic N-heterocyclic moiety having from 5 to 14 ring atoms which, after N-deprotonation of a residue selected from the group consisting of purinyl, Pyrryl, indyl, carbazolyl, triazolyl, benzotriazolyl, pyrazolyl, benzopyrazolyl, imidazolyl, benzimidazolyl, and tetrazolyl can be obtained and which may optionally be further substituted.

In one embodiment, residue D of the D, [B] _n and N '^' comprising ligand (N ^"A D) of formula A or A 'is selected from the group consisting of (wherein the ligand has not more than 20 carbon atoms):

(i) a carbene C ^* which is part of a carbene ligand selected from the group consisting of

wherein the two dots ":" represent a divalent carbene which coordinates to the Cu atom and the linkage to B occurs at one of the # marked sites, the other one then selecting the other # - characterized formation site with a residue from the group consisting of hydrogen, deuterium, halogen, -OR ^s, -OC (O) -R ^s, -NR ^S R ^S, -SiR ^s R ^s R ^{s ",} -GeR ^s R ^s R ^s, - SR ^8, -SOR and -SO ₂ R ^s ^s may be connected wherein each R is independently selected from the group consisting of hydrogen, deuterium, halogen, -R -OR ^s ^s, -OC (O) -R ^s, -NR ^S R ^S , -SiR ^s R ^s R ^{s "} , -Ge R ^s R ^s R ^s" , -SR ⁸ , -SOR ^s and -SO ₂ R ^s , where R ^s , R ^s and R ^{s are} independently selected from hydrogen, Deuterium, OH, NH ₂ , a halogen, a substituted or unsubstituted, linear, branched or cyclic C 1-20 alkyl, 20-heteroalkyl, C2-2o-alkenyl, Ci-io-Heteroalkenylrest and a substituted or unsubstituted C6-2o-aryl, C _5- 2o-heteroaryl, C ₇ 32 arylalkyl, heteroarylalkyl C6-3i -, Cs-33-Alkylarylalkylrest and a C _7- 32 Heteroalkylarylalkylrest, where the radicals R, R ^s, R ^s and R ^s may also result in fused ring systems optional; wherein Y is nitrogen or CR ^r , wherein R ^{r is} a radical selected from the group consisting of hydrogen, deuterium, halogen, -R ^q , -OC (O) R ^q , -COOH, -OR ^q , -NR ^q R ^q , -SiR ^q R ^q R ^{q "} , - GeR ^q R ^q R ^q" , -SR ^q , -SOR ^q , -SO ₂ R ^q and other donor and acceptor groups, such as carboxylates and their esters and CF ₃ - Groups, wherein R ^q , R ^q and R ^{q are} independently selected from the group consisting of H, OH, NH ₂ , NR ^S R ^S , NHR ^S , a halogen, a substituted or unsubstituted, linear, branched or cyclic Ci-20 alkyl, Ci-20-heteroalkyl, C2-2o-alkenyl, Ci-io-Heteroalkenylrest and a substituted or unsubstituted C6-2o-aryl, C _5- 2o-heteroaryl, C _7- 32 arylalkyl, C6-3i-heteroarylalkyl, C8-33-Alkylarylalkylrest and a C _7- 32 Heteroalkylarylalkylrest, wherein two or more of R ^q, R ^q R ^q and R ^r may also result in fused ring systems, R, optionally, where z is the integer 1 , 2, 3 or 4;

(ii) an unsaturated or aromatic N-heterocyclic moiety having 4 to 8 ring atoms, wherein coordination to the Cu atom occurs via a nitrogen atom of the N-heterocyclic moiety selected from the group consisting of pyridyl, pyrimidyl, pyridazyl , Pyrazole, Pyranyl, coumaryl, pteridyl, thiophenyl, benzothiophenyl, furyl, benzofuryl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, thienothienyl, dithiaindacenyl, quinolyl, isoquinolyl, quinoxalyl, 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, which are optionally further substituted and / or fused, and an N-heterocyclic moiety selected from the group consisting of:

wherein the linkage to B takes place at the point marked with # point and ^* denotes the atom which enters the complex bond, Zi, Z _2, Z ₃ and Z each independently selected from CR ¹ or nitrogen, where R ¹ is a radical selected from the group consisting of hydrogen, deuterium, halogen, -R ^k , -OC (O) R ^k , -COOH, -OR ^k , -NR ^k R ^k , -SiR ^k R ^k R ^{k "} , - GeR ^k R ^k R ^{k "} , -SR ^k , -SOR ^k , -SO ₂ R ^k and other donor and acceptor groups such as carboxylates and their esters and CF ₃ - groups, wherein R ^k , R ^k and R ^{k are} independent of each other are selected from the group consisting of H, OH, NH ₂ , NR ^s R ^s , NHR ^s , a halogen, a substituted or unsubstituted, linear, branched or cyclic Ci-20-alkyl, Ci-20-heteroalkyl, C2 -2o-alkenyl, Ci-io-heteroalkenyl and a substituted or unsubstituted C6-2o-aryl, C _5- 2o-heteroaryl, C _7- 32-arylalkyl, C6-3i-heteroarylalkyl, C8-33-Alkylarylalkylrest and a C _7- 32 Heteroalkylarylalkylrest, the / R ^k, R ^k, R ^k and R ¹ may also result in fused ring systems, optionally, a phosphanyl, arsenyl or antimony moiety of the form -ER'R ^j , wherein E is selected from the group consisting of P, As and Sb which coordinate to the Cu atom, wherein R ¹ and R ^j independently of one another Radical selected from the group consisting of hydrogen, deuterium, halogen, -R ^k , - OC (O) R ^k , -COOH, -OR ^k , -NR ^k R ^k , -SiR ^k R ^k R ^{k "} , -GeR ^k R ^k R ^{k "} , -SR ^k , -SOR ^k , -SO 2 R ^k and other donor and acceptor groups such as carboxylates and their esters and CF ₃ groups, wherein R ^k , R ^k and R ^{k are} independently are selected from each other from the group consisting of H, OH, NH _2, NR ^S R ^S, NHR ^S, a halogen, a substituted or unsubstituted, linear, branched or cyclic Ci-20 alkyl, Ci-20-heteroalkyl , C 2-2o-alkenyl, Ci-io-Heteroalkenylrest and a substituted or unsubstituted C6-2o-aryl, C _5- 2o-heteroaryl, C ₇ 32 arylalkyl, C6-3i-heteroarylalkyl, C8-33 -Alkylarylalkylrest and a C _7- 32 Heteroalkylarylalkylrest, the / R ^■ R 'and R ^j may also result in fused ring systems, ^h, R ^h, R ^{h "optional,}

In one embodiment, the carbene C * of the D, [B] _n and N ^" comprising ligand (N ^{" A} D) of the formula A or A 'is part of a structure selected from the group consisting of:

wherein the two dots ":" represent a divalent carbene which coordinates to the Cu atom and the structure is linked to one of the sites marked # with B, the other one selecting the other site indicated by #, then with a residue from the group consisting of hydrogen, halogen, -OR ^g, -O- C (O) -R ^g, -NR ^g R ^g, -SiR ^g R ^g R ^{g ',} -GeR ^g R ^g R ^g', -SR ⁹ , -SOR ⁹ and -SO ₂ R ⁹ , wherein each R is independently selected from the group consisting of hydrogen, deuterium, halogen, -R ⁹ , -OR ⁹ , -OC (O) -R ⁹ , -NR ⁹ R ⁹ , -SiR ⁹ R ⁹ R ⁹ , - GeR ⁹ R ⁹ R ⁹ , -SR ⁹ , -SOR ⁹ and -SO ₂ R ⁹ , wherein R ^g , R ^g and R ^{g are} independently selected from H, OH, NH ₂ , NR ^S R ^s , NHR ^s , a halogen, a substituted or unsubstituted, linear, branched or cyclic Ci-20-alkyl-, Ci-20-heteroalkyl, C2-2o-alkenyl, Ci-io-Heteroalkenylrest and a substituted or unsubstituted C6-2o-aryl, C _5- 2o-heteroaryl, C ₇ 32 arylalkyl, C6-3i -Heteroarylalkyl-, C8-33-Alkylarylalkylrest and a C _7- 32-Heteroalkylarylalkylrest, where the radicals may also lead to ^g fused ring systems R, R ^g, R ^g and R optional; and wherein Y is nitrogen or CR ^f , wherein R ^{f is} a radical selected from the group consisting of hydrogen, deuterium, halogen, -R ^e , -OC (O) R ^e , -COOH, -OR ^e , -NR ^e R ^e , -SiR ^e R ^e R ^{e "} , - R ^e R ^e R ^e" , -SR ^e , -SOR ^e , -SO ₂ R ^e and other donor and acceptor groups such as carboxylates and their esters and CF. ₃ groups, wherein R ^e , R ^e and R ^{e are} independently selected from the group consisting of H, OH, NH ₂ , NR ^s R ^s , NHR ^s , a halogen, a substituted or unsubstituted, linear, branched or cyclic Ci-20-alkyl, Ci-2o heteroalkyl, C2-2o alkenyl, Ci-io-heteroalkenyl and a substituted or unsubstituted C6-2o-aryl, C _5- 2o-heteroaryl, C _7- 32-arylalkyl, C6-3i-heteroarylalkyl, Cs-33-Alkylarylalkylrest and a C _7- 32-Heteroalkylarylalkylrest, the / R ^e, R ^e, R ^e and R ^f optionally may also result in fused ring systems, where z for the integers 1, 2, 3 o the 4 stands.

