CN111362951B - Acenaphthene-aza-naphthalene derivative, preparation method thereof, infrared electronic device and infrared device - Google Patents

Abstract

The invention provides an acenaphthene aza naphthalene derivative, a preparation method thereof, an infrared electronic device and an infrared device, and relates to the technical field of organic photoelectric materials. The acenaphthene aza-naphthalene derivative obtained by introducing the condensed ring structure of the acenaphthene aza-naphthalene derivative has excellent film forming property and thermal stability and higher fluorescence quantum yield, and can be used for preparing organic electroluminescent devices, organic field effect transistors and organic solar cells. In addition, the acenaphthene aza naphthalene derivative can be used as a constituent material of a hole injection layer, a hole transport layer, a luminescent layer, an electron blocking layer, a hole blocking layer or an electron transport layer, and can reduce driving voltage, improve efficiency, brightness, prolong service life and the like. In addition, the preparation method of the acenaphthene aza-naphthalene derivative is simple, the raw materials are easy to obtain, and the industrial development requirement can be met.

Description

Acenaphthene and aza-naphthalene derivative, preparation method thereof, infrared electronic device and infrared device

Technical Field

The invention belongs to the technical field of organic photoelectric materials, and relates to acenaphthene and aza-naphthalene derivatives and an electronic device containing the same. More particularly, the present invention relates to acenaphthoazaphthalenes derivatives suitable for use in electronic devices, particularly organic electroluminescent devices, organic field effect transistors and organic solar cells, and infrared electronic devices and infrared devices using the same.

Background

The organic electroluminescent device has a series of advantages of self-luminescence, low-voltage driving, full curing, wide viewing angle, simple composition and process and the like, and compared with a liquid crystal display, the organic electroluminescent device does not need a backlight source. Therefore, the organic electroluminescent device has wide application prospect.

Organic electroluminescent devices generally comprise an anode, a metal cathode and an organic layer sandwiched therebetween. The organic layer mainly comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer. In addition, a host-guest structure is often used for the light-emitting layer. That is, the light emitting material is doped in the host material at a certain concentration to avoid concentration quenching and triplet-triplet annihilation, thereby improving the light emitting efficiency. Therefore, host materials are generally required to have a higher triplet energy level and, at the same time, a higher stability.

At present, research on organic electroluminescent materials has been widely conducted in academia and industry, and a large number of organic electroluminescent materials with excellent performance have been developed. In view of the above, the future direction of organic electroluminescent devices is to develop high efficiency, long lifetime, low cost white light devices and full color display devices, but many key problems still face to the organic electroluminescent materials with deep red and near infrared color, especially in the OLED devices in the infrared band, the external quantum efficiency will be rapidly reduced. Therefore, a stable and efficient infrared light-emitting compound material is designed and found, and is used as a novel material of an organic electroluminescent device to overcome the defects in the practical application process, and the wavelength increase and the quantum efficiency attenuation can be balanced and considered, so that the material is one of the key points in the research work of the organic electroluminescent device material and the future research and development trends.

Disclosure of Invention

The invention aims to provide an acenaphthene aza-naphthalene derivative. The acenaphthene aza-naphthalene derivative has high thermal stability, good transmission performance, high fluorescence quantum yield and simple preparation method, and the organic light-emitting device prepared from the acenaphthene aza-naphthalene derivative has the advantages of high light-emitting efficiency, long service life, long light-emitting wavelength and low driving voltage, and is an organic electroluminescent material with excellent performance.

It is another object of the present invention to provide an electronic device using the acenaphthoazaphthalene derivative, which has advantages of high efficiency, high durability and long lifetime.

The acenaphthene aza-naphthalene derivative compound adopted by the invention has a special condensed ring structure and has higher thermal stability, chemical stability and carrier transport property. The light color of the acenaphthene and single pyrazine derivatives reported at present can not reach an infrared light region, and the research and development team of the invention combines a large amount of theoretical calculation and experimental verification, and sets the introduction of electron pulling elements at appropriate sites, so that the derivatives have appropriate singlet states, triplet states, molecular orbital energy levels, strong electron pulling capacity and excellent fluorescence quantum yield. Therefore, the organic electroluminescent material is introduced into molecules with electroluminescent characteristics, so that the stability and the luminous efficiency of a device are improved, and the driving voltage of the device is reduced. In addition, the acenaphthene aza-naphthalene derivative compound has stronger electron pulling capability, can emit light more infrared, simultaneously keeps better external quantum efficiency, has more advantages in the fields of health physiotherapy and near infrared detection, and has better conductivity and the like.

Namely, the present invention is as follows.

[1] An acenaphthoazanaphthalene derivative represented by the following general formula (I):

wherein,

wherein,

ring A represents an aromatic nitrogen heterocycle;

L ₁ ，L ₂ ，L ₃ ，L ₄ each independently represents a single bond, a carbonyl group, an aromatic hydrocarbon group having 6 to 18 carbon atoms for a cyano group, or an aromatic heterocyclic group having 5 to 18 carbon atoms;

p represents an integer of 1 to 2;

m and n are each independently an integer of 0 to 3, and m and n are not 0 at the same time and m + n + p is not more than 4;

s and t are each independently an integer of 0 to 4, and s and t are not both 0;

A ₁ -A ₄ each independently represents Ar ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ 、

Ar ₁ ～Ar ₈ Each independently represents a hydrogen atom, a cyano group, optionally substituted by one or more R ¹ Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms or optionally substituted by one or more R ¹ A substituted aromatic heterocyclic group having 5 to 30 carbon atoms;

R ¹ represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, NO ₂ 、 N(R ² ) ₂ 、OR ² 、SR ² 、C(＝O)R ² 、P(＝O)R ² 、Si(R ² ) ₃ A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 40 carbon atoms;

R ² represents a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms.

[2] The acenaphthoazaphenanthracene derivative according to [1], which is represented by the following general formula (1) or (2):

[3]according to [1]]The acenaphthoazanaphthalene derivative is shown in the specification, wherein Ar is ₁ ～Ar ₈ Each independently selected from a hydrogen atom, a cyano group or the following groups:

wherein the dotted line represents and L ₁ 、L ₂ 、L ₃ 、L ₄ Or a bond of an N-bond,

R ¹ have the meaning as defined for the general formula (I).

[4] The acenaphthoazaphthalene derivative according to any one of [1] to [3],

L ₁ to L ₄ Each independently represents a single bond, a carbonyl group, a phenyl group or a triazinyl group;

R ¹ to R ² Each independently represents a cyano group, a phenyl group, a naphthyl group, a dimethylfluorenyl group, a dibenzothienyl group, a dibenzofuranyl group, a triazinyl group, a pyrimidinyl group, a pyridyl group, a biphenyl group, a terphenyl group, a quaterphenyl group, a pentabiphenyl group, a dianilino group, a trianilino group, a benzothienocarbazolyl group, a benzofurocarbazolyl group, a benzofluorenocarbazolyl group, a benzanthryl group, a spirobifluorenyl group, a carbazolyl group, an N-phenylcarbazolyl group, an indenocarbazolyl group, a benzimidazolyl group, a diphenyl-oxadiazolyl group, a diphenylboryl group, a triphenylphosphinoxy group, a diphenylphosphinyloxy group, a triphenylsilyl group, a tetraphenylsilyl group, an acridinyl group, a phenoxazinyl group, a phenothiazinyl group, or a phenanthroline group.

