CN107827853B - Blue light-emitting compound, organic electroluminescent device and application thereof - Google Patents

Blue light-emitting compound, organic electroluminescent device and application thereof Download PDF

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CN107827853B
CN107827853B CN201711141664.XA CN201711141664A CN107827853B CN 107827853 B CN107827853 B CN 107827853B CN 201711141664 A CN201711141664 A CN 201711141664A CN 107827853 B CN107827853 B CN 107827853B
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phenanthryl
phenanthroline
anthryl
naphthyl
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不公告发明人
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Nanjing Topto Materials Co Ltd
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Abstract

The invention relates to the field of luminescent materials, and particularly provides a blue luminescent compound, an organic electroluminescent device and application thereof. The structural formula of the blue luminescent compound is shown as follows:
Figure DDA0001469821520000011
wherein R is1Is any one of hydrogen, phenyl, pyridyl, naphthyl, phenanthryl, anthryl, phenanthridinyl, biphenyl, pyrimidyl or triazinyl; r2Is any one of hydrogen, C1-C20 straight chain or branched chain alkyl, phenyl, pyridyl, naphthyl, phenanthryl, anthryl, phenanthridinyl, biphenyl, pyrimidyl or triazinyl; r3Is any one of hydrogen, phenyl, pyridyl, naphthyl, phenanthryl, anthryl, phenanthridinyl, biphenyl, pyrimidyl or triazinyl; r4Is any one of hydrogen, C1-C20 straight chain or branched chain alkyl, phenyl, pyridyl, naphthyl, phenanthryl, anthryl, phenanthridinyl, biphenyl, pyrimidyl or triazinyl. The compound is used in a light-emitting device, and can improve the luminous efficiency and the service life of the device.

Description

Blue light-emitting compound, organic electroluminescent device and application thereof
Technical Field
The invention relates to the field of luminescent materials, in particular to a blue luminescent compound, an organic electroluminescent device and application thereof.
Background
Organic Light-emitting Devices (Organic Light-emitting Devices) are spontaneous Light-emitting Devices that utilize the following principle: when an electric field is applied, the fluorescent substance emits light by recombination of holes injected from the positive electrode and electrons injected from the negative electrode.
Since the low voltage driven layer type organic electroluminescent device was reported by C.W.Tang of Eastman Kodak Company (Applied Physics Letters, Volume51, page 913, 1987), many studies have been made on organic electroluminescent devices using organic substances as constituent materials. Tang et al used tris (8-hydroxyquinoline) aluminum as the light-emitting layer and triphenyldiamine derivatives as the hole-transporting layer. The layered structure has advantages in that the efficiency of hole injection into the light emitting layer can be improved, the efficiency of excited particles formed by blocking and recombining electrons injected from the negative electrode can be improved, and the excited particles formed in the light emitting layer can be enclosed. As the structure of the organic electroluminescent device, a two-layer structure having a hole transporting (injecting) layer and an electron transporting and light emitting layer, and a three-layer structure having a hole transporting (injecting) layer, a light emitting layer, and an electron transporting (injecting) layer are known. In order to improve the recombination efficiency of injected holes and electrons in a layered device, research into the structure of the device and methods of forming the device have been conducted.
Chelates, such as tris (8-hydroxyquinoline) aluminum, coumarin derivatives, tetraphenylbutadiene derivatives, bisstyrylarylene derivatives and oxadiazole derivatives are known as light-emitting materials. It is reported that these light emitting materials can emit blue to red light in the visible region, and thus it is desired to obtain a color display device by using these light emitting materials. However, organic electroluminescent devices that can emit blue light with high color purity and high luminous efficiency have been the subject of pursuit in this field. This also provides the chemist with great opportunity and challenge to develop functionalized materials of various structures.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the present invention is to provide a blue light-emitting compound, which can be used as a blue fluorescent host material in an organic electroluminescent device to reduce the driving voltage and improve the luminous efficiency, brightness, thermal stability, color purity and device lifetime.
The second object of the present invention is to provide an application of the blue light-emitting compound in the preparation of a light-emitting device, wherein the application of the blue light-emitting compound in the light-emitting device can improve the light-emitting efficiency and the device lifetime of the light-emitting device.
A third object of the present invention is to provide an organic electroluminescent device employing the above blue light-emitting compound as a host substance, which has excellent properties of high efficiency and long life.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
in a first aspect, the present invention provides a blue light-emitting compound having the formula:
Figure BDA0001469821510000021
wherein R is1Is any one of hydrogen, phenyl, pyridyl, naphthyl, phenanthryl, anthryl, phenanthridinyl, biphenyl, pyrimidyl or triazinyl,
R2is any one of hydrogen, C1-C20 straight chain or branched chain alkyl, phenyl, pyridyl, naphthyl, phenanthryl, anthryl, phenanthridinyl, biphenyl, pyrimidyl or triazinyl;
R3is any one of hydrogen, phenyl, pyridyl, naphthyl, phenanthryl, anthryl, phenanthridinyl, biphenyl, pyrimidyl or triazinyl;
R4is any one of hydrogen, C1-C20 straight chain or branched chain alkyl, phenyl, pyridyl, naphthyl, phenanthryl, anthryl, phenanthridinyl, biphenyl, pyrimidyl or triazinyl.
As a further preferred embodiment, R1At least one hydrogen atom in the phenyl, pyridyl, naphthyl, phenanthryl, anthryl, phenanthryl, biphenyl, pyrimidyl or triazinyl group of (A) may be independently substituted by a linear or branched alkyl group of C1-C20, a cycloalkyl group of C3-C20, an alkoxy group of C1-C20, a halogen, a cyano group, a trifluoromethyl group, Si (CH)3)3Or aryl of C6-C50.
As a further preferred embodiment, R2At least one hydrogen atom in the C1-C20 linear or branched alkyl group, phenyl group, pyridyl group, naphthyl group, phenanthryl group, anthryl group, phenanthryl group, biphenyl group, pyrimidyl group or triazinyl group can be independently replaced by a C1-C20 linear or branched alkyl group, a C3-C24 cycloalkyl group, a C1-C20 alkoxy group, a halogen group, a cyano group, a trifluoromethyl group, a trimethyl groupSilyl, naphthyl, anthryl, phenanthryl, dibenzofuranyl, fluorenyl, carbazolyl, spirofluorenyl or heteroaryl with 5-20 atoms.
As a further preferred embodiment, R3At least one hydrogen atom in the phenyl, pyridyl, naphthyl, phenanthryl, anthryl, phenanthryl, biphenyl, pyrimidyl or triazinyl group of (a) may be independently substituted by a linear or branched alkyl group of C1-C20, a cycloalkyl group of C3-C12, an alkoxy group of C1-C10, a halogen, a cyano group, a trifluoromethyl group, a trimethylsilyl group or an aryl group of C6-C30.
As a further preferred embodiment, R4At least one hydrogen atom in the C1-C20 linear or branched alkyl group, phenyl group, pyridyl group, naphthyl group, phenanthryl group, anthryl group, phenanthridinyl group, biphenyl group, pyrimidyl group or triazinyl group may be independently substituted by a C1-C10 linear or branched alkyl group, a C3-C12 cycloalkyl group, a C1-C10 alkoxy group, a halogen group, a cyano group, a trifluoromethyl group, a trimethylsilyl group, naphthyl group, an anthryl group, a phenanthryl group, a dibenzofuranyl group, a fluorenyl group, a carbazolyl group, a spirofluorenyl group or a heteroaryl group having 5-20 atoms.
