JP5964902B2 - Platinum complex, luminescent material, organic electroluminescent element, display device and lighting device - Google Patents

Description

  The present invention relates to a platinum complex, a light emitting material using the same, an organic electroluminescent element, a display device, and a lighting device.

  Organic electroluminescent elements (hereinafter also referred to as “organic EL elements” or simply “EL elements”) have been actively researched and developed in recent years because they emit light with high luminance when driven at a low voltage. In general, an organic EL element is composed of an organic layer including a light emitting layer and a pair of electrodes sandwiching the layer. Electrons injected from the cathode and holes injected from the anode are recombined in the light emitting layer and generated. The energy of the excitons is used for light emission. As the light emitting layer, a doped element in which a light emitting material is doped in a host material is widely used.

  By using a phosphorescent material, the efficiency of the device is increasing. Known phosphorescent materials include iridium complexes and platinum complexes (for example, Patent Documents 1 and 2), and platinum complexes capable of emitting blue to green light have been reported. In addition, as for the phenylpyrazole tetradentate platinum complex, for example, Patent Documents 3 to 5 disclose platinum complexes capable of emitting blue to green light.

  Patent Document 6 discloses a phenylpyrazole tetradentate platinum complex having better emission characteristics (emission wavelength, luminance, quantum yield, driving voltage, etc.) and durability than those disclosed in Patent Documents 3 to 5. ing. However, even in an organic electroluminescent device containing a phenylpyrazole tetradentate platinum complex disclosed in Patent Documents 3 to 6 in a light emitting layer, it has excellent blue purity (CIExy chromaticity coordinates (0.15, In the vicinity of 0.15), it was found that the light emission efficiency, drive voltage, power consumption, and durability were not sufficient, and further improvements were demanded from the structure identification of the platinum complex.

US Pat. No. 6,303,238 International Publication No. 00/57676 JP 2006-232784 A JP 2007-096255 A JP 2008-037848 A JP 2009-096800 A

The organic EL device can be applied to a wide range of applications including, for example, a display device such as a mobile phone display, a computer display, an automobile information display, a TV monitor, and general lighting. There is a need for a luminescent material that is excellent (near CIExy chromaticity coordinates (0.15, 0.15)).
However, the tetradentate platinum complexes described in Patent Documents 3 and 5 have a low blue purity, an emission wavelength of blue-green, and are not pure blue. Furthermore, there was a problem with luminous efficiency. Further, although the emission color of the tetradentate platinum complex described in Patent Documents 4 and 6 is close to pure blue, it has not reached a sufficient level from the viewpoint of emission efficiency. Moreover, when trying to obtain a highly efficient organic EL element with these platinum complexes, it was necessary to increase the doping concentration of the platinum complex in the host material. However, when the doping concentration of these platinum complexes is increased, excimer emission having light emission in a long wavelength region peculiar to the planar platinum complex appears remarkably. As a result, there has been a problem that the chromaticity is lowered and a desired emission color cannot be obtained.
The object of the present invention is to solve the above problems, and by introducing a bulky substituent into a tetradentate platinum complex having a maximum emission wavelength in the range of 440 to 480 nm and exhibiting blue emission, An object of the present invention is to provide a platinum complex that can exhibit high-efficiency emission characteristics while maintaining the blue CIExy chromaticity even when the doping concentration is increased.
Furthermore, another object of the present invention is to provide a light emitting material, an organic electroluminescent element, a display device and a lighting device using the platinum complex.

According to the present invention, by having a specific bulky group at a specific position of the phenylpyrazole tetradentate platinum complex, it is possible to obtain light emission excellent in blue purity in a thin film state and excellent in luminous efficiency. It was made by finding.
The inventors of the present invention have solved the above problems by the invention having the following constitution.

[1]
A platinum complex represented by the following general formula (1):
[In said general formula (1), R < ¹¹ > -R < ¹⁴ > represents a substituent each independently. n ¹¹ and ^{n 12} each independently represents an integer of 0 to ^2, represents an integer of ^{n 13} and ^{n 14} are each independently 0-3. When n ¹¹ and n ¹² are 2, two R ¹¹ and R ¹² may be the same or different, and R ¹¹ and R ¹² may be connected to each other to form a ring. When n ¹³ and n ¹⁴ are 2 or more, a plurality of R ¹³ and R ¹⁴ may be the same or different, and adjacent R ¹³ and R ¹⁴ may be connected to each other to form a ring. . S ^{11 to} S ¹⁴ each independently represents a hydrogen atom or a substituent. Adjacent R ¹³ and S ¹³ , R ¹⁴ and S ¹⁴ , and S ¹¹ and S ¹² may be connected to each other to form a ring. However, at least one of S ^{11 to} S ¹⁴ represents a substituent selected from the following substituent group S. ]
[2]
The platinum complex according to [1], wherein the platinum complex is represented by the following general formula (2).
[In the general formula (2), R ^{21 to} R ²⁵ each independently represents a substituent. ^{n 21,} n 22, n ²⁴ each independently represents an integer of 0 to ^{2, n 23} represents an integer of 0 to ^{3, n 25} represents an integer of 0-4. When n ²¹ , n ²² and n ²⁴ are 2, two R ²¹ , R ²² and R ²⁴ may be the same or different, and R ²¹ and R ²² are connected to each other to form a ring. May be. When n ²³ and n ²⁵ are 2 or more, a plurality of R ²³ and R ²⁵ may be the same or different, and adjacent R ²³ and R ²⁵ may be connected to each other to form a ring. . S ^{21 to} S ²³ each independently represents a hydrogen atom or a substituent. Adjacent R ²³ and S ²³ , S ²¹ and S ²² may be connected to each other to form a ring. However, at least one of S ^{21 to} S ²³ represents a substituent selected from the substituent group S. X represents O, S, Se, NR ²⁰¹ , SiR ²⁰² R ²⁰³ or CR ²⁰⁴ R ²⁰⁵ . R ²⁰¹ to R ²⁰⁵ each independently represent a hydrogen atom or a substituent. ]
[3]
The platinum complex according to [2], wherein X in the general formula (2) is NR ³⁶ [R ³⁶ represents a hydrogen atom or a substituent].
[4]
A light emitting material comprising the platinum complex according to any one of [1] to [3].
[5]
An organic material comprising a plurality of organic layers including a light emitting layer between a pair of electrodes, wherein any one of the organic layers contains the platinum complex according to any one of [1] to [3]. Electroluminescent device.
[6]
The display apparatus using the organic electroluminescent element as described in [5].
[7]
The illuminating device using the organic electroluminescent element as described in [5].

  According to the present invention, a platinum complex having a maximum emission wavelength in a thin film state of 440 to 480 nm, excellent blue purity (in the vicinity of CIExy chromaticity coordinates (0.15, 0.15)), and excellent emission efficiency. And a luminescent material can be provided. In addition, an organic electroluminescent element excellent in blue purity and luminous efficiency, and a display device and a lighting device using the organic electroluminescent element can be provided.

It is the schematic which shows an example (1st Embodiment) of the layer structure of the organic EL element which concerns on this invention. It is the schematic which shows an example (2nd Embodiment) of the light-emitting device which concerns on this invention. It is the schematic which shows an example (3rd Embodiment) of the illuminating device which concerns on this invention. It is a figure which shows the emission spectrum in Example 5 and Comparative Example 4. It is a figure which shows the emission spectrum in Example 9 and Comparative Example 5. It is a figure which shows the emission spectrum in Example 10. It is a figure which shows the emission spectrum in Example 12 and Comparative Example 6. It is a chart showing ¹ H-NMR data of the compound synthesized in Example (30). It is a chart showing ¹ H-NMR data of the compound synthesized in Example (29). It is a chart showing ¹ H-NMR data of the compound synthesized in Example (80). It is a chart showing ¹ H-NMR data of the compound synthesized in Example (26). It is a chart showing ¹ H-NMR data of the compound synthesized in Example (97). It is a chart showing ¹ H-NMR data of the compound synthesized in Example (127). It is a chart showing ¹ H-NMR data of the compound synthesized in Example (57).

In the description of the general formula of the present invention, a hydrogen atom includes an isotope (deuterium atom and the like), and an atom constituting a substituent further includes the isotope.
In the present invention, the “carbon number” of a substituent such as an alkyl group includes a case where a substituent such as an alkyl group may be substituted by another substituent, and also includes the carbon number of the other substituent. Used to mean

In the present invention, the substituent group A is defined as follows.
(Substituent group A)
An alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n- Decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, For example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, For example, propargyl, 3-pentynyl, etc.), aryl groups (preferably having 6 to 30 carbon atoms, more preferably A prime number of 6 to 20, particularly preferably a carbon number of 6 to 12, such as phenyl, p-methylphenyl, naphthyl, anthranyl, etc., an amino group (preferably a carbon number of 0 to 30, more preferably a carbon number). 0 to 20, particularly preferably 0 to 10 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, ditolylamino, etc.), an alkoxy group (preferably 1 to 1 carbon atoms). 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, and examples thereof include methoxy, ethoxy, butoxy, 2-ethylhexyloxy and the like, and aryloxy groups (preferably 6 carbon atoms). -30, more preferably 6-20 carbons, particularly preferably 6-12 carbons, Phenyloxy, 1-naphthyloxy, 2-naphthyloxy, etc.), a heterocyclic oxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms). For example, pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy, etc.), acyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, Acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl, Ethoxycarbonyl, etc.), aryloxycarbonyl group (preferably Alternatively, it has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonyl. ), An acyloxy group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms such as acetoxy and benzoyloxy), an acylamino group (preferably 2-30 carbon atoms, more preferably 2-20 carbon atoms, particularly preferably 2-10 carbon atoms, and examples thereof include acetylamino, benzoylamino, and the like, and an alkoxycarbonylamino group (preferably having 2-2 carbon atoms). 30, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino, etc.), aryloxycarbonylamino group (preferably 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl And sulfonylamino groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino and benzenesulfonylamino). ), A sulfamoyl group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenyl Sulfamoyl, etc.), a carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, Phenylcarbamoyl etc.), alkylthio group ( Preferably, it has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methylthio, ethylthio and the like, and an arylthio group (preferably 6 to 30 carbon atoms). , More preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, etc.), a heterocyclic thio group (preferably 1 to 30 carbon atoms, more preferably 1 to carbon atoms). 20, particularly preferably 1 to 12 carbon atoms, such as pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio and the like, and a sulfonyl group (preferably having a carbon number). 1 to 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl and tosyl). Rufinyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methanesulfinyl and benzenesulfinyl. ), A ureido group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as ureido, methylureido, phenylureido, etc.), phosphoric acid. An amide group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as diethyl phosphoric acid amide and phenylphosphoric acid amide), a hydroxy group , Mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocycle (hetero Aryl) group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 2 to 12 carbon atoms). Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom. Specific examples include imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, and carbazolyl groups. , An azepinyl group, etc.), a silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, such as trimethylsilyl and triphenylsilyl). ), A silyloxy group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, such as trimethylsilyloxy, triphenylsilyloxy, etc.), Phosphoryl group (eg diphenylphosphoryl group, dimethyl group) Such Ruhosuhoriru group.), And the like. These substituents may be further substituted, and examples of the further substituent include a group selected from the substituent group A described above.

