CN112094168B - Deuterated fluorene compound and light-emitting device thereof - Google Patents

Abstract

The invention provides a deuterated fluorene compound and a light-emitting device thereof. The invention introduces fluorene functional groups with rigid structures into an organic compound through unique large steric hindrance connection sites. The formed deuterated fluorene compound has excellent film-forming property and thermal stability, and can be used for preparing organic electroluminescent devices. The deuterated fluorene compound is particularly suitable for preparing a blue light organic electroluminescent device and can be used as a constituent material of a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer or an electron transport layer. More importantly, the deuterated fluorene compound has excellent transmission performance and luminescence performance, and can reduce the driving voltage of an organic electroluminescent device, improve the efficiency of the device and prolong the service life of the device when being used as a luminescent layer material, particularly a blue light luminescent layer material. The deuterated fluorene compound has excellent device performance, simple preparation method and easily obtained raw materials, and can meet the development requirements of industrialization.

Description

Deuterated fluorene compound and light-emitting device thereof

Technical Field

The invention belongs to the technical field of organic photoelectric materials, and relates to a deuterated fluorene compound and a luminescent device comprising the deuterated fluorene compound. More particularly, the present invention relates to a deuterofluorene compound suitable for an organic electroluminescent device, particularly a blue organic electroluminescent device, and a light emitting device using the deuterofluorene compound.

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 organic layers 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, the host material is 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. The third generation organic electroluminescent materials generally have a small singlet-triplet energy level difference (Δ E) _ST ) The triplet excitons can be converted into singlet excitons through reverse system cross-over (RISC) to emit light, which can simultaneously utilize singlet excitons and triplet excitons formed under electrical excitation, and the internal quantum efficiency of the device can reach 100%, thus being considered as one of organic light-emitting materials with wide application prospects in the future. However, the operational lifetime of devices, particularly blue devices, remains an open question in this area. In view of the above, the future development direction of organic electroluminescent devices will be high efficiency, long lifetime, low cost white light devices and full color display devices, but the industrialization process of the technology still faces many key problems. Therefore, designing and searching a stable and efficient compound as a novel material of an organic electroluminescent device to overcome the defects of the organic electroluminescent device in the practical application process is a key point in the research work of the organic electroluminescent device material and the future research and development trend.

Disclosure of Invention

Problems to be solved by the invention

The present invention provides a deuterated fluorene compound and a light emitting device using the same. The deuterated fluorene compound has a bridged biphenyl structure, so that the deuterated fluorene compound has high thermal stability, high chemical stability and high carrier transport property, and more importantly, has proper singlet state, triplet state, molecular orbital level and high luminescence quantum efficiency. 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.

Means for solving the problems

The invention adopts the 1,4 position of fluorene with large steric hindrance as a connecting site to introduce functional groups. The 1, 4-position connection mode runs through the benzene ring on one side of the fluorene structure, and the 9-position bridging carbon atom and the substituent group thereon of the fluorene and the benzene ring on the other side of the fluorene are skillfully used as the steric hindrance groups of the 1, 4-position functional groups respectively. The structure realizes the highly three-dimensional molecular conformation of the disubstituted fluorene compound without additionally adding steric hindrance groups, and simultaneously reserves the electronic and photophysical characteristics of fluorene, thereby finally achieving the purpose of improving the performance of a light-emitting device, particularly a blue light device. The connection mode is particularly suitable for constructing a blue light main body material, can realize main body molecules with a rod-shaped structure and a steric hindrance structure, improves the molecular arrangement, prevents the aggregation effect, ensures the carrier mobility, and avoids the reduction of quantum efficiency caused by aggregation.

That is, the present invention is as defined in the above-mentioned embodiments.

ADVANTAGEOUS EFFECTS OF INVENTION

The deuterated fluorene compound has a highly three-dimensional rigid structure and has good film-forming property and thermal stability. Due to no introduction of additional steric hindrance groups, the compound retains the photoelectric physical and chemical properties of fluorene to the maximum extent, and is very suitable for preparing various light-emitting devices, especially blue-light organic electroluminescent devices. The luminescent device prepared from the deuterated fluorene compound has the advantages of low driving voltage, high luminous efficiency and long service life. The concrete effects are as follows:

the deuterated fluorene compound has adjustable carrier transport performance. By connecting different functional groups, the organic electroluminescent material can obtain good hole transport performance, electron transport performance or bipolar transport performance, and is suitable for being used as a constituent material of a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer or an electron transport layer in an organic electroluminescent device. The luminescent device adopting the material has low driving voltage and high power efficiency.

The deuterated fluorene compound has adjustable HOMO and LUMO energy levels and appropriate singlet state and triplet state energy levels, can block the transmission of holes or electrons, is suitable to be used as an electron blocking layer or a hole blocking layer in an organic electroluminescent device, limits a carrier recombination region in a light-emitting layer, and improves the light-emitting efficiency of the device.

The deuterated fluorene compound has proper singlet and triplet energy levels and high fluorescence quantum yield, and is suitable to be used as a constituent material of a light-emitting layer in an organic electroluminescent device, particularly as a main material. The luminescent device prepared by the material, especially the blue light organic electroluminescent device, has the advantages of low driving voltage, high luminous efficiency and long service life, and is obviously superior to the existing organic electroluminescent device.

In addition, the preparation method of the deuterated fluorene compound is simple, the raw materials are easy to obtain, and the development requirements of industrial large-scale production can be met.

Drawings

FIG. 1 is a thermogravimetric plot (TGA) of the compounds of examples 1 and 4 of the present invention (compounds 1-3-D30 and 1-49-D30).

Fig. 2 is an organic electroluminescence spectrum of the organic electroluminescent devices 1 to 4 in examples 5 to 8 of the present invention.

Fig. 3 is an organic electroluminescence spectrum of the organic electroluminescent devices 5 to 8 in examples 9 to 12 of the present invention.

Fig. 4 is a view showing the configuration of organic electroluminescent devices in examples 5 to 12 and comparative examples 1 to 6.

FIG. 5 is a mass spectrum of the compound of example 1 (Compound 1-3-D30).

FIG. 6 is a mass spectrum of the compound of example 2 (Compound 1-2-D25).

FIG. 7 is a mass spectrum of the compound of example 3 (Compound 1-1-D25).

FIG. 8 is a mass spectrum of the compound of example 4 (Compound 1-49-D30).

Description of the reference numerals

1a 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 an 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.

