LT5783B - Organic iridium complexes, method of preparation thereof and organic electroluminescent element - Google Patents

Abstract

An organic electroluminescent element, consisting of a conductive anode coated with electrically conductive polymer and catode between which is an active layer, consisting of holes-transporting and light-emitting compound and electron transport material and wherein light-emitting and charge-transporting function performs the same organic iridium complex of general formula (I), wherein X denotes hydrogen or halogen atom, hidroxy-, alkoxy-, aryloxy-, alkanoyloxy-, or arenoyloxy- group, R denotes hydrogen or halogen atom, hydroxy-, aloxy-, aryloxy-, alkyl- group.@

Description

The present invention relates to novel organic complexes of iridium (III), which may be described as light emitting materials. The materials of the invention can be used in organic electro-optical devices, in particular, these materials are suitable for electroluminescent elements used in display screens on flat panel televisions, computers, laptops, digital cameras, automotive instrument panels, as well as illumination, indication devices. Their development is driven by high efficiency, the ability to produce large-area, completely flat and even flexible display screens, and the ability to obtain radiation of the required spectral composition.

BACKGROUND OF THE INVENTION

Organic light (electroluminescent element) consists of a glass plate or polymer film with a conductive transparent anode (usually consisting of an indium-tin oxide (ITO) layer), one or more organic layers, and a thin metal layer vaporized thereon, which is a cathode. . Above the cathode may be a protective layer formed by vacuum evaporation, molding, or otherwise. In the organic layer or in the system of such layers located between the anode and the cathode and which is the light emitting part of the luminaire, the voltages are injected with charge carriers: holes from the anode and electrons from the cathode. These charge carriers drift in contrast, recombining when they meet, releasing energy (creating excitons), which causes glow. In order to improve the injection of holes from the anode, as well as to hide possible small ITO defects, another conductive polymer layer is usually touched on the conductive ITO layer. This layer may be composed of two polymeric poly (styrene sulfonate) (PSS) and poly (2,3-dihydroxyethylene [3,4] -1,4-dioxin) (PEDOT) compositions. These polymers, the first of which is an electron acceptor and the second donor, form charge transfer complexes. The composition exhibits a relatively high hole conductivity (J.Shinar. Organic light emitting diodes. A survey. SpringerNew York, 2004).

The next layer of the luminaire is usually the hole transport layer and may be followed by either the electron transport layer or the light emitting layer and already the electron transport layer. A cathode is formed above the electron transport layer, usually by evaporation of the metal under vacuum. The cathode may also have an electron injection layer. As mentioned above, one or more protective layers are applied over the cathode. For example, U.S. Patent No. 6927537 describes a 7-layer luminaire.

Obtaining such a multilayer structure is not easy, and it would be most technologically acceptable if the functions of the hole and electron transport and light emission were compatible in one organic layer.

The light emitting portion of the organic light emitting diodes may be produced by evaporating the materials under vacuum or by casting them from solutions. Low-molecular-weight materials are usually evaporated because of the failure of the solutions to form integral layers due to their crystallization. For example, Japanese patent JP4363891 describes a luminaire whose active layer is obtained by evaporating a diphenylamine compound and an oxadiazole derivative. Although good results have been obtained, it is technically very difficult to form a display screen with a large number of illuminating elements by evaporation.

An alternative is polymeric materials, including polymers containing carbazole moieties, such as those mentioned in JP2002047271, WO2005092857, EP1594939. Polymeric materials can be cast from solutions, which would greatly simplify the production of larger displays. For example, Japanese Patent Application JP2003171524 describes an active layer of a luminaire made of a polymer having holes and electron transport groups. However, the molecular weight of polymeric materials is difficult to control. Even more difficult is the purification of polymeric materials to the required level, which determines the transport and capture properties of the charge carriers. The latter are very important for the efficiency and durability of LEDs.