The platinum complex of the present invention is represented by the general formula (1).
The light emitting material of the present invention contains a platinum complex represented by the general formula (1), and the organic electroluminescent element of the present invention is an organic electroluminescent element having a light emitting layer between a pair of electrodes, The light emitting layer has a platinum complex represented by the general formula (1).

Since the phenylpyrazole tetradentate platinum complex disclosed in Patent Documents 3 to 6 has a highly planar structure, stacking due to π-π interaction between platinum complexes and platinum-platinum interaction occur. Complexes with these interactions generally tend to form aggregates as the dope concentration increases, and the maximum emission wavelength in the thin film state is a dilute solution state or a thin film state with a low dope concentration (eg, 1-3%). It is known that the wavelength is longer than the maximum light emission wavelength (monomer light emission).
The platinum complex represented by the general formula (1) of the present invention introduces a specific bulky substituent into the planar tetradentate platinum complex disclosed in Patent Documents 3 to 6, thereby allowing interaction between the complexes to occur. By weakening, monomer light emission is possible even in a thin film state such as when used in a light emitting layer of an organic electroluminescence device, and light emission excellent in blue purity can be obtained. Further, even when doped at a high concentration, light emission excellent in blue purity can be obtained.
Furthermore, in general, introducing a flexible substituent such as an alkyl chain into a metal complex causes a thermal deactivation path from the excited state due to the thermal motion of the alkyl chain, and as a result, the introduction of the alkyl chain results in luminous efficiency. It was thought that this could lead to a decline. However, in the present invention, by using a platinum complex in which an alkyl chain or other substituent is introduced at a specific position, the light emission efficiency does not decrease, and the light emission efficiency is unexpectedly improved. I understood that.
It was also found that the platinum complex represented by the general formula (1) of the present invention has a greater effect of weakening the interaction between the complexes as the structure becomes asymmetric. It is thought that the decrease in the symmetry of the molecular structure led to a decrease in the interaction between the complexes.

[Platinum complex represented by general formula (1)]
Hereinafter, the platinum complex represented by the general formula (1) (hereinafter also referred to as “compound represented by the general formula (1)” or the like) will be described.

[In said general formula (1), R < ¹¹ > -R < ¹⁴ > represents a substituent each independently. n ¹¹ and ^{n 12} each independently represents an integer of 0 to ^2, represents an integer of ^{n 13} and ^{n 14} are each independently 0-3. When n ¹¹ and n ¹² are 2, two R ¹¹ and R ¹² may be the same or different, and R ¹¹ and R ¹² may be connected to each other to form a ring. When n ¹³ and n ¹⁴ are 2 or more, a plurality of R ¹³ and R ¹⁴ may be the same or different, and adjacent R ¹³ and R ¹⁴ may be connected to each other to form a ring. . S ^{11 to} S ¹⁴ each independently represents a hydrogen atom or a substituent. Adjacent R ¹³ and S ¹³ , R ¹⁴ and S ¹⁴ , and S ¹¹ and S ¹² may be connected to each other to form a ring. However, at least one of S ^{11 to} S ¹⁴ represents a substituent selected from the following substituent group S. ]

The general formula (1) will be described.
n ¹¹ and ^{n 12} each independently represents an integer of 0 to 2, preferably 0.
n ¹³ and n ¹⁴ each independently represents an integer of 0 to 3, preferably 0 or 1.
R ^{11 to} R ¹⁴ each independently represents a substituent. Although it does not specifically limit as a substituent, The substituent represented by the substituent group A is mentioned.
R ^{11 to} R ¹⁴ are preferably a halogen atom, an alkyl group, an aryl group, a heteroaryl group, a cyano group, an alkoxy group, a hydroxy group, or an amino group, an alkyl group having 1 to 20 carbon atoms, or a 6 to 18 carbon atoms. An aryl group, a C2-C18 heteroaryl group, a cyano group, and an alkoxy group are more preferable. A C1-C10 alkyl group, a C6-C12 aryl group, and a C2-C12 heteroaryl group are more preferable. Further preferred. When these groups can be further substituted, they may have further substituents, and the further substituents are preferably a halogen atom, an alkyl group, an aryl group, a heteroaryl group, or a cyano group. More preferred are a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 2 to 12 carbon atoms, and a cyano group, a fluorine atom, an alkyl group having 1 to 10 carbon atoms, and cyano. The group is particularly preferred.
When n ¹¹ and n ¹² are 2, two R ¹¹ and R ¹² may be the same or different, and R ¹¹ and R ¹² may be connected to each other to form a ring. When n ¹³ and n ¹⁴ are 2 or more, a plurality of R ¹³ and R ¹⁴ may be the same or different, and adjacent R ¹³ and R ¹⁴ may be connected to each other to form a ring. . Examples of the ring formed by connecting two R ^{11 s} , two R ^{12 s} , a plurality of R ^13s , or a plurality of R ^14s together include a saturated or unsaturated aromatic ring or non-aromatic ring. Benzene ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyrrole ring, thiophene ring, furan ring and the like. Although it does not specifically limit as a substituent of this ring, The substituent represented by the substituent group A is mentioned. In that case, the ring formed may have a substituent and may be further condensed.

S ^{11 to} S ¹⁴ represent a hydrogen atom or a substituent, and the substituent is not particularly limited, and examples thereof include a substituent represented by the substituent group A. As the substituent, a halogen atom, an alkyl group, an aryl group, a heteroaryl group, a cyano group, an alkoxy group, an amino group, and a silyl group are preferable, and an alkyl group having 1 to 20 carbon atoms and 6 to 18 carbon atoms is preferable. Are more preferable, a C2-C18 heteroaryl group, a cyano group, and a silyl group, a C1-C12 alkyl group, a C6-C12 aryl group, and a C2-C12 heteroaryl group Is more preferable. When these groups can be further substituted, they may have further substituents, and the further substituents are preferably a halogen atom, an alkyl group, an aryl group, a heteroaryl group, or a cyano group. , A fluorine atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 2 to 12 carbon atoms, and a cyano group are more preferable, and a fluorine atom and an alkyl group having 1 to 10 carbon atoms ( A trifluoromethyl group), an aryl group having 6 to 12 carbon atoms, and a cyano group are particularly preferred.

Adjacent R ¹³ and S ¹³ , R ¹⁴ and S ¹⁴ may be connected to each other to form a ring. Examples of the ring include a saturated or unsaturated aromatic ring or non-aromatic ring, such as a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, Examples include a pyrrole ring, a thiophene ring, and a furan ring. Preferably, it is an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyrrole ring or an indene ring, more preferably an imidazole ring, an oxazole ring, a pyrazole ring, an indole ring or a benzofuran ring, still more preferably an indole ring or It is a benzofuran ring. Although it does not specifically limit as a substituent of this ring, The substituent represented by the substituent group A is mentioned. In that case, the ring formed may have a substituent and may be further condensed.
S ¹¹ and S ¹² may be connected to each other to form a ring. In this case, S ¹³ or S ¹⁴ represents a substituent selected from the substituent group S. The ring formed by connecting S ¹¹ and S ¹² to each other is not particularly limited, and examples thereof include a cycloalkyl group and a cyclopentadienyl group (including a fluorene ring). In particular, a cyclopentyl group and a cyclohexyl group are preferable.

At least one of S ^{11 to} S ¹⁴ represents a substituent selected from the substituent group S.
The substituent of the substituent group S is a bulky group, and the platinum complex represented by the general formula (1) has the bulky group in at least one of the positions of S ^{11 to} S ^14. Interaction can be weakened, and even in the solid phase, it is difficult to form an aggregate, and the monomer state can be maintained.
Among the substituent group S, (a), (b), (e), (h), and (y) are preferable.

  In the present invention, the platinum complex represented by the general formula (1) is preferably a platinum complex represented by the following general formula (2).