In one embodiment, the ligand Ι_ ^Λ Ι_ 'of the formulas A and A' is a bidentate ligand of the form LG-L ', wherein G is a substituted or unsubstituted C 1-6 alkylene, C 2-8 alkenylene, C _2- s alkynylene or arylene group, -R ^d -NR ^d -, -NR ^{d '} - R ^d -, -R ^d -NR ^d -R ^d -, -R ^d -SiR ^{d "} R ^d" -R ^d -, -R ^d -SiR ^{d '} R ^{d "} -, -SiR ^d' R ^d" -, -R ^d -GeR ^{d "} R ^d" -R ^d -, -R ^d -GeR ^{d "} R ^{d '} -, -GeR ^d" R ^d' -, -R ^d , -R ^d - OR ^d -, -R ^d -CO-R ^d -, -R ^d -CO-OR ^d -, -R ^d -O-CO-OR ^d -, -R ^d -O-CO-R ^d -, -OR ^d -, -R ^d - CS-R ^d -, R ^d -CO-SR ^d -, -R ^d -SCO-R ^d -, -R ^d -CO-NH-R ^d -, -R ^d -NH-CO-R ^d -, -R ^d -O-, -R ^d -SR ^d -, -SR ^d -, -R ^d -S-, -R ^d -SO-R ^d -, -SO-R ^d -, -R ^d -SO-, - R ^{d is} -SO ₂ -R ^d -, -SO ₂ -R ^d -, or -R ^d -SO ₂ - wherein R ^d and R ^d are each independently a moiety of up to 20 carbon atoms selected from the group consisting of a linear, branched or cyclic alkylene radical, a linear, branched or cyclic heteroalkylene radical, an arylene radical, a heteroaryl radical, a linear, branched or cyclic alkenylene radical and a line arene, branched or cyclic Alkinylenrest, each optionally with one or more of the substituents selected from the group consisting of halogens, deuterium, linear, branched or cyclic alkyl radicals, linear, branched or cyclic heteroalkyl radicals, aryl radicals, heteroaryl radicals, linear, branched or cyclic alkenyl radicals , linear, branched or cyclic alkynyl radicals and other donor and acceptor groups such as amines, phosphines, carboxylates and their esters and CF ₃ groups, where the substituents with each other and / or with one or both of the radicals L and or L 'may optionally form a cyclized and / or fused structure, wherein R ^d and R ^d are each independently a radical of up to 20 carbon atoms, independently selected from the group consisting of hydrogen, halogen, -R ^c , - OC (O) R ^c , -COOH, -OR ^c , -NR ^C R ^C , - SiR ^c R ^c R ^{c "} , -GeR ^c R ^c R ^c" , -SR ^C , -SOR ^c , -SO ₂ R ^c and other donor and acceptor groups such as carboxylates and their esters and CF ₃ groups, wherein R ^c , R ^c and R ^{c are} independently selected alkyl- the group consisting of H, OH, NH _2, NR ^S R ^S, NHR ^S, a halogen, a substituted or unsubstituted, linear, branched or cyclic C1-20-AI, Ci _-2 o- Heteroalkyl, C2-2o-alkenyl, Ci-io-Heteroalkenylrest and a substituted or unsubstituted C6-2o-aryl, C _5- 2o-heteroaryl, C ₇ 32 arylalkyl, C6-3i-heteroarylalkyl, Cs-33-Alkylarylalkylrest and a C _7- 32-Heteroalkylarylalkylrest, where the radicals may also result in fused ring systems, R ^c, R ^{c ',} R ^{c ",} R ^d, R ^d', R ^{d 'and} R ^d" optional; wherein L and L 'are the same or different and which are independently selected from the group consisting of (wherein the ligand has not more than 20 carbon atoms):

(i) the fragment X ^b or an unsaturated or aromatic N-heterocyclic unit having 4 to 8 ring atoms, which is selected from the group consisting of pyridyl, pyrimidyl, pyridazyl, pyrazyl, pyranyl, cumaryl, pteridyl, thiophenyl, benzothiophenyl, Furyl, benzofuryl,

Oxazolyl, thiazolyl, imidazolyl, pyrazolyl, thienothienyl, dithiaindacenyl, quinolyl, isoquinolyl, quinoxalyl, 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, which are optionally further substituted and / or fused

wherein the coordination to the Cu atom via the nitrogen atom of the

Fragments X ^b or a nitrogen atom of N-heterocyclic takes place

wherein the fragment X ^{b is} selected from the group consisting of:

where the linkage to G takes place at the position marked # and ^* denotes the atom that undergoes complexation, wherein Zi, Z ₂ , Z ₃ and Z are each independently CR ^az or nitrogen, wherein R ^{az is} a radical selected from the group consisting of hydrogen, halogen, -R ^ay , -OC (O) R ^ay , -COOH, ^ay -OR, -NR R ^ay ^{ay ',} - SiR R ^ay ^ay' R ^{ay ",} -GeR R ^ay ^{ay 'R} ^ay", -SR ^ay, ^ay -SOR, -SO ₂ R ^ay and other donor and acceptor groups such as carboxylates and their esters and CF ₃ groups, wherein R ^ay , R ^ay and R ^{ay "are} independently selected from the group consisting of H, OH, NH ₂ , NR ^s R ^s , NHR ^s , a halogen , a substituted or unsubstituted, linear, branched or cyclic Ci-20-alkyl, Ci-20-heteroalkyl, C2-2o-alkenyl, Ci-io-heteroalkenyl and a substituted or unsubstituted C6-2o-aryl, C _5- 2o-heteroaryl, C ₇ 32 arylalkyl, C6-3i-heteroarylalkyl, C8-33-Alkylarylalkylrest and a C _7- 32 Heteroalkylarylalkylrest, the / R ^ay, ^ay R ^', R ^{ay "} and R ^az also leads to fused ring systems can,

(ii) a phosphanyl, arsenyl or antimony moiety of the form -ER'R ^j as defined above; and / or a C-containing group D selected from the group consisting of:

wherein the two dots ":" represent a divalent carbene which coordinates to the Cu atom and the structure is linked to one of the sites marked # with B, the other one selecting the other site indicated by # with a residue from the group consisting of hydrogen, halogen, -OR ^g, -OC (O) -R ^g, -NR ^g R ^g, -SiR ^g R ^g R ^{g ',} -GeR ^g R ^g R ^g', -SR ^9, - SOR ⁹ and -SO ₂ R ⁹ may be substituted, wherein the radicals R, R ⁹ , R ⁹ , R ⁹ and Y and z are as defined above. A further aspect of the invention relates to a process according to the present invention in which a Cu (I) complex is formed, which has a structure according to the following formula B and in analogy to the complexes described above, in a light-emitting layer S, in an optoelectronic device and a method of generating light as described herein. Examples of such complexes are also shown in WO 2013/007707 (Formulas I and A thereof) and in WO 2010/031485 (see, for example, Formulas II, IV and VI-IX thereof).

Formula B in which the L, L 'and Z-containing ligand (L ^A U) is a neutral, bidentate ligand bonded to the Cu via non-ionic groups; in which the ligand (Ν ^Λ Ν) comprising the ring systems A and A 'and the bridging ligand Z' can optionally be bonded to the Cu via an anionic group, the ligand Ν ^Λ Ν then neutralizing the positive charge of the Cu (I) can; wherein the ring systems A and A 'have one of the following structures:

wherein Zi, Z ₂ and Z _{3 are} each independently of the other nitrogen or CR, wherein R is independently selected from the group consisting of - H, -D, -F, -Cl, -Br, -I, -CN, -NO ₂ , -SO, -SO ₂ , -OH, -OR ^a , -SH, -SR ^a , -R ^a -NR ¹ R ² , - NR ¹ R ² , -R ^a -C (= O) R ¹ , -C (= O) R ¹ , -R ^a -SiR ¹ R ² R ³ , -SiR ¹ R ² R ³ , -R ^a -GeR ¹ R ² R ³ , - GeR ¹ R ² R ³ , - R ^a -SeR ¹ R ² R ³ , -SeR ¹ R ² R ³ , -R ^a -R ¹ C = CR ² R ³ , -R ¹ C = CR ² R ³ , -R ^a -C-C-R ¹ , -C ^ CR ¹ , -R ^a -C = O, -R ^a -C = S, -R ^a -C = Se, -R ^a -C = NR ¹ , -C = O, -C = S , -C = Se, -C = NR ¹ , -R ^a -CN = R ¹ , -CN = R ¹ , -R ^a -POR ¹ R ² R ³ , -R ^a -N = R ⁴ , -CO- NH-R ¹ , -R ^a -CO-NH-R ¹ , -NH-CO-R ¹ , -R ^a -NH-CO-R ¹ , wherein R ¹ , R ² and R ^{3 are} independently selected from each other the group consisting of H, D, F, I, Br, Cl, CN, an aliphatic hydrocarbon radical having 1 to 20 carbon atoms, aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more Wasserstoffa optionally substituted by D, F, Cl, Br, I or CN, wherein R ^{4 is} selected from the group consisting of an aliphatic hydrocarbon radical having 1 to 20 carbon atoms, in which one or more hydrogen atoms optionally by D, F, Cl , Br, I or CN may be substituted and which may optionally be substituted with one or more aromatic or heteroaromatic rings wherein R ^{a is} selected from the group consisting of a substituted or unsubstituted C 1-6 alkylene, C 2-8 alkenylene , C 2-8 -alkynylene or arylene radical, -R ^a -NR ^a -, -NR ^a -R ^a -, -R ^a -NR ^a -R ^a -, -R ^{a '} -SiR ^{a "} R ^a"" -R ^{a "} -, -R ^{a '} -SiR ^a" R ^{a ""} -, -SiR ^{a "} R ^a"" - R ^a -, -R ^a' -OR ^a" -, -R ^{a '} -CO- R ^{a "} , -R ^{a '} -CO-OR ^a" , -R ^a' -O-CO-OR ^{a "} -, -R ^{a '} -O-CO-R ^a" -, - OR ^{a "} , ^{-Ra '-CS-R} ^{a "-,} -R ^a' -CO-SR ^a" -, -R ^{a -S-CO-R} ^{a "-,} -R ^{a '-CO-NH-R} ^a' -, R ^{a '} -NH-CO- R ^{a '} -, -R ^a' - O-- ^, - R ^{a '} -SR ^a' -, -SR ^{a '} -, -R ^a' -S-, -R ^{a '} -SO-R ^a' -, - SO-R ^{3 '} -, -R ^a' -SO-, -R ^a - SO ₂ -R ^{a '} -, -SO ₂ -R ^{a "} - and -R ^a' -SO ₂ -, wherein R ^a and R ^a are each independently a radical having up to 20 carbon atoms, selected from the group consisting of a linear, branched or cyclic alkylene radical, a linear, branched or cyclic heteroalkylene radical, an arylene radical, a heteroaryl radical, a linear, branched or cyclic alkenylene radical and a linear, branched or cyclic alkynylene radical,

