JP7152816B2 - Nitrogen-containing compound, photoelectric conversion device and electronic device - Google Patents

Description

This application is filed on August 23, 2019, application number CN201910785145. X claims priority from the Chinese patent application, and the entire contents disclosed in the Chinese patent application are incorporated herein by reference as part of this disclosure.

The present application relates to the field of optoelectronic technology, in particular to nitrogen-containing compounds, photovoltaic devices and electronic devices.

In recent years, organic electroluminescent devices (OLEDs) have gradually attracted attention as a new generation of display technology. A typical organic electroluminescent device consists of an anode, a cathode and organic layers between the cathode and the anode. When a voltage is applied to the cathode and the anode, an electric field is generated between the two electrodes. Under the action of the electric field, the electrons on the cathode side and the holes on the anode side simultaneously move to the functional layer and are combined in the functional layer. It becomes an exciton, and the exciton in an excited state releases energy to the outside, and emits light to the outside in the process of changing from the excited state to the ground state. Therefore, it is of great importance to improve the recombination of electrons and holes in OLED devices.

A photoelectric conversion device is generally provided with an electron barrier layer, an electron transport layer, and the like in order to improve the life of the device. However, current devices suffer from low efficiency. Therefore, how to design new materials with better performance, such as electron barrier layers and electron transport layers, to achieve the effect of lowering the voltage, increasing the photoelectric conversion efficiency and extending the lifetime in all devices. has traditionally been a problem for those skilled in the art.

Prior art documents such as CN102224150B, CN103827257B, CN105061371B and CN108137500A have also investigated this.

It should be noted that the information disclosed in the Background section above is merely to enhance the understanding of the background of the present application and, therefore, may include information that does not constitute prior art known to those skilled in the art. good.

SUMMARY OF THE INVENTION It is an object of the present application to provide a nitrogen-containing compound and a photovoltaic device capable of overcoming the above deficiencies of the prior art, improving the photovoltaic conversion efficiency and extending the life of the device.

（式中、Ａｒ_１及びＡｒ_２は、それぞれ独立的に、置換又は未置換の炭素原子数６～３０のアリール基から選ばれ、前記Ａｒ_１及び前記Ａｒ_２の置換基は、同じであるか又は異なり、且つそれぞれ独立的に、重水素、トリチウム、ハロゲン、シアノ基、アミノ基、ヒドロキシ基、ニトロ基、炭素原子数１～２０のアルキル基、炭素原子数３～２０のシクロアルキル基、炭素原子数６～３０のアリール基から選ばれる。） According to one aspect of the present application, nitrogen-containing compounds having the general structural formula shown in Formula I are provided.

(In the formula, Ar ₁ and Ar ₂ are each independently selected from substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, and are the substituents of Ar ₁ and Ar ₂ the same? or different and each independently deuterium, tritium, halogen, cyano group, amino group, hydroxy group, nitro group, alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, carbon selected from aryl groups having 6 to 30 atoms.)

In some embodiments of the present application, said Ar ₁ and said Ar ₂ are each independently selected from substituted or unsubstituted cyclic aryl groups having 6 to 20 carbon atoms,
The substituents of said Ar ₁ and said Ar ₂ are the same or different and each independently deuterium, tritium, halogen, cyano group, amino group, hydroxy group, nitro group, 1-20 carbon atoms , cycloalkyl groups having 3 to 20 carbon atoms, and aryl groups having 6 to 30 carbon atoms.

（式中、＊は、上記の基が式Ｉにおける

基に結合されるためのものであることを示す。） In some embodiments of the present application, said Ar ₁ and said Ar ₂ are the same or different and each independently selected from the following groups.

(Wherein, * indicates that the above group is

Indicates that it is intended to be attached to a group. )

According to one aspect of the present application, comprising an anode and a cathode facing each other, and a functional layer provided between the anode and the cathode,
A photoelectric conversion device is provided, wherein the functional layer contains the nitrogen-containing compound.

In some embodiments of the present application, said functional layer comprises an electron barrier layer, said electron barrier layer comprising said nitrogen-containing compound.

In some embodiments of the application, the functional layer comprises:
a light-emitting layer provided on a side of the electron barrier layer remote from the anode;
a hole transport layer provided on the side of the electron barrier layer remote from the light emitting layer;
An electron transport layer provided between the light emitting layer and the cathode is further included.

In some embodiments of the application, the photovoltaic device is an organic electroluminescent device.

According to one aspect of the present application, there is provided an electronic apparatus comprising the photoelectric conversion device according to any one of the above.

In some embodiments of the application, the photovoltaic device is a solar cell.

