Spiro compound having azafluorene ring structure, light-emitting material, and organic electroluminescent device

Abstract

A compound that emits fluorescence and delayed fluorescence is provided as a material for an organic electroluminescent device of high efficiency, and an organic photoluminescent device and an organic electroluminescent device of high efficiency and high luminance are provided using this compound. The spiro compound of a general formula (1) having an azafluorene ring structure is used as a constituent material of at least one organic layer in an organic electroluminescent device that includes a pair of electrodes, and one or more organic layers sandwiched between the pair of electrodes. ##STR00001##

Claims

1. A spiro compound of the following general formula (1-1) having an azafluorene ring structure ##STR00060## wherein, X.sup.1 and X.sup.2 in the general formula (1-1) represent a substituted or unsubstituted phenoxazinyl, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted phenazinyl, or a diphenylamino group, X.sup.3 represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, cyano, nitro, linear or branched alkyl of 1 to 6 carbon atoms that may have a substituent, cycloalkyl of 5 to 10 carbon atoms that may have a substituent, linear or branched alkenyl of 2 to 6 carbon atoms that may have a substituent, linear or branched alkyloxy of 1 to 6 carbon atoms that may have a substituent, cycloalkyloxy of 5 to 10 carbon atoms that may have a substituent, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, substituted or unsubstituted aryloxy, or a disubstituted amino group substituted with a group selected from an aromatic hydrocarbon group, an aromatic heterocyclic group, and a condensed polycyclic aromatic group, at least one of X.sup.1, X.sup.2, and X.sup.3 is a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a disubstituted amino group substituted with a group selected from an aromatic hydrocarbon group, an aromatic heterocyclic group, and a condensed polycyclic aromatic group, Ar.sup.1 represents a divalent group of an unsubstituted aromatic hydrocarbon wherein the unsubstituted aromatic hydrocarbon is not fluorenyl, and R.sup.1 to R.sup.6, and R.sup.9 to R.sup.14 may be the same or different, and represent a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, cyano, nitro, linear or branched alkyl of 1 to 6 carbon atoms that may have a substituent, cycloalkyl of 5 to 10 carbon atoms that may have a substituent, linear or branched alkenyl of 2 to 6 carbon atoms that may have a substituent, linear or branched alkyloxy of 1 to 6 carbon atoms that may have a substituent, cycloalkyloxy of 5 to 10 carbon atoms that may have a substituent, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, substituted or unsubstituted aryloxy, or a disubstituted amino group substituted with a group selected from an aromatic hydrocarbon group, an aromatic heterocyclic group, and a condensed polycyclic aromatic group, wherein R.sup.1 to R.sup.6, and R.sup.9 to R.sup.14 may bind to each other via a single bond, substituted or unsubstituted methylene, an oxygen atom, or a sulfur atom to form a ring.

2. The spiro compound having an azafluorene ring structure according to claim 1, wherein the spiro compound is represented by the following general formula (1a-1) ##STR00061## wherein, X.sup.1 and X.sup.2 in the general formula (1a-1) represent a substituted or unsubstituted phenoxazinyl, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted phenazinyl, or a diphenylamino group, X.sup.3 represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, cyano, nitro, linear or branched alkyl of 1 to 6 carbon atoms that may have a substituent, cycloalkyl of 5 to 10 carbon atoms that may have a substituent, linear or branched alkenyl of 2 to 6 carbon atoms that may have a substituent, linear or branched alkyloxy of 1 to 6 carbon atoms that may have a substituent, cycloalkyloxy of 5 to 10 carbon atoms that may have a substituent, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, substituted or unsubstituted aryloxy, or a disubstituted amino group substituted with a group selected from an aromatic hydrocarbon group, an aromatic heterocyclic group, and a condensed polycyclic aromatic group, at least one of X.sup.1, X.sup.2, and X.sup.3 is a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a disubstituted amino group substituted with a group selected from an aromatic hydrocarbon group, an aromatic heterocyclic group, and a condensed polycyclic aromatic group, Ar.sup.1 represents a divalent group of an unsubstituted aromatic hydrocarbon wherein the unsubstituted aromatic hydrocarbon is not fluorenyl, and R.sup.1 to R.sup.6, and R.sup.9 to R.sup.14 may be the same or different, and represent a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, cyano, nitro, linear or branched alkyl of 1 to 6 carbon atoms that may have a substituent, cycloalkyl of 5 to 10 carbon atoms that may have a substituent, linear or branched alkenyl of 2 to 6 carbon atoms that may have a substituent, linear or branched alkyloxy of 1 to 6 carbon atoms that may have a substituent, cycloalkyloxy of 5 to 10 carbon atoms that may have a substituent, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, substituted or unsubstituted aryloxy, or a disubstituted amino group substituted with a group selected from an aromatic hydrocarbon group, an aromatic heterocyclic group, and a condensed polycyclic aromatic group, wherein R.sup.1 to R.sup.6, and R.sup.9 to R.sup.14 may bind to each other via a single bond, substituted or unsubstituted methylene, an oxygen atom, or a sulfur atom to form a ring.