[5] The acenaphthoazaphthalene derivative according to any one of [1] to [4], wherein the acenaphthoazaphthalene derivative represented by the general formula (I) is selected from the following compounds:

[6] [1] A process for producing an acenaphthoazaphthalene derivative represented by the general formula (I), which comprises the steps of:

[7] an infrared electronic device comprising acenaphthoazaphthalene derivatives.

[8] The electronic device according to [7], wherein the electronic device is an organic electroluminescent device, an organic field effect transistor, or an organic solar cell;

wherein the organic electroluminescent device comprises: a first electrode, a second electrode provided so as to face the first electrode, and at least one organic layer interposed between the first electrode and the second electrode, wherein the at least one organic layer contains the acenaphthoazaphthalene derivative according to any one of [1] to [7 ].

[9] The electronic device according to [8], wherein the at least one organic layer is a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, a hole blocking layer, or an electron transport layer.

[10] An infrared device comprising acenaphthoazaphthalene derivatives and emitting light having a peak at not less than 780nm and an external quantum efficiency greater than 6%.

ADVANTAGEOUS EFFECTS OF INVENTION

The acenaphthene and aza-naphthalene derivative has a condensed ring structure by introducing the acenaphthene and aza-naphthalene derivative, so that the acenaphthene and aza-naphthalene derivative has good film forming property and thermal stability and higher fluorescence quantum yield, can be used for preparing electronic devices such as organic electroluminescent devices, organic field effect transistors and organic solar cells, particularly used as a constituent material of a hole injection layer, a hole transmission layer, a light emitting layer, an electron blocking layer, a hole blocking layer or an electron transmission layer in the organic electroluminescent devices, can show the advantages of high luminous efficiency, long service life, long luminous wavelength and low driving voltage, and is obviously superior to the existing organic electroluminescent devices.

In addition, the preparation method of the acenaphthene aza-naphthalene derivative is simple, the raw materials are easy to obtain, and the industrial development requirement can be met.

The acenaphthene aza naphthalene derivative has good application effect in organic electroluminescent devices, organic field effect transistors, organic solar cells and other electronic devices, and has wide industrialization prospect.

The acenaphthene aza naphthalene derivative has high electron injection and moving speed. Therefore, the organic electroluminescent device having the electron injection layer and/or the electron transport layer prepared using the acenaphtho-aza-naphthalene derivative of the present invention improves the electron transport efficiency from the electron transport layer to the light emitting layer, thereby improving the luminous efficiency. And, the driving voltage is reduced, thereby enhancing durability of the resulting organic electroluminescent device.

The acenaphthene aza naphthalene derivative has excellent capability of blocking holes, excellent electron transmission performance and stability in a thin film state. Therefore, the organic electroluminescent device having the hole blocking layer prepared using the acenaphthene and aza-naphthalene derivatives of the present invention has high luminous efficiency, a reduced driving voltage, and improved current resistance, so that the maximum luminous brightness of the organic electroluminescent device is increased.

The acenaphthene aza naphthalene derivative can be used as a material for forming a hole injection layer, a hole transmission layer, a luminescent layer, an electron blocking layer, a hole blocking layer or an electron transmission layer of an organic electroluminescent device. With the organic electroluminescent device of the present invention, excitons generated in the light-emitting layer can be confined, and the possibility of recombination of holes and electrons can be further increased to achieve high light-emitting efficiency and high external quantum efficiency.

Drawings

FIG. 1 is a fluorescence spectrum (PL) of the compounds of examples 1 and 2 of the present invention (compounds 1 to 28 and 1 to 46) in a toluene solution.

FIG. 2 shows organic electroluminescence spectra of examples 7 and 8 of the present invention.

Fig. 3 is a view showing the structures of organic electroluminescent devices of examples 7 to 12.

Description of the reference numerals

1-a substrate; 2-an anode; 3-a hole injection layer; 4-a hole transport layer; 5-an electron blocking layer;

6-a light-emitting layer; 7-a hole blocking layer; 8-an electron transport layer; 9-electron injection layer; 10-cathode.

Detailed Description

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

The acenaphthoazaphthalene derivative of the present invention is a novel compound having an acenaphthoazaphthalene ring structure, and is represented by the following general formula (I).

Specifically, the acenaphthene aza-naphthalene derivative of the invention has the following general formula (1) or (2):

in the above general formula (I) and (1) or (2),

ring A represents an aromatic nitrogen heterocycle;

L ₁ to L ₄ Each independently represents a single bond, a carbonyl group, a cyano group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic heterocyclic group having 5 to 18 carbon atoms;

A ₁ to A ₄ Each independently represents Ar ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ 、

Ar ₁ ～Ar ₈ Each independently represents a hydrogen atom, a cyano group, optionally substituted by one or more R ¹ Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms or optionally substituted by one or more R ¹ A substituted aromatic heterocyclic group having 5 to 30 carbon atoms;

p represents an integer of 1 to 2, m and n each independently represent an integer of 0 to 1, and m and n are not simultaneously 0,s and t each independently represent an integer of 0 to 1, and s and t are not simultaneously 0;

R ¹ represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, NO ₂ 、 N(R ² ) ₂ 、OR ² 、SR ² 、C(＝O)R ² 、P(＝O)R ² 、Si(R ² ) ₃ A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 40 carbon atoms.

R ² Represents a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms.

<L ₁ To L ₄ >

L ₁ 、L ₂ 、L ₃ And L ₄ Each independently represents a single bond, a carbonyl group, a cyano group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic heterocyclic group having 5 to 18 carbon atoms.

In the present invention, the hetero atom in the aromatic heterocyclic group having 5 to 18 carbon atoms is preferably selected from N, O and/or S. In the present invention, the number of hetero atoms may be 1 to 5. Aromatic hydrocarbon or aromatic heterocyclic groups in the sense of the present invention are understood to mean systems which do not necessarily contain only aryl or heteroaryl groups, but in which a plurality of aryl or heteroaryl groups may also be interrupted by non-aromatic units (preferably less than 10% of non-hydrogen atoms), which may be, for example, carbon atoms, nitrogen atoms, oxygen atoms or carbonyl groups. For example, systems of 9,9' -spirobifluorene, 9,9-diarylfluorene, triarylamines, diaryl ethers, etc., are also intended to be considered aromatic hydrocarbon groups in the sense of the present invention, as are systems in which two or more aryl groups are interrupted, for example, by linear or cyclic alkyl groups or by silyl groups. Furthermore, systems in which two or more aryl or heteroaryl groups are bonded directly to one another, such as biphenyl, terphenyl or quaterphenyl, are likewise intended to be regarded as aromatic hydrocarbon groups or aromatic heterocyclic groups.