Nitrogen-containing compounds, photoelectric conversion devices, and electronic devices according to the present application, on the one hand, reduce the distance between the nitrogen atoms by linking the nitrogen atoms of the carbazole and the nitrogen atoms of the triarylamine with a phenylene group; The angle between the plane of the amine and the carbazole can be made small. This allows the HOMO energy levels of the material to be distributed simultaneously on the triarylamine and carbazole groups by conjugation. Thereby, the hole mobility of the material can be increased and the photoelectric conversion efficiency of the device can be increased. On the one hand, different branch lengths reduce the symmetry of the molecule, further enhancing the amorphous alignment of the material, and on the other two branches of the triarylamine, the introduction of large-planar condensed ring groups on the other two branches of the triarylamine It can effectively disperse the electron cloud density for the amine, avoid the breaking of the C—N bond, and increase the molecular space volume by the vertical configuration condensed ring connection method, and the crystal effect due to the intermolecular stacking. can be reduced, thereby lowering the operating voltage of the device and extending the life of the device.

It should be understood that the above general description and the following detailed description are exemplary and interpretive only and are not intended to limit the present application.

The drawings herein are incorporated in and constitute a part of the specification, illustrate embodiments consistent with the application, and are used together with the specification to interpret the principles of the application. It is obvious that the drawings in the following description are only part of the embodiments of the present application, and those skilled in the art can obtain other drawings based on these drawings without creative efforts. can.
1 is a structural schematic diagram of an organic electroluminescent device in an embodiment of the present application; FIG. 1 is a hydrogen spectrum test diagram of compound 1 in an embodiment of the present application; FIG. FIG. 4 is a hydrogen spectrum test diagram of compound 5 in an embodiment of the present application; Figure 2 is a HOMO energy level diagram of Compound 1 in the present application; Figure 2 is a HOMO energy level diagram of compound A in the present application;

Exemplary embodiments are described more comprehensively below with reference to the drawings. However, the example embodiments may be embodied in multiple forms and should not be construed as limited to the examples set forth herein, but rather these embodiments provide a more thorough and It is provided for completeness and to fully convey the concept of the exemplary embodiments to those skilled in the art. The described features, structures or characteristics may be incorporated in one or more embodiments in any suitable manner. In the following description, numerous details are provided to provide a thorough understanding of the embodiments of the present application.

The terms "said," "this," and "said" mean the presence of one or more elements, components, etc., and the terms "including," and "having" are meant to include openly. and that there may be other elements, components, etc. in addition to the listed elements, components, etc.

（式中、Ａｒ_１及びＡｒ_２は、それぞれ独立的に、置換又は未置換の炭素原子数６～３０のアリール基から選ばれ、
前記Ａｒ_１及び前記Ａｒ_２の置換基は、同じであるか又は異なり、且つそれぞれ独立的に、重水素、トリチウム、ハロゲン、シアノ基、アミノ基、ヒドロキシ基、ニトロ基、炭素原子数１～２０のアルキル基、炭素原子数３～２０のシクロアルキル基、炭素原子数６～３０のアリール基から選ばれる。） Embodiments of the present application provide nitrogen-containing compounds whose general structural formula is shown in Formula I.

(wherein Ar ₁ and Ar ₂ are each independently selected from substituted or unsubstituted aryl groups having 6 to 30 carbon atoms,
The substituents of said Ar ₁ and said Ar ₂ are the same or different and each independently deuterium, tritium, halogen, cyano group, amino group, hydroxy group, nitro group, 1-20 carbon atoms , cycloalkyl groups having 3 to 20 carbon atoms, and aryl groups having 6 to 30 carbon atoms. )

The nitrogen-containing compound according to the present application, on the one hand, reduces the distance between the nitrogen atoms by linking the nitrogen atom of the carbazole and the nitrogen atom of the triarylamine with a phenylene group, and further reduces the distance between the nitrogen atoms and the plane of the triarylamine and the carbazole. The angle can be made smaller. This allows the HOMO energy levels of the material to be conjugatively distributed over the triarylamine and carbazole groups simultaneously. Thereby, the hole mobility of the material can be increased and the photoelectric conversion efficiency of the device can be increased. On the one hand, different branch lengths can reduce the symmetry of the molecule and further enhance the amorphous alignment of the material, and on the other two branches of the triarylamine, by introducing large planar fused ring groups, , can also effectively disperse the electron cloud density for triarylamines, avoid breaking the C—N bond, and increase the molecular space volume through the vertical configuration of condensed ring linkage method, and the intermolecular stacking can reduce the crystalline effect due to , thereby lowering the operating voltage of the device and extending the lifetime of the device.

Each portion of the nitrogen-containing compound in the embodiments of the present application will be described in detail below.

意味が同じであり、全て他の置換基又は結合位置と結合する位置を指すものである。 In this application,

They have the same meaning, and all refer to positions that bind to other substituents or binding positions.