< deuterated fluorene-based Compound >

The deuterated fluorene compound of the invention is a novel compound having a 1, 4-disubstituted fluorene structure and is represented by the following general formula (1),

wherein the content of the first and second substances,

each A independently represents Ar or N (Ar) ₂ ；

Each Ar independently represents a hydrogen atom, a cyano group, optionally substituted by one or more R ¹ Substituted C ₆ -C ₃₀ Aryl or optionally substituted by one or more R ¹ Substituted 5-30 membered heteroaryl;

each L independently represents a single bond, a carbonyl group, optionally substituted with one or more R ¹ Substituted C ₆ -C ₁₈ Arylene or optionally substituted by one or more R ¹ Substituted 5-18 membered heteroarylene;

m represents C (R) ¹ ) ₂ Or a group represented by any one of structural formulae (A) to (E):

the dotted line represents a bond;

x represents a single bond or C ₁ -C ₈ An alkyl group;

y represents a single bond, C (R) ¹ ) ₂ 、NR ¹ 、O、S、S(＝O) ₂ 、P(＝O)R ¹ 、Si(R ¹ ) ₂ Or Ge (R) ¹ ) ₂ 、；

Each Z independently represents CR ¹ Or N;

if present, each R ¹ Each independently represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, N (= O) ₂ 、N(R ² ) ₂ 、OR ² 、SR ² 、C(＝O)R ² 、P(＝O)R ² 、Si(R ² ) ₃ Or any of the following groups optionally substituted with one or more deuterium atoms: c ₁ -C ₂₀ Alkyl radical, C ₂ -C ₂₀ Alkenyl radical, C ₂ -C ₂₀ Alkynyl, C ₆ -C ₄₀ Aryl and 5-40 membered heteroaryl; if present, each R ² Each independently represents a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group or any of the following groups optionally substituted with one or more deuterium atoms: c ₁ -C ₂₀ Alkyl radical, C ₆ -C ₃₀ Aryl and 5-30 membered heteroaryl;

dn represents n hydrogen atoms substituted by deuterium atoms;

n represents any integer of 6 or more.

Specifically, the deuterated fluorene compound is represented by the following general formula (1-A) or (1-B):

wherein, the first and the second end of the pipe are connected with each other,

each Z independently represents CR ¹ Or N;

if present, each R ¹ Each independently represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, N (= O) ₂ 、N(R ² ) ₂ 、OR ² 、SR ² 、C(＝O)R ² 、P(＝O)R ² 、Si(R ² ) ₃ Or any of the following groups optionally substituted with one or more deuterium atoms: c ₁ -C ₂₀ Alkyl radical, C ₂ -C ₂₀ Alkenyl radical, C ₂ -C ₂₀ Alkynyl, C ₆ -C ₄₀ Aryl or 5-40 membered heteroaryl; if present, each R ² Each independently represents a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group or any of the following groups optionally substituted with one or more deuterium atoms: c ₁ -C ₂₀ Alkyl radical, C ₆ -C ₃₀ Aryl or 5-30 membered heteroaryl;

ar, L, M and Dn are as defined above.

More specifically, the deuterated fluorene compound of the invention is represented by the following general formula (1-A ') or (1-B'),

wherein the content of the first and second substances,

if present, each R ¹ Each independently represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, N (= O) ₂ 、N(R ² ) ₂ 、OR ² 、SR ² 、C(＝O)R ² 、P(＝O)R ² 、Si(R ² ) ₃ Or any of the following groups optionally substituted with one or more deuterium atoms: c ₁ -C ₂₀ Alkyl radical, C ₂ -C ₂₀ Alkenyl radical, C ₂ -C ₂₀ Alkynyl, C ₆ -C ₄₀ Aryl or 5-40 membered heteroaryl; if present, each R ² Each independently represents a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group or any of the following groups optionally substituted with one or more deuterium atoms: c ₁ -C ₂₀ Alkyl radical, C ₆ -C ₃₀ Aryl or 5-30 membered heteroaryl;

ar, L, M and Dn are as defined above.

In a preferred embodiment of the present invention, in the above general formula (1-A) or (1-B),

each Ar independently represents a hydrogen atom, optionally substituted by one or more R ¹ Substituted C ₆ -C ₁₃ Aryl or optionally substituted by one or more R ¹ Substituted 5-13 membered heteroaryl;

each L independently represents a single bond, optionally substituted by one or more R ¹ Substituted C ₆ -C ₁₄ Arylene or optionally substituted by one or more R ¹ A substituted 5-13 membered heteroarylene;

m represents C (R) ¹ ) ₂ ；

Each Z independently represents CR ¹ Or N;

each R ¹ Each independently represents any of the following groups optionally substituted with one or more deuterium atoms: c ₁ -C ₆ Alkyl radical, C ₆ -C ₁₀ Aryl and 5-10 membered heteroaryl;

dn represents the replacement of n hydrogen atoms by deuterium atoms;

n represents any integer of 6 or more.

In a preferred embodiment of the present invention, in the above general formula (1-A ') or (1-B'),

each Ar independently represents a hydrogen atom, optionally substituted by one or more R ¹ Substituted C ₆ -C ₁₃ Aryl or optionally substituted by one or more R ¹ Substituted 5-13 membered heteroaryl, more preferably a hydrogen atom or optionally substituted by one or more R ¹ Any one of the following substituted groups:

each L independently represents a single bond, optionally substituted by one or more R ¹ Substituted C ₆ -C ₁₄ Arylene or optionally substituted with one or more R ¹ Substituted 5-13 membered heteroarylene, preferably single bond or optionally substituted with one or more R ¹ Any one of the following substituted groups:

m represents C (R) ¹ ) ₂ ；

Each R ¹ Each independently represents any of the following groups optionally substituted with one or more deuterium atoms: methyl and

dn represents n hydrogen atoms substituted by deuterium atoms;

n represents any integer of 6 or more.

[ radical definitions ]

<A>

In the present invention, A in the above general formula (1) is a structural fragment to which an L fragment is ligated, and A's may be the same or different from each other. Specifically, each A independently represents Ar or N (Ar) ₂ . When A is Ar, it means that the Ar fragment is directly linked to the L fragment in the general formula (1); when A is N (Ar) ₂ When used, means that both Ar moieties are simultaneously bonded to the L moiety in formula (1) through a nitrogen atom.

<Ar>

When there are a plurality of Ar's in the general formula, they may be the same as or different from each other. Specifically, each Ar in the above general formula (1-A), (1-B), (1-A ') or (1-B') independently represents a hydrogen atom, a cyano group, optionally substituted with one or more R ¹ Substituted C ₆ -C ₃₀ Aryl or optionally substituted by one orPlural R ¹ Substituted 5-30 membered heteroaryl.

In the present invention, the term "aryl" refers to a monovalent group derived from an aromatic hydrocarbon, which may be linked to another structural fragment; accordingly, "C ₆ -C ₃₀ Aryl "refers to an aryl group having from 6 to 30 carbon atoms in the structure; for example, phenyl, naphthyl, anthracenyl, fluorenyl, and the like.