In organic compounds, 25% of all excitons bound to conjugated double bonds are in the singlet state, the other 75% in the triplet state. When appropriate phosphorescent additives are introduced, light is emitted from both states. Therefore, triplet emitters, which are excited by both singlet and triplet excitons, are the most promising and currently most intensively studied luminescent materials. This increases the quantum yield of both organic and external organic luminaires (MA Baldo, DF O'Brien, Y. You, A. Shoustikov, S. Sibley, ME Thompson, SR Forrest, Nature 395 (1998) 151; Q. Zhang, Q. Zhou, Y. Cheng, L. Wang, D. Ma, X. Jing, F. Wang, Adv. Mater. 11 (1999) 852).

One of the best studied and most effective triplet emitters is the iridium complex (MA Baldo, SR Forrest, Appl. Phys. Lett. 75 (1999) 4; JP Duan, PP Sun, CH Cheng, Adv. Mater. 15 (2003) 224). . However, most of them are poorly soluble crystalline materials, and the expensive vacuum evaporation method is used to make the layers. Recently, there has been a shift towards the use of ligands of a more complex chemical structure. Fragments having hole and electron transport properties, functional groups improving the solubility of compounds, etc. are introduced into their composition. (V. Grushin, N. Herron, D. D. LeCloux, W. J. Marshall, V. Petrov, Y. Wang, Chem. Commun. (2001) 1494; J. Ding, J. Gao, Y. Cheng, Z. Xie, L. Wang, D. Ma, X. Jing, F. Wang, Adv. Funct. Mater. 16 (2006) 575). Such changes make it simpler to produce luminaires using simpler and less expensive spraying and molding techniques and reduce the number of layers required.

Therefore, the object and main problem of the invention is to develop new light-emitting and co-transporting materials which are non-polymeric but which form integral and non-crystallizable films from the solutions and further facilitate the production of organic light, for example by reducing the number of layers.

The solution to the problems of molding from solution and crystallization was to synthesize small molecule materials which would be molecular glasses, i.e. would not crystallize at room temperature or higher and could be used without polymeric binders. On the other hand, some compounds containing carbazole ring groups are known to have sufficient conjugated moieties which determine the charge transfer ability required for light emission. For example, the publication JP2005213188 discloses that compounds having two carbazole ring moieties linked by a certain non-conjugated linking group may be suitable for use in organic electroluminescent elements. The Lithuanian patent LT5444 (published July 20, 2007) describes novel non-polymeric materials for organic electroluminescent elements having hole transporting properties, which also have two carbazole ring fragments linked through unconjugated linker chains.

In order to meet the requirements for organic light emitting cells, there is a need to search for new materials with an optimal combination of light emission and charge transfer and properties that determine the technology of producing electroluminescent cells.

The essence of the invention

The above object is achieved by the totality of the features set forth in claims 1-10 of the claims.

The main object of the present invention is a new material - organic complexes of iridium of general formula (I):

(I) wherein X represents a hydrogen or halogen atom, a hydroxy, an alkoxy, an aryloxy; alkanoyloxy, or arenyloxy; and R represents a hydrogen or halogen atom, a hydroxy, an alkoxy, an aryloxy, an alkyl group.

Optimally, X represents a hydrogen or halogen atom, a hydroxy, Cι-Οβ-alkoxy, aryloxy, C 1 -C 6 alkanoyloxy or arenyloxy group, preferably a hydrogen atom, Cl, Br, hydroxy, methanoyloxy, ethanoyloxy or benzoyloxy group, and R represents a hydrogen or halogen atom, a hydroxy, a C 1 -C 8 alkoxy, an aryloxy, a C 1 -C 8 alkyl group, preferably a hydrogen atom, a chlorine or a methyloxy group.