From L ₁ 、L ₂ 、L ₃ And L ₄ The aromatic hydrocarbon group having 6 to 18 carbon atoms or the aromatic heterocyclic group having 5 to 18 carbon atoms represented may be exemplified by: <xnotran> , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , -3236 zxft 3236- , -5262 zxft 5262- , -3763 zxft 3763- , , , , , , , , , </xnotran>A benzimidazolyl group, a pyrazino imidazolyl group, a quinoxalinyl group, an oxazolyl group, a benzoxazolyl group, a naphthoxazolyl group, an anthraoxazolyl group, a phenanthrooxazolyl group, an isoxazolyl group, 1,2-thiazolyl group, 1,3-thiazolyl group, a benzothiazolyl group, a pyridazinyl group, a pyrimidinyl group, a benzopyrimidinyl group, a quinoxalinyl group, 1,5-diazanthryl group, 2,7-diazpyrenyl group, 3575-diazpyrenyl group, 1,6-diazpyrenyl group, 1,8-diazpyrenyl group, 4,5-diazpyrenyl group, 4,5,9,10-tetraazapyrenyl group, a pyrazinyl group, a phenazinyl group, phenothiazinyl group, a rubryl group, naphthyridinyl group, azacarbazolyl group, benzocarbazinyl group, phenanthrolinyl group, 5483 zxft 5283-triazolyl group, 3278-triazolyl group, benzoxazolyl group, 357446 zft-3258-diazenyl group, 359692-4248-oxadiazolyl group, 3246 zft-349692-oxadiazolyl group, 34zft-3446-oxadiazolyl group, 34zft-3258-oxadiazolyl group, 34zft-349692-oxadiazolyl group, 349692-oxadiazolyl group, 34zft-349635-34zft-oxadiazolyl group, 34zft-349692-349635-34zft-349692, and the like.

In the present invention, preferably, L ₁ 、L ₂ 、L ₃ And L ₄ Each independently represents a single bond, a carbonyl group, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aromatic heterocyclic group having 5 to 12 carbon atoms. More preferably, L ₁ 、L ₂ 、L ₃ And L ₄ Each independently represents a single bond, a carbonyl group, a phenyl group, a triazinyl group or a biphenyl group.

From L ₁ 、L ₂ 、L ₃ And L ₄ The aromatic hydrocarbon group having 6 to 18 carbon atoms or the aromatic heterocyclic group having 5 to 18 carbon atoms represented may be unsubstituted, but may also have a substituent. The substituents may be exemplified as follows: a deuterium atom; a cyano group; a nitro group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkyl group having 1 to 6 carbon atoms, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a neopentyl group, or a n-hexyl group; alkoxy having 1 to 6 carbon atoms such as methoxy, ethoxy or propoxy; alkenyl radicals, e.g. ethyleneA radical or an allyl radical; aryloxy groups such as phenoxy or tolyloxy; arylalkoxy, such as benzyloxy or phenethyloxy; aromatic hydrocarbon radicals or condensed polycyclic aromatic radicals, e.g. phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluorenyl, indenyl, pyrenyl, perylenyl, fluoranthryl, benzo [9,10]Phenanthryl or spirobifluorenyl; an aromatic heterocyclic group such as pyridyl, thienyl, furyl, pyrrolyl, quinolyl, isoquinolyl, benzofuryl, benzothienyl, indolyl, carbazolyl, benzoxazolyl, benzothiazolyl, quinoxalyl, benzimidazolyl, pyrazolyl, dibenzofuryl, dibenzothienyl, azafluorenyl, diazafluorenyl, carbolinyl, azaspirobifluorenyl or diazaspiro-bifluorenyl; arylethenyl, such as styryl or naphthylethenyl; and acyl groups such as acetyl or benzoyl and the like.

The alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms may be linear or branched. Any of the above substituents may be further substituted with the above exemplary substituents. The above substituents may be present independently of each other, but may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.

<A ₁ To A ₄ >

A ₁ And A ₄ Each independently represents Ar ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ 、

(Ar ₁ To Ar ₈ )

Ar ₁ ～Ar ₈ Each independently represents a hydrogen atom, a cyano group, optionally substituted by one or more R ¹ Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms or optionally substituted by one or more R ¹ Substituted aromatic heterocyclic group having 5 to 30 carbon atoms.

From Ar ₁ ～Ar ₈ The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented may be exemplified by: phenyl, naphthyl, anthracenyl, benzanthracenyl, phenanthrenyl, benzophenanthrenyl, pyrenyl, perylenyl, fluoranthenyl, benzofluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, biphenylyl, terphenyl, quaterphenyl, pentabiphenyl, terphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthrenyl, dihydropyrenyl, tetrahydropyrenyl, cis-or trans-indenofluorenyl, cis-or trans-monobenzindenofluorenyl, cis-or trans-dibenzoindenofluorenyl, dianilinyl, trianiliyl, triindenylyl, isotridenylyl, spirotrimeric indenyl, spiroisotridenylindenyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, benzothiophenyl, benzothiophenocarbazolyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, indolocarbazolyl indenocarbazolyl, pyridyl, bipyridyl, terpyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5,6-quinolyl, benzo-6,7-quinolyl, benzo-7,8-quinolyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthrimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinyl, oxazolyl, benzoxazolyl, benzooxadiazolyl, naphthooxazolyl, anthraoxazolyl, phenanthrooxazolyl, isoxazolyl, thiazolyl, isothiazolyl, benzothiazolyl, benzothiadiazolyl, pyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, quinazolinyl, azafluorenyl, diazahrenyl, diazapyrenyl, tetrazapyrenyl, naphthyridinyl, phenanthridinyl, benzimidazolyl, etc, <xnotran> , , , , , , , , , , , , , , , , , , , , , , , , , N- , </xnotran>Diphenyl-benzimidazolyl, diphenyl-oxadiazolyl, diphenyl boronyl, triphenyl phosphinyloxy, diphenyl phosphinyloxy, triphenyl silyl, tetraphenyl silyl and the like.

In the present invention, preferably, ar ₁ 、Ar ₂ 、Ar ₃ 、Ar ₄ 、Ar ₅ 、Ar ₆ 、Ar ₇ And Ar ₈ Each independently selected from a hydrogen atom, a cyano group or the following groups:

wherein the dotted line represents and L ₁ 、L ₂ 、L ₃ 、L ₄ Or a N-bonded bond, R ¹ Have the meaning as defined for the general formula (I).

From Ar ₁ ～Ar ₈ The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented may be unsubstituted, but may also have a substituent. Preferably, from Ar ₁ ～Ar ₈ The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented by ¹ Substituted, aromatic hydrocarbon radicals having 5 to 30 carbon atoms or substituted by one or more R ¹ A substituted aromatic heterocyclic group having 5 to 30 carbon atoms.