In the present invention, the term "heteroaryl" refers to a monovalent group derived from a heteroarene, to which another fragment may be attached; correspondingly, "5-30 membered heteroaryl" refers to heteroaryl groups containing from 5 to 30 ring atoms in the structure; for example, pyridyl, dibenzofuranyl, dibenzothienyl, carbazolyl, and the like. In the 5-30 membered heteroaryl group, the heteroatom is selected from N, O, S, P, as and/or Si, preferably N, O and/or S; the number of heteroatoms may be from 1 to 10, preferably from 1 to 5.

Aryl or heteroaryl groups in the present invention also encompass systems which do not contain only aryl or heteroaryl groups, but also include those 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, monovalent moieties derived from 9,9' -spirobifluorenes, 9-diarylfluorenes, triarylamines, diaryl ethers, and the like are also considered aryl or heteroaryl groups in the sense of the present invention, as are systems in which two or more aryl groups are interrupted by linear or cyclic alkylene or silylene groups. Furthermore, monovalent moieties in which two or more aryl or heteroaryl groups are linked to one another, such as biphenyl, terphenyl or quaterphenyl, are likewise to be regarded as aryl or heteroaryl in the sense of the present invention.

C represented by Ar ₆ -C ₃₀ Aryl or 5-30 membered heteroaryl may be exemplified by: phenyl, naphthyl, anthryl, benzanthryl, phenanthryl, benzophenanthryl, pyrenyl, perylenyl, fluoranthenyl, benzofluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, idophenyl, terphenyl, quaterphenyl, pentabiphenyl, terphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis-or trans-indeneAnd a fluorenyl group, a cis-or trans-monobenzindenofluorenyl group, a cis-or trans-dibenzoindenofluorenyl group, a trimerization indenyl group, an isotridecyl group, a spirotrimerization indenyl group, a benzofuranyl group, an isobenzofuranyl group, a dibenzofuranyl group, a benzothienyl group, an isobenzothiophenyl group, a dibenzothiophenyl group, an indolyl group, an isoindolyl group, a carbazolyl group, an indolocarbazolyl group, an indenocarbazolyl group, a pyridyl group, a quinolyl group, an isoquinolyl group, an acridinyl group, a phenanthridinyl group, a benzo-5, 6-quinolyl group, a benzo-6, 7-quinolyl group, a benzo-7, 8-quinolyl group, an indazolyl group, a benzimidazolyl group, a naphthoimidazolyl group, a phenanthroimidazolyl group, a pyridoimidazolyl group, a pyrazinoimidazolyl, quinoxalinimidazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, phenanthrooxazolyl, benzothiazolyl, pyridazinyl, benzopyrazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazahthranyl, 2, 7-diazpyrenyl, 2, 3-diazpyrenyl, 1, 6-diazpyrenyl, 1, 8-diazpyrenyl, 4,5,9, 10-tetraazaperylenyl, pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluorescentrynyl, naphthyridinyl, azacarbazolyl, benzocainenyl, phenanthrolinyl, benzotriazolyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, and the like.

Preferably, in the present invention, each Ar independently represents a hydrogen atom, a cyano group, optionally substituted by one or more R ¹ Substituted C ₆ -C ₃₀ Aryl or optionally substituted by one or more R ¹ Substituted 5-30 membered heteroaryl, preferably a hydrogen atom, cyano or any one of the following groups:

wherein the dotted line represents a bond to the L fragment or nitrogen atom.

<L>

In the present invention, L in the above general formula (1), (1-A), (1-B), (1-A ') or (1-B') is a group of L and L together with the parent nucleus and the A fragment or Ar fragment/N (Ar) ₂ Fragment-linked structural fragments, a plurality of L's being the same or different from each other. Specifically, each L independently represents a single bond, a carbonyl group, optionally substituted with one or more R ¹ Substituted C ₆ -C ₁₈ Arylene or optionally substituted by one or more R ¹ Substituted 5-18 membered heteroarylenes.

In the present invention, the term "arylene" refers to a divalent group derived from an aromatic hydrocarbon, which may link two additional structural segments; accordingly, "C ₆ -C ₁₈ Arylene "refers to arylene groups containing from 6 to 18 carbon atoms in the structure; for example, phenylene, naphthylene, anthracenylene, fluorenylene, and the like.

In the present invention, the term "heteroarylene" refers to a divalent group derived from a heteroarene, to which two additional segments may be attached; correspondingly, "5-18 membered heteroarylene" refers to a heteroarylene group containing from 5 to 18 ring atoms in the structure; for example, pyridinylene, dibenzofuranylene, dibenzothiophenylene, carbazolyl, etc. In the 5-18 membered heteroarylene group, the heteroatom is selected from N, O, S, P, as and/or Si, preferably N, O and/or S; the number of heteroatoms may be from 1 to 10, preferably from 1 to 5.

Arylene or heteroarylene groups in the present invention also encompass systems which do not contain only arylene or heteroarylene groups, but also include those in which a plurality of arylene or heteroarylene 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, as with systems in which two or more arylene groups are interrupted by linear or cyclic alkylene or silylene groups, divalent moieties derived from 9,9' -spirobifluorene, 9-diarylfluorene, triarylamine, diarylether, and the like are also considered arylene or heteroarylene groups in the sense of the present invention. Furthermore, divalent fragments in which two or more arylene or heteroarylene groups are linked to one another, such as biphenylene, terphenylene or quaterphenylene groups, are likewise considered arylene or heteroarylene in the sense of the present invention.

C represented by L ₆ -C ₁₈ Arylene or 5-18 membered heteroarylene can be exemplified by: <xnotran> , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , -5,6- , -6,7- , -7,8- , , , , , , , , , , , , , , , , , , 1,5- </xnotran>Anthracenyl, 2, 7-diazpyrenyl, 2, 3-diazpyrenyl, 1, 6-diazpyrenyl, 1, 8-diazpyrenyl, 4, 5-diazenyl, 4,5,9, 10-tetraazaperylenyl, pyrazinylene, phenazinylene, phenoxazinyl, phenothiazinylene, fluorescentlenyl, naphthyrylene, azacarbazolyl, benzocarbazolyl, phenanthroline, benzotriazolylene, purinylene, pteridinylene, indolizinylene, benzothiadiazolylene, and the like.

Preferably, in the present invention, each L independently represents a single bond, a carbonyl group, optionally substituted by one or more R ¹ Substituted C ₆ -C ₁₃ Arylene or optionally substituted by one or more R ¹ A substituted 5-13 membered heteroarylene, preferably a single bond, a carbonyl group or any of the following groups optionally deuterated: phenylene, biphenylene, naphthylene, anthracenylene, fluorenylene, dibenzofuranylene and carbazolyl, more preferably a single bond or any of the following optionally deuterated groups: naphthylene, anthracenylene, fluorenylene, dibenzofuranylene and carbazolyl groups, most preferably a single bond or any one of the following groups:

wherein the dotted line represents the bond to the parent nucleus and the A fragment.