3. The spiro compound having an azafluorene ring structure according to claim 1, wherein, X.sup.3 in the general formula (1-1) is substituted or unsubstituted carbazolyl, substituted or unsubstituted phenoxazinyl, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted acridinyl, substituted or unsubstituted phenazinyl, or a disubstituted amino group substituted with an aromatic hydrocarbon group or a condensed polycyclic aromatic group.

4. The spiro compound having an azafluorene ring structure according to claim 1, wherein, X.sup.3 in the general formula (1-1) is a hydrogen atom.

5. A light-emitting material comprising the Spiro compound having an azafluorene ring structure according to claim 1.

6. The light-emitting material according to claim 5, which emits delayed fluorescence.

7. An organic electroluminescent device comprising a pair of electrodes, and one or more organic layers sandwiched between the pair of electrodes, wherein the spiro compound having an azafluorene ring structure according to claim 1 is used as a constituent material of at least one organic layer.

8. The organic electroluminescent device according to claim 7, wherein one of the one or more organic layers is a light emitting layer.

9. The organic electroluminescent device according to claim 8, wherein one of the one or more organic layers emits delayed fluorescence.

10. The organic electroluminescent device according to claim 7, wherein one of the one or more organic layers is a hole transport layer.

11. The organic electroluminescent device according to claim 7, wherein one of the one or more organic layers is an electron blocking layer.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a .sup.1H-NMR chart of the compound of Example 1 of the present invention (Compound 1).

(2) FIG. 2 is a .sup.1H-NMR chart of the compound of Example 2 of the present invention (Compound 2).

(3) FIG. 3 is a .sup.1H-NMR chart of the compound of Example 3 of the present invention (Compound 3).

(4) FIG. 4 is a .sup.1H-NMR chart of the compound of Example 4 of the present invention (Compound 4).

(5) FIG. 5 is a diagram illustrating the configuration of the organic EL device of Example 10.

(6) FIG. 6 is a graph representing the current density-voltage characteristics, and the luminance-voltage characteristics of the organic EL device of Example 10.

(7) FIG. 7 is a graph representing the current density-external quantum efficiency characteristics of the organic EL device of Example 10.

MODE FOR CARRYING OUT THE INVENTION

(8) The spiro compounds of general formula (1) having an azafluorene ring structure of the present invention are novel compounds, and can be synthesized, for example, as follows. A halogen-substituted triarylamine is reacted first with a Grignard reagent, and then with azafluorenone to synthesize a carbinol product. The carbinol product is then subjected to a ring-closing reaction using an acid catalyst or the like to synthesize a spiro compound having an azafluorene ring structure.

(9) This spiro compound having an azafluorene ring structure may be brominated with a compound such as N-bromosuccinimide to synthesize a bromo-substituted product, which is then reacted with various diarylamines in Buchwald-Hartwig reaction or other condensation reactions to synthesize the spiro compound having an azafluorene ring structure of the present invention.

(10) The spiro compound having an azafluorene ring structure of the present invention also can be synthesized by reacting the bromo-substituted product with various boronic acids or borates in a cross-coupling reaction such as Suzuki coupling (refer to Non-Patent Document 2, for example).

(11) The following presents specific examples of preferred compounds among the spiro compounds of general formula (1) having an azafluorene ring structure. The present invention, however, is not restricted to these compounds.

(12) ##STR00006## ##STR00007## ##STR00008## ##STR00009## ##STR00010## ##STR00011## ##STR00012## ##STR00013## ##STR00014## ##STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022## ##STR00023## ##STR00024## ##STR00025## ##STR00026## ##STR00027## ##STR00028## ##STR00029## ##STR00030## ##STR00031##

(13) These compounds were purified by methods such as column chromatography; adsorption using, for example, a silica gel, activated carbon, or activated clay; recrystallization or crystallization using a solvent; and sublimation. The compounds were identified by an NMR analysis. A work function was measured as a material property value. The work function can be used as an index of energy level as a material for a light emitting layer.