each optionally with one or more of the substituents selected from the group consisting of halogens, deuterium, linear, branched or cyclic alkyl, linear, branched or cyclic heteroalkyl, aryl, heteroaryl, linear, branched or cyclic alkenyl, linear, branched or cyclic alkynyl and other donor and acceptor groups, such as, for example, amines, phosphines, carboxylates and their esters and CF ₃ groups, where the substituents with one another and / or with the radical Z 'can optionally form a cyclized and / or fused-on structure in which R ^a and R ^a are each independently a radical having up to 20 carbon atoms, independently of one another selected from the group consisting of hydrogen, halogen, -R ^c , -OC (O) R ^c , -COOH, -OR ^c , -NR ^C R ^C , -SiR ^c R ^c R ^{c "} -SR ^C , -SOR ^c , -SO ₂ R ^c and other donor and acceptor groups, such as Carboxyla and their esters and CF ₃ groups, wherein R ^c , R ^c and R ^{c are} independently selected from the group consisting of H, OH, NH ₂ , NHR ^{a "} , NR ^{a '} R ^a"" , a halogen , a substituted or unsubstituted, linear, branched or cyclic Ci- ₂ o-alkyl, Ci _-2 o-heteroalkyl, C _2-2 o-alkenyl, Ci-io-heteroalkenyl and a substituted or unsubstituted C 6 _-2 o aryl, C _5-2 o-heteroaryl, C ₇ 32 arylalkyl, C6-3i-heteroarylalkyl, C8-33-Alkylarylalkylrest and a C ₇ 3 ₂ - Heteroalkylarylalkylrest, wherein the radicals R ^c , R ^{c '} , R ^{c "} , R ^a' , R ^a" , R ^{a "} and R ^a"" can optionally also lead to fused ring systems, wherein two or more adjacent substituents with each other a mono-, di -, tri- or polycyclic, aliphatic, aromatic or heteroaromatic ring system, and wherein Y is O, S or NR, wherein R is as defined above, wherein Z 'is BR ¹ R ² , wherein R ¹ and R ^{2 are} as defined above and B is a boron atom, in particular wherein Z 'is selected from the group consisting of H ₂ B, BPh ₂ , B (CH ₃ ) ₂ and B (NR ¹ R ² ) ₂ , where Ph is a phenyl radical, where R ¹ and R ^{2 are} as defined above and B is a boron atom, in particular wherein Z 'is selected from the group consisting of H ₂ B, BPh ₂ , B (CH ₃ ) ₂ and B (NR ¹ R ² ) ₂ , wherein Ph is a phenyl radical, where " ^* " denotes the atom which undergoes complex binding and "#" denotes the atom linked via Z 'to the second moiety in which L and L' are as above r may be defined Formula A wherein Z can be as defined above for formula A, and / or is a radical selected from the group consisting of -R ^ub - -R ^ub -NR ^ub -, -NR ^{ub "-R} ^ub -, -R ^ub - NR ^ub -R ^ub -, -R ^ub ^ub -SiR ^"R ^ub" -R ^ub -, -R ^ub ^ub -SiR ^"R ^ub" -, -SiR ^{ub "R} ^ub" -R ^ub -, ^-Rub ^-ORub -, ^-Rub -CO- ^Rub- , ^-Rub -CO- ^ORub- , ^-Rub -O-CO- ^ORub- , ^-Rub -O-CO- ^Rub -, -OR ^ub -, R ^ub - CS-R ^ub -, -R ^ub -CO-SR ^ub -, -R ^ub -S-CO-R ^ub -, -R ^ub -CO-NH-R ^ub - , -R ^ub -NH-CO-R ^ub -, - R ^ub -O-, -R ^ub -SR ^ub -, -SR ^ub -, -R ^ub -S-, -SO-R -R ^ub ^ub -, -SO- ^Rub- , ^-Rub -SO-, ^-Rub -SO ₂ - R ^ub -, -SO ₂ ^{-Rub '} or ^-Rub -SO ₂ -, wherein R ^ub and R ^ub independently each are a radical having up to 40 carbon atoms, selected from the group consisting of a linear, branched or cyclic alkylene radical, a linear, branched or cyclic heteroalkylene radical, an arylene radical, a heteroarylene radical, a linear, branched or cyclic alkenylene radical and a linear, branched or cyclic alkynylene radical,

each optionally with one or more of the substituents selected from the group consisting of halogens, deuterium, linear, branched or cyclic alkyl, linear, branched or cyclic heteroalkyl, aryl, heteroaryl, linear, branched or cyclic alkenyl, linear, branched or cyclic alkynyl and other donor and acceptor groups, such as, for example, amines, phosphines, carboxylates and their esters and CF ₃ groups, where the substituents with one another and / or with the radical Z can optionally form a cyclized and / or fused-on structure, wherein R ^{ub "} and R ^ub" are each independently a radical of up to 40 carbon atoms, independently selected from the group consisting of hydrogen, halogen, -R ^r , -OC (O) R ^r , -COOH, -OR ^r , -NR * ^'R' ^"'-SiR'^'R' ^'' ^ -SR"^', -SOR ^r, -SO ₂ R ^r and other donor and acceptor groups, such as Carboxylates and their esters and CF ₃ groups, wherein R ^r , R ^r and R * are independently selected from the group consisting of H, OH, NH ₂ , NHR ^{a "} , NR ^a" R ^{a ""} , a halogen , a substituted or unsubstituted, linear, branched or cyclic Ci-2o-alkyl, Ci-20-heteroalkyl, C2-2o-alkenyl, Ci-io-heteroalkenyl and a substituted or unsubstituted C6-2o-aryl, C _5- 2o-heteroaryl, C ₇ 32 arylalkyl, C6-3i-heteroarylalkyl, Cs-33-Alkylarylalkylrest and a C _7- 32 Heteroalkylarylalkylrest, where the radicals R ^r, R ^{r ",} R ^4, R ^ub , R ^{ub '} , R ^{ub "} and R ^ub" can optionally lead to fused ring systems; and wherein at least one of Z or Z 'is substituted by at least one non-complexed ionic group, preferably one

Ammonium group, a carboxyl group, a sulfonate group, a phosphonate group, in particular with -SO3 ^"is substituted. The follo- wing examples are intended to clarify these lines Ν ^Λ Ν:

where Me is a methyl radical and Ph ür a phenyl radical.

A further aspect of the invention relates to a process according to the present invention in which a metal (I) complex is formed, which has a structure according to the following formula C and in analogy to the complexes described above, in a light-emitting layer S, in an opto-electronic Apparatus and a method for generating light as described herein can be used. Examples of such complexes are also shown in WO 2014/102079 (see, for example, Formulas A and I-IX thereof).

Formula C wherein M and M 'are independently selected from the group consisting of Cu, Ag and Au, in particular both are each Cu; wherein X and X 'are independently selected from the group consisting of Cl, Br, I, CN, OCN, SCN, alkynyl and azide; in which the ligands (EnD) comprising E, Y, Z, Q and D and the ligands (E'nD ') comprising the E', Υ ', Ζ', Q 'and D' are each a bidentate ligand, where E and E 'are each independently RR'E ^* , where E ^{* is} N, P, As or Sb, where N is or is not an imine nitrogen or part of an N-heteroaromatic ring, or E and E each independently is RE ^* , where E ^{* is} a divalent carbene C ^* , O or S, where R and R 'are each independently selected from the group consisting of hydrogen, halogen, deuterium, -R ¹ , -OC (O) R ¹ , -COOH, -OR ¹ , - NR ¹ R ¹ , -SiR ¹ R ¹ R ¹ -SR ¹ , -SOR ¹ , -SO ₂ R ¹ and other donor and acceptor groups, such as Carboxylates and their esters and CF ₃ groups, wherein R ¹ , R ¹ and R ^{1 are} independently selected from the group consisting of H, OH, NH ₂ , NHR ^X , NR ^x R ^y , a halogen, a substituted or unsubstituted, linear, branched or cyclic Ci-20-alkyl, Ci-2o heteroalkyl, C2-2o alkenyl, Ci-io-heteroalkenyl and a substituted or unsubstituted C6-2o-aryl, C _5- 2o heteroaryl, C ₇ 32 arylalkyl, C6-3i-heteroarylalkyl, Cs-33-Alkylarylalkylrest and a C _7- 32-Heteroalkylarylalkylrest, wherein R ^x and R ^y are independently selected from each other from the group consisting of a substituted or unsubstituted, linear, branched or cyclic Ci-20-alkyl, Ci-20-heteroalkyl, C2-2o-alkenyl, Ci-io heteroalkenyl and a substituted or unsubstituted Cs ^ o-aryl, C _5- 2O heteroaryl, C ₇ 32 arylalkyl, C6-3i-heteroarylalkyl, Cs-33-Alkylarylalkylrest and a C _7- 32-Heteroalkylarylalkylrest, wherein the / the radicals R ^1, R ^1, R ^1, R and R 'may optionally lead to fused ring systems; where D and D 'are each independently either R "R"' D *, where D * is N, P, As or Sb, where N is or is not an imine nitrogen or part of an N-heteroaromatic ring, or D and D 'are each independently R "D *, where D * is a divalent carbene C *, O or S, where R" and R'"are each independently selected from the group consisting of hydrogen, halogen, and deuterium , -R ² , -OC (O) R ² , -COOH, -OR ² , - NR ² R ² , -SiR ² R ² R ^{2 "} -SR ² , -SOR ² , -SO ₂ R ² and further donor and acceptor groups such as carboxylates and their esters and CF ₃ groups, wherein R ² , R ² and R ^{2 are} independently selected from the group consisting of H, OH, NH ₂ , NHR ¹ , NR ¹ R ¹ , a halogen, a substituted or unsubstituted, linear, branched or cyclic Ci-20-alkyl, Ci-2o heteroalkyl, C2-2o alkenyl, Ci-io-heteroalkenyl and a substituted or unsubstituted Cs ^ o- aryl , C _5- 2o-heteroaryl, C ₇ 32 arylalkyl, C6-3i-heteroarylalkyl, Cs-33-Alkylarylalkylrest and a C _7- 32-Heteroalkylarylalkylrest, wherein the radicals R ² , R ² , R ² and R "and R '" can optionally also lead to fused ring systems; where D and E are different or similar; wherein Q, Y, Z, Q ', Y' and Z 'independently of one another are each selected from the group consisting of a substituted or unsubstituted Ci-g-alkylene, C _2- 8 alkenylene, C _2- 8 Alkynylene or arylene radical, -R ^a -NR ^a -, -NR ^{a '} - R ^a -, -R ^a -NR ^a - R ^a -, -R ^a -SiR ^{a "} R ^a" - R ^a' -, - R ^a -SiR ^{a 'R} ^a' -, -SiR ^{a "R} ^{a '-R} ^a -, -R ^a -O-R ^a -, -R ^a -CO-R ^a -, -R ^a - CO-OR ^3' -, R ^a -O-CO-OR ^a -, -R ^a -O-CO-R ^a -, -OR ^a -, -R ^a -CS-R ^a -, -R ^a -CO-SR ^a - , - R ^a -S-CO-R ^a -, -R ^a -CO-NH-R ^a -, -R ^a -NH-CO-R ^a -, -R ^a -O-, -R ^a -SR ^a -, -SR ^a -, -R ^a -S-, -R ^a -SO-R ^a -, -SO-R ^{3 '} -, -R ^a -SO-, -R ^a -SO ₂ -R ^a' - , -SO ₂ -R ^{a '} -, or -R ^a -SO ₂ -, wherein R ^a and R ^a are each independently a radical having up to 20 carbon atoms, selected from the group consisting of a linear, branched or cyclic Alkylene radical, a linear, branched or cyclic heteroalkylene radical, an arylene radical, a heteroaryl radical, a linear, branched or ode r is a cyclic alkenylene radical and a linear, branched or cyclic alkynylene radical, each optionally containing one or more of the substituents selected from the group consisting of halogens, deuterium, linear, branched or cyclic alkyl radicals, linear, branched or cyclic heteroalkyl radicals, aryl radicals, heteroaryl radicals, linear , branched or cyclic alkenyl radicals, linear, branched or cyclic alkynyl radicals and other donor and acceptor groups such as amines, phosphines, carboxylates and their esters and CF ₃ groups may be substituted, wherein the substituents with each other and / or with the rest D optionally form a cyclized and / or fused structure, wherein R ^a and R ^a are each independently a radical having up to 20 carbon atoms, independently selected from the group consisting of hydrogen, deuterium, halogen, -R ^c , -OC (O) R ^c , -COOH, -OR ^c , - NR ^C R ^C , -SiR ^c R ^c R ^{c "} -SR ^C , -SOR ^c , -SO ₂ R ^c and other donor and acceptor groups such as carboxylates and their esters and CF ₃ groups, wherein R ^c R ^c and R ^{c are} independently selected from the group consisting of H, OH, NH ₂ , NHR ¹ , NR ¹ R ¹ , a halogen, a substituted or unsubstituted, linear, branched or cyclic Ci-20-alkyl , Ci-2O heteroalkyl, C2-2o-alkenyl, Ci-io-Heteroalkenylrest and a substituted or unsubstituted C6-2o-aryl, C _5- 2o-heteroaryl, C ₇ 32 arylalkyl, C6- 3i heteroarylalkyl, Cs-33-Alkylarylalkylrest and a C _7- 32-Heteroalkylarylalkylrest, where the radicals R ^c, R ^{c ',} R ^{c ",} R ^a, R ^a', R ^{a 'and} R ^a" optionally also can lead to annulated ring systems; and wherein at least one of the radicals Q, Z, Y, Q ', Z' and / or Y 'is substituted by at least one non-complexed ionic group, preferably with an ammonium group, a carboxyl group, a sulfonate group, a phosphonate group, in particular with SO3 ^"is substituted.