<M>

In the present invention, M in the general formula (1), (1-A), (1-B), (1-A ') or (1-B') is a structural fragment at the 9-position of the fluorene ring, specifically C (R) ¹ ) ₂ Or a group represented by any one of structural formulae (A) to (E):

wherein the dotted lines represent bonds to the carbon atoms at positions 1a and 8a, respectively, of the fluorene ring.

<X>

In the structural formula (A), X represents a single bond or C ₁ -C ₈ Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, 2-methylhexyl, n-octyl and the like.

<Y>

In the structural formulae (D) and (E), Y represents a single bond, C (R) ¹ ) ₂ 、NR ¹ 、O、S、S(＝O) ₂ 、P(＝O)R ¹ 、Si(R ¹ ) ₂ Or Ge (R) ¹ ) ₂ Specific examples are C (CH) ₃ ) ₂ 、O、S、S(＝O) ₂ PH (= O), and the like.

<Z>

When there are a plurality of Z in the above general formula and/or structural formula, they may be the same as or different from each other. Specifically, each Z independently represents CR ¹ Or N. When Z is CR ¹ And R is ¹ In the case of a hydrogen atom, the ring atom in the corresponding ring system is an sp 2-hybridized carbon atom and is unsubstituted; when Z is CR ¹ And R is ¹ When not a hydrogen atom, the ring atom in the corresponding ring system is still an sp2 hybridized carbon atom, but is substituted by a corresponding substituent; when Z is N, the ring atoms in the corresponding ring systems are sp2 hybridized nitrogen atoms.

<R ¹ And R ² >

As optionally substituted substituents, each of the Ar and/or L moieties may have one or more R ¹ . In addition, one or more R may be present in a fragment of M and/or Z ¹ . When there are multiple R in the structure ¹ They may be the same or different from each other. Specifically, each R ¹ Each independently represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, N (= O) ₂ 、N(R ² )、OR ² 、SR ² 、C(＝O)R ² 、P(＝O)R ² 、Si(R ² ) ₃ Or any of the following groups optionally substituted with one or more deuterium atoms: c ₁ -C ₂₀ Alkyl radical, C ₂ -C ₂₀ Alkenyl radical, C ₂ -C ₂₀ Alkynyl, C ₆ -C ₄₀ Aryl or 5-to 40-memberedA heteroaryl group.

In the present invention, the term "alkyl" refers to a monovalent group derived from an alkane, which may be linked to another structural fragment; accordingly, "C ₁ -C ₂₀ Alkyl "refers to an alkyl group having 1 to 20 carbon atoms in the structure. From R ¹ Is represented by C ₁ -C ₂₀ Alkyl groups 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. C ₁ -C ₂₀ The alkyl group may be linear, branched or cyclic.

In the present invention, the term "alkenyl" refers to a monovalent group derived from an alkene, which may be attached to another structural fragment; accordingly, "C ₂ -C ₂₀ Alkenyl "means alkenyl containing from 2 to 20 carbon atoms in the structure. From R ¹ Is represented by C ₂ -C ₂₀ Alkenyl groups may be exemplified by: vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, 2-ethylhexenyl, allyl, cyclohexenyl and the like. C ₂ -C ₂₀ The alkenyl group may be linear, branched or cyclic.

In the present invention, the term "alkynyl" refers to a monovalent group derived from an alkyne, which may be linked to another structural fragment; accordingly, "C ₂ -C ₂₀ Alkynyl "refers to alkynyl groups having 2 to 20 carbon atoms in the structure. From R ¹ Is represented by C ₂ -C ₂₀ Alkynyl groups may illustrate: ethynyl, isopropynyl, butynyl, pentynyl, hexynyl,Heptynyl, octynyl, nonynyl, decynyl and the like. C ₂ -C ₂₀ Alkynyl groups may be straight chain, branched chain or cyclic.

From R ¹ Is represented by C ₆ -C ₄₀ Aryl and 5-40 membered heteroaryl groups may be exemplified by: phenyl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, benzothienocarbazolyl, benzofurocarbazolyl, benzofluorenocarbazolyl, benzanthracenyl, benzophenanthryl, fluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, indenocarbazolyl, benzimidazolyl, diphenyl-oxadiazolyl, diphenylboryl, triphenylphosphinyl, diphenylphosphinyloxy, triphenylsilyl, tetraphenylsilyl, and the like. From R ¹ Is represented by C ₆ -C ₄₀ The aryl or 5-40 membered heteroaryl may be substituted by one or more R ² And (4) substitution.

Each R ¹ All of which may have one or more R ² . When there are multiple R in the structure ² When they are the same or different from each other. Specifically, each R ² Each independently represents a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group or any of the following groups optionally substituted with one or more deuterium atoms: c ₁ -C ₂₀ Alkyl radical, C ₆ -C ₃₀ Aryl or 5-30 membered heteroaryl.

From R ² Is represented by C ₁ -C ₂₀ Alkyl groups can be exemplified by the groups described above for R ¹ Is represented by C ₁ -C ₂₀ Alkyl groups are the same group.

From R ² Is represented by C ₆ -C ₃₀ Aryl radicals may be illustrated by the above-mentioned radicals R ¹ Is represented by C ₆ -C ₄₀ Aryl is the same group.

From R ² The 5-30 membered heteroaryl group represented may be exemplified by R ¹ 5-to 40-membered heteroaryl groups represented by the formula are the same.

From R ² Is represented by C ₁ -C ₂₀ Alkyl radical, C ₆ -C ₃₀ The aryl or 5-30 membered heteroaryl group may be unsubstituted or substitutedAnd (4) a base. 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 groups, and the like.

In some embodiments of the present invention, the deuterated fluorene compound of the present invention is selected from the following compounds:

< production method >

The deuterated fluorene compound of the invention can be produced, for example, by the following method:

the purification of the resulting compound can be carried out by the following method: 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.

< organic electroluminescent device >

The organic electroluminescent device of the present invention comprises: the organic light-emitting 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 a deuterated fluorene compound of the present invention.

Fig. 4 is a view showing the configuration of an organic electroluminescent device of the present invention. As shown in fig. 4, 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, a configuration may be adopted 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 finally the anode 2, the hole transport layer 4, the electron blocking layer 5, the light-emitting layer 6, the electron transport layer 8, and the cathode 10 are provided in this order on the substrate 1.

The organic electroluminescent device according to the present invention can be manufactured by materials and methods well known in the art, except that the above organic layer contains a compound represented by the above general formula (1), (1-a), (1-B), (1-a ') or (1-B'). 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. In this case, the following production is possible: 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.