In a further preferred embodiment, the linear or branched alkyl group of C1 to C20 is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, or n-octyl.
As a further preferred embodiment, the compound is any one of the following compounds:
Figure BDA0001469821510000022
Figure BDA0001469821510000031
Figure BDA0001469821510000041
Figure BDA0001469821510000051
Figure BDA0001469821510000061
Figure BDA0001469821510000071
Figure BDA0001469821510000081
Figure BDA0001469821510000091
Figure BDA0001469821510000101
Figure BDA0001469821510000111
Figure BDA0001469821510000121
in a second aspect, the present invention provides the use of a blue light-emitting compound in the manufacture of a light-emitting device.
In a third aspect, the present invention provides an organic electroluminescent device comprising an anode, a light-emitting layer and a cathode, wherein the light-emitting layer comprises the blue light-emitting compound.
As a further preferable technical solution, a hole injection layer and a hole transport layer are further provided between the anode and the light emitting layer, and an electron transport layer and an electron injection layer are further provided between the light emitting layer and the cathode.
Compared with the prior art, the invention has the beneficial effects that:
the blue luminescent compound provided by the invention can be used as a blue fluorescent main body material, and can be used in an organic electroluminescent device to reduce the driving voltage, improve the luminous efficiency, the brightness, the thermal stability, the color purity and the service life of the device.
The blue luminescent compound provided by the invention is applied to the preparation of luminescent devices, and can improve the luminescent efficiency and the service life of the luminescent devices.
The organic electroluminescent device provided by the invention adopts the blue luminescent compound as a host substance, so that the organic electroluminescent device has excellent performances of high efficiency and long service life.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer.
In a preferred embodiment of the blue light-emitting compound provided by the present invention, R1At least one hydrogen atom in the phenyl, pyridyl, naphthyl, phenanthryl, anthryl, phenanthryl, biphenyl, pyrimidyl or triazinyl group of (a) may be independently substituted by a linear or branched alkyl group of C1-C20, a cycloalkyl group of C3-C20, an alkoxy group of C1-C20, a halogen, a cyano group, a trifluoromethyl group, a trimethylsilyl group or an aryl group of C6-C50;
wherein, the cycloalkyl of C3-C20 is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
the alkoxy structure of C1-C20 is as follows: -OR wherein R represents a group which is alkyl, which is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl OR n-eicosyl;
the aryl group having C6 to C50 is phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-tetracenyl, 2-tetracenyl, 9-tetracenyl, 1-pyrenyl, 2-pyrenyl, 4-pyrenyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p-tert-butylphenyl, p- (2-phenylpropyl) phenyl, 3-methyl-2-naphthyl, 4-methyl-1-anthryl, 4 '-methylbiphenyl or 4' -tert-butyl-p-terphenyl-4-yl.
In a preferred embodiment, R2At least one hydrogen atom in the C1-C20 linear or branched alkyl group, phenyl group, pyridyl group, naphthyl group, phenanthryl group, anthryl group, phenanthridinyl group, biphenyl group, pyrimidyl group or triazinyl group can be independently substituted by a C1-C20 linear or branched alkyl group, a C3-C24 cycloalkyl group, a C1-C20 alkoxy group, a halogen group, a cyano group, a trifluoromethyl group, a trimethylsilyl group, naphthyl group, an anthryl group, a phenanthryl group, a dibenzofuranyl group, a fluorenyl group, a carbazolyl group, a spirofluorenyl group or a heteroaryl group with 5-20 atoms;
wherein, the cycloalkyl of C3-C24 is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
the alkoxy structure of C1-C20 is as follows: -OR wherein R represents an alkyl group which is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl OR eicosyl;
the heteroaryl group having 5 to 20 atoms is a 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, pyridyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 1-indolyl group, 2-indolyl group, 3-indolyl group, 4-indolyl group, 5-indolyl group, 6-indolyl group, 7-indolyl group, 1-isoindolyl group, 2-isoindolyl group, 3-isoindolyl group, 4-isoindolyl group, 5-isoindolyl group, 6-isoindolyl group, 7-isoindolyl group, 2-furyl group, 3-furyl group, 2-benzofuryl group, 3-benzofuryl group, 4-benzofuryl group, 5-benzofuryl group, 6-benzofuryl group, 7-benzofuryl group, 1-isobenzofuranyl, 3-isobenzofuranyl, 4-isobenzofuranyl, 5-isobenzofuranyl, 6-isobenzofuranyl, 7-isobenzofuranyl, 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl, 2-quinoxalyl, 5-quinoxalyl, 6-quinoxalyl, 1-pridinyl, 2-pridinyl, 3-pridinyl, 4-pridinyl, 6-pridinyl, 7-pridinyl, 8-phenanthroline-based, 9-phenanthroline-based, 10-phenanthroline-based, 1, 7-phenanthroline-2-based, 1, 7-phenanthroline-3-based, 1, 7-phenanthroline-4-based, 1, 7-phenanthroline-5-based, 1, 7-phenanthroline-6-based, 1, 7-phenanthroline-8-based, 1, 7-phenanthroline-9-based, 1, 7-phenanthroline-10-based, 1, 8-phenanthroline-2-based, 1, 8-phenanthroline-3-based, 1, 8-phenanthroline-4-based, 1, 8-phenanthroline-5-based, 1, 8-phenanthroline-6-based, 1, 8-phenanthroline-7-yl, 1, 8-phenanthroline-9-yl, 1, 8-phenanthroline-10-yl, 1, 9-phenanthroline-2-yl, 1, 9-phenanthroline-3-yl, 1, 9-phenanthroline-4-yl, 1, 9-phenanthroline-5-yl, 1, 9-phenanthroline-6-yl, 1, 9-phenanthroline-7-yl, 1, 9-phenanthroline-8-yl, 1, 9-phenanthroline-10-yl, 1, 10-phenanthroline-2-yl, 1, 10-phenanthroline-3-yl, 1, 10-phenanthroline-4-yl, 1, 10-phenanthroline-5-yl, 2, 9-phenanthroline-1-yl, 2, 9-phenanthroline-3-yl, 2, 9-phenanthroline-4-yl, 2, 9-phenanthroline-5-yl, 2, 9-phenanthroline-6-yl, 2, 9-phenanthroline-7-yl, 2, 9-phenanthroline-8-yl, 2, 9-phenanthroline-10-yl, 2, 8-phenanthroline-1-yl, 2, 8-phenanthroline-3-yl, 2, 8-phenanthroline-4-yl, 2, 8-phenanthroline-5-yl, 2, 8-phenanthroline-6-yl, 2, 8-phenanthroline-7-yl, 2, 8-phenanthroline-9-yl, 2, 8-phenanthroline-10-yl group, 2, 7-phenanthroline-1-yl group, 2, 7-phenanthroline-3-yl group, 2, 7-phenanthroline-4-yl group, 2, 7-phenanthroline-5-yl group, 2, 7-phenanthroline-6-yl group, 2, 7-phenanthroline-8-yl group, 2, 7-phenanthroline-9-yl group, 2, 7-phenanthroline-10-yl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 2-oxadiazolyl group, 5-oxadiazolyl group, 3-furazanyl group, 2-thienyl group, 3-thienyl group, 2-methylpyridin-1-yl group, 2-methylpyrrole-3-yl group, 2-phenanthroline-1-yl group, 2-phenanthroline-3-yl group, 2-phenanthroline-6-yl group, 2, 7-phenanthroline-, 2-methylpyrrol-4-yl, 2-methylpyrrol-5-yl, 3-methylpyrrol-1-yl, 3-methylpyrrol-2-yl, 3-methylpyrrol-4-yl or 3-methylpyrrol-5-yl.
