METAL COMPLEXES

Abstract

The invention relates to iridium complexes that are suitable for use in organic electroluminescent devices, in particular as emitters.

Claims

1.-14. (canceled)

15. A compound of formula (1) ##STR00367## where the symbols and indices used are as follows: L.sup.1 is a bidentate subligand which coordinates to the iridium via one carbon atom and one nitrogen atom or via two carbon atoms; L.sup.2, L.sup.3 are the same or different at each instance and are selected from an aryl or heteroaryl group having 5 to 14 aromatic ring atoms or a heteroalicyclic group having 5 to 7 ring atoms, each of which coordinates to the iridium via a carbon atom or a nitrogen atom, each of which is part of the aryl or heteroaryl group or the heteroalicyclic group, and which may be substituted by one or more R radicals; L.sup.4 is a bidentate ligand or is the same or different at each instance and is a monodentate ligand; a is 1 when L.sup.4 is a bidentate ligand, and is 2 when L.sup.4 is a monodentate ligand; V is a group of formula (2) or (3) ##STR00368## where the dotted bonds each represent the position of linkage to the subligands L.sup.1, L.sup.2 and L.sup.3, and in addition: A is the same or different at each instance and is CR.sub.2—CR.sub.2 or a group of the following formula (4): ##STR00369## where the dotted bond in each case represents the position of the bond of the subligands L.sup.1, L.sup.2 or L.sup.3 and * represents the position of the linkage of the unit of the formula (4) to the central trivalent aryl or heteroaryl group in formula (2) or to the central cyclohexane group in formula (3); X.sup.1 is the same or different at each instance and is CR or N; X.sup.2 is the same or different at each instance and is CR or N; or two adjacent X.sup.2 groups together are NR, O or S, thus forming a five-membered ring, and the remaining X.sup.2 groups are the same or different at each instance and are CR or N; or two adjacent X.sup.2 groups together are CR or N when one of the X.sup.3 groups in the cycle is N, thus forming a five-membered ring, and the remaining X.sup.2 groups are the same or different at each instance and are CR or N; with the proviso that not more than two adjacent X.sup.2 groups in each ring are N; X.sup.3 is C at each instance in the same cycle or one X.sup.3 group is N and the other X.sup.3 group in the same cycle is C; with the proviso that two adjacent X.sup.2 groups together are CR or N when one of the X.sup.3 groups in the cycle is N; R is the same or different at each instance and is H, D, F, Cl, Br, I, N(R.sup.1).sub.2, OR.sup.1, SR.sup.1, CN, NO.sub.2, COOH, C(═O)N(R.sup.1).sub.2, Si(R.sup.1).sub.3, Ge(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(═O)R.sup.1, P(═O)(R.sup.1).sub.2, S(═O)R.sup.1, S(═O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R.sup.1 radicals and where one or more nonadjacent CH.sub.2 groups may be replaced by Si(R.sup.1).sub.2, C═O, NR.sup.1, O, S or CONR.sup.1, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.1 radicals; at the same time, two R radicals together may also form a ring system; R.sup.1 is the same or different at each instance and is H, D, F, Cl, Br, I, N(R.sup.2).sub.2, OR.sup.2, SR.sup.2, CN, NO.sub.2, Si(R.sup.2).sub.3, Ge(R.sup.2).sub.3, B(OR.sup.2).sub.2, C(═O)R.sup.2, P(═O)(R.sup.2).sub.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, OSO.sub.2R.sup.2, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R.sup.2 radicals and where one or more nonadjacent CH.sub.2 groups may be replaced by Si(R.sup.2).sub.2, C═O, NR.sup.2, O, S or CONR.sup.2, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.2 radicals; at the same time, two or more R.sup.1 radicals together may form a ring system; R.sup.2 is the same or different at each instance and is H, D, F or an aliphatic, aromatic and/or heteroaromatic organic radical, especially a hydrocarbyl radical, having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F.

16. The compound as claimed in claim 15, wherein the group of the formula (2) is represented by formula (2a) and in that the group of the formula (3) is represented by formula (3 a): ##STR00370## where the symbols have the definitions given in claim 15.

17. The compound as claimed in claim 15, wherein the group of the formula (4) is represented by formula (4′): ##STR00371## where the symbols have the definitions detailed in claim 15 and X.sup.2 is the same or different at each instance and is CR.

18. The compound as claimed in claim 15, wherein all three A groups are the same group of the formula (4′) with X.sup.2═CR, or in that two A groups are the same group of the formula (4′) with X.sup.2═CR and the third A group is CR.sub.2—CR.sub.2, or in that one A group is a group of the formula (4′) with X.sup.2═CR and the two other A groups are the same CR.sub.2—CR.sub.2 group, or in that all three A groups are the same CR.sub.2—CR.sub.2 group.

19. The compound as claimed in claim 15, wherein the group of the formula (2) is selected from the groups of the formulae (2a-1) to (2d-1) and in that the group of the formula (3) is selected from the groups of the formulae (3a-1) to (3d-1): ##STR00372## ##STR00373## where the symbols have the definitions given in claim 15.

20. The compound as claimed in claim 15, wherein the subligand L.sup.1 has a structure of one of the following formulae (L.sup.1-1) and (L.sup.1-2): ##STR00374## where the dotted bond represents the bond of the subligand L.sup.1 to V and the other symbols are as follows: CyC is the same or different at each instance and is a substituted or unsubstituted aryl or heteroaryl group which has 5 to 14 aromatic ring atoms and coordinates in each case to the iridium via a carbon atom and which is bonded to CyD via a covalent bond; CyD is the same or different at each instance and is a substituted or unsubstituted heteroaryl group which has 5 to 14 aromatic ring atoms or a substituted or unsubstituted heteroalicyclic group having 5 to 7 ring atoms, each of which coordinates to the iridium via a nitrogen atom or via a carbene carbon atom and which is bonded to CyC via a covalent bond; at the same time, two or more of the optional substituents together may form a ring system.