において、式中、各ｑは独立的に０、１、２又は３であり、各Ｒ”は独立的に、水素、フッ素、塩素から選ばれる」という説明において、その意味は、式Ｑ－１は、ベンゼン環にｑ個の置換基Ｒ”を有し、各Ｒ”が同じであってもよく、異なってもよく、各Ｒ”の選択肢同士が互いに影響を与えないことを意味し、式Ｑ－２はビフェニルのそれぞれのベンゼン環上にｑ個の置換基Ｒ”を有し、２つのベンゼン環におけるＲ”置換基の個数ｑが同じであってもよく、異なってもよく、各Ｒ”が同じであってもよく、異なってもよく、各Ｒ”の選択肢同士が互いに影響を与えないことを意味する。 As used in this application, the expressions "each independently", "each independently", and "independently selected from" are interchangeable and are all broadly understood. It may mean that specific options represented by the same symbols in different groups do not affect each other, and specific options represented by the same symbols in the same group do not affect each other. may mean not giving for example,"

in the formula, wherein each q is independently 0, 1, 2 or 3, and each R″ is independently selected from hydrogen, fluorine, and chlorine” means the formula Q-1 has q substituents R″ on the benzene ring, each R″ may be the same or different, meaning that the choices for each R″ do not affect each other; Q-2 has q substituents R″ on each benzene ring of biphenyl, and the number q of R″ substituents on the two benzene rings may be the same or different, and each R " may be the same or different, meaning that the alternatives for each R" do not affect each other.

As used in this application, the term "substituted or unsubstituted" means free of substituents or substituted with one or more substituents. The substituents include deuterium, halogen groups (F, Cl, Br), cyano groups, alkyl groups, alkenyl groups, alkynyl groups, halogenated alkyl groups, aryl groups, heteroaryl groups, aryloxy groups, arylthio groups, and alkylamines. arylamine groups, cycloalkyl groups, heterocyclic groups, trialkylsilyl groups, alkyl groups, cycloalkyl groups, alkoxy groups, alkylthio groups.

を指し、当該結合の一端がこの結合の貫通する環系の任意の位置に連結され、他端が化合物分子の残りの部分に連結されてもよいことを意味する。例えば、下記式（Ｘ’）に示されるように、式（Ｘ’）に示されるフェナントリル基は、一側のベンゼン環の中間から張り出した位置の非特定する結合を介して分子の残りの位置に連結され、それが表す意味として、式（Ｘ’－１）～式（Ｘ’－４）に示されるようないずれか１つの可能な連結方式を含むことである。

A non-specifying bond in the present application refers to a single bond pendent from the ring system

means that one end of the bond may be attached to any position of the ring system through which the bond passes and the other end may be attached to the remainder of the compound molecule. For example, as shown in formula (X′) below, the phenanthryl group shown in formula (X′) is attached to the remaining position of the molecule via a non-specified bond at a position overhanging from the middle of the benzene ring on one side. and is meant to include any one possible linking scheme as shown in formulas (X'-1) to (X'-4).

式中、Ａｒ_１及びＡｒ_２は、それぞれ独立的に、置換又は未置換の炭素原子数６～３０のアリール基から選ばれてもよい。説明すべきことは、Ａｒ_１及びＡｒ_２のうちの１又は２は識別子として使用されるものに過ぎず、数を限定するためのものではない。 The general structural formula for the nitrogen-containing compounds of the present application is shown in Formula I.

In the formula, Ar ₁ and Ar ₂ may be independently selected from substituted or unsubstituted aryl groups having 6 to 30 carbon atoms. It should be noted that 1 or 2 of Ar ₁ and Ar ₂ are only used as identifiers and not for limiting numbers.

In this application, an aryl group refers to any functional group or substituent derived from an aromatic carbocycle. The aryl group may be a monocyclic aryl group or a polycyclic aryl group, in other words, the aryl group may be a monocyclic aryl group, a fused ring aryl group, or two groups conjugated through a carbon-carbon bond. the above monocyclic aryl groups, monocyclic aryl groups and condensed ring aryl groups conjugated through a carbon-carbon bond, and two or more condensed ring aryl groups conjugated through a carbon-carbon bond; There may be. That is, two or more aromatic groups conjugated via carbon-carbon bonds can also be considered aryl groups in the present application. Here, the condensed ring aryl group may include, for example, a bicyclic condensed aryl group (eg, naphthyl group), a tricyclic condensed aryl group (eg, phenanthryl group, fluorene group, anthryl group), and the like. Here, the aryl group does not contain heteroatoms such as B, N, O, S, P, Se and Si. For example, in this application, biphenyl groups, terphenyl groups, etc. are aryl groups. Examples of aryl groups are phenyl, naphthyl, fluorene, anthryl, phenanthryl, biphenyl, terphenyl, quaterphenyl, quinquephenyl, benzo[9,10]phenanthryl, pyrenyl. , a benzofluoranthenyl group, a chrysene group, and the like, but are not limited thereto. An "aryl group" of the present application may contain from 6 to 20 carbon atoms, and in some embodiments the number of carbon atoms in an aryl group may be from 6 to 18; By way of example, the aryl group may have from 6 to 12 carbon atoms. For example, the aryl group may have 6, 12, 13, 15, 18 or 20 carbon atoms, but may of course have other numbers of carbon atoms, I cannot list them one by one here.