In a preferred embodiment, R3At least one hydrogen atom in the phenyl, pyridyl, naphthyl, phenanthryl, anthryl, phenanthryl, biphenyl, pyrimidyl or triazinyl group of (a) may be independently substituted by a linear or branched alkyl group of C1-C20, a cycloalkyl group of C3-C12, an alkoxy group of C1-C10, a halogen, a cyano group, a trifluoromethyl group, a trimethylsilyl group or an aryl group of C6-C30;
wherein, the cycloalkyl of C3-C12 is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
the alkoxy structure of C1-C10 is as follows: -OR wherein R represents a group which is alkyl, which is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl OR n-decyl;
the aryl group having C6 to C30 is phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-tetracenyl, 2-tetracenyl, 9-tetracenyl, 1-pyrenyl, 2-pyrenyl, 4-pyrenyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p-tert-butylphenyl, p- (2-phenylpropyl) phenyl, 3-methyl-2-naphthyl, 4-methyl-1-anthryl, 4 '-methylbiphenyl or 4' -tert-butyl-p-terphenyl-4-yl.
In a preferred embodiment, R4At least one hydrogen atom in the C1-C20 linear or branched alkyl group, phenyl group, pyridyl group, naphthyl group, phenanthryl group, anthryl group, phenanthridinyl group, biphenyl group, pyrimidyl group or triazinyl group can be independently substituted by a C1-C10 linear or branched alkyl group, a C3-C12 cycloalkyl group, a C1-C10 alkoxy group, a halogen group, a cyano group, a trifluoromethyl group, a trimethylsilyl group, naphthyl group, an anthryl group, a phenanthryl group, a dibenzofuranyl group, a fluorenyl group, a carbazolyl group, a spirofluorenyl group or a heteroaryl group with 5-20 atoms;
wherein, the cycloalkyl of C3-C12 is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
the alkoxy structure of C1-C10 is as follows: -OR wherein R represents a group which is alkyl, which is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl OR n-decyl;
the heteroaryl group having 5 to 20 atoms is a 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, pyridyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 1-indolyl group, 2-indolyl group, 3-indolyl group, 4-indolyl group, 5-indolyl group, 6-indolyl group, 7-indolyl group, 1-isoindolyl group, 2-isoindolyl group, 3-isoindolyl group, 4-isoindolyl group, 5-isoindolyl group, 6-isoindolyl group, 7-isoindolyl group, 2-furyl group, 3-furyl group, 2-benzofuryl group, 3-benzofuryl group, 4-benzofuryl group, 5-benzofuryl group, 6-benzofuryl group, 7-benzofuryl group, 1-isobenzofuranyl, 3-isobenzofuranyl, 4-isobenzofuranyl, 5-isobenzofuranyl, 6-isobenzofuranyl, 7-isobenzofuranyl, 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl, 2-quinoxalyl, 5-quinoxalyl, 6-quinoxalyl, 1-pridinyl, 2-pridinyl, 3-pridinyl, 4-pridinyl, 6-pridinyl, 7-pridinyl, 8-phenanthroline-based, 9-phenanthroline-based, 10-phenanthroline-based, 1, 7-phenanthroline-2-based, 1, 7-phenanthroline-3-based, 1, 7-phenanthroline-4-based, 1, 7-phenanthroline-5-based, 1, 7-phenanthroline-6-based, 1, 7-phenanthroline-8-based, 1, 7-phenanthroline-9-based, 1, 7-phenanthroline-10-based, 1, 8-phenanthroline-2-based, 1, 8-phenanthroline-3-based, 1, 8-phenanthroline-4-based, 1, 8-phenanthroline-5-based, 1, 8-phenanthroline-6-based, 1, 8-phenanthroline-7-yl, 1, 8-phenanthroline-9-yl, 1, 8-phenanthroline-10-yl, 1, 9-phenanthroline-2-yl, 1, 9-phenanthroline-3-yl, 1, 9-phenanthroline-4-yl, 1, 9-phenanthroline-5-yl, 1, 9-phenanthroline-6-yl, 1, 9-phenanthroline-7-yl, 1, 9-phenanthroline-8-yl, 1, 9-phenanthroline-10-yl, 1, 10-phenanthroline-2-yl, 1, 10-phenanthroline-3-yl, 1, 10-phenanthroline-4-yl, 1, 10-phenanthroline-5-yl, 2, 9-phenanthroline-1-yl, 2, 9-phenanthroline-3-yl, 2, 9-phenanthroline-4-yl, 2, 9-phenanthroline-5-yl, 2, 9-phenanthroline-6-yl, 2, 9-phenanthroline-7-yl, 2, 9-phenanthroline-8-yl, 2, 9-phenanthroline-10-yl, 2, 8-phenanthroline-1-yl, 2, 8-phenanthroline-3-yl, 2, 8-phenanthroline-4-yl, 2, 8-phenanthroline-5-yl, 2, 8-phenanthroline-6-yl, 2, 8-phenanthroline-7-yl, 2, 8-phenanthroline-9-yl, 2, 8-phenanthroline-10-yl group, 2, 7-phenanthroline-1-yl group, 2, 7-phenanthroline-3-yl group, 2, 7-phenanthroline-4-yl group, 2, 7-phenanthroline-5-yl group, 2, 7-phenanthroline-6-yl group, 2, 7-phenanthroline-8-yl group, 2, 7-phenanthroline-9-yl group, 2, 7-phenanthroline-10-yl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 2-oxadiazolyl group, 5-oxadiazolyl group, 3-furazanyl group, 2-thienyl group, 3-thienyl group, 2-methylpyridin-1-yl group, 2-methylpyrrole-3-yl group, 2-phenanthroline-1-yl group, 2-phenanthroline-3-yl group, 2-phenanthroline-6-yl group, 2, 7-phenanthroline-, 2-methylpyrrol-4-yl, 2-methylpyrrol-5-yl, 3-methylpyrrol-1-yl, 3-methylpyrrol-2-yl, 3-methylpyrrol-4-yl or 3-methylpyrrol-5-yl.
The blue light-emitting compound provided by the present invention is described in further detail below with reference to examples 1 to 6.
Example 1
Blue luminescent compound
Figure BDA0001469821510000151
The compound 2 is prepared by the following method:
synthesis of intermediate-1
[ reaction formula 1]
Figure BDA0001469821510000152
In a 1L three-necked flask, 25.4g (100mmol) of 2-phenanthrene was charged, dissolved in 500ml of glacial acetic acid, and 63.9g of Br was added dropwise at room temperature2(400 mml). After the end of the dropwise addition, the temperature was raised to 120 ℃ and the mixture was refluxed overnight for 18 hours. After the reaction is finished, adding saturated Na2SO3Stirring the solution for 1 hr to form solid, vacuum filtering, washing the filter cake with water and then with ethanolWashed once, dried and recrystallized from toluene and ethanol to give 36.7g of intermediate-1 in 89% yield.