21. The compound as claimed in claim 20, wherein CyC is selected from the structures of the formulae (CyC-1) to (CyC-20), where the CyC group binds in each case at the position identified by #to CyD and at the position identified by * to the iridium: ##STR00375## ##STR00376## ##STR00377## and in that CyD is selected from the structures of the formulae (CyD-1) to (CyD-23), where the CyD group binds in each case at the position identified by #to CyC and coordinates at the position identified by * to the iridium, ##STR00378## ##STR00379## ##STR00380## wherein X is the same or different at each instance and is CR or N, with the proviso that at most two symbols X per ring are N; W is the same or different at each instance and is NR, O or S, and in CyD may additionally also be CR.sub.2; with the proviso that the symbol X bonded to the bridge V is C, where the bond to the bridge V is preferably via the position marked “o”.

22. The compound as claimed in claim 15, wherein L.sup.1 is selected from the structures of the formulae (L.sup.1-1-1) to (L.sup.1-1-3) and (L.sup.1-2-1) to (L.sup.1-2-5) that coordinate to the iridium via the two positions identified by *: ##STR00381## ##STR00382## where the symbols have the definitions given in claim 15 and “o” represents the position of the bond to the bridge V, or in that L.sup.1 is selected from the structures of the formula (L.sup.1-39) or (L.sup.1-40) that coordinate to the iridium by the two positions identified by *: ##STR00383## where “o” denotes the position of linkage to the bridge V, and in addition: X is the same or different at each instance and is CR or N; Z is CR′, CR or N, with the proviso that exactly one Z is CR′ and the other Z is CR or N; where a maximum of one symbol X or Z in total per cycle is N; R′ is a group of the following formula (16) or (17): ##STR00384## where the dotted bond indicates the linkage of the group to the subligands of the formula (L.sup.1-39) or (L.sup.1-40); R″ is the same or different at each instance and is H, D, F, CN, a straight-chain alkyl group having 1 to 10 carbon atoms in which one or more hydrogen atoms may also be replaced by D or F, or a branched or cyclic alkyl group having 3 to 10 carbon atoms in which one or more hydrogen atoms may also be replaced by D or F, or an alkenyl group having 2 to 10 carbon atoms in which one or more hydrogen atoms may also be replaced by D or F; at the same time, two adjacent R″ radicals or two R″ radicals on adjacent phenyl groups together may also form a ring system; or two R″ on adjacent phenyl groups together are a group selected from C(R.sup.1).sub.2, NR.sup.1, O or S, such that the two phenyl rings together with the bridging group are a carbazole, fluorene, dibenzofuran or dibenzothiophene, and the further R″ are as defined above; n is 0, 1, 2, 3, 4 or 5.

23. The compound as claimed in claim 15, wherein L.sup.2 and L.sup.3 are the same or different at each instance and are selected from the structures of the formulae (L.sup.2-1)/(L.sup.3-1) to (L.sup.2-55)/(L.sup.3-55), where the groups each coordinate to the iridium at the position identified by * and to the bridgehead V at the position identified by “o”: ##STR00385## ##STR00386## ##STR00387## where R has the definitions given in claim 15 and the other symbols are as follows: X is the same or different at each instance and is CR or N, with the proviso that at most two symbols X per ring are N; W is the same or different at each instance and is NR, O or S.

24. The compound as claimed in claim 15, wherein the monodentate ligands L.sup.4 are the same or different at each instance and are selected from the group consisting of carbon monoxide, nitrogen monoxide, alkyl cyanides, aryl cyanides, alkyl isocyanides, aryl isocyanides, amines, phosphines, phosphites, arsines, stibines, nitrogen heterocycles, carbenes, hydride, deuteride, fluoride, chloride, bromide, iodide, alkylacetylidene, arylacetylidene, cyanide, cyanate, isocyanate, thiocyanate, isothiocyanate, aliphatic or aromatic alkoxides, aliphatic or aromatic thioalkoxides, amides, carboxylates or aryl groups, and in that the bidentate ligands L.sup.4 are selected from the group consisting of diamines, imines, diimines, heterocycles containing two nitrogen atoms, diphosphines, 1,3-diketonates derived from 1,3-diketones, 3-ketonates derived from 3-keto esters, carboxylates derived from aminocarboxylic acids, salicyliminates derived from salicylimines, dialkoxides derived from dialcohols, dithiolates derived from dithiols, bis(pyrazolylborates), bis(imidazolyl)borates, 3-(2-pyridyl)diazoles, or 3-(2-pyridyl)triazoles; or L.sup.4 is a ligand of one of the formulae (L.sup.4-1), (L.sup.4-2) and (L.sup.4-3): ##STR00388## where the symbols used are as follows: CyC is the same or different at each instance and is a substituted or unsubstituted aryl or heteroaryl group which has 5 to 14 aromatic ring atoms and coordinates in each case to the metal via a carbon atom and which is bonded to CyD via a covalent bond; CyD is the same or different at each instance and is a substituted or unsubstituted heteroaryl group which has 5 to 14 aromatic ring atoms and coordinates to the metal via a nitrogen atom or via a carbene carbon atom and which is bonded to CyC via a covalent bond; at the same time, two or more of the optional substituents together may form a ring system; or L.sup.4 is a ligand of one of the formulae (L.sup.4-19) to (L.sup.4-24), where these ligands each coordinate to the iridium via the two atoms identified by *: ##STR00389## where R has the definitions given in claim 15 and X is the same or different at each instance and is CR or N, with the proviso that not more than two X are N.

25. A formulation comprising at least one compound as claimed in claim 15 and at least one further compound and/or a solvent.

26. A method comprising including the compound as claimed in claim 15 in an electronic device or utilizing the compound as oxygen sensitizer or as photoinitiator or as photocatalyst.

27. An electronic device comprising at least one compound as claimed in claim 15.

28. The electronic device as claimed in claim 27, which is an organic electroluminescent device, wherein the compound is used as emitter in an emitting layer in combination with one or more matrix materials selected from the group consisting of ketones, phosphine oxides, sulfur oxides, sulfones, triarylamines, carbazole derivatives, biscarbazoles, bridged carbazole derivatives, indolocarbazole derivatives, indenocarbazole derivatives, azacarbazoles, bipolar matrix materials, azaboroles, boronic esters, diazasilole derivatives, diazaphosphole derivatives, triazine derivatives, zinc complexes, dibenzofuran derivatives, dibenzothiophene derivatives or triphenylene derivatives.