[In the general formula (2), R ^{21 to} R ²⁵ each independently represents a substituent. ^{n 21,} n 22, n ²⁴ each independently represents an integer of 0 to ^{2, n 23} represents an integer of 0 to ^{3, n 25} represents an integer of 0-4. When n ²¹ , n ²² and n ²⁴ are 2, two R ²¹ , R ²² and R ²⁴ may be the same or different, and R ²¹ and R ²² are connected to each other to form a ring. May be. When n ²³ and n ²⁵ are 2 or more, a plurality of R ²³ and R ²⁵ may be the same or different, and adjacent R ²³ and R ²⁵ may be connected to each other to form a ring. . S ^{21 to} S ²³ each independently represents a hydrogen atom or a substituent. Adjacent R ²³ and S ²³ , S ²¹ and S ²² may be connected to each other to form a ring. However, at least one of S ^{21 to} S ²³ represents a substituent selected from the substituent group S. X represents O, S, Se, NR ²⁰¹ , SiR ²⁰² R ²⁰³ or CR ²⁰⁴ R ²⁰⁵ . R ²⁰¹ to R ²⁰⁵ each independently represent a hydrogen atom or a substituent. ]

The general formula (2) will be described.
Examples of the substituent of ^{R 21 ~R 25, S 21 ~S} 23 in the general formula (2) is the same as the substituent in ^{R 11 ~R 14, S 11 ~S} 14 of the general formula (1), preferably The thing is the same.
Each of n ^{21 to} n ^{23 in} the general formula (2) is the same as each of n ^{11 to} n ^{13 in} the general formula (1), and preferable ones are also the same.
^{N 24} in the general formula (2) represents an integer of 0 to 2, preferably ^{0, n 25} represents an integer of 0 to 4, preferably 0.
At least one position of S ^{21 to} S ²³ is substituted with a group selected from the substituent group S. Among them, preferred is the same as in the general formula (1).
X represents O, S, Se, NR ²⁰¹ , SiR ²⁰² R ²⁰³ or CR ²⁰⁴ R ²⁰⁵ , and R ^{201 to} R ²⁰⁵ each independently represent a hydrogen atom or a substituent. X is preferably O, S, or NR ²⁰¹ , and more preferably O or NR ²⁰¹ .
Examples of the substituent of R ²⁰¹ to R ^205, but are not limited to, include substituents represented by substituent group A. The substituent is preferably an alkyl group, an aryl group, or a heteroaryl group, more preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a heteroaryl group having 2 to 18 carbon atoms. An alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a heteroaryl group having 2 to 12 carbon atoms are more preferable. When these groups can be further substituted, they may have a further substituent, and examples of the further substituent include a substituent represented by the substituent group A, and a hydrogen atom or An alkyl group is preferable, and a hydrogen atom is more preferable.
When there are two such substituents in SiR ²⁰² R ²⁰³ or CR ²⁰⁴ R ²⁰⁵ , the two substituents may be bonded to form a ring.

In the present invention, the platinum complex represented by the general formula (2) is preferably a platinum complex in which X in the general formula (2) is NR ³⁶ [R ³⁶ represents a hydrogen atom or a substituent].
R ³⁶ represents a hydrogen atom or a substituent, and the substituent is not particularly limited, and examples thereof include a substituent represented by Substituent Group A. The substituent is preferably an alkyl group, an aryl group, or a heteroaryl group, more preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a heteroaryl group having 2 to 18 carbon atoms. An alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a heteroaryl group having 2 to 12 carbon atoms are more preferable. When these groups can be further substituted, they may have a further substituent, and examples of the further substituent include a substituent represented by the substituent group A, and a hydrogen atom or an alkyl group. Are preferable, and a hydrogen atom is more preferable.

  Although the specific example of the platinum complex represented by general formula (1)-(2) in this invention is illustrated below, this invention is not limited to these.

  Even if the platinum complex represented by the general formulas (1) to (2) in the present invention is a low molecular compound, an oligomer compound and a polymer compound (mass average molecular weight (polystyrene conversion) is preferably 1000 to 5000000, More preferably, it is 2000 to 1000000. More preferably, it is 3000 to 100,000. In the case of an oligomer compound or a polymer compound, the structure represented by the general formula may be included in the polymer main chain, or may be included in the polymer side chain. The polymer compound may be a homopolymer compound or a copolymer. The present invention is preferably a low molecular compound. Moreover, when vacuum-depositing a low molecular weight compound, from the viewpoint of deposition suitability, the molecular weight is preferably 250 or more and 2000 or less, more preferably 350 or more and 1500 or less, and particularly preferably 400 or more and 1200 or less.

  The platinum complex represented by the general formulas (1) to (2) in the present invention can be applied to an organic layer of an organic electroluminescent element, and includes a hole injection layer, a hole transport layer, an electron transport material, and a hole block. It can be used for any of materials, electron block materials, exciton block materials, and light emitting materials, and is preferably a hole injection layer, a hole transport layer, a hole blocking material, and a light emitting material, more preferably holes. A transport material and a light emitting material are preferable, and a light emitting material is more preferable.

  The platinum complex represented by the general formulas (1) to (2) of the present invention can be synthesized by various methods. For example, a ligand or a dissociated product thereof and a platinum ion as a solvent (for example, a halogen solvent, an alcohol solvent, an ether solvent, an ester solvent, a ketone solvent, a nitrile solvent, an amide solvent, a sulfone solvent, In the presence of a sulfoxide solvent, water, etc., or in the absence of a solvent, in the presence of a base (inorganic or organic bases such as sodium methoxide, t-butoxypotassium, triethylamine, potassium carbonate, etc.) Or in the absence of a base, at room temperature or below, or by heating (in addition to normal heating, a method of heating with a microwave is also effective).

The compound illustrated as a platinum complex represented by the said General formula (1)-(2) can be manufactured, for example by the process shown below.
For example, referring to the method described in paragraphs [0112] to [0121] of JP-A-2009-161524, the method described in Synthesis, 5, 409-411 (1986), etc., the corresponding dicarbonyl compound and hydrazine A phenylpyrazole compound is synthesized by reacting with a hydrate, and further reacting with an alkyl halide or phosgene to synthesize the corresponding ligand, and then the obtained organic ligand is converted into an appropriate platinum source. Can be synthesized by reacting in a solvent as described above, but is not limited thereto.
Specifically, the platinum complex represented by any one of the general formulas (1) to (2) of the present invention can be synthesized by applying the following synthesis scheme.

In the synthetic scheme, R represents a group corresponding to S ¹¹ and / or S ¹² in the general formula (1), and R ′ represents a group corresponding to S ¹³ and / or S ¹⁴ in the general formula (1). Represent.

[Luminescent material]
The light emitting material of the present invention contains a platinum complex represented by any one of the general formulas (1) to (2).
Since the maximum emission wavelength in the thin film state of the platinum complex represented by any one of the general formulas (1) to (2) is in the range of 440 to 480 nm, the light emitting material of the present invention has excellent blue purity and emits light. It is excellent in efficiency and can be advantageously used for an organic electroluminescent device.
Here, “the maximum emission wavelength is in the range of 440 to 480 nm” means that at least one of the emission maximums is in the range of 440 to 480 nm. More preferably, the platinum complex represented by any one of the general formulas (1) to (2) is in a thin film state and at least one of the maximum emission wavelengths is in the range of 440 to 470 nm. The platinum complex represented by any one of the general formulas (1) to (2) may have a plurality of emission maxima in the range of 440 to 480 nm in a thin film state.

[Organic electroluminescence device]
The organic electroluminescent element of the present invention will be described in detail.
The organic electroluminescent element of the present invention is an organic electroluminescent element having a luminescent layer between a pair of electrodes, and the platinum complex represented by any one of the general formulas (1) to (2) is formed on the luminescent layer. contains.

In the organic electroluminescent element of the present invention, the layer containing the platinum complex represented by any one of the general formulas (1) to (2) is a light emitting layer, and may further have a plurality of organic layers. In view of the properties of the light-emitting element, at least one of the anode and the cathode is preferably transparent or translucent.
FIG. 1 shows an example of the configuration of an organic electroluminescent device according to the present invention. In the organic electroluminescent device 10 according to the present invention shown in FIG. 1, a light emitting layer 6 is sandwiched between an anode 4 and a cathode 9 on a support substrate 2. Specifically, a hole injection layer 4, a hole transport layer 5, an electron block layer 6, a light emitting layer 7, and an electron transport layer 8 are laminated in this order between the anode 4 and the cathode 9.

<Structure of organic layer>
There is no restriction | limiting in particular as a layer structure of the said organic layer, Although it can select suitably according to the use and objective of an organic electroluminescent element, It is preferable to form on the said transparent electrode or the said back electrode. . In this case, the organic layer is formed on the entire surface or a part of the transparent electrode or the back electrode.
There is no restriction | limiting in particular about the shape of a organic layer, a magnitude | size, thickness, etc., According to the objective, it can select suitably.

Specific examples of the layer configuration include the following, but the present invention is not limited to these configurations.
Anode / hole transport layer / light emitting layer / electron transport layer / cathode / anode / hole transport layer / light emitting layer / block layer / electron transport layer / cathode / anode / hole transport layer / light emitting layer / block layer / electron Transport layer / electron injection layer / cathode / anode / hole injection layer / hole transport layer / light emitting layer / blocking layer / electron transport layer / cathode / anode / hole transport layer / block layer / light emitting layer / electron transport layer / Cathode / anode / hole transport layer / block layer / light emitting layer / electron transport layer / electron injection layer / cathode / anode / hole injection layer / hole transport layer / block layer / light emitting layer / electron transport layer / cathode / anode / Hole injection layer / hole transport layer / block layer / light emitting layer / electron transport layer / electron injection layer / cathode / anode / hole injection layer / hole transport layer / block layer / light emitting layer / block layer / electron transport Layer / electron injection layer / cathode / anode / hole injection layer / hole transport layer / block layer / light emitting layer / block layer / electric Injection layer / cathode / anode / hole injection layer / hole transport layer / block layer / light-emitting layer / block layer / electron transport layer / cathode / anode / hole injection layer / hole transport layer / light-emitting layer / block layer / Electron transport layer / electron injection layer / cathode / anode / hole injection layer / hole transport layer / block layer / light emitting layer / block layer / electron transport layer / electron injection layer / cathode / anode / hole injection layer / hole Transport layer / light emitting layer / electron transport layer / electron injection layer / cathode

  Although it does not specifically limit as an organic layer, In addition to a light emitting layer, a positive hole injection layer, a positive hole transport layer, an electron injection layer, an electron transport layer, a positive hole block layer, an electron block layer, an exciton block layer, a protective layer, etc. You may have. Each of these layers may have other functions.

As an aspect of lamination of the organic layer in the present invention, an aspect in which a hole transport layer, a light emitting layer, and an electron transport layer are laminated in this order from the anode side is preferable. Further, a charge blocking layer or the like may be provided between the hole transport layer and the light-emitting layer, or between the light-emitting layer and the electron transport layer. A hole injection layer may be provided between the anode and the hole transport layer, and an electron injection layer may be provided between the cathode and the electron transport layer. Each layer may be divided into a plurality of secondary layers.
Each element constituting the element of the present invention will be described in detail.