Synthesis of intermediate-2
[ reaction formula 2]
Figure BDA0001469821510000161
A dry 2L three-necked flask was charged with 36.7g (89.1mmol) of intermediate-1 and 21.9g (98mmol) of 6-bromo-1-hydroxynaphthalene, dissolved in 800ml of DMF, and purged with nitrogen under stirring for 15 minutes, followed by addition of 0.6g (3% mol) of Pd (OAc)2，1.4g(6％mol)PPh3Finally, 87.1g (267.3mmol) of Cs were slowly added2CO3The temperature was raised to 160 ℃ and the mixture was refluxed for 24 hours. After the reaction is finished, cooling to room temperature, adding activated carbon, passing through a silica gel short column, extracting the filtrate by using toluene and water, washing the organic phase for 4 times, removing the solvent by rotation, and recrystallizing by using toluene and ethanol to obtain 33.3g of intermediate-2 with the yield of 79%.
Synthesis of Compound 2
[ reaction formula 3]
Figure BDA0001469821510000162
33.3g (70.4mmol) of intermediate-2 and 9.4g (77.4mmol) of phenylboronic acid were put into a 2L three-necked flask, dissolved in 600ml of toluene and 150ml of ethanol, purged with nitrogen for 15 minutes, and then added with 106ml of K2CO3(211.2mmol,2M) in water, and finally 1.6g Pd (PPh3)4(2 mol%). The temperature was raised to 110 ℃ and the reaction was terminated for 12 hours. Adding activated carbon for adsorption, performing suction filtration, removing the solvent by rotation, drying, and recrystallizing by using toluene and ethanol to obtain 28.5g of compound 2 with the yield of 86%.
1H NMR(DMSO,300Hz):(ppm)＝9.26-9.01(m,2H),8.62-8.40(s,1H),8.38-8.21(d,1H),8.19-8.04(d,1H),8.02-7.86(m,2H),7.83-7.46(m,H),7.42-7.07(m,8H),6.74-6.46(d,1H)
MS(FAB):470(M+)
Example 2
Blue luminescent compound
Figure BDA0001469821510000163
Compound 24 was prepared by the following method:
synthesis of intermediate-1
[ reaction formula 4]
Figure BDA0001469821510000171
In a 1L three-necked flask, 25.4g (100mmol) of 2-phenanthrene was charged, dissolved in 500ml of glacial acetic acid, and 63.9g of Br was added dropwise at room temperature2(400 mml). After the end of the dropwise addition, the temperature was raised to 120 ℃ and the mixture was refluxed for 18 hours. After the reaction is finished, adding saturated Na2SO3After stirring the solution for 1 hour, a solid formed, which was filtered, the filter cake was washed with water and once with ethanol, dried and recrystallized from toluene and ethanol to give 36.7g of intermediate-1, 89% yield.
Synthesis of intermediate-2
[ reaction formula 5]
Figure BDA0001469821510000172
A dry 2L three-necked flask was charged with 36.7g (89.1mmol) of intermediate-1 and 21.9g (98mmol) of 6-bromo-1-hydroxynaphthalene, dissolved in 800ml of DMF, and purged with nitrogen under stirring for 15 minutes, followed by addition of 0.6g (3% mol) of Pd (OAc)2，1.4g(6％mol)PPh3Finally, 87.1g (267.3mmol) of Cs were slowly added2CO3The temperature was raised to 160 ℃ and the mixture was refluxed for 24 hours. After the reaction is finished, cooling to room temperature, adding activated carbon, passing through a silica gel short column, extracting the filtrate by using toluene and water, washing the organic phase for 4 times, removing the solvent by rotation, and recrystallizing by using toluene and ethanol to obtain 33.3g of intermediate-2 with the yield of 79%.
Synthesis of intermediate-3
[ reaction formula 6]
Figure BDA0001469821510000173
33.3g (70.3mmol) of intermediate-2 was put into a 2L three-necked flask, and then 13.8g (77.4mmol) of NBS was added thereto with exclusion of light at room temperature using 600ml of DMF as a solvent, followed by reaction for 18 hours with exclusion of light at room temperature. After the reaction is finished, adding saturated Na2SO3The solution was precipitated as a solid, stirred for 1 hour, filtered, washed with water several times, washed with ethanol 1 time, dried and recrystallized with toluene and ethanol to yield 35.3g of intermediate-3 in 91% yield.
Synthesis of intermediate-4
[ reaction formula 7]
Figure BDA0001469821510000181
35.3g (64mmol) of intermediate-3 and 8.6g (77.4mmol) of phenylboronic acid were put into a 2L three-necked flask, dissolved in 700ml of toluene and 150ml of ethanol, purged with nitrogen for 15 minutes, and 64ml of K was added2CO3(128mmol,2M) in water and finally 1.5g of Pd (PPh)3)4(2 mol%). The temperature was raised to 110 ℃ and the reaction was terminated for 12 hours. Adding activated carbon for adsorption, performing suction filtration, rotatably removing the solvent, drying, and recrystallizing by using toluene and ethanol to obtain 22.9g of intermediate-4 with the yield of 65%.
Synthesis of Compound 24
[ reaction formula 8]
Figure BDA0001469821510000182
22.9g (41.6mmol) of intermediate-4 and 7.9g (45.8mmol) of 2-naphthalene boronic acid were charged into a 1L three-necked flask, dissolved in 400ml of toluene and 100ml of ethanol, purged with nitrogen for 15 minutes, and then 62ml of K was added2CO3(124.8mmol,2M) in water and finally 1.0g of Pd (PPh)3)4(2 mol%). The temperature was raised to 110 ℃ and the reaction was terminated for 12 hours. Adding activated carbon for adsorption, performing suction filtration, removing the solvent by rotation, drying, and recrystallizing by using toluene and ethanol to obtain 21.8g of the compound 24 with the yield of 88 percent.
1H NMR(DMSO,300Hz):(ppm)＝9.26-9.01(m,2H),8.62-8.40(s,1H),8.35-8.01(m,6H),7.99-7.81(s,1H),7.78-7.51(m,9H),7.49-7.15(m,9H)
MS(FAB):596(M+)
Example 3
Blue luminescent compound
Figure BDA0001469821510000183
Compound 36 was prepared by the following method:
synthesis of intermediate-5
[ reaction formula 9]
Figure BDA0001469821510000191
Adding 25.7g (100mmol) of 4-bromophenanthrene and 18.9g (110mmol) of 1-naphthalene boric acid into a 1L three-neck flask, adding 500ml of toluene and 125ml of ethanol for dissolving, introducing nitrogen for 15 minutes, and adding 150ml of K2CO3(300mmol,2M) in water and finally 2.3g Pd (PPh)3)4(2 mol%). The temperature was raised to 110 ℃ and the reaction was terminated for 12 hours. Adding activated carbon for adsorption, performing suction filtration, rotatably removing the solvent, drying, and recrystallizing with toluene and ethanol to obtain 28g of intermediate-5, wherein the yield is 92%.
Synthesis of intermediate-6
[ reaction formula 10]
Figure BDA0001469821510000192
28g (92mmol) of intermediate-5 was put into a 2L three-necked flask, and 18g (101.2mmol) of NBS was added thereto with exclusion of light at room temperature using 600ml of DMF as a solvent, followed by reaction for 18 hours with exclusion of light at room temperature. After the reaction is finished, adding saturated Na2SO3The solution was precipitated as a solid, stirred for 1 hour, filtered, washed with water several times, washed with ethanol 1 time, dried and recrystallized with toluene and ethanol to give 29.3g of intermediate-6, a yield of 82%.