Description

DESCRIPTION OF THE FIGURES

[0292] FIG. 1 shows the x-ray structure of the inventive complex Ir617, the synthesis of which is described in the examples that follow.

EXAMPLES

[0293] The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The metal complexes are additionally handled with exclusion of light or under yellow light. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. The respective figures in square brackets or the numbers quoted for individual compounds relate to the CAS numbers of the compounds known from the literature. In the case of compounds that can display multiple tautomeric, isomeric, enantiomeric or diastereomeric forms, one form is shown in a representative manner.

[0294] A: Synthesis of the Synthons S:

Example S1

[0295] ##STR00196##

[0296] To a mixture of 18.2 g (50 mmol) of 2,2′-(5-chloro-1,3-phenylene)bis[4,4,5,5-tetramethyl-1,3,2-dioxaborolane [1417036-49-7], 28.3 g (100 mmol) of 1-bromo-2-iodobenzene, 31.8 g (300 mmol) of sodium carbonate, 200 ml of toluene, 100 ml of ethanol and 200 ml of water are added, with very good stirring, 788 g (3 mmol) of triphenylphosphine and then 225 mg (1 mmol) of palladium(II) acetate, and the mixture is heated under reflux for 48 h. After cooling, the organic phase is removed and washed once with 300 ml of water and once with 300 ml of saturated sodium chloride solution, and dried over magnesium sulfate. The desiccant is filtered off and the filtrate is concentrated fully under reduced pressure. The residue is flash-chromatographed (Torrent automatic column system from A. Semrau). Yield: 16.5 g (39 mmol), 78%; purity: about 97% by .sup.1H NMR.

Example S2

[0297] ##STR00197##

[0298] Stage S2a:

##STR00198##

[0299] A well-stirred mixture of 23.9 g (100 mmol) of 2-chloro-4-iodopyridine [153034-867], 19.8 g (100 mmol) of biphenylboronic acid [5122-8941], 21.2 g (200 mmol) of sodium carbonate, 1.16 g (1 mmol) of tetrakis(triphenylphosphino)palladium(0), 150 ml of toluene, 50 ml of dioxane and 100 ml of water is heated under reflux for 16 h. After cooling, the precipitated solids are filtered off with suction and washed three times with 100 ml each time of water and twice with 50 ml of methanol, and dried under reduced pressure. The solids are extracted by stirring in 150 ml of hot acetonitrile, filtered off with suction and dried under reduced pressure. Yield; 24.2 g (91 mmol), 91%; purity: about 97% by .sup.1H NMR.

[0300] Stage S2b:

##STR00199##

[0301] A well-stirred mixture of 26.6 g (100 mmol) of S2a, 15.6 g (100 mmol) of 4-chlorophenylboronic acid [1679-18-1], 27.6 g (200 mmol) of potassium carbonate, 702 mg (1 mmol) of bis(triphenylphosphino)palladium(II) chloride, 50 g of glass beads (diameter 3 mmol), 200 ml of acetonitrile and 100 ml of methanol is heated under reflux for 16 h. After cooling, the precipitated solids are filtered off with suction and washed three times with 100 ml each time of water and twice with 50 ml of methanol, and dried under reduced pressure. The solids are dissolved in 500 ml of dichloromethane (DCM) and 100 ml of ethyl acetate (EA) and filtered through a silica gel bed in the form of a DCM slurry. The filtrate is concentrated under reduced pressure. The remaining solids are extracted by stirring with 150 ml of hot ethanol, filtered off with suction and dried under reduced pressure. Yield: 27.3 g (80 mmol), 80%; purity: about 97% by .sup.1H NMR.

[0302] Stage S2c:

##STR00200##

[0303] To a mixture of 34.2 g (100 mmol) of S2b, 26.7 g (105 mmol) of bis(pinacolato)diborane, 29.4 g (300 mmol) of potassium acetate (anhydrous), 50 g of glass beads (diameter 3 mm) and 500 ml of THF are added, with good stirring, 821 mg (2 mmol) of S-Phos and then 225 mg (1 mmol) of palladium(II) acetate, and the mixture is heated under reflux for 16 h. While the mixture is still hot, the salts and glass beads are removed by suction filtration through a Celite bed in the form of a THF slurry, which is washed through with a little THF, and the filtrate is concentrated to dryness. The residue is taken up in 100 ml of MeOH and stirred in the warm solvent, and the crystallized product is filtered off with suction, washed twice with 30 ml each time of methanol and dried under reduced pressure. Yield: 36.4 g (84 mmol), 84%; purity: about 95% by .sup.1H NMR.

[0304] Stage S2:

[0305] To a well-stirred mixture of 21.3 g (100 mmol) of S2c, 13.6 g (100 mmol) of 1-bromo-2-iodobenzene [583-55-1], 53.0 g (500 mmol) of sodium carbonate, 400 ml of toluene, 200 ml of ethanol and 400 ml of water are added 1.57 g (6 mmol) of triphenylphosphine and then 449 mg (2 mmol) of palladium(II) acetate, and the mixture is heated under reflux for 16 h. After cooling, the organic phase is removed and washed twice with 200 ml each time of water and once with 200 ml of saturated sodium chloride solution, and dried over magnesium sulfate. The filtrate is filtered through a celite bed in the form of a toluene slurry and concentrated to dryness, and the residue is recrystallized from about 50 ml of methanol with addition of a little ethyl acetate. Yield: 37.4 g (83 mmol), 83%; purity: about 95% by .sup.1H NMR.

