TW201127932A - Light emitting material - Google Patents

Abstract

A light emitting material comprising a complex of formula I (L1)x-M-(L2)y (I) wherein L1 is a mono-anionic bidentate carbon-coordinating ligand comprising the structural element in a ring system, wherein R1 is a substituent selected from the group consisting of R1-1 to R1-8 the use thereof as emissive materials in organic light emitting devices and organic light emitting devices comprising said emissive material.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a luminescent material, use of the material, and a light-emitting device capable of converting electrical energy into light. [Prior Art] Due to the potential role of organic light-emitting devices (0 led) in the development of new display systems for various applications, there has been an increasing interest in them recently. OLEDs are based on electroluminescence (EL) from organic materials. Compared to photoluminescence, that is, light emission from an active material due to relaxation caused by light absorption and radiation decay of an excited state, electroluminescence is caused by heat generation of light due to application of an electric field to a substrate. . In the latter case, the excitation system is completed by the recombination of charge carriers (electrons and holes) of the opposite-numbered charges injected into an organic semiconductor in the presence of an external circuit. - A simple prototype of an organic light-emitting diode (OLED), a single-layer OLED, typically consisting of a thin film of active organic material sandwiched between two electrodes, one of which needs to be translucent In order to observe the light emission from the organic layer; a glass substrate coated with indium tin oxide (ITO) is usually used as the anode. If an external voltage is applied to the two electrodes, the charge carriers (ie, holes) at the anode, as well as the electrons at the cathode, are injected into the organic layer beyond a specific threshold voltage depending on the applied organic material. . In the presence of an electric field of -5-201127932, the charge carriers move through the active layer and are non-radiatively discharged as they reach the oppositely charged electrodes. However, if the holes and electrons meet each other while drifting through the organic layer, an excited single-line (antisymmetric) and three-wire (symmetric) state (so-called excitons) is formed. Thereby, light is generated in the organic material from the decay of the molecular excited state (or exciton). For every three triplet excitons formed by electrical excitation in a single LED, only one antisymmetric state (single line state) is generated. Many organic materials exhibit fluorescence from singlet excitons (i.e., luminescence from a symmetrically permissive process): because this process occurs between similarly symmetric states, it can be very efficient. Conversely, if the symmetry of the excitons is different from the symmetry of the ground state, the radioactivity relaxation of the excitons will not be allowed and the luminescence will be slow and inefficient. Since the ground state is usually antisymmetric, the symmetry is broken from the decay of the triplet state; thus this process is not allowed and the E L efficiency is very low. Therefore, most of the energy contained in the triplet state is wasted, and the maximum achievable theoretical quantum efficiency is only 25% (where quantum efficiency refers to the efficiency with which holes and electrons recombine to produce luminescence). Luminescence from a symmetry-forbidden process is called phosphorescence. Significantly compared to the fluorescence that decays rapidly due to the high probability of transition, the phosphorescence will last for a few seconds after excitation. The successful application of phosphorescent materials has great promise for organic electroluminescent devices. For example, the advantage of using a phosphorescent material is that all of the excitons based on the triplet state (formed by the holes 201127932 and the electron combination in the EL) in the phosphorescent device can participate in energy transfer and luminescence. This can be achieved by improving the efficiency of the fluorescence process by phosphorescence emission itself or by using a phosphorescent material as a phosphorescent host or as a dopant in a fluorescent guest, where the bulk is derived from the body. Phosphorescence transfers energy from the triplet state of the body to the singlet state of the guest. Due to the spin-orbit coupling resulting in singlet-triplet mixing, multiple heavy metal complexes exhibit effective phosphorescence from the triplet state at room temperature, and OLEDs including such complexes have been shown to have more than 75 The intrinsic quantum yield of %. In particular, some organometallic ruthenium complexes exhibit intense phosphorescence, and effective OLEDs that illuminate in the red and green spectra have been prepared with such complexes. As a means for improving the performance of light-emitting devices, a green light-emitting device has been reported which utilizes the ortho-metallated ruthenium complex Ir(PPy)3 (铱(III) and 2-phenylpyridine). Tri-ortho-metallization complexes, see for example Appl. phys_lett.. 1999, vol. 75, p. 4. In any case, it is important that the luminescent material provide electroluminescent emission in a relatively narrow band concentrated near the selected spectral region, the selected spectral region corresponding to one of the three primary colors (red, green and blue), Thus, they can be used as a coloring layer in an OLED. U.S. Patent No. 6,8 5,3,273, to U.S. Patent No. 6,8,8,8,8,8, discloses a bis-ortho-metallization comprising ruthenium (in) and 2-phenylpyridine (ppy)-coordination. A compounded organic light-emitting material and a device comprising the same. 201127932 This type of complex has the following general structure

0, wherein the L1 system may have an auxiliary ligand having a plurality of structures. The phenyl ring of the ppy-ligand may be substituted in the ortho or para position to the carbon atom bonded to the pyridine ring, and in particular a 2,4-difluoro substitution is disclosed in the compound 2 of the reference. Compounds 3 and 4 of the reference documents show corresponding complexes having an additional substituent on the pyridine ring. US 7,03 7,5 98 discloses novel bis-ortho-metallated rhodium-compounds in which a plurality of different substituents can be used for R1 to R8 in the subsequent formula.

And L1 can also have multiple meanings. Among the many specific examples given for the ppy-ligand are 2-(4-fluorophenyl)-pyridine '2-(2,4-.201127932 difluorophenyl)-pyridine and 2-(2) , 3,4-Trifluorophenyl)-pyridine, even I difluorophenyl)-4-dimethylaminopyridine. For the 3-position of the benzene ring, a substituent other than fluorine. US 2004/0121184 discloses a double-ortho-metallated Ir(ppy) complex in the chemical formula 7 of column 9, wherein the ppy_coordination has two fluorine substituents at the 2 and 4 positions and is in the 3 position. The upper group is a group in which a pyridine ring is also likely to be substituted. An electroluminescent ruthenium compound having a fluorinated phenylpyrimidine and a phenylquinoline is disclosed in US 2004/0 1 88673. This reference is directed to a ruthenium complex having at least two phenylpyridine ligands having at least one fluorine or fluorinated group on the ligand. Although the ketone group can occupy any position on the pyridine or benzene ring, the preferred 4-position of the phenyl ring or the ppy-coordinated fluorine-containing substituent at the 4-position of the pyridine ring is fluorine, perfluorinated. Alkyl or perfluoro group.