(14) For the measurement of work function, a 100 nm-thick thin film was fabricated on an ITO substrate, and an atmosphere photoelectron spectrometer (AC-3 produced by Riken Keiki Co., Ltd.) was used.

(15) The organic EL device of the present invention may have a structure including an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and a cathode successively formed on a substrate, optionally with an electron injection layer between the electron transport layer and the cathode. In such a multilayer structure, some of the organic layers may be omitted. For example, the device may be configured to include an anode, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode successively formed on a substrate, or to include an anode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode successively formed on a substrate.

(16) Each of the light emitting layer, the hole transport layer, and the electron transport layer may have a laminate structure of two or more layers.

(17) Electrode materials with high work functions such as ITO and gold are used as the anode of the organic EL device of the present invention. Examples of the material used for the hole injection layer of the organic EL device of the present invention can be naphthalenediamine derivatives; starburst-type triphenylamine derivatives; triphenylamine trimers and tetramers such as an arylamine compound having a structure in which three or more triphenylamine structures are joined within the molecule via a single bond or a divalent group that does not contain a heteroatom; accepting heterocyclic compounds such as hexacyano azatriphenylene; and coating-type polymer materials, in addition to porphyrin compounds as represented by copper phthalocyanine. These materials may be formed into a thin film by a vapor deposition method, or other known methods such as a spin coating method and an inkjet method.

(18) Examples of the material used for the hole transport layer of the organic EL device of the present invention can be compounds containing a m-carbazolylphenyl group; benzidine derivatives such as N,N-diphenyl-N,N-di(m-tolyl)-benzidine (TPD), N,N-diphenyl-N,N-di(-naphthyl)-benzidine (NPD), and N,N,N,N-tetrabiphenylylbenzidine; 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC); various triphenylamine trimers and tetramers; and carbazole derivatives, in addition to the spiro compounds of general formula (1) having an azafluorene ring structure of the present invention. These may be individually deposited for film forming, may be used as a single layer deposited as a mixture with other materials, or may be formed as a laminate of individually deposited layers, a laminate of mixedly deposited layers, or a laminate of an individually deposited layer and a mixedly deposited layer. Examples of the material used for the hole injection/transport layer can be coating-type polymer materials such as poly(3,4-ethylenedioxythiophene) (PEDOT)/poly(styrene sulfonate) (PSS). These materials may be formed into a thin-film by a vapor deposition method, or other known methods such as a spin coating method and an inkjet method.

(19) The material used for the hole injection layer or the hole transport layer may be obtained by p-doping trisbromophenylamine hexachloroantimony into a material commonly used for these layers, or may be, for example, polymer compounds each having, as a part of the compound structure, a structure of a benzidine derivative such as TPD.

(20) Examples of the material used for the electron blocking layer of the organic EL device of the present invention can be compounds having an electron blocking effect, including carbazole derivatives such as 4,4,4-tri(N-carbazolyl)triphenylamine (TCTA), 9,9-bis[4-(carbazol-9-yl)phenyl]fluorene, 1,3-bis(carbazol-9-yl)benzene (mCP), and 2,2-bis(4-carbazol-9-ylphenyl)adamantane (Ad-Cz); and compounds having a triphenylsilyl group and a triarylamine structure, as represented by 9-[4-(carbazol-9-yl)phenyl]-9-[4-(triphenylsilyl)phenyl]-9H-fluorene, in addition to the spiro compounds of general formula (1) having an azafluorene ring structure of the present invention. These may be individually deposited for film forming, may be used as a single layer deposited as a mixture with other materials, or may be formed as a laminate of individually deposited layers, a laminate of mixedly deposited layers, or a laminate of an individually deposited layer and a mixedly deposited layer. These materials may be formed into a thin film by a vapor deposition method, or other known methods such as a spin coating method and an inkjet method.