<Board>
The substrate used in the present invention is preferably a substrate that does not scatter or attenuate light emitted from the organic layer. In the case of an organic material, it is preferable that it is excellent in heat resistance, dimensional stability, solvent resistance, electrical insulation, and workability.
<Anode>
The anode usually only needs to have a function as an electrode for supplying holes to the organic layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element, It can select suitably from well-known electrode materials. As described above, the anode is usually provided as a transparent anode.
<Cathode>
The cathode usually has a function as an electrode for injecting electrons into the organic layer, and there is no particular limitation on the shape, structure, size, etc., and it is known depending on the use and purpose of the light-emitting element. The electrode material can be selected as appropriate.

  Regarding the substrate, anode, and cathode, the matters described in paragraphs [0070] to [0089] of JP-A-2008-270736 can be applied to the present invention.

<Organic layer>
The organic layer in the present invention will be described.
The organic layer includes a light emitting layer. As described above, the organic layer other than the light emitting layer is a hole transport layer, an electron transport layer, a hole block layer, an electron block layer, a hole injection layer, an electron injection layer, or the like. Is mentioned.

-Formation of organic layer-
In the organic electroluminescence device of the present invention, each organic layer can be suitably formed by any of dry film forming methods such as vapor deposition and sputtering, wet film forming methods such as solution coating, transfer methods, and printing methods. it can.

-Light emitting layer-
The light-emitting layer receives holes from the anode, the hole injection layer, or the hole transport layer when an electric field is applied, receives electrons from the cathode, the electron injection layer, or the electron transport layer, and recombines holes and electrons. It is a layer which has the function to provide light emission.
The light emitting layer in the present invention may be composed of only a light emitting material, or may be a mixed layer of a host material and a light emitting material. As the light emitting material, in addition to the platinum complex represented by any one of the general formulas (1) to (2) of the present invention, a fluorescent light emitting material or a phosphorescent light emitting material can be used. It may be more than seeds. The host material is preferably a charge transport material. The host material may be one kind or two or more kinds, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed. Furthermore, the light emitting layer may include a material (binder material) that does not have charge transporting properties and does not emit light. As a light emitting layer, what uses the platinum complex represented by either general formula (1)-(2) as a host material and a light emitting material is preferable.
The light emitting layer may be a single layer or a multilayer of two or more layers. When there are a plurality of light emitting layers, the platinum complex represented by any one of the general formulas (1) to (2) may be included in two or more light emitting layers. In addition, each light emitting layer may emit light with different emission colors.

(Fluorescent material)
Examples of fluorescent light-emitting materials that can be used in the present invention include, for example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives. , Condensed aromatic compounds, perinone derivatives, oxadiazole derivatives, oxazine derivatives, aldazine derivatives, pyralidine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styryl Complexes of amine derivatives, diketopyrrolopyrrole derivatives, aromatic dimethylidin compounds, 8-quinolinol derivatives and pyromethene derivatives Various complexes represented, polythiophene, polyphenylene, polyphenylene vinylene polymer compounds include compounds such as organic silane derivatives.

(Phosphorescent material)
Examples of the phosphorescent material that can be used in the present invention include, in addition to the compound represented by the general formula (1), for example, US6303238B1, US6097147, WO00 / 57676, WO00 / 70655, WO01 / 08230, WO01 / 39234A2, WO01 / 41512A1, WO02 / 02714A2, WO02 / 15645A1, WO02 / 44189A1, WO05 / 19373A2, JP2001-247859, JP2002-302671, JP2002-117978, JP2003-133074, JP2002-235076, JP2003 123982, JP2002-170684, EP121257, JP2002-226495, JP2002-234894, JP2001247478, JP2001-29 470, JP 2002-173675, JP 2002-203678, JP 2002-203679, JP 2004-357799, JP 2006-256999, JP 2007-19462, JP 2007-84635, JP 2007-96259, etc. The phosphorescent light emitting compounds described in the above patent documents are mentioned. Among them, more preferable luminescent dopants include Ir complex, Pt complex, Cu complex, Re complex, W complex, Rh complex, Ru complex, Pd complex, Os complex. Eu complex, Tb complex, Gd complex, Dy complex, and Ce complex. Particularly preferred is an Ir complex, a Pt complex, or a Re complex, among which an Ir complex or a Pt complex containing at least one coordination mode of a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, and a metal-sulfur bond. Or Re complexes are preferred. Furthermore, from the viewpoints of luminous efficiency, driving durability, chromaticity, etc., an Ir complex, a Pt complex, or a Re complex containing a tridentate or higher polydentate ligand is particularly preferable.

  The content of the platinum complex represented by any one of the general formulas (1) to (2) is in the range of 0.1% by mass to 50% by mass with respect to the total mass of the light emitting layer in the light emitting layer. Preferably, the range of 1% by mass to 50% by mass is more preferable, the range of 3% by mass to 40% by mass is more preferable, and the range of 5% by mass to 30% by mass is most preferable.

  The content of the phosphorescent material (the platinum complex represented by any one of the general formulas (1) to (2) and / or the phosphorescent material used in combination) that can be used in the present invention is based on the total mass of the light emitting layer. The range of 0.1% to 50% by mass is preferable, the range of 1% to 40% by mass is more preferable, and the range of 5% to 30% by mass is most preferable. In particular, in the range of 5% by mass or more and 30% by mass or less, the chromaticity of light emission of the organic electroluminescent element is less dependent on the addition concentration of the phosphorescent light emitting material.

(Host material)
The host material is a compound mainly responsible for charge injection and transport in the light emitting layer, and itself is a compound that does not substantially emit light. In this specification, “substantially no light emission” means that the light emission amount from the substantially non-light emitting compound is preferably 5% or less, more preferably 3% or less of the total light emission amount of the entire device. More preferably, it means 1% or less.

In the present invention, the light emitting layer preferably contains a host material.
As the host material used together with the platinum complex represented by any one of the general formulas (1) to (2) of the present invention, a so-called bipolar property having a hole transporting host material, an electron transporting host material, or both. Examples of the host material include a bipolar host material.
The concentration of the host material in the light emitting layer is not particularly limited, but is preferably the main component (the component having the largest content) in the light emitting layer, more preferably 50% by mass or more and 99.9% by mass or less, 50 mass% or more and 99.8 mass% or less are still more preferable, 60 mass% or more and 99.7 mass% or less are especially preferable, and 70 mass% or more and 95 mass% or less are the most preferable.

  The glass transition point of the host material is preferably 60 ° C. or higher and 500 ° C. or lower, more preferably 70 ° C. or higher and 300 ° C. or lower, and still more preferably 90 ° C. or higher and 250 ° C. or lower.

In the light emitting layer, the triplet lowest excitation energy (T ₁ energy) of the host material is preferably higher than the T ₁ energy of the light emitting material from the viewpoint of light emission efficiency and driving durability.

  As a host material used in the present invention, the following compounds may be contained in the partial structure. For example, pyrrole, indole, carbazole (eg, CBP (4,4′-di (9-carbazoyl) biphenyl)), azaindole, azacarbazole, triazole, oxazole, oxadiazole, pyrazole, imidazole, thiophene, polyarylalkane, Pyrazoline, pyrazolone, phenylenediamine, arylamine, amino-substituted chalcone, styrylanthracene, fluorenone, hydrazone, stilbene, silazane, aromatic tertiary amine compound, styrylamine compound, porphyrin compound, polysilane compound, poly (N-vinyl) Carbazole), aniline copolymer, thiophene oligomer, conductive polymer oligomer such as polythiophene, organic silane, carbon film, pyridine, pyrimidine, triazine, ant Quinodimethane, anthrone, diphenylquinone, thiopyran dioxide, carbodiimide, fluorenylidenemethane, distyrylpyrazine, fluorine-substituted aromatic compounds, heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, phthalocyanine, 8-quinolinol derivatives Various metal complexes typified by metal complexes having metal complexes, metal phthalocyanines, benzoxazoles or benzothiazoles as ligands and their derivatives (which may have substituents or condensed rings) Examples thereof include the materials exemplified in the sections of the hole injection layer, the hole transport layer, the electron injection layer, and the electron transport layer.

  Further, as host materials used in the present invention, for example, compounds described in paragraphs [0113] to [0161] of JP-A No. 2002-1000047 and paragraphs [0087] to [0098] of JP-A No. 2004-214179 are described. These compounds can be suitably used, but are not limited thereto.

  The host material used in the present invention preferably contains at least one compound represented by the following general formula (A-1) or (A-2).

(In the general formula (A-1) and (A-2), d, e represents an integer of 0 to 3, the .rc ₈ representing a is .f is an integer of 1 to 3 at at least one of the one or more following Represents a carbazole group represented by the general formula (B).)

(In the general formula (B), .g representing a substituent on Rc ₉ independently represents an integer of 0-8.)

Rc ₈ and Rc ₉ each independently represent a substituent, specifically a halogen atom, an alkoxy group, a cyano group, a trifluoromethyl group, a nitro group, an alkyl group, an aryl group, a heteroaryl group, or a general formula (B ). An alkyl group having 10 or less carbon atoms or a substituted or unsubstituted aryl group having 10 or less carbon atoms is preferable, and an alkyl group having 6 or less carbon atoms is more preferable.
g represents an integer of 0 to 8, and is preferably 0 to 4 from the viewpoint of not excessively shielding the carbazole skeleton responsible for charge transport. Further, from the viewpoint of ease of synthesis, when carbazole has a substituent, those having a substituent so as to be symmetrical left and right are preferable.
In the general formula (A-1), the sum of d and e is preferably 2 or more from the viewpoint of maintaining the charge transport ability. Further, from the viewpoint of driving durability, it is preferable that Rc ₈ is substituted at the meta position with respect to the other benzene ring. Specifically, a compound represented by the following structure is preferable.

In the general formula (A-2), f is preferably 2 or more from the viewpoint of maintaining the charge transport ability. When f is 2 or 3, it is preferable that Rc ₈ substitutes at the meta position from the same viewpoint. Specifically, a compound represented by the following structure is preferable.

When general formula (A-1) and (A-2) have a hydrogen atom, an isotope (deuterium atom etc.) is also included. In this case, all hydrogen atoms in the compound may be replaced with isotopes, or a mixture in which a part is a compound containing an isotope may be used. Rc ₉ in general formula (B) is preferably substituted with deuterium, and the following structures are particularly preferable.

  In addition, the atom which comprises the substituent of general formula (A-1) and (A-2) may also contain the isotope.