The inventors have shown that the new materials can be obtained by the process described in the invention, wherein

a) 5-Amino-2-phenyl-1,2,3-benzothiazole or its corresponding derivative is treated with glycidic ether of 1,3-di (carbazol-9-yl) 2-propanol to give an organic ligand of general formula (XVI).

wherein R and X are as defined above,

b) modifying said ligands, if necessary, by known methods by substitution of X and R groups 5 with other X and R groups or their esters;

c) Organic ligands obtained in step a) or modified organic ligands in step b) are treated with iridium trichloride in a mixture of IrCf 'nH ₂ O water and 2-ethoxyethanol at reflux in an inert gas to obtain intermediate dimers of iridium (III) organic complexes of general formula (XVII) )

wherein X and R are as defined above;

d) Intermediate dimers of formula (XVII) are treated with acetylacetone in the presence of a base such as sodium carbonate to yield the organic complexes of iridium of general formula (I) and are isolated, for example, by column chromatography.

Examples of targeted iridium organic complexes which do not limit all possible substances of general formula (I) are compounds (II) to (X):

(ΙΠ)

(VI)

(IX)

(X)

Another object of the invention are novel organic compounds of general formula (XVI),

wherein X and R are as defined above, which are intermediates for the preparation of iridium organic complexes of formula (I).

Studies have shown that the target compounds of the invention exhibit not only hole transport properties but also phosphorescent light emission; Due to these properties, the compounds of the general formula (I) or their mixtures can be used as organic non-polymeric semiconductors - phosphorescent organic emitters in electroluminescent devices, where the active layer is obtained by solution molding.

Accordingly, the present invention also relates to an organic electroluminescent element (luminaire) consisting of a transparent electrically conductive anode, optionally coated with an electrically conductive polymer, and a cathode comprising an active layer having a general formula (I) for emitting light and holes. . The active layer of the organic electroluminescent element of the present invention consists of at least one layer of light emitting and hole transporting materials according to general formula (I) and an electron transporting material composition. In the active layer composition, the positive charge transporting and light emitting substance is the same iridium organic complex of general formula (I) or mixtures thereof, and its ratio to the electron transporting substance is 0.1-9: 1.

Brief description of the drawings

The essential properties of the materials of the invention are illustrated in FIGS. 1 and FIG. 2 depicting:

FIG. 1: Second-curve DSK curves of organic iridium complexes of formulas (II) and (III) demonstrating that these compounds are in a stable amorphous state.

FIG. 2: organic iridium complex (II), (III) and their ligands (XI), (XII) in DMSO solution (c = 10 ^"5 mol / l) to normalize the fluorescence spectra. The excitation wavelength is 365 nm.

Detailed Description of the Invention

General Synthesis Scheme of Compounds of Formula (I).

The hole transporting carbazole chromophores and light emitting materials of general formula (I) were synthesized in several steps.

In a first step, 5-amino-2-phenyl-1,2,3-benzotriazole (Sigma-Aldrich) is treated with 1,3-di (carbazol-9-yl) -2-propanol glycidic ether at 160 ° C (G. Sinkeviciute, A. Stanisauskaite, V. Gaidelis, V. Jankauskas, E. Montrim, Mol. Cryst. Liq. Cryst. 468 (2007) 163) by isolating the ligand (XI) with carbazolyl chromophores.

Other novel ligands can be used as starting materials, for example, 5-amino2- (4-chloro) phenyl-1,2,3-benzthiazole (where IR = p-Cl in the general formula, Sigma-Aldrich), 5 amino-2- (3 -chloro) phenyl-1,2,3-benzothiazole (when in the general formula IR = w-Cl, Sigma 5 Aldrich), 5-amino-2- (4-methoxy) phenyl-1,2,3-benzothiazole (when in the general formula IR = pOCH3, Sigma-Aldrich) and other appropriate materials.

The resulting ligand is replaced by acetic anhydride or benzoyl chloride, the hydroxy group being replaced by ethanoyloxy or benzoyloxy groups; alkylating with alkyl, aryl halides, alkyloxy (ligand XII, when in the general formula I X = OC 2 H 5), aryloxy groups, and

POCl 3, POBr 3, SOCl 2 - halogen (chlorine, bromine) atoms.

