DE102014116314A1 - Triplex ligand metal complex compounds for improved singlet harvesting by combined singlet and triplet emission for OLEDs and other optoelectronic devices - Google Patents

Abstract

The invention relates to light-emitting metal complex compounds according to formula A, comprising emission from a singlet state (S1) (based on a thermally activated delayed fluorescence, TADF) and in addition to shortening the total emission lifetime further emission from an energetically underlying triplet state (T1), where the occupation of the states and the resulting emissions are in rapid thermal equilibrium.

Description

The invention relates to metal complex compounds of the formula A and their use as emitters in organic light-emitting diodes (OLEDs) and in other optoelectronic devices.

introduction

Currently, new processes are being implemented in the area of screen and lighting technology. It is possible to produce flat displays or illuminated surfaces with a thickness of less than 0.5 mm. These are distinguished by many fascinating properties. So z. B. illuminated surfaces as wallpapers with very low energy consumption and color screens with previously unattainable color authenticity, brightness and viewing angle independence, be produced with low weight and very low power consumption. The screens can be designed as micro-displays or large screens with several square meters of surface in rigid form or flexible, but also as transmission or reflection displays. Furthermore, it will be possible to use simple and cost-saving production methods such as screen printing or inkjet printing. As a result, a very inexpensive production is possible compared to conventional flat screens. This new technology is based on the principle of OLEDs, Organic Light Emitting Diodes. In addition, the use of special metal-organic materials (molecules) many new opto-electronic applications, eg. B. in the field of organic field effect transistors, organic photodiodes, etc. from.

Thus, it can be seen, especially for the OLED sector, that such arrangements are already economically significant, since mass production has already begun. Such OLEDs consist predominantly of organic layers, which are also flexible and inexpensive to manufacture. OLED components can be designed over a large area as lighting fixtures, but also as small pixels for displays.

Compared to conventional technologies, such as liquid crystal displays (LCDs), plasma displays or cathode ray tubes (CRTs), OLEDs have numerous advantages, such as a low operating voltage of a few volts, a thin structure of several hundred nm, high-efficiency self-luminous pixels , a high contrast and a good resolution as well as the possibility to display all colors. Furthermore, light is generated directly in the application of electrical voltage in an OLED, instead of modulating it only polarization optically.

An overview of the function of OLEDs can be found, for example H. Yersin, Top. Curr. Chem. 2004, 241, 1 ; H. Yersin, Ed., "Highly Efficient OLEDs with Phosphorescent Materials"; Wiley-VCH, Weinheim, Germany, 2008 and W. Brütting, C. Adachi, Eds., "Physics of Organic Semiconductors", Wiley-VCH, Weinheim, Germany, 2012 ,

Since the first reports on OLEDs (see eg Tang et al., Appl. Phys. Lett. 1987, 51, 913 ), these devices have been further developed, in particular with regard to the emitter materials used, in particular in recent years so-called triplet or other phosphorescent emitters, which use the triplet harvesting effect, as well as emitters, which use the singlet harvesting effect, are of interest.

The triplet emitters suitable for triplet harvesting typically use transition metal complex compounds in which the metal is selected from the third transition metal series (6th period). These are mainly very expensive precious metals such as iridium, platinum or gold (see also H. Yersin, Top. Curr. Chem. 2004, 241, 1 and MA Baldo, DF O'Brien, ME Thompson, SR Forrest, Phys. Rev. B 1999, 60, 14422 ). The main reason for this is the high spin-orbit coupling (SBK) of the noble metal central ions (SBK constant Ir (III): ≈4000 cm ^-1 , Pt (II): ≈4500 cm ^-1 , Au (I) : ≈5100 cm ^-1 ; Ref .: SL Murov, J. Carmicheal, GL Hug, Handbook of Photochemistry, 2nd Edition, Marcel Dekker, New York 1993, p. 338 ff ). By virtue of this quantum mechanical property, the triplet-singlet transition strictly forbidden for optical transitions without SBK is allowed and the short emission lifetime of a few μs required for the OLED application is achieved.

In addition to triplet harvesting, another mechanism has been established in recent years, which also leads to the exploitation of all generated excitons in OLEDs. This mechanism is called singlet harvesting (see H. Yersin, AF Rausch, R. Czerwieniec, T. Hofbeck, T. Fischer, Coord. Chem Rev. 2011, 255, 2622 ). In singlet harvesting, as in triplet harvesting, the lowest excited triplet state is occupied. However, the emission then does not come from the lowest triplet state T ₁ , but rather from a thermal reoccupation from the lowest excited singlet State S ₁ instead (see 1 ). This process is referred to as thermally activated delayed fluorescence (TADF). To facilitate this process, a comparatively small singlet-triplet distance ΔE (S ₁ -T ₁ ) of, for example, less than about 2000 cm ^{-1 is} necessary. Suitable emitters are, above all, molecules which show a high charge transfer character, such as, for example, B. copper (I) compounds ( H. Yersin, AF Rausch, R. Czerwieniec, T. Hofbeck, T. Fischer, Coord. Chem Rev. 2011, 255, 2622 ). Thus, Cu (I) -based emitters could be represented that use the TADF and achieve high emission quantum yields (cf. R. Czerwieniec, J. Yu, H. Yersin, Inorg. Chem., 2011, 50, 8293 ).

The aim of this invention is to provide emitter materials with improved properties for opto-electronic devices.

Description of the invention

Surprisingly, suitable emitter molecules have been found in the form of metal complex compounds which have small singlet-triplet energy distances and exhibit a short (triplet radiative) lifetime through efficient spin-orbit coupling. This utilizes TADF-based singlet harvesting, and the emitters additionally exhibit triplet emission at room temperature; H. a combined singlet and triplet emission occurs. As a result, the radiative lifetime of the emitter molecule is significantly shortened. This reduces saturation effects that lead to a roll-off in an OLED application. This mechanism, which uses TADF emission combined with triplet emission, may be referred to as an improved singlet harvesting process when used in OLEDs.

The efficiency of the spin-orbit coupling correlates with the zero field splitting of the substates I, II and III of the T ₁ state. The greater the total zero field splitting ΔE (III-I), ie the energetic distance between the triplet substates III and I, fails, the greater the efficiency of the spin-orbit coupling and the shorter the (radiative) lifetime of the triplet Condition (see. H. Yersin, AF Rausch, R. Czerwieniec, T. Hofbeck, T. Fischer, Coord. Chem Rev. 2011, 255, 2622 ). Zero field splitting ΔE (III-I) is an experimentally accessible quantity that can either be determined directly from high-resolution spectra or, as is known to those skilled in the art, via the temperature-dependent measurement of the emission decay times. When using the latter method, emission decay times in the temperature range between 1.3 K and 300 K are measured. The triplet emission lifetime can be determined at low temperature, e.g. B. at T = 77 K, determine directly. With knowledge of the emission quantum yield, the radiative lifetime can be easily determined from this, as known to the person skilled in the art.

In 1 An energy level scheme for an emitter is shown schematically. Based on this scheme, the photophysical electroluminescence properties of this emitter will be explained. The hole-electron recombination, as is done, for example, in an opto-electronic device, leads to a statistical average of 25% for the occupation of the singlet state (1 singlet path) and 75% for the occupation of the ΔE ₁ (S ₁ -T ₁ ) deeper triplet state (3 triplet paths). Due to the intersystem crossing (ISC) process, the excitation reaching the S ₁ state (in the case of transition metal-organic emitters usually relaxes faster than a prompt fluorescence, eg in 10 ^-11 s; M. Iwamura et al. J. Am. Chem. Soc. 2011, 133, 7728 ) In the T ₁ state. From there, either an emission occurs directly (triplet harvesting) or indirectly by a thermally activated delayed fluorescence via the excited singlet state (TADF) in the electronic ground state. If the triplet emission lifetime is short enough, both effects can occur simultaneously, ie there is a combined emission from the S ₁ and T ₁ states, which, when used, e.g. B. in an OLED, leads to an improved singlet harvesting.

mit folgender Bedeutung
M: Das Metallion M ist entweder Cu⁺ oder Ag⁺. Jedes M bindet gemäß der Formel A über je eine Einfachbindung an das N-Atom der drei Pyridin-Ringe und über eine Einfachbindung an den Liganden X.
G: G ist ein schwach oder nicht-koordinierendes negatives (anionisches) Gegenion, insbesondere ein einfach negativ geladenes Anion, insbesondere ausgewählt aus der Gruppe bestehend aus
PF₆ ^–, BF₄ ^–, BH₄ ^–, BH₃R^–, BH₂R₂ ^–, BHR₃ ^–, BR₄ ^–, Tri(1H-pyrazol-1-yl)hydroborat, Tetrakis(1H-pyrazol-1-yl)borat, Tris(3,5-dimethylpyrazol-1-yl)hydroborat, Tetrakis(1-imidazolyl)borat, SbF₆ ^–, F₃CSO₃ ^–, FSO₃ ^–, RSO₃ ^–, (RO)SO₃ ^–, RCO₂ ^–, F₃CCO₂ ^–, (RO)CO₂ ^–, ClO₃ ^–, ClO₄ ^–, NO₂ ^–, NO₃ ^–, F^–, Cl^–, Br^– und I^–. The invention relates in one aspect to a light-emitting metal complex compound having a structure or consisting of a structure according to formula A with a tridentate, so-called "tripod ligand". Formula A

with the following meaning
M: The metal ion M is either Cu ⁺ or Ag ⁺ . Each M binds according to the formula A via a single bond to the N atom of the three pyridine rings and via a single bond to the ligand X.
G: G is a weakly or non-coordinating negative (anionic) counterion, in particular a singly negatively charged anion, in particular selected from the group consisting of
PF ₆ ^- , BF ₄ ^- , BH ₄ ^- , BH ₃ R ^- , BH ₂ R ₂ ^- , BHR ₃ ^- , BR ₄ ^- , tri (1H-pyrazol-1-yl) hydroborate, tetrakis (1H-pyrazole-1 -yl) borate, tris (3,5-dimethylpyrazol-1-yl) hydroborate, tetrakis (1-imidazolyl) borate, SbF ₆ ^- , F ₃ CSO ₃ ^- , FSO ₃ ^- , RSO ₃ ^- , (RO) SO ₃ ^-, RCO ₂ ^-, F ₃ CCO ₂ ^-, (RO) CO ₂ ^-, ClO ₃ ^-, ClO ₄ ^-, NO ₂ ^-, NO ₃ ^-, F ^-, Cl ^-, Br ^- and I ^-.

G is not present in a particular embodiment (m = 0), in one alternative embodiment exactly once (m = 1).

If G is not present, negatively charged (anionic) ligands can be used for X, i. H. then the part of the compound in the square brackets in formula A is a neutral metal complex.

But if G is present then only the neutral ligands can be chosen for X, i. H. then the part of the compound in the square brackets in formula A is a simply positively charged (cationic) metal complex.

The groups R partially contained in the counterion G are selectable from the quantity defined below.

• – die Alkylgruppen unverzweigt, verzweigt und/oder substituiert sein können und insbesondere einer Kettenlänge von C1 bis C12 aufweisen;
• – die Cycloalkyl-, Aryl- oder Heteroarylgruppen insbesondere bis zu 12 C-Atome aufweisen können, wobei die Cycloalkyl-, Aryl- oder Heteroarylgruppen jeweils substituiert, insbesondere mit Alkylgruppen substituiert sein können, die insbesondere eine Kettenlänge von C1 bis C12 aufweisen.

R: R is selected from the group consisting of alkyl (saturated or unsaturated), cycloalkyl, aryl or heteroaryl groups, wherein

• - The alkyl groups may be unbranched, branched and / or substituted and in particular have a chain length of C1 to C12;
• - The cycloalkyl, aryl or heteroaryl groups may in particular have up to 12 carbon atoms, wherein the cycloalkyl, aryl or heteroaryl groups in each case substituted, in particular may be substituted with alkyl groups which have in particular a chain length of C1 to C12.

In one embodiment, R is selected from the group consisting of: methyl, trifluoromethyl, ethyl, propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neo Pentyl, iso-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl , p-toluyl, 2-naphthyl, mesityl, pentafluorophenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl and thiophen-2-yl group.

R always bonds via a C atom of an alkyl, cycloalkyl, aryl or heteroaryl group.

R in G, X, L ¹ , L ² , ..., L ⁹ and Z are independently selected. For example, in BR ₄ ^- for G, the R may be replaced by a phenyl group (Ph) and in RCN for X by a methyl group (Me), resulting in BPh ₄ ^- and MeCN.

If R is contained several times in G, X, L ¹ , L ² , ..., L ⁹ or Z (for example, three times in NR ₃ ), in one embodiment identical groups are always selected (eg NEt ₃ ie with the ethyl group (Et) selected from R).

When R is multiple in G, X, L ¹ , L ² , ..., L ⁹ or Z (eg, three in NR ₃ ), in an alternative embodiment the groups are independently selected (e.g. N (Me) (Et) (n Bu), ie with the methyl, ethyl and n-butyl group selected from R).

In an alternative embodiment, the index to the counterion may be 0 <m <1, for example m = 1/2 (with a counter ion of the type 1/2 G ^2- ), m = 1/3 (with a counterion of the type 1 / 3 G ^3- ) or m = 1/4 (with a counterion of the type 1/4 G ^4- ). Examples are: 1/2 G ^2- : CO ₃ ^2- , SO ₃ ^2- , SO ₄ ^2- , S ₂ O ₃ ^2- 1/3 G ^3- : AsO ₃ ^3- , AsO ₄ ^3- , PO ₃ ^3- , PO ₄ ^3- 1/4 G ^4- : SiO ₄ ^4- .

X: The ligand X can simply be negatively charged (anionic) or neutral.

In one embodiment of the singly negatively charged ligand X is selected from the group consisting of H ^- D ^-, F ^-, Cl ^-, Br ^-, I ^-, NO ^2-, NO ^3-, (SnR ₃₎ ^-, SnCl ^{3 -,} OCN ^-, NCO ^-, (OR) ^-, (SR) ^- (Ser) ^-, (TER) ^-, SCN ^-, SeCN ^-, TeCN ^-. In this case there is no counterion G (m = 0).

In a further embodiment, the neutral ligand X is selected from the group consisting of azoaromatics (in particular pyridine, 4-phenylpyridine, 4-methylpyridine, 4-cyano-pyridine, 4-dimethylaminopyridine, pyridine-4-carboxylic acid methyl ester, N- Methylimidazole, N-phenylimidazole, N-methylpyrazole and N-phenylpyrazole), the N-heterocyclic carbenes (in particular, 1-methyl-3-methylimidazol-2-ylidene, 1-methyl-3 -phenyl-imidazol-2-ylidene and 1-phenyl-3-phenyl-imidazol-2-ylidene), tetrahydrofuran, tetrahydrothiophene, NH ₃ , NH ₂ R, NHR ₂ , NR ₃ , PH ₃ , PH ₂ R, PHR ₂ , PR ₃ , tris (2-pyridyl) phosphine (short: Tpyp or tpyp), tris (6-methyl-2-pyridyl) phosphine (short: T ^me pyp or t ^me pyp), AsH ₃ , AsH ₂ R, AsHR ₂ , AsR ₃ , SbR ₃ , OPR ₃ , SPR ₃ , SePR ₃ , R ₂ SO, SR ₂ , SeR ₂ , SC (NR ₂ ) ₂ , SeC (NR ₂ ) ₂ , RCN and RNC. These neutral ligands can only be used with existing counterion G.

The atom printed in bold at the listed ligands X binds according to the formula A via a single bond to the metal M. Even with the ligands in which no element could be printed in bold, the bond to the metal M takes place via a single bond. The pyridines bind via the N atom of the pyridine ring, the imidazoles via the free N atom of the imidazole ring, the pyrazoles via the free N atom of the pyrazole ring, the N-heterocyclic carbenes via the bivalent C Atom, tetrahydrofuran via the O atom, tetrahydrothiophene via the S atom and Tpyp and T ^me pyp via the P atom.

Z: The bridge Z is selected from the group consisting of PO, PS, PSe, As, AsO, CH, CR, C (CR _3), CF, CCF _3, CCl, CCCl _3, CBr, ccbr _3, C (I ), SiH, SiR and Si (CR ₃ ).