(21) Examples of the material used for the light emitting layer of the organic EL device of the present invention can be the spiro compounds of general formula (1) having an azafluorene ring structure of the present invention; delayed fluorescence-emitting materials such as CDCB derivatives of PIC-TRZ (refer to Non-Patent Document 1, for example), CC2TA (refer to Non-Patent Document 3, for example), PXZ-TRZ (refer to Non-Patent Document 4, for example), 4CzIPN or the like (refer to Non-Patent Document 5, for example); various metal complexes including, for example, quinolinol derivative metal complexes such as tris(8-hydroxyquinoline)aluminum (Alq.sub.3); anthracene derivatives; bis(styryl)benzene derivatives; pyrene derivatives; oxazole derivatives; and polyparaphenylene vinylene derivatives. Further, the light emitting layer may be made of a host material and a dopant material. In this case, examples of the host material can be the spiro compounds of general formula (1) having an azafluorene ring structure of the present invention, mCP, thiazole derivatives, benzimidazole derivatives, and polydialkyl fluorene derivatives. Examples of the dopant material can be the spiro compounds of general formula (1) having an azafluorene ring structure of the present invention, delayed fluorescence-emitting materials such as CDCB derivatives of PIC-TRZ, CC2TA, PXZ-TRZ, 4CzIPN or the like; quinacridone, coumarin, rubrene, anthracene, perylene, and derivatives thereof; benzopyran derivatives; rhodamine derivatives; and aminostyryl derivatives. These may be individually deposited for film forming, may be used as a single layer deposited as a mixture with other materials, or may be formed as a laminate of individually deposited layers, a laminate of mixedly deposited layers, or a laminate of an individually deposited layer and a mixedly deposited layer.

(22) Further, the light-emitting material may be phosphorescent light-emitting material. Phosphorescent materials as metal complexes of metals such as iridium and platinum may be used as the phosphorescent light-emitting material. Examples of the phosphorescent materials include green phosphorescent materials such as Ir(ppy).sub.3, blue phosphorescent materials such as Flrpic and FIr6, and red phosphorescent materials such as Btp.sub.2Ir(acac) and Ir(piq).sub.3. Here, carbazole derivatives such as 4,4-di(N-carbazolyl)biphenyl (CBP), TCTA, and mCP may be used as the hole injecting and transporting host material. Compounds such as p-bis(triphenylsilyl)benzene (UGH2), and 2,2,2-(1,3,5-phenylene)-tris(1-phenyl-1H-benzimidazole) (TPBI) may be used as the electron transporting host material. These may be individually deposited for film forming, may be used as a single layer deposited as a mixture with other materials, or may be formed as a laminate of individually deposited layers, a laminate of mixedly deposited layers, or a laminate of an individually deposited layer and a mixedly deposited layer.

(23) In order to avoid concentration quenching, the doping of the host material with the phosphorescent light-emitting material should preferably be made by co-evaporation in a range of 1 to 30 weight percent with respect to the whole light emitting layer.

(24) These materials may be formed into a thin-film by using a vapor deposition method, or other known methods such as a spin coating method and an inkjet method.

(25) It is also possible to produce a device of a structure that includes a light emitting layer produced with the compound of the present invention, and an adjacently laminated light emitting layer produced by using a compound of a different work function as the host material (refer to Non-Patent Document 6, for example).

(26) The hole blocking layer of the organic EL device of the present invention may be formed by using hole blocking compounds such as various rare earth complexes, oxazole derivatives, triazole derivatives, and triazine derivatives, in addition to the metal complexes of phenanthroline derivatives such as bathocuproin (BCP), and the metal complexes of quinolinol derivatives such as aluminum(III) bis(2-methyl-8-quinolinate)-4-phenylphenolate (BAlq). These materials may also serve as the material of the electron transport layer. These may be individually deposited for film forming, may be used as a single layer deposited as a mixture with other materials, or may be formed as a laminate of individually deposited layers, a laminate of mixedly deposited layers, or a laminate of an individually deposited layer and a mixedly deposited layer. These materials may be formed into a thin-film by using a vapor deposition method, or other known methods such as a spin coating method and an inkjet method.

(27) The electron transport layer of the organic EL device of the present invention may be formed by using various metal complexes, triazole derivatives, triazine derivatives, oxadiazole derivatives, thiadiazole derivatives, carbodiimide derivatives, quinoxaline derivatives, phenanthroline derivatives, silole derivatives, and benzimidazole derivatives such as TPBI, in addition to metal complexes of quinolinol derivatives such as Alq.sub.a and BAlq. These may be individually deposited for film forming, may be used as a single layer deposited as a mixture with other materials, or may be formed as a laminate of individually deposited layers, a laminate of mixedly deposited layers, or a laminate of an individually deposited layer and a mixedly deposited layer. These materials may be formed into a thin-film by using a vapor deposition method, or other known methods such as a spin coating method and an inkjet method.