Int. J. Mol. Sci. 2008, 9, 1 527 pp discloses the operation of a ruthenium-based emitter material in an organic light-emitting device and gives light on the structure of such a complex with a ligand structure. Information about the characteristics. It is said that the nature of the cyclometallated ligand is altered to tune the color. WO 2002/1 5 645 discloses a phosphorescent Ir complex having a phenylpyridine ligand-based auxiliary ligand which is disubstituted with a fluorine atom on a benzene ring, and reveals the influence of the structural pair of the auxiliary ligand. . Division 2 - (2, 4- did not reveal a base benzene ring with a cyanopyridine, phenyl test population, in which the fluorine is taken as an example. The preferred hospital oxygen is in the principle of phosphorescence The change can be used with the complex, with multiple emission wavelengths -9 - 201127932. Although luminescent materials exhibiting EL luminescence in the green and red regions have been developed, such luminescent materials exhibit luminescent yield and stability. An acceptable combination still requires improvement of the luminescent material that illuminates in the blue region. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide luminescence that exhibits good stability and a satisfactory EL luminescence. Materials. It is therefore another object of the present invention to provide a luminescent material having a maximum emission in the blue range of the spectrum, particularly at wavelengths from 440 nm to 500 nm. This is achieved with a luminescent material as claimed in claim 1 A preferred embodiment is set forth in the dependent claims and the following detailed description. Other objects of the invention include an emissive layer of the luminescent material and Organic light-emitting device comprising the luminescent material 》 The luminescent material according to the invention has the following general formula I (L!) x - Μ - (L2) y (I) wherein L1 is a monoanionic bidentate carbon coordination ligand The ligand includes the following structural elements in a ring system

-10- 201127932 R2 〇R2 / " S \\^ R2 - Se \\^ 0 Ra- ϋ R1 - 1 R, -2 R, - 3 R, *4 〇R-Se- 〇NC-S-- - II R2 R—P=0 RV g II 〇1 0 0 R, -5 R】-6 R1 - 7 u Rr8 wherein R 2 represents a linear, branched or cyclic substituted group having from 1 to 20 carbon atoms a home base chain, or __ optionally substituted alkoxy groups having 1 to 20 carbon atoms, & and Cy represents a 4 to 7 membered carbocyclic or heterocyclic ring, which may be part or Substituted completely by a substituent selected from the group consisting of a substituted straight-chain, branched or cyclic alkyl or alkoxy chain optionally having from 1 to 20 carbon atoms. R2 preferably represents a partially or fully fluorinated alkyl group having 1 to 20, preferably 1 to 8 carbon atoms, and particularly preferably 1 to 4 carbon atoms. Particularly preferred substituents R2 are isomers of trifluoromethyl, hexafluoroethyl and fluorinated propanes. A preferred group of substituents Ri-8 has a ring-like awakening class of the following formula [S] -11 - 201127932

Wherein each IT' may be the same or different, and may each independently and independently come from other substituents having the same meaning as R2, and may further represent a corresponding unsubstituted radical j R2. The L2 in the formula I is a non-monoanionic, non-bidentate or carbon-coordinated ligand. The oxime in Formula I represents a transitional genus having an atomic order of at least 40, preferably 8 to 12 of the periodic system. Preferred transition metals Re, Os ' Ir, Pt, Au, Ru, Rh, Pd and Cu, of which Ir Pt are particularly preferred. The x in the formula I is an integer from 1 to 3 and the y is zero or 2. L 1 is designated as a carbon coordinating ligand 'this is because the metal is bonded to the ligand by a carbon-metal bond; and it is designated as a single anion, since the ligand has only one carbon The atom is connected to the metal. L1 is a bidentate ligand, i.e., it has two points attached to the metal. Preferred luminescent materials are described in more detail below and also in the scope of the dependent patent application. The preferred ligand L1 has the following general formula and is not a gold system and a seed. -12- 201127932

Wherein: E represents a group forming a 5- or 6-membered carbocyclic or heterocyclic ring, preferably an aromatic or heteroaromatic ring, optionally free of a plurality of additional aromatic groups a partially or non-aromatic ring fused, the ring optionally having one or more substituents, optionally forming a fused structure with a ring comprising E2, the ring Ε by a sp2 mixed carbon with the metal ruthenium Coordination and the ring E: comprises the structural element (II) as defined above; Ε2 represents a group forming a 5- or 6-membered heterocyclic ring, preferably a non-metal atom required for the heteroaromatic ring, Optionally fused to a plurality of additional aromatic moieties or non-aromatic rings, optionally having one or more substituents, optionally forming a fused structure with a ring comprising E1, A sp2 mixed nitrogen is coordinated to the metal ruthenium, and X represents a coordinating atom selected from the group IVa, Va or Via of the periodic table: Preferred coordinating atoms X are C, N, 0, S, Se, Te and P, with C and N being particularly preferred. El in the chemical formula III preferably represents a 5- to 10-member, preferably a 5- to 6-membered aromatic or heteroaromatic ring, i.e., an aryl or heteroaryl group. As used herein, an aryl group is typically a [-13-201127932

The Cfi-Cw aryl group 'e.g., phenyl or naphthyl, these groups may be substituted by one or more substituents. It is mentioned that an aryl group may also include a fused ring group in which an aryl group as defined above is fused to one carbocyclic group, heterocyclic group or heteroaryl group 'which may themselves be fused to another ring The system may carry one or more substituents. Ring E! includes a structural element having the chemical formula n, that is, a difluoro-substituted element having two fluorine substituents each bonded to one carbon atom, the fluorine-substituted carbon atom separated by one carbon atom having the same as above The substituent R1 is defined. According to a preferred embodiment, E is a 2,4-difluoro-substituted benzene ring of formula V.

Wherein the benzene ring is bonded to the transition metal atom by an ortho carbon atom and according to another preferred embodiment, E2 represents a five or six membered aromatic or heteroaromatic ring, wherein 5- and 6-membered Aromatic rings, especially pyridine, are preferred. In a particular embodiment, E2 represents a 卩ϋD ring that is linked to Ei by a carbon atom 2 of the steep ring. An exemplary ligand L1 including structural element II is as follows: -14 - .201127932

-15 - i 201127932

-16- 201127932

Among them, L 1 -1 and L 1 - 2 9 to L 1 - 3 5 are preferred. As described above, the ring E2 of the ligand L 1 may carry a ~ or poly substituent, preferably selected from the group consisting of a strong electron donor group, i.e., a group having a Hammett substitution constant. Preferred substituents on ring E: Ci-Cs-alkyl, CrCs-thioalkyl', amine, (^-(:8-alkylamino, CrCs-dialkylamine, in stereo A disubstituted amino group of a rigid structure, such as, for example, a cyclic ethyl group. Particularly preferred dialkylamino substituents have a stereorigid group, a dimethylamino group, and a diethylamine group, preferably Is in the para position of the atom to which E is attached, that is, in a shame H ring as e2' at the 4-position of the pyridine ring. By way of example, the amine group on the pyridine ring (at 1^-30 to a stereorigid structure referred to as L]-35). A particularly preferred ligand L1 is an optionally substituted 2-phenylpyridine (ppy) of the above formula U-1, and L1 L1-〗1 and phenylpyridine compounds depicted in L1-33. L2 is a "non-monoanionic", "non-bidentate" or "coordination of a position" by more than one anion atom ( Non-single