  The compounds represented by the general formulas (A-1) and (A-2) can be synthesized by combining various known synthesis methods. Most commonly, carbazole compounds are synthesized by dehydroaromatization after the Athercorp rearrangement reaction of a condensate of an aryl hydrazine and a cyclohexane derivative (LF Tieze, by Th. Eicher, translated by Takano, Ogasawara, Precision organic synthesis, page 339 (published by Nankodo). Regarding the coupling reaction of the obtained carbazole compound and halogenated aryl compound using a palladium catalyst, Tetrahedron Letters 39: 617 (1998), 39: 2367 (1998) and 40: 6393 (1999) and the like. The reaction temperature and reaction time are not particularly limited, and the conditions described in the above literature can be applied. Some compounds such as mCP which are commercially available can be preferably used.

  The compounds represented by the general formulas (A-1) and (A-2) preferably form a thin layer by a vacuum deposition process, but a wet process such as solution coating can also be suitably used. The molecular weight of the compound is preferably 2000 or less, more preferably 1500 or less, and particularly preferably 1200 or less, from the viewpoints of deposition suitability and solubility. Also, from the viewpoint of vapor deposition suitability, if the molecular weight is too small, the vapor pressure becomes small, the change from the gas phase to the solid phase does not occur, and it is difficult to form an organic layer. Particularly preferred.

  Specific examples of the compounds represented by the general formulas (A-1) and (A-2) in the present invention are illustrated below, but the present invention is not limited thereto.

  The compound represented by formula (A-1) or (A-2) is more preferably compound (H-1) (H-2) or (H-51).

  Furthermore, arylamine compounds represented by formulas (A-1) and (A-2) other than the general formulas (A-1) and (A-2) as host compounds, organic compounds containing silicon (the following general formula (C-1) ) Is also preferable as the host material of the present invention, but the host compound of the present invention is not limited thereto.

(In the formula, plural Ar ^{1 s} each independently represent a substituent, and plural Ar ^{2 s} each independently represent a substituent.)

General formulas (B-1) and (C-1) will be described.
A plurality of Ar ¹ each independently represents a substituent, specifically an aryl group or a heteroaryl group. A benzene ring is preferred. Further, each Ar ¹ may have a substituent, and the substituent is an aryl group, a heteroaryl group, or an alkyl group. An aryl group and an alkyl group are preferable, and an aryl group is more preferable.

A plurality of Ar ² each independently represents a substituent, specifically an aryl group or a heteroaryl group. An aryl group is preferable. Further, each Ar ² may have a substituent, and the substituent is an aryl group, a heteroaryl group (particularly a carbazole group), or an alkyl group. An aryl group and a carbazole group are preferable, and a carbazole group is more preferable.

  Specific examples of the compounds represented by formulas (B-1) and (C-1) in the present invention are illustrated below, but the present invention is not limited to these.

  When the compounds represented by the general formulas (A-1), (A-2), (B-1), and (C-1) are introduced into a layer other than the light emitting layer (for example, a charge transport layer), The layer preferably contains 10% by mass to 100% by mass, more preferably 30% by mass to 100% by mass.

The organic electroluminescent element using the platinum complex of the present invention preferably further contains a hydrocarbon compound as a binder material in the light emitting layer. Since the coordination mode of the platinum complex of the present invention is a planar tetradentate coordination, it is considered that it is susceptible to π orbital interaction from surrounding host molecules and light emitting materials. By adding a nonpolar material such as a hydrocarbon compound to the light emitting layer, this interaction is reduced, and by suppressing variations in energy levels, the light emission waveform becomes sharper, and the device has excellent blue purity. Can be obtained. The hydrocarbon compound is saturated or unsaturated, and preferably has a molecular weight of 1200 or less in order to impart vapor deposition suitability. In addition, since the T ₁ energy needs to be a value larger than that of the light emitting material, a structure containing saturated hydrocarbons such as alkane, cycloalkane, bicycloalkane, adamantane and the like is preferable.
The hydrocarbon compound is preferably a compound represented by the following general formula (VI).
The compound represented by the general formula (VI) used in the organic electroluminescence device is excellent in chemical stability, has little alteration such as decomposition of the material during driving of the device, and the organic electric field due to the decomposition product of the material. It is possible to prevent the efficiency of the light emitting element from decreasing and the element life from decreasing.
The compound represented by the general formula (VI) will be described.

In general formula (VI), R ₄ , R ₆ , R ₈ , R ₁₀ , and X _{4 to} X ₁₅ each independently represent a hydrogen atom or a substituent. Specific examples of the substituent include the substituent group A, and R ₄ , R ₆ , R ₈ , R ₁₀ , and X _{4 to} X ₁₅ are preferably a hydrogen atom, an alkyl group, or an aryl group.

The alkyl group represented by R ₄ , R ₆ , R ₈ , R ₁₀ , X _{4 to} X ₁₅ in the general formula (VI) may be substituted with an adamantane structure or an aryl structure, and has 1 to 70 carbon atoms. Is preferable, C1-50 is more preferable, C1-30 is still more preferable, C1-10 is still more preferable, C1-6 is especially preferable, C2-C6 linear alkyl The group is most preferred.

Examples of the alkyl group represented by R ₄ , R ₆ , R ₈ , R ₁₀ , X _{4 to} X ₁₅ in the general formula (VI) include an nC ₅₀ H ₁₀₁ group and an nC ₃₀ H ₆₁ group. 3- (3,5,7-triphenyladamantan-1-yl) propyl group (31 carbon atoms), trityl group (19 carbon atoms), 3- (adamantan-1-yl) propyl group (13 carbon atoms) , 9-decalyl group (10 carbon atoms), benzyl group (7 carbon atoms), cyclohexyl group (6 carbon atoms), n-hexyl group (6 carbon atoms), n-pentyl group (5 carbon atoms), n-butyl Examples include a group (4 carbon atoms), an n-propyl group (3 carbon atoms), a cyclopropyl group (3 carbon atoms), an ethyl group (2 carbon atoms), a methyl group (1 carbon atom), and the like.

The aryl group represented by R ₄ , R ₆ , R ₈ , R ₁₀ , X _{4 to} X ₁₅ in the general formula (VI) may be substituted with an adamantane structure or an alkyl structure, and has 6 to 30 carbon atoms. Is preferable, carbon number 6-20 is more preferable, carbon number 6-15 is still more preferable, carbon number 6-10 is especially preferable, and carbon number 6 is the most preferable.

Examples of the aryl group represented by R ₄ , R ₆ , R ₈ , R ₁₀ , X _{4 to} X ₁₅ in the general formula (VI) include, for example, a 1-pyrenyl group (16 carbon atoms), a 9-anthracenyl group ( Carbon number 14), 1-naphthyl group (carbon number 10), 2-naphthyl group (carbon number 10), pt-butylphenyl group (carbon number 10), 2-m-xylyl group (carbon number 8), 5-m-xylyl group (carbon number 8), o-tolyl group (carbon number 7), m-tolyl group (carbon number 7), p-tolyl group (carbon number 7), phenyl group (carbon number 6), etc. Is mentioned.

R ₄ , R ₆ , R ₈ and R ₁₀ in the general formula (VI) may be a hydrogen atom, an alkyl group or an aryl group, but the above-mentioned high glass transition temperature is preferable. From the viewpoint, at least one is preferably an aryl group, more preferably at least two are aryl groups, and particularly preferably 3 to 4 are aryl groups.

X _{4 to} X _{15 in} the general formula (VI) may be a hydrogen atom, an alkyl group, or an aryl group, but are preferably a hydrogen atom or an aryl group, Particularly preferred is an atom.

  The molecular weight of the compound represented by the general formula (VI) in the present invention is 2000 or less from the viewpoint of vapor deposition suitability and solubility since an organic electroluminescent device is prepared using a vacuum vapor deposition process or a solution coating process. Is preferable, 1200 or less is more preferable, and 1000 or less is particularly preferable. Further, from the viewpoint of vapor deposition suitability, if the molecular weight is too small, the vapor pressure becomes small, the change from the gas phase to the solid phase does not occur, and it is difficult to form an organic layer. Is more preferable, and 400 or more is particularly preferable.

The compound represented by the general formula (VI) is preferably solid at room temperature (25 ° C), more preferably solid at room temperature (25 ° C) to 40 ° C, and from room temperature (25 ° C). Particularly preferred is a solid in the range of 60 ° C.
When the compound represented by the general formula (VI) that does not form a solid at room temperature (25 ° C.) is used, a solid phase can be formed at room temperature by combining with other materials.

  The content of the compound represented by the general formula (VI) in the light emitting layer needs to be limited to an amount that does not suppress the charge transport property, and the compound represented by the general formula (VI) is 0.1 to 0.1%. It is preferably contained 70% by mass, more preferably 0.1-30% by mass, and particularly preferably 0.1-25% by mass.

  The compound represented by general formula (VI) may contain only 1 type, and may contain combining the compound represented by several general formula (VI) in arbitrary ratios.

Although the specific example of a compound represented by general formula (VI) is enumerated below, it is not limited to the following.

The compound represented by the general formula (VI) can be synthesized by appropriately combining adamantane or a halogenated adamantane with an alkyl halide or an alkylmagnesium halide (Grignard reagent). For example, a halogenated adamantane and an alkyl halide can be coupled using indium (Reference 1). Alternatively, alkyl halides can be converted to alkyl copper reagents and coupled with aromatic Grignard reagents (Reference 2). Alkyl halides can also be coupled using an appropriate aryl boric acid and a palladium catalyst (Reference 3).
Reference 1: Tetrahedron Lett. 39, 1998, 9557-9558.
Reference 2: Tetrahedron Lett. 39, 1998, 2095-2096.
Reference 3: J.M. Am. Chem. Soc. 124, 2002, 13662-13663.

  The adamantane skeleton having an aryl group can be synthesized by appropriately combining adamantane or a halogenated adamantane with the corresponding arene or aryl halide.

  In the production method shown above, when the defined substituent changes under the conditions of a certain synthesis method or is inappropriate for carrying out the method, the functional group is protected or deprotected (for example, Protective Groups in Organic Synthesis, by TW Greene, John Wiley & Sons Inc. (198) ) Etc.) and the like can be easily manufactured. Moreover, it is also possible to change the order of reaction steps such as introduction of substituents as necessary.