(28) Examples of the material used for the electron injection layer of the organic EL device of the present invention can be alkali metal salts such as lithium fluoride and cesium fluoride; alkaline earth metal salts such as magnesium fluoride; and metal oxides such as aluminum oxide. However, the electron injection layer may be omitted in the preferred selection of the electron transport layer and the cathode.

(29) The material used for the electron injection layer or the electron transport layer may be obtained by N-doping metals such as cesium into a material commonly used for these layers.

(30) The cathode of the organic EL device of the present invention may be made of an electrode material with a low work function such as aluminum, or an alloy of an electrode material with an even lower work function such as a magnesium-silver alloy, a magnesium-indium alloy, and an aluminum-magnesium alloy.

(31) Specific examples of preferred materials that may be used in the organic EL device of the present invention are shown below, but the materials that may be used in the present invention are not construed as being limited to the following exemplified compounds. The compound that is shown as a material having a particular function may also be used as a material having another function. In the structural formulae of the following exemplary compounds, R and R.sub.2 to R.sub.7 each independently represent a hydrogen atom or a substituent, and n represents an integer of 3 to 5.

(32) Preferred examples of a compound that may also be used as the host material of the light emitting layer are shown below.

(33) ##STR00032## ##STR00033## ##STR00034## ##STR00035## ##STR00036## ##STR00037##

(34) Preferred examples of a compound that may also be used as the material of the hole injection layer are shown below.

(35) ##STR00038## ##STR00039##

(36) Preferred examples of a compound that may also be used as the material of the hole transport layer are shown below.

(37) ##STR00040## ##STR00041## ##STR00042## ##STR00043## ##STR00044## ##STR00045## ##STR00046## ##STR00047##

(38) Preferred examples of a compound that may also be used as the material of the electron blocking layer are shown below.

(39) ##STR00048## ##STR00049##

(40) Preferred examples of a compound that may also be used as the material of the hole blocking layer are shown below.

(41) ##STR00050## ##STR00051## ##STR00052##

(42) Preferred examples of a compound that may also be used as the material of the electron transport layer are shown below.

(43) ##STR00053## ##STR00054## ##STR00055## ##STR00056## ##STR00057##

(44) Preferred examples of a compound that may also be used as the material of the electron injection layer are shown below.

(45) ##STR00058##

(46) Preferred examples of a compound as a material that may be added are shown below. For example, the compound may be added as a stabilizing material.

(47) ##STR00059##

(48) The following describes an embodiment of the present invention in more detail based on Examples. The present invention, however, is not restricted to the following Examples.

Example 1

Synthesis of 2,7-bis(Diphenylamino)-10-phenyl-10H-spiro{acridine-9,9-(4,5-diazafluorene)} (Compound 1)

(49) A THF solution of a 1.3 M isopropylmagnesium chloride-lithium chloride complex was added into a nitrogen-substituted reaction vessel, and cooled to 20 C. A solution containing 8.2 g of 2-iodotriphenylamine in 12 ml of THF was then dropped at 20 C., and the mixture was stirred for 30 min. Thereafter, a solution of 4,5-diazafluorenone in 70 ml of THF was dropped at 20 C., and the mixture was stirred for 2 h after raising the temperature to room temperature. After adding 100 ml of a 20% (w/v) ammonium chloride aqueous solution, the mixture was concentrated under reduced pressure, and the precipitated crude product was collected by filtration. The precipitate was then washed by being heated to reflux with methanol to obtain a white powder of 9-{2-(diphenylamino)phenyl-4,5-diazafluoren-9-ol (7.8 g; yield 83%).

(50) 7.8 g of the 9-{2-(diphenylamino)phenyl-4,5-diazafluoren-9-ol product, and 15 mL of Eaton's reagent were added into a nitrogen-substituted reaction vessel, heated, and stirred at 60 C. for 24 h. After adding 50 ml of water, a 20% (w/v) sodium hydroxide aqueous solution was added, and the precipitated crude product was collected by filtration. The precipitate was purified by column chromatography (support: NH silica gel, eluent: toluene/ethyl acetate), and through crystallization with a mixture of toluene and methanol to obtain a white powder of 10-phenyl-10H-spiro{acridine-9,9-(4,5-diazafluorene)} (5.5 g; yield 74%).

