JP2012188355A - Novel organic compound, and organic light-emitting device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel organic compound suitable for red light emission and an organic light emitting device having the same.
An organic compound having a structure represented by the following general formula (1) is provided.
In the formula (1), R _{1 to} R ₁₆ are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted aryl group, Each is independently selected from a substituted or unsubstituted heterocyclic group.
[Chemical 1]

[Selection] Figure 1

Description

  The present invention relates to a novel organic compound and an organic light emitting device having the same.

  An organic light-emitting element is an element having an anode, a cathode, and an organic compound layer disposed therebetween. By injecting electrons and holes from the electrodes, excitons of the light-emitting organic compound in the organic compound layer are generated, and light is emitted when the excitons return to the ground state.

  The organic light emitting element is also called an organic electroluminescence element or an organic EL element.

  Recent advances in organic light-emitting elements are remarkable, and it is possible to make light-emitting devices with high luminance, a wide variety of emission wavelengths, high-speed response, thinness, and light weight at low applied voltage.

  So far, new luminescent organic compounds have been actively created. This is because the creation of the compound is important in providing a high-performance organic light-emitting device.

  For example, Patent Documents 1 to 3 and Non-Patent Document 1 describe the following organic compounds 1-A, 1-B, and 1-C, and these organic compounds emit orange light.

Japanese Patent Laid-Open No. 10-340785 Japanese Patent Laid-Open No. 2000-252068 JP 2008-288247 A

  The basic skeletons of Patent Documents 1 to 3 emit orange light and do not become red light emitting compounds.

  It is known to adjust the emission wavelength by providing a substituent in an organic compound. However, the provision of a substituent may impair the stability of the compound.

  Therefore, the present invention aims to provide a novel organic compound that, unlike these structures, realizes a red emission color with the basic skeleton itself.

  Accordingly, the present invention provides an organic compound represented by the following general formula (1).

In the formula (1), R _{1 to} R ₁₆ are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted aryl group, Each is independently selected from a substituted or unsubstituted heterocyclic group.

  According to the present invention, an organic compound capable of emitting red light with the basic skeleton itself can be provided. The organic compound according to the present invention is a novel organic compound having a basic skeleton itself with a narrow band gap and a deep LUMO. In addition, a novel organic compound capable of suppressing concentration quenching can be provided by introducing a substituent into the basic skeleton. And the organic light emitting element which has these novel organic compounds can be provided.

It is a cross-sectional schematic diagram which shows an organic light emitting element and the TFT element connected to the organic light emitting element.

  The novel organic compound according to the present invention is a compound represented by the following general formula (1).

In the formula (1), R _{1 to} R ₁₆ are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted aryl group, Each is independently selected from a substituted or unsubstituted heterocyclic group.

  Here, in the formula (1), as the alkyl group of the substituted or unsubstituted alkyl group, methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, secondary butyl group, tertiary butyl group, octyl Group, 1-adamantyl group, 2-adamantyl group and the like are exemplified, but the group is of course not limited thereto.

  Here, in the formula (1), as an alkoxy group of a substituted or unsubstituted alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a 2-ethyl-octyloxy group, a phenoxy group, a 4-tertiarybutylphenoxy group, a benzyloxy Group, thienyloxy group and the like, but of course, the group is not limited thereto.

  Here, in the formula (1), as an amino group of a substituted or unsubstituted amino group, N-methylamino group, N-ethylamino group, N, N-dimethylamino group, N, N-diethylamino group, N-methyl -N-ethylamino group, N-benzylamino group, N-methyl-N-benzylamino group, N, N-dibenzylamino group, anilino group, N, N-diphenylamino group, N, N-dinaphthylamino Group, N, N-difluorenylamino group, N-phenyl-N-tolylamino group, N, N-ditolylamino group, N-methyl-N-phenylamino group, N, N-dianisolylamino group, N- Mesityl-N-phenylamino group, N, N-dimesitylamino group, N-phenyl-N- (4-tert-butylphenyl) amino group, N-phenyl-N- (4-trifluorome Butylphenyl) amino group, and the like, but the invention is of course not limited thereto.

  Here, in the formula (1), examples of the aryl group of the substituted or unsubstituted aryl group include a phenyl group, a naphthyl group, an indenyl group, a biphenyl group, a terphenyl group, and a fluorenyl group. It is not a thing.

  Here, in the formula (1), examples of the heterocyclic group of the substituted or unsubstituted heterocyclic group include a pyridyl group, an oxazolyl group, an oxadiazolyl group, a thiazolyl group, a thiadiazolyl group, a carbazolyl group, an acridinyl group, and a phenanthroyl group. Of course, it is not limited to these.

  In the formula (1), the above-mentioned substituents, that is, the substituents of the alkyl group, alkoxy group, amino group, aryl group, heterocyclic group, alkyl groups such as methyl group, ethyl group, propyl group, and tertiary butyl group, benzyl An aryl group such as a phenyl group, an aryl group such as a phenyl group and a biphenyl group, a heterocyclic group such as a pyridyl group and a pyrrolyl group, an amino group such as a dimethylamino group, a diethylamino group, a dibenzylamino group, a diphenylamino group and a ditolylamino group, Examples thereof include alkoxyl groups such as methoxyl group, ethoxyl group, propoxyl group and phenoxyl group, cyano group, halogen atoms such as fluorine, chlorine, bromine and iodine, but are not limited thereto.