In this application, substituted aryl groups are those in which one or more hydrogen atoms in the aryl group are, for example, deuterium, tritium, halogen, cyano groups, amino groups, hydroxy groups, nitro It may be substituted with a group such as an alkyl group, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 30 carbon atoms. It is to be understood that the number of carbon atoms in a substituted aryl group refers to the total number of carbon atoms in the aryl group and the substituents on the aryl group, e.g. and that the total number of carbon atoms in the substituent is 18.

In this application, an "alkyl group" may include linear or branched alkyl groups. Alkyl groups may have from 1 to 20 carbon atoms, and in this application a numerical range such as "1 to 20" refers to each integer within a given range, such as 1, 2, 3 , 4, 5, 6, 7, 8, 9, 10, 11 and 12, and for example, “alkyl group having 1 to 12 carbon atoms” refers to 1 carbon atom, 2 carbon atoms , 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms, 10 carbon atoms, 11 Refers to alkyl groups containing 1 or 12 carbon atoms. The alkyl group may be a medium size alkyl group having from 1 to 10 carbon atoms. Alkyl groups may also be lower alkyl groups having 1 to 6 carbon atoms. In some other embodiments, alkyl groups contain 1-4 carbon atoms, and in some further embodiments, alkyl groups contain 1-3 carbon atoms. Said alkyl groups may be optionally substituted with one or more substituents described in this invention. Examples of alkyl groups are methyl (Me, —CH ₃ ), ethyl (Et, —CH ₂ CH ₃ ), n-propyl (n-Pr, —CH ₂ CH ₂ CH ₃ ), isopropyl (i —Pr, —CH(CH ₃ ) ₂ ), n-butyl group (n-Bu, —CH ₂ CH ₂ CH ₂ CH ₃ ), isobutyl group (i-Bu, —CH ₂ CH(CH ₃ ) ₂ ), Including, but not limited to, s-butyl groups (s-Bu, --CH(CH ₃ )CH ₂ CH ₃ ), t-butyl groups (t-Bu, --C(CH ₃ ) ₃ ), and the like. Furthermore, alkyl groups can be substituted or unsubstituted.

In one embodiment, Ar ₁ and Ar ₂ may each be independently selected from substituted or unsubstituted aryl groups having 6 to 20 ring carbon atoms.

For example, the number of carbon atoms forming the ring may be 6, 10, 14, 16 or 20, but of course the number of carbon atoms forming the ring may be other numbers, I cannot list them one by one here. Here, substituted means that at least one hydrogen atom in Ar ₁ and Ar ₂ is replaced with a substituent. The substituents of Ar ₁ and Ar ₂ may be the same or different, and both Ar ₁ and Ar ₂ are each independently deuterium, tritium, halogen, cyano group, amino group, hydroxy nitro group, alkyl group of 1 to 20 carbon atoms, cycloalkyl group of 3 to 20 carbon atoms, aryl group of 6 to 30 carbon atoms. In the present application, "an aryl group having 6 to 20 carbon atoms forming a ring" refers to an aryl group having 6 to 20 carbon atoms on the aromatic ring, and a substituent on the aryl group The number of carbon atoms in is omitted. In some embodiments of the present invention, the aryl group of the present invention has 6 to 20 ring carbon atoms, and in some further embodiments of the present invention, the aryl group of the present invention has The number of carbon atoms forming the ring is 6 to 12, but is not limited thereto. Illustratively, the fluorene group is an aryl group having 13 carbon atoms forming a ring, and the 9,9-dimethylfluorene group is a substituted aryl group having 15 carbon atoms.

In some embodiments of the present application, the substituents on said Ar ₁ and said Ar ₂ are each independently deuterium, tritium, fluorine, chlorine, bromine, cyano, methyl, ethyl, isopropyl , t-butyl group, phenyl group, naphthyl group, dibiphenyl group, terphenyl group, fluorene group and 9,9-dimethylfluorene group.