(51) 5.0 g of the 10-phenyl-10H-spiro{acridine-9,9-(4,5-diazafluorene)} product, and 100 mL of chloroform were added into a nitrogen-substituted reaction vessel, and 4.4 g of N-bromosuccinimide was added while stirring the mixture at room temperature. The resulting mixture was further stirred for 6 h. After adding methanol, the mixture was concentrated under reduced pressure, and washed by being heated to reflux with methanol to obtain a white powder of 2,7-dibromo-10-phenyl-10H-spiro{acridine-9,9-(4,5-diazafluorene)} (6.5 g; yield 94%).

(52) 1.5 g of the 2,7-dibromo-10-phenyl-10H-spiro{acridine-9,9-(4,5-diazafluorene)} product, 1.8 g of diphenylamine, 1.1 g of sodium tert-butoxide, 0.09 g of palladium acetate, 0.1 g of 2-(dicyclohexylphosphino)biphenyl, and 30 ml of o-xylene were added into a nitrogen-substituted reaction vessel, and heated to reflux for 48 h. After adding 100 ml of toluene, the mixture was heated, and stirred at 100 C. The filtrate was collected by thermal filtration, and concentrated under reduced pressure to obtain a crude product. The crude product was then purified by column chromatography (support: silica gel, eluent: toluene/ethyl acetate), and through crystallization with a mixed solvent of toluene and methanol to obtain a yellow powder of 2,7-bis(diphenylamino)-10-phenyl-10H-spiro{acridine-9,9-(4,5-diazafluorene)} (Compound 1; 0.8 g; yield 42%).

(53) The structure of the yellow powder product was identified by NMR. The .sup.1H-NMR measurement result is shown in FIG. 1.

(54) .sup.1H-NMR (DMSO-d.sub.6) detected 37 hydrogen signals, as follows. (ppm)=8.58 (2H), 7.92 (2H), 7.76 (2H), 7.64 (3H), 7.38 (2H), 7.08 (8H), 6.86 (4H), 6.68 (10H), 6.27 (2H), 5.92 (2H).

Example 2

Synthesis of 2,7-bis(9H-Carbazol-9-yl)-10-phenyl-10H-spiro{acridine-9,9-(4,5-diazafluorene)} (Compound 2)

(55) 1.2 g of the 2,7-dibromo-10-phenyl-10H-spiro{acridine-9,9-(4,5-diazafluorene)} synthesized in Example 1, 1.4 g of carbazole, 2.0 g of tripotassium phosphate, 0.4 g of copper(I) iodide, 0.1 g of 2-(dicyclohexylphosphino)biphenyl, and 24 ml of o-xylene were added into a nitrogen-substituted reaction vessel, and heated to reflux for 48 h. After adding 100 ml of toluene, the mixture was heated, and stirred at 100 C. The filtrate was collected by thermal filtration, and concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (support: silica gel, eluent: toluene/ethyl acetate), and through crystallization with a mixed solvent of toluene and methanol to obtain a pale yellow powder of 2,7-bis(9H-carbazol-9-yl)-10-phenyl-10H-spiro{acridine-9,9-(4,5-diazafluorene)} (Compound 2; 0.8 g; yield 50%).

(56) The structure of the pale yellow powder product was identified by NMR. The .sup.1H-NMR measurement result is shown in FIG. 2.

(57) .sup.1H-NMR (DMSO-d.sub.6) detected 33 hydrogen signals, as follows. (ppm)=8.60 (2H), 8.32 (2H), 8.13 (4H), 7.95 (4H), 7.75 (1H), 7.58 (2H), 7.43 (2H), 7.25 (4H), 7.17 (4H), 6.98 (4H), 6.68 (2H), 6.45 (2H).

Example 3

Synthesis of 2,7-bis{9,9-Dimethylacrydan-10-yl}-10-phenyl-10H-spiro{acridine-9,9-(4,5-diazafluorene)} (Compound 3)

(58) 1.2 g of the 2,7-dibromo-10-phenyl-10H-spiro{acridine-9,9-(4,5-diazafluorene)} synthesized in Example 1, 1.8 g of 9,9-dimethylacrydan, 1.3 g of potassium carbonate, 0.4 g of copper(I) iodide, 0.1 g of 2-(dicyclohexylphosphino)biphenyl, and 24 ml of o-xylene were added into a nitrogen-substituted reaction vessel, and heated to reflux for 48 h. After adding 100 ml of toluene, the mixture was heated, and stirred at 100 C. The filtrate was collected by thermal filtration, and concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (support: silica gel, eluent: toluene/ethyl acetate), and through crystallization with a mixed solvent of toluene and methanol to obtain a pale yellow powder of 2,7-bis{9,9-dimethylacrydan-10-yl}-10-phenyl-10H-spiro{acridine-9,9-(4,5-diazafluorene)} (Compound 3; 0.5 g; yield 27%).