[0306] The following compounds can be prepared analogously:

TABLE-US-00003 Ex. Reactants Product Yield S3 [00201] [00202] 54% S4 [00203] [00204] 47% * over three stages

Example S20

[0307] ##STR00205##

[0308] Stage S20a:

##STR00206##

[0309] A well-stirred mixture of 27.4 g (100 mmol) of 2,5-dichloro-4-iodopyridine [796851-03-1], 19.8 g (100 mmol) of biphenylboronic acid [5122-94-1], 27.6 g (200 mmol) of potassium carbonate, 702 mg (1 mmol) of bis(triphenylphosphino)palladium(II) chloride, 50 g of glass beads (diameter 3 mmol), 150 ml of acetonitrile and 150 ml of methanol is heated under reflux for 16 h. After cooling, the reaction mixture is stirred into 1000 ml of water. The precipitated solids are filtered off with suction, washed three times with 100 ml each time of water and once with 50 ml of methanol, and dried under reduced pressure. Yield: 29.4 g (98 mmol), 98%: purity: about 97% by .sup.1H NMR.

[0310] Stage S20b:

##STR00207##

[0311] Procedure analogous to 20a, except using, rather than biphenylboronic acid [5122-94-1], 12.2 g (100 mmol) of phenylboronic acid [98-80-6]. The crude product is dissolved in 300 ml of DCM and 100 ml of EA, and filtered through a silica gel bed. After the filtrate has been concentrated, the solids are extracted by hot stirring with 70 ml of acetonitrile. Yield: 27.3 g (80 mmol), 80%: purity: about 97% by .sup.1H NMR.

[0312] Stage S20:

[0313] To a well-stirred mixture of 34.2 g (100 mmol) of S20b, 17.2 g (110 mmol) of 2-chlorophenylboronic acid [3900-89-8], 41.5 g (300 mmol) of potassium carbonate, 600 ml of THF and 200 ml of water are added 1.64 g (4 mmol) of S-Phos and 499 mg (2 mmol) of palladium(II) acetate, and then the mixture is heated under gentle reflux for 16 h. After cooling, the organic phase is removed, washed twice with 200 ml each time of saturated sodium chloride solution and concentrated to dryness. The residue is boiled in 100 ml of ethanol for 4 h. After cooling, the solids are filtered off with suction, washed with 50 ml of ethanol and dried. Further purification is effected by recrystallization from about 200 ml of ethyl acetate. Yield: 25.9 g (62 mmol); 62%; purity: about 95% by .sup.1H NMR.

[0314] The following compounds can be prepared analogously:

TABLE-US-00004 Ex. Reactants Product Yield S21 [00208]   877993-09-4 Stage 20a [00209] 50% S22 [00210]   654664-63-8 Stage 20a [00211] 54% S23 [00212]   1383628-42-9 Stage 20a [00213] 46% S24 [00214]   364050-45-3 Stage 20a [00215] 48% S25 [00216]   395087-89-5 Stage 20a [00217] 50% S26 [00218]   845952-58-2 Stage 20a [00219] 52% S27 [00220]   313454-72-1 Stage 20 [00221] 44% S28 [00222]   Stage S20 only For preparation see KR 2018045695 [00223] 81% S29 [00224]   22960-25-4 Stage 20 only [00225] 87% S30 [00226]   2222066-63-7 Stage 20 only [00227] 85% * over three stages

Example S50

[0315] ##STR00228##

[0316] To a mixture of 21.1 g (50 mmol) of S1, 20.4 g (100 mmol) of 4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane [24388-23-6], 63.4 g (600 mmol) of sodium carbonate, 400 ml of toluene, 200 ml of ethanol and 400 ml of water are added, with very good stirring, 1.58 g (6 mmol) of triphenylphosphine and then 449 mg (2 mmol) of palladium(II) acetate, and the mixture is heated under reflux for 48 h. After cooling; the organic phase is removed and washed once with 300 ml of water and once with 300 ml of saturated sodium chloride solution, and dried over magnesium sulfate. The desiccant is filtered off and the filtrate is concentrated fully under reduced pressure. The residue is flash-chromatographed (Torrent automatic column system from A. Semrau). Yield: 17.1 g (41 mmol), 82%; purity: about 97% by .sup.1H NMR.

[0317] The following compounds can be prepared analogously:

TABLE-US-00005 Ex. Reactants Product Yield S51 [00229]   329214-79-1 [00230] 73% S52 [00231]   1171891-42-1 [00232] 70% S53 [00233]   2225172-53-0 [00234] 75% S54 [00235]   1171891-07-8 [00236] 77% S55 [00237]   685103-98-4 [00238] 70% S56 [00239]   171364-85-5 [00240] 67% S57 [00241]   2225172-53-0, 50 mmol [00242] 20% [00243]   24388-23-6, 50 mmol

Example S100

[0318] ##STR00244##

[0319] A well-stirred mixture of 31.4 g (200 mmol) of bromobenzene [108-86-1], 16.1 g (100 mmol) of 1-chloro-3,5-ethynylbenzene [1378482-52-0], 194.5 ml (1.5 mol) of triethylamine, 700 ml of DMF and 2.31 g (2 mmol) of tetrakis(triphenylphosphino)palladium(0) is stirred at 70° C. for 16 h. The triethylammonium hydrobromide formed is filtered out of the mixture with suction while it is still warm and washed once with 50 ml of DMF. The filtrate is concentrated to dryness and the residue is taken up in 1000 ml of dichloromethane. The organic phase is washed three times with 300 ml each time of water and once with 300 ml of saturated sodium chloride solution and dried over magnesium sulfate. The organic phase is concentrated to about 300 ml, 100 ml of ethyl acetate is added, the mixture is filtered through a silica gel bed, and the solvent is removed under reduced pressure. The solids thus obtained are extracted once by stirring with 150 ml of methanol and then dried under reduced pressure.

[0320] The solids are hydrogenated in a mixture of 500 ml of THF and 100 ml of MeOH with addition of 10.7 g (200 mmol) of ammonium chloride, 5 g of palladium (5%) on charcoal, at 40° C. under a 2 bar hydrogen atmosphere until uptake of hydrogen has ended (about 12 h). The catalyst is filtered off using a Celite bed in the form of a THF slurry, the solvent is removed under reduced pressure and the residue is flash-chromatographed using an automated column system (CombiFlashTorrent from A Semrau). Yield: 26.3 g (82 mmol), 82%; purity: about 97% by .sup.1H NMR.