Examples of a non-cyclic one having a negative group - the oxygen of the courtyard and the amine 2 having an acetal structure and the case of Ei being substituted are preferably -2 9 to a non-carbon complex ion) [S -17- 201127932 is attached to the metal, or Forming only one bond (non-bidentate) with the metal or a ligand coordinated to a metal atom (non-carbon coordinated) by an atom other than carbon. L2 generally refers to an auxiliary ligand. Exemplary ancillary ligands are for example as described in WO 02/015645. According to a first preferred embodiment, the ligand L2 is a monoanionic, non-C-coordinated, bidentate ligand selected from the structures represented by the following chemical formulas L2 · 1 to L2-7 or their Tautomers:

Wherein: A is a substituent selected from the group consisting of: halogen, such as -Cl, -F, -Br; -〇R7; -SR7; -N(R7)2; -P(〇R7)2 and " 18 - 201127932 -P(R7)2, wherein R7 is an alkyl, fluoro- or perfluoroalkyl group such as -CH3, -nC4H9, -iC3H7, -CF3, -C2F5, -C3F7 or has one or more a C^-Ce alkyl group, a fluorine- or a perfluoroalkyl group of an ether group, ???J such as -CH2パCH2.0-CH2)n-CH3, -CH2-[CH2(CH3)-0-CH2 n -CH3, -(CF2〇)n-C2F5, wherein n is an integer from 1 to 8: Preferably, the A is selected from the group consisting of -OR7 and -N(R7)2, wherein R7 has the above meaning. D is a group selected from the group consisting of ···CHR8-, -CR8R8-, -CR8 = CH-, -CR8 = CR8-, NH, N-R9, Ο, S or Se; R3, R5, R6 Between each other and each occurrence is the same or different, representing F, Cl, Br, NO2, CN, a straight or branched or cyclic alkyl or alkoxy group having from 1 to 20 carbon atoms a group wherein one or more of the non-adjacent -CH2- groups of 0 may be replaced by -0, -S-, -NR9-, or -CONR1Q-, and one or more of their respective hydrogen atoms May be replaced by F; or an aryl or heteroaryl group having from 4 to 14 carbon atoms which may be substituted by one or more non-aryl-R'; and on the same ring or in two different On the ring, a plurality of substituents R' may together form an additional monocyclic or polycyclic ring system, which may be intentionally aromatic; R4, R8, R9 and R1Q are the same for each other and each occurrence Or different 'and each are an anthracene or an optionally substituted aliphatic or aromatic hydrocarbon group having from 1 to 20 carbon atoms; c is an integer from 1 to 3; d is an integer from 〇 to 4. [ -19- 201127932 According to a second preferred embodiment, L2 comprises two monodentate ligands which may be the same or different. One of the monodentate ligands (hereinafter referred to as T) is preferably selected from the group consisting of cyanide (CN), thiocyanate (NCS), and cyanate (NCO): preferably Cyanide (CN): and the second monodentate ligand (hereinafter referred to as u) is a monodentate neutral ligand, a nitrogen atom mixed by a sp2 or sp3, preferably by A sp2 mixed nitrogen atom is coordinated to the metal ruthenium. The luminescent material according to this embodiment may be characterized by the following general formula

Non-limiting examples of monodentate neutral coordination groups U coordinated to a metal by a sp3 mixed nitrogen atom are noted for those contained in the following chemical formula:

Wherein, RN2, RN3, which are the same or different from each other, are independently selected from the group consisting of c--2 anthracene hydrocarbon groups, such as aliphatic and/or aromatic, and the straight-chain or branched-chain 'optionally substituted. Preferred monodentate neutral ligands coordinated to a metal by a Sp3 mixed nitrogen atom are those ligands of the following formula:

-20- 201127932 wherein rn1, rN2 have the same meaning as defined above, preferably RN1, RN2 are independently selected from a Ci-20 aliphatic group, linear or branched, optionally substituted, Optionally, a substituent containing a hetero atom such as nitrogen or oxygen, such as, in particular, a C, alkoxy, a C 1 -6 dialkylamino group, and the like; preferably a Rah methoxy group The radical group; n A r is an integer from 0 to 5, preferably from 1 to 3, more preferably 2. Preferably, the monodentate neutral ligand u is coordinated to the metal by a nitrogen atom mixed with sp2. The monodentate neutral ligand L2 coordinated to the metal by a SP2 mixed nitrogen atom advantageously comprises at least one imine group. Particularly preferred monodentate neutral ligands U are selected from the following structures u-1 to U-8 or their tautomers.

-21 - 201127932 (A)c

R

(R3)d

(A)c

U-6 wherein A, D and R3 to R 1 ° have the meanings as defined above for the ligands L2 _ j to L2-5; G is a group selected from the group consisting of: -CH = CH-, - CR8 = CH-, -CR8 = CR8-, NH ' N-R9 and CR8 = N-; c is an integer from 0 to 3 and d is an integer from 〇 to 3. As used herein, the term tautomer is intended to mean one of two or more structural isomers that are present in equilibrium and are easy, for example, by electrons and/or a hydrogen atom. Displacement changes from one heterogeneous form to another. According to another preferred embodiment, the ligand L2 is a bidentate phosphinocarboxylate monoanion ligand which is attached to the metal by an oxygen and a phosphorus atom. PL representation

Wherein X1 and X2 are the same or different and are selected from the group consisting of -22-201127932, aryl, heteroaryl, etc. Each of these groups may be optionally substituted with one or more substituents. The chelating bidentate phosphinocarboxylate monoanion ligand PL in the present embodiment is generally a metalacycle of 5, 6 or 7 members with the central transition metal atom, ie, The phosphino group and the carboxylate moiety may be particularly preferably one, two or three carbon atoms, particularly preferably those in which the phosphino group and the carboxylate group are bonded to the same carbon atom. These ligands advantageously form a complex comprising a 5-membered metal cyclization, which is particularly stable in most cases. According to a fourth preferred embodiment, the ligand L2 is selected from the following preferred ligands L2-8 to L2-2 from the WO 0 2 / 1 5 6 4 5 :

23-201127932

L2 - 26 L2 · 27 Any substituent depicted by a bond symbol in the above structure may be independently selected from a hydrogen, halogen-alkyl or aryl group. The above description has included the possibility of different elements of the emitter material according to the invention. In this regard, any of the preferred ligands L1 can be combined with any of the preferred ligands L2 (including ligands T, U, and PL), and in such possible combinations Any of the above is within the scope of the present invention. For those skilled in the art, any ligand L1 considered by Formula I (particularly any of the preferred ligands I/-1 to I/-35) may preferably be Any of the ligands L2 considered in Formula I (particularly with any of the preferred ligands L2-l to L2-5, T, U and PL, and above according to WO 0 2 / 1 5 6 4 5 Preferred ligands are well known.