In the next step, the synthesized ligands in the first step are treated with iridium trichloride (IrCl3-nH2O) to isolate intermediate trimeric iridium organic dimer complexes, such as XIII (in the general formula IR = H, X = OH) and XIV (in the general formula IR = H, X = OC ₂ H ₅ ).

XI, XII + IrCL

Photoconductive chromophore-containing organic ligands - previously obtained intermediates of the general formula (XVI) - are treated with iridium trichloride IrCb '11H2O (Sigma-Aldrich) in a 2.5: 1 ratio of water to 2-ethoxyethanol (1: 2) at reflux and inert gas (argon). or nitrogen) in the environment.

In the final step, the intermediate dimers of general formula (XVII), such as compounds (XIII), (XIV), are reacted with acetylacetone in the presence of a base such as sodium carbonate. Column chromatography separates the target trivalent iridium and

2-phenyl-1,2,3-benzothiazole complexes, such as compounds (II), (III), which exhibit hole transport and light emission.

The synthesis of certain specific materials of the general formula (I) and their intermediates and their use in the production and testing of LEDs are illustrated in Examples 1-10, which illustrate but do not limit the scope of the invention.

Example 1 - 5-Bis [3-Hydroxy-7- (carbazol-9-yl) -6- (carbazol-9-methyl) -5-oxa-1-heptylamino] -2-phenyl-1,2,3-benzthiazole

g (0.014 mol) of 5-amino-2-phenyl-1,2,3-benzthiazole and 19.2 g (0.043 mol) of 1,3-di (carbazol-9-yl) -2-propanol glycidic ether are heated at 160 ° C for 24 hours. . At the end of the reaction (thin layer chromatography, eluent: acetone-hexane, 1: 4), the benzthiazole derivative (XI) is purified by column chromatography (silica gel 230-400 µm,

60 A, eluent: acetone-hexane, 1: 4). The resulting pure product fraction is dissolved in toluene.

After a while, the greenish-yellow crystals formed were filtered off, washed with 2-propanol and dried in vacuo. Yield: 62% (9.8 g); melt 126-127 ° C (recrystallized from toluene). 1 H NMR (300 MHz, CDCl ₃ , δ, md): 8.37-8.28 (m, 2H, 2-H, 6-H 1-subst Ar); 8.09-7.92 (m, 8H, 4-H, 5-H carbazole); 7.65-7.47 (m, 3H, 3-H, 5-H1-substituent, 7-H triazole); 7.45-7.07 (m, 25H, Ht); 6.61-6.33 (m, 2H, 4-H1-substituent Ar, 4-H triazole); 4.59- 4:40 (m, 4H, N _{2 k} arbazoioCH one branch); 4:38 to 4:20 (m, 6H, N _karbazo I _O CH ₂ CH ₂ N _karbaz oioCH other branches); 4.43-4.32 (m, 1H, NCH ₂ CH singlet);

3:22 to 3:09 (m, 1H, NCH ₂ CH other branches); 2.84-2.66 (m, 4H, one branch of CHCl 3); 2.59-2.28 (m, 4H, other branches of NCH ₂ CHCH ₂ O); 2.28-2.15 (m, 2H, OH). IR (KBr, cni ¹ ):

3542 (OH pi.); 3048 (CH _Ar ); 2927, 2870 (CH _A i); 1121 (COC). Found, (%): C 78.42; H

5.69; N, 10.06. C ₇₂ H ₆₂ N ₈ O ₄ . Calculated (%): C 78.38; H, 5.66; N, 10.16.