The organic compound represented by the formula (1) has a structure with high planarity. By introducing an alkyl group or an aryl group as a substituent into R _{1 to} R ₁₆ in Formula (1), planarity can be suppressed due to steric hindrance.

  Thereby, the sublimation property at the time of vacuum deposition and the amorphous property in a thin film state can be improved.

  The substituent provided for improving the amorphous property is preferably a phenyl group. This is because it has the effect of steric hindrance and has a small molecular weight.

In particular, when a substituent is introduced at the position of R _1, R _2, R _7, R _8, R _11, R ₁₄ in formula (1), the effect of the steric hindrance of the substituent is increased.

Therefore, it is preferable to introduce a substituent at the position of R _1, R _2, R _7, R _8, R _11, R ₁₄ in formula (1).

  R1, R2, R7, and R8 are more preferable as the position where the substituent is provided in order to improve the amorphous property.

  That is, an organic compound represented by the following general formula (A) is more preferable.

In the general formula (A), R _{1 to} R ₂ and R _{7 to} R ₈ are each independently selected from a hydrogen atom or a phenyl group.

  In the organic compound according to the present invention, the emission wavelength of the molecule having only the basic skeleton falls within the desired emission wavelength region. In the present invention, the desired emission wavelength region is a red region, specifically, 580 nm or more and 650 nm or less. Here, the basic skeleton refers to a condensed ring structure having conjugation, and the basic skeleton of the organic compound according to the present invention is a structure in which R1 to R16 in the general formula (1) are all hydrogen atoms.

  In order to obtain a desired emission wavelength, it is known to provide a substituent on the basic skeleton. In general, the higher the molecular weight of the organic compound, the higher the sublimation temperature. Therefore, a higher temperature is required during sublimation purification. Then, thermal decomposition of the compound due to high temperature tends to occur.

  That is, if the molecular weight is increased by providing a substituent on the basic skeleton, the stability of the compound may be impaired during purification. In order to prevent excessive heating during sublimation purification, the molecular weight of the organic compound according to the present invention is preferably 1000 or less.

  The organic compound according to the present invention is compared with the compounds shown in (2), (3) and (4).

  The comparison targets (2), (3), and (4) are represented by the following structural formulas.

  The basic skeleton of the organic compound according to the present invention is represented by the following structural formula (5).

  The light emission wavelength and molecular weight of the organic compound according to the present invention and each of the organic compounds (2), (3), and (4) were compared and are shown in Table 1. The emission wavelength was calculated from photoluminescence measurement in a toluene solution of an organic compound using Hitachi F-4500.

  The organic compound shown by a in Table 1 is rubicene. The organic compound represented by b in Table 1 has a structure in which one benzene ring is linked to the organic compound a in Table 1 to increase the molecular weight by 50. The organic compound represented by c in Table 1 has a structure in which one more benzene ring is linked to the organic compound of b in Table 1 to increase the molecular weight by 50. The organic compound represented by d in Table 1 has a structure in which one benzene ring is added to the organic compound of b of Table 1 and the molecular weight is increased by 50 as in the case of the organic compound of Table 1c. The place is different. The compound represented by d is the organic compound according to the present invention.

  When the four types of organic compounds shown by a to d in Table 1 are compared, the emission wavelength change is different due to the difference in the connection position of the benzene rings.

  The organic compound represented by b in Table 1 has a longer emission wavelength of 15 nm than the organic compound represented by a in Table 1, and the change in the emission wavelength due to the connection of one benzene ring is +15 nm. Similarly, from the comparison of the organic compound represented by c in Table 1 and the organic compound represented by b in Table 1, the change in emission wavelength due to the connection of one benzene ring is +10 nm. Similarly, from the comparison of the organic compound represented by d in Table 1 and the organic compound represented by b in Table 1, the change in emission wavelength due to the connection of one benzene ring is +30 nm. The organic compounds represented by a, b, and c in Table 1 could only obtain the effect of increasing the wavelength of about +10 to 15 nm by increasing one benzene ring, but are represented by d in Table 1 of the present invention. In organic compounds, the wavelength is greatly increased to +30 nm.

  That is, the organic compound represented by d in Table 1 of the present invention has a great effect of increasing the wavelength even when the molecular weight changes due to the difference in the connecting position of the benzene rings.

  Therefore, when the structure d in Table 1 of the present invention is used, the emission wavelength can be increased in the basic skeleton having a small molecular weight.

  When the molecular weight of the basic skeleton is small, the degree of freedom in selecting a substituent when introducing the substituent is increased.

  By introducing a substituent into the organic compound, the emission wavelength and crystallinity can be adjusted. However, as the molecular weight of the organic compound increases, the sublimation property decreases. Therefore, when a substituent is introduced, the molecular weight increases, and thermal decomposition due to high temperatures during sublimation purification becomes a problem.

  Therefore, if the molecular weight of the basic skeleton is small, the range of molecular weights of the substituents that can be used is widened, and the degree of freedom in selecting substituents is increased.