Particularly preferred emitter materials to L are those having the formula ’ wherein E 1 and E 2 have the meanings as defined above, and wherein L 2 is selected from L 2 -1 -27, T, Ui to U8 or PL. -24- 201127932 Particularly preferred are the following emitter materials, ie, a 2-phenylpyridine moiety in which L is substituted 'this moiety is 4 in the pyridine ring and optionally one or more substituents, preferably The substituent of the Hammett substitution constant of j, i.e., the strong donor group gram, represents that a particularly preferred emitter material according to the present invention represents a structure having a negative. Following

A particularly preferred emitter material has a 2-phenyl group which is optionally substituted for the pyridine moiety as the ligand L 1 and which includes a freely acceptable acid salt or an acetamidine moiety as the ligand L2. : Pyridine A?. The error [S1 -25-201127932 shows a good chemical and thermal (for sublimation) stability which may be advantageous during processing of such materials. The above complex having the formula (I), that is, the above-mentioned synthesis of a metal complex including two ortho-metalated ligands (CAN ligands) and an auxiliary ligand (L), can be borrowed This is done by any known method. Details of synthetic methods suitable for the preparation of the above complexes of formula (I) are noted with interest in "Inorg. Chem.", No. 30, pag. 1 685 (1 99 1 ); "Inorg. Chem. , No. 27, pag. 3464 (1988); Inorg. Chem.”, No. 33, pag. 545 (1994): “Inorg·Chem. Acta”, No. 181, pag. 2 4 5 (1991) , "J.

Organomet. Chem.", No. 35, pag. 2 9 3 (1987), J. Am. Chem. S o c _ ” , No. 107, pag. 1 43 1 (1985). Typically, the synthesis is carried out in two steps according to the following protocol: Step 1 X0 [CAN]MX \[ΓΝ], 2ζ (XVIII) 2 "MX°3" precursor (XVII) H-CTN Bit group (XIX) -► -2HX° Step 2 X0 [C〇N]2 乩-H-2 [rN] M_L x (XVIII) *2 H* (I) where X° is a halogen, preferably Cl, and M, L, CAN have the meanings as defined above. The acid form of the ortho-metalated ligand (H-CAN) and the ancillary ligand (L-H) is either commercially available or can be synthesized very easily by the well-known organic synthesis reaction path -26-201127932. If the transition metal is ruthenium, a trihalogenated ruthenium (III) compound such as IrCl3_H2 ruthenium or a ruthenium hexafluoride compound such as M°3IrX°6 (where X° is a preferred C1 halogen and M° system) A preferred K alkali metal), hexahalogenated ruthenium (IV) compound such as M°2IrX°6 (where X is a preferred C1 halogen and is a preferred K alkali metal) (lr The halogenated precursor, hereinafter, can be used as a starting material for the synthesis of a complex of formula (I) as described above. [CAN] 2IrQ-X°) 2Ir[CAN] 2 complex (chemical formula XVIII, where M = Ir), where X° is halogen (preferably C1), and therefore can be processed by the literature (S. Sprouse) , KA King, PJ Spellane, RJ Watts, J. Am. Chem. Soc., 1 984, 106, 6647-6653; ME Thompson et al., Inorg. Chem., 200 1,40(7), 1 704; ME Thompson et al., J. Am. Chem. Soc., 200 1,1 23 (1 8), 43 04-43 1 2 ) Prepared from the Ir halogenated precursor and the appropriate ortho-metallated ligand. The reaction is advantageously carried out using an excess of the neutral form of the ortho-metallated ligand (H-CAN); a solvent having a high boiling temperature is preferred. For the purposes of the present invention, the term high-boiling temperature solvent is used. A solvent having a boiling point of at least 80 ° C, preferably at least 85 ° C, more preferably at least 90 ° C is indicated. Suitable solvents are, for example, ethoxyethanol, glycerol, dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), and the like; the solvent can be used as it is or Use with a mixture of water. -27- 201127932 Optionally, the reaction can be carried out in the presence of a suitable Brensted base. The [CAN]2IrL complex can be finally reacted by reacting the [(:ΑΝ]2Ιι·(μ-Χ °)2Ir[C^N] 2 complex with the acid form of the auxiliary ligand (LH). Obtained: [αΛΝ]2ΐΓ(μ-Χ0)2ΐΓ[€ΛΝ]2+ LH [CAN]2IrL + HX° can be carried out in a solvent at a high boiling temperature or in a solvent at a low boiling temperature. The solvent having a high boiling temperature is noted to be an alcohol such as ethoxyethanol, glycerin, DMF, NMP, DMSO, and the like; the solvent may be used as it is or in a mixture with water. It is carried out in the presence of a Bronsted domain, such as a metal carbonate, in particular potassium carbonate (K2C03), a metal hydride, in particular sodium hydride (NaH), a metal ethoxylate or a metal methoxylate, in particular NaOCH3 'NaOC2H5. Suitable low boiling temperature solvents are noted to be chlorinated hydrocarbons, especially like methyl chlorides (eg CH3C1; CH2C12; CHC13); dichloromethane is preferred. Optionally, for ligand L A precursor can be used in the second step of the synthesis as defined above, the precursor being in the second The reaction medium in the reaction is advantageously reacted to give the target L ligand. Another object of the invention is the use of a luminescent material as described above in an emissive layer of an organic light-emitting device. In particular, the invention is also directed to the above The luminescent material is used in a body -28-201127932 layer (the function of the OLED in the organic light-emitting device (OLED) as a dopant. Suitable OLEDs are preferably depicted by a multi-layered junction, wherein: 1 series a glass substrate; 2 series (IT0) '3 series a hole transport layer (hTL), 4 materials and a luminescent material-emitting layer-hole blocking layer (HBL) as defined above; 6 series one electron transmission and 7 is an A1 layer cathode. The emitter materials according to the invention show a good result so that they are expected in an OLED device. Of particular interest is the fact that the emitter material is in the blue region of the spectrum. It shows a problem that has not been satisfactorily solved before. The preferred material has a maximum emission of lanthanum from 430, in particular from 4 40 nm to 4 95 nm. Invented emission The bulk material also exhibits an illuminating yield, which is an additional advantage. The following examples are merely illustrative of the invention and are not intended to limit the invention to the embodiments. Other emitter materials may be prepared. An Oxford NMR spectrometer or a Plus spectrometer recorded NMR spectra, both of which were in an emissive layer. As in Figure 1, an indium tin oxide layer consisted of a host material (EML); ETL): a combination of properties that are particularly suitable for most stable emissions of the present invention and provides a solution that solves a range of nm to 500 nm, showing good electrical performance in a similar manner.