The bold atom binds according to the formula A via a single bond to the respective C atom of the three pyridine rings.

Q ¹ , Q ² , Q ³ : are independently H or D.

L ¹ , L ² ,..., L ⁹ : Independently selected neutral substituents, in one embodiment are selected from the group consisting of H, D, F, Cl, Br, I, R, CN, NO ₂ , OH, OR, SH, SR, NH ₂ , NHR, NR ₂ , SiR ₃ , B (OH) ₂ and B (OR) ₂ .

The bold atom binds according to the formula A via a single bond to the respective C atom of the three pyridine rings.

The compounds of the present invention have a ΔE (S ₁ -T ₁ ) value between the lowest excited singlet and underlying triplet states of less than 2000 cm ^-1 and efficient spin-orbit coupling which has a short radiative emission lifetime of the lowest excited triplet state. Due to the small energy difference .DELTA.E (S ₁ -T ₁ ), a thermal reoccupation of the S ₁ state from the T ₁ state according to a Boltzmann distribution or according to the thermal energy k _B T is possible. As a result, a temperature-dependent thermal equilibrium sets in. This can be a thermally activated light emission from the S ₁ state. In addition, an efficient spin-orbit coupling enables the direct emission path from the lowest excited triplet state. Thus, the emission paths from the triplet state and the singlet state are available for the light emission.

This mechanism of combined triplet and singlet emission results in the effect referred to as improved singlet harvesting. This effect is more pronounced the smaller the energy difference ΔE (S ₁ -T ₁ ) and the more effective the spin-orbit coupling is. Therefore, emitters are preferred which have a ΔE (S ₁ -T ₁ ) value between the lowest excited singlet and the underlying triplet state of less than 2000 cm ^-1 , preferably less than 1000 cm ^-1 and more preferably of less than 300 cm ^-1 and a triplet lifetime of less than 100 microseconds, preferably less than 50 microseconds, more preferably less than 20 microseconds and more preferably less than 5 microseconds.

The average emission lifetime τ _{therm of} an emitter as a function of the temperature T can be approximately expressed by the following equation:

Here, τ (T ₁ ) is the phosphorescence lifetime of the lowest excited triplet state, τ (S ₁ ) is the prompt fluorescence lifetime of the lowest excited singlet state (for this consideration, it is assumed that τ (T ₁ ) and τ (S ₁ ) are temperature independent are). τ _therm is the mean emission _lifetime determined by emissions from states T ₁ and S ₁ (see 1 ). The other sizes have been defined above.

Equation 1 will be explained by a numerical example. For an assumed energy difference of ΔE (S ₁ - T ₁ ) = 500 cm ^-1 and an assumed decay time of the fluorescing S ₁ state of 500 ns and an assumed decay time of the phosphorescent T ₁ state of 10 μs, a (thermalized) Emission decay time (of the two states) at ambient temperature (300 K) of τ _therm ≈ 6 μs. This decay time is shorter than that of the known mononuclear Cu (I) -based singlet emitters, which show only the TADF effect. On the other hand, if in this example the emission is limited only to the singlet emission, that is, if one takes a value of z for the triplet lifetime. B. 500 μs, which is realistic in the case of a non-efficient spin-orbit coupling (see. R. Czerwieniec, J. Yu, H. Yersin, Inorg. Chem., 2011, 50, 8293 ), one obtains an emission decay time at 300 K of τ _therm ≈ 17 μs. By shortening the phosphorescence lifetime τ (T ₁ ), the emission decay time at ambient temperature drastically decreases to about one-third in this example.

In summary, using this improved singlet harvesting method, ideally, all, i. H. a maximum of 100% of the excitons, capture and convert to light through the use of triplet and singlet emissions. In addition, the Cu (I) and Ag (I) emitters according to the invention have cooldowns which are significantly shorter than the values of other Cu (I) or Ag (I) emitters which either have only one triplet or only one Show TADF emission. Therefore, the use according to the invention of corresponding emitters is particularly suitable for opto-electronic components.

Metal complex compounds according to the invention are characterized by the use of Cu (I) or Ag (I) central ions, the resulting neutral or cationic Cu (I) or Ag (I) complexes being mononuclear and the lowest excited electronic states being a distinct metal have to-ligand charge transfer (MLCT) character, ie, the states of the complexes have a pronounced HOMO content predominantly in the region of the d-orbitals of the central ion and a LUMO portion predominantly a π * orbital of the tripod ligand, which is a ligand bound via its three N-atoms by single bonds to the central ion.

The synthesis of the Cu (I) compounds of formula A can be subdivided into two production processes. To prepare the cationic Cu (I) complexes (m = 1), a copper salt with a weakly coordinating counterion, for example [Cu (MeCN) ₄ PF ₆ ] or [Cu (MeCN) ₄ BF ₄ ], with a tripod ligand and a neutral ligand. If no suitable copper salts are available, the reaction can proceed via an anion exchange reaction. To prepare neutral Cu (I) complexes (m = 0), the tripod ligand is reacted with a suitable copper salt, for example CuCl, CuBr or CuI.

In a further aspect, the invention relates to the use of metal complex compounds of the type described herein in an optoelectronic device, in particular for the emission of light.

In this case, an emitter layer in an optoelectronic device can have a metal complex compound according to the invention, the concentrations of the compound in the emitter layer in one embodiment being from 2% by weight to 100% by weight.

In a further aspect, the invention relates to an opto-electronic device comprising a metal complex compound according to the invention.

In one embodiment of such a device, the proportion of the metal complex compound in an emitter layer or absorber layer is 2% by weight to 100% by weight, preferably 20% by weight to 80% by weight, based on the total weight of the emitter layer or the absorber layer ,

Said opto-electronic device is selected from the group consisting of: organic light-emitting diodes (OLEDs), light-emitting electrochemical cells (LEECs), OLED sensors, in particular in non-hermetically shielded gas and vapor sensors, organic solar cells (organic solar cells, organic photovoltaics, OPVs), organic field effect transistors, organic lasers, organic diodes, organic photodiodes and "down conversion" systems for converting UV radiation into visible light or for converting Light of a shorter wavelength in light of a longer wavelength.

In a further aspect, the invention relates to a method for producing an optoelectronic device, wherein a metal complex compound according to the invention is used, wherein the compound is applied in particular wet-chemically, by means of colloidal suspension or by sublimation on a solid support.

In a further aspect, the invention relates to a method for producing light of a particular wavelength, comprising the step of providing a metal complex compound of the type described herein. The metal complex compounds of the invention in particular allow the generation of light, for example blue, green, yellow, red color.

characters

1 Energy Level Scheme to Illustrate the Triplet and Singlet Harvesting Effects. τ (T ₁ ): triplet lifetime; τ (S ₁ ): singlet lifetime; τ _therm : mean (thermalized) emission lifetime; ISC: Intersystem Crossing; SOC: spin-orbit coupling (= spin-orbit coupling, SBK); ΔE (S ₁ - T ₁ ): singlet-triplet distance. k _B is the Boltzmann constant.

2 : Temperature dependence of the emission lifetime of [Cu (AsPh ₃ ) tpypo] PF ₆ (Example Compound 1). The solid line shows a fit according to equation 1. The following fit values result: τ (S ₁ ) = 300 ns, ΔE (S ₁ -T ₁ ) = 800 cm ^-1 .

3 : Frontier orbitals of [Cu (AsPh ₃ ) tpypo] PF ₆ (Example Compound 1), the HOMO (top) and the LUMO (bottom). The TD-DFT calculations performed for this compound clearly show the appearance of the charge transfer transition required to achieve a small ΔE (S ₁ -T ₁ ) energy difference.

4 : Emission spectrum (top) and molecular structure resulting from a crystal structure determination (bottom) of [Cu (AsPh ₃ ) tpypo] PF ₆ (Example Compound 1). The molecular structure also shows the negatively charged PF ₆ counterion.

5 : Emission spectrum (top) and molecular structure resulting from a crystal structure determination (bottom) of [Cu (PPh ₃ ) tpypo] PF ₆ (Example Compound 2). The molecular structure also shows the negatively charged PF ₆ counterion.

6 : Emission spectrum (top) and molecular structure resulting from a crystal structure determination (below) of [Cu (PPh ₃ ) tpym] PF ₆ (Example Compound 3). The molecular structure also shows the negatively charged PF ₆ counterion.

7 : Emission spectrum (top) and molecular structure resulting from a crystal structure determination (bottom) of [Cu (AsPh ₃ ) tpym] PF ₆ (Example Compound 4). The molecular structure also shows the negatively charged PF ₆ counterion.

8th : Emission spectrum (top) and molecular structure resulting from a crystal structure determination (bottom) of [Cu (PnBu ₃ ) tpym] PF ₆ (Example Compound 5). The molecular structure also shows the negatively charged PF ₆ counterion.

9 : Emission spectrum (top) and molecular structure resulting from a crystal structure determination (bottom) of [Cu (PPh ₃ ) tpym] BF ₄ (Example Compound 6). The molecular structure also shows the negatively charged BF ₄ counterion.

10 : Emission spectrum (top) and molecular structure resulting from a crystal structure determination (bottom) of [Cu (PPh ₃ ) tpym] BPh ₄ (Example Compound 10). The molecular structure also shows the negatively charged BPh ₄ counterion.

11 : Emission spectrum (top) and molecular structure resulting from a crystal structure determination (bottom) of [CuCl (tpypo)] (example compound 13).

12 : Emission spectrum (top) and molecular structure resulting from a crystal structure determination (bottom) of [CuBr (tpypo)] (Example Compound 14).

13 : Emission spectrum (top) and molecular structure resulting from a crystal structure determination (bottom) of [CuI (tpypo)] (Example Compound 15).

14 : Molecular structure resulting from a crystal structure determination of [CuCl (tpyps)] (Example Compound 16).

15 : Molecular structure resulting from a crystal structure determination of [CuBr (tpyps)] (Example 17).

16 : Emission spectrum (top) and molecular structure resulting from a crystal structure determination (bottom) of [CuI (tpyps)] (Example Compound 18).

17 : Emission spectrum (top) and molecular structure resulting from a crystal structure determination (bottom) of [CuI (tpypse)] (Example Compound 19).

18 : Emission spectrum (top) and molecular structure resulting from a crystal structure determination (bottom) of [CuI (tpyaso)] (Example Compound 20).

19 : Emission spectrum (top) and molecular structure resulting from a crystal structure determination (bottom) of [CuI (tpym)] (example compound 21).

Examples

The invention relates to the provision and provision of novel light-emitting metal complex compounds. These new compounds are characterized in particular by the following special properties: Relatively short emission life of only a few microseconds, high Emission quantum yields, singlet-triplet distance less than 1500 cm ^-1 , triplet radiative lifetime less than 100 μs, singlet radiative lifetime less than 500 ns, triplet state emission greater than 3%.

In the following, examples are given with the tripod ligands according to formula A shown here

The synthetic instructions for these tripod ligands are summarized below.

General Synthesis and Analysis for the Cationic Cu (I) Complexes of Formula A (m = 1) for Examples 1, 2, 3, 4, 5, 6, 7, 8 and 9

Numbering of the illustrated cationic metal complexes for better assignment of the ¹ H and ¹³ C signals in the NMR (nuclear magnetic resonance) spectrum:

General Synthesis Instructions

The syntheses described here were carried out with dried and degassed solvents in a protective gas atmosphere. The copper salt [Cu (MeCN) ₄ ] PF ₆ or [Cu (MeCN) ₄ ] BF ₄ was dissolved in MeCN and the reaction solution with tris (2-pyridyl) phosphine oxide (tpypo), tris (2-pyridyl) methane (tpym ) or tris (2-pyridyl) arsine (tpyas). After stirring for 10 minutes, the phosphine (PPh ₃ , PnBu ₃ ), phosphine oxide (OPPh ₃ ) and arsine (AsPh ₃ ) were added to the clear solution. After stirring at room temperature for 1 day, the reaction solution was completely concentrated. The residue was digested twice with about 10 mL Et ₂ O and then dried under a fine vacuum. Single crystals could be obtained from a saturated solution of the product in chloroform by overlaying with n-pentane. Example 1: [Cu (AsPh ₃ ) tpypo] PF ₆

Synthesis and chemical characterization:

cm^–1: 2017 (w), 1581 (m), 1483 (w), 1453 (w), 1433 (m), 1315 (w), 1285 (w), 1250 (w), 1226 (m), 1187 (w), 1168 (w), 1168 (m), 1150 (w), 1132 (w), 1088 (w), 1078 (w), 1052 (w), 1005 (m), 926 (w), 873 (m), 828 (ss), 772 (s), 745 (ss), 698 (s), 670 (w), 638 (w), 616 (w), 543 (ss), 477 (s), 454 (m), 437 (w), 409 (m). ATR: attenuated total reflection, abgeschwächte Totalreflexion, IR: infra-red, infrarot. Prepared from [Cu (MeCN) ₄ ] PF ₆ (67 mg, 0.18 mmol, 1.0 eq), tpypo (50 mg, 0.18 mmol, 1.0 eq) and AsPh ₃ (55 mg, 0.18 mmol, 1.0 eq) in MeCN (5 mL); gray powder. Yield: quantitative. Elemental analysis: C 49.87, H 3.40, N 5.31% (for C ₃₃ H ₂₇ AsCuF ₆ N ₃ OP ₂ , expected is C 49.79, H 3.42, N 5.28%). ¹ H-NMR (300.1 MHz, CD ₃ CN): δ (ppm) = 8.58-8.69 (m, 3H, H 6), 8.41 (dd, 3H, H ³ ), 8.13 (dddd, ³ J ₄₃ = 7.8 Hz, ³ J ₄₅ = 7.8 Hz, ⁴ J _4P = 3.7 Hz, ⁴ J ₄₆ = 1.4 Hz, 3H, H4), 7.55-7.65 (m, 3H H5), 7.35-7.52 (m, 15H, PPh ₃ ). ¹³ C-NMR (75.5 MHz, CD ₃ CN): δ (ppm) = 152.5 (d, ³ J _CP = 13.6 Hz, C6), 151.7 (d, ¹ J _CP = 125.1 Hz, C 2), 139.8 (d, ³ J _CP = 9.6 Hz, C4), 134.3 (s, C8), 130.6 (d, ² J _CP = 17.4 Hz, C3), 130.5 (s, C7), 130.5 (s, C10), 130.2 (s, C9 ), 128.4 (d, ⁴ J _CP = 2.4 Hz, C5). ³¹ P NMR (101.25 MHz, CD ₃ CN): δ (ppm) = -8.39 (s, tpypo), -142.94 (sec, ¹ J _PF = 707 Hz, PF ₆ ^- ). IR (ATR)

cm ^-1 : 2017 (w), 1581 (m), 1483 (w), 1453 (w), 1433 (m), 1315 (w), 1285 (w), 1250 (w), 1226 (m), 1187 (w), 1168 (w), 1168 (m), 1150 (w), 1132 (w), 1088 (w), 1078 (w), 1052 (w), 1005 (m), 926 (w), 873 (m), 828 (ss), 772 (s), 745 (ss), 698 (s), 670 (w), 638 (w), 616 (w), 543 (ss), 477 (s), 454 (m), 437 (w), 409 (m). ATR: attenuated total reflection, attenuated total reflection, IR: infra-red, infrared.

The compound according to Example 1 has an extremely high quantum efficiency of Φ _PL = 75% at room temperature and a short emission decay time of τ = 13 μs. In addition, the emission maximum at λ _max = 470 nm in the blue spectral range. These properties make the connection very attractive for use in optoelectronic, in particular electroluminescent devices.