  Furthermore, since the organic compound according to the present invention has two 5-membered ring structures in the skeleton, the HOMO energy level is low. That is, the oxidation potential is low. That is, the organic compound according to the present invention is stable against oxidation. Moreover, since the basic skeleton of the organic compound according to the present invention has a low HOMO energy level, the LUMO energy level is also low.

  The organic compound according to the present invention does not have a hetero atom such as a nitrogen atom in the basic skeleton. This also contributes to a low oxidation potential. That is, the organic compound contributes to stability against oxidation.

  The organic compound according to the present invention is used as a guest material or a host material for a light emitting layer of an organic light emitting device. Further, each layer other than the light emitting layer, that is, a hole injection layer, a hole transport layer, a hole / exciton blocking layer, an electron transport layer, an electron injection layer, or the like may be used.

  The organic compound according to the present invention can be preferably used as a guest material for a light emitting layer of an organic light emitting device. In particular, it is preferably used as a guest material for a red light emitting element.

  It is preferable to use the organic compound according to the present invention as a guest material of the light emitting layer, and to use a material having a LUMO energy level higher than that of the organic compound, in other words, a host material closer to the vacuum order.

  This is because the organic compound according to the present invention has a low HOMO energy level and a low LUMO energy, so that electrons supplied to the host material in the light emitting layer can be better received from the host material to the guest material. Good reception of electrons from the host material to the guest material is preferable in order to achieve high luminous efficiency.

  Here, the host material and the guest material have the largest weight ratio among the compounds constituting the light emitting layer, and the host material and the guest material are mainly smaller in weight ratio than the host material among the compounds constituting the light emitting layer. The guest material is responsible for light emission.

  Among the light emitting layers, a material having a weight ratio smaller than that of the host material and assisting the light emission of the guest material is called an assist material or a second host material.

  The organic compound according to the present invention can be preferably used as a guest material for a light emitting layer of an organic light emitting device. As a result, an organic light-emitting element that emits red light can be provided by causing the organic compound according to the present invention to emit light.

(Examples of organic compounds according to the present invention)
Specific examples of the organic compound according to the present invention are shown below. However, the present invention is not limited to these.

(Each property of the exemplified compound group)
Of the exemplified compounds, those shown in Group A are composed entirely of hydrocarbons. Compounds composed solely of hydrocarbons have a low HOMO energy level. Therefore, the oxidation potential is low, meaning that the organic compound is stable against oxidation.

  Therefore, among the organic compounds according to the present invention, the compounds shown in Group A composed of only hydrocarbons are preferable because of high molecular stability.

  In addition, when the substituent as in the group B contains a hetero atom, the molecule greatly changes in oxidation potential. Or intermolecular interaction changes. Moreover, when a substituent contains a hetero atom, it can be used for applications such as electron transportability, hole transportability, and use at a high concentration of 100% when used as a hole trap type light emitting material.

  As described above, exemplary compounds are listed as A to B groups. The exemplified compounds are preferably used for the light emitting layer of the organic light emitting device.

  In that case, the light emission color of the organic light emitting element is not limited to red, and more specifically may be white or an intermediate color.

(Description of synthesis route)
An example of the synthetic route of the organic compound according to the present invention will be described. The reaction formula is shown below.

  Among these, when a substituent is introduced in the following formula, it can be synthesized by replacing the hydrogen atom at the introduced position with another substituent. Examples of the substituent to be substituted include an alkyl group, a halogen atom, and a phenyl group.

(Other organic compounds and raw materials)
In the above reaction formula 1, various organic compounds can be synthesized by changing each of D1 to D3. Specific examples are shown as synthetic compounds in Table 2. The following table also shows D1 to D3, which are raw materials for obtaining a synthetic compound.

  In the above reaction formula 2, various organic compounds can be synthesized by changing D4 to D5. Specific examples thereof are shown as synthetic compounds in Table 3. The table below also shows D4 to D5, which are raw materials for obtaining synthetic compounds.

(Description of organic light emitting device)
Next, the organic light emitting device according to the present invention will be described.

  The organic light-emitting device according to the present invention has at least an anode and a cathode as a pair of electrodes, and an organic compound layer disposed between them. This organic compound layer has an organic compound represented by the general formula (1). The organic light-emitting device is a device that generates excitons of a light-emitting organic compound in the organic compound layer by injecting carriers from the anode and the cathode, and emits light when the excitons return to the ground state. It is.

  When this organic compound layer is a light emitting layer, the light emitting layer may be composed of only the organic compound according to the present invention, or other components may be present in the light emitting layer.

  The case where the light emitting layer may have a part of the organic compound according to the present invention means that the organic compound according to the present invention may be a main component or a subcomponent of the light emitting layer.

  Here, as the main component and the subcomponent, a compound having the largest weight ratio among the compounds constituting the light emitting layer is called a main component, and a compound having a weight ratio smaller than the main component is called a subcomponent.

  The material that is the main component can also be called a host material.

  The material that is an accessory component is a dopant (guest) material. In addition, a light emission assist material and a charge injection material can be listed as subcomponents.

  When the organic compound according to the present invention is used as a guest material, the concentration of the guest material with respect to the host material is preferably 0.01 wt% or more and 20 wt% or less, and more preferably 0.2 wt% or more and 5 wt% or less. preferable.