Varian Mercury 400 MHz operation -29-201127932. Photoluminescence Spectroscopy The spectrum of photoluminescence was measured on a JASCO FP-750 spectrofluorometer. Spectrophotometric measurements of the photoluminescence (from 0.001 mM to 0.002 mM) were carried out at room temperature in ethanol solution at an excitation wavelength of 3 75 nm unless otherwise indicated. The emission quantum yield was determined using fac-lr(tpy)3 as a reference. Thin layer chromatography was performed using a seesaw. EXAMPLES Example 1: 2-(2,4-Difluoro-3-(2,2,2-trifluoroethanol)phenyl)pyridine (1) and 2-(2,4-difluoro-3- Synthesis of (2,2,2-trifluoroethanone)phenyl)pyridine (2)

Cool a solution of 2-(2,4-diphenyl)-steep (1.7 g, 8.89 mmol, 1 when -30-201127932) in tetrahydrofuran (THF, 30 ml) to -78 ° C and n-Butyllithium (n-BuLi) (6.12 ml, 9.78 mmol, 1.1 equivalent) in hexane was added dropwise to the stirred mixture over 15 min. After stirring at about -78 ° C for 1 hour, ethyl trifluoroacetic acid (1.17 ml, 9.78 mmol, 1.1 equivalents) was added dropwise to the solution over 10 minutes. After the cooling was removed, the temperature of the mixture was increased to At room temperature (23 ° C), the temperature of the mixture was maintained at this temperature overnight with constant stirring. Thereafter, water (50 ml) was added to the mixture, and then the organic compound was extracted with dichloromethane (3 times) and the organic phase was washed with brine (50 ml). The organic extract was dried over MgS04 and the solvent was removed on a rotary evaporator. The crude product was purified by column chromatography eluting EtOAc EtOAc EtOAc:EtOAc 2: Rf = 〇.4, 0.53 g, 2 1 %). Yellow oil turns pale yellow crystals after several hours under air conditions (1) !H NMR (400 MHz, CDC13): 8.73 (d, 1H), 8.04 (dd, 1H), 7.79 (t, 1H), 7.73 (d, 1H), 7.30 (t, 1H), 7.11 (t, 1H), 5.47 (bs, 1H), 3.51 (bs, 1H). (2) 'H NMR (400 MHz, CDC13): 8.73 (d, 1H), 8.31 (dd, 1H), 7.80 (t, 1H), 7.78 (s, 1H), 7.32 (t, 1H), 7.18 ( t, -31 - 201127932 1 Η). 2-(2,4·Difluoro-3-(2,2,2-trifluoroethanone)phenyl)pyridine (2)

A 25 mL two-necked flask was equipped with a reflux condenser and an oxygen inlet. Toluene (1 5 m 1 ) was added, followed by sequential addition of C u C 1 (0 · 0 1 〇g, 0·10 mmol '5 % equivalent) and 1.1 〇-phenanthroline (〇. 〇1 9 S ' 0 . 1 0 mm ο 1 ' 5 % equivalent). Stirring was continued until the color of the solution at room temperature turned transparent black for 20 minutes. Thereafter, 1,2-diethoxycarbonylindole (〇.〇9 g, 0.52 mm〇l '25 % equivalent) was added, followed by the addition of solid K2C03 (0.56 g, 4.15 mm〇l '2 equivalents), and stirring was continued. 1 minute. Add undiluted 2-(2,4-difluoro-3-(2,2,2-trifluoroethanol)phenyl)pyridine (1: 〇·6 g, 2.07 mmol, 1 eq.), and in an oxygen drum The solution is heated to reflux under the conditions of the bubble. After 2 hours, the reaction was found to be complete by thin layer chromatography (TLC), the mixture was cooled to room temperature and the solvent was evaporated in vacuo. The crude product was purified by chromatography eluting EtOAc EtOAc (EtOAc) Example 2: Synthesis of Compound 3 32 · 201127932

3 IrCI3.nH20 (1 equivalent) was dissolved in 2-ethoxyethanol and argon was used at 75. Degas for 30 minutes under C. Then 2.2 equivalents of the cyclometallated ligand (C ΛΝ ) was added directly. The mixture was heated to 125 ° C under argon for 18 hours and protected from light with an aluminum foil. After cooling to about 5 Q ° C, the solvent was reduced to half volume by vacuum. After cooling to room temperature, the mixture was poured into an Erlenmeyer flask containing deionized water. The flask was stored in a refrigerator (approx. 6 Torr for 4 hours. The precipitate was separated by vacuum filtration (by glass-glass frit) and washed thoroughly with water. The yellow solid chamber iW was vacuum dried overnight with a hint The box was protected from light to give the compound 3' as a yellow solid. 'H-NMR (CDC13, 400 MHz): 9.08 (d, 4H); 8.41 (d. 4H); 7.99 (t, 4H); 6.97 ( t, 4H); 5.42 (d, 4H). Example 3: Synthesis of Compound 4 -33- 201127932

4 A mixture of acetamidine acetone (4 equivalents) and TB A OH (3 equivalents) in methylene chloride was refluxed at 40 ° C for half an hour and cooled to 30 ° C. Compound 3 (1 equivalent) was dissolved in dichloromethane and added to a mixture of TBA acetonide. The mixture was heated to 3 ° C for 12 hours under argon and protected from light with an aluminum foil. The mixture was cooled to room temperature and deposited on top of a silica gel column (SiO 2 /CH 2 C 12 ). The product was eluted with CH2C12 / acetone (0 to 25%) to give compound 4 as a yellow powder. 'H-NMR (CDC13, 400 MHz): 8.43 (d, 2H); 8.34 (d, 2H); 7.94 (t, 2H); 7.34 (t, 2H); 5.83 (d, 2H); 5. 30 ( s, 1 H); 1.82 (s, 6H). Figure 2 shows the emission spectrum of Compound 4 at 375 nm after excitation. Example 4: Synthesis of Compound 5 -34- .201127932