Optionally, the two bidentate ligands EnD and E'nD 'can also be linked to one another via a spacer unit S (for example a Ci-io-alkylene group), resulting in a tetradentate ligand.

Optionally, an improvement in the solubility of the metal complex can be achieved by at least one of the ligands EnD and E'nD 'carries a corresponding substituent. A further aspect of the invention relates to a process according to the present invention in which a metal (I) complex is formed, which has a structure according to the following formula D and in analogy to the complexes described above, in a light-emitting layer S, in an optoelectronic device and a method of generating light as described herein. Examples of such complexes are also shown in European Patent Application No. EP14164815.

Formula D wherein M and M 'are independently selected from the group consisting of Cu, Ag and Au, especially both are Cu; wherein X and X 'are independently halides, especially selected from the group consisting of Cl, Br, I, or pseudohalides; wherein E 'and E "are independently selected from the group consisting of P, As and Sb, wherein R, R', R" and R '"are independently selected from the group consisting of optionally substituted alkyl groups. , Aryl, heteroaryl and alkoxy radicals each having up to 20 carbon atoms; where N is nitrogen; in the Y and Y 'of the ring systems G1 and G2 are each independently selected from the group consisting of a substituted or unsubstituted Ci-g-alkylene, C2-8 alkenylene, C2-8 alkynylene or arylene radical, = R ^a -NR ^a -, = NR ^a -, = R ^a -NR ^a -R ^a -, = R ^a -SiR ^{a "} R ^a" -R ^a - = R ^a -SiR ^{a "} R ^a" -, = R ^a -OR ^a -, = R ^a -CO-R ^a -, = R ^a -CO-OR ^a -, = R ^a -O-CO-OR ^a -, = R ^a -O-CO-R ^a - , -OR ^a -, = R ^a -CS-R ^a -, = R ^a -CO-SR ^a -, = R ^a -S-CO-R ^a -, = R ^a -CO-NH-R ^a -, = R ^a -NH-CO-R ^a -, = R ^a -O-, = R ^a -SR ^a -, = R ^a -S-, = R ^a -SO-R ^a -, = R ^a -SO- , = R ^a -SO ₂ -R ^a - and = R ^a -SO ₂ -, wherein R ^a and R ^a are each independently a radical having up to 20 carbon atoms, selected from the group consisting of a linear, branched or cyclic alkylene radical, a linear, branched or cyclic heteroalkylene radical, an arylene radical, a heteroaryl radical, a linear, branched or cyclic alkenylene radical and a linear, branched or z yklischen Alkinylenrest, each optionally with one or more of the substituents selected from the group consisting of halogens, deuterium, linear, branched or cyclic alkyl, linear, branched or cyclic heteroalkyl, aryl, heteroaryl, linear, branched or cyclic alkenyl, linear, branched or cyclic alkynyl radicals and other donor and acceptor groups such as, for example, amines, phosphines, carboxylates and their esters and CF ₃ groups, where the substituents may optionally form a cyclized and / or fused-together structure with each other, wherein R ^a and R ^a are each independently a radical of up to 20 carbon atoms, independently selected from the group consisting of hydrogen, deuterium, halogen, -R ^c , -OC (O) R ^c , -COOH, -OR ^c , - NR ^C R ^C , -SiR ^c R ^c R ^{c "} -SR ^C , -SOR ^c , -SO ₂ R ^c and other donor and acceptor groups, such as Carboxylates and their esters and CF ₃ groups, wherein R ^c , R ^c and R ^{c are} independently selected from the group consisting of H, OH, NH ₂ , NHR ^X , NR ^x R ^y , a halogen, a substituted or unsubstituted, linear, branched or cyclic Ci-20-alkyl, Ci-2o heteroalkyl, C2-2o alkenyl, Ci-io-heteroalkenyl and a substituted or unsubstituted C6-2o-aryl, C _5- 2o heteroaryl, C ₇ 32 arylalkyl, C6-3i-heteroarylalkyl, Cs-33-Alkylarylalkylrest and a C _7- 32-Heteroalkylarylalkylrest, wherein R ^x and R ^y are independently selected from each other from the group consisting of a substituted or unsubstituted, linear, branched or cyclic Ci-20-alkyl, Ci-20-heteroalkyl, C2-2o-alkenyl, Ci-io heteroalkenyl and a substituted or unsubstituted Cs ^ o-aryl, C _5- 2O heteroaryl, C ₇ 32 arylalkyl, C6-3i-heteroarylalkyl, Cs-33-Alkylarylalkylrest and a C _7- 32-Heteroalkylarylalkylrest, where the radicals R ^c, R ^{c ',} R ^{c ",} R ^a Optionally, R ^{a '} , R ^{a "} and R ^a" can also lead to fused ring systems; B and B' each independently of one another bridging a chain length of at least 2 and at most 17 atoms,

wherein the members of -CH ₂ -, -CHR ¹ -, -CR ¹ R ² -, -SiR ¹ R ² -, -GeR ¹ R ² -, -O-, -S-, -Se-, - NR ¹ -, -PR ¹ - and / or -AsR ¹ - may exist,

wherein R ¹ and R ² each independently represent a group selected from the group consisting of alkyl, aryl, heteroaryl, -OR ³ , -SR ³ , -SeR ³ , -H and -D each having up to 20 carbon atoms wherein R ^{3 is} an alkyl, aryl, heteroaryl, each having up to 20 carbon atoms, -H or -D; and wherein at least one of the radicals R-R '''and / or G1 and / or G1 is substituted by at least one non-complexed ionic group, preferably with an ammonium group, a carboxyl group, a sulfonate group, a phosphonate group, in particular substituted with -SO 3 ^' is. The ring systems G1 and G2 are each preferably a five- or six-membered heteroaromatic ring system which is optionally substituted by further radicals such as R, R '; R ", R '", R ^a and / or R ^{a may be} substituted or fused with other aromatic rings. A further aspect of the invention relates to a process according to the present invention in which a metal (I) complex is formed, which has a structure according to the following formula E and in analogy to the complexes described above, in a light-emitting layer S, in an optoelectronic device and a method of generating light as described herein. Examples of such complexes are also shown in WO 2013/014066 (see, for example, Formula IV thereof).