  The present inventors have conducted various studies, and a device using the organic compound represented by the general formula (1) of the present invention as a host material or a guest material of a light emitting layer, particularly as a guest material has high efficiency and high luminance. It has been found that it has light output and is extremely durable.

  Below, the example of the organic light emitting element using the organic compound which concerns on this invention is shown.

  Examples of the organic light emitting device produced using the organic compound according to the present invention include a structure in which an anode, a light emitting layer, and a cathode are sequentially provided on a substrate. In addition, a structure in which an anode, a hole transport layer, an electron transport layer, and a cathode) are sequentially provided may be mentioned. Sequentially provided with anode, hole transport layer, light emitting layer, electron transport layer and cathode, or sequentially provided with anode, hole injection layer, hole transport layer, light emitting layer, electron transport layer and cathode, and anode, hole Examples include a transport layer, a light emitting layer, a hole / exciton blocking layer, an electron transport layer, and a cathode.

  The configuration of the organic light emitting device according to this embodiment is not limited thereto. For example, it can take various layer configurations, such as providing an insulating layer at the interface between the electrode and the organic compound layer, providing an adhesive layer or interference layer, and the electron transport layer or hole transport layer comprising two layers having different ionization potentials. it can.

  The organic compound represented by the general formula (1) according to the present invention can be used in any layer structure as the organic compound layer of the light emitting device.

  Here, in addition to the organic compound of the present invention, conventionally known low-molecular and high-molecular hole-injecting compounds, transporting compounds, host compounds that are host materials, light-emitting compounds, or electron-injecting properties, if necessary. A compound or an electron transporting compound can be used together.

  Examples of these compounds are given below.

  The hole injecting compound or the hole transporting compound is preferably a material having a high hole mobility. Low molecular and high molecular weight materials having hole injection performance or hole transport performance include triarylamine derivatives, phenylenediamine derivatives, stilbene derivatives, phthalocyanine derivatives, porphyrin derivatives, poly (vinylcarbazole), poly (thiophene), In addition, although a conductive polymer is mentioned, of course, it is not limited to these.

  Table 4 shows specific structural formulas of the host compound. The host compound may be a compound that is a derivative having the structural formula shown in Table 4. In addition to these, condensed ring compounds (for example, fluorene derivatives, naphthalene derivatives, anthracene derivatives, pyrene derivatives, carbazole derivatives, quinoxaline derivatives, quinoline derivatives, etc.), organoaluminum complexes such as tris (8-quinolinolato) aluminum, organozinc complexes, And polymer derivatives such as a triphenylamine derivative, a poly (fluorene) derivative, and a poly (phenylene) derivative, but of course not limited thereto.

  The electron injecting compound or the electron transporting compound is selected in consideration of the balance with the hole mobility of the hole injecting compound or the hole transporting compound. Examples of compounds having electron injection performance or electron transport performance include oxadiazole derivatives, oxazole derivatives, pyrazine derivatives, triazole derivatives, triazine derivatives, quinoline derivatives, quinoxaline derivatives, phenanthroline derivatives, organoaluminum complexes, etc. It is not limited to.

  An anode material having a work function as large as possible is preferable. For example, simple metals such as gold, platinum, silver, copper, nickel, palladium, cobalt, selenium, vanadium, tungsten, or alloys thereof, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide, etc. It is a metal oxide. Further, conductive polymers such as polyaniline, polypyrrole, and polythiophene may be used. These electrode materials may be used alone or in combination. Further, the anode may have a single layer structure or a multilayer structure.

  On the other hand, a cathode material having a small work function is preferable. Examples thereof include alkali metals such as lithium, alkaline earth metals such as calcium, and simple metals such as aluminum, titanium, manganese, silver, lead, and chromium. Or the alloy which combined these metal single-piece | units can also be used. For example, magnesium-silver, aluminum-lithium, aluminum-magnesium, etc. can be used. A metal oxide such as indium tin oxide (ITO) can also be used. These electrode materials may be used alone or in combination. Further, the cathode may have a single layer structure or a multilayer structure.

  In the organic light-emitting device according to the present invention, the layer containing the organic compound according to the present invention and the layer made of another organic compound are formed by the following method. In general, a thin film is formed by a vacuum deposition method, an ionization deposition method, sputtering, plasma, or a known coating method (for example, spin coating, dipping, casting method, LB method, inkjet method, etc.) after dissolving in an appropriate solvent. Here, when a layer is formed by a vacuum deposition method, a solution coating method, or the like, crystallization or the like hardly occurs and the temporal stability is excellent. Moreover, when forming into a film by the apply | coating method, a film | membrane can also be formed combining with a suitable binder resin.

  Examples of the binder resin include, but are not limited to, polyvinyl carbazole resin, polycarbonate resin, polyester resin, ABS resin, acrylic resin, polyimide resin, phenol resin, epoxy resin, silicone resin, urea resin, and the like. . Moreover, these binder resins may be used alone as a homopolymer or a copolymer, or may be used as a mixture of two or more. Furthermore, you may use together additives, such as a well-known plasticizer, antioxidant, and an ultraviolet absorber, as needed.