5 A mixture of picolinic acid (4 equivalents) and TBAOH (3 equivalents) in methylene chloride was refluxed at 40 ° C for half an hour and cooled to 30. (: Compound 3 (1 eq.) was dissolved in dichloromethane and added to the TBA pyridine formate mixture. The mixture was heated to 30 under argon. (: for 12 hours, protected from light with an aluminum foil. The mixture was cooled to room temperature and deposited on top of a silica gel column (SiO 2 /CH 2 C 12 ). The product was eluted with CH 2 C 12 /acetone ( 〇 to 25%) to give compound 5 as a yellow powder. *H-NMR (CDC13 , 400 MHz): 8.78 (d, 1H); 8.38 (m, 2H); 8.33 (d, 1H); 8.03 (t, 1H) 7.92 (t, 2H); 7.76 (d, 1H); 7.53 (t, 1H); 7.45 (d, 1H); 7.35 (t, 1H); 7.13 (t, 1H); 6.02 (d, 1H); 5.72 (d, 1H); Figure 3 shows compound 5 after excitation at 375 Emission spectrum at nm. Example 5: Synthesis of compound 6 [S] -35- 201127932

A mixture of bipyridine (4 eq.) and compound 3 (1 eq.) was dissolved in dichloromethane and refluxed under argon overnight. The solvent was evaporated and the mixture was dissolved in a minimum amount of dichloromethane and then poured into diethyl ether. The precipitate was filtered and washed with diethyl ether. The solid was dissolved in acetone and a saturated aqueous solution of ammonium hexafluorophosphate was added. The acetone was slowly removed under vacuum, and the precipitate was filtered, washed with water and dried to give compound 6 as a pale blue solid.]H-NMR (CDC13, 400 MHz): 8.70 (d, 2H); 8.39 (d, 2H); 8.25 (t, 2H); 7.92 (m, 4H) 7.62 (d, 2H); 7.57 (t, 2H); 7.28 (d, 2H); 5.86 (d, 2H). Figure 4 shows the emission spectrum of Compound 6 at 3 75 urn after excitation. Example 6: Synthesis of 3-(2,4-difluorophenyl)-5,6,7,8-tetrahydroisoquinoline

-36 201127932 A 500 mL two-necked flask was equipped with a reflux condenser under a drop funnel and an Ar inlet. After drying 2,4-oxabenzene (4.4 g, 31.6 mmol, 1 equivalent) in vacuo, 1,7-octadiyne (1,05 ml ' 7.91 mmol '0.2 5 equivalents) was added to the flask. 'Distilled toluene (200 ml) was then added to the mixture. Toluene (150 ml) was added to the dropping funnel, followed by the sequential addition of 1,7-octadiyne (3.15 ml, 23.7 mmol, 0.75 eq.) and CpCo (CO) 2 (0.28 g, 1.58 mmol, 5% equivalent). The toluene solution with a catalyst was added dropwise to another mixture solution in the flask under reflux for a period of 36 hours under h v (200 W ) and Ar bubbling. The color of the solution turned dark brown after the catalyst was added. After the completion of the dropwise addition, stirring was continued for another 12 hours under the same conditions. The mixture was cooled to room temperature and the solvent was removed on a rotary evaporator. The crude product was purified by EtOAc (EtOAc) elute The light brown material crystallized after a few hours in the air. !H NMR (400 MHz, CDC13): 8.38 (s, 1H), 7.92 (q, 1H), 7.41 (s, 1H), 6.96 (t, 1H), 6.89 (t, 1H), 2.79 (d, 4H ), 1.84 (t, 4H). Example 7: 3-(2,4-Difluoro-3-(2,2,2-trifluoroethanol)phenyl)-5,6,7,8-tetrahydroisoquinoline (8) and 3-( Synthesis of 2,4-difluoro-3-(2,2,2-trifluoroethyl-37-201127932 ketone)phenyl)-5,6,7,8-tetrahydroisoquinoline (9)

Cool a solution of 3-(2,4-difluorophenyl)-5,6,7,8-tetrahydroisoquinoline 7 (2 g, 8.15 mmol, 1 eq.) in THF (50 mL) _ 78 ° C and n-BuLi (5.6 ml ' 8.97 mmol, 1.1 eq.) in hexane was added dropwise to the stirred mixture over 15 minutes. After the cooling was removed, the temperature of the mixture was increased to room temperature ( 23 ° C), and the temperature of the mixture was maintained at this temperature overnight with constant stirring. Thereafter, water (50 ml) was added to the mixture, and then the organic compound was extracted with dichloromethane (3 times) and the organic phase was washed with brine (50 ml). The organic extract was dried over MgS04 and the solvent was removed on a rotary evaporator. The product was purified by column chromatography on silica gel eluting with a 1:2 mixture of ethyl acetate/hexanes to give a yellow oil (8:

Rf = 0.4, 1.13 g, 40%. 9: Rf = 0.2, 0.51 g, 18%). (8) 'H NMR (400 MHz, CDC13): 8.34 (s, 1H), 7.68 (q, -38- 201127932 1H), 7.28 (s, 1H), 6.89 (t, 1H), 5.35 (q, 1Η) ), 4·1〇U, 1H), 2.77 (d, 4H), 1.82 (t, 4H). (9) *H NMR (400 MHz, CDC13): 8.40 (s, 1H), 8.24 (q, 1H), 7.44 (s, 1H), 7.14 (t, 1H), 2.80 (d, 4H), 1- 86 (t, 4H). Example 8: Synthesis of 3-(2,4-difluoro-3-(2,2,2-trifluoroethanone)phenyl-5,6·7·8-tetrahydroisoquinoline (9)

A 25 mL two-necked flask was equipped with a reflux condenser and an oxygen inlet. Toluene (15 ml) was added. Then CuCl (0.014 g, 0.15 mmol, 5% equivalent) and 1.10-phenanthroline (〇·026 g Ο·15 mmol, 5% equivalent) were sequentially added. Stirring is continued until the color of the solution becomes clear at room temperature @胃色1 Stomach for 20 minutes. 1,2-Diethoxycarbonylindole (0.13 g' 〇 · 73 mmol '25 % by volume) was added, followed by solid K 2 CO 3 (0.81 g '5.83 mmol' 2 equivalent), and stirring was continued for another 1 minute. Add undiluted 2-(2,4-difluoro-3-(2,2,2-trifluoroethanol)phenyl) mouth to steep (8: 1.0 g' 2.91 mmol' 1 equivalent)' and in an oxygen drum The solution is heated to reflux under the conditions of the bubble. After 3 hours, the reaction was completed by TLC, the mixture was cooled to room temperature and solvent was evaporated in vacuo. The crude product was purified by chromatography on EtOAc (EtOAc:EtOAc:EtOAc: 41%). Example 9: Synthesis of Compound 1