(59) The structure of the pale yellow powder product was identified by NMR. The .sup.1H-NMR measurement result is shown in FIG. 3.

(60) .sup.1H-NMR (DMSO-d.sub.6) detected 45 hydrogen signals, as follows. (ppm)=8.64 (2H), 8.17 (2H), 7.89 (4H), 7.74 (1H), 7.45 (2H), 7.36 (4H), 7.06 (2H), 6.80 (8H), 6.66 (2H), 6.11 (2H), 5.88 (4H), 3.35 (12H).

Example 4

Synthesis of 2,7-bis(10H-Phenoxazin-10-yl)-10-phenyl-10H-spiro{acridine-9,9-(4,5-diazafluorene)} (Compound 4)

(61) 1.5 g of the 2,7-dibromo-10-phenyl-10H-spiro{acridine-9,9-(4,5-diazafluorene)} synthesized in Example 1, 1.9 g of phenoxazine, 1.1 g of sodium tert-butoxide, 0.09 g of palladium acetate, 0.1 g of 2-(dicyclohexylphosphino)biphenyl, and 30 ml of o-xylene were added into a nitrogen-substituted reaction vessel, and heated to reflux for 48 h. After adding 100 ml of toluene, the mixture was heated, and stirred at 100 C. The filtrate was collected by thermal filtration, and concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (support: silica gel, eluent: toluene/ethyl acetate), and through recrystallization with toluene to obtain a pale yellowish green powder of 2,7-bis(10H-phenoxazin-10-yl)-10-phenyl-10H-spiro{acridine-9,9-(4,5-diazafluorene)} (Compound 4; 0.6 g; yield 30%).

(62) The structure of the pale yellowish green powder product was identified by NMR. The .sup.1H-NMR measurement result is shown in FIG. 4.

(63) .sup.1H-NMR (DMSO-d.sub.6) detected 33 hydrogen signals, as follows. (ppm)=8.67 (2H), 8.11 (2H), 7.86 (2H), 7.81 (2H), 7.71 (1H), 7.44 (2H), 7.12 (2H), 6.62-6.55 (10H), 6.49 (4H), 6.17 (2H), 5.60 (4H).

Example 5

(64) A 100 nm-thick vapor-deposited film was fabricated on an ITO substrate using the compounds of the present invention. The work function was measured using an atmosphere photoelectron spectrometer (AC-3 produced by Riken Keiki Co., Ltd.).

(65) TABLE-US-00001 Work function Compound of Example 1 of the present invention 5.12 eV Compound of Example 2 of the present invention 5.52 eV CBP 6.00 eV

(66) As demonstrated above, the compounds of the present invention have preferable energy levels as a light emitting layer material, comparable to that of CBP used as a common light emission host.

Example 6

(67) A 10.sup.5 mol/L toluene solution was prepared for the compound of Example 1 of the present invention (Compound 1). This toluene solution was irradiated with ultraviolet light at 300 K while being aerated with nitrogen, and fluorescence having a peak wavelength of 527 nm was observed.

(68) The time-resolved spectrum of the above toluene solution was also measured before and after the aeration with nitrogen, using a compact fluorescence lifetime spectrometer (Quantaurus-tau produced by Hamamatsu Photonics K.K.). The emission lifetime was observed as a shorter life component (fluorescence) of 0.080 s, and a longer life component (delayed fluorescence) of 2.35 s.

(69) The PL quantum efficiency of the above toluene solution was also measured before and after the aeration with nitrogen, using an absolute PL quantum yields measurement system (Quantaurus-QY produced by Hamamatsu Photonics K.K.) at 300 K. The PL quantum efficiency was 4.4% before the aeration with nitrogen, and 33.5% after the aeration with nitrogen.

Example 7

(70) A 10.sup.5 mol/L toluene solution was prepared for the compound of Example 2 of the present invention (Compound 2) instead of the compound of Example 1 of the present invention (Compound 1) used in Example 6, and the characteristics of the toluene solution were evaluated in the same manner as in Example 6. As a result, fluorescence having a peak wavelength of 445 nm was observed. The emission lifetime was observed as a shorter life component (fluorescence) of 0.016 s, and a longer life component (delayed fluorescence) of 15.0 s. The PL quantum efficiency was 1.2% before the aeration with nitrogen, and 4.8% after the aeration with nitrogen.