An investigation of the temperature dependence of the emission lifetime ( 2 ) shows that at low temperature it is τ (77 K) = 20 μs. As the temperature increases, it decreases and amounts to τ (300 K) = 13 μs at room temperature. At the same time, a blue shift of the emission spectrum from λ _max (77 K) = 480 nm to λ _max (300 K) = 470 nm is observed. Both effects, the shortening of the emission lifetime and the blue shift due to temperature increase, show the occurrence of the TADF effect, as explained below: At low temperature, only one phosphorescence from the lowest energy triplet state T _{1 is} observed. By increasing the temperature, a thermal occupation of the energetically only slightly higher singlet state S _{1 is} possible. Since the transition from S ₁ to the S ₀ ground state is much more permissible than the T ₁ → S ₀ transition, a significant reduction in the emission decay time takes place. In addition, a blue shift is observed, since the S ₁ state is higher in energy than the T ₁ state. This mechanism thus corresponds to a thermally activated delayed fluorescence (TADF). From the measurement of the temperature dependence of the emission lifetime ( 2 ), the energetic splitting ΔE (S ₁ -T ₁ ) between the excited singlet S ₁ and the triplet T ₁ state can be determined from equation (1).

For the energetic splitting there is thus a value of ΔE (S ₁ - T ₁ ) = 800 cm ^-1 , for the decay time of the S ₁ state (prompt fluorescence) τ (S ₁ ) = 300 ns and for the decay time of T ₁ State τ (T ₁ ) = 20 μs. The energetic splitting between S ₁ and T ₁ state of the Cu (I) compound described here is thus small in comparison to other transition metal complexes (Ir (III), Pt (II)), in which this splitting partly significantly larger than 3000 cm ^-1 is. (see. Yersin et al., Top. Curr. Chem. 2001, 214, 81 ; Hill et al., Inorg. Chem. 1996, 35, 4585 ). A consideration of the molecular orbitals ( 3 ) explains the small value found. The highest occupied molecular orbital (HOMO) lies mostly at the Cu (I) center, whereas the lowest unoccupied molecular orbital (LUMO) lies on the tpypo ligand. The small spatial overlap of both molecular orbitals results in a small exchange integral and thus a small singlet-triplet splitting.

Surprisingly, the triplet decay time of the present Cu (I) compound is τ (T ₁ ) = 20 μs compared to other Cu (I) compounds (eg, longer than 400 μs, cf. Leitl et al., J. Phys. Chem. A 2013, 117, 11823 ; Czerwieniec et al., Inorg. Chem. 2011, 50, 8293 ) very short. Thus, at room temperature, emission occurs not only from the S ₁ state, as with other Cu (I) compounds, but from both the S ₁ and T ₁ states. With reference to equation (2), the emission components of S ₁ and T _{1 can} be determined more accurately (cf. Leitl et al., J. Phys. Chem. A 2013, 117, 11823 ).

Here, I (S ₁ ) and I (T ₁ ) are the intensity components which are emitted from the S ₁ or T ₁ state, Φ _PL (S ₁ ) and Φ _PL (T ₁ ), the emission quantum yields of S ₁ and T ₁ state, τ (T ₁ ) and τ (S ₁ ) the emission decay times of the S ₁ or T ₁ state, ΔE (S ₁ - T ₁ ) the energetic splitting between S ₁ and T ₁ state, T the Temperature and k _B the Boltzmann constant.

It turns out that the emission occurs at room temperature to about 70% from the T ₁ state and about 30% from the S ₁ state. Thus, the emission mechanism, using phosphorescence and TADF, allows a significant reduction in the emission decay time from 20 μs (pure phosphorescence) or 37 μs (pure TADF) to 13 μs (phosphorescence and TADF). Thus, there is a significant improvement in the singlet harvesting effect based on only one TADF emission.

The zero field splitting for this Cu (I) compound is 10 cm ^-1 . Photophysical Data for Example 1 [Cu (AsPh ₃ ) tpypo] PF ₆ (Powder Data) Temp. [K] λ _max [nm] τ [μs] Φ _PL [%] k _r [10 ⁴ s ^-1] k _nr [10 ⁴ s ^-1 ] 300 470 13 75 5.8 1.9 77 480 20 85 4.3 0.8

The named compound has a particularly high quantum efficiency Φ _PL and short emission decay times. In addition, the compound emits in the blue spectral range. The emission of the compound is composed at room temperature of a phosphorescence (70%) and a TADF (30%). Thus, this compound shows improved singlet harvesting performance. The emission spectrum and the molecular structure are in 4 shown. Example 2: [Cu (PPh ₃ ) tpypo] PF ₆

Synthesis and characterization

cm^–1: 1783 (w), 1580 (w), 1482 (w), 1435 (m), 1285 (w), 1228 (m), 1153 (w), 1092 (m), 10512 (w), 1004 (w), 828 (ss), 747 (s), 698 (s), 639 (w), 543 (ss), 508 (s), 460 (m), 420 (m). Photophysikalische Daten für Beispiel 2 [Cu(PPh₃)tpypo]PF₆ (Pulverdaten) Temp. [K] λ_max [nm] τ [µs] Φ_PL [%] k_r [10⁴s^–1] k_nr [10⁴s^–1] 300 475 13 53 4.1 3.6 77 485 22 60 2.7 1.8 Prepared from [Cu (MeCN) ₄ ] PF ₆ (67 mg, 0.18 mmol, 1.0 eq), tpypo (50 mg, 0.18 mmol, 1.0 eq) and PPh ₃ (47 mg, 0.18 mmol, 1.0 eq) in MeCN (5 mL); pale yellow powder. Yield: quantitative. Elemental analysis: C 52.94, H 3.64, N 5.33% (for C ₃₃ H ₂₇ CuF ₆ N ₃ OP ₃ , expected is C 52.70, H 3.62, N 5.59%). ¹ H-NMR (300.1 MHz, CD ₃ CN): δ (ppm) = 8.44 (ddd, ³ J ₃₄ = 7.8 Hz, ³ J ³ _P = 6.9 Hz, 3H, H ³ ), 8.34 (d, ³ J ₆₅ = 4.7 Hz, 3H, H6), 8.13 (dddd, ³ J ₄₃ = 7.8 Hz, ³ J ₄₅ = 7.8 Hz, ⁴ J _4P = 3.7 Hz, ⁴ J ₄₆ = 1.6 Hz, 3H, H4), 7.52-7-77 (m, 9H, PPh ₃ ), 7:41 to 7:52 (m, 9H, PPh ₃ + H5). ¹³ C-NMR (75.5 MHz, CD ₃ CN): δ (ppm) = 153.1 (d, ³ J _CP = 13.3 Hz, C6), 151.6 (d, ¹ J _CP = 127.3 Hz, C2), 140.1 (d, ³ J _CP = 9.5 Hz, C4), 134.6 (d, ² J _CP = 16.0 Hz, C8), 133.4 (d, ¹ J _CP = 35.9 Hz, C7), 131.9 (d, ⁴ J _CP = 1.3 Hz, C10 ), 130.6 (d, ² J _CP = 17.6 Hz, C3), 130.4 (d, ³ J _CP = 10.1 Hz, C9), 128.5 (d, ⁴ J _CP = 2.8 Hz, C5). ³¹ P-NMR (101.25 MHz, CD ₃ CN): δ (ppm) = -2.00-10.00 (bs, PPh ₃ ), -7.50 (s, tpypo), -142.94 (sept, ¹ J _PF = 706 Hz, PF ₆ ^- ). IR (ATR)

cm ^-1 : 1783 (w), 1580 (w), 1482 (w), 1435 (m), 1285 (w), 1228 (m), 1153 (w), 1092 (m), 10512 (w), 1004 (w), 828 (ss), 747 (s), 698 (s), 639 (w), 543 (ss), 508 (s), 460 (m), 420 (m). Photophysical Data for Example 2 [Cu (PPh ₃ ) tpypo] PF ₆ (Powder Data) Temp. [K] λ _max [nm] τ [μs] Φ _PL [%] k _r [10 ⁴ s ^-1 ] k _nr [10 ⁴ s ^-1 ] 300 475 13 53 4.1 3.6 77 485 22 60 2.7 1.8

The compound shows very high quantum efficiency and short emission decay times. In addition, the compound emits in the blue spectral range. The emission of the compound is composed at room temperature in approximately equal parts of a phosphorescence and a TADF. Thus, this compound shows improved singlet harvesting performance. The zero field splitting is greater than 5 cm ^-1 . The emission spectrum and the molecular structure are in 5 shown. Example 3: [Cu (PPh ₃ ) tpym] PF ₆

Synthesis and characterization

cm^–1: 1597 (m), 1573 (w), 1473 (w), 1438 (m), 1351 (w), 1305 (w), 1161 (w), 1161 (w), 1096 (w), 1059 (w), 1018 (w), 910 (w), 834 (ss), 783 (m), 750 (m), 696 (m), 648 (w), 619 (m), 556 (m), 529 (m), 501 (m), 423 (m). Photophysikalische Daten für Beispiel 3 [Cu(PPh₃)tpym]PF₆ (Pulverdaten) Temp. [K] λ_max [nm] τ [µs] Φ_PL [%] 300 465 14 43 77 475 26 Prepared from [Cu (MeCN) ₄ ] PF ₆ (75 mg, 0.20 mmol, 1.0 eq), tpym (50 mg, 0.20 mmol, 1.0 eq) and PPh ₃ (53 mg, 0.20 mmol, 1.0 eq) in MeCN (8 mL); gray powder. Yield: quantitative. Elemental analysis: C 56.46, H 3.84, N 5.68% (for C ₃₄ H ₂₈ CuF ₆ N ₃ P ₂ , expected is C 56.87, H 3.93, N 5.85%). ¹ H-NMR (300.1 MHz, CDCl ₃ ): δ (ppm) = 8.15 (d, ³ J ₃₄ = 7.8 Hz, 3H, H ₃ ), 8.08 (dd, ³ J ₆₅ = 5.1 Hz, ⁴ J ₆₄ = 1.0 Hz , 3H, H6), 7.82 (ddd, ³ J ₄₃ = 7.8 Hz, ³ J ₄₅ = 7.8 Hz, ⁴ J ₄₆ = 1.8 Hz, 3H, H4), 7.42-7.64 (m, 15H, PPh ₃ ), 7.15 ( ddd, ³ J ₅₄ = 7.8 Hz, ³ J ₅₆ = 5.1 Hz, ⁴ J ₅₃ = 1.1 Hz, 3H, H5), 6.46 (s, 1H, H11). ¹³ C-NMR (75.5 MHz, CDCl _3): δ (ppm) = 155.1 (s, C2), 149.7 (s, C6), 139.6 (s, C4), 133.7 (d, ² J _CP = 16.2 Hz, C8 ), 133.0 (d, ¹ J _CP = 36.4 Hz, C7), 130.9 (d, ⁴ J _CP = 1.2 Hz, C10), 129.5 (d, ³ J _CP = 9.9 Hz, C9), 127.2 (s, C3) , 123.6 (s, C5), 57.6 (s, C11). ³¹ P-NMR (101.25 MHz, CDCl _3): δ (ppm) = 3:00 to 8:00 (bs, PPh _3), -143.52 (sept, ¹ J = 713 Hz _PF, PF ₆ ^-). IR (ATR)

cm ^-1 : 1597 (m), 1573 (w), 1473 (w), 1438 (m), 1351 (w), 1305 (w), 1161 (w), 1161 (w), 1096 (w), 1059 (w), 1018 (w), 910 (w), 834 (ss), 783 (m), 750 (m), 696 (m), 648 (w), 619 (m), 556 (m), 529 (m), 501 (m), 423 (m). Photophysical Data for Example 3 [Cu (PPh ₃ ) tpym] PF ₆ (Powder Data) Temp. [K] λ _max [nm] τ [μs] Φ _PL [%] 300 465 14 43 77 475 26

The compound described here has a high quantum efficiency and short emission decay times. In addition, the compound shows an emission in the deep blue spectral range. The emission of the compound is composed at room temperature in approximately equal parts of a phosphorescence and a TADF. The zero-field splitting is greater than 5 cm ^-1. The emission spectrum and the molecular structure are in 6 displayed. Example 4: [Cu (AsPh ₃ ) tpym] PF ₆

Synthesis and chemical characterization:

cm^–1: 1597 (w), 1473 (w), 1438 (m), 1349 (w), 1161 (w), 1079 (w), 1018 (w), 911 (w), 834 (ss), 782 (m), 738 (m), 693 (m), 649 (w), 618 (m), 555 (m), 465 (m), 419 (w). Photophysikalische Daten für Beispiel 4 [Cu(AsPh₃)tpym]PF₆ (Pulverdaten) Temp. [K] λ_max [nm] τ [µs] Φ_PL [%] k_r [10⁴s^–1] k_nr [10⁴s^–1] 300 460 12 41 3.4 4.9 77 465 21 63 3.0 1.8 Prepared from [Cu (MeCN) ₄ ] PF ₆ (75 mg, 0.20 mmol, 1.0 eq), tpym (50 mg, 0.20 mmol, 1.0 eq) and AsPh ₃ (62 mg, 0.20 mmol, 1.0 eq) in MeCN (8 mL); gray powder. Yield: quantitative. Elemental analysis: C 53.26, H 3.62, N 5.16% (for C ₃₄ H ₂₈ AsCuF ₆ N ₃ P, expected is C 53.59, H 3.70, N 5.51%). ¹ H-NMR (300.1 MHz, CD ₃ CN): δ (ppm) = 8.38 (d, ³ J ₆₅ = 4.9 Hz, 3H, H 6), 7.82-8.00 (m, 6H, H 3 / H 4), 7.40-7.60 (m, 15H, PPh ₃ ), 7.30 (ddd, 3H, ³ J ₅₆ = 5.1 Hz, ⁴ J ₅₃ = 1.7 Hz, H5), 6.18 (s, 1H, H11). ¹³ C-NMR (75.5 MHz, CD ₃ CN): δ (ppm) = 155.4 (s, C2), 151.2 (s, C6), 140.5 (s, C4), 137.0 (s, C7), 134.1 (s, C8), 130.9 (s, C10), 130.3 (s, C9), 127.0 (s, C3), 124.8 (s, C5), 58.6 (s, C11). ³¹ P NMR (101.25 MHz, CD ₃ CN): δ (ppm) = -139.09 (sec, ¹ J _PF = 707 Hz, PF ₆ ^- ). IR (ATR)

cm ^-1 : 1597 (w), 1473 (w), 1438 (m), 1349 (w), 1161 (w), 1079 (w), 1018 (w), 911 (w), 834 (ss), 782 (m), 738 (m), 693 (m), 649 (w), 618 (m), 555 (m), 465 (m), 419 (w). Photophysical Data for Example 4 [Cu (AsPh ₃ ) tpym] PF ₆ (Powder Data) Temp. [K] λ _max [nm] τ [μs] Φ _PL [%] k _r [10 ⁴ s ^-1 ] k _nr [10 ⁴ s ^-1 ] 300 460 12 41 3.4 4.9 77 465 21 63 3.0 1.8

This compound has an intense emission in the deep blue spectral range. At the same time, it shows short emission decay times. The emission of the compound is composed at room temperature in approximately equal parts of a phosphorescence and a TADF. The zero field splitting is greater than 5 cm ^-1 . The emission spectrum and the molecular structure are 7 in the picture. Example 5: [Cu (PnBu ₃ ) tpym] PF ₆