Formula E wherein M and M 'are independently selected from the group consisting of Cu, Ag and Au, especially both Cu; wherein X and X 'are independently selected from the group consisting of Cl, Br, I, CN, OCN, SCN, Ci.io-alkynyl and azide. the ligands comprising the E, Y, Z and D (EnD) and the ligands (E'nD ') comprising the Ε', Y ', Z' and D 'are each a bidentate ligand; where E and E 'are each independently RR'E ^* , where E ^{* is} N, P, As or Sb, where N is or is not an imine nitrogen or part of an N-heteroaromatic ring, or E and E 'are each independently RE ^* , where E ^{* is} a divalent carbene C ^* , O or S, where R and R' are each independently selected from the group consisting of hydrogen, halogen, deuterium, -R ¹ , -OC (O) R ¹ , -COOH, -OR ¹ , - NR ¹ R ¹ , -SiR ¹ R ¹ R ¹ -SR ¹ , -SOR ¹ , -SO ₂ R ¹ and other donor and acceptor groups, such as carboxylates and their esters and CF ₃ groups, wherein R ¹ , R ¹ and R ^{1 are} independently selected from the group consisting of H, OH, NH ₂ , NHR ^X , NR ^x R ^y , a halogen, a substituted or unsubstituted, linear, branched or cyclic Ci-20-alkyl, Ci-2O heteroalkyl, C2-2o-alkenyl, Ci-io-Heteroalkenylrest and a substituted or unsubstituted C6-2o-aryl, C _5- 2o-heteroaryl, C ₇ 32 arylalkyl, C6-3i -Heteroarylalkyl-, C8-33-Alkylarylalkylrest and a C _7- 32-Heteroalkylarylalkylrest, wherein R ^x and R ^y are selected independently from the group consisting of a substituted or unsubstituted, linear, branched or cyclic Ci-20 alkyl , Ci-20-heteroalkyl, C2-2o-alkenyl, CMO Heteroalkenylrest and a substituted or unsubstituted C6-2o-aryl, C _5- 2O heteroaryl, C _7- 32-arylalk yl, C6-3i-heteroarylalkyl, C8-33-Alkylarylalkylrest and a C _7- 32-Heteroalkylarylalkylrest, wherein the / the radicals R ^1, R ^1, R ¹ and R and R 'optionally also result in fused ring systems; where D and D 'are each independently either R "R"' D *, where D * is N, P, As or Sb, where N is or is not an imine nitrogen or part of an N-heteroaromatic ring, or D and D 'are each independently R "D *, where D * is a divalent carbene C *, O or S, where R" and R'"are each independently selected from the group consisting of hydrogen, halogen, and deuterium , -R ² , -OC (O) R ² , -COOH, -OR ² , - NR ² R ² , -SiR ² R ² R ^{2 "} -SR ² , -SOR ² , -SO ₂ R ² and further donor and acceptor groups such as carboxylates and their esters and CF ₃ groups, wherein R ² , R ² and R ^{2 are} independently selected from the group consisting of H, OH, NH ₂ , NHR ^X , NR ^x R ^y , a halogen, a substituted or unsubstituted, linear, branched or cyclic Ci-20-alkyl, Ci-2o heteroalkyl, C2-2o alkenyl, Ci-io-heteroalkenyl and a substituted or unsubstituted C6-2o-aryl, C _5- 2o heteroaryl, C ₇ 32 arylalkyl, C6-3i-heteroarylalkyl, Cs-33-Alkylarylalkylrest and a C _7- 32-Heteroalkylarylalkylrest, the / R ^2, R ^2, R ² and R ", and R '"can optionally lead to fused ring systems; where D and E are different or similar; wherein Y, Z, Y 'and Z' independently of one another are each selected from the group consisting of a substituted or unsubstituted Ci-g-alkylene, C _2- 8 alkenylene, C _2- 8 alkynylene, or arylene group -R ^a -NR ^{a '} -, -NR ^a' -R ^a -, -R ^a -NR ^{a "} -R ^a -, -R ^a -SiR ^a" R ^{a "} -R ^a -, -R ^a -SiR ^{a '} R ^a' -, -SiR ^{a "} R ^a" - R ^a -, -R ^a -OR ^a -, -R ^a -CO-R ^a -, -R ^a -CO- OR ^a -, -R ^a -O-CO-OR ^a -, -R ^a -O-CO-R ^a -, -OR ^{a '} , -R ^a -CS-R ^a -, -R ^a -CO-SR ^a -, -R ^a - S-CO-R ^a -, -R ^a -CO-NH-R ^a -, -R ^a -NH-CO-R ^a -, -R ^a -CO-NR ^x -R ^a -, -R ^a -NR ^{x is} -CO-R ^a -, -R ^a - O-, -R ^a -SR ^a -, -SR ^{a '} , -R ^a -S-, -R ^a -SO-R ^a -, -SO-R ^{3 '} , -R ^a -SO-, -R ^a -SO ₂ -R ^a -, -SO ₂ -R ^a' or -R ^a -SO ₂ -, wherein R ^a and R ^a independently of one another in each case a radical with bis to 20 carbon atoms selected from the group consisting of a linear, branched or cyclic alkylene radical, a linear, branched or cyclic heteroalkylene radical, an arylene radical, a Heteroarylenres t, a linear, branched or cyclic alkenylene radical and a linear, branched or cyclic alkynylene radical, each optionally containing one or more of the substituents selected from the group consisting of halogens, deuterium, linear, branched or cyclic alkyl radicals, linear, branched or cyclic heteroalkyl radicals , Aryl radicals, heteroaryl radicals, linear, branched or cyclic alkenyl radicals, linear, branched or cyclic alkynyl radicals and other donor and acceptor groups such as, for example, amines, phosphines, carboxylates and their esters and CF ₃ groups, where the substituents are substituted with one another and / or with the radical D can optionally form a cyclized and / or fused structure, wherein R ^a and R ^a are each independently a radical having up to 20 carbon atoms, independently selected from the group consisting of hydrogen, deuterium, halogen, R ^c , -OC (O) R ^c , -COOH, -OR ^c , - NR ^C R ^C , -SiR ^c R ^c R ^{c "} -SR ^C , -SOR ^c , -SO ₂ R ^c and other donor and acceptor groups such as carboxylates and their esters and CF ₃ groups, wherein R ^c , R ^c and R ^{c are} independently selected from the group consisting of H, OH, NH ₂ , NHR ^x , NR ^x R ^y , a halogen, a substituted or unsubstituted, linear, branched or cyclic Ci-20-alkyl, Ci-2o heteroalkyl, C2-2o alkenyl, Ci-io-heteroalkenyl and a substituted or unsubstituted C6-2o-aryl -, C _5- 2o-heteroaryl, C ₇ 32 arylalkyl, C6-3i-heteroarylalkyl, Cs-33-Alkylarylalkylrest and a C _7- 32-Heteroalkylarylalkylrest, wherein the R este R ^c , R ^{c '} , R ^{c "} , R ^a , R ^a' , R ^a" , R ^{a "} can optionally also lead to fused ring systems; and wherein at least one of Z, Y, Y 'or Z' with at least one non-complexed ionic group is substituted, is preferably substituted with an ammonium group, a carboxyl group, a sulfonate group, a phosphonate group, in particular with -SO3 ^".

Optionally, the two bidentate ligands EnD and E'nD 'can also be linked to one another via a spacer unit S (for example a Ci-io-alkylene group), resulting in a tetradentate ligand. Optionally, an improvement in the solubility of the metal complex can be achieved by at least one of the ligands EnD and E'nD 'carries a corresponding substituent. A further aspect of the invention relates to a process according to the present invention in which a metal (I) complex is formed, which has a structure according to the following formula F and in analogy to the complexes described above, in a light-emitting layer S, in an optoelectronic device and a method of generating light as described herein. Examples of such complexes are also shown in WO 2013/017675 (see, for example, Formula A thereof).

Formula F wherein X and X 'each independently are selected from the group consisting of Cl, Br, I, CN, OCN, SCN, _Ci-i0 alkynyl, and azide; where Z and Z 'independently represent a covalent bridge comprising at least two carbon and / or nitrogen atoms, where P is phosphorus and N is nitrogen; in which the ligand (PnN) comprising P, Z and N and the ligand (ΡηΝ 'comprising P, Z' and N) is in each case an N-heterocycle-substituted phosphine ligand which has a structure according to formula G:

Formula G wherein P is phosphorus and N is nitrogen;

wherein E is a carbon or nitrogen atom;

wherein E 'is a carbon or nitrogen atom which is not bonded to a hydrogen atom;

wherein the dotted bond is a single or double bond; wherein R is an optionally substituted, optionally branched Ci-20-alkyl radical, preferably a C6-2o-alkyl radical or an optionally alkylated C6-2o-aryl radical, in particular phenyl, wherein a substitution in this case is a substitution with a or more halogens (eg, F, Cl, Br, and / or I), silane groups, ether groups, or optionally in turn substituted alkyl, alkenyl, and / or alkynyl groups; in which R 'and R "are independently selected from the group consisting of alkyl groups, preferably C6-2o-alkyl groups, which may also be branched or cyclic, or

Aryl or heteroaryl groups which may be optionally substituted with alkyl groups, halogens (eg, F, Cl, Br and / or I), silane groups or ether groups, wherein R 'and R "are each directly bonded to the phosphorus atom of the phosphane ligand in which R '"is selected from the group consisting of alkyl groups, preferably C6-2o-alkyl groups, which may also be branched or cyclic, or aryl or heteroaryl groups which are optionally substituted by alkyl groups, Halogens (eg, F, Cl, Br and / or I), silane groups or ether groups may be substituted,

where R '"with Z can also form a ring system, therefore an aliphatic or aromatic heterocycle, wherein Z, Z' and Z ^x are each independently selected from the group consisting of a substituted or unsubstituted C 1-6 -alkylene, _2- C 8 alkenylene, C _2- 8 alkynylene, or arylene, -R ^a -NR ^{a '-,} -NR ^a' -R ^a -, -R ^a -NR ^{a "-R} ^a -, -R ^a -SiR ^{a "} R ^a" R ^a -, -R ^a -SiR ^{a '} R ^a' -, -SiR ^{a "} R ^a" - R ^a -, -R ^a -OR ^a -, -R ^a -CO -R ^a -, -R ^a -CO- OR ^a -, -R ^a -O-CO-OR ^a -, -R ^a -O-CO-R ^a -, -OR ^a -, -R ^a -CS- R ^a -, -R ^a -CO-SR ^a -, -R ^a - S-CO-R ^{3 '-,} -R ^a -CO-NH-R ^a -, -R ^a -NH-CO-R ^a - , -R ^a -O-, -R ^a -SR ^a -, -SR ^{a ',} R ^a S-, R ^a - SO-R ^a -, -SO-R ^3' -, -R ^a - SO, -R ^a -SO ₂ -R ^a -,, -R ^a -CO-NR ^a -R ^a -, -R ^a -NR ^a -CO-R ^a -, - SO ₂ -R ^{a '} and - R ^a -SO ₂ -, wherein R ^a and R ^a are each independently a radical having up to 20 carbon atoms, selected from the group consisting of a linear, branched or cyclic alkylene radical, a linear, branched or cyclic heteroalkylene radical, an arylene radical , a heteroarylene radical, a linear, branched or cyclic alkenylene radical and a linear, branched or cyclic alkynylene radical,