[0321] The following compounds can be prepared analogously:

TABLE-US-00006 Reactants Ex. Variant Product Yield S101 [00245]   3972-64-3 [00246] 78% S102 [00247]   626-55-1 [00248] 80% S103 [00249]   4595-59-9 [00250] 75% S104 [00251]   1209459-74-4 [00252] 85% S105 [00253]   626-55-1 Use of: MeOD/ND.sub.4Cl/D.sub.2 [00254] 70%

Example S200

[0322] ##STR00255##

[0323] To a mixture of 41.7 g (100 mmol) of S50, 26.7 g (105 mmol) of bis(pinacolato)diborane [73183-34-3], 29.4 g (300 mmol) of potassium acetate (anhydrous), 50 g of glass beads (diameter 3 mm) and 300 ml of THF are added, with good stirring, 821 mg (2 mmol) of S-Phos and then 225 mg (1 mmol) of palladium(II) acetate, and the mixture is heated under reflux for 16 h. After cooling, the salts and glass beads are removed by suction filtration through a Celite bed in the form of a THF slurry, which is washed through with a little THF, and the filtrate is concentrated to dryness. The residue is taken up in 100 ml of MeOH and stirred in the warm solvent, and the crystallized product is filtered off with suction, washed twice with 30 ml each time of methanol and dried under reduced pressure. Yield: 45.8 g (90 mmol), 90%; purity: about 95% by .sup.1H NMR.

[0324] The following compounds can be prepared analogously:

TABLE-US-00007 Ex. Reactants Product Yield S201 S51  [00256] 88% S202 S52  [00257] 85% S203 S53  [00258] 87% S204 S54  [00259] 91% S205 S55  [00260] 90% S206 S56  [00261] 93% S207 S57  [00262] 90% S300 S100 [00263] 84% S301 S101 [00264] 81% S302 S102 [00265] 86% S303 S103 [00266] 77% S304 S104 [00267] 88% S305 S105 [00268] 80%

Example S400

[0325] ##STR00269##

[0326] A well-stirred mixture of 50.8 g (100 mmol) of S200, 31.4 g (120 mmol) of triisopropylsilylethynyl bromide [111409-79-1], 26.5 g (250 mmol) of sodium carbonate, 2.31 g (2 mmol) of tetrakis(triphenylphosphino)palladium(0), 600 ml of toluene, 300 ml of ethanol and 100 ml of water is stirred at 80° C. for 24 h. After cooling, the organic phase is removed, washed twice with 200 ml each time of saturated sodium chloride solution and dried over magnesium sulfate. The desiccant is filtered off, the filtrate is concentrated at 30° C. under reduced pressure, the residue is taken up in 500 ml of dichloromethane, 110 ml of TBAF (1 M in THF) [10549-76-5] is added, and the mixture is stirred for a further 1 h, then washed twice with 300 ml each time of water and twice with 200 ml each time of saturated sodium chloride solution and concentrated at 30° C., and the residue is chromatographed using an automated column system (CombiFlashTorrent from A Semrau). Storage of the product in a freezer. Yield: 29.4 g (72 mmol), 72%; purity: about 97% by .sup.1H NMR.

[0327] The following compounds can be prepared analogously:

TABLE-US-00008 Ex. Reactants Product Yield S401 S201 [00270] 68% S402 S202 [00271] 65% S403 S203 [00272] 71% S500 S301 [00273] 70% S501 S302 [00274] 67%

[0328] B: Synthesis of the Ligands L:

Example L1

[0329] ##STR00275##

[0330] To a mixture of 50.9 g (100 mmol) of S200, 31.0 g (100 mmol) of 2-(2′-bromo[1,1′-biphenyl]-4-yl)pyridine [1374202-353], 63.7 g (300 mmol) of tripotassium phosphate, 400 ml of toluene, 200 ml of dioxane and 400 ml of water are added, with good stirring, 1.64 g (4 mmol) of S-Phos and then 449 mg (2 mmol) of palladium(II) acetate, and the mixture is heated under reflux for 24 h. After cooling, the organic phase is removed and washed twice with 300 ml each time of water and once with 300 ml of saturated sodium chloride solution, and dried over magnesium sulfate. The desiccant is filtered off, the filtrate is concentrated to dryness under reduced pressure and the glassy crude product is recrystallized at boiling from acetonitrile (˜150 ml) and then for a second time from acetonitrile/ethyl acetate. Yield: 43.3 g (71 mmol), 71%; purity: about 95% by .sup.1H NMR.

[0331] The following compounds can be prepared analogously:

TABLE-US-00009 Reactants Ex. Variant Product Yield L2  S2 S200 [00276] 75% L3  S3 S200 [00277] 79% L4  S4 S200 [00278] 70% L5  [00279] [00280] 73% L6  [00281] [00282] 70% L7  S20 S201 [00283] 77% L8  S21 S202 [00284] 72% L9  S22 S203 [00285] 67% L10  S26 S204 [00286] 69% L11  S29 S205 [00287] 76% L12  S30 S206 [00288] 75% L13  S20 S207 [00289] 65% L100 S24 S300 [00290] 67% L101 S3 S301 [00291] 78% L102 S21 S302 [00292] 74% L103 S25 S303 [00293] 70% L104 S23 S304 [00294] 69% L105 S27 S304 [00295] 72% L106 S28 S304 [00296] 75% L107 S21 S305 [00297] 72%

Example L200

[0332] ##STR00298##

[0333] A well-stirred mixture of 23.4 g (100 mmol) of 2-(4-bromophenyl)pyridine [63993-36-1], 40.7 g (100 mmol) of S400, 81.5 g (250 mmol) of cesium carbonate, 50 g of glass beads (diameter 3 mm), 787 mg (1 mmol) of XPhos-Pd-G2 [1310584-14-5], 477 mg (1 mmol) of XPhos [564483-18-7] and 500 ml of acetonitrile is stirred at 90° C. for 16 h. The salts are filtered off while the mixture is still warm and washed twice with 200 ml each time of DCM. The filtrate is concentrated to dryness. The residue is taken up in 1000 ml of dichloromethane. The organic phase is washed three times with 300 ml each time of water and once with 300 ml of saturated sodium chloride solution and dried over magnesium sulfate. The organic phase is concentrated to about 500 ml, 200 ml of ethyl acetate is added, the mixture is filtered through a silica gel bed, and the solvent is removed under reduced pressure. The solids thus obtained are extracted once by stirring with 150 ml of methanol and then dried under reduced pressure. The solids are hydrogenated in a mixture of 500 ml of THF and 100 ml of MeOH with addition of 10.7 g (200 mmol) of ammonium chloride, 5 g of palladium (5%) on charcoal, at 40° C. under a 2 bar hydrogen atmosphere until uptake of hydrogen has ended (about 12 h). The catalyst is filtered off using a Celite bed in the form of a THF slurry, the solvent is removed under reduced pressure and the residue is flash-chromatographed using an automated column system (CombiFlashTorrent from A Semrau). Yield: 35.6 g (63 mmol), 63%; purity: about 97% by .sup.1H NMR.