Synthesis and chemical characterization:

cm^–1: 1596 (s), 1574 (s), 1530 (s), 1481 (s), 1469 (s), 1437 (s), 1407 (s), 1330 (s), 1232 (s), 1095 (s), 1057 (s), 1013 (s), 998 (s), 907 (s), 876 (s), 836 (s), 779 (s), 755 (s), 739 (s), 689 (s), 646 (s), 618 (s), 557 (s), 528 (s), 505 (s), 467 (s), 451 (s), 438 (s), 422 (s), 397 (s). Photophysikalische Daten für Beispiel 5 [Cu(PnBu₃)tpym]PF₆ (Pulverdaten) Temp. [K] λ_max [nm] τ [µs] Φ_PL [%] 300 510 12 67 77 500 30 Prepared from [Cu (MeCN) ₄ ] PF ₆ (113 mg, 0.30 mmol, 1.0 eq), tpym (75 mg, 0.30 mmol, 1.0 eq) and PnBu ₃ (1.0 mL, 0.41 mmol, 1.4 eq) in MeCN (7 mL); pale yellow powder. Yield: quantitative. Elemental analysis: C 51.57, H 6.22, N 6.42% (for C ₂₈ H ₄₀ CuF ₆ N ₃ P ₂ , expected C 51.10, H 6.13, N 6.38%). ¹ H-NMR (500.1 MHz, CD ₃ CN): δ (ppm) = 8.60 (dd, ³ J ₆₅ = 5.1 Hz, ⁴ J ₆₄ = 0.8 Hz, 3H, H 6), 7.92 (ddd, ³ J ₄₃ = 7.7 Hz, ³ J ₄₅ = 7.7 Hz, ⁴ J ₄₆ = 1.7 Hz, 3H, H4), 7.83 (d, ³ J ₃₄ = 7.7 Hz, 3H, H3), 7.40 (ddd, ³ J ₅₄ = 7.6 Hz, ³ J ₅₆ = 5.1 Hz, ⁴ J ₅₃ = 1.1 Hz, 3H, H5), 6.10 (s, 1H, H11), 1.85-1.93 (m, 6H, C7), 1.59-1.70 (m, 6H, C8), 1.43- 1.53 (m, 6H, C9), 0.89 (t, ³ J ₁₀₉ = 7.3 Hz, 9H, C10). ¹³ C-NMR (75.5 MHz, CD ₃ CN): δ (ppm) = 155.6 (s, C2), 151.6 (s, C6), 140.4 (s, C4), 126.7 (s, C3), 124.7 (s, C5), 58.8 (s, C11), 28.5 (d, ² J _CP = 5.3 Hz, C8), 26.9 (d, ¹ J _CP = 21.7 Hz, C7), 25.0 (d, ³ J _CP = 13.6 Hz, C9 ), 14.0 (s, C10). ³¹ P-NMR (101.25 MHz, CD ₃ CN): δ (ppm) = -4.00--12.00 (bs, P ⁿ Bu ₃ ), -140.74 (sept, ¹ J _PF = 706 Hz, PF ₆ ^- ). IR (ATR)

cm ^-1 : 1596 (s), 1574 (s), 1530 (s), 1481 (s), 1469 (s), 1437 (s), 1407 (s), 1330 (s), 1232 (s), 1095 (s), 1057 (s), 1013 (s), 998 (s), 907 (s), 876 (s), 836 (s), 779 (s), 755 (s), 739 (s), 689 (s), 646 (s), 618 (s), 557 (s), 528 (s), 505 (s), 467 (s), 451 (s), 438 (s), 422 (s), 397 (s). Photophysical Data for Example 5 [Cu (PnBu ₃ ) tpym] PF ₆ (Powder Data) Temp. [K] λ _max [nm] τ [μs] Φ _PL [%] 300 510 12 67 77 500 30

This compound has an intense emission with high emission quantum yield in the blue-green spectral range. At the same time, the substance shows short emission decay times. The emission of the compound is composed at room temperature in approximately equal parts of a phosphorescence and a TADF. The zero-field splitting is greater than 5 cm ^-1. The emission spectrum and the molecular structure are in 8th displayed. Example 6: [Cu (PPh ₃ ) tpym] BF ₄

Synthesis and chemical characterization:

cm^–1: 1597 (m), 1574 (w), 1473 (m), 1438 (m), 1355 (w), 1303 (w), 1287 (w), 1158 (w), 1097 (m), 1053 (s), 1021 (m), 1001 (m), 967 (w), 910 (w), 881 (w), 850 (w), 784 (m), 759 (m), 744 (m), 706 (m), 691 (s), 647 (m), 619 (m), 528 (s), 500 (s), 434 (w), 420 (m). Photophysikalische Daten für Beispiel 6 [Cu(PPh₃)tpym]BF₄ (Pulverdaten) Temp. [K] λ_max [nm] τ [µs] Φ_PL [%] 300 450 7 19 77 460 19 Prepared from [Cu (MeCN) ₄ ] BF ₄ (64 mg, 0.20 mmol, 1.0 eq), tpym (50 mg, 0.20 mmol, 1.0 eq) and PPh ₃ (53 mg, 0.20 mmol, 1.0 eq) in MeCN (8 mL); beige powder. Yield: quantitative. Elemental analysis: C 60.60, H 4.41, N 6.40% (for C ₃₄ H ₂₈ BCuF ₄ N ₃ P, expected C 61.88, H 4.28, N 6.37%). ¹ H-NMR (300.1 MHz, CD ₃ CN): δ (ppm) = 8.18-8.23 (m, 3H, H 6), 7.85-7.97 (m, 6H, H ₃ / H 4), 7.40-7.70 (m, 15H, PPh ₃ ), 7.25 (ddd, ³ J ₅₄ = 7.5 Hz, ³ J ₅₆ = 5.1 Hz, ⁴ J ₅₃ = 1.4 Hz, 3H, H5), 6.21 (s, 1H, H11). ¹³ C-NMR (75.5 MHz, CD ₃ CN): δ (ppm) = 155.5 (s, C2), 151.3 (s, C6), 140.6 (s, C4), 134.5 (d, ² J _CP = 16.2 Hz, C8), 134.1 (d, ¹ J _CP = 36.8 Hz, C7), 131.6 (d, ⁴ J _CP = 1.2 Hz, C10), 130.3 (d, ³ J _CP = 9.9 Hz, C9), 126.9 (s, C3 ), 124.8 (s, C5), 58.6 (s, C11). ¹⁹ F-NMR (282.40 MHz, CD ₃ CN): δ (ppm) = -150.97 (s, BF ₄ ^- ). IR (ATR)

cm ^-1 : 1597 (m), 1574 (w), 1473 (m), 1438 (m), 1355 (w), 1303 (w), 1287 (w), 1158 (w), 1097 (m), 1053 (s), 1021 (m), 1001 (m), 967 (w), 910 (w), 881 (w), 850 (w), 784 (m), 759 (m), 744 (m), 706 (m), 691 (s), 647 (m), 619 (m), 528 (s), 500 (s), 434 (w), 420 (m). Photophysical Data for Example 6 [Cu (PPh ₃ ) tpym] BF ₄ (Powder Data) Temp. [K] λ _max [nm] τ [μs] Φ _PL [%] 300 450 7 19 77 460 19

This compound has an emission in the deep blue spectral range. At the same time, it shows short emission decay times. The emission of the compound is composed at room temperature in approximately equal parts of a phosphorescence and a TADF. The zero field splitting is greater than 5 cm ^-1 . The emission spectrum and the molecular structure are in 9 displayed. Example 7: [Cu (AsPh ₃ ) tpym] BF ₄

Synthesis and chemical characterization:

cm^–1: 1597 (m), 1574 (w), 1470 (w), 1440 (m), 1349 (w), 1306 (w), 1284 (w), 1181 (w), 1161 (w), 1076 (m), 1058 (m), 1022 (m), 997 (m), 911 (w), 847 (w), 783 (w), 762 (m), 741 (s), 695 (m), 672 (w), 646 (w), 620 (m), 520 (w), 505 (w), 485 (m), 468 (m), 454 (w), 422 (m), 399 (w). Prepared from [Cu (MeCN) ₄ ] BF ₄ (64 mg, 0.20 mmol, 1.0 eq), tpym (50 mg, 0.20 mmol, 1.0 eq) and AsPh ₃ (62 mg, 0.20 mmol, 1.0 eq) in MeCN (5 mL); beige powder. Yield: quantitative. Elemental analysis: C 57.43, H 3.97, N 5.99% (for C ₃₄ H ₂₈ BCuF ₄ N ₃ As, expect C 58.02, H 4.01, N 5.97%). ¹ H-NMR (300.1 MHz, CD ₃ CN): δ (ppm) = 8.40 (d, ³ J ₆₅ = 4.8 Hz, 3H, H 6), 7.84-7.96 (m, 6H, H 3 / H 4), 7.40-7.58 (m, 15H, PPh ₃ ), 7.31 (ddd, ³ J ₅₄ = 7.2 Hz, ³ J ₅₆ = 5.1 Hz, ⁴ J ₅₃ = 1.7 Hz, 3H, H5), 6.17 (s, 1H, H11). ¹³ C-NMR (75.5 MHz, CD ₃ CN): δ (ppm) = 155.4 (s, C2), 151.1 (s, C6), 140.5 (s, C4), 137.4 (s, C8), 134.2 (s, C7), 130.7 (s, C10), 130.3 (s, C9), 126.9 (s, C3), 124.8 (s, C5), 58.6 (s, C11). IR

cm ^-1 : 1597 (m), 1574 (w), 1470 (w), 1440 (m), 1349 (w), 1306 (w), 1284 (w), 1181 (w), 1161 (w), 1076 (m), 1058 (m), 1022 (m), 997 (m), 911 (w), 847 (w), 783 (w), 762 (m), 741 (s), 695 (m), 672 (w), 646 (w), 620 (m), 520 (w), 505 (w), 485 (m), 468 (m), 454 (w), 422 (m), 399 (w).

This compound shows a deep blue emission. Example 8: [Cu (OPPh ₃ ) tpypo] PF ₆

Synthesis and chemical characterization:

cm^–1: 1581 (w), 1433 (m), 1293 (w), 1232 (m), 1153 (m), 1119 (m), 1005 (w), 913 (w), 834 (ss), 781 (m), 746 (m), 724 (m), 693 (m), 641 (m), 538 (ss), 453 (m), 406 (w). Prepared from [Cu (MeCN) ₄ ] PF ₆ (67 mg, 0.18 mmol, 1.0 eq), tpypo (50 mg, 0.18 mmol, 1.0 eq) and OPPh ₃ (50 mg, 0.18 mmol, 1.0 eq) in MeCN (5 mL); pale yellow powder. Yield: quantitative. Elemental analysis: C 50.82, H 3.62, N 6.17% (for C ₃₃ H ₂₇ CuF ₆ N ₃ O ₂ P ₃ , expected is C 51.61, H 3.54, N 5.47). ¹ H-NMR (300.1 MHz, CD ₃ CN): δ (ppm) = 8.80 (ddd, ³ J ₆₅ = 4.7 Hz, ⁴ J ₆₄ = 1.4 Hz, 3H, H6), 8.36 (ddd, ³ J ₃₄ = 7.8 Hz, ³ J _3P = 6.7 Hz, 3H, H3), 8.12 (dddd, 3H, ³ J ₄₃ = 7.8 Hz, ³ J ₄₅ = 7.8 Hz, ⁴ J _4P = 3.8 Hz, ⁴ J ₄₆ = 1.6 Hz, H4) , 7.55-7.72 (m, 12H, OPPh ₃ + H5), 7:46 to 7:55 (m, 6H, OPPh _3). ¹³ C-NMR (75.5 MHz, CD ₃ CN): δ (ppm) = 151.9 (d, ³ J _CP = 13.4 Hz, C6), 151.9 (d, ¹ J _CP = 128.3 Hz, C 2), 139.6 (d, ³ J _CP = 9.6 Hz, C4), 134.2 (d, ¹ J _CP = 103.1 Hz, C7), 133.0 (d, ⁴ J _CP = 2.6 Hz, C10), 132.7 (d, ³ J _CP = 9.7 Hz, C9 ), 130.5 (d, ² J _CP = 17.6 Hz, C3), 129.6 (d, ² J _CP = 11.8 Hz, C8), 128.3 (d, ⁴ J _CP = 2.8 Hz, C5). ³¹ P NMR (101.25 MHz, CD ₃ CN): δ (ppm) = 27.75 (s, OPPh ₃ ), -9.14 (s, tpypo), -142.91 (sept, ¹ J _PF = 706 Hz, PF ₆ ^- ) , IR

cm ^-1 : 1581 (w), 1433 (m), 1293 (w), 1232 (m), 1153 (m), 1119 (m), 1005 (w), 913 (w), 834 (ss), 781 (m), 746 (m), 724 (m), 693 (m), 641 (m), 538 (ss), 453 (m), 406 (w).

This compound shows a yellow-green emission. Example 9: [Cu (AsPh ₃ ) tpyas] PF ₆

Synthesis and chemical characterization:

cm^–1: 1578 (w), 1480 (w), 1427 (m), 1279 (w), 1161 (w), 1077 (w), 1051 (w), 1008 (w), 906 (w), 832 (ss), 766 (m), 738 (s), 695 (m), 555 (m), 475 (m), 414 (w). Prepared from [Cu (MeCN) ₄ ] PF ₆ (60 mg, 0.16 mmol, 1.0 eq), tpyas (50 mg, 0.16 mmol, 1.0 eq) and AsPh ₃ (50 mg, 0.16 mmol, 1.0 eq) in MeCN (7 mL); pale yellow powder. Yield: quantitative. Elemental analysis: C 47.58, H 3.27, N 5.00% (for C ₃₃ H ₂₇ As ₂ CuF ₆ N ₃ P, expected C 48.11, H 3.30, N 5.10%). ¹ H-NMR (300.1 MHz, CD ₃ CN): δ (ppm) = 8.57 (s, 3H, H 6), 8.11 (d, ³ J ₃₄ = 7.7 Hz, 3H, H ³ ), 7.89 (ddd, ³ J ₄₃ = 7.7 Hz, ³ J ₄₅ = 7.7 Hz, ⁴ J ₄₆ = 1.6 Hz, 3H, H4), 7.34-7.55 (m, 18H, AsPh ₃ + H5). ¹³ C-NMR (75.5 MHz, CD ₃ CN): δ (ppm) = 160.0 (C2), 152.2 (C6), 138.9 (C4), 134.8 (C3), 134.3 (C8), 130.6 (C10), 130.6 ( C7), 130.3 (C9), 126.7 (C5). ³¹ P NMR (101.25 MHz, CD ₃ CN): δ (ppm) = -142.92 (sec, 1J _PF = 706 Hz, PF ₆ ^- ). IR

cm ^-1 : 1578 (w), 1480 (w), 1427 (m), 1279 (w), 1161 (w), 1077 (w), 1051 (w), 1008 (w), 906 (w), 832 (ss), 766 (m), 738 (s), 695 (m), 555 (m), 475 (m), 414 (w).