Synthesis of intermediate-7
[ reaction formula 11]
Figure BDA0001469821510000193
The experimental apparatus was thoroughly dried, 29.3g (76.4mmol) of intermediate-6 was added to a 2L three-necked flask, 600ml of dried tetrahydrofuran was added, and after dissolution, the temperature was lowered to-78 ℃ and 33.6ml of 2.5M n-BuLi was added dropwise. After the completion of the dropwise addition, the mixture was stirred at that temperature for 1 hour, 10.3g of trimethyl borate (1.3eq.) was further added dropwise at that temperature, and the mixture was stirred at room temperature for 12 hours after the completion of the dropwise addition. After the reaction is finished, adding a 4M hydrochloric acid solution, extracting by using dichloromethane, washing an organic phase to be neutral by using saturated salt water, drying, removing a solvent by rotation, boiling the organic phase by using ethyl acetate to obtain a crude product, and filtering to obtain a filter cake, namely a boric acid product, 22.6g of intermediate-7, wherein the yield is 85%.
Synthesis of intermediate-8
[ reaction formula 12]
Figure BDA0001469821510000201
22.3g (100mmol) of 3-bromo-1-hydroxynaphthalene and 18.9g (110mmol) of 1-naphthylboronic acid are added into a 1L three-neck flask, 400ml of toluene and 100ml of ethanol are added for dissolution, nitrogen is introduced for 15 minutes, and 150ml of K is added2CO3(300mmol,2M) in water and finally 2.3g Pd (PPh)3)4(2 mol%). The temperature was raised to 110 ℃ and the reaction was terminated for 12 hours. Adding activated carbon for adsorption, performing suction filtration, rotatably removing the solvent, drying, and recrystallizing by using toluene and ethanol to obtain 24.6g of intermediate-8 with the yield of 91%.
Synthesis of intermediate-9
[ reaction formula 13]
Figure BDA0001469821510000202
In a 1L three-necked flask, 25.7g (100mmol) of 2-bromophenanthrene was charged, dissolved in 500ml of glacial acetic acid, and 63.9g of Br was added dropwise at room temperature2(400 mml). After the end of the dropwise addition, the temperature was raised to 120 ℃ and the mixture was refluxed overnight for 18 hours. When the reaction is finished, adding saturatedNa2SO3After stirring the solution for 1 hour, a solid was formed, which was filtered, the filter cake was washed with water and once with ethanol, dried and recrystallized from toluene and ethanol to yield 35.7g of intermediate-9, 86%.
Synthesis of intermediate-10
[ reaction formula 14]
Figure BDA0001469821510000203
A dry 2L three-necked flask was charged with 34.3g (82.7mmol) of intermediate-9 and 24.6g (91mmol) of intermediate-8, and then introduced with 600ml of DMF as a solvent, followed by stirring and introducing nitrogen gas for 15 minutes, and further added with 0.56g (3% mol) of Pd (OAc)2，1.3g(6％mol)PPh3Finally, 80.8g (248.1mmol) of Cs are slowly added2CO3The temperature was raised to 160 ℃ and the mixture was refluxed for 24 hours. After the reaction is finished, cooling to room temperature, adding activated carbon, passing through a silica gel short column, extracting the filtrate by using toluene and water, washing the organic phase for 4 times, removing the solvent by rotation, and recrystallizing by using toluene and ethanol to obtain 31.2g of intermediate-10 with the yield of 72%.
Synthesis of intermediate-11
[ reaction formula 15]
Figure BDA0001469821510000211
The experimental apparatus was thoroughly dried, 31.2g (59.5mmol) of intermediate-10 was added to a 2L three-necked flask, 600ml of dried tetrahydrofuran was added, and after dissolution, the temperature was lowered to-78 ℃ and 31.3ml of a 2M solution of LDA (62.5mmol) in THF was added dropwise. After the completion of the dropwise addition, the mixture was stirred at that temperature for 1 hour, 16.6g of iodine (65.5eq.) was further added at that temperature, and after the completion of the dropwise addition, the mixture was stirred at room temperature for 12 hours. After the reaction was complete, 4M hydrochloric acid solution was added, extraction was performed with dichloromethane, the organic phase was washed with saturated brine to neutrality, dried, the solvent was removed by rotation, and recrystallization was performed with toluene and ethanol to give 30.9g of intermediate-11 with a yield of 80%.
Synthesis of intermediate-12
[ reaction formula 16]
Figure BDA0001469821510000212
30.9g (47.6mmol) of intermediate-11 and 15.6g (52.4mmol) of 9- (3-phenylboronic acid) anthracene were charged into a 2L three-necked flask, dissolved in 600ml of toluene and 150ml of ethanol, purged with nitrogen for 15 minutes, and then 72ml of K was added2CO3(142.8mmol,2M) in water and finally 1.1g Pd (PPh)3)4(2 mol%). The temperature was raised to 110 ℃ and the reaction was terminated for 12 hours. Adding activated carbon for adsorption, performing suction filtration, rotatably removing the solvent, drying, and recrystallizing with toluene and ethanol to obtain 34g of intermediate-12 with the yield of 92%.
Synthesis of Compound 36
[ reaction formula 17]
Figure BDA0001469821510000213
34g (43.8mmol) of intermediate-12 and 16.8g (48.2mmol) of 9- (3-phenylboronic acid) anthracene were charged into a 2L three-necked flask, dissolved in 600ml of toluene and 150ml of ethanol, purged with nitrogen for 15 minutes, and 66ml of K was added2CO3(131.4mmol,2M) in water and finally 1.0g of Pd (PPh)3)4(2 mol%). The temperature was raised to 110 ℃ and the reaction was terminated for 12 hours. Adding activated carbon for adsorption, performing suction filtration, removing the solvent by rotation, drying, and recrystallizing by using toluene and ethanol to obtain 39g of the compound 36 with the yield of 89%.
1H NMR(DMSO,300Hz):(ppm)＝9.26-8.86(m,6H),8.54-8.35(m,5H),8.32-8.19(m,6H),8.17-7.95(m,4H),7.93-7.81(m,3H),7.78-7.32(m,21H),7.24-7.02(s,1H)
MS(FAB):999(M+)
Example 4
Blue luminescent compound
Figure BDA0001469821510000221
Compound 67 was prepared by the following method:
synthesis of intermediate-13
[ reaction formula 18]
Figure BDA0001469821510000222
In a dry 2L three-necked flask, 33.6g (100mmol) of 9, 10-dibromophenanthrene and 24.5g (110mmol) of 2-bromo-1-naphthol were charged, and 600ml of DMF was used as a solvent, and nitrogen was introduced under stirring for 15 minutes, followed by addition of 0.67g (3% mol) of Pd (OAc)2,1.6g(6％mol)PPh3Finally, 97.7g (300mmol) of Cs were slowly added2CO3The temperature was raised to 160 ℃ and the mixture was refluxed for 24 hours. After the reaction is finished, cooling to room temperature, adding activated carbon, passing through a silica gel short column, extracting the filtrate by using toluene and water, washing the organic phase for 4 times, removing the solvent by spinning, and recrystallizing by using toluene and ethanol to obtain 31g of intermediate-13 with the yield of 78%.