[0334] The following compounds can be prepared analogously:

TABLE-US-00010 Ex. Reactants Product Yield L201 S20b S201 [00299] 55% L202 S22b S202 [00300] 58% L203 S28 reactant S203 [00301] 61% L300 S2b S501 [00302] 57% L301 S21b S502 [00303] 60%

[0335] C: Synthesis of the Complexes:

[0336] C1: Uncharged Monodentate Co Ligands

Example Ir100

[0337] ##STR00304##

[0338] A mixture of 6.12 g (10 mmol) of L1, 4.15 g (10 mmol) of [(1,2,5,6-η)-1,5-cyclooctadiene][(1,2,3,3a,7a-η)-1H-inden-1-yl]iridium (=(Ind)Ir(COD)) [102525-11-1], 100 ml of glacial acetic acid and 100 ml of dioxane is stirred at 100° C. for 24 h. The red solution is concentrated to dryness, the residue is taken up in 1000 ml of DCM, 5 ml of triarylamine is added, and a carbon monoxide stream is passed through the solution at 25° C. with good stirring for 3 h. Then the DCM is distilled off, and the DCM distilled off is replaced continuously by methanol. Finally, the mixture is concentrated under reduced pressure to a volume of about 50 ml, and the product is filtered off with suction, washed three times with 30 ml each time of methanol and dried under reduced pressure. Purification is effected by two chromatography runs on silica gel with DCM/n-heptane (2:1, vv). The product thus obtained can, as described in WO 2016/124304, be purified further by means of hot extraction and heat treatment or fractional sublimation. Yield: 4.42 g (6.3 mmol); 63% of theory; purity: >99.5% by .sup.1H NMR.

[0339] The following compounds can be prepared analogously:

TABLE-US-00011 Ex. Ligand Product Yield Ir101 L2 [00305] 48% Ir102 L3 [00306] 45% Ir103 [00307] [00308] 49% Ir104 [00309] [00310] 37% Ir105 L101 [00311] 55% Ir106 L200 PMe.sub.3 504-09-2 25 mmol Rather than CO [00312] 51% Ir107 L300 PF.sub.3 7783-55- 3 25 mmol Rather than CO [00313] 37%

[0340] C2: Monoanionic Monodentate Co Ligands

Example Ir200

[0341] ##STR00314##

[0342] A mixture of 6.14 g (10 mmol) of L.sup.5 and 3.53 g (10 mmol) of IrCl.sub.3×3 H.sub.2O [13569-57-8], 150 ml of ethoxyethanol and 50 ml of water is heated under reflux for 24 h. The brown suspension is concentrated to dryness, the residue is taken up in 50 ml of DMSO, 1.08 g (22 mmol) of sodium cyanide [143-33-9] is added, and the mixture is stirred at 50° C. for 8 h. After the solvent has been removed under reduced pressure, the residue is taken up in 200 ml of DCM and chromatographed on silica gel. The yellow core fraction (Rf˜0.8) is selected, and the DCM is distilled off on a rotary evaporator at water bath temperature 50° C. under standard pressure, continuously replacing the volume of DCM distilled off by addition of EtOH. After the DCM distillation has ended, the mixture is concentrated under reduced pressure to a volume of about 100 ml, the yellow solid is filtered off by means of a double-ended frit, and the solids are washed twice with 50 ml of ethanol each time and dried first in an argon stream and then under reduced pressure (p˜10.sup.−3 mbar, T˜100° C.). The product thus obtained can, as described in WO 2016/124304, be purified further by means of hot extraction and fractional sublimation. Yield: 4.06 g (4.7 mmol); 4.7% of theory; purity: >99.5% by .sup.1H NMR and HPLC.

[0343] The following compound can be obtained analogously:

TABLE-US-00012 Ex. Ligand Product Yield Ir201 L7 [00315] 43%

[0344] C3: Monoanionic and Uncharged Monodentate Co Ligands

Example Ir300

[0345] ##STR00316##

[0346] Preparation analogous to C2. Use of 8.21 g (10 mmol) of L13, 490 mg (10 mmol) of NaCN and 1.03 g (10 mmol) of phenylisonitrile [931-54-4]. Yield: 2.65 g (2.3 mmol); 23% of theory, diastereomer mixture; purity: >99.0% by .sup.1H NMR.

[0347] C4: Uncharged Bidentate Co Ligands

Example Ir400

[0348] ##STR00317##

[0349] A mixture of 7.64 g (10 mmol) of L2, 4.15 g (10 mmol) of [(1,2,5,6-η)-1,5-cyclooctadiene][(1,2,3,3a,7a-η)-1H-inden-1-yl]iridium (=(Ind)Ir(COD)) [102525-11-1], 100 ml of glacial acetic acid and 100 ml of dioxane is stirred at 100° C. for 24 h. The red solution is concentrated to dryness, the residue is taken up in 100 ml of DCM, 5 ml of triarylamine and then 1.87 g (12 mmol) of 2,2′-bipyridine [366-18-7] are added, and the mixture is stirred for a further 12 h. Then the DCM is distilled off, and the DCM distilled off is replaced continuously by methanol. Finally, the mixture is concentrated under reduced pressure to a volume of about 50 ml, and the product is filtered off with suction, washed three times with 30 ml each time of methanol and dried under reduced pressure. Purification is effected by two chromatography runs on silica gel with DCM/EA (2:1, vv). The product thus obtained can, as described in WO 2016/124304, be purified further by means of hot extraction and heat treatment or fractional sublimation. Yield: 3.67 g (3.3 mmol); 33% of theory; purity: >99.5% by .sup.1H NMR.