This compound shows a green-blue emission. Procedure for [Cu (PPh ₃ ) tpym] BPh ₄ of Example 10:

Numbering of the cationic Cu (I) complex and its anionic counterion for better assignment of the ¹ H and ¹³ C signals in the NMR spectrum:

Synthesis and chemical characterization:

The synthesis was carried out with dried and degassed solvents in a protective gas atmosphere. Tpym (50 mg, 0.20 mmol, 1.0 eq) was dissolved in abs. MeCN (5 mL) was dissolved and the solution was added with CuCl (20 mg, 0.20 mmol, 1.0 eq). An orange-colored solid precipitated, which was added by adding 45 mL abs. MeCN could be brought back into solution. The orange-colored reaction solution was stirred for 10 min at room temperature and then treated with NaBPh ₄ (70 mg, 0.20 mmol, 1.0 eq). It had formed a fine precipitate, which was separated after stirring for 20 min. The filtrate was added with PPh ₃ (53 mg, 0.20 mmol, 1.0 eq). After stirring for 30 minutes, the reaction solution was completely concentrated and the residue was washed twice with 20 mL abs. Et ₂ O digested. After drying in a fine vacuum, a beige-colored solid could be obtained.

cm^–1: 1594 (m), 1573 (m), 1499 (m), 1466 (m), 1435 (m), 1364 (m), 1326 (m), 1302 (m), 1264 (m), 1228 (m), 1204 (m), 1179 (m), 1158 (m), 1118 (m), 1094 (m), 1069 (m), 1031 (m), 996 (m), 955 (m), 936 (m), 843 (m), 813 (m), 801 (w), 782 (m), 744 (m), 732 (s), 706 (s), 693 (s), 645 (m), 611 (m), 542 (w), 529 (s), 494 (m), 469 (m), 439 (w), 619 (m), 406 (w). Photophysikalische Daten für Beispiel 10 [Cu(PPh₃)tpym]BPh₄ (Pulverdaten) Temp. [K] λ_max [nm] τ [µs] 300 450 5 77 465 25 Yield: 61 mg (35%). Elemental analysis: C 77.60, H 5.44, N 4.62% (for C ₅₈ H ₄₈ BCuN ₃ P, expected C 78.07, H 5.42, N 4.71%). ¹ H-NMR (500.2 MHz, CD ₃ CN): δ (ppm) = 8.20 (d, ³ J ₆₅ = 4.9 Hz, 3H, H 6), 7.81-7.90 (m, 6H, H 3 / H 4), 7.40-7.70 (m, 15H, phenyl protons of PPh ₃ ), 7.25-7.33 (m, 8H, H13), 7.21 (ddd, ³ J ₅₄ = 7.1 Hz, ³ J ₅₆ = 5.1 Hz, ⁴ J ₅₃ = 1.7 Hz, 3H, H5 ), 6.96 (t, 8H, H14), 6.81 (t, 4H, H15), 6.16 (s, 1H, H11). ¹³ C-NMR (75.5 MHz, CD ₃ CN): δ (ppm) = 164.8 (q, ¹ J _CB = 49 Hz, C12), 155.4 (s, C2), 151.4 (s, C6), 140.6 (s, C4), 136.7 (d, ² J _CB = 1.1 Hz, C13), 134.5 (d, ² J _CP = 16.7 Hz, C8), 131.6 (bs, C10), 130.2 (d, ³ J _CP = 9.7 Hz, C9 ), 126.9 (s, C3), 126.5 (q, ³ J _CB = 2.7 Hz, C14), 124.9 (s, C5), 122.7 (s, C15), 58.8 (s, C11). Note: The quaternary carbon atom C7 can not be resolved in ¹³ C NMR. IR (ATR)

cm ^-1 : 1594 (m), 1573 (m), 1499 (m), 1466 (m), 1435 (m), 1364 (m), 1326 (m), 1302 (m), 1264 (m), 1228 (m), 1204 (m), 1179 (m), 1158 (m), 1118 (m), 1094 (m), 1069 (m), 1031 (m), 996 (m), 955 (m), 936 (m), 843 (m), 813 (m), 801 (w), 782 (m), 744 (m), 732 (s), 706 (s), 693 (s), 645 (m), 611 (m), 542 (w), 529 (s), 494 (m), 469 (m), 439 (w), 619 (m), 406 (w). Photophysical Data for Example 10 [Cu (PPh ₃ ) tpym] BPh ₄ (Powder Data) Temp. [K] λ _max [nm] τ [μs] 300 450 5 77 465 25

This compound has an intense emission in the deep blue spectral range. At the same time, it shows short emission decay times. The emission of the compound is composed at room temperature in approximately equal parts of a phosphorescence and a TADF. The zero field splitting is greater than 5 cm ^-1 . The emission spectrum and the molecular structure are in 10 displayed.

General procedure for the compounds of Examples 11 and 12

Numbering of the cationic Cu (I) complex for better assignment of the ¹ H and ¹³ C signals in the NMR (Nuclear Magnetic Resonance) spectra:

The syntheses of the two compounds described below (Examples 11 and 12) were carried out with dried solvents in a protective gas atmosphere. The copper salt [Cu (MeCN) ₄ ] PF ₆ or [Cu (MeCN) ₄ ] BF ₄ was dissolved in MeCN and tris (2-pyridyl) methane (tpym) was added to the reaction solution. After stirring for 10 min, tris (6-methyl-2-pyridyl) phosphine (t ^me pyp) was added to the clear solution. This precipitated a solid. After stirring at room temperature for 1 day, the solid was removed by centrifugation and washed with MeCN or Et ₂ O, respectively. Single crystals could be obtained from the centrifugate after 3 days storage at RT. Example 11: [Cu (t ^me pyp) tpym] PF ₆

cm^–1: 1597 (m), 1574 (m), 1557 (m), 1474 (m), 1443 (m), 1356 (w), 1247 (w), 1176 (w), 1156 (w), 1092 (w), 1058 (w), 1013 (w), 981 (w), 914 (w), 879 (w), 854 (w), 837 (ss), 790 (s), 783 (s), 762 (s), 739 (m), 674 (w), 644 (w), 619 (m), 575 (m), 556 (s), 502 (w), 479 (m), 460 (s), 422 (m), 383 (m). Prepared from [Cu (MeCN) _4] PF ₆ (75 mg, 0:20 mmol, 1.0 eq), tpym (50 mg, 0:20 mmol, 1.0 eq) and t ^me pyp (62 mg, 0:20 mmol, 1.0 eq) in MeCN ( 6 mL). Washed with Et ₂ O (5 mL); beige-colored powder. Yield: 120 mg (0.16 mmol, 80%). Elemental analysis: C 52.96, H 3.94, N 10.84% (for C ₃₄ H ₃₁ CuF ₆ N ₆ P ₂ , expected is C 53.51, H 4.09, N 11.01%). ¹ H-NMR (300.1 MHz, CD ₃ CN): δ (ppm) = 9.23 (d, ³ J ₆₅ = 4.6 Hz, 3H, H 6), 7.90 (ddd, ³ J ₄₃ = 7.7 Hz, ³ J ₄₅ = 7.7 Hz, ⁴ J ₄₆ = 1.8 Hz, 3H, H4), 7.81 (d, ³ J ₃₄ = 7.8 Hz, 3H, H3), 7.69 (ddd, ³ J ₉₁₀ = 7.8 Hz, ³ J ₉₈ = 7.8 Hz, ⁴ J _9P = 3.0Hz, 3H, H9), 7.30-7.50 (m, 6H, H5 / H10), 7.18 (d, 3H, H8) 6.11 (s, 1H, H13), 2.61 (s, 9H, H12). ¹³ C-NMR (75.5 MHz, CD ₃ CN): δ (ppm) = 160.9 (d, ³ J _CP = 17.1 Hz, C11), 155.4 (s, C2), 152.5 (s, C6), 140.4 (s, C4), 138.1 (d, ³ J _CP = 5.2 Hz, C9), 126.8 (d, J _CP = 17.0 Hz, C8), 126.6 (s, C3), 125.1 (s, C10), 124.4 (s, C5) , 58.6 (s, C13), 24.5 (s, C12). Note: The quaternary carbon atom C7 on the ligand t ^me pyp could not be resolved in ¹³ C NMR. ³¹ P NMR (101.25 MHz, CD ₃ CN): δ (ppm) = -143.42 (sept, PF ₆ ^- ). Note: The signal for the P atom of the ligand t ^me pyp could not be resolved in ³¹ P NMR, as it is very strongly broadened. IR

cm ^-1 : 1597 (m), 1574 (m), 1557 (m), 1474 (m), 1443 (m), 1356 (w), 1247 (w), 1176 (w), 1156 (w), 1092 (w), 1058 (w), 1013 (w), 981 (w), 914 (w), 879 (w), 854 (w), 837 (ss), 790 (s), 783 (s), 762 (s), 739 (m), 674 (w), 644 (w), 619 (m), 575 (m), 556 (s), 502 (w), 479 (m), 460 (s), 422 (m), 383 (m).

This compound shows a deep blue emission. Example 12: [Cu (t ^me pyp) tpym] BF ₄

cm^–1: 1596 (m), 1580 (m), 1558 (w), 1475 (w), 1444 (m), 1377 (w), 1359 (w), 1285 (w), 1250 (w), 1178 (w), 1155 (w), 1141 (w), 1091 (m), 1054 (s), 1020 (m), 998 (m), 915 (w), 850 (w), 792 (m), 783 (m), 763 (m), 740 (m), 675 (w), 644 (w), 620 (m), 584 (m), 565 (w), 547 (w), 520 (w), 501 (w), 473 (m), 420 (m), 380 (w). Prepared from [Cu (MeCN) _4] BF ₄ (64 mg, 0:20 mmol, 1.0 eq), tpym (50 mg, 0:20 mmol, 1.0 eq) and t ^me pyp (62 mg, 0:20 mmol, 1.0 eq) in MeCN ( 8 mL). Washed with MeCN (5 mL); pale yellow powder. Yield: 127 mg (0.18 mmol, 90%). Elemental analysis: C 57.01, H 4.33, N 11.83% (for C ₃₄ H ₃₁ BCuF ₄ N ₆ P, expected C 57.93, H 4.43, N 11.92%). ¹ H-NMR (300.1 MHz, CD ₃ CN): δ (ppm) = 9.22 (bs, 3H, H 6), 7.90 (ddd, ³ J ₄₃ = 7.7 Hz, ³ J ₄₅ = 7.7 Hz, ⁴ J ₄₆ = 1.7 Hz, 3H, H4), 7.81 (d, ³ J ₃₄ = 7.7 Hz, 3H, H3), 7.70 (ddd, ³ J ₉₁₀ = 7.8 Hz, ³ J ₉₈ = 7.8 Hz, ⁴ J _9P = 3.0 Hz, 3H, H9), 7.30-7.42 (m, 6H, H5 / H10), 7.19 (bs, 3H, H8) 6.11 (s, 1H, H13), 2.62 (s, 9H, H12). IR

cm ^-1 : 1596 (m), 1580 (m), 1558 (w), 1475 (w), 1444 (m), 1377 (w), 1359 (w), 1285 (w), 1250 (w), 1178 (w), 1155 (w), 1141 (w), 1091 (m), 1054 (s), 1020 (m), 998 (m), 915 (w), 850 (w), 792 (m), 783 (m), 763 (m), 740 (m), 675 (w), 644 (w), 620 (m), 584 (m), 565 (w), 547 (w), 520 (w), 501 (w), 473 (m), 420 (m), 380 (w).

This compound shows a blue emission.

General Method of Synthesis and Analysis for the Neutral Cu (I) Complexes According to Formula A (m = 0) for Examples 13, 14, 15, 16, 17, 18, 19, 20, 21:

Numbering of the Tripod Ligands in the Neutral Cu (I) Complexes for Better Assignment of the ¹ H and ¹³ C Signals in the NMR Spectra:

General Synthesis Instructions

The syntheses described here were carried out with dried and degassed solvents in a protective gas atmosphere. The ligand tris (2-pyridyl) phosphine oxide (tpypo), tris (2-pyridyl) phosphine sulfide (tpyps), tris (2-pyridyl) phosphine selenide (tpypse), tris (2-pyridyl) arsine oxide (tpyaso) or tris (2-pyridyl) pyridyl) methane (tpym) was dissolved in a minimal amount of MeCN and treated with CuCl, CuBr or CuI. After stirring for 1 d at room temperature, the precipitate was centrifuged off. After drying in a fine vacuum, the product could be kept pure. The centrifugate was used to prepare crystals. After a few days storage at 4 ° C single crystals could be obtained. Example 13: [CuCl (tpypo)]

cm^–1: 1578 (w), 1434 (m), 1341 (w), 1275 (w), 1221 (m), 1143 (m), 1079 (w), 1050 (w), 1003 (w), 914 (w), 876 (w), 829 (w), 780 (m), 740 (m), 682 (w), 641 (w), 538 (ss), 455 (m), 410 (m). Photophysikalische Daten für Beispiel 13 [CuCl(tpypo)] (Pulverdaten) Temp. [K] λ_max [nm] τ [µs] 300 645 3 77 645 13 Prepared from CuCl (35 mg, 0.36 mmol, 1.0 eq) and tpypo (100 mg, 0.36 mmol, 1.0 eq) in MeCN (5 mL); orange-red powder. Yield: 59 mg (0.16 mmol, 44%). Elemental analysis: C 46.75, H 3.16, N 10.81% (for C ₁₅ H ₁₂ N ₃ POCuCl, expected C 47.38, H 3.18, N 11.05%). ¹ H-NMR (300.1 MHz, CDCl ₃ ): δ (ppm) = 9.00-9.06 (m, 3H, H6), 8.39 (ddd, ³ J ₃₄ = 7.7 Hz, ³ J _3P = 6.6 Hz, 3H, H3) , 7.95 (dddd, ³ J ₄₃ = 7.8 Hz, ³ J ₄₅ = 7.8 Hz, ⁴ J _4P = 3.9 Hz, ⁴ J ₄₆ = 1.6 Hz, 3H, H4), 7.52 (dddd, ³ J ₅₄ = 7.8 Hz, ³ J ₅₆ = 5.0 Hz, ⁵ J _5P = 1.9 Hz, ⁴ J ₅₃ = 1.4 Hz, 3H, H5). ¹³ C-NMR (75.5 MHz, CDCl _3): δ (ppm) = 151.2 (d, ³ J _CP = 13.8 Hz, C6), 150.9 (d, ¹ J _CP = 130.1 Hz, C2), 137.0 (d, ³ J _CP = 9.9 Hz, C4), 129.1 (d, ² J _CP = 18.4 Hz, C3), 126.7 (d, ⁴ J _CP = 2.9 Hz, C5). ³¹ P-NMR (101.3 MHz, CDCl _3): δ (ppm) = -9.79. IR (ATR)

cm ^-1 : 1578 (w), 1434 (m), 1341 (w), 1275 (w), 1221 (m), 1143 (m), 1079 (w), 1050 (w), 1003 (w), 914 (w), 876 (w), 829 (w), 780 (m), 740 (m), 682 (w), 641 (w), 538 (ss), 455 (m), 410 (m). Photophysical Data for Example 13 [CuCl (tpypo)] (Powder Data) Temp. [K] λ _max [nm] τ [μs] 300 645 3 77 645 13

This compound shows a deep red emission and a short emission lifetime. The emission of the compound is composed at room temperature in approximately equal parts of a phosphorescence and a TADF. The zero field splitting is greater than 5 cm ^-1 . The emission spectrum and the molecular structure are 11 displayed. Example 14: [CuBr (tpypo)]

Synthesis and chemical characterization:

cm^–1: 1579 (w), 1435 (m), 1325 (w), 1275 (w), 1223 (m), 1144 (m), 1080 (w), 1049 (w), 1004 (w), 914 (w), 878 (w), 829 (w), 779 (m), 741 (s), 687 (w), 642 (w), 538 (ss), 454 (m), 411 (m). Photophysikalische Daten für Beispiel 14 [CuBr(tpypo)] (Pulverdaten) Temp. [K] λ_max [nm] τ [µs] Φ_PL [%] k_r [10⁴s^–1] k_nr [10⁴s^–1] 300 620 4 18 5 20 77 615 20 36 2 3 Prepared from CuBr (51 mg, 0.36 mmol, 1.0 eq) and tpypo (100 mg, 0.36 mmol, 1.0 eq) in MeCN (5 mL); orange powder. Yield: 71 mg (0.17 mmol, 47%). Elemental analysis: C 42.25, H 2.82, N 9.74% (for C ₁₅ H ₁₂ N ₃ POCuBr, expected C 42.42, H 2.85, N 9.89%). ¹ H NMR (300.1 MHz, CDCl ₃ ): δ (ppm) = 9.03 (d, ³ J ₆₅ = 4.9 Hz, 3H, H6), 8.39 (dd, ³ J ₃₄ = 7.5 Hz, ³ J _3P = 6.8 Hz , 3H, H3), 7.96 (dddd, ³ J ₄₃ = 7.8 Hz, ³ J ₄₅ = 7.8 Hz, ⁴ J _4P = 3.9 Hz, ⁴ J ₄₆ = 1.5 Hz, 3H, H4), 7.46-7.57 (m, 3H , H5). ¹³ C-NMR (75.5 MHz, CDCl _3): δ (ppm) = 151.4 (d, ³ J _CP = 13.7 Hz, C6), 150.8 (d, ¹ J _CP = 130.0 Hz, C2), 137.1 (d, ³ J _CP = 9.9 Hz, C4), 129.1 (d, ² J _CP = 18.4 Hz, C3), 126.8 (d, ⁴ J _CP = 2.9 Hz, C5). ³¹ P-NMR (101.3 MHz, CDCl _3): δ (ppm) = -9.29. IR (ATR)

cm ^-1 : 1579 (w), 1435 (m), 1325 (w), 1275 (w), 1223 (m), 1144 (m), 1080 (w), 1049 (w), 1004 (w), 914 (w), 878 (w), 829 (w), 779 (m), 741 (s), 687 (w), 642 (w), 538 (ss), 454 (m), 411 (m). Photophysical Data for Example 14 [CuBr (tpypo)] (Powder Data) Temp. [K] λ _max [nm] τ [μs] Φ _PL [%] k _r [10 ⁴ s ^-1 ] k _nr [10 ⁴ s ^-1 ] 300 620 4 18 5 20 77 615 20 36 2 3