Synthesis of Compound 67
[ reaction formula 19]
Figure BDA0001469821510000223
31g (78mmol) of intermediate-13 and 17g (85.8mmol) of 2-biphenylboronic acid were charged into a 2L three-necked flask, dissolved in 600ml of toluene and 150ml of ethanol, purged with nitrogen for 15 minutes, and added with 117ml of K2CO3(234mmol,2M) in water and finally 1.8g of Pd (PPh)3)4(2 mol%). The temperature was raised to 110 ℃ and the reaction was terminated for 12 hours. Adding activated carbon for adsorption, performing suction filtration, removing the solvent by rotation, drying, and recrystallizing by using toluene and ethanol to obtain 31.2g of a compound 67 with the yield of 85 percent.
1H NMR(DMSO,300Hz):(ppm)＝9.26-9.01(d,1H),8.97-8.84(d,1H),8.62-8.40(d,1H),8.38-8.06(m,4H),8.01-7.86(m,2H),7.83-7.23(m,13H)
MS(FAB):470(M+)
Example 5
Blue luminescent compound
Figure BDA0001469821510000231
Compound 92 was prepared by the following method:
synthesis of intermediate-9
[ reaction formula 20]
Figure BDA0001469821510000232
In a 1L three-necked flask, 25.4g (100mmol) of 2-bromophenanthrene was charged, dissolved in 500ml of glacial acetic acid, and 63.9g of Br was added dropwise at room temperature2(400 mml). After the end of the dropwise addition, the temperature was raised to 120 ℃ and the mixture was refluxed overnight for 18 hours. After the reaction is finished, adding saturated Na2SO3After stirring the solution for 1 hour, a solid was formed, which was filtered, the filter cake was washed with water and once with ethanol, dried and recrystallized from toluene and ethanol to yield 35.7g of intermediate-9, 86%.
Synthesis of intermediate-14
[ reaction formula 21]
Figure BDA0001469821510000233
22.3g (100mmol) of 2-bromo-5-hydroxynaphthalene and 18.9g (110mmol) of 1-naphthylboronic acid are added into a 1L three-neck flask, 400ml of toluene and 100ml of ethanol are added for dissolution, nitrogen is introduced for 15 minutes, and 150ml of K is added2CO3(300mmol,2M) in water and finally 2.3g Pd (PPh)3)4(2 mol%). The temperature was raised to 110 ℃ and the reaction was terminated for 12 hours. Adding activated carbon for adsorption, performing suction filtration, rotatably removing the solvent, drying, and recrystallizing by using toluene and ethanol to obtain 23.8g of intermediate-14 with the yield of 88%.
Synthesis of intermediate-15
[ reaction formula 22]
Figure BDA0001469821510000241
A dry 2L three-necked flask was charged with 33.2g (80mmol) of intermediate-9 and 23.8g (88mmol) of intermediate-14, and then introduced with 600ml of DMF as a solvent, followed by introducing nitrogen gas under stirring for 15 minutes, and further added with 0.54g (3%mol)Pd(OAc)2,1.3g(6％mol)PPh3Finally, 78.2g (240mmol) of Cs were slowly added2CO3The temperature was raised to 160 ℃ and the mixture was refluxed for 24 hours. After the reaction is finished, cooling to room temperature, adding activated carbon, passing through a silica gel short column, extracting the filtrate by using toluene and water, washing the organic phase for 4 times, removing the solvent by rotation, and recrystallizing by using toluene and ethanol to obtain 31.4g of intermediate-15 with the yield of 75%.
Synthesis of Compound 92
[ reaction formula 23]
Figure BDA0001469821510000242
31.4g (60mmol) of intermediate-15 and 18.9g (66mmol) of 3- (9H-carbazol-9-yl) phenylboronic acid are added into a 2L three-neck flask, 600ml of toluene and 150ml of ethanol are added for dissolving, nitrogen is introduced for 15 minutes, and 90ml of K is added2CO3(180mmol,2M) in water and finally 1.4g of Pd (PPh)3)4(2 mol%). The temperature was raised to 110 ℃ and the reaction was terminated for 12 hours. Adding activated carbon for adsorption, performing suction filtration, rotatably removing the solvent, drying, and recrystallizing by using toluene and ethanol to obtain 33.7g of a compound 92 with the yield of 82%.
1H NMR(DMSO,300Hz):(ppm)＝9.26-9.01(m,2H),8.97-8.89(d,1H),8.71-8.59(d,1H),8.56-8.32(m,3H),8.29-8.09(m,5H),8.06-7.86(m,2H),7.83-7.35(m,15H),7.32-7.07(t,1H),6.61-6.32(d,1H)
MS(FAB):685(M+)
Example 6
Blue luminescent compound
Figure BDA0001469821510000243
Compound 114 was prepared by the following method:
synthesis of intermediate-16
[ reaction formula 24]
Figure BDA0001469821510000251
In a 2L three-necked flask, 30.4g (100mmol) of 2-iodophenanthrene was charged, dissolved in 600ml of glacial acetic acid, and 63.9g of Br was added dropwise at room temperature2(400 mml). After the end of the dropwise addition, the temperature was raised to 120 ℃ and the mixture was refluxed overnight for 18 hours. After the reaction is finished, adding saturated Na2SO3Solution, forming a solid, after stirring for 1 hour, suction filtration, washing the filter cake with water, then with ethanol once, drying and then recrystallizing with toluene and ethanol to give 37.4g of intermediate-16 with a yield of 81%.
Synthesis of intermediate-17
[ reaction formula 25]
Figure BDA0001469821510000252
A dry 2L three-necked flask was charged with 37.4g (81mmol) of intermediate-16 and 19.9g (89.1mmol) of 2-bromo-1-naphthol, using 800ml of DMF as a solvent, stirred with nitrogen for 15 minutes, and then charged with 0.55g (3% mol) of Pd (OAc)2,1.3g(6％mol)PPh3Finally, 79.2g (243mmol) of Cs were slowly added2CO3The temperature was raised to 160 ℃ and the mixture was refluxed for 24 hours. After the reaction is finished, cooling to room temperature, adding activated carbon, passing through a silica gel short column, extracting the filtrate by using toluene and water, washing the organic phase for 4 times, removing the solvent by rotation, and recrystallizing by using toluene and ethanol to obtain 32.2g of intermediate-17 with the yield of 76%.
Synthesis of intermediate-18
[ reaction formula 26]
Figure BDA0001469821510000253
25.8g (100mmol) of 4-bromophenanthridine and 23.3g (110mmol) of dibenzofuran-4-boronic acid are added into a 2L three-neck flask, 500ml of toluene and 125ml of ethanol are added for dissolution, nitrogen is introduced for 15 minutes, and then 150ml of K is added2CO3(300mmol,2M) in water and finally 2.3g Pd (PPh)3)4(2 mol%). The temperature was raised to 110 ℃ and the reaction was terminated for 12 hours. Adding active carbon for adsorption, filtering, removing solvent by rotation, drying, recrystallizing with toluene and ethanol to obtain 29.4g of intermediate-18 with yieldAt 85%.
Synthesis of intermediate-19
[ reaction formula 27]
Figure BDA0001469821510000254
29.4g (85mmol) of intermediate-18 was put into a 2L three-necked flask, and then 16.6g (93.5mmol) of NBS was added thereto with exclusion of light at room temperature using 600ml of DMF as a solvent, followed by reaction for 18 hours with exclusion of light at room temperature. After the reaction is finished, adding saturated Na2SO3The solution was precipitated as a solid, stirred for 1 hour, filtered, washed with water several times, washed with ethanol 1 time, dried and recrystallized with toluene and ethanol to yield 27g of intermediate-19, 75% yield.