(R ¹ )

R ¹ Represents a hydrogen atom, a deuterium atom,Fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, NO ₂ 、 N(R ² )、OR ² 、SR ² 、C(＝O)R ² 、P(＝O)R ² 、Si(R ² ) ₃ A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 40 carbon atoms.

From R ¹ The alkyl group having 1 to 20 carbon atoms represented may be exemplified by: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, 2-methylhexyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, 3-methylheptyl, n-nonyl, n-decyl, hexadecyl, octadecyl, eicosyl, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl and the like. The alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic.

From R ¹ The alkyl group having 1 to 20 carbon atoms represented may be unsubstituted, but may also have a substituent. Preferably, from R ¹ Alkyl having 1 to 20 carbon atoms represented by one or more of the following R ² And (4) substitution. In addition, one or more non-adjacent CH in the alkyl group ₂ The group can be represented by R ² C＝CR ² 、 C≡C、Si(R ² ) ₃ 、C＝O、C＝NR ² 、P(＝O)R ² 、SO、SO ₂ 、NR ² O, S or CONR ² And wherein one or more hydrogen atoms may be replaced with deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, nitro group.

From R ¹ The alkenyl group having 2 to 20 carbon atoms represented may be exemplified by: vinyl, propenyl, butanesAlkenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, 2-ethylhexenyl, allyl, or cyclohexenyl, and the like. The alkenyl group having 2 to 20 carbon atoms may be linear, branched or cyclic.

From R ¹ The alkenyl group having 2 to 20 carbon atoms represented may be unsubstituted or may have a substituent. The substituents can be exemplified by the group consisting of R ¹ The alkyl group having 1 to 20 carbon atoms represented by (b) may have the same substituent as that represented by the substituent(s). The substituents may take the same pattern as that of the exemplary substituents.

From R ¹ The alkynyl group having 2 to 20 carbon atoms represented may be exemplified by: ethynyl, isopropynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl and the like.

From R ¹ The alkynyl group having 2 to 20 carbon atoms represented may be unsubstituted or may have a substituent. The substituents may be exemplified by R ¹ The alkyl group having 1 to 20 carbon atoms represented by (b) may have the same substituent as that represented by the substituent(s). The substituents may take the same pattern as that of the exemplary substituents.

From R ¹ The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms represented by the above formula may be exemplified by the group consisting of Ar ₁ ～Ar ₈ The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented by the above formula represent the same groups.

From R ¹ The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms represented may be unsubstituted, or may have a substituent. The substituents can be exemplified by the group consisting of R ¹ The alkyl group having 1 to 20 carbon atoms represented by (b) may have the same substituent as that represented by the substituent(s). The substituents may take the same pattern as that of the exemplary substituents. This is achieved byOuter, two adjacent R ¹ Substituents or two adjacent R ² The substituents may optionally form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system which may be interrupted by one or more R ² Substitution; where two or more substituents R ¹ May be connected to each other and may form a ring.

Preferably represented by R ¹ The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms represented by (a) may be exemplified by: phenyl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, benzothienocarbazolyl, benzofurocarbazolyl, benzofluorenocarbazolyl, benzanthracenyl, benzophenanthryl, fluorenyl, spirobifluorenyl, triazinyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, indenocarbazolyl, benzimidazolyl, diphenyl-oxadiazolyl, diphenyl boron, triphenyl phosphoxy, diphenyl phosphoxy, triphenyl silicon group, tetraphenyl silicon group, and the like. The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms may be substituted with one or more R ² And (4) substitution.

(R ² )

R ² Represents a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms.

From R ² The alkyl group having 1 to 20 carbon atoms represented by R can be enumerated by ¹ The alkyl groups represented by the formulae having 1 to 20 carbon atoms represent the same groups.

From R ² The aromatic hydrocarbon group having 6 to 30 carbon atoms or the substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms represented by the formula R ¹ The same groups as those shown for the aromatic hydrocarbon group having 6 to 30 carbon atoms or the substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms.

From R ² The alkyl group having 1 to 20 carbon atoms, the aromatic hydrocarbon group having 6 to 30 carbon atoms, or the substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms represented may be unsubstituted, or may also have a substituent. The substituents may be exemplified by: a deuterium atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; cyano, and the like.

< production method >

The acenaphthoazanaphthalene derivative of the present invention can be produced, for example, by the following method:

the obtained compound can be purified by, for example, purification by column chromatography, adsorption purification using silica gel, activated carbon, activated clay, or the like, recrystallization or crystallization using a solvent, sublimation purification, or the like. Identification of compounds can be carried out by mass spectrometry, elemental analysis.

< electronic device >

Various electronic devices containing the acenaphthoazaphthalenes derivatives of the present invention can be produced using the acenaphthoazaphthalenes derivatives according to the present invention for the production of organic materials that can be configured, in particular, in the form of layers. In particular, the acenaphthene aza-naphthalene derivative of the invention can be used in organic electroluminescent devices, organic solar cells, organic diodes, especially organic field effect transistors. Particularly in the case of an organic electroluminescent device or a solar cell, the assembly may have a plug structure (the device has one or more p-doped hole transport layers and/or one or more n-doped electron transport layers) or an inverted structure (from the light emitting layer, the upper electrode and the hole transport layer are located on the same side while the substrate is on the opposite side), without being limited to these structures. The injection layer, the transport layer, the light-emitting layer, the barrier layer, and the like can be fabricated, for example, by forming a layer containing or consisting of the acenaphthylanthrazene derivative according to the present invention between electrodes. However, the use of the acenaphthoazaphthalenes derivatives according to the present invention is not limited to the above exemplary embodiments.

< organic electroluminescent device >

The organic electroluminescent device of the present invention comprises: the organic electroluminescence device includes a first electrode, a second electrode provided so as to face the first electrode, and at least one organic layer interposed between the first electrode and the second electrode, wherein the at least one organic layer includes an acenaphthonazenaphthalene derivative of the present invention.

Fig. 3 is a view showing the configuration of an organic electroluminescent device of the present invention. As shown in fig. 3, in the organic electroluminescent device of the present invention, for example, an anode 2, a hole injection layer 3, a hole transport layer 4, an electron blocking layer 5, a light emitting layer 6, a hole blocking layer 7, an electron transport layer 8, an electron injection layer 9, and a cathode 10 are sequentially disposed on a substrate 1.

The organic electroluminescent device of the present invention is not limited to such a structure, and for example, some organic layers may be omitted in the multi-layer structure. For example, it may be a configuration in which the hole injection layer 3 between the anode 2 and the hole transport layer 4, the hole blocking layer 7 between the light emitting layer 6 and the electron transport layer 8, and the electron injection layer 9 between the electron transport layer 8 and the cathode 10 are omitted, and the anode 2, the hole transport layer 4, the light emitting layer 6, the electron transport layer 8, and the cathode 10 are sequentially provided on the substrate 1.