10 IrClrn H20 (i equivalent) was dissolved in 2 - ethoxyethanol and degassed with argon at 75 ° C for 30 minutes. Then 2.2 equivalents of the cyclometallated ligand (C ΛΝ ) was added directly. The mixture was heated to 1 25 ° C under argon for 18 hours' and protected from light with an aluminum foil. After cooling to about 5 ° C, the solvent was reduced to half volume under vacuum. After cooling to room temperature, the mixture was poured into an Erlenmeyer flask containing deionized water. The flask was stored in a refrigerator (about 6 ° C) for 4 hours. The sink was separated by vacuum filtration (by a frit glass) and washed thoroughly with water. The yellow solid was dried under vacuum at room temperature -40 - 201127932 overnight and was protected from light with an aluminum foil to give 10 as a yellow solid. *H-NMR (CDC13, 400 MHz): 8.92 (s, 4H); 4H); 5.69 (d, 4H); 3.07 (m, 1H); 2.89 (m, 1H); 1H); 2.42 (m, 1H) ); 1.83 (m, 2H); 1.70 (m, 2H). Compound 7.76 (s, >.60 (m, Example 1 〇 : Synthesis of Compound 1 1

A mixture of acetamidine acetone (4 equivalents) and TBAOH (3 equivalents) dexane was refluxed at 40 ° C for half an hour and cooled to dissolve compound 10 (1 equivalent) in dichloromethane and add 7 acetonitrile. In the mixture of compounds. The mixture was heated under argon for 12 hours and protected from light with an aluminum foil. The mixture was cooled 3 and deposited onto the top of a silica gel column (Si02/CH2C12). CH2C12/acetone (0 to [| 25%] was eluted to give a compound 11' color powder. *H-NMR (CDC13, 400 MHz): 8.04 (s, 2H); E dichloromethyl 3 0 ° C. , to TBA to 30 °C i room temperature and the product is used as a yellow 8 · 00 (s, 41 - 201127932 2H); 5.84 (d, 2H); 5.27 (s, 1H); 3.05 (m, 4H); 2.80 (m, 4H); 1.92 (m, 8H); 1.83 (s, 6H). Figure 5 shows the emission spectrum of Compound 11 at 3 75 nm after excitation. Example 11. Results of Compound 5 in an OLED device Spin-coated OLED 0 LED structure: ITO/CH8000/PVK: OXD7: EB166/TPBI/Cs2CO3/Al Compound 5 (Example 4) - Different concentrations: 1.5% w ; 2.5% w ; 5 % w and 10 0 w. Separate! J from SP 2 |Π Luminescence Technology Corp. to lj poly(9-vinylcarbazole) (PVK, Mw = 1.100.000) and OXD-7 (1,3-bis[2-(4-tert-butyl) Phenyl)-1,3,4-oxadiazol-5-yl]benzene). Poly(3,4-ethanedienethiophene): poly(sulfostyrene) (PEDOT:PSS, Clevios CH8000) and 1,3,5-tris[N-(phenyl)benzimidazole]benzene (TP BI) is commercially available from HC Starck and Luminescence Technology Corp., respectively. The device structure consists of a 120 nm transparent IT0 (indium/tin oxide) layer as the bottom electrode (loaded on a glass substrate). The PED0T:PSS layer and the emissive layer were sequentially spin coated on top of the IT0 using a Delta6 RC spin coater from Suss Microtec. The TPBI, Cs2C03, and aluminum top metal contacts were then vaporized in sequence using a Lesker Spectros system. The ITO surface was pretreated with a 〇2-plasma cleaner prior to any further processing. The emissive layer was spin coated from -42 - .201127932 PVK:OXD 7 and a solution of compound 5 in different mass ratios of monochlorobenzene. The OLED was optically and electrically characterized using a C9920-12 External quantum efficiency measurement system from HAMAMATSU. The maximum efficiency obtained was 0.9 1%, 1.2 Cd/A and 0.74 lm/W, of which 1% was doped. The turn-on voltage is 6V. The device containing Compound 5 as the emissive material showed a deeper blue coordinate than the standard emitter FIrpic. The C IE coordinates are as follows: Compound 5 : ( 0.1 7 ; 0.2 8 ) FIrpic ( 0.18 ' 0.39 ) The electroluminescence spectrum is shown in Figure 6.

Evaporated OLED Ο LED structure: ITO/AI 4083/ NPD/mCP: Compound 5/TP BI/C s 2 CO 3 / A1 Emissive layer (EML): 1) mCP: Compound 5. Concentration of compound 5 doped It is 7 % w. 2) TPBI: Compound 5. The concentration of the compound 5 doped is 10% w. PEDOT: PSS (Clevios AI 4083) is commercially available from HC Starck. NPD (N,N'-bis[naphthalen-1-yl]-N,N'-bis[phenyl]-benzidine) and mCP (1,3-bis[carbazol-9-yl]benzene) Lumi nescence

Purchased by Technology Corp. The NPD, mCP: Compound 5, TPBI, Cs2C03, and aluminum top gold-43-201127932 contact points were vapor-deposited using a Lesker Spectros system. Maximum efficiency was achieved when using TPBi as the main body, and they reached 1.84%, 3.63 Cd/A and 1 · 8 1 lm/W. The turn-on voltage is approximately 5·5 V. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the multilayer structure of an OLED of the present invention. Figure 2 is an emission spectrum of the luminescent material (Compound 4) of the present invention at 375 nm after excitation. Figure 3 is an emission spectrum of the luminescent material (Compound 5) of the present invention at 375 nm after excitation. Figure 4 is an emission spectrum of the luminescent material (compound 6) of the present invention at 3 75 nm after excitation. Figure 5 is an emission spectrum of the luminescent material (Compound 11) of the present invention at 375 nm after excitation. Figure 6 is a comparison of the electroluminescence spectrum obtained by a ruthenium LED device containing the luminescent material (Compound 5) of the present invention and a standard emitter FIRpic. [Main component symbol description] 1 : Glass substrate 2 : Indium tin oxide layer 3 : Hole transport layer 4 : Emissive layer 5 : Hole barrier layer -44- 201127932 6 : Electron transport layer 7 : A1 layer cathode -45

Claims (1)