[0350] C5: Monoanionic Bidentate Co Ligands

Example Ir500

[0351] ##STR00318##

[0352] A mixture of 8.21 g (10 mmol) of L13 and 3.53 g (10 mmol) of IrCl.sub.3×3 H.sub.2O [13569-57-8], 150 ml of ethoxyethanol and 50 ml of water is heated under reflux for 24 h. The brown suspension is concentrated to dryness, the residue is taken up in 100 ml of 2-ethoxyethanol, 7.76 g (50 mmol) of 2-phenylpyridine [1008-89-5] and then 7.71 g (30 mmol) of silver trifluoromethanesulfonate [2923-28-6] are added, and the mixture is stirred at 130° C. for 16 h. The solvent is removed under reduced pressure, the residue is taken up in 300 ml of DCM and filtered through a Celite bed in the form of a DCM slurry, and the DCM is distilled off and replaced continuously with methanol. Finally, the mixture is concentrated to about 100 ml, and the precipitated product is filtered off with suction, washed three times with 30 ml each time of methanol and dried under reduced pressure. Purification is effected by two chromatography runs on silica gel with toluene/DCM (9:1, vv). The product thus obtained can, as described in WO 2016/124304, be purified further by means of hot extraction and heat treatment or fractional sublimation. Yield: Ir500a, Diastereomer1: 2.50 g (2.1 mmol); Ir500b, Diastereomer2: 2.24 g (1.9 mmol); purity: >99.5% by .sup.1H NMR.

[0353] C6: Dianionic Bidentate Co Ligands

Example Ir600

[0354] ##STR00319##

[0355] A 1000 ml three-neck flask with magnetic stirrer bar, water separator with reflux condenser and argon blanketing, internal thermometer (Pt-100 thermocouple) and dropping funnel is charged, under an argon atmosphere, with 6.14 g (10 mmol) of ligand L5, 3.53 g (10 mmol) of IrCl.sub.3×3 H.sub.2O [13569-57-8], 29.45 g (300 mmol) of potassium acetate (anhydrous) [127-08-2], 244 g (2 mol) of benzoic acid [65-85-0] and 9.47 ml (100 mmol) of acetic anhydride [108-24-7]. The reaction mixture is heated rapidly up to 250° C. and then stirred at that temperature for 3 h. The acetic acid distilled off is discharged via the water separator. After 3 h, the reaction mixture is allowed to cool to 130° C., and then 500 ml of methanol is added gradually (caution: delayed boiling possible!). The precipitated product is allowed to sediment, the supernatant is decanted off and transferred with methanol onto a double-ended frit, and the product is filtered off with suction, washed three times with 50 ml of hot methanol and dried under reduced pressure. The solids are suspended in 300 ml of warm DCM for 1 h and then chromatographed with DCM on 300 g of silica gel 60 (Merck). The yellow-orange core fraction (Rf˜0.9) is selected, and the DCM is distilled off on a rotary evaporator at water bath temperature 50° C. under standard pressure, continuously replacing the volume of DCM distilled off by addition of EtOH. After the DCM distillation has ended, the mixture is concentrated under reduced pressure to a volume of about 100 ml, the yellow solid is filtered off by means of a double-ended frit, and the solids are washed twice with 50 ml of ethanol each time and dried first in an argon stream and then under reduced pressure (p 10.sup.−3 mbar, T˜100° C.). The product thus obtained can, as described in WO 2016/124304, be purified further by means of hot extraction and fractional sublimation. Yield: 8.5 g (9.00 mmol); 90% of theory; purity: >99.5% by .sup.1H NMR and HPLC.

[0356] The following compounds can be prepared analogously:

TABLE-US-00013 Ex. Ligand Product Yield Ir- 601 [00320] [00321] 67% Ir- 602 [00322] [00323] 70% Ir- 603 [00324] [00325] 64% Ir- 604 [00326] [00327] 34% Ir- 605 [00328] [00329] 67% Ir- 606 [00330] [00331] 63% Ir- 607 [00332] [00333] 48% Ir- 608 [00334] [00335] 77% Ir- 609 [00336] [00337] 60% Ir- 610 [00338] [00339] 38% Ir- 611 [00340] [00341] 55% Ir- 612 [00342] [00343] 22% Ir- 613 [00344] [00345] 69% Ir- 614 [00346] [00347] 55% Ir- 615 [00348] [00349] 61% Ir- 616 [00350] [00351] 67% Ir- 617 [00352] [00353] 70% Ir- 618 [00354] [00355] 77%

Example: Production of the OLEDs

[0357] 1) Vacuum-Processed Devices:

[0358] OLEDs of the invention and OLEDs according to the prior art are produced by a general method according to WO 2004/058911, which is adapted to the circumstances described here (variation in layer thickness, materials used).

[0359] In the examples which follow, the results for various OLEDs are presented. Cleaned glass plates (cleaning in Miele laboratory glass washer, Merck Extran detergent) coated with structured ITO (indium tin oxide) of thickness 50 nm are pretreated with UV ozone for 25 minutes (PR-100 UV ozone generator from UVP) and, within 30 min, for improved processing, coated with 20 nm of PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), purchased as CLEVIOS™ P VP Al 4083 from Heraeus Precious Metals GmbH Deutschland, spun on from aqueous solution) and then baked at 180° C. for 10 min. These coated glass plates form the substrates to which the OLEDs are applied.

[0360] The OLEDs basically have the following layer structure: substrate/hole injection layer 1 (HIL1) consisting of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm/hole transport layer 1 (HTL1) consisting of HTM1, 150 nm for blue devices, 215 nm for green/yellow devices, 110 nm for red devices/hole transport layer 2 (HTL2)/emission layer (EML)/hole blocker layer (HBL)/electron transport layer (ETL) and finally a cathode. The cathode is formed by an aluminum layer of thickness 100 nm.