The organic electroluminescent device according to the present invention may be manufactured by materials and methods well known in the art, except that the organic layer includes the compound represented by the above general formula (I). In addition, in the case where the organic electroluminescent device includes a plurality of organic layers, the organic layers may be formed of the same substance or different substances.

For example, the organic electroluminescent device according to the present invention may be manufactured by sequentially laminating a first electrode, an organic layer, and a second electrode on a substrate. At this time, the following can be made: an anode is formed by depositing metal, a metal oxide having conductivity, or an alloy thereof on a substrate by a PVD (physical vapor deposition) method such as a sputtering method or an electron beam evaporation method, an organic layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed on the anode, and a substance which can be used as a cathode is deposited on the organic layer. However, the production method is not limited thereto.

In one example, the first electrode is an anode and the second electrode is a cathode, or the first electrode is a cathode and the second electrode is an anode.

The anode of the organic electroluminescent element of the present invention may be made of a known electrode material. For example, an electrode material having a large work function, such as a metal of vanadium, chromium, copper, zinc, gold, or an alloy thereof; metal oxides such as zinc oxide, indium Tin Oxide (ITO), indium Zinc Oxide (IZO), and the like; such as ZnO, al or SNO ₂ A combination of a metal such as Sb and an oxide; poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene]And conductive polymers such as PEDOT, polypyrrole, and polyaniline. Among these, ITO is preferable.

As the hole injection layer of the organic electroluminescent device of the present invention, a known material having a hole injection property can be used. Examples thereof include: porphyrin compounds represented by copper phthalocyanine, naphthalenediamine derivatives, star-shaped triphenylamine derivatives, triphenylamine trimers such as arylamine compounds having a structure in which 3 or more triphenylamine structures are connected by a single bond or a divalent group containing no heteroatom in the molecule, tetramers, receptor-type heterocyclic compounds such as hexacyanoazatriphenylene, and coating-type polymer materials. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.

As the hole transport layer of the organic electroluminescent device of the present invention, it is preferable to use a compound containing the acenaphthoazaphthalenes derivatives of the present invention. In addition, other known materials having a hole-transporting property can be used. Examples thereof include: a compound containing a m-carbazolylphenyl group; benzidine derivatives such as N, N '-diphenyl-N, N' -di (m-tolyl) benzidine (TPD), N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4,4' -diamine (NPB), N, N, N ', N' -tetrabiphenylylbenzidine, etc.; 1,1-bis [ (di-4-tolylamino) phenyl ] cyclohexane (TAPC); various triphenylamine trimers and tetramers; 9,9',9 "-triphenyl-9H, 9' H-3,3', 6', 3" -tricarbazole (Tris-PCz), and the like. These may be used as a single layer formed by separately forming a film or by mixing them with other materials to form a film, or may be used as a laminated structure of layers formed by separately forming a film, a laminated structure of layers formed by mixing films, or a laminated structure of layers formed by separately forming a film and layers formed by mixing films. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.

In addition, in the hole injection layer or the hole transport layer, a material obtained by P-doping tribromoaniline antimony hexachloride, an axial olefin derivative, or the like with a material generally used for the layer, a polymer compound having a structure of a benzidine derivative such as TPD in a partial structure thereof, or the like can be used.

As the electron blocking layer of the organic electroluminescent device of the present invention, it is preferable to use a compound containing the acenaphthoazaphthalenes derivative of the present invention. In addition, other known compounds having an electron blocking effect may be used. Examples thereof include: carbazole derivatives such as 4,4',4 ″ -tris (N-carbazolyl) triphenylamine (TCTA), 9,9-bis [4- (carbazol-9-yl) phenyl ] fluorene, 1,3-bis (carbazol-9-yl) benzene (mCP), 2,2-bis (4-carbazol-9-ylphenyl) adamantane (Ad-Cz); a compound having a triphenylsilyl and triarylamine structure represented by 9- [4- (carbazol-9-yl) phenyl ] -9- [4- (triphenylsilyl) phenyl ] -9H-fluorene; and compounds having an electron-blocking effect, such as monoamine compounds having a high electron-blocking property and various triphenylamine dimers. These may be used alone or in a form of a single layer mixed with other materials to form a film, or may be used in a laminated structure of layers formed alone, a laminated structure of layers mixed to form a film, or a laminated structure of layers formed alone and layers mixed to form a film. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.

As the light-emitting layer of the organic electroluminescent device of the present invention, it is preferable to use a compound containing the acenaphthoazaphthalene derivative of the present invention. In addition to this, alq can also be used ₃ Various metal complexes such as metal complexes of a hydroxyquinoline derivative, compounds having a pyrimidine ring structure, anthracene derivatives, bisstyrylbenzene derivatives, pyrene derivatives, oxazole derivatives, polyparaphenylene vinylene derivatives, and the like.

The light emitting layer may be composed of a host material and a dopant material. As the host material, it is preferable to use a compound containing the acenaphthoazaphthalene derivative of the present invention. In addition to these, mCBP, mCP, thiazole derivatives, benzimidazole derivatives, polydialkylfluorene derivatives, heterocyclic compounds having a partial structure in which an indole ring is a condensed ring, and the like can be used.

As the doping material, it is preferable to use a material containing the azanaphthalene derivative of the present invention. In addition to these, aromatic amine derivatives, styryl amine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like can also be used. Examples thereof include pyrene derivatives, anthracene derivatives, quinacridones, coumarins, rubrenes, perylenes and their derivatives, benzopyran derivatives, rhodamine derivatives, aminostyryl derivatives, spirobifluorene derivatives, and the like. These may be used as a single layer formed by film formation alone or by mixing with other materials to form a film, or may be used as a laminated structure of layers formed by film formation alone, a laminated structure of layers formed by mixing into a film, or a laminated structure of layers formed by film formation alone and layers formed by mixing into a film. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.

As the hole blocking layer of the organic electroluminescent device of the present invention, it is preferable to use a compound containing the acenaphthoazaphthalenes derivative of the present invention. In addition, the hole-blocking layer may be formed using another compound having a hole-blocking property. For example, 2,4,6-tris (3-phenyl) -1,3,5-triazine (T2T), 1,3,5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi), phenanthroline derivatives such as Bathocuproine (BCP), metal complexes of quininol derivatives such as aluminum (III) bis (2-methyl-8-hydroxyquinoline) -4-phenylphenate (BAlq), and compounds having a hole-blocking effect such as various rare earth complexes, oxazole derivatives, triazole derivatives, and triazine derivatives can be used. These may be used as a single layer formed by separately forming a film or by mixing them with other materials to form a film, or may be used as a laminated structure of layers formed by separately forming a film, a laminated structure of layers formed by mixing films, or a laminated structure of layers formed by separately forming a film and layers formed by mixing films. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.

The above-described material having a hole-blocking property can also be used for formation of an electron transport layer described below. That is, by using the known material having a hole-blocking property, a layer functioning as both a hole-blocking layer and an electron-transporting layer can be formed.