As an 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 device 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; gold such as zinc oxide, indium Tin Oxide (ITO), indium Zinc Oxide (IZO), etcA metal oxide; 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, naphthylenediamine compounds, star-shaped triphenylamine compounds, triphenylamine trimers and tetramers 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, 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.

The hole transport layer of the organic electroluminescent device of the present invention preferably contains the deuterated fluorene compound of the present invention. In addition, other known materials having a hole-transporting property can be used. Examples thereof include: a compound containing m-carbazolylphenyl; 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' -tetrakisbiphenylylbenzidine, 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 further P-doping tribromoaniline antimony hexachloride, an axial olefin derivative, or the like to a material generally used in the layer, a polymer compound having a structure of a benzidine derivative such as TPD in a partial structure thereof, or the like may be used.

As the electron blocking layer of the organic electroluminescent device of the present invention, the deuterated fluorene compound of the present invention is preferably contained. In addition, other known compounds having an electron blocking effect may be used. For example, there may be mentioned: carbazole derivatives such as 4,4',4 ″ -tris (N-carbazolyl) triphenylamine (TCTA), 9-bis [4- (carbazol-9-yl) phenyl ] fluorene, 1, 3-bis (carbazol-9-yl) benzene (mCP), and 2, 2-bis (4-carbazol-9-ylphenyl) adamantane (Ad-Cz); 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 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.

The light-emitting layer of the organic electroluminescent device of the present invention preferably contains the deuterated fluorene compound of the present invention. In addition to this, alq can also be used ₃ Various metal complexes such as metal complexes of a first 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. The deuterated fluorene compound of the present invention is preferably contained as the host material. 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, the deuterated fluorene derivative of the present invention is preferably contained. In addition to these, aromatic amine derivatives, styrylamine 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, the deuterated fluorene compound of the present invention is preferably contained. In addition, the hole-blocking layer may be formed using another compound having a hole-blocking property. For example, a phenanthroline derivative such as 2,4,6-tris (3-phenyl) -1,3,5-triazine (T2T), 1,3,5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi), bathocuproine (BCP), a metal complex of a quinolyl derivative such as aluminum (III) bis (2-methyl-8-hydroxyquinoline) -4-phenylphenylphenolate (BAlq), and a compound 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 which serves as both a hole-blocking layer and an electron-transporting layer can be formed.

As organic matter of the inventionThe electron transport layer of the electroluminescent device preferably comprises the deuterated fluorene compound. 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 element 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.

The production of the compound represented by the above general formula (1) 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 Compound 1-3-D30

[ Synthesis of Compound M1 ]

The synthetic route for compound M1 is shown below:

to a clean 250mL three-necked flask, 2- (methoxycarbonyl) phenylboronic acid (8.6g, 47.8mmol), anhydrous sodium carbonate (8.4g, 79.6mmol), 1-bromo-4-chloro-2-iodobenzene (12.6g, 39.8mmol), tetrakis (triphenylphosphine palladium) (470.8mg, 4.8mmol), and a mixed solvent of toluene, water, and ethanol (100 mL, toluene: water: ethanol =5 (1V/V)) were sequentially added under a nitrogen atmosphere. The system was gradually warmed to reflux and reacted under reflux overnight. After the reaction is completed, the heating is stopped and the reaction product is cooled to room temperature. The reaction solution was poured into water (about 200 mL) and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (stationary phase was 350 mesh silica gel, eluent was petroleum ether: dichloromethane =15 (V/V)) to obtain a white liquid (11.4 g) in 88% yield, which was the compound M1. M/z 324.26[ MS (EI) ] ⁺ ]. Elemental analysis by Combustion method C ₁₄ H ₁₀ BrClO ₂ (%), calculated C51.65 and H3.10, found C51.50 and H3.05.

[ Synthesis of Compound M2 ]

The synthetic route for compound M2 is shown below:

under a nitrogen atmosphere, compound M1 (13.0 g, 40mmol) and aqueous sodium hydroxide (100mL, 3.2g, 80mmol) were added to a clean 250mL single-neck bottle in that order. Gradually heating the system to returnFlowed and reacted under reflux overnight. And after the reaction is finished, stopping heating, and cooling to room temperature. The reaction solution was poured into a 1L beaker, 2N hydrochloric acid was added dropwise to neutralize the system until it became acidic (pH = 1.0), during which time a large amount of white solid was formed, collected by suction filtration, pressed and drained, and washed with water until the eluate became neutral. The filter cake was dried at 80 ℃ overnight to give a white solid. The white solid was placed in a 250mL two-necked flask equipped with a mechanical stirring device, polyphosphoric acid (about 80 g) was added, the temperature was gradually raised to 160 ℃, and the reaction was carried out at this temperature for 4h. After the reaction, the heating was stopped, the system was poured into a large beaker containing 1kg of ice while hot under constant stirring, and the system was neutralized to alkaline with 1N sodium hydroxide solution. The yellow solid was collected by suction filtration and washed with water until the eluate was neutral. The filter cake was dried at 80 ℃ overnight to give a yellow solid (about 8.2 g) in 70% yield, compound M2.MS (EI) m/z 291.99[ M ] ⁺ ]. Elemental analysis by Combustion method C ₁₃ H ₆ BrClO (%), calculated C53.19, H2.06, found C53.18, H2.06.

[ Synthesis of Compound M3 ]

The synthetic route for compound M3 is shown below:

under nitrogen atmosphere, a 250mL three-necked flask equipped with a reflux condenser tube and a dropping funnel was charged with elemental iodine (1g, 5.9mmol) and glacial acetic acid (100 mL), stirred to dissolve, added with hypophosphorous acid (about 3.9g,29.6 mmol), and heated to 120 ℃ to react until the system color fades. Then, compound M2 (4.3g, 14.8mmol) was added in one portion, and after further heating and refluxing for 4 hours, cooling to room temperature, pouring into water to precipitate a large amount of white solid, filtering, washing with water, and drying to obtain a white crystalline solid (3.4 g), which was compound M3, in 82% yield. MS (EI) m/z 277.48[ M ] ⁺ ]. Elemental analysis by Combustion method C ₁₃ H ₈ BrCl (%), calculated C55.85, H2.88, found C55.80, H2.85.

[ Synthesis of Compound M4 ]

The synthetic route for compound M4 is shown below:

compound M3 (3.9 g,13.9 mmol) was transferred to a 250mL three-necked flask equipped with a dropping funnel under a nitrogen atmosphere, tetrahydrofuran (100 mL) was added, dissolved with stirring, and cooled with an ice-water bath. Sodium tert-butoxide (4.0g, 41.7mmol) was added thereto in an ice bath, and after stirring for 10min at a constant temperature, methyl iodide (5.9g, 41.7mmol) was added thereto. After stirring the system for a further 30min, the ice bath was removed, the temperature was raised to room temperature and the reaction was continued at room temperature overnight. After the reaction, insoluble materials were removed by suction filtration, and the filtrate was concentrated and purified by column chromatography (stationary phase: 350 mesh silica gel, eluent: petroleum ether: dichloromethane =10 (V/V)) to obtain white crystals (3.5 g) with a yield of 82%, which was the compound M4.MS (EI) m/z 306.18[ M ] ⁺ ]. Elemental analysis by Combustion method C ₁₅ H ₁₂ BrCl (%), calculated C58.57, H3.93, found C58.50, H3.90.