式中、各Ａ_１～Ａ_１９は、それぞれ独立的に、重水素、トリチウム、フッ素、塩素、臭素、シアノ基、炭素原子数１～４のアルキル基、炭素原子数３～１０のシクロアルキル基、炭素原子数６～１５のアリール基から選ばれ、
ｂ_１～ｂ_１９はｂ_ｋで示され、Ａ_１～Ａ_１９はＡ_ｋで示され、ｋは１～１９の任意の整数を示す変数であり、ｂ_ｋは置換基Ａ_ｋの個数を示す場合には、ｂ_ｋが１よりも大きい場合、対応する置換基Ａ_ｋは、同じであるか又は異なり、
ここで、ｋが１、３、６、１４、１５、１７又は１９から選ばれる場合、ｂ_ｋは０、１、２、３、４又は５から選ばれ、
ｋが２、４、９、１１、１３又は１８から選ばれる場合、ｂ_ｋは０、１、２、３又は４から選ばれ、
ｋが５、１２、１６から選ばれる場合、ｂ_ｋは０、１、２又は３から選ばれ、
ｋが１０から選ばれる場合、ｂ_ｋは１、２、３、４、５又は６から選ばれ、
ｋが７から選ばれる場合、ｂ_ｋは０、１、２、３、４、５、６又は７から選ばれ、
ｋが８から選ばれる場合、ｂ_ｋは０、１、２、３、４、５、６、７、８又は９から選ばれる。 In some embodiments of the present application, said Ar ₁ and said Ar ₂ are each independently selected from the group consisting of the following general formulae.

In the formula, each of A ₁ to A ₁₉ is independently deuterium, tritium, fluorine, chlorine, bromine, cyano group, alkyl group having 1 to 4 carbon atoms, cycloalkyl group having 3 to 10 carbon atoms , an aryl group having 6 to 15 carbon atoms,
b ₁ to b ₁₉ are represented by b _k , A ₁ to A ₁₉ are represented by A _k , k is a variable representing an arbitrary integer from 1 to 19, and b _k represents the number of substituents A _k optionally, when b _k is greater than 1, the corresponding substituents A _k are the same or different,
wherein b _k is selected from 0, 1, 2, 3, 4 or 5 when k is selected from 1, 3, 6, 14, 15, 17 or 19;
b _k is selected from 0, 1, 2, 3 or 4 when k is selected from 2, 4, 9, 11, 13 or 18;
when k is chosen from 5, 12, 16, b _k is chosen from 0, 1, 2 or 3;
when _k is selected from 10, bk is selected from 1, 2, 3, 4, 5 or 6;
when k is selected from 7, b _k is selected from 0, 1, 2, 3, 4, 5, 6 or 7;
When _k is chosen from 8, bk is chosen from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9.

In some embodiments of the present application, said Ar ₁ and said Ar ₂ are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted dibiphenyl group, a substituted or unsubstituted terphenyl group; substituted or unsubstituted naphthyl group, substituted or unsubstituted anthryl group, substituted or unsubstituted phenanthryl group, substituted or unsubstituted pyrenyl group, substituted or unsubstituted perylene group, substituted or unsubstituted chrysene group or substituted or selected from unsubstituted fluorene groups, wherein said substitution is deuterium, tritium, fluorine, chlorine, bromine, cyano, methyl, ethyl, isopropyl, t-butyl, phenyl or naphthyl; substituted with substituents independently selected from

In some embodiments of the present application, said Ar ₁ and said Ar ₂ are each independently selected from the following groups.

式中、＊は、上記の基が式Ｉにおける

に結合されるためのものであることを示す。勿論、Ａｒ_１及びＡｒ_２は、他の基から選ばれてもよく、ここでは特に限定しない。 In some embodiments, Ar ₁ and Ar ₂ may be the same or different, and each Ar ₁ and Ar ₂ may be independently selected from the following groups.

wherein * indicates that the above group is

indicates that it is intended to be bound to Of course, Ar ₁ and Ar ₂ may be selected from other groups and are not particularly limited here.

となることはない。
一実施形態では、窒素含有化合物は、下記化合物から選ばれてもよい。

In some embodiments, in Formula I, Ar ₁ and Ar ₂ are simultaneously

will not be.
In one embodiment, the nitrogen-containing compound may be selected from the following compounds.

It should be noted that the above nitrogen-containing compounds are only exemplary nitrogen-containing compounds, and other nitrogen-containing compounds may also be included and are not listed here one by one.

EXAMPLES The process of synthesizing the nitrogen-containing compound of the present application will be described in detail below through examples. However, the examples below are merely illustrative of the present application and are not intended to limit the present application.

All reagents and materials used in the examples herein are purchased from commercial suppliers unless otherwise specified.

Low resolution mass spectrometry (MS): Agilent 6120 quadrupole HPLC-M (column specifications: Zorbax SB-C18, 2.1 x 30 mm, 3.5 μm, 6 min, flow rate 0.5 mL/min; mobile phase: 5 %-95% (percentage of CH ₃ CN with 0.1% formate in H ₂ O with 0.1% formate, detected by UV at 210 nm/254 nm using electrospray ionization (ESI)).