As the electron transport layer of the organic electroluminescent device of the present invention, it is preferable to use a compound containing the acenaphtho-aza-naphthalene derivative of the present invention. In addition, the compound may be formed using other compounds having an electron-transporting property. For example, alq can be used ₃ Metal complexes of quinolinol derivatives including BAlq; various metal complexes; a triazole derivative; a triazine derivative; an oxadiazole derivative; a pyridine derivative; bis (10-hydroxybenzo [ H ]]Quinoline) beryllium (Be (bq) ₂ ) (ii) a Such as 2- [4- (9,10-dinaphthalen-2-anthracen-2-yl) phenyl]Benzimidazole derivatives such as-1-phenyl-1H-benzimidazole (ZADN); a thiadiazole derivative; an anthracene derivative; a carbodiimide derivative; quinoxaline derivatives; pyridoindole derivatives; phenanthroline derivatives; silole derivatives and the like. These may be used as a single layer formed by separately forming a film or by mixing them with other materials to form a film, or may be used as a laminated structure of layers formed by separately forming a film, a laminated structure of layers formed by mixing films, or a laminated structure of layers formed by separately forming a film and layers formed by mixing films. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.

As the electron injection layer of the organic electroluminescent device of the present invention, a material known per se can be used. For example, alkali metal salts such as lithium fluoride and cesium fluoride; alkaline earth metal salts such as magnesium fluoride; metal complexes of hydroxyquinoline derivatives such as lithium hydroxyquinoline; and metal oxides such as alumina.

In the electron injection layer or the electron transport layer, a material obtained by further N-doping a metal such as cesium, a triarylphosphine oxide derivative, or the like can be used as a material generally used for the layer.

As the cathode of the organic electroluminescent device of the present invention, an electrode material having a low work function such as aluminum, magnesium, or an alloy having a low work function such as magnesium-silver alloy, magnesium-indium alloy, aluminum-magnesium alloy is preferably used as the electrode material.

As the substrate of the present invention, a substrate in a conventional organic light emitting device, such as glass or plastic, can be used. In the present invention, a glass substrate is selected.

Examples

The production of the compound represented by the above general formula (I) and the organic electroluminescent device comprising the same is specifically described in the following examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

Example 1: synthesis of Compounds 1-28

(Synthesis of intermediate M1)

The synthetic route for intermediate M1 is shown below:

7.0g (30 mmol) 5,6-dicyanoacenaphthene-1,2-dione, 5.7g (30 mmol) 5-bromo-2,3-diaminopyrazine and 100mL glacial acetic acid were added sequentially in a clean 250mL single-neck flask, gradually warmed to reflux and reacted overnight under reflux. After the reaction is finished, stopping heating, and automatically cooling the system. The reaction solution was poured into 1L of ice water, collected by suction filtration, compressed and dried, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane =2:3 (V/V)) to give 9.4g of a yellow solid with a yield of 82%. MS (EI): m/z:383.92[ m ] ⁺ ]。Anal.calcd for C ₁₈ H ₅ BrN ₆ (％)：C 56.13，H 1.31； found：C 56.01，H 1.26。

(Synthesis of Compounds 1 to 28)

The synthetic routes for compounds 1-28 are shown below:

a250 mL two-necked flask was charged with 8.8g (23.0 mmol) of M1, and 9.6g (29.0 mmol) of 5,7-dihydro-5-phenylindolo [2,3-B]Carbazole, 3.0g (29.0 mmol) of sodium tert-butoxide, 0.1g (0.3 mmol) of tri-tert-butylphosphine tetrafluoroborate and 0.27g (0.3 mmol) of tris (dibenzylideneacetone) dipalladium, the reaction system was degassed, 150mL of toluene was added under the protection of nitrogen, and the mixture was stirred and heated to reflux for 12 hours. After the reaction is completed, cooling the system to room temperature, carrying out vacuum filtration, washing filter residue with a large amount of dichloromethane, concentrating the filtrate to obtain a crude product, and adding petroleum ether: dichloromethane =3:2 (volume ratio) on silica gel column to obtain 13.4g red solid with 92% yield. MS (EI) m/z 636.23[ M ] ⁺ ]。Anal.calcd for C ₄₂ H ₂₀ N ₈ (％)：C 79.23，H 3.17；found： C 79.09，H 3.11。

Example 2: synthesis of Compounds 1-46

(Synthesis of Compounds 1 to 46)

The synthetic routes for compounds 1-46 are shown below:

to a clean 250mL three-necked flask were added 13.8g (47.8 mmol) of N-phenyl-3-carbazolboronic acid, 8.4g (79.6 mmol) of anhydrous sodium carbonate, 15.3g (39.8 mmol) of M1, 470.8mg (4.8 mmol) of tetrakis (triphenylphosphine palladium), and 100mL of a mixed solvent (toluene: water: ethanol = 5. The system was gradually warmed to reflux and reacted overnight under reflux. After the reaction is finished, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200mL of water and extracted with dichloromethane. The organic phase is dried over anhydrous sodium sulfate, concentrated under reduced pressure, andfurther purification by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane =3:2 (V/V)) gave 18.3g of a red solid in 84% yield. MS (EI): m/z:547.83[ M ] ⁺ ]。Anal.calcd for C ₃₆ H ₁₇ N ₇ (％)：C 78.96，H 3.13；found：C 78.81，H 3.09。

Example 3: synthesis of Compounds 1-54

(Synthesis of intermediate M2)

The synthetic route for intermediate M2 is shown below:

7.0g (30 mmol) 5,6-dicyanoaphthene-1,2-dione, 5.3g (30 mmol) 4.5-dichloro-2.3-diaminopyrazine and 100mL glacial acetic acid are added in sequence to a clean 250mL single-neck flask, gradually heated to reflux and reacted under reflux overnight. After the reaction is finished, stopping heating, and automatically cooling the system. The reaction solution was poured into 1L of ice water, collected by suction filtration, compressed and dried, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane =2:3 (V/V)) to obtain 9.2g of a yellow solid with a yield of 82%. MS (EI): m/z:374.32[ 2] M ⁺ ]。Anal.calcd for C ₁₈ H ₄ Cl ₂ N ₆ (％)：C 57.63，H 1.07；found：C 57.51，H 1.05。

(Synthesis of Compound M3)

The synthetic route for compound M3 is shown below:

to a clean 250mL three-necked flask, 5.8g (47.8 mmol) of phenylboronic acid, 8.4g (79.6 mmol) of anhydrous sodium carbonate, 14.9g (39.8 mmol) of M2, 470.8mg (4.8 mmol) of tetrakis (triphenylphosphine palladium), and 100mL of a mixed solvent (toluene: water: ethanol =5:1:1 (V/V)) were sequentially added under nitrogen. The system was gradually warmed to reflux and reacted under reflux overnight. After the reaction is finished, stopping heating, and allowing the reaction system to reactThen cooled to room temperature. The reaction solution was poured into about 200mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane =3:2 (V/V)) to give 14.0 g as a yellow solid in 84% yield. MS (EI): m/z:416.83[ M ] ⁺ ]。Anal.calcd for C ₂₄ H ₉ ClN ₆ (％)：C 69.16，H 2.18；found：C 69.01，H 2.11。