  Although the thickness of a light emitting layer is not specifically limited, Usually, it is preferable that they are 1 nm-500 nm, it is more preferable that they are 5 nm-200 nm, and it is still more preferable that they are 10 nm-100 nm.

-Hole injection layer, hole transport layer-
The hole injection layer and the hole transport layer are layers provided between the anode and the light emitting layer, and have a function of receiving holes from the anode or the anode side and transporting them to the cathode side. Specifically, the hole injection layer and the hole transport layer are carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamines. Derivatives, amino-substituted chalcone derivatives, styryl anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styryl amine compounds, porphyrin compounds, organosilane derivatives, carbon, etc. Preferably there is.

The thicknesses of the hole injection layer and the hole transport layer are each preferably 500 nm or less from the viewpoint of lowering the driving voltage.
The thickness of the hole transport layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and even more preferably 5 nm to 100 nm. In addition, the thickness of the hole injection layer is preferably 0.1 nm to 500 nm, more preferably 0.5 nm to 300 nm, and still more preferably 1 nm to 200 nm.
The hole injection layer and the hole transport layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

-Electron injection layer, electron transport layer-
The electron injection layer and the electron transport layer are layers provided between the cathode and the light emitting layer, and have a function of receiving electrons from the cathode or the cathode side and transporting them to the anode side. Specifically, the electron injection layer and the electron transport layer are triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, Carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, aromatic tetracarboxylic anhydrides such as naphthalene and perylene, phthalocyanine derivatives, phenanthrene derivatives, phenanthroline derivatives, complexes of 8-quinolinol derivatives, metal phthalocyanines, benzoxazoles and benzoates A layer containing various complexes typified by complexes having thiazole as a ligand, organosilane derivatives, and the like is preferable.

The thicknesses of the electron injection layer and the electron transport layer are each preferably 100 nm or less from the viewpoint of lowering the driving voltage.
The thickness of the electron transport layer is preferably 1 nm to 100 nm, more preferably 5 nm to 50 nm, and still more preferably 10 nm to 30 nm. In addition, the thickness of the electron injection layer is preferably 0.1 nm to 100 nm, more preferably 0.2 nm to 80 nm, and still more preferably 0.5 nm to 50 nm.
The electron injection layer and the electron transport layer may have a single-layer structure made of one or more of the materials described above, or may have a multilayer structure made up of a plurality of layers having the same composition or different compositions.

-Hole blocking layer-
The hole blocking layer is a layer provided between the cathode and the light emitting layer and having a function of preventing holes transported from the anode side to the light emitting layer from passing through to the cathode side. In the present invention, a hole blocking layer can be provided as an organic layer adjacent to the light emitting layer on the cathode side.
Examples of organic compounds constituting the hole blocking layer include aluminum (III) bis (2-methyl-8-quinolinato) 4-phenylphenolate (Aluminum (III) bis [2-methyl-8-quinolinato] 4- aluminum complexes such as phenylphenolate (abbreviated as BAlq), carbazole derivatives, triazole derivatives, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (2,9-Dimethyl-4,7-diphenyl-1) , 10-phenanthroline (abbreviated as BCP)) and the like.
The thickness of the hole blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm.
The hole blocking layer may have a single layer structure made of one or more of the materials described above, or may have a multilayer structure made of a plurality of layers having the same composition or different compositions.
-Electronic block layer-
The electron blocking layer is a layer provided between the anode and the light emitting layer and having a function of preventing electrons transported from the cathode side to the light emitting layer from passing through to the anode side. In the present invention, an electron blocking layer can be provided as an organic layer adjacent to the light emitting layer on the anode side.
As an example of the organic compound constituting the electron blocking layer, for example, those mentioned as the hole transport material described above can be applied.
The thickness of the electron blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and even more preferably 10 nm to 100 nm.
The electron blocking layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

<Protective layer>
In the present invention, the entire organic EL element may be protected by a protective layer.
Regarding the protective layer, the matters described in paragraph numbers [0169] to [0170] of JP-A-2008-270736 can be applied to the present invention.

<Sealing container>
The element of this invention may seal the whole element using a sealing container.
Regarding the sealing container, the matters described in paragraph No. [0171] of JP-A-2008-270736 can be applied to the present invention.

(Drive)
The element of the present invention can obtain light emission by applying a direct current (which may include an alternating current component if necessary) voltage (usually 2 to 15 volts) or a direct current between the anode and the cathode. it can.

  Regarding the driving method of the element of the present invention, JP-A-2-148687, JP-A-6-301355, JP-A-5-29080, JP-A-7-134558, JP-A-8-234665, and JP-A-8-214447, The driving methods described in Japanese Patent No. 2784615, US Pat. Nos. 5,828,429 and 6023308, etc. can be applied.

  The element of the present invention can improve the light extraction efficiency by various known devices. For example, by processing the substrate surface shape (for example, forming a fine concavo-convex pattern), controlling the refractive index of the substrate / ITO layer / organic layer, controlling the film thickness of the substrate / ITO layer / organic layer, etc. It is possible to improve light extraction efficiency and external quantum efficiency.

  The element of the present invention may be a so-called top emission method in which light emission is extracted from the anode side.

The organic electroluminescent element in the present invention may have a resonator structure. For example, a multilayer film mirror made of a plurality of laminated films having different refractive indexes, a transparent or translucent electrode, a light emitting layer, and a metal electrode are superimposed on a transparent substrate. The light generated in the light emitting layer resonates repeatedly with the multilayer mirror and the metal electrode as a reflection plate.
In another preferred embodiment, a transparent or translucent electrode and a metal electrode each function as a reflecting plate on a transparent substrate, and light generated in the light emitting layer repeats reflection and resonates between them.
In order to form a resonant structure, the optical path length determined from the effective refractive index of the two reflectors and the refractive index and thickness of each layer between the reflectors is adjusted to an optimum value to obtain the desired resonant wavelength. Is done. The calculation formula in the case of the first embodiment is described in JP-A-9-180883. The calculation formula in the case of the second aspect is described in Japanese Patent Application Laid-Open No. 2004-127795.

The external quantum efficiency of the organic electroluminescent element of the present invention is preferably 3% or more, and more preferably 5% or more. The value of the external quantum efficiency should be the maximum value of the external quantum efficiency when the device is driven at 20 ° C., or the value of the external quantum efficiency near 100 to 500 cd / m ² when the device is driven at 20 ° C. Can do.

  The internal quantum efficiency of the organic electroluminescent element of the present invention is preferably 15% or more, more preferably 25% or more, and further preferably 50% or more. The internal quantum efficiency of the device is calculated by dividing the external quantum efficiency by the light extraction efficiency. In a normal organic EL element, the light extraction efficiency is about 20%. However, the substrate shape, electrode shape, organic layer thickness, inorganic layer thickness, organic layer refractive index, inorganic layer refractive index, etc. By devising it, it is possible to increase the light extraction efficiency to 20% or more.

(Use of the element of the present invention)
The element of the present invention can be suitably used for a display element, a display, a backlight, electrophotography, an illumination light source, a recording light source, an exposure light source, a reading light source, a sign, a signboard, an interior, or optical communication. In particular, it is preferably used for a device driven in a region having a high light emission luminance, such as a lighting device and a display device.

Next, the light emitting device of the present invention will be described with reference to FIG.
The light emitting device of the present invention uses the organic electroluminescent element.
FIG. 2 is a cross-sectional view schematically showing an example of the light emitting device of the present invention.
The light emitting device 20 in FIG. 2 includes a transparent substrate (supporting substrate) 2, an organic electroluminescent element 10, a sealing container 16, and the like.

The organic electroluminescent device 10 is configured by sequentially laminating an anode (first electrode) 3, an organic layer 11, and a cathode (second electrode) 9 on a substrate 2. A protective layer 12 is laminated on the cathode 9, and a sealing container 16 is provided on the protective layer 12 with an adhesive layer 14 interposed therebetween. In addition, a part of each electrode 3 and 9, a partition, an insulating layer, etc. are abbreviate | omitted.
Here, as the adhesive layer 14, a photocurable adhesive such as an epoxy resin or a thermosetting adhesive can be used, and for example, a thermosetting adhesive sheet can also be used.

  The use of the light-emitting device of the present invention is not particularly limited, and for example, in addition to a lighting device, a display device such as a television, a personal computer, a mobile phone, and electronic paper can be used.

Next, an illumination device according to an embodiment of the present invention will be described with reference to FIG.
FIG. 3 is a cross-sectional view schematically showing an example of a lighting device according to an embodiment of the present invention.
As shown in FIG. 3, the illumination device 40 according to the embodiment of the present invention includes the organic EL element 10 and the light scattering member 30 described above.
More specifically, the lighting device 40 is configured such that the substrate 2 of the organic EL element 10 and the light scattering member 30 are in contact with each other. The light scattering member 30 is not particularly limited as long as it can scatter light. In FIG. 3, the light scattering member 30 is a member in which fine particles 32 are dispersed on a transparent substrate 31.
As the transparent substrate 31, for example, a glass substrate can be preferably cited. As the fine particles 32, transparent resin fine particles can be preferably exemplified. As the glass substrate and the transparent resin fine particles, known ones can be used. In such an illuminating device 40, when light emitted from the organic electroluminescent element 10 is incident on the light incident surface 30A of the scattering member 30, the incident light is scattered by the light scattering member 30, and the scattered light is emitted from the light emitting surface 30B. It is emitted as illumination light.

EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the scope of the present invention is not limited to the following specific examples. The following “Example 6”, “Example 7”, “Example 9”, “Example 10”, “Example 11”, and “Example 13” are respectively referred to as “Reference Example 6”, “ It should be read as “Reference Example 7”, “Reference Example 9”, “Reference Example 10”, “Reference Example 11”, and “Reference Example 13”.

(Synthesis example)
Synthesis of Compound (30) A synthesis scheme of the compound (30) is shown below.