Nuclear magnetic resonance hydrogen spectra: Bruker 400 MHz nuclear magnetic resonance instrument, room temperature conditions, CD ₂ Cl ₂ or CDCl ₃ as solvent (in ppm), TMS (0 ppm) as reference standard.

４’－クロロビフェニル－４－ボロン酸（３０．００ｇ、１２９．０４ｍｍｏｌ）、１－ブロモナフタレン（２６．７２ｇ、１２９．０４ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム（７．４５ｇ、６．４５ｍｍｏｌ）、炭酸カリウム（３５．６７ｇ、２５８．０９ｍｍｏｌ）、テトラブチルアンモニウムクロリド（１．４７ｇ、６．４５ｍｍｏｌ）、トルエン（２４０ｍＬ）、エタノール（１２０ｍＬ）、及び脱イオン水（３６ｍＬ）を三口フラスコに加え、窒素ガス保護下で、７５℃～８０℃に昇温させ、加熱して還流させ、４ｈ撹拌した。反応の終了後、溶液を室温に冷却させて、ジクロロメタン及び水を加えて反応液を抽出し、有機相を合併し、無水硫酸マグネシウムで有機相を乾燥させて、ろ過してろ液を得て濃縮させ、シリカゲルカラムクロマトグラフィーにより粗品を精製し、中間体－Ａ－１（３０．４５ｇ、収率７５％）を得た。

１－ナフタレンボロン酸（３０ｇ、１７４．４２ｍｍｏｌ）、４－ブロモアニリン（２８．５７ｇ、１６６．１２ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム（９．５９ｇ、８．３０ｍｍｏｌ）、炭酸カリウム（４５．９２ｇ、３３２．２４ｍｍｏｌ）、テトラブチルアンモニウムクロリド（１．８９ｇ、８．３１ｍｍｏｌ）、トルエン（２４０ｍＬ）、エタノール（１２０ｍＬ）、及び脱イオン水（３６ｍＬ）を三口フラスコに加え、窒素ガス保護下で、７５℃～８０℃に昇温させ、加熱して還流させ、４ｈ撹拌した。反応の終了後、溶液を室温に冷却させて、ジクロロメタン及び水を加えて反応液を抽出し、有機相を合併し、無水硫酸マグネシウムで有機相を乾燥させて、ろ過してろ液を得て濃縮させ、シリカゲルカラムクロマトグラフィーにより粗品を精製し、中間体－Ｂ－１（２７．３１ｇ、収率７５％）を得た。

中間体－Ｂ－１（２７．３１ｇ、１２４．５３ｍｍｏｌ）、９－（４－ブロモフェニル）カルバゾール（４０．１２ｇ、１２４．５３ｍｍｏｌ）、トリス（ジベンジリデンアセトン）ジパラジウム（１．１４ｇ、１．２４ｍｍｏｌ）、２－ジシクロヘキシルホスフィノ－２，４，６－トリイソプロピルビフェニル（１．１９ｇ、２．５０ｍｍｏｌ）、ｔ－ブトキシドナトリウム（１７．９５ｇ、１８６．８１ｍｍｏｌ）を溶媒としてのトルエン（２６０ｍＬ）に加え、窒素ガス保護下で、１０５℃～１１０℃に昇温させ、加熱して還流させ、１０ｈ撹拌した。反応液を室温に冷却させた後、ジクロロメタン及び水で反応溶液を抽出し、無水硫酸マグネシウムで有機層を乾燥させてろ過し、ろ過後にろ液をショートシリカカラムに通過させて、減圧して溶媒を除去し、ジクロロメタン／ｎ－ヘプタン系を用いて粗品を再結晶させて精製し、中間体－Ｃ－１（４３．０２ｇ、収率７６％）を得た。

中間体－Ｃ－１（１０．００ｇ、２１．７１ｍｍｏｌ）、中間体－Ａ－１（６．８３ｇ、２１．７１ｍｍｏｌ）、トリス（ジベンジリデンアセトン）ジパラジウム（０．２０ｇ、０．２２ｍｍｏｌ）、２－ジシクロヘキシルホスフィノ－２´，６´－ジメトキシビフェニル（０．１８ｇ、０．４３ｍｍｏｌ）、ｔ－ブトキシドナトリウム（３．１３ｇ、３２．５６ｍｍｏｌ）を溶媒としてのトルエン（２６０ｍＬ）に加え、窒素ガス保護下で、１０５℃～１１０℃に昇温させ、加熱して還流させ、１０ｈ撹拌した。反応液を室温に冷却させた後、ジクロロメタン及び水で反応溶液を抽出し、無水硫酸マグネシウムで有機層を乾燥させてろ過し、ろ過後にろ液をショートシリカカラムに通過させて、減圧して溶媒を除去し、ジクロロメタン／ｎ－ヘプタン系を用いて粗品を再結晶させて精製し、化合物１（１１．１２ｇ、収率７０％）を得た。質量分析：m/z=738.93(M+H)⁺。図２に示すように、化合物１の水素スペクトル：¹H NMR (400MHz,CDCl₃)(ppm):8.17(d,2H),8.07(d,1H),8.01(d,1H),7.93(d,2H),7.88(t,2H),7.76(d,2H),7.71(d,2H),7.60(d,2H),7.56(t,2H),7.53-7.44(m,16H),7.43(d,2H),7.40(d,2H),7.31(t,2H)。 Synthesis of Compound 1:

4′-chlorobiphenyl-4-boronic acid (30.00 g, 129.04 mmol), 1-bromonaphthalene (26.72 g, 129.04 mmol), tetrakis(triphenylphosphine) palladium (7.45 g, 6.45 mmol) , potassium carbonate (35.67 g, 258.09 mmol), tetrabutylammonium chloride (1.47 g, 6.45 mmol), toluene (240 mL), ethanol (120 mL), and deionized water (36 mL) were added to a three-neck flask, Under nitrogen gas protection, the temperature was raised to 75° C.-80° C., heated to reflux and stirred for 4 h. After the reaction is completed, the solution is cooled to room temperature, dichloromethane and water are added to extract the reaction solution, the organic phases are combined, the organic phase is dried over anhydrous magnesium sulfate, filtered to obtain a filtrate, and concentrated. The crude product was purified by silica gel column chromatography to obtain Intermediate-A-1 (30.45 g, yield 75%).

1-naphthaleneboronic acid (30 g, 174.42 mmol), 4-bromoaniline (28.57 g, 166.12 mmol), tetrakis(triphenylphosphine)palladium (9.59 g, 8.30 mmol), potassium carbonate (45.92 g) , 332.24 mmol), tetrabutylammonium chloride (1.89 g, 8.31 mmol), toluene (240 mL), ethanol (120 mL), and deionized water (36 mL) were added to a three-necked flask and under nitrogen gas protection, 75 C. to 80.degree. C., heated to reflux and stirred for 4 h. After the reaction is completed, the solution is cooled to room temperature, dichloromethane and water are added to extract the reaction solution, the organic phases are combined, the organic phase is dried over anhydrous magnesium sulfate, filtered to obtain a filtrate, and concentrated. The crude product was purified by silica gel column chromatography to obtain Intermediate-B-1 (27.31 g, yield 75%).

Intermediate-B-1 (27.31 g, 124.53 mmol), 9-(4-bromophenyl)carbazole (40.12 g, 124.53 mmol), tris(dibenzylideneacetone) dipalladium (1.14 g, 1. 24 mmol), 2-dicyclohexylphosphino-2,4,6-triisopropylbiphenyl (1.19 g, 2.50 mmol), sodium t-butoxide (17.95 g, 186.81 mmol) in toluene (260 mL) as solvent. In addition, under nitrogen gas protection, the temperature was raised to 105° C.-110° C., heated to reflux, and stirred for 10 h. After the reaction solution is cooled to room temperature, the reaction solution is extracted with dichloromethane and water, the organic layer is dried over anhydrous magnesium sulfate and filtered. After filtration, the filtrate is passed through a short silica column, and the solvent is was removed and the crude was purified by recrystallization using a dichloromethane/n-heptane system to give Intermediate-C-1 (43.02 g, yield 76%).

Intermediate-C-1 (10.00 g, 21.71 mmol), Intermediate-A-1 (6.83 g, 21.71 mmol), Tris(dibenzylideneacetone) dipalladium (0.20 g, 0.22 mmol), 2-Dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.18 g, 0.43 mmol), sodium t-butoxide (3.13 g, 32.56 mmol) were added to toluene (260 mL) as a solvent and nitrogen gas was added. The temperature was raised to 105-110° C. under protection and heated to reflux and stirred for 10 h. After the reaction solution is cooled to room temperature, the reaction solution is extracted with dichloromethane and water, the organic layer is dried over anhydrous magnesium sulfate and filtered. After filtration, the filtrate is passed through a short silica column, and the solvent is was removed and the crude was purified by recrystallization using dichloromethane/n-heptane system to give compound 1 (11.12 g, yield 70%). Mass Spec: m/z=738.93(M+H) ⁺ . Hydrogen spectrum of compound 1 as shown in Figure 2: ¹ H NMR (400 MHz, CDCl ₃ ) (ppm): 8.17(d,2H), 8.07(d,1H), 8.01(d,1H), 7.93(d ,2H),7.88(t,2H),7.76(d,2H),7.71(d,2H),7.60(d,2H),7.56(t,2H),7.53-7.44(m,16H),7.43( d, 2H), 7.40 (d, 2H), 7.31 (t, 2H).