(Applications of organic light emitting devices)
Hereinafter, the use of the organic light emitting device according to the present invention will be described.

  The organic light emitting device according to the present invention can be used in a display device or a lighting device. In addition, there are an exposure light source of an electrophotographic image forming apparatus and a backlight of a liquid crystal display device.

  The display device includes the organic light emitting element according to the present invention in a display portion. The display unit includes a plurality of pixels. The pixel includes an organic light emitting element according to the present invention and a TFT element which is an example of a switching element. The anode or cathode of the organic light emitting element and the TFT element. A drain electrode or a source electrode is connected. The display device can be used as a display device such as a PC. The display device may be an image input device further including an image input unit.

  The image input device includes an image input unit that inputs image information from an area CCD, linear CCD, memory card, and the like, and a display unit that displays the input information. If an image pickup optical system is further provided, an image pickup apparatus such as a digital camera is obtained. In addition, the display unit of the imaging apparatus or the inkjet printer has both an image output function for displaying an image based on image information input from the outside and an input function for inputting processing information to the image as an operation panel. It may be. The display device may be used for a display unit of a multifunction printer.

  Next, a display device using the organic light emitting device according to the present invention will be described.

  FIG. 1 is a schematic cross-sectional view of a display device having an organic light emitting element according to the present invention and a TFT element which is an example of a switching element for controlling light emission / non-light emission or light emission luminance of the organic light emitting element. In this figure, two sets of organic light emitting elements and TFT elements are shown. Although not shown, a transistor for controlling light emission luminance may be further included. The display device displays the information by turning on or off the organic light emitting element by driving the switching element according to the information, and transmits the information. Details of the structure will be described below.

  The display device of FIG. 1 is provided with a substrate 1 made of glass or the like and a moisture-proof film 2 for protecting the TFT element or the organic compound layer on the substrate 1. Reference numeral 3 denotes a metal gate electrode 3. Reference numeral 4 denotes a gate insulating film, and reference numeral 5 denotes a semiconductor layer.

  The TFT element 8 has a semiconductor layer 5, a drain electrode 6, and a source electrode 7. An insulating film 9 is provided on the TFT element 8. The anode 11 and the source electrode 7 of the organic light emitting element are connected through the contact hole 10. The display device is not limited to this configuration, and any one of the anode and the cathode may be connected to either the source electrode or the drain electrode of the TFT element.

  In this figure, the organic compound layer 12 is illustrated as a single layer of multiple organic compound layers. A first protective layer 14 and a second protective layer 15 for suppressing deterioration of the organic light emitting element are provided on the cathode 13.

  In the organic light emitting device according to this embodiment, the light emission luminance is controlled by the TFT device. By providing the organic light emitting elements in a plurality of planes, an image can be displayed with each light emission luminance. It is also possible to create an active matrix driver on a Si substrate instead of the TFT and provide an organic light emitting element on the active matrix driver for control. This is selected depending on the definition. For example, in the case of a definition of about 1 inch and QVGA, it is preferable to provide an organic light emitting element on the Si substrate.

  By driving the display device using the organic light emitting element according to the present embodiment, it is possible to perform stable display even with long-time display with good image quality.

  Examples will be described below. The present invention is not limited to these.

Example 1
[Synthesis of Exemplary Compound A37]

  11.6 g (50 mmol) of E1 and 10.5 g (50 mmol) of E2 were placed in 200 ml of ethanol and heated to 60 ° C., and then 20 ml of 5M aqueous sodium hydroxide solution was added dropwise. After completion of the dropwise addition, the mixture was heated to 80 ° C. and stirred for 2 hours. After cooling, the precipitate was filtered, washed with water and ethanol, dried under reduced pressure at 80 ° C., and 15.2 g of dark green solid E3 ( (Yield: 75%).

  Next, 4.06 g (10 mmol) of E3 and 2.25 g (12 mmol) of E4 were put in 50 ml of toluene, heated to 80 ° C., and then 1.40 g (12 mmol) of isoamyl nitrite was slowly added dropwise at 110 ° C. Stir for 3 hours. After cooling, it was washed twice with 100 ml of water. The organic layer was washed with saturated brine, dried over magnesium sulfate, filtered, and the filtrate was concentrated to give a brown liquid. This was purified by column chromatography (chloroform / heptane = 1: 5) and then recrystallized from chloroform / methanol to obtain 3.28 g (yield: 65%) of yellow crystals E5 as a mixture of isomers. It was.

2.70 g (5 mmol) of E5 is dissolved in 20 ml of methylene chloride, and 8.0 g (5 mmol) of bromine dissolved in 5 ml of methylene chloride is added dropwise in a water bath. After returning to room temperature, the mixture was stirred for 4 hours. After completion of the reaction, washing was performed twice with 50 ml of water. The organic layer was washed with saturated brine, dried over magnesium sulfate, filtered, and the filtrate was concentrated to give a brown liquid. Recrystallization was performed twice with chlorobenzene / methanol to obtain 2.6 g (yield: 90%) of E6 as dark red crystals.