201127932 VII. Patent application scope 1. A luminescent material 'comprises a complex compound of the following formula I (L^xM-^y (I) wherein L1 is a monoanionic bidentate carbon coordination ligand, the The bit base includes the following structural elements in a ring system. Wherein R1 is selected from the following R i _] to Ri- R2 R2 R2 / \\ a S' / -Se R, 1 R! -2 R! -3 base is taken from where R represents 1 to 20 carbons a linearly substituted 'branched or cyclic alkyl chain substituted with an atom, or an optionally substituted alkoxy group having from 1 to 20 carbon atoms, Cy representing a carbocyclic or heterocyclic ring of 4 to 7 members The ring may be partially or completely substituted with a substituent selected from the group consisting of a linear, branched or cyclic alkyl or alkoxy group -46- having 1 to 20 carbon atoms which may be optionally substituted. .201127932 chain, L2 is a non-monoanionic, non-bidentate or non-carbon coordination ligand, Μ represents a transition metal with an atomic sequence of at least 40, and X is an integer from 1 to 3 and y is zero, 丨Or 2. 2. The luminescent material according to claim 1, wherein the transition metal is selected from the group consisting of Re, Os, Ir'pt, Au, Ru, Rh, Pd, and Cu o 3 · Illumination as in claim 1 a material wherein the transition metal is Ir or Pt. 4. For the luminescent material of claim 1, wherein L1 has the following chemical formula III Wherein: Ει represents a non-metal atomic group required to form a 5- or 6-membered carbocyclic or heterocyclic ring, preferably an aromatic or heteroaromatic ring, optionally in combination with a plurality of additional aromatic moieties or non- The aromatic ring is fused, and the ring may optionally have one or more substituents which are optionally fused to a ring comprising E2, which is coordinated with the metal by a sp2 mixed carbon And the ring Ε! includes the structural element (II) as defined above; -47- 201127932 e2 represents a non-metal atomic group required for forming a 5- or 6-membered heterocyclic ring, preferably a heteroaromatic ring. a group optionally fused to a plurality of additional aromatic moieties or non-aromatic rings, optionally having one or more substituents, optionally forming a fused structure with a ring comprising E! Ring E2 is coordinated to the metal ruthenium by a sp2 mixed nitrogen: X represents a coordination element selected from Group IVa, Va or via of the periodic table. 5. The luminescent material of claim 4, wherein X is selected From: C, N, 0, S, Se, Te, and P. 6. The luminescent material of claim 1, wherein e 1 is a 2,4-difluoro substituted benzene ring having the following chemical formula V Wherein the bond of the heavy metal atom and the E2 is via the adjacent carbonogen-J··* 〇7. The luminescent material of the sixth aspect of the patent application, wherein the carbon atom 2 is connected to the ring E! Substituted pyridine ring, 8. The luminescent material of claim 1, wherein the ligand L1 is selected from the group consisting of U-1 to L1-35 -48-201127932 [S 3 -49- 201127932 F L1 -23 L1 -24 L1 -25 L1 -26 L1 -27 L1 -28 L1 -29 L1 -30 L1 -31 9. The luminescent material of claim 6 wherein L1 is selected from the group consisting of: 1^-1 and from IJ-29 to 1^-35. 10. For the luminescent material of claim 1, wherein L2 has one of the chemical formulas L2-l to L2-7, U-1 to U-8, PL and L2-8 to L2-27 -50-201127932 Wherein: A is a substituent selected from the group consisting of: halogen, such as -Cl, -F, -Br; -OR7; -SR7; -N(R7)2; -P(OR7)2 and -P(R7 2) wherein R7 is a Ci-Ce alkyl, fluoro- or perfluoroalkyl group, such as -CH3, -nC4H9, -iC3H7, -CF3, -C2F5, -C3F7 or 'having one or more ether groups a monoalkyl, fluoro- or perfluoroalkyl group, for example -CH2 - (CH2-0-CH2)n-CH3, -CH2-[CH2(CH3)-0-CH2] n-CH3, -(CF20) n-C2F5, n is an integer from 1 to 8; preferably, the oxime is selected from the group consisting of -OR7 and -N(R7)2, wherein R7 has the above meaning, and D is a group selected from the group consisting of: -CHR8-, -CR8R8-, -51 - 201127932 -CR8 = CH-, -CR8 = Cr8_, Ν·Η, N-R9, 〇, s or Se; R3, R5, R6 are between each other and each time Is identical, representing F, Cl, Br, N〇2, CN, a linear or branched or cyclic alkyl or alkoxy group having from 1 to 20 atoms, which is one or more Non-adjacent - CH2 - groups may be replaced by -〇_, -S-, or -CONR1()-, and their respective one or more hydrogen atoms are replaced by F; or may be one or more Non-fragrance -R' takes an aryl or heteroaryl group having from 4 to 14 carbon atoms; and a plurality of substituents R' on the same ring or on two different rings may form an additional single ring or more The ring system of the ring may optionally be an aromatic R4, R8, R9 and R1() which are the same or different from each other and each occurrence and are each hydrazine or have a freely replaceable fat from 1 to 20 a family or aromatic hydrocarbon group; c is an integer from 1 to 3; d is an integer from 〇 to 4, or alternatively, each NR9-sub can be replaced by a phase: 52- 201127932 (R )d (A), (R )d U-2 U-3 u-1 R5 Wherein A, D and R3 to R1Q have the meanings as defined above for the ligands L2- 1 to L2-5; G is a group selected from the group consisting of: -CH = CH-, -CR8 = CH-, -CR8 = CR8-, NH, N-R9 and CR8 = N-; c is an integer from 0 to 3 and d is an integer from 0 to 3, where R8 and R9 have the meanings as defined above, or -53- 201127932 (PL) wherein f and X2 are the same or different and are selected from the group consisting of: (^-(:8_), aryl, heteroaryl, each of which may be optionally substituted by one or more substituents ,or , P-X-p4 η w z z L2 -23 X:CH or NZ: O, S, Se, or Te wherein any substituent depicted by a bond symbol in structures L2-8 to L2-27 can be independently selected from: hydrogen, halogen, Cl_C8 - Alkyl or aryl-54- 201127932 base group. 11. The luminescent material of claim 1 is selected from the group consisting of compounds EM-1 to EM-5 Any substituent wherein one of the substituents is depicted in the structures EM-1 to EM-5 may be independently selected from the group consisting of: hydrogen, halogen-alkyl or aryl groups. 12. Use of a luminescent material as claimed in claim 1 in an emissive layer of an organic light-emitting device. -55-201127932 1 3. A use of a luminescent material according to claim 1 in a bulk layer as a dopant in an organic light-emitting device as an emissive layer. An organic light-emitting device (OLED) comprising an emissive layer comprising an emissive material as described in the scope of the claims. • 56 -