2,4-pentanedione (50 mL), dimethylacetamide (300 mL), and potassium carbonate (200 g) were added to a three-necked flask and allowed to stir at 80 ° C. After dropwise addition of benzyl bromide (127 mL), the mixture was reacted at 140 ° C. for 9 hours, distilled water (250 mL) was added, and the precipitate was collected by filtration. Isopropyl alcohol (150 mL) was added to the precipitate collected by filtration, and washed with heating and stirring to obtain Compound (W-1) (56.8 g).
Compound (W-1) (25.0 g) and dimethylformamide (150 mL) were added to a three-necked flask, and compound (G-1) (37 mL) was added dropwise with stirring. The reaction was carried out at 150 ° C. for 7 hours. The mixture was stirred in an ice bath and stirred, and the resulting precipitate was collected by filtration to obtain compound (W-2) (21.0 g).
The compound (W-2) (20.0 g) and ethanol (200 mL) were added to a three-necked flask and heated to reflux. Hydrazine monohydrate (5.64 g) dissolved in ethanol (10 mL) was slowly added dropwise thereto and reacted for 4.5 hours. Ethanol was distilled off, poured into distilled water (600 mL) and precipitated. Isopropanol (30 mL) was added to the resulting precipitate, washed with stirring in an ice bath, and further washed with isopropanol / hexane = 1/1 to give compound (W-3) (12.0 g). Obtained.
The compound (W-3) (1.00 g), potassium carbonate (1.68 g) and 1,3-dimethylimidazolidinone (10 mL) were added to a three-necked flask, and the mixture was heated and stirred at 100 ° C. Then, the compound (G-2) (810 mg) was added, and the temperature was raised to 135 ° C. and reacted for 8.5 hours. Distilled water (50 mL) was added to form a white precipitate, and the precipitate was collected by filtration. The compound (W-4) (660 mg) was obtained by performing purification by silica gel column chromatography.
Compound (W-4) (550 mg), platinum chloride (276 mg), and m-tolunitrile (5 mL) were added to a three-necked flask and reacted at an external temperature of 220 ° C. for 4 hours. The reaction solution was concentrated under reduced pressure, and purified by silica gel column chromatography to obtain compound (30) (390 mg). The obtained compound was identified by ¹ H-NMR. ^{The 1} H-NMR data is shown in FIG.

Synthesis of Compound (29) A synthesis scheme of the compound (29) is shown below.

The compound (W-3) (1.00 g), potassium carbonate (1.68 g) and 1,3-dimethylimidazolidinone (10 mL) were added to a three-necked flask, and the mixture was heated and stirred at 100 ° C. Then, the compound (G-3) (1.16 g) was added, and the temperature was raised to 155 ° C. and reacted for 6 hours. Distilled water (50 mL) was added to form a white precipitate, and the precipitate was collected by filtration. The product was purified by silica gel column chromatography and washed with isopropyl alcohol to obtain Compound (W-5) (610 mg).
Compound (W-5) (610 mg), platinum chloride (263 mg) and m-tolunitrile (5 mL) were added to a three-necked flask, and the mixture was heated to reflux and allowed to react for 11 hours. The reaction solution was concentrated under reduced pressure, and purified by silica gel column chromatography to obtain compound (29) (330 mg). The obtained compound was identified by ¹ H-NMR. ^{The 1} H-NMR data is shown in FIG.

Synthesis of Compound (80) A synthesis scheme of the compound (80) is shown below.

In a three-necked flask, compound (W-3) (450 mg), compound (G-4) (1.55 g), copper (I) oxide (78 mg), compound (G-5) (75 mg), cesium carbonate (3.60 g) ), 1,3-dimethylimidazolidinone (10 mL) was added and reacted at 170 ° C. for 6 hours. The reaction solution was concentrated under reduced pressure, and purified by silica gel column chromatography to obtain compound (W-6) (440 mg).
Compound (W-6) (430 mg), platinum chloride (173 mg), and m-tolunitrile (5 mL) were added to a three-necked flask, and the mixture was heated to reflux and reacted for 8 hours. The solvent was distilled off under reduced pressure, methanol was added, and the precipitate was collected by filtration. The obtained precipitate was dissolved in m-tolunitrile, and hexane was added for reprecipitation. The resulting precipitate was collected by filtration and washed with isopropyl alcohol to obtain Compound (80) (170 mg). The obtained compound was identified by ¹ H-NMR. ¹ H-NMR data is shown in FIG.

Synthesis of Compound (26) A synthesis scheme of the compound (26) is shown below.

2,4-pentanedione (20 mL), dimethylacetamide (100 mL), and potassium carbonate (80.3 g) were added to a three-necked flask, and the mixture was heated and stirred at 80 ° C. After dropwise addition of 1-bromo-2-methylpropane (78.4 g), the temperature was raised to 135 ° C. and reacted for 18 hours. Distilled water was added, extraction was performed with ethyl acetate, and the organic layer was concentrated. Then, purification by silica gel column chromatography was performed to obtain compound (W-7) (6.6 g).
Compound (W-8) was obtained by carrying out the same method as the method for obtaining compound (W-2).
Compound (W-9) was obtained by carrying out the same method as the method for obtaining compound (W-3).
Compound (W-10) was obtained by carrying out the same method as the method for obtaining compound (W-6).
Compound (26) was obtained by carrying out the same method as the method for obtaining compound (29). The obtained compound was identified by ¹ H-NMR. ¹ H-NMR data is shown in FIG.

Synthesis of Compound (32) The following compound (32) can be synthesized by the same method by replacing 1-bromo-2-methylpropane which is the starting material of the compound (26) with 1-bromo-2,2-dimethylpropane. .

Synthesis of Compound (97) A synthesis scheme of the compound (97) is shown below.

Compound (W-11) was obtained by carrying out a method similar to the method for obtaining compound (W-2) or compound (W-8).
Compound (W-12) was obtained by carrying out a method similar to the method for obtaining compound (W-3) or compound (W-9).
In a three-necked flask, compound (W-12) (6.00 g), compound (G-7) (10.9 g), copper (I) oxide (487 mg), compound (G-5) (1.87 g), cesium carbonate (22.2 g) and dimethylformamide (100 mL) were added and reacted at 175 ° C. for 26 hours. Distilled water was added, extraction was performed with ethyl acetate, and the organic layer was concentrated. Then, the refinement | purification by a silica gel column chromatography was performed, and the compound (W-13) (6.00g) was obtained.
In a three-necked flask, compound (W-13) (2.00 g), compound (G-4) (3.20 g), copper (I) oxide (93 mg), compound (G-5) (356 mg), cesium carbonate (4 20 g), 1,3-dimethylimidazolidinone (50 mL) was added and reacted at 200 ° C. for 20 hours. Distilled water was added, extraction was performed with ethyl acetate, and the organic layer was concentrated. Then, the refinement | purification by a silica gel column chromatography was performed, and the compound (W-14) (2.82g) was obtained.
Compound (W-14) (3.32 g), platinum chloride (1.90 g) and m-tolunitrile (70 mL) were added to a three-necked flask, and the mixture was heated to reflux and allowed to react for 30 hours. The reaction solution was concentrated under reduced pressure and purified by silica gel column chromatography to obtain compound (97) (2.92 g). The obtained compound was identified by ¹ H-NMR. ¹ H-NMR data is shown in FIG.

Synthesis of Compound (127) A synthesis scheme of the compound (127) is shown below.

In a three-necked flask, compound (W-13) (2.65 g), compound (G-8) (3.35 g), copper (I) oxide (123 mg), compound (G-5) (471 mg), cesium carbonate (5 6 g), 1,3-dimethylimidazolidinone (70 mL) was added, and the mixture was reacted at 185 ° C. for 23 hours. Distilled water was added, extraction was performed with ethyl acetate, and the organic layer was concentrated. Then, the refinement | purification by silica gel column chromatography was performed, and the compound (W-15) (2.75g) was obtained.
Compound (W-15) (500 mg), platinum chloride (273 mg), and m-tolunitrile (10 mL) were added to a three-necked flask, and the mixture was heated to reflux and reacted for 13 hours. The reaction solution was concentrated under reduced pressure, and purified by silica gel column chromatography to obtain compound (127) (450 mg). The obtained compound was identified by ¹ H-NMR. ^{The 1} H-NMR data is shown in FIG.

Synthesis of Compound (57) A synthesis scheme of the compound (57) is shown below.

Compound (W-13) (1.10 g), potassium carbonate (1.97 g), compound (G-2) (864 mg), 1,3-dimethylimidazolidinone (25 mL) was added to a three-necked flask at 150 ° C. The mixture was heated and stirred for 48 hours. Distilled water was added, extraction was performed with ethyl acetate, and the organic layer was concentrated. Purification by silica gel column chromatography gave Compound (W-16) (1.22 g).
Compound (W-16) (1.22 g), platinum chloride (792 mg) and m-tolunitrile (10 mL) were added to a three-necked flask, and the mixture was heated to reflux and reacted for 8 hours. The reaction solution was filtered hot on Celite to remove insolubles. Thereafter, the resulting precipitate was collected by filtration and washed with methanol to obtain Compound (57) (1.08 g). The obtained compound was identified by ¹ H-NMR. ^{The 1} H-NMR data is shown in FIG.

[Examples 1-4 and Comparative Examples 1-3]
The following compounds (26), (29), (30), (80) and comparative compounds (R-1) to (R-3) were each dissolved in dichloromethane so as to be 10% by mass, and each compound was dissolved. A solution was obtained.
The emission wavelength and quantum yield of these solutions were measured using SPECTROFLUOROPHOMETER (RF-5300PC) manufactured by SHIMADZU. The results are shown in Table 1 below.

[Production and evaluation of organic thin films]
Example 5
10% of the compound (26) used in Example 4 and the following compound (H-64) as a host material were vacuum-deposited on a glass substrate at a ratio (mass ratio) of 90%.
About the obtained organic thin film, the light emission wavelength and the photoluminescence intensity | strength were calculated | required as follows.
The emission spectrum and quantum yield were measured using a spectrum analyzer PMA-11 manufactured by Hamamatsu Photonics, and CIExy chromaticity coordinates were obtained. When the luminescence measurement of the obtained organic thin film was performed, λ _max = 437,462 nm and φ = 0.57 were obtained, and complete monomer luminescence was obtained. The CIExy chromaticity coordinates were (0.14, 0.12), and it was confirmed that pure blue light was emitted. The emission spectrum was as shown in FIG.