Example 5-Bis [3-ethoxy-7- (carbazol-9-yl) -6- (carbazole-9-methyl) -5-oxa-1-heptylamino] -2-phenyl-1,2,3-benzthiazole

4.8 g (4.35 mmol) of 5-bis [3-hydroxy-7- (carbazol-9-yl) -6- (carbazol-9-methyl) -5-oxa-1-heptylamino] -2-phenyl-1,2,3 Benzothiazole (XI), 0.31 g (2.18 mmol) of Na ₂ SO 4 and 0.86 g (13.1 mmol) of 85% potassium hydroxide are boiled in 40 mL of iodetane for 24 hours. After completion of the reaction (thin layer chromatography, eluent: acetone-hexane, 1: 4), the reaction mixture is cooled and filtered. The filtrate is diluted with ethyl acetate and extracted with a neutral water reaction. The organic layer was dried over magnesium sulfate and filtered. The residue obtained by distilling off the solvent is purified by chromatography on a column of silica gel (230-400 µm, 60 A, eluent: acetone-hexane, 1: 4). Yield: 74% (3.73 g), a greenish-yellow amorphous powder. 1 H NMR (300 MHz, CDCl 3, δ, md): 8.38-8.30 (m, 2H, 2-H, 6-H1-subst Ar); 8.01 (d, J = 7.5 Hz, 8H, 4-H, 5-H carbazole); 7.71-7.60 (m, 1H, 7-H triazole); 7.59-7.49 (m, 2H, 3-H, 5-H1-subst Ar); 7.45-7.04 (m, 25H, Ht); 6.856.75 (m, 1H, 4-H1-substituent Ar); 6.69-6.63 (m, 1H, 4-H triazole); 4.59-4.45 (m, 4H,

N _carba2 oioCH ₂ single branches); 4:43 to 4:20 (m, 6H, N _karbaz0 | ₀ CH ₂ CH _Z N _Karb a oioCH _two other branches); 3.07-2.70 (m, 14H, NCH ₂ CHCH ₂ O, OCH ₂ CH ₃ ); 0.73 (t, J = 7.0 Hz, 6H, CH ₃ ). IR (KBr, cm -1): 3048 (CH 2 O); 2969, 2867 (CH _A i); 1120 (COC). Found, (%): C 78.79; H 6.15; N, 9.71. C76H70N8O4. Calculated (%): C 78.73; H, 6.09; N, 9.66.

Example - Tetrakis {5-bis [3-hydroxy-7- (carbazol-9-yl) -6- (carbazol-9-methyl) -5-oxa-1-heptylamino] -2-phenyl-1,2,3-benzothiazole -N, C ² '} (p-dichloro) diiridis

0.2 g (0.67 mmol) of iridium (III) chloride hydrate and 1.85 g (1.67 mmol) of 5-bis [3-hydroxy-7- (carbazol-9-yl) -6- (carbazole-9-methyl) -5-oxa-1 -heptylamino] -2-phenyl-1,2,3-benzthiazole (XI) is dissolved in a mixture of 2-ethoxyethanol (10 ml) and water (5 ml). The resulting solution was heated under argon for 24 hours. The precipitated orange precipitate is filtered off, washed with water, ethanol and dried. The complex dimer (XIII) was purified by column chromatography (silica gel 230-400 µm, 60 A eluent: acetone-hexane, 7:18 and 1: 1). Yield: 40% (1.3 g). IR spectrum (KBr, cm ^-1 ): 3400 (OH pi); 3045 (CH _Ar ); 2924 (CH _A i); 1698 (C = O); 1120 (COC). Found, (%): C 71.01; H, 5.14; 'N 8.99.

C288H244Cl2lr ₂ N32O ₁₆ . Calculated (%): C 71.11; H, 5.06; N, 9.21.