[ Synthesis of Compound M5 ]

The synthetic route for compound M5 is shown below:

to a clean 250mL three-necked bottle, 10- (2-naphthyl) anthracene-9-boronic acid (16.6g, 47.8mmol), anhydrous sodium carbonate (8.4g, 79.6mmol), compound M4 (12.2g, 39.8mmol), tetrakis (triphenylphosphine palladium) (470.8mg, 4.8mmol), and a mixed solvent of toluene, water, and ethanol (100 mL, toluene: water: ethanol =5 (V/V)) were sequentially added in this order under a nitrogen atmosphere. The system was gradually warmed to reflux and reacted under reflux overnight. And after the reaction is finished, stopping heating, and cooling to room temperature. The reaction solution was poured into water (about 200 mL) and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (stationary phase was 350 mesh silica gel, eluent was petroleum ether: dichloromethane =15 (V/V)) to obtain a yellow solid (17.9 g), yield 85%, which was the compound M5.MS (EI) m-z 530.24[M ⁺ ]. Elemental analysis by Combustion method C ₃₉ H ₂₇ Cl (%), calculated C88.20, H5.12, found C88.10, H5.10.

[ Synthesis of Compound M6 ]

The synthetic route for compound M6 is shown below:

to a clean 250mL three-necked bottle, phenylboronic acid (2.9g, 23.9mmol), anhydrous sodium carbonate (4.2g, 39.8mmol), compound M5 (10.6g, 19.9mmol), tetrakis (triphenylphosphine palladium) (235.4mg, 2.4mmol), and a mixed solvent of toluene, water, and ethanol (100 mL, toluene: water: ethanol = 5. The system was gradually warmed to reflux and reacted under reflux overnight. After the reaction is completed, the heating is stopped and the reaction product is cooled to room temperature. The reaction solution was poured into water (about 200 mL) and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (stationary phase was 350 mesh silica gel, eluent was petroleum ether: dichloromethane =15 (V/V)) to obtain a yellow solid (7.4 g) in a yield of 65%, which was the compound M6.MS (EI) m/z 572.24[ M ] ⁺ ]. Elemental analysis by Combustion method C ₄₅ H ₃₂ (%), calculated C94.37, H5.63, found C94.30, H5.60.

[ Synthesis of Compound 1-3-D30 ]

The synthetic route for compounds 1-3-D30 is shown below:

a300 mL autoclave was charged with compound M6 (5.7g, 10.0 mmol), 10% palladium on carbon (0.2 g) and heavy water (150 mL) and heated to 240 ℃ for 12h. The reaction system was cooled to room temperature, extracted with dichloromethane, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and further purified by column chromatography (stationary phase was 350 mesh silica gel, eluent was petroleum ether: dichloromethane =15 (V/V)) to give a yellow solid (4.6 g), yield 80.7%, which was compound 1-3-D30.

The thermogravimetric curves of the compounds 1-3-D30 were measured by using a thermogravimetric analyzer model SDT-2960, and the results are shown in FIG. 1. As can be seen from FIG. 1, the compounds 1-3-D30 had excellent thermal stability and a thermal decomposition temperature (the temperature at which the mass percentage was reduced to 95%) of 428 ℃. The compounds 1-3-D30 have good thermodynamic properties, and have important significance for device preparation and device service life.

The molecular weight of the compounds 1-3-D30 was measured by a mass spectrometer, and the results are shown in FIG. 5. The molecular weight of compound 1-3-D30 was 602.9.

Example 2: synthesis of Compound 1-2-D25

[ Synthesis of Compound M7 ]

The synthetic route for compound M7 is shown below:

to a clean 250mL three-necked flask, phenylboronic acid (5.8g, 47.8mmol), anhydrous sodium carbonate (8.4g, 79.6mmol), compound M4 (12.2g, 39.8mmol), tetrakis (triphenylphosphine palladium) (470.8mg, 4.8mmol), and a mixed solvent of toluene, water, and ethanol (100 mL, toluene: water: ethanol = 5. The system was gradually warmed to reflux and reacted under reflux overnight. And after the reaction is finished, stopping heating, and cooling to room temperature. The reaction solution was poured into water (about 200 mL) and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (stationary phase was 350 mesh silica gel, eluent was petroleum ether: dichloromethane =15 (V/V)) to obtain a white solid (10.6 g) in 88% yield, which was the compound M7.MS (EI) m/z 304.04[ m ], [ ⁺ ]. Elemental analysis by Combustion method C ₂₁ H ₁₇ Cl (%), calculated C82.75, H5.62, found C82.70, H5.60.

[ Synthesis of Compound M13 ]

The synthetic route for compound M13 is shown below:

to a clean 250mL three-necked bottle, under a nitrogen atmosphere, were added (10-phenylanthracen-9-yl) boronic acid (7.1g, 23.9mmol), anhydrous sodium carbonate (4.2g, 39.8mmol), compound M7 (6.0g, 19.9mmol), tetrakis (triphenylphosphine palladium) (235.4mg, 2.4mmol), and a mixed solvent of toluene, water, and ethanol (100 mL, toluene: water: ethanol =5 (V/V). The system was gradually warmed to reflux and reacted under reflux overnight. After the reaction is completed, the heating is stopped and the reaction product is cooled to room temperature. The reaction solution was poured into water (about 200 mL) and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (stationary phase was 350 mesh silica gel, eluent was petroleum ether: dichloromethane =15 (V/V)) to obtain a yellow solid (6.6 g) in a yield of 63%, which was the compound M13. M/z 522.23[ MS (EI) ] ⁺ ]. Elemental analysis by Combustion method C ₄₅ H ₃₂ (%), calculated C94.21 and H5.79, found C94.11 and H5.70.

[ Synthesis of Compound 1-2-D25 ]

The synthetic route for compounds 1-2-D25 is shown below:

a300 mL autoclave was charged with Compound M13 (5.2g, 10.0 mmol), 10% palladium on carbon (0.2 g) and heavy water (150 mL), heated to 240 ℃ and reacted for 12h. The reaction system was cooled to room temperature, extracted with dichloromethane, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and further purified by column chromatography (stationary phase was 350 mesh silica gel, eluent was petroleum ether: dichloromethane =15 (V/V)) to give a yellow solid (4.2 g), yield 80.7%, which was compound 1-2-D25.