This compound shows a high emission quantum yield for the red spectral region and a short emission lifetime. The emission of the compound is composed at room temperature in approximately equal parts of a phosphorescence and a TADF. The zero field splitting is greater than 5 cm ^-1 . The emission spectrum and the molecular structure are in 12 displayed. Example 15: [CuI (tpypo)]

Synthesis and chemical characterization:

cm^–1: 3046 (m), 1578 (m), 1444 (m), 1430 (m), 1413 (m), 1282 (m), 1250 (m), 1220 (s), 1139 (m), 1125 (m), 1080 (m), 1038 (m), 1005 m), 777 (m), 748 (s), 732 (s), 638 (w), 540 (ss), 451 (m), 409 (m). Photophysikalische Daten für Beispiel 15 [CuI(tpypo)] (Pulverdaten) Temp. [K] λ_max [nm] τ [µs] Φ_PL [%] k_r [10⁴s^–1] k_nr [10⁴s^–1] 300 600 4 20 5 20 77 610 24 63 3 2 Prepared from CuI (72 mg, 0.38 mmol, 1.0 eq) and tpypo (106 mg, 0.38 mmol, 1.0 eq) in MeCN (8 mL); orange powder. Yield: 84 mg (0.18 mmol, 47%). Elemental analysis: C 38.10, H 2.53, N 8.81% (for C ₁₅ H ₁₂ N ₃ POCuI, expected C 38.19, H 2.56, N 8.91%). ¹ H-NMR (300.1 MHz, CDCl ₃ ): δ (ppm) = 9.05 (ddd, ³ J ₆₅ = 5.0 Hz, ⁴ J ₆₄ = 1.5 Hz, 3H, H6), 8.40 (dddd, ³ J ₃₄ = 7.7 Hz , ³ J _3P = 6.6 Hz, 3H, H3), 7.97 (dddd, ³ J ₄₃ = 7.8 Hz, ³ J ₄₅ = 7.8 Hz, ⁴ J _4P = 3.8 Hz, ⁴ J ₄₆ = 1.6 Hz, 3H, H4), 7.54 (dddd, ³ J ₅₄ = 7.9 Hz, ³ J ₅₆ = 5.0 Hz, ⁵ J _5P = 2.0 Hz, ⁴ J ₅₃ = 1.4 Hz, 3H, H5). ¹³ C-NMR (75.5 MHz, CDCl _3): δ (ppm) = 152.0 (d, ³ J _CP = 13.4 Hz, C6), 150.5 (d, ¹ J _CP = 129.8 Hz, C2), 137.3 (d, ³ J _CP = 9.8 Hz, C4), 129.1 (d, ² J _CP = 18.4 Hz, C3), 126.8 (d, ⁴ J _CP = 3.0 Hz, C5). ³¹ P-NMR (101.3 MHz, CDCl _3): δ (ppm) = -8.08. IR (ATR)

cm ^-1 : 3046 (m), 1578 (m), 1444 (m), 1430 (m), 1413 (m), 1282 (m), 1250 (m), 1220 (s), 1139 (m), 1125 (m), 1080 (m), 1038 (m), 1005 m), 777 (m), 748 (s), 732 (s), 638 (w), 540 (ss), 451 (m), 409 ( m). Photophysical Data for Example 15 [CuI (tpypo)] (Powder Data) Temp. [K] λ _max [nm] τ [μs] Φ _PL [%] k _r [10 ⁴ s ^-1 ] k _nr [10 ⁴ s ^-1 ] 300 600 4 20 5 20 77 610 24 63 3 2

This compound has high quantum efficiency and short emission decay time for the red spectral region. The emission of the compound is composed at room temperature in approximately equal parts of a phosphorescence and a TADF. The zero field splitting is greater than 5 cm ^-1 . The emission spectrum and the molecular structure are in 13 displayed. Example 16: [CuCl (tpyps)]

Synthesis and chemical characterization:

cm^–1: 1574 (m), 1439 (m), 1426 (m), 1279 (m), 1245 (w), 1152 (w), 1127 (m), 1080 (m), 1045 (m), 1002 (m), 771 (m), 739 (s), 727 (m), 661 (s), 634 (m), 518 (ss), 435 (m), 408 (m), 382 (w). Prepared from CuCl (33 mg, 0.34 mmol, 1.0 eq) and tpyps (100 mg, 0.34 mmol, 1.0 eq) in MeCN (8 mL); red powder. Yield: 89 mg (0.22 mmol, 65%). Elemental analysis: C 44.56, H 3.27, N 10.36, S 7.67% (for C ₁₅ H ₁₂ N ₃ PSCuCl, expected C 45.46, H 3.05, N 10.60, S 8.09%). ¹ H-NMR (300.1 MHz, CDCl _3): δ (ppm) = 9:00 to 9:06 (m, 3H, H6), 8.73 (ddd, ³ J _3P = 8.8 Hz, ³ J ₃₄ = 7.9 Hz, 3H, H3) , 7.95 (dddd, ³ J ₄₃ = 7.8 Hz, ³ J ₄₅ = 7.8 Hz, ⁴ J _4P = 4.2 Hz, ⁴ J ₄₆ = 1.7 Hz, 3H, H4), 7.50 (dddd, ³ J ₅₄ = 7.6 Hz, ³ J ₅₆ = 4.9 Hz, ⁵ J _5P = 2.4 Hz, ⁴ J ₅₃ = 1.3 Hz, 3H, H5). ¹³ C-NMR (75.5 MHz, CDCl _3): δ (ppm) = 150.7 (d, ³ J _CP = 12.5 Hz, C6), 150.6 (d, ¹ J _CP = 108.3 Hz, C2), 137.1 (d, ³ J _CP = 11.6 Hz, C4), 129.5 (d, ² J _CP = 24.6 Hz, C3), 126.3 (d, ⁴ J _CP = 3.0 Hz, C5). ³¹ P-NMR (121.5 MHz, CDCl _3): δ (ppm) = 9.10. IR (ATR)

cm ^-1 : 1574 (m), 1439 (m), 1426 (m), 1279 (m), 1245 (w), 1152 (w), 1127 (m), 1080 (m), 1045 (m), 1002 (m), 771 (m), 739 (s), 727 (m), 661 (s), 634 (m), 518 (ss), 435 (m), 408 (m), 382 (w).

The molecular structure of this compound is in 14 shown. Example 17: [CuBr (tpyps)]

Synthesis and chemical characterization:

cm^–1: 1574 (m), 1440 (m), 1426 (m), 1279 (m), 1153 (w), 1126 (m), 1081 (m), 1044 (m), 1003 (m), 771 (m), 739 (s), 726 (m), 661 (s), 634 (m), 518 (ss), 436 (m), 408 (m), 382 (m). Prepared from CuBr (49 mg, 0.34 mmol, 1.0 eq) and tpyps (100 mg, 0.34 mmol, 1.0 eq) in MeCN (8 mL); deep red powder. Yield: 99 mg (0.22 mmol, 65%). Elemental analysis: C 40.52, H 2.87, N 9.50, S 6.89% (for C ₁₅ H ₁₂ N ₃ PSCuBr, expected is C 40.88, H 2.74, N 9.53, S 7.27%). ¹ H-NMR (300.1 MHz, CDCl _3): δ (ppm) = 9:00 to 9:06 (m, 3H, H6), 8.74 (ddd, ³ J _3P = 8.8 Hz, ³ J ₃₄ = 7.8 Hz, 3H, H3) , 7.95 (dddd, ³ J ₄₃ = 7.8 Hz, ³ J ₄₅ = 7.8 Hz, ⁴ J _4P = 4.2 Hz, ⁴ J ₄₆ = 1.7 Hz, 3H, H4), 7.51 (dddd, ³ J ₅₄ = 7.6 Hz, ³ J ₅₆ = 4.9 Hz, ⁵ J _5P = 2.5 Hz, ⁴ J ₅₃ = 1.3 Hz, 3H, H5). ¹³ C-NMR (75.5 MHz, CDCl _3): δ (ppm) = 151.0 (d, ³ J _CP = 12.2 Hz, C6), 150.5 (d, ¹ J _CP = 108.2 Hz, C2), 137.2 (d, ³ J _CP = 11.5 Hz, C4), 129.5 (d, ² J _CP = 24.6 Hz, C3), 126.4 (d, ⁴ J _CP = 3.0 Hz, C5). ³¹ P-NMR (121.5 MHz, CDCl _3): δ (ppm) = 9.67. IR (ATR)

cm ^-1 : 1574 (m), 1440 (m), 1426 (m), 1279 (m), 1153 (w), 1126 (m), 1081 (m), 1044 (m), 1003 (m), 771 (m), 739 (s), 726 (m), 661 (s), 634 (m), 518 (ss), 436 (m), 408 (m), 382 (m).

The molecular structure of this compound is in 15 shown. Example 18: [CuI (tpyps)]

Synthesis and chemical characterization:

cm^–1: 1574 (m), 1442 (m), 1425 (m), 1364 (w), 1277 (w), 1245 (w), 1150 (w), 1126 (w), 1080 (w), 1045 (w), 1004 (m), 906 (w), 786 (m), 771 (m), 740 (s), 725 (m), 664 (s), 635 (m), 518 (ss), 445 (w), 434 (w), 413 (m), 384 (m). Photophysikalische Daten für Beispiel 18 [CuI(tpyps)] (Pulverdaten) Temp. [K] λ_max [nm] τ [µs] Φ_PL [%] 300 595 8 34 77 595 24 Prepared from CuI (66 mg, 0.35 mmol, 1.0 eq) and tpyps (104 mg, 0.35 mmol, 1.0 eq) in MeCN (8 mL); orange-red powder. Yield: 97 mg (0.20 mmol, 57%). Elemental analysis: C 36.77, H 2.47, N 8.60, S 6.62% (for C ₁₅ H ₁₂ N ₃ PSCuI, expected C 36.94, H 2.48, N 8.61, S 6.57%). ¹ H-NMR (300.1 MHz, CDCl ₃ ): δ (ppm) = 9.06 (ddd, ³ J ₆₅ = 5.0 Hz, ⁴ J ₆₄ = 1.7 Hz, 3H, H6), 8.71-8.79 (ddd, ³ J _3P = 8.9 Hz, ³ J ₃₄ = 7.7 Hz, 3H, H3), 7.96 (dddd, ³ J ₄₃ = 7.8 Hz, ³ J ₄₅ = 7.8 Hz, ⁴ J _4P = 4.1 Hz, ⁴ J ₄₆ = 1.7 Hz, 3H, H4 ), 7.52 (dddd, ³ J ₅₄ = 7.6 Hz, ³ J ₅₆ = 5.0 Hz, ⁵ J _5P = 2.5 Hz, ⁴ J ₅₃ = 1.3 Hz, 3H, H5). ¹³ C-NMR (75.5 MHz, CDCl _3): δ (ppm) = 151.5 (d, ³ J _CP = 12.0 Hz, C6), 150.3 (d, ¹ J _CP = 107.9 Hz, C2), 137.4 (d, ³ J _CP = 11.5 Hz, C4), 129.5 (d, ² J _CP = 24.6 Hz, C3), 126.4 (d, ⁴ J _CP = 3.0 Hz, C5). ³¹ P-NMR (101.3 MHz, CDCl _3): δ (ppm) = 11:47. IR (ATR)

cm ^-1 : 1574 (m), 1442 (m), 1425 (m), 1364 (w), 1277 (w), 1245 (w), 1150 (w), 1126 (w), 1080 (w), 1045 (w), 1004 (m), 906 (w), 786 (m), 771 (m), 740 (s), 725 (m), 664 (s), 635 (m), 518 (ss), 445 (w), 434 (w), 413 (m), 384 (m). Photophysical Data for Example 18 [CuI (tpyps)] (Powder Data) Temp. [K] λ _max [nm] τ [μs] Φ _PL [%] 300 595 8th 34 77 595 24

This compound has a high quantum efficiency. The emission of the compound is composed at room temperature in approximately equal parts of a phosphorescence and a TADF. The zero field splitting is greater than 5 cm ^-1 . The emission spectrum and the molecular structure are in 16 displayed. Example 19: [CuI (tpypse)]

Synthesis and chemical characterization:

cm^–1: 1573 (m), 1441 (m), 1423 (m), 1363 (w), 1277 (m), 1244 (w), 1150 (w), 1121 (w), 1079 (m), 1046 (m), 1003 (m), 905 (w), 784 (m), 770 (m), 739 (m), 719 (m), 665 (w), 635 (w), 576 (ss), 513 (ss), 441 (w), 427 (m), 411 (m). Photophysikalische Daten für Beispiel 19 [CuI(tpypse)] (Pulverdaten) Temp. [K] λ_max [nm] τ [µs] 300 640 2 77 675 9 Prepared from CuI (56 mg, 0.29 mmol, 1.0 eq) and tpypse (101 mg, 0.29 mmol, 1.0 eq) in MeCN (8 mL); orange-red powder. Yield: 25 mg (0.05 mmol, 17%). Elemental analysis: C 33.52, H 2.35, N 7.69% (for C ₁₅ H ₁₂ N ₃ PSeCuI, expected is C 33.70, H 2.26, N 7.86%). ¹ H-NMR (300.1 MHz, CDCl _3): δ (ppm) = 9:03 to 9:09 (m, 3H, H6), 8.89 (ddd, 3H, H3), 7.96 (dddd, ³ J ₄₃ = 7.8 Hz, ³ J ₄₅ = 7.8 Hz, ⁴ J _4P = 4.2 Hz, ⁴ J ₄₆ = 1.7 Hz, 3H, H4), 7.51 (dddd, ³ J ₅₄ = 7.7 Hz, ³ J ₅₆ = 4.9 Hz, ⁵ J _5P = 2.6 Hz, ⁴ J ₅₃ = 1.3 Hz, 3H, H5). ¹³ C-NMR (75.5 MHz, _CDCl3): δ (ppm) = 151.4 (d, ³ J _CP = 11.3 Hz, C6), 148.9 (d, ¹ J _CP = 97.4 Hz, C2), 137.5 (d, ³ J _CP = 12.1 Hz, C4), 130.7 (i.e. , ² J _CP = 27.0 Hz, C3), 126.4 (d, ⁴ J _CP = 3.0 Hz, C5). ³¹ P-NMR (101.3 MHz, CDCl _3): δ (ppm) = 12.7. IR

cm ^-1 : 1573 (m), 1441 (m), 1423 (m), 1363 (w), 1277 (m), 1244 (w), 1150 (w), 1121 (w), 1079 (m), 1046 (m), 1003 (m), 905 (w), 784 (m), 770 (m), 739 (m), 719 (m), 665 (w), 635 (w), 576 (ss), 513 (ss), 441 (w), 427 (m), 411 (m). Photophysical Data for Example 19 [CuI (tpypse)] (Powder Data) Temp. [K] λ _max [nm] τ [μs] 300 640 2 77 675 9

This compound has a deep red emission. The emission of the compound is composed at room temperature in approximately equal parts of a phosphorescence and a TADF. The zero field splitting is greater than 5 cm ^-1 . The emission spectrum and the molecular structure are in 17 displayed. Example 20: [CuI (tpyaso)]