each optionally with one or more of the substituents selected from the group consisting of halogens, deuterium, linear, branched or cyclic alkyl, linear, branched or cyclic heteroalkyl, aryl, heteroaryl, linear, branched or cyclic alkenyl, linear, branched or cyclic alkynyl and other donor and acceptor groups such as amines, phosphines, carboxylates and their esters, and CF ₃ groups, which substituents may optionally form a cyclized and / or fused-together structure with each other, wherein R ^a and R ^{a are} independently each are each a radical having up to 20 carbon atoms, independently of one another selected from the group consisting of hydrogen, deuterium, halogen, -R ^c , -OC (O) R ^c , -COOH, -OR ^c , - NR ^C R ^C , -SiR ^c R ^c R ^{c "} -SR ^C , -SOR ^c , -SO ₂ R ^c and other donor and acceptor groups, such as carboxylates and their Esters and CF ₃ groups, wherein R ^c , R ^c and R ^{c are} independently selected from the group consisting of H, OH, NH ₂ , NHR ^X , NR ^x R ^y , a halogen, a substituted or unsubstituted, linear , branched or cyclic Ci _-2 o alkyl, Ci _-2 o- heteroalkyl, C _2-2 o alkenyl, Ci-io-Heteroalkenylrest and a substituted or unsubstituted C6-2o-aryl, C _5- 2o-heteroaryl, C ₇ 32 arylalkyl, C6-3i-heteroarylalkyl, C8-33-Alkylarylalkylrest and a C _7- 32-Heteroalkylarylalkylrest, wherein R ^x and R ^{y are} independently selected from the group consisting of a substituted or unsubstituted, linear, branched or cyclic Ci-20-alkyl, Ci-20-heteroalkyl, C2-2o-alkenyl, CMO-heteroalkenyl and a substituted or unsubstituted C6-2o aryl, C _5- 2O heteroaryl, C ₇ 32 arylalkyl, C6-3i-heteroarylalkyl, Cs-33-Alkylarylalkylrest and a C _7- 32-Heteroalkylarylalkylrest, where the radicals R ^c, R ^{c '} , R ^{c "} , R ^a , R ^a' , R ^a" and R ^{a "} can optionally also lead to fused ring systems, and wherein at least one of Z or Z 'is substituted by at least one non-complexed ionic group , preferably with an ammonium group, a carboxyl group, a sulfonate group, a phosphonate group, in particular with -SO3 ^"is substituted.

A further aspect of the invention relates to a process according to the present invention in which a Cu (I) complex is formed, which has a structure according to the following formula H and in analogy to the complexes described above, in a light-emitting layer S, in an optoelectronic device and a method of generating light as described herein. Examples of such complexes are also shown in WO 2013/072508 (see, for example, Formula A thereof), WO 2010/149748 (see, for example, Formula A thereof), and WO 2013/001086 (see, for example, Formula A thereof).

Formula H where X and X * are each independently selected

A group consisting of Cl, Br, I, CN, OCN, SCN, di-o-alkynyl and azide; in the case of N * a nitrogen atom which binds with Cu; wherein E is RR'E *, where E * is N, P, As or Sb, where N is or is not an imine nitrogen atom or part of an N-heteroaromatic ring, or E RE *, where E * is a divalent carbene C *, O or S, where R and R 'are each independently selected from the group consisting of hydrogen, halogen, deuterium, -R ¹ , -OC (O) R ¹ , -COOH, -OR ¹ , - NR ¹ R ¹ , -SiR ¹ R ¹ R ¹ -SR ¹ , -SOR ¹ , -SO ₂ R ¹ and other donor and acceptor groups, such as carboxylates and their esters and CF ₃ groups, wherein R ¹ R ¹ and R ^{1 are} independently selected from the group consisting of H, OH, NH ₂ , NHR ^X , NR ^x R ^y , a halogen, a substituted or unsubstituted, linear, branched or cyclic Ci-20-alkyl , Ci-2O heteroalkyl, C2-2o-alkenyl, Ci-io-Heteroalkenylrest and a substituted or unsubstituted C6-2o-aryl, C _5- 2o-heteroaryl, C ₇ 32 arylalkyl, C6- 3i-heteroarylalkyl, Cs-33-alkylarylalkyl and a C _7- 32-Heteroalkylarylalkylrest, wherein R ^x and R ^y are independently selected from each other from the group consisting of a substituted or unsubstituted, linear, branched or cyclic Ci-20 alkyl, Ci-20 heteroalkyl, C2 -2O alkenyl, CMO Heteroalkenylrest and a substituted or unsubstituted C6-2o-aryl, C _5- 2O heteroaryl, C ₇ 32 arylalkyl, C6-3i-heteroarylalkyl, C8-33-Alkylarylalkylrest and a C _7- 32-Heteroalkylarylalkylrest, wherein the / the radicals R ^1, R ^1, R ¹ and R and R may also lead to fused ring systems'optional; Z is a covalent bridge comprising at least two carbon and / or nitrogen atoms; wherein the ligands L and L 'are each independently any organic ligand of from 1 to 20 carbon atoms, preferably containing one or more groups selected from the group consisting of - OC (O) R ^c , -COOH, -OR ^c , -NR ^C R ^C , -SiR ^c R ^c R ^{c "} -SR ^C , -SOR ^c , -SO ₂ R ^c and other donor and acceptor groups such as carboxylates and their esters, CF ₃ groups, phosphorus -, arsenic- or antimony-containing groups,

wherein R ^c , R ^c and R ^{c are} independently selected from the group consisting of H, OH, NH ₂ , NHR ^a , NR ^{a "} R ^a"' , a halogen, a substituted or unsubstituted, linear, branched or cyclic Ci-20 alkyl, Ci-2O heteroalkyl, C2-2o-alkenyl, Ci-io-Heteroalkenylrest and a substituted or unsubstituted C6-2o-aryl, C _5- 2o-heteroaryl, C _7- 32 arylalkyl, C6-3i-heteroarylalkyl, Ce-33 AI ky I a ry I a I ky I residue and a C _7- 32-Heteroalkylarylalkylrest,

where the radicals R ^c , R ^{c '} , R ^{c "} , R ^d , R ^d' , R ^d" and R ^{d "} can optionally also lead to fused ring systems, where L and L 'are also bonded together and as in formula A above or as defined below according to formula K, in which the N ^* , Z and E-comprising ligand (EnN ^* ) may be a bidentate ligand according to the structure of formula K:

Formula K, where Y is a carbon or nitrogen atom,

wherein Y 'is a carbon or nitrogen atom substituted with 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 dotted bond is a single or double bond; wherein N represents a nitrogen atom incorporated in an imine group, the

Component of a heteroaromatic group comprising N, Y, Y ^' and Z ^x , wherein the heteroaromatic group is preferably selected from the group consisting of pyridyl, pyrimidyl, pyridazinyl, triazinyl, oxazolyl, thiazolyl, imidazolyl, which may be optionally substituted (for example with one or more of the substituents of the above-mentioned group) and / or may be fused to other groups of the complex in which R ^u and R ^{v are} independently selected from the group consisting of alkyl groups, preferably C 6-2o-alkyl Groups which may also be branched or cyclic, or aryl or heteroaryl groups, which may be optionally substituted with alkyl groups, halogens (eg, F, Cl, Br and / or I), silane or ether groups; are each selected independently from one another in the ^x Z and Z is selected from the group consisting of a substituted or unsubstituted Ci-g-alkylene, C _2- 8 alkenylene, C _2- 8 alkynylene, or arylene, -R ^a - NR ^{a "} , -NR ^a" -R ^a , -R ^a -NR ^{a "} -R ^a -, -R ^a -SiR ^a" R ^{a "} -R ^a -, -R ^a -SiR ^{a '} R ^{a '} -, -SiR ^{a "} R ^a" - R ^a -, -R ^a -OR ^a -, -R ^a -CO-R ^a -, -R ^a -CO- OR ^a -, -R ^a -O-CO -OR ^a -, -R ^a -O-CO-R ^a -, -OR ^a -, -R ^a -CS-R ^a -, -R ^a -CO-SR ^a -, -R ^a - S-CO- R ^{3 '} -, -R ^a -CO-NH-R ^a -, -R ^a -NH-CO-R ^a -, -R ^a -O-, -R ^a -SR ^a -, -SR ^a -, - R ^a -S-, - R ^a -SO-R ^a -, -SO-R ^{3 '} -, -R ^a -SO-, -R ^a -SO ₂ -R ^a -, -SO ₂ -R ^a - and R ^{a is} -SO ₂ -, wherein R ^a and R ^a are each independently a radical of up to 20 carbon atoms selected from the group consisting of a linear, branched or cyclic alkylene radical, a linear, branched or cyclic heteroalkylene radical, a Arylene radical, a heteroaryl radical, a linear, branched or cyclic Alkenylene radical and a linear, branched or cyclic alkynylene radical,

each optionally with one or more of the substituents selected from the group consisting of halogens, deuterium, linear, branched or cyclic alkyl radicals, linear, branched or cyclic heteroalkyl radicals, Aryl radicals, heteroaryl radicals, linear, branched or cyclic alkenyl radicals, linear, branched or cyclic alkynyl radicals and other donor and acceptor groups such as amines, phosphines, carboxylates and their esters and CF ₃ groups may be substituted, wherein the substituents with each other optional form a cyclized and / or fused structure, wherein R ^a and R ^a are each independently a radical having up to 20 carbon atoms, independently selected from the group consisting of hydrogen, deuterium, halogen, -R ^c , -OC (O ) R ^c , -COOH, -OR ^c , - NR ^C R ^C , -SiR ^c R ^c R ^{c "} -SR ^C , -SOR ^c , -SO ₂ R ^c and other donor and acceptor groups, such as carboxylates and their esters and CF ₃ groups, wherein R ^c , R ^c and R ^{c are} independently selected from the group consisting of H, OH, NH ₂ , NHR ^X , NR ^x R ^y , a halogen, a substituted or unsubstituted , linear, branched n or cyclic Ci-20-alkyl, Ci-2o heteroalkyl, C2-2o alkenyl, Ci-io-heteroalkenyl and a substituted or unsubstituted C6-2o-aryl, C _5- 2o-heteroaryl, C _7- 32-arylalkyl, C6-3i-heteroarylalkyl, Cs-33-Alkylarylalkylrest and a C _7- 32-Heteroalkylarylalkylrest, wherein R ^x and R ^y are selected independently from the group consisting of a substituted or unsubstituted, linear , branched or cyclic Ci-20-alkyl, Ci-20-heteroalkyl, C2-2o-alkenyl, CMO-heteroalkenyl and a substituted or unsubstituted C6-2o-aryl, C _5- 2o-heteroaryl, C _{7 -} 32-arylalkyl, C6-3i-heteroarylalkyl, C8-33-Alkylarylalkylrest and a C _7- 32-Heteroalkylarylalkylrest, where the radicals R ^c, R ^{c ',} R ^{c ",} R ^a, R ^a', R ^{a "} and R ^a" can optionally lead to fused ring systems; and wherein at least one of Z (or Z ^x ) is substituted by at least one non-complexed ionic group, preferably one

Ammonium group, a carboxyl group, a sulfonate group, a phosphonate group, in particular with -SO3 ^"is substituted. wherein the heteroaromatic group is preferably selected from the group consisting of pyridyl, pyrimidyl, pyridazinyl, triazinyl, oxazolyl, thiazolyl, imidazolyl, which may be optionally substituted (for example with one or more of the substituents of the aforementioned group) and / or with other groups of the complex can be fused

Preferably, the ligands L and L 'according to formula H are monodentate ligands having up to 42 carbon atoms.