The molecular weight of the compounds 1-2-D25 was measured by a mass spectrometer, and the results are shown in FIG. 6. The molecular weight of compound 1-2-D25 is 547.1.

Example 3: synthesis of Compound 1-1-D25

[ Synthesis of Compound M9 ]

The synthetic route for compound M9 is shown below:

to a clean 250mL three-necked bottle were added (10-phenylanthracen-9-yl) boronic acid (14.2g, 47.8mmol), anhydrous sodium carbonate (8.4g, 79.6mmol), compound M4 (12.2g, 39.8mmol), tetrakis (triphenylphosphine palladium) (470.8mg, 4.8mmol), and a mixed solvent of toluene, water, and ethanol (100 mL, toluene: water: ethanol =5 (V/V)) in this order under a nitrogen atmosphere. The system was gradually warmed to reflux and reacted under reflux overnight. After the reaction is completed, the heating is stopped and the reaction product is cooled to room temperature. The reaction solution was poured into water (about 200 mL) and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (stationary phase was 350 mesh silica gel, eluent was petroleum ether: dichloromethane =15 (V/V)) to obtain a yellow solid (15.7 g), yield 82%, which was the compound M9.MS (EI) m/z 480.24[ m ] ⁺ ]. Elemental analysis by Combustion method C ₃₅ H ₂₅ Cl (%), calculated C87.39, H5.24, found C87.30, H5.20.

[ Synthesis of Compound M10 ]

The synthetic route for compound M10 is shown below:

to a clean 250mL three-necked flask, phenylboronic acid (2.9g, 23.9mmol), anhydrous sodium carbonate (4.2g, 39.8mmol), compound M9 (9.6g, 19.9mmol), tetrakis (triphenylphosphine palladium) (235.4mg, 2.4mmol), and a mixed solvent of toluene, water, and ethanol (100 mL, toluene: water: ethanol = 5. The system was gradually warmed to reflux and reacted under reflux overnight. After the reaction is completed, the heating is stopped and the reaction product is cooled to room temperature. The reaction solution was poured into water (about 200 mL) and extracted with dichloromethane. Anhydrous sulfur for organic phaseSodium salt is dried, concentrated under reduced pressure, and further purified by column chromatography (stationary phase is 350 mesh silica gel, eluent is petroleum ether: dichloromethane =15 (V/V)) to give a yellow solid (6.8 g), yield 65%, which is compound M10. M/z 522.24[ MS (EI) ] ⁺ ]. Elemental analysis by Combustion method C ₄₁ H ₃₀ (%), calculated C94.21 and H5.79, found C94.10 and H5.75.

[ Synthesis of Compounds 1-1-D25 ]

The synthetic route for compounds 1-1-D25 is shown below:

a300 mL autoclave was charged with Compound M10 (5.3 g,10.1 mmol), 10% palladium on carbon (0.2 g) and heavy water (150 mL), heated to 240 ℃ and reacted for 12h. The reaction system was cooled to room temperature, extracted with dichloromethane, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and further purified by column chromatography (stationary phase was 350 mesh silica gel, eluent was petroleum ether: dichloromethane =15 (V/V)) to give a yellow solid (4.4 g), yield 82.7%, which was compound 1-1-D25.

The molecular weights of the compounds 1-1-D25 were measured by a mass spectrometer, and the results are shown in FIG. 7. The molecular weight of compounds 1-1-D25 was 547.2.

Example 4: synthesis of Compounds 1-49-D30

[ Synthesis of Compound M11 ]

The synthetic route for compound M11 is shown below:

to a clean 250mL three-necked flask, 2-naphthoic acid (3.4g, 23.9mmol), anhydrous sodium carbonate (4.2g, 39.8mmol), compound M5 (10.6g, 19.9mmol), tetrakis (triphenylphosphine palladium) (235.4mg, 2.4mmol), and a mixed solvent of toluene, water, and ethanol (100 mL, toluene: water: ethanol = 5. Gradually heating the system to reflux and keeping the system in a reflux stateThe reaction was continued overnight. After the reaction is completed, the heating is stopped and the reaction product is cooled to room temperature. The reaction solution was poured into water (about 200 mL) and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (stationary phase was 350 mesh silica gel, eluent was petroleum ether: dichloromethane =15 (V/V)) to obtain a yellow solid (7.5 g) in a yield of 60%, which was the compound M11.MS (EI) m/z 622.27[ M ] ⁺ ]. Elemental analysis by Combustion method C ₄₉ H ₃₄ (%), calculated C94.50, H5.50, found C94.40, H5.45.

[ Synthesis of Compounds 1-49-D30 ]

The synthetic routes for compounds 1-49-D30 are shown below:

a300 mL autoclave was charged with Compound M11 (6.2g, 10.0 mmol), 10% palladium on carbon (0.2 g) and heavy water (150 mL), heated to 240 ℃ and reacted for 12h. The reaction system was cooled to room temperature, extracted with dichloromethane, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and further purified by column chromatography (stationary phase was 350 mesh silica gel, eluent was petroleum ether: dichloromethane =15 (V/V)) to give a yellow solid (5.1 g), yield 81.6%, which was compound 1-49-D30.

The thermogravimetric curves of the compounds 1 to 49 to D30 were measured by using a thermogravimetric analyzer model SDT-2960, and the results are shown in FIG. 1. As can be seen from FIG. 1, the compounds 1 to 49-D30 had excellent thermal stability and a thermal decomposition temperature (a temperature at which the mass percentage was reduced to 95%) of 442 ℃. The compounds 1-49-D30 have good thermodynamic properties, and have important significance for device preparation and device service life.

The molecular weights of compounds 1-49-D30 were measured using a mass spectrometer, and the results are shown in FIG. 8. Compounds 1-49-D30 have a molecular weight of 652.9.

Example 5: preparation of organic electroluminescent device 1 (organic EL device 1)

A hole injection layer 3, a hole transport layer 4, a light emitting layer 6, an electron transport layer 8, an electron injection layer 9, and a cathode 10 were sequentially formed on a transparent anode 2 previously formed on a glass substrate 1 to prepare an organic electroluminescent device as shown in fig. 4 (but without an electron blocking layer 5 and a hole blocking layer 7).