Example 8

(71) A 10.sup.5 mol/L toluene solution was prepared for the compound of Example 3 of the present invention (Compound 3) instead of the compound of Example 1 of the present invention (Compound 1) used in Example 6, and the characteristics of the toluene solution were evaluated in the same manner as in Example 6. As a result, fluorescence having a peak wavelength of 489 nm was observed. The emission lifetime was observed as a shorter life component (fluorescence) of 0.054 s, and a longer life component (delayed fluorescence) of 9.0 s. The PL quantum efficiency was 5.8% before the aeration with nitrogen, and 13.8% after the aeration with nitrogen.

Example 9

(72) A 10.sup.5 mol/L toluene solution was prepared for the compound of Example 4 of the present invention (Compound 4) instead of the compound of Example 1 of the present invention (Compound 1) used in Example 6, and the characteristics of the toluene solution were evaluated in the same manner as in Example 6. As a result, fluorescence having a peak wavelength of 507 nm was observed. The emission lifetime was observed as a shorter life component (fluorescence) of 0.014 s, and a longer life component (delayed fluorescence) of 0.122 s. The PL quantum efficiency was 3.9% before the aeration with nitrogen, and 21.1% after the aeration with nitrogen.

Example 10

(73) An organic EL device was fabricated by vapor-depositing a hole transport layer 3, a light emitting layer 4, an electron transport layer 5, an electron injection layer 6, and a cathode (aluminum electrode) 7 in this order on a glass substrate 1 on which an ITO electrode was formed as a transparent anode 2 beforehand, as shown in FIG. 5.

(74) Specifically, the glass substrate 1 having ITO (a thickness of 100 nm) formed thereon was washed with an organic solvent, and subjected to a UV ozone treatment to wash the surface. The glass substrate with the ITO electrode was then installed in a vacuum vapor deposition apparatus, and the pressure was reduced to 0.001 Pa or less.

(75) This was followed by formation of the hole transport layer 3 by vapor depositing NPD over the transparent anode 2 in a thickness of 35 nm at a vapor deposition rate of 2.0 /sec. Then, the light emitting layer 4 was formed on the hole transport layer 3 in a thickness of 15 nm by dual vapor deposition of mCP and the compound of Example 1 of the present invention (Compound 1) at a vapor deposition rate ratio of 95:5 (mCP: compound of Example 1 of the present invention (Compound 1)). The electron transport layer 5 was then formed on the light emitting layer 4 by forming TPBI in a thickness of 50 nm at a deposition rate of 2.0 /sec. The electron injection layer 6 was then formed on the electron transport layer 5 by forming lithium fluoride in a thickness of 0.8 nm at a deposition rate of 0.1 /sec. Finally, the cathode 7 was formed by vapor depositing aluminum in a thickness of 70 nm. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature.

(76) The organic EL device fabricated with the compound of Example 1 of the present invention (compound 1) was measured for emission characteristics by applying DC voltage. FIG. 6 represents the current density-voltage characteristics, and the luminance-voltage characteristics. FIG. 7 represents the external quantum efficiency-current density characteristics.

(77) The organic EL device had high emission characteristics, with a luminance of 1,393 cd/m.sup.2, and a current efficiency of 13.6 cd/A upon passing current at a current density of 10 mA/cm.sup.2. The external quantum efficiency was as high as 9.6%, a value that far exceeds the theoretical external quantum efficiency of 5% with a common fluorescence material.

(78) As demonstrated above, the organic EL device using the compounds of the present invention was shown to be capable of achieving high luminous efficiency, and high external quantum efficiency.

INDUSTRIAL APPLICABILITY

(79) The spiro compounds having an azafluorene ring structure of the present invention can emit delayed fluorescence and have desirable thin-film stability, and the spiro compounds are excellent as material of a light emitting layer, especially as a dopant material of a light emitting layer. An organic EL device produced by using the compounds can have improved luminous efficiency, and high external quantum efficiency. This makes the present invention highly useful in industry.

DESCRIPTION OF REFERENCE NUMERAL

(80) 1 Glass substrate

(81) 2 Transparent anode

(82) 3 Hole transport layer

(83) 4 Light emitting layer

(84) 5 Electron transport layer

(85) 6 Electron injection layer

(86) 7 Cathode