Synthesis and chemical characterization:

cm^–1: 3046 (w), 1577 (m), 1556 (w), 1444 (m), 1429 (m), 1414 (m), 1371 (w), 1270 (w), 1242 (w), 1154 (w), 1140 (w), 1117 (w), 1043 (m), 1004 (m), 914 (s), 796 (m), 770 (s), 761 (s), 706 (w), 634 (w), 479 (ss), 410 (s). Photophysikalische Daten für Beispiel 20 [CuI(tpyaso)] (Pulverdaten) Temp. [K] λ_max [nm] τ [µs] 300 600 4 77 610 23 Prepared from CuI (30 mg, 0.16 mmol, 1.0 eq) and tpyaso (51 mg, 0.16 mmol, 1.0 eq) in MeCN (8 mL); yellow powder. Yield: 49 mg (0.10 mmol, 62%). Elemental analysis: C 34.79, H 2.35, N 8.09% (for C ₁₅ H ₁₂ N ₃ AsOCuI, expected is C 34.94, H 2.35, N 8.15%). ¹ H-NMR (300.1 MHz, CDCl ₃ ): δ (ppm) = 9.06 (ddd, ³ J ₆₅ = 5.0 Hz, ⁵ J ₆₃ = 0.9 Hz, 3H, H6), 8.28 (dd, ³ J ₃₄ = 7.7 Hz , 3H, H3), 7.99 (ddd, ³ J ₄₃ = 7.7 Hz, ³ J ₄₅ = 7.7 Hz, ⁴ J ₄₆ = 1.7 Hz, 3H, H4), 7.56 (ddd, ³ J ₅₄ = 7.8 Hz, ³ J ₅₆ = 5.1 Hz, ⁴ J ₅₃ = 1.3 Hz, 3H, H5). ¹³ C-NMR (75.5 MHz, CDCl _3): δ (ppm) = 154.6 (C2), 152.5 (C6), 138.1 (C4), 128.0 (C3), 127.2 (C5). IR (ATR)

cm ^-1 : 3046 (w), 1577 (m), 1556 (w), 1444 (m), 1429 (m), 1414 (m), 1371 (w), 1270 (w), 1242 (w), 1154 (w), 1140 (w), 1117 (w), 1043 (m), 1004 (m), 914 (s), 796 (m), 770 (s), 761 (s), 706 (w), 634 (w), 479 (ss), 410 (s). Photophysical Data for Example 20 [CuI (tpyaso)] (Powder Data) Temp. [K] λ _max [nm] τ [μs] 300 600 4 77 610 23

This compound shows orange emission with a short emission lifetime. The emission of the compound is composed at room temperature in approximately equal parts of a phosphorescence and a TADF. The zero field splitting is greater than 5 cm ^-1 . The emission spectrum and the molecular structure are in 18 displayed. Example 21: [CuI (tpym)]

Synthesis and chemical characterization:

cm^–1: 1592 (w), 1466 (w), 1434 (m), 1347 (w), 1187 (w), 1155 (w), 1083 (w), 1054 (w), 1013 (w), 960 (w), 914 (w), 878 (w), 832 (m), 782 (m), 751 (m), 692 (w), 645 (w), 616 (m), 553 (m), 500 (w), 464 (w), 418 (m). Photophysikalische Daten für Beispiel 21 [CuI(tpym)] (Pulverdaten) Temp. [K] λ_max [nm] τ [µs] Φ_PL [%] 300 555 5 28 77 550 22 Prepared from CuI (39 mg, 0.20 mmol, 1.0 eq) and tpym (50 mg, 0.20 mmol, 1.0 eq) in MeCN (15 mL); pale yellow powder. Yield: 64 mg (0.15 mmol, 75%). Elemental analysis: C 43.81, H 2.96, N 9.68% (for C ₁₆ H ₁₃ CuIN ₃ , expected C 43.90, H 2.99, N 9.60%). ¹ H-NMR (300.1 MHz, CDCl _3): δ (ppm) = 8.83 (d, 3H, H6), 7.64-7.74 (m, 3H, H4), 7:55 (d, 3H, H3), 7:20 to 7:25 ( m, 3H, H5), 5.57 (s, 1H, H7). ¹³ C-NMR (75.5 MHz, CDCl _3): δ (ppm) = 154.1 (C2), 150.8 (C6), 137.7 (C4), 124.6 (C3), 123.4 (C5), 60.0 (C7). IR (ATR)

cm ^-1 : 1592 (w), 1466 (w), 1434 (m), 1347 (w), 1187 (w), 1155 (w), 1083 (w), 1054 (w), 1013 (w), 960 (w), 914 (w), 878 (w), 832 (m), 782 (m), 751 (m), 692 (w), 645 (w), 616 (m), 553 (m), 500 (w), 464 (w), 418 (m). Photophysical Data for Example 21 [CuI (tpym)] (Powder Data) Temp. [K] λ _max [nm] τ [μs] Φ _PL [%] 300 555 5 28 77 550 22

This compound shows intense yellow emission with high quantum efficiency and short emission lifetime. The emission of the compound is composed at room temperature in approximately equal parts of a phosphorescence and a TADF. The zero field splitting is greater than 5 cm ^-1 . The emission spectrum and the molecular structure are in 19 displayed.

Description of ligand syntheses

General numbering of the ligands for better assignment of the ¹ H and ¹³ C signals in the NMR spectra:

The subsequent ligand syntheses were carried out with dried solvents in a protective gas atmosphere. Tris (2-pyridyl) phosphine (tpyp)

2-Bromopyridine (15 mL, 156.4 mmol, 3.0 eq) was dissolved in Et ₂ O (360 mL). After cooling to -78 ° C., nBuLi (2.55M in n-hexane, 63 mL, 160.7 mmol, 3.1 eq) was added rapidly. The solution turned dark red. The reaction solution was first stirred for 1 h at -78 ° C, then the cold bath was removed and stirred for an additional 1 h. Subsequently, the reaction solution was further cooled to -100 ° C and freshly distilled phosphorus trichloride (4.5 mL, 51.6 mmol, 1.0 eq), dissolved in Et ₂ O (150 mL), slowly added dropwise at a constant temperature (5-10 mmol / h) before the reaction solution was slowly warmed to room temperature overnight. The reaction solution turned brownish and a colorless precipitate formed. After adding 2M HCl (100 mL), the precipitate went into solution. The aqueous phase was separated and the organic phase extracted four times with 2M HCl (20 mL). The combined aqueous phases were made alkaline with a saturated NaOH solution (pH = 8-10). A solid formed, which was filtered off and washed four times with degassed ice-water (20 mL). After drying in a fine vacuum, a yellow-brown powder was obtained as a crude product. The crude product can be washed in an oxygen-free atmosphere with cold degassed isopropanol to a colorless solid or recrystallized therein.

Yield: 8.31 g (31.3 mmol, 61%). Elemental analysis: C 67.90, H 4.80, N 15.42% (for C ₁₅ H ₁₂ N ₃ P, expected C 67.92, H 4.56, N 15.84%). ¹ H-NMR (300.1 MHz, DMSO-d ₆ ): δ (ppm) = 8.68 (d, ³ J ₆₅ = 4.6 Hz, 3H, H6), 7.75 (dddd, ³ J ₄₃ = 7.7 Hz, ³ J ₄₅ = 7.7 Hz, ⁴ J _4P = 1.9 Hz, ⁴ J ₄₆ = 1.9 Hz, 3H, H4), 7.36 (dddd, ³ J ₅₄ = 7.4 Hz, ³ J ₅₆ = 4.8 Hz, ⁴ J ₅₃ = 1.1 Hz, ⁵ J _5P = 1.1 Hz, 3H, H5), 7.21 (dd, ³ J ₃₄ = 7.8 Hz, ⁴ J ₃₅ = 1.1 Hz, 3H, H3). ¹³ C-NMR (75.5 MHz, DMSO-d _6): δ (ppm) = 161.3 (d, ¹ J _CP = 4.7 Hz, C2), 150.2 (d, ³ J _CP = 12.8 Hz, C6), 136.2 (d , ³ J _CP = 3.1 Hz, C4), 128.7 (d, ² J _CP = 17.1 Hz, C3), 123.1 (C5). ³¹ P-NMR (202.5 MHz, DMSO-d ₆ ): δ (ppm) = -1.68. Tris (2-pyridyl) phosphine oxide (tpypo)

Tpyp (375 mg, 1.4 mmol, 1.0 eq) was dissolved in toluene (30 mL). After addition of tBuOOH solution (80% in DTBP, 2.0 mL, 16 mmol, 11 eq), the reaction solution was stirred for 5 d at room temperature. The progress of the reaction was monitored by ³¹ P-NMR. After complete conversion of the reaction, the solvent was removed and the crude product was digested with isopropanol (10 mL). After drying in a fine vacuum, the product could be obtained as a colorless powder.

cm^–1: 3044 (m), 1573 (m), 1454 (m), 1419 (m), 1281 (m), 1242 (w), 1209 (s), 1145 (m), 1125 (m), 1086 (m), 1043 (m), 989 (s), 788 (m), 780 (m), 769 (m), 749 (s), 737 (s), 619 (w), 542 (ss), 502 (s), 458 (m), 445 (s), 400 (m). Tris(2-pyridyl)phosphinsulfid (tpyps)

Yield: 372 mg (1.3 mmol, 94%). Elemental analysis: C 63.81, H 4.35, N 14.98% (for C ₁₅ H ₁₂ N ₃ OP, expected C 64.06, H 4.30, N 14.94%). ¹ H-NMR (300.1 MHz, CDCl _3): δ (ppm) = 8.77 (bs, 3H, H6), 8.18 (bs, 3H, H3), 7.79 (bs, 3H, H4), 7:36 (bs, 3H, H5). ¹³ C-NMR (75.5 MHz, CDCl _3): δ (ppm) = 154.9 (d, ¹ J _CP = 133.0 Hz, C2), 150.5 (d, ³ J _CP = 19.3 Hz, C6), 136.0 (d, ³ J _CP = 9.4 Hz, C4), 128.9 (d, ² J _CP = 21.0 Hz, C3), 126.4 (d, ⁴ J _CP = 3.3 Hz, C5). ³¹ P-NMR (101.3 MHz, CDCl _3): δ (ppm) = 14.65. IR (ATR)

cm ^-1 : 3044 (m), 1573 (m), 1454 (m), 1419 (m), 1281 (m), 1242 (w), 1209 (s), 1145 (m), 1125 (m), 1086 (m), 1043 (m), 989 (s), 788 (m), 780 (m), 769 (m), 749 (s), 737 (s), 619 (w), 542 (ss), 502 (s), 458 (m), 445 (s), 400 (m). Tris (2-pyridyl) phosphine sulfide (tpyps)

Tpyp (1.01 g, 3.80 mmol, 1.0 eq) was dissolved in degassed toluene (20 mL) and the reaction solution was treated with sulfur (134 mg, 4.17 mmol, 1.1 eq). The suspension was heated at reflux for 24 h. The progress of the reaction was monitored by ³¹ P-NMR. After complete conversion of the reaction, the suspension was cooled to room temperature and the slight excess of sulfur was separated via a syringe filter. The filtrate was completely concentrated and the residue recrystallized in ethanol. After drying in a fine vacuum, the product was obtained as a pale beige solid.

cm^–1: 3037 (w), 1570 (m), 1448 (m), 1418 (m), 1279 (m), 1235 (w), 1161 (w), 1151 (m), 1131 (m), 1085 (m), 1043 (m), 986 (m), 773 (m), 739 (s), 730 (s), 651 (s), 613 (m), 516 (s), 473 (m), 438 (m), 395 (m). Tris(2-pyridyl)phosphinselenid (tpypse)

Yield: 517 mg (1.74 mmol, 46%). Elemental analysis: C 60.59, H 4.13, N 14.04, S 10.74% (for C ₁₅ H ₁₂ N ₃ SP, expected C 60.60, H 4.07, N 14.13, S 10.78%). ¹ H-NMR (300.1 MHz, DMSO-d ₆ ): δ (ppm) = 8.69 (d, ³ J ₆₅ = 4.7 Hz, 3H, H 6), 8.03-8.11 (m, 3H, H 3), 7.98 (dddd, ³ J ₄₃ = 7.7 Hz, ³ J ₄₅ = 7.7 Hz, ⁴ J _4P = 4.7 Hz, ⁴ J ₄₆ = 1.7 Hz, 3H, H4), 7.55 (dddd, ³ J ₅₄ = 7.6 Hz, ³ J ₅₆ = 4.5 Hz , ⁵ J _5P = 3.0 Hz, ⁴ J ₅₃ = 1.3 Hz, 3H, H5). ¹³ C-NMR (75.5 MHz, DMSO-d _6): δ (ppm) = 155.0 (d, ¹ J _CP = 115.2 Hz, C2), 149.8 (d, ³ J _CP = 19.3 Hz, C6), 136.7 (d , ³ J _CP = 9.8 Hz, C4), 128.4 (d, ² J _CP = 24.7 Hz, C3), 125.5 (d, ⁴ J _CP = 3.2 Hz, C5). ³¹ P-NMR (161.9 MHz, DMSO-d ₆ ): δ (ppm) = 35.17. IR (ATR)

cm ^-1 : 3037 (w), 1570 (m), 1448 (m), 1418 (m), 1279 (m), 1235 (w), 1161 (w), 1151 (m), 1131 (m), 1085 (m), 1043 (m), 986 (m), 773 (m), 739 (s), 730 (s), 651 (s), 613 (m), 516 (s), 473 (m), 438 (m), 395 (m). Tris (2-pyridyl) phosphine selenide (tpypse)

Tpyp (300 mg, 1.14 mmol, 1.0 eq) was dissolved in degassed toluene (15 mL) and the reaction solution was treated with gray selenium (90 mg, 1.14 mmol, 1.0 eq). The suspension was refluxed for 4 days. The progress of the reaction was monitored by ³¹ P-NMR. After complete conversion of the reaction, the suspension was cooled to room temperature and the slight excess of selenium was separated off via a syringe filter. The filtrate was completely concentrated and the residue digested with Et ₂ O (15 mL). After drying in a fine vacuum, the product was obtained as a beige-colored solid.

cm^–1: 1570 (m), 1451 (m), 1422 (s), 1287 (m), 1127 (m), 1086 (m), 1052 (m), 988 (s), 906 (m), 770 (a), 738 (a), 730 (m), 715 (m), 619 (w), 560 (ss), 502 (ss), 449 (s), 396 (m). Tris(2-pyridyl)arsin (tpyas)

Yield: 185 mg (0.54 mmol, 47%). Elemental analysis: C 52.55, H 3.67, N 12.01% (for C ₁₅ H ₁₂ N ₃ SeP, expected is C 52.34, H 3.51, N 12.21%). ¹ H-NMR (300.1 MHz, CDCl ₃ ): δ (ppm) = 8.71 (ddd, ³ J ₆₅ = 4.7 Hz, ⁴ J ₆₄ = 1.7 Hz, 3H, H6), 8.33 (ddd, ³ J ₃₄ = 7.8 Hz , ³ J _3P = 6.7 Hz, 6H, H3), 7.80 (dddd, ³ J ₄₃ = 7.8 Hz, ³ J ₄₅ = 7.8 Hz, ⁴ J _4P = 4.6 Hz, ⁴ J ₄₆ = 1.8 Hz, 6H, H4), 7.34 (dddd, ³ J ₅₄ = 7.8 Hz, ³ J ₅₆ = 4.6 Hz, ⁵ J _5P = 3.1 Hz, ⁴ J ₅₃ = 1.2 Hz, 3H, H5). ¹³ C-NMR (75.5 MHz, CDCl _3): δ (ppm) = 154.5 (d, ¹ J _CP = 106.0 Hz, C2), 150.1 (d, ³ J _CP = 19.0 Hz, C6), 136.4 (d, ³ J _CP = 10.4 Hz, C4), 129.5 (d, ² J _CP = 26.1 Hz, C3), 125.1 (d, ⁴ J _CP = 3.2 Hz, C5). ³¹ P-NMR (101.3 MHz, CDCl _3): δ (ppm) = 30.54. IR (ATR)

cm ^-1 : 1570 (m), 1451 (m), 1422 (s), 1287 (m), 1127 (m), 1086 (m), 1052 (m), 988 (s), 906 (m), 770 (a), 738 (a), 730 (m), 715 (m), 619 (w), 560 (ss), 502 (ss), 449 (s), 396 (m). Tris (2-pyridyl) arsine (tpyas)