E6 1.75 g (3 mmol), (E7) 516 mg (3.3 mmol), Pd (PPh3) 4 0.05 g, toluene 20 ml, ethanol 10 ml, 2M-sodium carbonate aqueous solution 20 ml were charged into a 100 ml eggplant flask, under a nitrogen stream, Stirring was performed at 80 ° C. for 8 hours. After completion of the reaction, the mixture was cooled and washed with 100 ml of water twice. The organic layer was washed with saturated brine, dried over magnesium sulfate, and concentrated. This was purified by column chromatography (toluene / heptane = 1: 5) and then recrystallized from chloroform / methanol to obtain 1.4 g (yield: 76%) of E8 as dark red crystals.

  Next, 1.23 g (2 mmol) of E8 was placed in 10 ml of DMF, 0.46 g (0.5 mmol) of tris (dibenzylideneacetone) dipalladium, 0.28 g (1 mmol) of tricyclohexylphosphine and 1,8-diazabicyclo [5]. 4.0] Undec-7-ene 2.28 g (15 mmol) was added, and the mixture was heated to 150 ° C. and stirred for 4 hours. After cooling this, 30 ml of methanol was added to precipitate a precipitate, followed by filtration to obtain a black solid. This solid was purified by column chromatography (chloroform / heptane = 1: 4) and then recrystallized twice with chloroform / methanol to obtain 0.62 g (yield: 54%) of Example Compound A37 as dark red crystals. It was.

  It was confirmed that the purity of this compound was 99% or more using HPLC.

The emission spectrum of the toluene solution of Exemplified Compound A37 at 1 × 10 ⁻⁵ mol / L is a spectrum having the maximum intensity at 597 nm as a result of measuring photoluminescence at an excitation wavelength of 480 nm using Hitachi F-4500. Got.

It identified by measuring molecular weight using JEOL (JEOL) company make JMS-T100TD (DART-TOF-MASS).
DART-TOF-MASS: M ⁺ 579.2

(Example 2)
[Synthesis of Exemplary Compound A54]
Exemplified compound A54 was obtained by the same reaction and purification as in Example 1 except that the organic compound E7 used in Example 1 was changed to E9.

The purity of this compound was confirmed to be 99.5% or higher by HPLC.

The emission spectrum of the toluene solution of Exemplified Compound A54 at 1 × 10 ⁻⁵ mol / L is a spectrum having the maximum intensity at 602 nm as a result of measuring photoluminescence at an excitation wavelength of 480 nm using Hitachi F-4500. Got.

It identified by measuring molecular weight using JEOL (JEOL) company make JMS-T100TD (DART-TOF-MASS).
DART-TOF-MASS: M ⁺ 731.3

(Example 3)
[Synthesis of Exemplary Compound A50]
Exemplified compound A50 was obtained by the same reaction and purification as in Example 1 except that the organic compound E7 used in Example 1 was changed to E10.

  The purity of this compound was confirmed to be 99.5% or higher by HPLC.

The emission spectrum of the toluene solution of Exemplified Compound A50 at 1 × 10 ⁻⁵ mol / L is a spectrum having the maximum intensity at 609 nm as a result of measuring photoluminescence at an excitation wavelength of 480 nm using Hitachi F-4500. Got.

It identified by measuring molecular weight using JEOL (JEOL) company make JMS-T100TD (DART-TOF-MASS).
DART-TOF-MASS: M ⁺ 731.3

Example 4
[Synthesis of Exemplary Compound A73]
Exemplified compound A73 was obtained by the same reaction and purification as in Example 1 except that the organic compound E4 used in Example 1 was changed to E11.

  The purity of this compound was confirmed to be 99.5% or higher by HPLC.

The emission spectrum of the toluene solution of Exemplified Compound A73 at 1 × 10 ⁻⁵ mol / L is a spectrum having the maximum intensity at 612 nm as a result of measuring photoluminescence at an excitation wavelength of 480 nm using Hitachi F-4500. Got.
It identified by measuring molecular weight using JEOL (JEOL) company make JMS-T100TD (DART-TOF-MASS).
DART-TOF-MASS: M ⁺ 731.3

(Example 5)
[Synthesis of Exemplary Compound A44]
Exemplified compound A44 was obtained by the same reaction and purification as in Example 1 except that the organic compound E2 used in Example 1 was changed to E12.

  The purity of this compound was confirmed to be 99.5% or higher by HPLC.

The emission spectrum of the toluene solution of Exemplified Compound A44 at 1 × 10 ⁻⁵ mol / L is a spectrum having the maximum intensity at 610 nm as a result of measuring photoluminescence at an excitation wavelength of 480 nm using Hitachi F-4500. Got.