Specifically, a glass substrate on which an ITO film having a film thickness of 100nm was formed was subjected to ultrasonic treatment in a Decon 90 alkaline cleaning solution, rinsed in deionized water, washed three times in acetone and ethanol, respectively, baked in a clean environment to completely remove moisture, washed with ultraviolet light and ozone, and bombarded on the surface with a low-energy cation beam. Placing the glass substrate with ITO electrode into a vacuum chamber, and vacuumizing to 4 × 10 ^-4 -2×10 ^-5 Pa. Then, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene (HAT-CN) was vapor-deposited on the above glass substrate with an ITO electrode at a vapor deposition rate of 0.2nm/s to form a layer having a film thickness of 10nm as a Hole Injection Layer (HIL). N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB) was vapor-deposited on the hole injection layer at a vapor deposition rate of 0.2 nm/sec to form a layer having a film thickness of 30nm as a Hole Transport Layer (HTL). On the hole transport layer, the evaporation rate of the compound (compound 1-3D 30) in example 1 as a host material was 0.2nm/s and N as a dopant material ¹ ,N ⁶ -bis (dibenzo [ b, d)]Furan-4-yl) -3, 8-diisopropyl-N ¹ ,N ⁶ Double-source co-evaporation was performed at an evaporation rate of 0.2nm/s for bis (4-isopropylphenyl) pyrene-1, 6-diamine (BD 1) to form a layer having a thickness of 20nm as a light-emitting layer, and the doping weight ratio of BD1 was 8wt%. 2- [4- (9, 10-dinaphthalene-2-anthracene-2-yl) phenyl is evaporated on the luminescent layer at an evaporation rate of 0.2nm/s]-1-phenyl-1H-benzimidazole (ZADN) to form a layer with a thickness of 40nm as Electron Transport Layer (ETL). 8-hydroxyquinoline-lithium (Liq) was vapor-deposited on the electron transport layer at a vapor deposition rate of 0.02nm/s to form a layer having a thickness of 2nm as an Electron Injection Layer (EIL). Finally, aluminum is deposited on the electron injection layer at a deposition rate of 0.5nm/s or more to form a cathode having a film thickness of 100 nm.

Examples 6 to 12: preparation of organic EL devices 2-8

Organic EL devices 2 to 8 were prepared, respectively, with reference to the preparation conditions of the organic EL device 1 in example 5 and using the compounds corresponding to the respective layer structures in table 1.

Comparative examples 1 to 6: preparation of organic EL devices comparative examples 1 to 6

Organic EL device comparative examples 1 to 6 were prepared, respectively, referring to the preparation conditions of the organic EL device 1 in example 5 and using the compounds corresponding to the respective layer structures in table 1.

The structures of the organic EL devices prepared in inventive examples 6 to 12 (organic EL devices 2 to 8) and comparative examples 1 to 6 (organic EL devices comparative examples 1 to 6) and the film thicknesses of the respective layers are shown in table 1.

TABLE 1

The examples and comparative examples relate to the following structures of compounds:

the light emission characteristics of the organic EL devices 1 to 8 produced in examples 5 to 12 and the organic EL devices produced in comparative examples 1 to 6 were measured in the atmosphere at normal temperature while applying a direct current voltage. The current-luminance-voltage characteristics of the device were obtained from a Keithley source measuring system (Keithley 2400 Sourcemeter, keithley 2000 Currentmeter) with a calibrated silicon photodiode, the electroluminescence spectrum was measured by a Photo research PR655 spectrometer, the external quantum efficiency of the device was calculated by the method described in adv.mater.,2003,15,1043-1048, and the measurement results are shown in table 2.

TABLE 2

The devices in the embodiment shown in table 2 adopt different deuterated fluorene materials containing 1, 4-position substitution as host materials of the blue light emitting layer, and are matched with three different blue light guest materials. The comparative example devices in table 2 used BH1 containing deuterium atoms and dibenzofuran fragments, and BH2 and BH3 belonging to aromatic hydrocarbons as host materials for the blue light emitting layer, and the same blue light guest. As can be seen from table 2, the efficiency and lifetime of the devices of the examples are significantly higher than those of the devices of the comparative examples, and the devices using the 1,4-position disubstituted deuterofluorene materials generally have better efficiency and lifetime.

Therefore, compared with the materials commonly used in the prior art, the deuterated fluorene compound can effectively reduce the working voltage, improve the external quantum efficiency and prolong the service life of the device.

Industrial applicability

The deuterated fluorene compound has excellent luminous efficiency, life characteristics and low driving voltage. Therefore, organic electroluminescent devices, especially blue organic electroluminescent devices, having excellent service life can be prepared from the compound.

Claims (13)

1. A deuterated fluorene compound represented by the following general formula (1):

wherein, the first and the second end of the pipe are connected with each other,

each A independently represents Ar;

each Ar independently represents C ₆ -C ₃₀ An aryl group; said C is ₆ -C ₃₀ Each aryl group independently represents any one of the following groups: phenyl, naphthyl or anthracenyl;

each L independently represents a single bond or C ₆ -C ₁₈ An arylene group; said C is ₆ -C ₁₈ Each arylene group independently represents any one of the following groups: phenylene, naphthylene or anthracenylene;

m represents C (R) ¹ ) ₂ (ii) a Wherein each R is ¹ Each independently represents C ₁ -C ₂₀ An alkyl group; said C is ₁ -C ₂₀ Alkyl radicalEach independently represents any one of the following groups: 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 or n-decyl;

each Z independently represents CR ¹ (ii) a Wherein each R is ¹ Each independently represents a hydrogen atom;

dn represents n hydrogen atoms substituted by deuterium atoms;

n represents any integer of 6 or more.

2. The deuterated fluorene compound according to claim 1, wherein each Ar independently represents any one of the following groups:

wherein, the first and the second end of the pipe are connected with each other,

the dotted line represents a bond;

each R ¹ Each independently represents a hydrogen atom.

3. The deuterated fluorene compound of claim 1, wherein each L independently represents a single bond or any one of the following groups:

wherein the dotted line represents the bond to the parent nucleus and the A fragment.

4. The deuterated fluorene-based compound according to claim 1, which is selected from the following compounds:

5. a light-emitting device comprising the deuterated fluorene-based compound according to any one of claims 1-4.

6. The light-emitting device according to claim 5, wherein the light-emitting device is an organic electroluminescent device, and the light-emitting 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, the at least one organic layer containing the deuterated fluorene-based compound according to any one of claims 1 to 4.

7. The light-emitting device according to claim 6, wherein the light-emitting device is a blue organic electroluminescent device.

8. The light-emitting device according to claim 6, wherein the at least one organic layer is a hole-transport layer, an electron-blocking layer, a light-emitting layer, a hole-blocking layer, or an electron-transport layer.

9. The light-emitting device according to claim 8, wherein the at least one organic layer is a light-emitting layer.

10. The light-emitting device according to claim 8, wherein the light-emitting layer comprises a host material and a guest material, and wherein the host material comprises the deuterated fluorene compound according to any one of claims 1 to 4.

11. Use of the deuterated fluorene-based compound according to any one of claims 1-4 as a light-emitting material in a light-emitting device.

12. Use according to claim 11, characterized in that the light-emitting device is an organic electroluminescent device.

13. Use according to claim 11, characterized in that the light-emitting device is a blue organic electroluminescent device.

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