Example - Tetrakis {5-bis [3-ethoxy-7- (carbazol-9-yl) -6- (carbazol-9-methyl) -5-oxa-1-heptylamino] -2-phenyl-1,2,3-benzothiazole -N, C ² '} (p-dichIor) diiridis

(XIV)

Compound (XIV) is synthesized and isolated using analogous procedure to compound 5 (XIII), except that 2.46 g (2.12 mmol) of 5-bis [3-ethoxy-7 (carbazol-9-yl) is used instead of ligand (XI). -6- (carbazole-9-methyl) -5-oxa-1-heptylamino] -2-phenyl-1,2,3-benzothiazole (XII) and 0.253 g (0.849 mmol) of iridium (III) chloride hydrate. The reaction is carried out in a mixture of 2-ethoxyethanol (25 mL) and water (5 mL). Yield: 39% (1.7 g), orange amorphous powder. IR spectrum (KBr, cm ^-1 ): 3046 (CHaf); 2924 (CH _A i); 1698 (C = O); 1120 (COC).

Found (%): C 72.37; H, 5.64; N, 8.52. Cso ^ eCIzI ^ Oie. Calculated (%): C 71.75; H, 5.47; N, 8.81.

example - Iridium (III) -bis {5-bis [3-hydroxy-7- (carbazol-9-yl) -6- (carbazol-9-methyl) -5-oxa-1-heptylamino] -2-phenyl-1, 2,3-Benzothiazolate-N, C ² '} acetylacetonate

(II)

Dissolve 1.3 g (0.267 mmol) of dimer (XIII), 0.08 g (0.802 mmol) of 2,4-pentandione in 2-ethoxyethanol (10 mL) and add 0.28 g (2.67 mmol) of sodium carbonate. The resulting reaction mixture is degassed and refluxed for 24 hours under argon. The resulting product (II) is purified by column chromatography over silica gel (230-400 µm, 60 A, eluent:

acetone-hexane, 1: 4 and 7:18). Yield: 59% (0.79 g), orange amorphous powder. 'H

NMR (300 MHz, CDC1 _3, δ, ppm): 8.21-7.87 (m, 16H, 4-H, 5-H carbazole) 7.84-6.03 (m, 62H, Ht, Ar); 5.03 (s, 1H, CCHC); 4.72-4.06 (m, 20H, NCH ₂ CHCH ₂ N); 3.21-2.51 (m,

24H, NCH ₂ CHCH ₂ O, OH); 1.43 (s, 6H, CCH ₃ ). IR (KBr, cm ^-1 ): 3400 (OH ppm); 3047 (CH _Ar ); 2926 (CH2a); 1698 (C = O); 1121 (COC). Found, (%): C 71.79; H, 5.14; N, 8.93.

Ci49H ₁₂ 9lrN ₁₆ Oio. Calculated (%): C 71.70; H, 5.21; N, 8.98.

example - Iridium (III) -bis {5-bis [3-ethoxy-7- (carbazol-9-yl) -6- (carbazol-9-methyl) -5-oxa-1-heptylamino] -2-phenyl-1, 2,3-benzotriazolate-N, C ² '} acetylacetonate

(III)

The target product (III) was synthesized from 1.6 g (0.314 mmol) of dimer (XIV) and 0.094 g (0.943 mmol) of 2,4-pentanedione using a procedure similar to Example 5. The product was purified by column chromatography (silica gel 230-400 µm, 60 A, eluent: acetone-hexane, 3:22 and 1: 4). Yield: 53% (0.87 g), orange amorphous powder. ¹ H NMR (300 MHz, CDCl ₃ , δ, md): 8.20-7.88 (m, 16H, 4-H, 5-H carbazole); 7.87-6.08 (m, 62H, Ht, Ar); 5.00 (s, 1H, CCHC); 4.70M.03 (m, 20H, NCH ₂ CHCH ₂ N); 3.19-2.50 (m,

28H, NCH ₂ CHCH ₂ O, OCH ₂ CH ₁ ); 1.43 (s, 6H, CCH ₃ ); 0.85-0.54 (m, 12H, CH ₃ ). IR (KBr, cm ^-1 ): 3047 (CH _Ar ); 2925 (CH ₁ ); 1698 (C = O); 1120 (COC). Found (%): C 72.37; H, 5.64; N, 8.52. C _I57 Hi45lrNi ₆ Oi ₀ . Calculated (%): C 72.30; H, 5.60; N, 8.59.