[Comparative Example 4]
The compound (26) of Example 5 was replaced with the comparative compound (R-1), and the others were vacuum-deposited on a glass substrate in the same manner as in Example 5. When luminescence measurement was performed on the obtained organic thin film, λ _max As a result, the aggregate emission was mainly obtained. The CIExy chromaticity coordinates were (0.46, 0.50), pure blue light emission could not be achieved, and yellow light emission was achieved. The emission spectrum of the emitted light was as shown in FIG.

[Examples 6 to 8]
The following compounds (97), (127), and (57) were prepared for each compound solution in the same manner as in Examples 1 to 4, and the emission wavelength and quantum yield in the solution were adjusted in the same manner as in Examples 1 to 4. It was measured. The results are shown in Table 2 below.

Example 9
Except that the compound (97) used in Example 6 was 10% and the following compound (H-75) as a host material had a ratio (mass ratio) of 90%, it was vacuum-deposited on a glass substrate in the same manner as in Example 5, When the luminescence measurement of the obtained organic thin film was performed, λ _max = 455,481 nm and φ = 0.40 were obtained, and complete monomer luminescence was obtained. The CIExy chromaticity coordinates were (0.15, 0.17), and it was confirmed that pure blue light was emitted. The emission spectrum of the emitted light was as shown in FIG.

[Comparative Example 5]
Substituting the compound of Example 9 (97) to Comparative Compound (R-4), others were vacuum deposited on the glass substrate in the same manner as in Example 9 was subjected to luminescence measurement of organic thin film obtained, lambda _max = 456,482 nm, φ = 0.49, but the CIExy chromaticity coordinates are (0.20, 0.27) because the long wavelength region has a tail as shown in the emission spectrum shown in FIG. Compared with Example 9, it was found that the blue purity was inferior.

Example 10
Replace the host materials used in Examples 9 to Compound (H-64), others were vacuum deposited on the glass substrate in the same manner as in Example 9 was subjected to luminescence measurement of organic thin film obtained, lambda _max = At 453,481 nm and φ = 0.68, complete monomer emission was obtained. CIExy color coordinates were (0.16, 0.19), and it was confirmed that blue light was emitted. The emission spectrum was as shown in FIG.

Example 11
A vacuum evaporation was performed on a glass substrate in the same manner as in Example 9 except that 10% of the compound (127) used in Example 7 and 90% of the compound (H-64) as a host material were used (mass ratio). When the luminescence measurement of the obtained organic thin film was performed, λ _max = 454, 480 nm and φ = 0.67 were obtained, and complete monomer luminescence was obtained. CIExy color coordinates were (0.14, 0.17), and it was confirmed that blue light was emitted.

Example 12
Organic obtained by vacuum-depositing on a glass substrate in the same manner as in Example 9, except that 10% of the compound (57) used in Example 8 and 90% of the following compound (H-1) as a host material were used. When the light emission of the thin film was measured, λ _max = 463, 490 nm, φ = 0.71, and the CIExy color coordinates were (0.22, 0.33), indicating light blue light emission. The emission spectrum was as shown in FIG. Compared with Comparative Example 6 below, the excimer emission component was extremely weak, and an emission spectrum mainly composed of monomer emission was obtained. Also, the quantum yield was improved about 10 times. This is considered to be an effect of the present invention in which a t-butyl group which is a bulky substituent is introduced.

[Comparative Example 6]
The compound (57) of Example 12 was replaced with the comparative compound (R-3), and the others were vacuum-deposited on a glass substrate in the same manner as in Example 12. When luminescence measurement was performed on the obtained organic thin film, λ _max = 602 nm, φ = 0.07, and aggregate emission was mainly obtained, and blue emission could not be achieved. The emission spectrum was as shown in FIG.

[Production and Evaluation of Organic Electroluminescent Device]
Example 13
A glass substrate having an ITO film of 0.5 mm thickness and 2.5 cm square (manufactured by Geomatek Co., Ltd., surface resistance 10 Ω / □) is placed in a cleaning container, ultrasonically cleaned in 2-propanol, and then subjected to UV-ozone treatment for 30 minutes. Went. The following organic layers (organic compound layers) were sequentially deposited on the transparent anode (ITO film) by vacuum deposition.
In addition, the vapor deposition rate in the Example of this specification is 0.2 nm / sec unless there is particular notice. The deposition rate was measured using a quartz resonator. The film thicknesses described below were also measured using a crystal resonator.

The cleaned ITO substrate was put into a vapor deposition apparatus, and 4,4 ′, 4 ″ -tris (2-naphthylphenylamino) triphenylamine (2-TNATA), 2,3,5,6-tetrafluoro-7,7 , 8,8-Tetracyanoquinodimethane (F ₄ -TCNQ) was co-evaporated at a mass ratio of 99.7: 0.3 to 120 nm, and α-NPD was further evaporated thereon to a thickness of 7 nm. Compound (H-26) was deposited by 3 nm. On this, the above compound (127) as a platinum complex, the above compound (H-75) as a host material, and the following compound (1-7) as a binder material were co-deposited at a mass ratio of 10:45:45 (light emitting layer). ) Further, BAlq was deposited thereon by 30 nm.
A patterned mask (with a light emitting area of 4 mm × 5 mm) was placed on the organic thin film obtained, and 1 nm of lithium fluoride was deposited, and then 100 nm of aluminum was deposited. Without exposing it to the atmosphere, put it in a glove box substituted with argon gas, and seal it with a stainless steel sealing can and an ultraviolet curable adhesive (XNR5516HV, manufactured by Nagase Ciba). The organic electroluminescent element of Example 13 was produced.

(Evaluation of light emitting element)
About the obtained organic electroluminescent element, the light emission wavelength, the electroluminescence intensity | strength, and the external quantum efficiency were calculated | required as follows.
Using a source measure unit 2400 manufactured by Toyo Technica, a direct current voltage was applied to the device to emit light, and the luminance was measured using a luminance meter BM-8 manufactured by Topcon Corporation. The emission spectrum and emission wavelength were measured using a spectrum analyzer PMA-11 manufactured by Hamamatsu Photonics, and CIExy chromaticity coordinates were obtained. Based on these, the external quantum efficiency was calculated by the brightness conversion method.

  When a DC constant voltage was applied to the produced organic electroluminescent device, blue light emission derived from the exemplary compound (127) of the present invention was obtained. Table 3 shows the relative external quantum yield ηext and CIExy chromaticity coordinate values of the fabricated devices.

[Comparative Example 7]
A device was fabricated and evaluated in the same manner as in Example 13 except that the compound (127) in Example 13 was replaced with the comparative compound (R-4). Table 3 shows the evaluation results.

  From the above, by introducing a bulky substituent into the tetradentate ligand-containing platinum complex, the emission quantum yield in solution is greatly improved, and monomer emission is possible without aggregation in the organic thin film. became. Thereby, it turned out that the compound of this invention is very excellent in the point of color purity and luminous efficiency compared with the conventional platinum complex.

2 ... substrate 3 ... anode 4 ... hole injection layer 5 ... hole transport layer 6 ... electron blocking layer 7 ... light emitting layer 8 ... electron transport layer 9 ... Cathode 10 ... Organic electroluminescent device (organic EL device)
DESCRIPTION OF SYMBOLS 11 ... Organic layer 12 ... Protective layer 14 ... Adhesive layer 16 ... Sealing container 20 ... Light emitting device 30 ... Light scattering member 30A ... Light incident surface 30B ... Light Outgoing surface 32 ... fine particles 31 ... transparent substrate 40 ... illumination device

Claims (5)

A platinum complex represented by the following general formula (1):
[In said general formula (1), R < ¹¹ > -R < ¹⁴ > represents a substituent each independently. n ¹¹ and ^{n 12} each independently represents an integer of 0 to ^2, represents an integer of ^{n 13} and ^{n 14} are each independently 0-3. When n ¹¹ and n ¹² are 2, two R ¹¹ and R ¹² may be the same or different, and R ¹¹ and R ¹² are connected to each other to form a single ring or a condensed ring. Also good. When n ¹³ and n ¹⁴ are 2 or more, a plurality of R ¹³ and R ¹⁴ may be the same or different, and adjacent R ¹³ and R ¹⁴ are connected to each other to form a single ring or a condensed ring . May be. S ^{11 to} S ¹⁴ each independently represents a hydrogen atom or a substituent. Adjacent R ¹³ and S ¹³ , R ¹⁴ and S ¹⁴ , S ¹¹ and S ¹² may be connected to each other to form a single ring or a condensed ring . ^{However, S 11} or ^{S 12} represents a substituent selected from Substituent Group S.
However, the platinum complex represented by the following general formula (2 ′) is excluded.
In the general formula (2 ′), R ^{21 to} R ²⁵ each independently represent a substituent. ^{n 21,} n 22, n ²⁴ each independently represents an integer of 0 to ^{2, n 23} represents an integer of 0 to ^{3, n 25} represents an integer of 0-4. When n ²¹ , n ²² , and n ²⁴ are 2, two R ²¹ , R ²² , and R ²⁴ may be the same or different, and R ²¹ and R ²² are connected to each other to form a single ring or A condensed ring may be formed. When n ²³ and n ²⁵ are 2 or more, a plurality of R ²³ and R ²⁵ may be the same or different, and adjacent R ²³ and R ²⁵ are connected to each other to form a single ring or a condensed ring. May be. S ^{21 to} S ²³ each independently represents a hydrogen atom or a substituent. Adjacent S ²¹ and S ²² may be connected to each other to form a single ring or a condensed ring. However, at least one of S ^{21 to} S ²³ represents a substituent selected from the substituent group S. X represents O or NR ²⁰¹ . R ²⁰¹ each independently represents a hydrogen atom or a substituent. ]   A light emitting material comprising the platinum complex according to claim 1.   An organic electroluminescent device comprising a plurality of organic layers including a light emitting layer between a pair of electrodes, wherein any one of the organic layers contains the platinum complex according to claim 1.   The display apparatus using the organic electroluminescent element of Claim 3. The illuminating device using the organic electroluminescent element of Claim 3.