The figures and exemplary embodiments and claims presented below serve to illustrate and explain the invention in more detail.

characters

FIG. 1 shows the emission spectrum (emission as a function of wavelength) of light-emitting layers S of metal complexes MK1 which have been produced differently:

solid line: production of MK1 by bulk synthesis, therefore classical synthesis in the reaction vessel in solution with subsequent purification;

dotted line: on the surface in situ produced MK1 with M: L-molar ratio M: L of 2: 3, therefore more complete

complexation;

dotted line: on the surface in situ produced MK1 with M: L-molar ratio M: L of 2.1: 3, therefore 5% excess of metal salt.

As the excitation wavelength, light having a wavelength of 350 nm was used. FIG. 2 represents the excitation and emission spectrum of the metal complex MK2 (solid line) and the emission spectrum of the metal complex MK1 (dashed line). Examples

example 1

Complexation of M and L on a surface

The concept of applying separate compositions Z1 and Z2 to a surface of a component T is exemplified by the formation of a Cu (I) complex of copper iodide (Cul) as the salt of the metal M and 4-methyl-2- (diphenylphosphino) pyridine (MePyrPHOS) shown as ligand L1. This results in the following complexing scheme of the metal complex MK1:

Ligand L1 metal complex MK1 The synthesis of ligand L1 is analogous to WO 2013/007710. Furthermore, the synthetic route can also be taken from WO 2013/072508 and WO 2013/007709.

Thus, a Cu ₂ L ₃ complex consisting of two Cu (I) and three ligands is formed. Thus, the entire Cu (l) and the entire ligand L are fully complexed, and neither uncomplexed metal M nor uncomplexed ligand L are present, therefore, the molar ratio M: L of 2: 3 must be selected. To form the metal complex MK1, a 0.066 molar solution of Cul in acetonitrile (composition Z1) and a 0.066 molar solution of Ligand L1 in toluene (composition Z2) was mixed so that the molar ratio M: L of 2: 3 was reached.

The emission spectrum of a light-emitting layer S, which consisted of a metal complex MK1 thus produced on the surface in situ, was compared with that from a metal complex synthesized and purified by bulk synthesis (classical synthesis in the reaction vessel in solution) MK1 passed (Fig. 1). It showed almost identical spectra, which shows that the metal complexes MK1 were made similar. After three days of standing at room temperature, there was no visual change.

Example 2

Complexation of M and L with an excess of metal salt on a surface

The procedure was as described above in Example 1, with the difference that for the formation of the metal complex MK1, the molar ratio M: L of 2.1: 3 was used.

The emission spectrum of a light-emitting layer S, which consisted of a metal complex MK1 thus produced on the surface in situ, was compared with that from a metal complex synthesized and purified by bulk synthesis (classical synthesis in the reaction vessel in solution) MK1 passed (Fig. 1). Nearly identical spectra were observed, demonstrating that the metal complexes MK1 were formed identically.

Even when an excess of metal salt was used, the desired metal complex MK1 was formed, the uncoordinated copper iodide presumably being present as non-luminescent species [Cul (MeCN) _n ] in the light-emitting layer S. After storing a mixed solution with Cul excess for 2 hours, a small amount of an insoluble, luminescent precipitate formed. This was identified by elemental analysis as [Cu ₄ l ₄ (MePyrPHOS) 2].

Example 3

Processing of a sparingly soluble metal complex on a surface

By mixing copper iodide with the ligands

(Ligand L1) and PPh3 (Ligand L2) became the metal complex MK2 of a structure of the formula

formed, which had advantageous properties in the powder: The quantum efficiency is nearly 100%, the emission decay time just below 1 s. However, due to its insolubility in conventional processing solvents such as toluene, it could not be used successfully as a bulk material for the production of OLED devices. However, by applying separate compositions Z1 (containing Cul) and Z2 (containing the ligand), a thin light-emitting layer S could be prepared from the complex. In this case, analogously to Example 1, the copper iodide dissolved in acetonitrile and the ligands dissolved in toluene used and adjusted the stoichiometry by the volumes to complete complexing. In each case, a concentration of 0.066 M was used and dried by heating to 60 ° C for 45 min. The emission and excitation spectra are set forth in Figure 2 and the quantum efficiencies of the light emitting layers S in Table 1.

Table 1 . Wavelength of the emission maximum λ and quantum yield φ of the light-emitting layers S of MK1 and MK2

Thus, for both the heteroleptic and homoleptic complexes, an emission maximum near 550 nm is achieved. The quantum efficiency is - similar to the powder samples - significantly higher for the heteroleptic complex. Example 4

Screening of metal complexes by formation on surfaces

Various copper complexes and ligands were prepared directly on the surface without prior presentation of a bulk material. The variation of the HOMO was evaluated by the choice of the copper halide and the variation of the LUMO by the choice of the N-donor. The complexes were prepared analogously to Example 1, but also the ligands were dissolved in acetonitrile were used and the drying was carried out at 50 ° C for 10 min. The concentration of all reactants was due to the poor solubility of some of the copper salts used even in acetonitrile 0.01 M reduced. The results for various copper salts are summarized in Table 2.

Table 2. Influence of the copper salt used on the photophysical properties of the copper complexes prepared on the surface

The emission color shifts from Cl over Br to I into the blue. Of particular interest is the emission wavelength of the Cul complex MK5, which lies at 434 nm at Tiefblau. The quantum efficiency does not follow a simple trend, the CuBr complex has a much higher quantum efficiency than the corresponding Cul complex. The CuSCN complex occupies a middle position between CuCI- and CuBr-based complexes. To influence the LUMO energy of the complexes MK3-MK6 different pyridine derivatives were used as ligands:

(Ligand L4) (ligand L5) (ligand L6) (ligand L7) (ligand L7)

Table 3 shows the emission characteristics of the obtained films. The aim of the optimization was to shift the emission color to blue, which is why mainly electron-rich pyridines were used. Due to the expected higher quantum efficiency, bromide was chosen as the counterion.

Table 3: Influence of the pyridine derivative used on the photophysical properties of the metal complexes prepared on the surface

It was possible to shift the maximum of the emission band starting from the original metal complex MK4 from 475 nm to 460 nm by introducing NH ₂ as a substituent (MK8). However, presumably due to intermolecular hydrogen bonding and vibration quenching, the quantum efficiency achieved was 5%, too low to allow use in an efficient OLED device. Although an alkyl substituent on the nitrogen (MK9 and MK10) significantly increased the quantum efficiency, a bathochromic shift of the emission color was observed: Although the basicity of the pyridine derivatives increases, the alkyl substituent on the amine nitrogen decreases the free LUMO energy Ligands off. The mere shift of the alkylic substitution pattern (see MK4 vs. MK7) did not lead to any significant influence. For a further reason, amine-containing substituents are not a favorable tool for manipulating the emission color: the oxidation sensitivity of the dissolved complexes is markedly higher than for amine-free complexes. In air contact, the solutions degraded within minutes after combining copper salt with the ligands, resulting in dark green discoloration was observed with the naked eye. The decomposition was probably due to oxidation with atmospheric oxygen. In solution, the electron-rich pyridines destabilize by coordination via the amine nitrogen Cu (I) and favor the oxidation to Cu (II) (HSAB concept).

In summary, it has been shown that the production of metal complexes directly on the surface in situ allows the investigation of photophysical properties even without the preparation of bulk materials.