The following examples describe measurements of the ionization potential and hole drift motility of the inventive materials, and the production and testing of LEDs, the electroluminescent elements containing the inventive material.

Example 7 - Setting the glass transition temperature

The glass transition temperature of Iridium Organic Complexes (II) and (III) was determined using a Mettler DSC 30 Differential Scanning Calorimeter. Samples of 5-10 mg were heated in two parallel cycles at 10 ° C / min, heating range 25-225 ° C, standard Al crucible, N2 atmosphere. From the second heating curves (Fig. 1), the glass transition temperature of complexes (II) and (III) was determined to be 146 ° C and 117 ° C, respectively. Differential scanning calorimetric (DSK) analysis clearly shows (Fig. 1) that these substances exhibit a stable amorphous state, i.e. they are molecular glasses and the ethyl groups in compound (III) effectively influence the glass transition temperatures.

Example 8 - Optical Properties of Iridium Organic Complexes II, III and Their Ligands XI, XII The fluorescence spectra of the ligands (XI) and (XII) consisting of 2-phenyl-1,2,3-benzthiazole and carbazole are identical, having the maximum spectrum in the blue region at 466 nm (Fig. 2). The formation of the trivalent iridium and ligand complexes (XI) or (XII), respectively of the compounds (II) or (III) of the invention, results in a new spectral band having a maximum in the red spectral region at 660 nm. In contrast to ligands (XI), (XII), the intensity of this new spectral band is strongly influenced by the presence of molecular oxygen in the environment. By removing oxygen (II) or (III) from solutions containing iridium organic complexes (by blowing inert gas solutions), an increase in fluorescence efficiency up to ten-fold was observed.

On the other hand, the excited state lifetime measurements of iridium organic complexes (II), (III) and their ligands (XI), (XII) showed that excitons have an exciton lifetime of about 7 ns (fluorescence), whereas iridium complexes reaches up to 9 µs (phosphorescence). Thousands of times longer than the ligand (XI), (XII) microsecond excited state lifetime in iridium complexes (II), (III) and strong phosphorescence quenching by molecular oxygen proves that optical jumps in these complexes proceed from the triplet level. This is typical of triplet (phosphorescent) emitters, in which optical jumps from triplet energy levels become partially permissible due to the strong spin-orbit interaction in heavy metals (such as osmium, platinum, iridium) (MA Baldo, DF O'Brien, Y). You, A. Shoustikov, S. Sibley, ME Thompson, SR Forrest, Nature 395 (1998) 151; MA Baldo, S. Lamansky, PE Burrows, ME Thompson and SR Forrest, Appl Phys Phys Lett 75 (1999) 4 ). The color coordinates of the (II) and (III) iridium complexes according to the International Commission on Illumination (CIE, 1931). the standard is (0.69, 0.30).

Fluorescence spectroscopic studies show that these iridium organic complexes (II) and (III) are triplet emitters illuminated in the red spectral region and can be used in the production of phosphorescent organic luminaires.

example - Fabrication and testing of a butterfly (electroluminescent cell) A 50 nm light emitting layer containing a hole emitting carbazole chromophore is applied to a glass coated with a conductive (impedance 8-10 Ω) indium-tin oxide (ITO), - for example, compound (II). The resulting composition was placed in a thermostat and heated at 80 ° C for 1 h. After drying in vacuo, a 50 nm layer of electron transport material (compound XV) is evaporated, followed by a 0.5 nm layer of LiF electron injection and an Al (150 nm layer) cathode.

Compound XV was obtained from Luminescence Technology Corp. (Taiwan).

This produces a LED which, when connected to a voltage of 5.2 V, illuminates red. The main characteristics of the butter are given in Table 1 below.