Synthesis of intermediate-20
[ reaction formula 28]
Figure BDA0001469821510000261
The experimental apparatus was thoroughly dried, 24.9g (63.8mmol) of intermediate-19 was added to a 2L three-necked flask, 600ml of dried tetrahydrofuran was added, and after dissolution, the temperature was lowered to-78 ℃ and 28.1ml of 2.5M n-BuLi was added dropwise. After the completion of the dropwise addition, the mixture was stirred at that temperature for 1 hour, and further 8.6g of trimethyl borate (1.3eq.) was added dropwise thereto, followed by stirring at room temperature for 12 hours. After the reaction is finished, adding a 4M hydrochloric acid solution, extracting by using dichloromethane, washing an organic phase to be neutral by using saturated salt water, drying, removing a solvent by rotation, boiling the organic phase by using ethyl acetate to obtain a crude product, and filtering to obtain a filter cake, namely a boric acid product, 20.4g of intermediate-20, wherein the yield is 82%.
Synthesis of intermediate-21
[ reaction formula 29]
Figure BDA0001469821510000262
24.9g (47.6mmol) of intermediate-17 and 20.4g (52.4mmol) of intermediate-20 were put into a 2L three-necked flask, dissolved in 500ml of toluene and 125ml of ethanol, and introduced with nitrogen for 15 minutesClock, then add 71ml K2CO3(142.8mmol,2M) in water and finally 1.1g Pd (PPh)3)4(2 mol%). The temperature was raised to 110 ℃ and the reaction was terminated for 12 hours. Adding activated carbon for adsorption, performing suction filtration, rotatably removing the solvent, drying, and recrystallizing by using toluene and ethanol to obtain 29.3g of intermediate-21 with the yield of 83 percent.
Synthesis of intermediate-22
[ reaction formula 30]
Figure BDA0001469821510000263
29.3g (39.5mmol) of intermediate-21 and 5.3g (43.5mmol) of phenylboronic acid were put into a 2L three-necked flask, dissolved in 600ml of toluene and 150ml of ethanol, purged with nitrogen for 15 minutes, and then 59.3ml of K was added2CO3(118.5mmol,2M) in water and finally 0.91g Pd (PPh)3)4(2 mol%). The temperature was raised to 110 ℃ and the reaction was terminated for 12 hours. Adding activated carbon for adsorption, performing suction filtration, rotatably removing the solvent, drying, and recrystallizing by using toluene and ethanol to obtain 25.3g of intermediate-22 with the yield of 87%.
Synthesis of intermediate-23
[ reaction formula 31]
Figure BDA0001469821510000271
25.3g (34.2mmol) of intermediate-22 was put into a 2L three-necked flask, and 6.7g (37.6mmol) of NBS was added thereto with exclusion of light at room temperature using 500ml of DMF as a solvent, followed by reaction for 18 hours with exclusion of light at room temperature. After the reaction is finished, adding saturated Na2SO3The solution is precipitated into a solid, stirred for 1 hour, filtered, washed with water for multiple times, washed with ethanol for 1 time, dried and recrystallized with toluene and ethanol to obtain 22.3g of intermediate-23 with the yield of 80 percent.
Synthesis of Compound 114
[ reaction formula 32]
Figure BDA0001469821510000272
22.3g (27.4mmol) of intermediate-23 and 5.3g (43.5mmol) of 3- (9H-carbazol-9-yl) phenylboronic acid are introduced into a 1L three-necked flask, dissolved in 400ml of toluene and 100ml of ethanol, purged with nitrogen for 15 minutes, and then 41.1ml of K is added2CO3(82.2mmol,2M) in water and finally 0.63g Pd (PPh)3)4(2 mol%). The temperature was raised to 110 ℃ and the reaction was terminated for 12 hours. Adding activated carbon for adsorption, performing suction filtration, removing the solvent by rotation, drying, and recrystallizing by using toluene and ethanol to obtain 21.7g of a compound 114 with the yield of 81 percent.
1H NMR(DMSO,300Hz):(ppm)＝9.26-9.01(m,2H),8.91-8.76(s,1H),8.71-8.43(m,2H),8.41-8.15(m,4H),8.11-7.35(m,31H),7.23-7.07(m,2H)
MS(FAB):979(M+)
The above compounds 1 to 120 can be synthesized using the methods of the above reaction formulae 1 to 32.
The structure of the organic electroluminescent device of the present invention is typically, but not limited to, the following:
(1) anode/light emitting layer/cathode;
(2) anode/hole injection layer/light emitting layer/cathode;
(3) anode/hole injection layer/hole transport layer/light emitting layer/cathode;
(4) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/cathode;
(5) anode/light emitting layer/electron injection layer/cathode;
(6) anode/light-emitting layer/electron transport layer/electron injection layer/cathode;
(7) anode/light-emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode;
(8) anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode;
(9) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode/capping layer.
The manufacturing method of the organic electroluminescent device with the structure (8) comprises the following steps:
step 1, overmoulding an anode material on the surface of a substrate to form an anode, wherein the adopted substrate is a glass substrate or a transparent plastic substrate with good transparency, surface smoothness, operability and waterproofness, and the anode material can be ITO, IZO or SnO with transparency and excellent conductivity2ZnO, etc.
And 2, carrying out vacuum thermal deposition or spin coating on the surface of the anode by using a hole injection layer material (HIL), wherein the hole injection layer material can be CuPc, m-MTDATA, m-MTDAPB, TCTA of star amine, 2-TNATA or IDE406 available from Nippon Kyoto co.
And 3, carrying out vacuum thermal deposition or spin coating on the surface of the hole injection layer by using a hole transport layer material (HTL) to form the hole transport layer. The hole transport layer material may be alpha-NPD, NPB or TPD.
And 4, carrying out vacuum thermal deposition or spin coating on the surface of the hole transport layer to form a light-emitting layer. The used luminescent layer material is formed by doping a host substance formed by the blue luminescent compound of the invention and a blue light fluorescent dopant matched with the host substance.
And 5, carrying out vacuum thermal deposition or spin coating on the surface of the light-emitting layer to form the electron transport layer. The electron transport layer material is not particularly limited, and Alq3 is preferably used.
And 6, carrying out vacuum thermal deposition or spin coating on the surface of the electron transport layer by using an electron injection layer material (EIL) to form the electron injection layer. The electron injection layer material may be LiF, Liq, Li2O, BaO, NaCl, CsF, etc.
And 7, carrying out vacuum thermal deposition or spin coating on the cathode material on the electron injection layer to form a cathode. The cathode material can be Li, Al, Al-Li, Ca, Mg, Mg-In, Mg-Ag, etc. In addition, a transparent cathode that transmits light may be formed using Indium Tin Oxide (ITO) or Indium Zinc Oxide (IZO).
Further, a Hole Blocking Layer (HBL) may be further added between the light emitting layer and the electron transport layer, and the effect of preventing triplet excitons or holes from diffusing into the electron transport layer can be achieved by using phosphorescent doping together with the light emitting layer. And (3) carrying out vacuum thermal deposition or spin coating on the surface of the light-emitting layer by using a hole barrier layer material (HBL) to form a hole barrier layer. The hole-blocking layer material is not particularly limited, and Liq, 2-methyl-8-hydroxyquinoline p-hydroxybiphenyl aluminum, BCP, LiF, and the like are preferable.
Further, the light emitting layer is formed by laminating the blue light emitting host substance and the dopant substance of the present invention and any conventionally known light emitting material other than the present invention, as long as it does not hinder the achievement of the object of the present invention.