Example 5

Formation of particularly preferred Cu (I) complexes

Particularly preferred is a Cu (I) complex formed by the process which has one of the following structures (I) to (VII):

\ (vii) wherein X is selected from the group consisting of halide (preferably I, Br or Cl), CN, SCN, OCN, SPh and an acetylide (preferably a phenylacetylide), especially where X is a halide; where the radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a radical having up to 40 carbon atoms, preferably those independently selected from the group consisting of -R ^r , -OC (O) R ^r , -COOH, -OR ^r , -NR ^ ^'R' ^"'-SiR' R ^,,, ^r" R ^t, -GeR '^"R ^r" R ^t -SR ^"', -SOR ^r, -SO 2 R ^r and other donor and acceptor groups, such as for example, carboxylates and their esters and CF ₃ groups, wherein R ^r , R ^r and R * are independently selected from the group consisting of H, OH, NH ₂ , a halogen, a substituted or unsubstituted, linear, branched or cyclic Ci-20-alkyl, Ci-2o heteroalkyl, C2-2o-alkenyl, Ci-io-Heteroalkenylrest and a substituted or unsubstituted C6-2o-aryl, C _5- 2o-heteroaryl, C ₇ 32 arylalkyl, C6-3i-heteroarylalkyl, Cs-33-Alkylarylalkylrest and a C _7- 32-Heteroalkylarylalkylrest,

where two or more of the radicals can also form substituted or unsubstituted ring systems with one another; wherein each E represents N, P, As or Sb; and wherein Z is any divalent group, preferably a selected those from the group consisting of -R ^ub - -R ^ub -NR ^ub -, -NR ^{ub "-R} ^ub -, -R ^ub -NR ^ub -R ^ub -, - R ^ub -SiR ^{ub "} R ^ub"' R ^ub' -, R ^ub -SiR ^{ub "} R ^ub"' -, -SiR ^{ub "} R ^ub" - R ^ub -, R ^ub -GeR ^{ub "} R ^{ub "'-R} ^ub' -, -R ^ub - GeR ^ub" R ^{ub '-,} -GeR ^{ub "R} ^ub" -R ^ub -, -R -OR ^ub ^ub -, -R ^ub -CO-R ^ub , ^-Rub -CO-OR ^ub- , ^-Rub -O-CO- ^ORub -, ^-Rub -O-CO- ^Rub -, ^-ORub' , ^-Rub - ^C-S-Rub - , ^-Rub -CO- ^SRub- , ^-Rub -S-CO- ^Rub- , ^-Rub -CO-NH- ^Rub- , ^-Rub -NH-CO- ^Rub- , ^-Rub -CO-NR ^{v "-R} ^ub -, -R ^ub -NR ^v" -CO-R ^ub -, -R ^ub -O-, -R ^ub -SR ^ub -, -SR ^{ub ',} -R ^ub -S -, ^SRub -SO- ^Rub- , -SO- ^{Rub '} , ^-Rub -SO-, ^-Rub -SO ₂ - R ^ub -, -SO ₂ ^-Rub' or ^-Rub -SO ₂ - or Z is missing and thus there is no bond between L and L ',

wherein R ^ub and R ^ub are each independently a radical of up to 40 carbon atoms selected from the group consisting of a linear, branched or cyclic alkylene radical, a linear, branched or cyclic heteroalkylene radical, an arylene radical, a heteroarylene radical, a linear, branched one or cyclic alkenylene radical and a linear, branched or cyclic alkynylene radical,

each optionally with one or more of the substituents selected from the group consisting of halogens, deuterium, linear, branched or cyclic alkyl, linear, branched or cyclic heteroalkyl, aryl, heteroaryl, linear, branched or cyclic alkenyl, linear, branched or cyclic alkynyl and other donor and acceptor groups such as amines, phosphines, carboxylates and their esters and CF ₃ groups, may be substituted, wherein the substituents may optionally form together a cyclized and / or fused structure, wherein R ^{ub "} and R ^ub" are each independently a radical having up to 40 carbon atoms, independently selected from the group consisting of hydrogen, halogen, -R ^r, -OC (O) R ^r, -COOH, -OR ^r, -NR * ^'R' ^"'-SiR'^'' FF ^'R', -GeFfFf ^' R '-SR'^" , -SOR ^r , -SO ₂ R ^V" and other donor and acceptor groups, such as carboxylates and their esters and CF ₃ - groups,

wherein R ^r , R ^r and R * are independently selected from the group consisting of H, OH, NH ₂ , a halogen, a substituted or unsubstituted, linear, branched or cyclic Ci-20-alkyl, Ci-2o heteroalkyl, C2-2o-alkenyl, Ci-io-Heteroalkenylrest and a substituted or unsubstituted C6-2o-aryl, C _5- 2o-heteroaryl, C ₇ 32 arylalkyl, C6-3i-heteroarylalkyl, Cs-33-Alkylarylalkylrest and a C _7- 32-Heteroalkylarylalkylrest.

Therefore, CuCI, CuBr, CuI, CuCN, CuSCN, CuOCN, CuBH ₄ , CuSPh and Cu-C ^ C-Ph are particularly preferably used as copper salts.

One skilled in the art can recognize which organic ligands to use to obtain such Cu (I) complexes.

According to preferred examples, the radicals in one of the structures of the formulas (I) to (VII) (if present) are defined as follows: R ^{1 "6} : in each case H or a Ci-io-alkyl;

R ⁷ and R ^{8 are} each an aryl radical, in particular phenyl;

R ⁹ and R ^{10 are} each an alkyl radical, especially a methyl radical, or together with the N or E to which they are attached, forming a ring system such as a piperidyl, piperidyl or morpholinyl ring;

R ¹¹ and R ^{12 are} each phenyl;

R ¹³ and R ^{14 are} each an alkyl radical, in particular a methyl radical, or together with the N or E to which they are attached, a ring system such as a piperidyl, piperidyl or

morpholinyl;

R ^{15 "18} : in each case an aryl radical, in particular phenyl;

X: in each case a halide, in particular I, Br or Cl; and

Z: a Ci _-7 alkylene, in particular butylene, or forms with the -N = C zusannnnen residue is a pyridinyl; and

E: N or P, in particular N.

Table 4. Examples of producible within the meaning of the invention Cu (I) complexes of formula (I).

Examples of complexes of the structure of the formula (I) are therefore:

Therefore, for the preparation of a complex of a structure of structure of formula (I) as ligands L, for example, the following may be used: ligands L selected from:

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Table 5. Examples of producible in the context of the invention Cu (I) complexes of formula (II).

Therefore, for the preparation of a complex of a structure of structure of formula (II) as ligands L, for example, the following may be used: ligands L selected from:

Table 6. Examples of producible according to the invention Cu (I) complexes according to formula (III).

Table 7. Examples of producible according to the invention Cu (I) complexes according to formula (IV).

Table 8. Examples of producible according to the invention Cu (I) complexes according to formula (V).

Table 9. Examples of producible according to the invention Cu (I) complexes according to formula (VI).

Therefore, a ligand L of the following formula can be used:

Table 10. Examples of producible according to the invention Cu (I) complexes of formula (VII).

Therefore, a ligand L of the following formula can be used:

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WO 2014/102079

Liu, Z .; Qayyum, M.F .; Wu, C; Whited, M. T .; Djurovich, P.I .; Hodgson, K.O .; Hedman, B .; Solomon, E.I .; Thompson, M.E .; A Code Position Route to Cul- Pyridine Coordination Complexes for Organic Light-Emitting Diodes; J. Am. Chem. Soc. 201 1, 133, 3700-3703;

Liu, Z .; Qiu, J .; Wei, F .; Wang, J .; Liu, X .; Heiander, M.G .; Rodney, S .; Wang, Z .; Bian, Z .; Lu, Z .; Thompson, M.E .; Huang, C; Simple and High Efficiency Phosphorescence Organic Light-Emitting Diodes with Codeposited Copper (l) Emitter; Chem. Mater. 2014, 26 (7), 2368-2373;

So, F. and Kondakov, D .; Degradation Mechanism in Small-Molecule and Polymer Organic Light-Emitting Diodes; Adv. Mater. 2010, 22, 3762-3777;

Yamamoto, H .; Adachi, C; Weaver, MS; Brown, JJ; Identification of device degradation positions in multi-layered phosphorescent organic light emitting devices using water probes; Appl. Phys. Lett. 2012, 100, 183306); Schmid, G .; Wemken, JH; Maltenberger, A .; Diez, C; Jaeger, A .; Dobbertin, T .; Hietsoi, O .; Dubceac, C; Petrukhina, MA; Fluorinated Copper (l) Carboxylates as Advanced Tunable p-Dopants for Organic Light-Emitting Diodes; Adv. Mater. 2014, 26, 878-885.

Claims

claims

1 . Method for applying a light-emitting layer S on the surface of a component T, comprising the steps:

(i) providing:

(ii) applying the compositions Z1, Z2 and optionally Z3 to the surface of the component T, wherein the Cu (I) complexes with the ligand L or several of the ligands L and thereby forms a Cu (I) complex, which is at room temperature can emit light in the visible region of the electromagnetic spectrum at the excited singlet level following the singlet harvesting mechanism.

2. The method according to claim 1, wherein the Cu (I) complex in the powder or film state has a photoluminescence quantum efficiency of at least 50%.

3. The method according to any one of claims 1 or 2, wherein the Cu (l) complex has a singlet-triplet energy splitting AE (S1 -T1) of not more than 3000 cm ^"1 _, preferably not more than 2500 cm ^{" 1} and more preferably not more than 2000 cm ^"1 .

4. The method according to any one of claims 1 to 3, wherein the compositions Z1 and Z2 are applied simultaneously to the surface of the component T.

A process according to any one of claims 1 to 4, wherein the compositions Z1 and Z2 are chosen such that an excess of at least 0.1 mol%, preferably at least 0.5 mol%, more preferably at least 1 mol%, in particular at least 5 mol% of Cu over ligand L is applied to the surface of the component T.

6. The method according to any one of claims 1 to 4, wherein the compositions Z1 and Z2 are chosen so that an excess of at least 1 mol%, preferably at least 5 mol%, more preferably at least 10 mol%, in particular at least 20 mol -% of ligand L to Cu (l) is applied to the surface of the component T.

7. The method according to any one of claims 1 to 6, wherein the step (ii) of applying the compositions Z1, Z2 and optionally Z3 on the surface of the component T by co-evaporation in vacuo and subsequent sublimation from the gas phase or by spin coating in the Liquid phase is performed.

8. Light-emitting layer S preparable by a method according to one of claims 1 to 7.

9. Light-emitting layer S containing:

(b) either a portion of uncomplexed Cu (I) salt capable of being complexed by the ligand L, or one Proportion of uncomplexed ligand L capable of complexing the Cu (I).

10. The light-emitting layer S according to any one of claims 8 or 9, wherein the light-emitting layer S additionally contains a dye F.

1 1. Light-emitting layer S according to any one of claims 8 to 10, wherein in the light-emitting layer S at least 0.1 mol%, preferably at least 0.5 mol%, more preferably at least 1 mol%, in particular at least 2 mol% of the total Cu (l) is present as uncomplexed Cu (I).

12. The light-emitting layer S according to any one of claims 8 to 10, wherein in the light-emitting layer S at least 1 mol%, preferably at least 5 mol%, more preferably at least 10 mol%, especially at least 20 mol% of the entire ligand L. present as uncomplexed ligand L.

13. An opto-electronic device comprising a light-emitting layer S according to any one of claims 8 to 12.

14. The optoelectronic device according to claim 13, wherein the optoelectronic device is an organic light-emitting diode, an organic laser, an organic solar cell or an optical sensor, in particular an organic light-emitting diode.

15. A method for generating light of a specific wavelength, comprising the step of providing an opto-electronic device according to one of claims 13 or 14.