(Synthesis of Compounds 1 to 54)

The synthetic routes for compounds 1-54 are shown below:

into a 250mL two-necked flask were charged 9.6g (23.0 mmol) of M3, 9.6g (29.0 mmol) of 5,7-dihydro-5-phenylindolo [2,3-B]Carbazole, 3.0g (29.0 mmol) of sodium tert-butoxide, 0.1g (0.3 mmol) of tri-tert-butylphosphine tetrafluoroborate and 0.27g (0.3 mmol) of tris (dibenzylideneacetone) dipalladium, 150mL of toluene is added under the protection of nitrogen after the reaction system is degassed, and the mixture is stirred and heated until the reflux reaction is carried out for 12 hours. After the reaction is completed, cooling the system to room temperature, carrying out suction filtration under reduced pressure, washing filter residues by using a large amount of dichloromethane, concentrating the filtrate to obtain a crude product, and reacting the crude product with petroleum ether: dichloromethane =3:2 (volume ratio) of eluent was separated and purified on a silica gel column to obtain 15.0g of red solid with a yield of 92%. MS (EI) m/z 712.23[ M ] ⁺ ]。Anal.calcd for C ₄₈ H ₂₄ N ₈ (％)：C 80.88，H 3.39；found： C 80.69，H 3.35。

Example 4: synthesis of Compounds 1-64

(Synthesis of Compounds 1-64)

The synthetic routes for compounds 1-64 are shown below:

under nitrogen, the mixture was added to a clean 250mL three-necked flask13.7g (47.8 mmol) of N-phenyl-3-carbazolboronic acid, 8.4g (79.6 mmol) of anhydrous sodium carbonate, 16.6g (39.8 mmol) of M3, 470.8mg (4.8 mmol) of tetrakis (triphenylphosphine palladium) and 100mL of a mixed solvent (toluene: water: ethanol = 5. The system was gradually warmed to reflux and reacted under reflux overnight. After the reaction is finished, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane =3:2 (V/V)) to give 20.9g of a red solid in 84% yield. MS (EI): m/z:623.83[ 2] M ⁺ ]。Anal.calcd for C ₄₂ H ₂₁ N ₇ (％)：C 80.88，H 3.39；found：C 80.70，H 3.31。

Example 5: synthesis of Compounds 1-58

(Synthesis of Compound M4)

The synthetic route for compound M4 is shown below:

7.0g (30 mmol) 5,6-dicyanoaphthene-1,2-dione, 5.3g (30 mmol) 5,6-dichloropyridine-2,3-diamine and 100mL glacial acetic acid were added sequentially in a clean 250mL single-necked flask, gradually warmed to reflux and reacted overnight under reflux. After the reaction is finished, stopping heating, and automatically cooling the system. The reaction solution was poured into 1L of ice water, collected by suction filtration, compressed and dried, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane =2:3 (V/V)) to give 9.2g as a yellow solid with a yield of 82%. MS (EI): m/z:373.32[ 2] M ⁺ ]。Anal.calcd for C ₁₉ H ₅ Cl ₂ N ₃ (％)： C 60.99，H 1.35；found：C 60.81，H 1.32。

(Synthesis of Compound M5)

The synthetic route for compound M5 is shown below:

to a clean 250mL three-necked flask, 5.8g (47.8 mmol) of phenylboronic acid, 8.4g (79.6 mmol) of anhydrous sodium carbonate, 14.9g (39.8 mmol) of M4, 470.8mg (4.8 mmol) of tetrakis (triphenylphosphine palladium), and 100mL of a mixed solvent (toluene: water: ethanol =5:1:1 (V/V)) were sequentially added under nitrogen. The system was gradually warmed to reflux and reacted under reflux overnight. After the reaction is finished, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane =3:2 (V/V)) to give 13.9 g as a yellow solid in 84% yield. MS (EI): m/z:415.83[ M ] ⁺ ]。Anal.calcd for C ₂₅ H ₁₀ ClN ₅ (％)： C 72.21，H 2.42；found：C 70.01，H 2.39。

(Synthesis of Compounds 1 to 58)

The synthetic routes for compounds 1-58 are shown below:

9.5g (23.0 mmol) of M5, 9.6g (29.0 mmol) of 5,7-dihydro-5-phenylindolo [2,3-B ] were added in this order to a 250mL two-necked flask]Carbazole, 3.0g (29.0 mmol) of sodium tert-butoxide, 0.1g (0.3 mmol) of tri-tert-butylphosphine tetrafluoroborate and 0.27g (0.3 mmol) of tris (dibenzylideneacetone) dipalladium, 150mL of toluene is added under the protection of nitrogen after the reaction system is degassed, and the mixture is stirred and heated until the reflux reaction is carried out for 12 hours. After the reaction is completed, cooling the system to room temperature, carrying out suction filtration under reduced pressure, washing filter residues by using a large amount of dichloromethane, concentrating the filtrate to obtain a crude product, and reacting the crude product with petroleum ether: dichloromethane =3:2 (volume ratio) on silica gel column to obtain 15.0g yellow solid with 92% yield. MS (EI) m/z 711.43[ M ] ⁺ ]。Anal.calcd for C ₄₉ H ₂₅ N ₇ (％)：C 82.68，H 3.54；found： C 82.59，H 3.52。

Example 6: synthesis of Compounds 1-72

(Synthesis of Compound M6)

The synthetic route for compound M6 is shown below:

7.0g (30 mmol) 5,6-dicyanoaphthene-1,2-dione, 5.3g (30 mmol) 2,6-dichloro-4,5-pyrimidinediamine and 100mL glacial acetic acid were added sequentially in a clean 250mL single-necked flask, gradually warmed to reflux and reacted overnight under reflux. After the reaction is finished, stopping heating, and automatically cooling the system. The reaction solution was poured into 1L of ice water, collected by suction filtration, compressed and dried, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane =2:3 (V/V)) to obtain 9.2g of a yellow solid with a yield of 82%. MS (EI): m/z:373.92[ 2] M ⁺ ]。Anal.calcd for C ₁₈ H ₄ Cl ₂ N ₆ (％)：C 57.63，H 1.07； found：C 57.51，H 1.05。

(Synthesis of Compound M7)

The synthetic route for compound M7 is shown below:

to a clean 250mL three-necked flask were added 5.8g (47.8 mmol) of phenylboronic acid, 8.4g (79.6 mmol) of anhydrous sodium carbonate, 14.9g (39.8 mmol) of M4, 470.8mg (4.8 mmol) of tetrakis (triphenylphosphine palladium), and 100mL of a mixed solvent (toluene: water: ethanol =5:1:1 (V/V)) in this order under nitrogen. The system was gradually warmed to reflux and reacted under reflux overnight. After the reaction is finished, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane =3:2 (V/V)) to give 14.0 g as a yellow solid in 84% yield. MS (EI): m/z:416.83[ M ] ⁺ ]。Anal.calcd for C ₂₄ H ₉ ClN ₆ (％)：C 69.16，H 2.18；found：C 69.01，H 2.12。