[0361] First of all, vacuum-processed OLEDs are described. For this purpose, all the materials are applied by thermal vapor deposition in a vacuum chamber. In this case, the emission layer always consists of at least one matrix material (host material) and an emitting dopant (emitter) which is added to the matrix material(s) in a particular proportion by volume by co-evaporation. Details given in such a form as M1:M2:Ir(L1) (55%:35%:10%) mean here that the material M1 is present in the layer in a proportion by volume of 55%, M2 in a proportion by volume of 35% and Ir(L1) in a proportion by volume of 10%. Analogously, the electron transport layer may also consist of a mixture of two materials. The exact structure of the OLEDs can be found in table 1. The materials used for production of the OLEDs are shown in table 4.

[0362] The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A), the power efficiency (measured in Im/VV) and the external quantum efficiency (EQE, measured in percent) as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian emission characteristics, and also the lifetime are determined. Electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and these are used to calculate the CIE 1931 x and y color coordinates. The OLEDs can initially also be operated at different starting luminances. The values for the lifetime can then be converted to a figure for other starting luminances with the aid of conversion formulae known to those skilled in the art.

[0363] Use of Compounds of the Invention as Emitter Materials in Phosphorescent OLEDs

[0364] One use of the compounds of the invention is as phosphorescent emitter materials in the emission layer in OLEDs. The results for the OLEDs are collated in table 2.

TABLE-US-00014 TABLE 1 Structure of the OLEDs HTL2 EML HBL ETL Ex. thickness thickness thickness thickness D1 HTM3 M3:M4:Ir101 ETM1 ETM1:ETM2 20 nm (30%:60%:10%) 10 nm (50%:50%) 30 nm 30 nm D2 HTM2 M1:M2:Ir201 ETM1 ETM1:ETM2 10 nm (30%:60%:10%) 10 nm (50%:50%) 30 nm 30 nm D3 HTM2 M1:M2:Ir500a ETM1 ETM1:ETM2 10 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm D4 HTM2 M1:M2:Ir608 ETM1 ETM1:ETM2 10 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm D5 HTM2 M1:M2:Ir617 ETM1 ETM1:ETM2 10 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm

TABLE-US-00015 TABLE 2 Results for the vacuum-processed OLEDs EQE (%) Voltage (V) CIE x/y Ex. 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 D1 23.2 3.6 0.16/0.35 D2 25.7 3.1 0.32/0.63 D3 23.8 3.0 0.51/0.48 D4 27.3 3.1 0.52/0.48 D5 27.9 3.0 0.56/0.43

[0365] Solution-Processed Devices:

[0366] A: From Soluble Functional Materials of Low Molecular Weight

[0367] The iridium complexes of the invention can also be processed from solution and lead therein to OLEDs which are much simpler in terms of process technology compared to the vacuum-processed OLEDs, but nevertheless have good properties. The production of such components is based on the production of polymeric light-emitting diodes (PLEDs), which has already been described many times in the literature (for example in WO 2004/037887). The structure is composed of substrate/ITO/hole injection layer (60 nm)/interlayer (20 nm)/emission layer (60 nm)/hole blocker layer (10 nm)/electron transport layer (40 nm)/cathode. For this purpose, substrates from Technoprint (soda-lime glass) are used, to which the ITO structure (indium tin oxide, a transparent conductive anode) is applied. The substrates are cleaned in a cleanroom with DI water and a detergent (Deconex 15 PF) and then activated by a UV/ozone plasma treatment. Thereafter, likewise in a cleanroom, a 20 nm hole injection layer (PEDOT:PSS from Clevios™) is applied by spin-coating. The required spin rate depends on the degree of dilution and the specific spin-coater geometry. In order to remove residual water from the layer, the substrates are baked on a hotplate at 200° C. for 30 minutes. The interlayer used serves for hole transport, with use of HL-X from Merck in this case. The interlayer may alternatively also be replaced by one or more layers which merely have to fulfill the condition of not being leached off again by the subsequent processing step of EML deposition from solution. For production of the emission layer, the triplet emitters of the invention are dissolved together with the matrix materials in toluene or chlorobenzene. The typical solids content of such solutions is between 16 and 25 g/I when, as here, the layer thickness of 60 nm which is typical of a device is to be achieved by means of spin-coating. The solution-processed devices contain an emission layer composed of M5:M6:IrL (20%:55%:25%). The emission layer is spun on in an inert gas atmosphere, argon in the present case, and baked at 160° C. for 10 min. Vapor-deposited above the latter are the hole blocker layer (10 nm ETM1) and the electron transport layer (40 nm ETM1 (50%)/ETM2 (50%)) (vapor deposition systems from Lesker or the like, typical vapor deposition pressure 5×10.sup.−6 mbar). Finally, a cathode of aluminum (100 nm) (high-purity metal from Aldrich) is applied by vapor deposition. In order to protect the device from air and air humidity, the device is finally encapsulated and then characterized. The OLED examples cited have not yet been optimized. Table 3 summarizes the data obtained.

TABLE-US-00016 TABLE 3 Results with materials processed from solution EQE Voltage Emitter (%) (V) CIE x/y Ex. Device 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 Sol-D1 Ir107 20.0 4.6 0.28/0.60 Sol-D2 Ir300 19.3 4.5 0.48/0.51 Sol-D3 Ir400 16.2 4.7 0.56/0.41 Sol-D4 Ir602 21.8 4.5 0.56/0.43 Sol-D5 Ir606 20.7 4.4 0.66/0.34 Sol-D6 Ir613 19.8 4.6 0.47/0.49 Sol-D7 Ir616 21.5 4.4 0.49/0.50

TABLE-US-00017 TABLE 4 Structural formulae of the materials used [00356] HTM1 [136463-07-5] [00357] HTM2 [140933-43-3] [00358] HTM3 [1206465-62-4] [00359] M1 [1257248-13-7] [00360] M2 [1357150-54-9] [00361] M3 [1201800-83-0] [00362] M4 [550378-78-4] [00363] M5 [1616231-60-7] [00364] M6 [1246496-85-4] [00365] ETM1 = M10 [1233200-52-6] [00366] ETM2 [25387-93-3]