It identified by measuring molecular weight using JEOL (JEOL) company make JMS-T100TD (DART-TOF-MASS).
DART-TOF-MASS: M ⁺ 731.3

(Example 6)
[Synthesis of Exemplary Compound A2]

  E13 1.89 g (5 mmol), E14 2.0 g (5 mmol), tris (dibenzylideneacetone) dipalladium 0.46 g (0.5 mmol), 2-dicyclohexylphosphino 2 ′, 6′-dimethoxybiphenyl 0.41 g ( 1.0 mmol), 5 ml of toluene, 0.1 ml of distilled water, and 1.27 g of potassium phosphate were charged into a 30 ml eggplant flask and stirred at 100 ° C. for 8 hours under a nitrogen stream. After completion of the reaction, after cooling, 100 ml of toluene was added and washed with water 100 ml × twice. The organic layer was washed with saturated brine, dried over magnesium sulfate, and concentrated. This was purified by column chromatography (toluene / heptane = 1: 5) and then recrystallized from chloroform / methanol to obtain 2.6 g (yield: 85%) of dark red crystals of E10. Next, 1.23 g (2 mmol) of E15 was placed in 10 ml of DMF, 0.46 g (0.5 mmol) of tris (dibenzylideneacetone) dipalladium, 0.28 g (1 mmol) of tricyclohexylphosphine and 1,8-diazabicyclo [5]. 4.0] Undec-7-ene 2.28 g (15 mmol) was added, and the mixture was heated to 150 ° C. and stirred for 4 hours. After cooling this, 30 ml of methanol was added to precipitate a precipitate, followed by filtration to obtain a black solid. This solid was purified by column chromatography (chloroform / heptane = 1: 4) and then recrystallized twice with chloroform / methanol to obtain 0.76 g (yield: 66%) of exemplary compound A2 as dark red crystals. It was.

  It was confirmed that the purity of this compound was 99% or more using HPLC.

The emission spectrum of the toluene solution of Exemplified Compound A2 at 1 × 10 ⁻⁵ mol / L is a spectrum having the maximum intensity at 598 nm as a result of measuring photoluminescence at an excitation wavelength of 480 nm using Hitachi F-4500. Got.

It identified by measuring molecular weight using JEOL (JEOL) company make JMS-T100TD (DART-TOF-MASS).
DART-TOF-MASS: M ⁺ 579.7

(Example 7)
[Synthesis of Exemplary Compound A1]
Exemplified compound A1 was obtained by the same reaction and purification as in Example 4 except that the organic compound E14 used in Example 1 was changed to E16.

  The purity of this compound was confirmed to be 99.5% or higher by HPLC.

The emission spectrum of the toluene solution of Exemplified Compound A1 at 1 × 10 ⁻⁵ mol / L is a spectrum having the maximum intensity at 600 nm as a result of measuring photoluminescence at an excitation wavelength of 480 nm using Hitachi F-4500. Got.

It identified by measuring molecular weight using JEOL (JEOL) company make JMS-T100TD (DART-TOF-MASS).
DART-TOF-MASS: M ⁺ 427.5

(Example 8)
[Synthesis of Exemplary Compound A15]
Exemplified compound A15 was obtained by the same reaction and purification as in Example 4 except that the organic compound E13 used in Example 1 was changed to E17.

  The purity of this compound was confirmed to be 99.5% or higher by HPLC.

The emission spectrum of the toluene solution of Exemplified Compound A15 at 1 × 10 ⁻⁵ mol / L is a spectrum having the maximum intensity at 606 nm as a result of measuring photoluminescence at an excitation wavelength of 480 nm using Hitachi F-4500. Got.

It identified by measuring molecular weight using JEOL (JEOL) company make JMS-T100TD (DART-TOF-MASS).
DART-TOF-MASS: M ⁺ 731.9

Example 9
[Synthesis of Exemplary Compound A86]
Exemplified compound A86 was obtained by the same reaction and purification as in Example 4 except that the organic compound E14 used in Example 1 was changed to E18.

  The purity of this compound was confirmed to be 99.5% or higher by HPLC.

The emission spectrum of the toluene solution of Exemplified Compound A86 at 1 × 10 ⁻⁵ mol / L is a spectrum having the maximum intensity at 607 nm as a result of measuring photoluminescence at an excitation wavelength of 480 nm using Hitachi F-4500. Got.

It identified by measuring molecular weight using JEOL (JEOL) company make JMS-T100TD (DART-TOF-MASS).
DART-TOF-MASS: M ⁺ 731.9

(Examples 10 to 20)
In this example, an element having a configuration of (anode / hole transport layer / light emitting layer / hole exciton blocking layer / electron transport layer / cathode) was produced. 100 nm ITO was patterned on the glass substrate. On the ITO substrate, the following organic layers and electrode layers were continuously formed by vacuum deposition by resistance heating in a vacuum chamber of 10 ⁻⁵ Pa so that the opposing electrode area was 3 mm ² .
Hole transport layer (40 nm) G-1
Light emitting layer (30 nm) Host: G-2 (weight ratio 60%), G-3 (weight ratio 39%) Guest: Exemplified compound (weight ratio 1%)
Hole-exciton blocking layer (10 nm) G-4
Electron transport layer (30 nm) G-5
Metal electrode layer 1 (0.5 nm) LiF
Metal electrode layer 2 (100 nm) Al

As for the characteristics of the EL element, the current-voltage characteristics were measured with a microammeter 4140B manufactured by Hured Packard, and the light emission luminance was measured with BM7 manufactured by Topcon.
Table 5 shows the light emission efficiencies and voltages of Examples 10 to 20 at a luminance of 1000 cd · m ⁻² .

(Examples 21 to 25)
In this example, an element having a configuration of (anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode) was produced.