Example 10 - Manufacture and Testing of a Butter (Electroluminescent Cell) 25 A glass coated with a conductive (impedance 8-10 Ω) indium-tin oxide (ITO) molded with a conductive polymer layer - Aldrich supplied with poly (styrenesulfonate) / poly (2,3-dihydrothieno). 3,4Z>] - 1,4-Dioxin), commonly referred to as PEDOT: PSS. Place the slide with the ITO layer on the centrifuge, pipette ~ 0.3 ml of PEDOT: PSS solution, distribute the solution over the entire surface of the slide, and run the centrifuge at 2800 rpm. speed and rotation for 30 s. Remove the slide from the centrifuge, place in the thermostat and leave for 1 hour. heated at 100 ° C. A 50 nm light emitting layer containing a light emitter containing carbazole chromophores transporting the holes, such as compound (II), is applied onto this layer. The resulting composition was placed in a thermostat and heated at 80 ° C for 1 h. After drying in vacuo, a 50 nm layer of electron transport material (Compound XV) is evaporated followed by a 0.5 nm layer of LiF electron injection and a 150 nm layer of Al at the cathode. An incandescent lamp is obtained which, when connected to 4.8 V, illuminates red. The main characteristics of the luminaire are given in Table 1.

Table 1

Button Characteristics

The LED light Starting voltage, V Anaks? cd / y External quantum performance, ^ / external, max A Example 9 5.2 230V (18V) 1.8 Example 10 4.8 120 (12V) 1.85

Thus, the OLED characteristics in the table indicate that the synthesized iridium organic complexes function together as emitters and as hole transporting agents. The materials of the invention are non-polymeric, do not crystallize at room temperature or higher (molecular glasses are present). Furthermore, the inventive materials, which have both hole transfer and light emission functions in a single compound, prevent or alleviate the problem of multi-layer alignment. There are also many opportunities to modify and optimize the structure of an organic light fixture while improving the properties of the electroluminescent device. By using mixtures of the materials of the invention, for example, the spectral characteristics of the LEDs can be modified.

Claims (4)

DEFINITION OF INVENTION 1. Organic complexes of iridium of general formula (I): (I) wherein X represents a hydrogen or halogen atom, a hydroxy, an alkoxy, an aryloxy, an alkanoyloxy, Or R is a hydrogen or halogen atom, a hydroxy, an alkoxy, an aryloxy, an alkyl group. The iridium organic complexes of claim 1, wherein X represents a hydrogen or halogen atom, a hydroxy, a C 1 -C 6 alkoxy, an aryloxy, a C 1 -C 6 alkanoyloxy or arenyloxy group, Optically hydrogen atom, Cl, Br, hydroxy, methanoyloxy, ethanoyloxy or benzoyloxy group, and R represents hydrogen or halogen atom, hydroxy, C 1 -C 6 alkoxy, aryloxy, C 1 -C 8 alkyl group, preferably hydrogen atom, chlorine or methyloxy. The production of an iridium organic complex of the general formula (I) according to claim 1 or 2 Method 20, wherein: a) 5-Amino-2-phenyl-1,2,3-benzthiazole or a corresponding derivative is treated with a glycidic ether of 1,3-di (carbazol-9-yl) 2-propanol to give an organic ligand of the general formula (XVI): R and X are as defined in point 1, b) modifying said ligands, if necessary, by known methods by substitution of X and R groups 5 with other X and R groups or their esters; c) Organic ligands obtained in step a) or modified organic ligands in step b) are reacted with iridium trichloride in a mixture of IrCb'nHiO water and 2-ethoxyethane in an inert gas to obtain intermediate dimers of iridium (III) organic complexes of general formula (XVII) wherein X and R are as defined in claim 1; d) Intermediate dimers of formula (XVII) are treated with acetylacetone in the presence of a base to obtain the iridium organic complexes of general formula (I) and are isolated, for example, by column chromatography. Organic iridium complexes of the general formula (I) according to claim 1 and / or obtained by the process according to claim 3, selected from the group consisting of compounds (II) - (X):