(Synthesis of Compounds 1-72)

The synthetic routes for compounds 1-72 are shown below:

into a 250mL two-necked flask were charged 9.6g (23.0 mmol) of M7, 9.6g (29.0 mmol) of 5,7-dihydro-5-phenylindolo [2,3-B]Carbazole, 3.0g (29.0 mmol) of sodium tert-butoxide, 0.1g (0.3 mmol) of tri-tert-butylphosphine tetrafluoroborate and 0.27g (0.3 mmol) of tris (dibenzylideneacetone) dipalladium, the reaction system was degassed, 150mL of toluene was added under the protection of nitrogen, and the mixture was stirred and heated to reflux for 12 hours. After the reaction is completed, cooling the system to room temperature, carrying out vacuum filtration, washing filter residue with a large amount of dichloromethane, concentrating the filtrate to obtain a crude product, and adding petroleum ether: dichloromethane =3:2 (volume ratio) of eluent was separated and purified on a silica gel column to obtain 15.0g of red solid with a yield of 92%. MS (EI) m/z 712.43[ M ] ⁺ ]。Anal.calcd for C ₄₈ H ₂₄ N ₈ (％)：C 80.88， H 3.39；found：C 80.75，H 3.35。

Preparation of organic electroluminescent device (organic EL device)

Specifically, the ITO transparent conductive layer coated glass plate was sonicated in a commercial detergent, rinsed in deionized water, washed three times each in acetone and ethanol, baked in a clean environment to completely remove moisture, washed with ultraviolet light and ozone, and bombarded on the surface with low energy cationic beams. Placing ITO conductive glass into a vacuum chamber, and vacuumizing to less than 5 × 10 ^-4 Pa. Using ITO conductive glass as an anode, and sequentially evaporating a Hole Injection Layer (HIL), a hole transport layer (HIL), an Electron Blocking Layer (EBL), an organic light emitting layer (EML), an Electron Transport Layer (ETL) and a cathode on the ITO conductive glass; wherein, the evaporation rate of the organic material is 0.2nm/s, and the evaporation rate of the metal electrode is 0.5nm/s.

The electroluminescence spectra were collected using a photon multichannel analyzer PMA-12 (Hamamatsu C10027-01), which can be detected in the spectral region of 200-950 nm. The external quantum efficiency of the device was obtained by measuring the forward light intensity using an integrating sphere (Hamamatsu a 10094). All measurements were performed at room temperature in an atmospheric environment.

The method for forming each structural layer in the organic electroluminescent device of the present invention is not particularly limited, and conventional vacuum evaporation methods, spin coating methods, and the like may be used.

Examples 7 to 12

The following description will be made for the OLEDs 1-6 with reference to examples 7 to 12, wherein the materials used for the OLEDs 1-6 are compounds 1-28,1-46,1-54,1-64,1-58 and 1-72 shown in the present invention, and the film thickness of each OLED device structure and each layer is as follows:

OLED-l：

ITO/HAT-CN(5nm)/NPB(60nm)/TCTA(5nm)/10wt％1-28:TPBi(20nm)/TPBi(50 nm)/Liq(2nm)/Al(100nm)

OLED-2：

ITO/HAT-CN(5nm)/NPB(60nm)/TCTA(5nm)/20wt％1-46:TPBi(20nm)/TPBi(50 nm)/Liq(2nm)/Al(100nm)

OLED-3：

ITO/HAT-CN(5nm)/NPB(60nm)/TCTA(5nm)/15wt％1-54:TPBi(20nm)/TPBi(50 nm)/Liq(2nm)/Al(100nm)

OLED-4：

ITO/HAT-CN(5nm)/NPB(60nm)/TCTA(5nm)/12wt％1-64:TPBi(20nm)/TPBi(50 nm)/Liq(2nm)/Al(100nm)

OLED-5：

ITO/HAT-CN(5nm)/NPB(60nm)/TCTA(5nm)/15wt％1-58:TPBi(20nm)/TPBi(50 nm)/Liq(2nm)/Al(100nm)

OLED-6：

ITO/HAT-CN(5nm)/NPB(60nm)/TCTA(5nm)/20wt％1-72:TPBi(20nm)/TPBi(50 nm)/Liq(2nm)/Al(100nm)

the examples relate to compounds having the following structure:

TABLE 1

Device numbering	Luminescent layer	Maximum external quantum efficiency (%)	Organic electroluminescence spectrum peak (nm)
				OLED1	10wt％1-28:TPBi	8.05	860
OLED2	20wt％1-46:TPBi	9.75	780
				OLED3	15wt％1-54:TPBi	6.97	865
OLED4	12wt％1-64:TPBi	11.21	785
				OLED5	15wt％1-58:TPBi	8.54	840
OLED6	20wt％1-72:TPBi	6.22	865

The light emission characteristics of the organic EL devices OLED1 to 6 produced in examples 1 to 6 were measured when a direct current voltage was applied in the atmosphere at normal temperature. The measurement results are shown in table 1.

As can be seen from table 1, the acenaphtho-aza-naphthalene derivative of the present invention, through modification and introduction of other different chemical groups, especially by disposing an electron-withdrawing group such as cyano on acenaphtho, still obtains excellent external quantum efficiency in deep red and infrared regions of the spectrum, and has excellent luminescent properties, stable structure and high color purity, and at the same time, the preparation cost is low. In addition, the deep red/near infrared organic electroluminescent device prepared by the acenaphthene aza-naphthalene derivative has higher luminous efficiency and excellent performance.

Industrial applicability

The organic electroluminescent compounds according to the present invention have excellent luminous efficiency and excellent color purity of materials. Therefore, the compound can be used for preparing a deep red/infrared organic electroluminescent device or an infrared generating device with excellent performance.

The above description is only an embodiment of the present application, and does not limit the scope of the present application, and all equivalent molecular structures or equivalent transformations that are made by the contents of the specification and the drawings of the present application, or that are directly or indirectly applied to other related technical fields, are included in the scope of the present application.

Claims (4)

1. An acenaphthoazanaphthalene derivative selected from the group consisting of:

2. an infrared electronic device, characterized in that it comprises an acenaphthoazaphthalene derivative according to claim 1.

3. The electronic device according to claim 2, wherein the electronic device is an organic electroluminescent device, an organic field effect transistor, or an organic solar cell;

wherein the organic electroluminescent device comprises: a first electrode, a second electrode provided so as to face the first electrode, and at least one organic layer interposed between the first electrode and the second electrode, wherein the at least one organic layer contains the acenaphthoazaphthalene derivative according to claim 1.

4. An infrared device comprising the acenaphthoazanaphthalene derivative of claim 1, and emitting light having a peak value of not less than 780nm and an external quantum efficiency of more than 6%.

Images