2-Bromopyridine (10.93 g, 69.2 mmol, 3.9 eq) was dissolved in Et ₂ O (100 mL). After cooling to -78 ° C, nBuLi (2.55M in n-hexane, 28 mL, 71.4 mmol, 4.0 eq) was added quickly. The solution turned dark red. The reaction solution was first stirred for 1 h at -78 ° C, then the cold bath was removed and stirred for an additional 1 h. Subsequently, the reaction solution was further cooled to -100 ° C and Arsentrichlorid (1.5 mL, 17.9 mmol, 1.0 eq), dissolved in Et ₂ O (50 mL), slowly added dropwise at constant temperature (5-10 mmol / h), before the reaction solution was slowly warmed to room temperature overnight. The reaction solution turned dark green and a colorless precipitate formed. After adding 2M HCl (25 mL), the precipitate went into solution. The aqueous phase was separated and the organic phase extracted three times with 2M HCl (25 mL). The combined aqueous phases were made slightly alkaline (pH = 8-10) with a saturated NaOH solution. This formed a solid which was filtered off and washed twice with ice-water (10 mL). After drying in a fine vacuum, a colorless powder was obtained.

cm^–1: 3038 (m), 1568 (s), 1556 (s), 1445 (s), 1418 (s), 1281 (m), 1150 (m), 1112 (m), 1104 (m), 1082 (m), 1043 (m), 988 (s), 755 (ss), 743 (s), 696 (m), 618 (m), 485 (s), 469 (s), 449 (m), 396 (s). Tris(2-pyridyl)arsinoxid (tpyaso)

Yield: 1.13 g (3.7 mmol, 21%). Elemental analysis: C 58.05, H 3.99, N 13.51% (for C ₁₅ H ₁₂ AsN ₃ , expected C 58.27, H 3.91, N 13.59%). ¹ H-NMR (300.1 MHz, DMSO-d ₆ ): δ (ppm) = 8.66 (ddd, ³ J ₆₅ = 4.8 Hz, ⁴ J ₆₄ = 1.8 Hz, ⁵ J ₆₃ = 1.0 Hz, 3H, H6), 7.73 (ddd, ³ J ₄₃ = 7.7 Hz, ³ J ₄₅ = 7.7 Hz, ⁴ J ₄₆ = 1.9 Hz, 3H, H4), 7.35 (ddd, ³ J ₅₄ = 7.6 Hz, ³ J ₅₆ = 4.8 Hz, ⁴ J ₅₃ = 1.2 Hz, 3H, H5), 7.29 (ddd, ³ J ₃₄ = 7.7 Hz, ⁴ J ₃₅ = 1.1 Hz, ⁵ J ₃₆ = 1.1 Hz, 3H, H3). ¹³ C-NMR (75.5 MHz, DMSO-d ₆ ): δ (ppm) = 165.3 (C2), 150.2 (C6), 136.2 (C4), 128.8 (C3), 123.1 (C5). IR (ATR)

cm ^-1 : 3038 (m), 1568 (s), 1556 (s), 1445 (s), 1418 (s), 1281 (m), 1150 (m), 1112 (m), 1104 (m), 1082 (m), 1043 (m), 988 (s), 755 (ss), 743 (s), 696 (m), 618 (m), 485 (s), 469 (s), 449 (m), 396 (s). Tris (2-pyridyl) arsine oxide (tpyaso)

Tpyas (57 mg, 0.18 mmol, 1.0 eq) was dissolved in toluene (15 mL). After addition of tBuOOH solution (80% in DTBP, 0.12 mL, 0.96 mmol, 5.3 eq), the reaction solution was stirred for 5 d at room temperature. The solvent was removed under reduced pressure and the crude product was washed with n-pentane. After drying in a fine vacuum, the product could be obtained as a colorless powder.

cm^–1: 3037 (m), 1566 (s), 1449 (s), 1418 (ss), 1282 (m), 1154 (m), 1120 (m), 1083 (m), 1038 (m), 987 (m), 899 (s), 777 (s), 765 (s), 707 (m), 613 (m), 470 (s), 399 (m). Tris(2-pyridyl)methan (tpym)

Yield: 51 mg (0.16 mmol, 89%). Elemental analysis: C 55.04, H 3.83, N 12.51% (for C ₁₅ H ₁₂ N ₃ AsO, expected is C 55.40, H 3.72, N 12.92%). ¹ H-NMR (300.1 MHz, DMSO-d ₆ ): δ (ppm) = 8.74 (d, ³ J ₆₅ = 4.5 Hz, 3H, H 6), 7.92-8.10 (m, 6H, H 4 / H 3), 7.55- 7.66 (m, 3H, H5). ¹³ C-NMR (75.5 MHz, DMSO-d _6): δ (ppm) = 157.6 (C2), 150.8 (C6), 137.3 (C4), 128.1 (C3), 126.3 (C5). IR (ATR)

cm ^-1 : 3037 (m), 1566 (s), 1449 (s), 1418 (ss), 1282 (m), 1154 (m), 1120 (m), 1083 (m), 1038 (m), 987 (m), 899 (s), 777 (s), 765 (s), 707 (m), 613 (m), 470 (s), 399 (m). Tris (2-pyridyl) methane (tpym)

2-Picoline (6.05 g, 65.0 mmol, 1.0 eq) was dissolved in THF (125 mL) and the solution cooled to -78 ° C. NBuLi (2.5M in n-hexane, 30 mL, 75.0 mmol, 4.0 eq) was added dropwise and the reaction solution was slowly warmed to 0 ° C. After stirring for 1 h at the same temperature, 2-fluoropyridine (10.2 mL, 118.9 mmol, 1.8 eq) was added and the suspension was heated at 65 ° C for 3 h. The mixture was then cooled to room temperature overnight and water (150 mL) added. The mixture was extracted three times with EtOAc (50 mL) and the combined organic phases were washed with a sat. Saline (150 mL). After drying over MgSO ₄ (anhydrous), the solvent was removed under reduced pressure. The crude product was fractionally distilled. As a by-product, a yellowish oil (di (2-pyridyl) methane) (dpym), and as a product a brown solid (tpym) could be obtained.

Yield: 1.33 g (9.1 mmol, 8.3%). ¹ H-NMR (300.1 MHz, CDCl ₃ ): δ (ppm) = 8.58 (ddd, ³ J ₆₅ = 4.9 Hz, ⁴ J ₆₄ = 1.7 Hz, ⁵ J ₆₃ = 0.8 Hz, 3H, H6), 7.62 (ddd , ³ J ₄₃ = 7.7 Hz, ³ J ₄₅ = 7.7 Hz, ⁴ J ₄₆ = 1.8 Hz, 3H, H4), 7.31 (d, ³ J ₃₄ = 7.9 Hz, 3H, H3), 7.14 (ddd, ³ J ₅₄ = 7.5 Hz, ³ J ₅₆ = 4.9 Hz, ⁴ J ₅₃ = 1.0 Hz, 3H, H5), 5.99 (s, 1H, H7). ¹³ C-NMR (75.5 MHz, CDCl _3): δ (ppm) = 161.3 (C2), 149.6 (C6), 136.6 (C4), 124.3 (C3), 121.8 (C5), 64.3 (C7). Tris (6-methyl-2-pyridyl) phosphine (t ^me pyp)

nBuLi (2.6M in n-hexane, 35.5 mL, 92.3 mmol, 3.8 eq) was initially charged at -40 ° C in Et ₂ O (95 mL) and briskly treated with 2-bromo-6-methyl-pyridine (13 g, 75.6%) mmol, 3.2 eq). The solution first turned yellowish, then red. The reaction solution was cooled down to -65 ° C and stirred for 1.75 hours at a constant temperature. Then freshly distilled phosphorus trichloride (2.1 mL, 24.0 mmol, 1.0 eq) dissolved in Et ₂ O (30 mL) was added dropwise. The red-brown suspension was stirred for 1 h in the temperature range -55 ° C to -65 ° C. Then the cooling bath was removed and the suspension stirred for a further 4 h. After addition of 1 MH ₂ SO ₄ (100 mL), the precipitate went into solution. The aqueous phase was separated and made alkaline with a 2 M NaOH solution (pH = 8-10). This formed a colorless solid, which was filtered off and washed with degassed water (50 mL). The precipitate was digested with n-pentane and filtered again. After drying in a fine vacuum, a light beige solid could be obtained.

Yield: 4.97 g (16.2 mmol, 68%). ¹ H NMR (300.1 MHz, CDCl ₃ ): δ (ppm) = 7.45 (ddd ,, ³ J ₄₃ = 7.7 Hz, ³ J ₄₅ = 7.7 Hz, 3H, H4), 6.97-7.07 (m, 6H, H3 / H5), 2.54 (s, 9H, H7). ¹³ C-NMR (75.5 MHz, CDCl _3): δ (ppm) = 161.6 (d, ¹ J _CP = 4.7 Hz, C2), 159.0 (d, ³ J _CP = 13.8 Hz, C6), 136.0 (d, ³ J _CP = 2.4 Hz, C4), 126.0 (d, ² J _CP = 14.1 Hz, C3), 122.5 (d, ⁴ J _CP = 0.6 Hz, C5), 24.7 (s, C7). ³¹ P-NMR (101.3 MHz, CDCl _3): δ (ppm) = -2.46.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

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Claims (12)

A light-emitting metal complex compound having a structure according to formula A.

Formula A wherein: M is Cu ⁺ or Ag ⁺ ; X: is singly negatively charged or a neutral ligand, wherein X in particular from the following group singly negatively charged ligand is selected from: H ^- D ^-, F ^-, Cl ^-, Br ^-, I ^-, NO ₂ ^-, NO ₃ ^-, (SnR ₃₎ ^-, SnCl ₃ ^-, OCN ^-, NCO ^-, (OR) ^-, (SR) ^- (Ser) ^-, (TER) ^-, SCN ^-, SeCN ^- and TeCN ^-; or wherein X is in particular selected from the following group of neutral ligands: Azaaromaten (in particular, pyridine, 4-phenyl-pyridine, 4-methylpyridine, 4-cyanopyridine, 4-dimethylamino-pyridine, pyridine-4-carboxylic acid methyl ester, N-methyl-imidazole , N-phenyl-imidazole, N-methyl-pyrazole and N-phenyl-pyrazole), the N-heterocyclic carbenes (in particular, 1-methyl-3-methyl-imidazol-2-ylidene, 1-methyl-3-phenyl) imidazol-2-ylidene and 1-phenyl-3-phenyl-imidazol-2-ylidene), tetrahydrofuran, tetrahydrothiophene, NH ₃ , NH ₂ R, NHR ₂ , NR ₃ , PH ₃ , PH ₂ R, PHR ₂ , PR ₃ , Tris (2-pyridyl) phosphine (short: Tpyp or tpyp), tris (6-methyl-2-pyridyl) phosphine (short: T ^me pyp or t ^me pyp), AsH ₃ , AsH ₂ R, AsHR ₂ , AsR ₃ , SbR ₃ , OPR ₃ , SPR ₃ , SePR ₃ , R ₂ SO, SR ₂ , SeR ₂ , SC (NR ₂ ) ₂ , SeC (NR ₂ ) ₂ , RCN and RNC, where the binding of ligand X to M each carried over the bold atom; Z: the bridge Z is selected from the group consisting of PO, PS, PSe, As, AsO, CH, CR, C (CR ₃ ), CF, CCF ₃ , CCl, CCCl ₃ , CBr, CCBr ₃ , C (I ), SiH, SiR and Si (CR ₃ ), wherein the bold atom binds via a single bond to each one C atom of the three aromatic ring units; Q ¹ , Q ² , Q ³ : are independently selected from the group consisting of H or D; L ¹ , L ² ,..., L ⁹ : are neutral atoms or atomic groups, in particular independently selected from the group consisting of: H, D, F, Cl, Br, I, R, CN, NO ₂ , OH, OR, SH, SR, NH ₂ , NHR, NR ₂ , SiR ₃ , B (OH) ₂ and B (OR) ₂ , wherein the bold atom binds to a C atom of the aromatic ring moiety via a single bond; G: a non-coordinating counterion, in particular a single negative counterion, in particular selected from the group consisting of PF ₆ ^- , BF ₄ ^- , BH ₄ ^- , BH ₃ R ^- , BH ₂ R ₂ ^- , BHR ₃ ^- , BR ₄ ^-, tri (1H-pyrazol-1-yl) hydro-borate, tetrakis (1H-pyrazol-1-yl) borate, tris hydroborate (3,5-dimethylpyrazol-1-yl), tetrakis (1-imidazolyl) borate, SbF ₆ ^- , F ₃ CSO ₃ ^- , FSO ₃ ^- , RSO ₃ ^- , (RO) SO ₃ ^- , RCO ₂ ^- , F ₃ CCO ₂ ^- , (RO) CO ₂ ^- , ClO ₃ ^- , ClO ₄ ^- , NO ₂ ^- , NO ₃ ^- , F ^- , Cl ^- , Br ^- and I ^- ; m: an index with 0 less than or equal to or less than or equal to 1 (0 ≤ m ≤ 1), in particular where either m = 0 or m = 1, where m = 0 X is a singly negatively charged (anionic) ligand and where m = 1 X is a neutral ligand; where the abovementioned radical R is in each case selected from the group consisting of alkyl, cycloalkyl, aryl or heteroaryl group, where - the alkyl group may be unbranched, branched and / or substituted and in particular has a chain length of from C1 to C12, - the cycloalkyl -, Aryl or heteroaryl group may have in particular up to 12 C atoms, wherein the cycloalkyl, aryl or heteroaryl substituted, in particular each may be substituted by alkyl groups, in particular having a chain length of C1 to C12, in particular wherein R is independently selected from the group consisting of methyl, trifluoromethyl, ethyl, propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neo-pentyl, iso-pentyl -, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, p-toluyl, 2 Naphthyl, mesityl, pentafluorophenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl and thiophene-2 yl. The metal complex compound of claim 1, comprising a thermally activated delayed fluorescence (TADF), said compound preferably having a ΔE (S ₁ -T ₁ ) value between the lowest excited singlet and the underlying triplet state of less than 2000 cm ^-1 , preferably of less than 1000 cm ^-1 and more preferably of less than 300 cm ^-1 . A metal complex compound according to claim 1 or 2, wherein the lowest triplet state comprises zero field splitting of sub-states I, II, III, wherein the energetic distance between sub-states III and I ΔE (III-I) is greater than 3 cm ^-1 , preferably greater than 5 cm ^-1 , more preferably greater than 10 cm ^-1 and most preferably greater than 15 cm ^-1 . Metal complex compound according to claim 1 to 3, wherein the compound has a radiative life of the lowest triplet state (T ₁ ) of less than 100 microseconds, preferably less than 50 microseconds, more preferably less than 20 microseconds and more preferably less than 5 microseconds.  A metal complex compound according to claims 1 to 4, wherein the part shown in square brackets in formula A has a metal to ligand charge transfer transition and the MLCT states associated therewith essentially consist of the following molecular orbital moieties: - a HOMO part with a pronounced d orbital character with d orbitals of the central ion and - A LUMO moiety that is largely located on the π * orbital of the tridentate tripod ligand.  Use of a metal complex compound according to Claims 1 to 5 in an optoelectronic device, in particular for the emission of light.  Use according to claim 6, wherein an emitter layer in an optoelectronic device comprises a metal complex compound according to claims 1 to 5, wherein the concentration of the compound in the emitter layer is 2 wt% to 100 wt%. An opto-electronic device comprising a metal complex compound according to claims 1 to 5.  The device according to claim 8, wherein the proportion of the metal complex compound in an emitter layer or an absorber layer is from 2% by weight to 100% by weight, preferably from 20% by weight to 80% by weight, based on the total weight of the emitter layer or absorber layer, is.  Device according to claim 8 or 9, wherein the opto-electronic device is selected from the group consisting of organic light-emitting diodes (OLEDs), light-emitting electrochemical cells (LEECs), OLED sensors, in particular not in hermetically shielded gas and vapor sensors, organic solar cells (OPCs), organic field effect transistors, organic lasers, organic diodes, organic photodiodes and "down conversion" systems for the conversion of UV radiation into visible light or for converting light of a shorter wavelength into light of a longer wavelength.  A process for producing an opto-electronic device, wherein a metal complex compound according to claim 1 to 5 is used, wherein the compound is applied in particular wet-chemically, by colloidal suspension or by sublimation on a solid or flexible support. A method of producing light of a particular wavelength, comprising the step of providing a metal complex compound according to claims 1 to 5.

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