This organic light emitting device having a resonant structure was fabricated by the method shown below.
An aluminum alloy (AlNd) as a reflective anode is formed with a film thickness of 100 nm on a glass substrate as a support by a sputtering method. Furthermore, ITO is formed with a film thickness of 80 nm by sputtering as a transparent anode.

  Next, an acrylic element isolation film having a thickness of 1.5 μm was formed around the anode, and an opening having a radius of 3 mm was provided. This is successively subjected to ultrasonic cleaning with acetone and isopropyl alcohol (IPA), then boiled with IPA and dried. Further, UV / ozone cleaning is performed on the surface of the substrate.

In addition, the following organic layers were vacuum-deposited by resistance heating in a vacuum chamber of 10 ⁻⁵ Pa to form a continuous film, and then IZO was formed as a cathode by a sputtering method to form a transparent electrode having a thickness of 30 nm. To do. After forming, sealing is performed in a nitrogen atmosphere.
Thus, an organic light emitting element is formed.
Hole injection layer (135 nm) G-11
Hole transport layer (10nm) G-12
Light emitting layer (35 nm) Host G-13 (70% by weight), G-14 (29% by weight), guest: exemplary compound (1% by weight)
Electron transport layer (10 nm) G-14
Electron injection layer (70 nm) G-15 (weight ratio 80%), Li (weight ratio 20%)

  For G-13 and G-14, the exemplified compounds shown in Table 6 were used.

As for the characteristics of the EL element, the current-voltage characteristics were measured with a microammeter 4140B manufactured by Hured Packard, and the light emission luminance was measured with BM7 manufactured by Topcon.
Table 6 shows the light emission efficiencies and voltages of Examples 21 to 25 at a luminance of 1000 cd · m ⁻² .

(Examples 26 to 28)
In this example, an element having a configuration of (anode / hole transport layer / light emitting layer / hole exciton blocking layer / electron transport layer / cathode) was produced. However, two or more kinds of light emitting materials are made to emit light by making the light emitting layer into a multilayer.

100 nm ITO was patterned on the glass substrate. On the ITO substrate, the following organic layers and electrode layers were continuously formed by vacuum deposition by resistance heating in a vacuum chamber of 10 ⁻⁵ Pa so that the opposing electrode area was 3 mm ² .
Hole transport layer (40nm) G-21
Light-emitting layer 1 (30 nm) Host G-22 (weight ratio 60%), G-23 (weight ratio 39%) Guest: Exemplified compound (weight ratio 1%)
Light emitting layer 2 (10 nm) Host G-24 (98% by weight) Guest: G-25 (2% by weight)
Hole-exciton blocking layer (10 nm) G-26
Electron transport layer (30 nm) G-27
Metal electrode layer 1 (1 nm) LiF
Metal electrode layer 2 (100 nm) Al

  For G-24 and G-25, the exemplified compounds shown in Table 7 were used.

As for the characteristics of the EL element, the current-voltage characteristics were measured with a microammeter 4140B manufactured by Hured Packard, and the light emission luminance was measured with BM7 manufactured by Topcon.
Table 7 shows the light emission efficiencies and voltages of Examples 26 to 28 at a luminance of 1000 cd · m ⁻² .

(Results and discussion)
The organic compound according to the present invention is a novel compound having a high quantum yield and light emission suitable for red, and when used in an organic light-emitting device, a light-emitting device having good light-emitting characteristics can be produced.

8 TFT element 11 Anode 12 Organic compound layer 13 Cathode

Claims (9)

An organic compound represented by the following general formula (1):

In the formula (1), R _{1 to} R ₁₆ are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted aryl group, Each is independently selected from a substituted or unsubstituted heterocyclic group. 2. The organic compound according to claim 1, wherein R _{1 to} R ₁₆ are each independently selected from the hydrogen atom, the substituted or unsubstituted alkyl group, and the substituted or unsubstituted aryl group. R _1, R _2, R _7, R _8, R _11, R ₁₄ are each independently selected from the hydrogen atom, the substituted or unsubstituted alkyl group, and the substituted or unsubstituted aryl group;
The organic compound according to claim 1, wherein R _{3 to} R _6, R _{9 to} R _10, R _{12 to} R _13, and R _{15 to} R ₁₆ are all hydrogen atoms. R ₁ , R ₂ , R ₇ , R ₈ are each independently selected from a hydrogen atom or a phenyl group,
The organic compound according to claim 1, wherein R _{3 to} R ₆ and R _{9 to} R ₁₆ are all hydrogen atoms. An organic light emitting device having a pair of electrodes and an organic compound layer disposed between the pair of electrodes,
The organic compound layer includes the organic compound according to any one of claims 1 to 4.   The organic light emitting device according to claim 5, wherein the organic compound layer is a light emitting layer.   The organic light emitting device according to claim 6, which emits red light.   A plurality of pixels, wherein each of the plurality of pixels includes the organic light emitting element according to any one of claims 5 to 7 and a TFT element that controls light emission luminance of the organic light emitting element. Display device.   8. An input unit for inputting image information and a display unit for displaying an image, wherein the display unit includes a plurality of pixels, and the plurality of pixels are according to claim 5. An image input device comprising: the organic light-emitting device according to 1); and a TFT device for controlling light emission luminance of the organic light-emitting device.