The organic electroluminescent element provided by the present invention will be described in further detail with reference to examples 7 to 17 and comparative example 1.
Example 7
An organic electroluminescent device comprising an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, a cathode and a capping layer, which are sequentially disposed, wherein the light-emitting layer comprises a host substance and a dopant substance, and the host substance is compound 2 provided in example 1.
The organic electroluminescent device is prepared by the following steps: forming an ITO anode on a substrate having a reflective layer, using N2Ion or UV-Ozone for surface treatment. On top of this, HAT-CN was used as a Hole Injection Layer (HIL) material, and a thickness of 10nm was deposited by evaporation. Next, NPD was selected and vacuum-deposited on the hole injection layer to form a 120nm thick hole transport layer. In the light emitting layer (EML) above the hole transport layer, compound 2 was selected as a host material among the compounds of the present invention to be evaporated to a thickness of 25nm, and about 5% was doped with t-Bu-Perylene as a dopant. On this, an anthracene derivative and Liq were mixed at a weight ratio of 1:1, and an Electron Transport Layer (ETL) having a thickness of 35nm was deposited, and on the top thereof, Liq having a thickness of 2nm was deposited as an Electron Injection Layer (EIL). Then, a mixture of magnesium (Mg) and silver (Ag) in a ratio of 9:1 was used as a cathode to deposit N4, N4' -bis [4- [ bis (3-methylphenyl) ammonia ] with a thickness of 15nm and a thickness of 65nm on the cathode]Phenyl radical]-N4, N4 '-diphenyl- [1, 1' -biphenyl]-4, 4' -diamine (DNTPD) as capping layer (CPL). Finally, the paper is sealed with a water-absorbing material containing a UV-curable adhesive to protect the organic electroluminescent elementThe member is not affected by atmospheric oxygen or moisture.
The structural formulae of the compounds referred to in this example are as follows:
Figure BDA0001469821510000291
examples 8 to 17
The organic electroluminescent devices of examples 8 to 17 were produced by using compounds 13, 24, 28, 36, 48, 67, 73, 81, 92 and 114 as host materials in blue EML, respectively, and the other portions were the same as those in example 7.
Comparative example 1
The difference from example 7 is that 9, 10-bis (2-naphthyl) Anthracene (ADN) was used as a blue light host material in place of the compound of the present invention, and the rest was the same as example 7.
The organic electroluminescent devices prepared in examples 7 to 17 and comparative example 1 were used at a current density of 10mA/cm2The results of the performance test under the conditions of (1) are shown in the following table.
Figure BDA0001469821510000292
Figure BDA0001469821510000301
From the above table, it can be seen that, compared with the comparative example, in examples 7 to 17 of the organic electroluminescent devices prepared by using the compound of the present invention as the blue host material of the light-emitting layer, the light-emitting efficiency is significantly improved, and can be improved by 58.5% at most, and the driving voltage is significantly reduced. Further, from the results of measuring the color coordinates (CIE (x Y)), it was confirmed that the material had a deep blue (deep blue) characteristic in examples 7 to 17, since the value of the color coordinate CIE Y was lower than that in comparative example 1. Therefore, the blue light-emitting compound of the present invention, as a host material of a light-emitting layer in an organic electroluminescent device, can reduce the driving voltage of the device, increase the efficiency, and have a deep blue characteristic.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims (6)

1. A blue light-emitting compound having a structural formula as shown below:
Figure FDA0002512616570000011
wherein R is1Is any one of hydrogen, phenyl, pyridyl, naphthyl, phenanthryl, anthryl, phenanthridinyl, biphenyl, pyrimidyl or triazinyl;
R2is any one of hydrogen, C1-C20 straight chain or branched chain alkyl, phenyl, pyridyl, naphthyl, phenanthryl, anthryl, phenanthridinyl, biphenyl, pyrimidyl or triazinyl;
R3is any one of hydrogen, phenyl, pyridyl, naphthyl, phenanthryl, anthryl, phenanthridinyl, biphenyl, pyrimidyl or triazinyl;
R4is any one of hydrogen, C1-C20 straight chain or branched chain alkyl, phenyl, pyridyl, naphthyl, phenanthryl, anthryl, phenanthridinyl, biphenyl, pyrimidyl or triazinyl;
R1at least one hydrogen atom in the phenyl, pyridyl, naphthyl, phenanthryl, anthryl, phenanthryl, biphenyl, pyrimidyl or triazinyl group of (a) may be independently substituted by a linear or branched alkyl group of C1-C20, a cycloalkyl group of C3-C20, an alkoxy group of C1-C20, a halogen, a cyano group, a trifluoromethyl group, a trimethylsilyl group or an aryl group of C6-C50;
R2at least one hydrogen atom in the C1-C20 linear or branched alkyl group, phenyl group, pyridyl group, naphthyl group, phenanthryl group, anthryl group, phenanthryl group, biphenyl group, pyrimidyl group or triazinyl group may be independently substituted by a C1-C20 linear or branched alkyl group, a C3-C24 cycloalkyl group, a C1-C20 alkoxy group, a halogenSubstituted by a cyano group, a trifluoromethyl group, a trimethylsilyl group, a naphthyl group, an anthryl group, a phenanthryl group, a fluorenyl group, a spirofluorenyl group or a heteroaryl group with the atomic number of 5-20;
R3at least one hydrogen atom in the phenyl, pyridyl, naphthyl, phenanthryl, anthryl, phenanthryl, biphenyl, pyrimidyl or triazinyl group of (a) may be independently substituted by a linear or branched alkyl group of C1-C20, a cycloalkyl group of C3-C12, an alkoxy group of C1-C10, a halogen, a cyano group, a trifluoromethyl group, a trimethylsilyl group or an aryl group of C6-C30;
R4at least one hydrogen atom in the C1-C20 linear or branched alkyl group, phenyl group, pyridyl group, naphthyl group, phenanthryl group, anthryl group, phenanthridinyl group, biphenyl group, pyrimidyl group or triazinyl group can be independently substituted by a C1-C10 linear or branched alkyl group, a C3-C12 cycloalkyl group, a C1-C10 alkoxy group, a halogen group, a cyano group, a trifluoromethyl group, a trimethylsilyl group, naphthyl group, an anthryl group, a phenanthryl group, a fluorenyl group, a spirofluorenyl group or a heteroaryl group having 5-20 atoms.
2. The blue light-emitting compound according to claim 1, wherein the linear or branched alkyl group having 1 to 20 is a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group or an n-octyl group.
3. A blue light-emitting compound according to claim 1, wherein the compound is any one of the following compounds:
Figure FDA0002512616570000012
Figure FDA0002512616570000021
Figure FDA0002512616570000031
Figure FDA0002512616570000041
Figure FDA0002512616570000051
Figure FDA0002512616570000061
Figure FDA0002512616570000071
Figure FDA0002512616570000081
Figure FDA0002512616570000091
Figure FDA0002512616570000101
Figure FDA0002512616570000111
4. use of a blue light-emitting compound according to any one of claims 1 to 3 for the preparation of a light-emitting device.
5. An organic electroluminescent element comprising an anode, a light-emitting layer and a cathode, wherein the light-emitting layer comprises the blue light-emitting compound according to any one of claims 1 to 3.
6. The organic electroluminescent device according to claim 5, wherein a hole injection layer and a hole transport layer are further disposed between the anode and the light emitting layer, and an electron transport layer and an electron injection layer are further disposed between the light emitting layer and the cathode.
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