中間体－Ｃ－１（１０．００ｇ、２１．７１ｍｍｏｌ）、４－ブロモ－ｐ－テルフェニル（６．６５ｇ、２１．５２ｍｍｏｌ）、２－ジシクロヘキシルホスフィノ－２´，６´－ジメトキシビフェニル（０．１８ｇ、０．４３ｍｍｏｌ）、ｔ－ブトキシドナトリウム（３．１３ｇ、３２．５６ｍｍｏｌ）を溶媒としてのトルエン（２６０ｍＬ）に加え、窒素ガス保護下で、１０５℃～１１０℃に昇温させ、加熱して還流させ、１０ｈ撹拌した。反応液を室温に冷却させた後、ジクロロメタン及び水で反応溶液を抽出し、無水硫酸マグネシウムで有機層を乾燥させてろ過し、ろ過後にろ液をショートシリカカラムに通過させて、減圧して溶媒を除去し、ジクロロメタン／ｎ－ヘプタン系を用いて粗品を再結晶させて精製し、化合物２（１０．４３ｇ、収率７０％）を得た。質量分析：m/z=692.90(M+H)⁺。 Synthesis of compound 2:

Intermediate-C-1 (10.00 g, 21.71 mmol), 4-bromo-p-terphenyl (6.65 g, 21.52 mmol), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0 .18 g, 0.43 mmol), sodium t-butoxide (3.13 g, 32.56 mmol) in toluene (260 mL) as solvent and heated to 105° C.-110° C. under nitrogen gas protection. was brought to reflux and stirred for 10 h. After the reaction solution is cooled to room temperature, the reaction solution is extracted with dichloromethane and water, the organic layer is dried over anhydrous magnesium sulfate and filtered. After filtration, the filtrate is passed through a short silica column, and the solvent is was removed and the crude was purified by recrystallization using dichloromethane/n-heptane system to give compound 2 (10.43 g, yield 70%). Mass Spec: m/z=692.90 (M+H) ⁺ .

９－ブロモフェナントレン（３０ｇ、１１６．６７ｍｍｏｌ）、４’－クロロビフェニル－４－ボロン酸（２７．１２ｇ、１１６．６７ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム（７．４５ｇ、６．４５ｍｍｏｌ）、炭酸カリウム（３５．６７ｇ、２５８．０９ｍｍｏｌ）、テトラブチルアンモニウムクロリド（１．４７ｇ、６．４５ｍｍｏｌ）、トルエン（２４０ｍＬ）、エタノール（１２０ｍＬ）、及び脱イオン水（３６ｍＬ）を三口フラスコに加え、窒素ガス保護下で、７５℃～８０℃に昇温させ、加熱して還流させ４ｈ撹拌した。反応の終了後、溶液を室温に冷却させて、ジクロロメタン及び水を加えて反応液を抽出し、有機相を合併し、無水硫酸マグネシウムで有機相を乾燥させて、ろ過してろ液を得て濃縮させ、シリカゲルカラムクロマトグラフィーにより粗品を精製し、中間体－Ｄ－１（２９．７９ｇ、収率７０％）を得た。

中間体－Ｃ－１（１０．００ｇ、２１．７１ｍｍｏｌ）、中間体－Ｄ－１（８．８１ｇ、２１．５２ｍｍｏｌ）、トリス（ジベンジリデンアセトン）ジパラジウム（０．２０ｇ、０．２２ｍｍｏｌ）、２－ジシクロヘキシルホスフィノ－２´，６´－ジメトキシビフェニル（０．１８ｇ、０．４３ｍｍｏｌ）、ｔ－ブトキシドナトリウム（３．１３ｇ、３２．５６ｍｍｏｌ）をトルエン溶媒（２６０ｍＬ）に加え、窒素ガス保護下で、１０５℃～１１０℃に昇温させ、加熱して還流させ１０ｈ撹拌した。反応液を室温に冷却させた後、ジクロロメタン及び水で反応溶液を抽出し、無水硫酸マグネシウムで有機層を乾燥させてろ過し、ろ過後にろ液をショートシリカカラムに通過させて、減圧して溶媒を除去し、ジクロロメタン／ｎ－ヘプタン系を用いて粗品を再結晶させて精製し、化合物３（１２．１１ｇ、収率７１％）を得た。質量分析：m/z=793.02(M+H)⁺。 Synthesis of compound 3:

9-bromophenanthrene (30 g, 116.67 mmol), 4′-chlorobiphenyl-4-boronic acid (27.12 g, 116.67 mmol), tetrakis(triphenylphosphine) palladium (7.45 g, 6.45 mmol), carbonate Potassium (35.67 g, 258.09 mmol), tetrabutylammonium chloride (1.47 g, 6.45 mmol), toluene (240 mL), ethanol (120 mL), and deionized water (36 mL) were added to a three-necked flask and nitrogen gas was added. The temperature was raised to 75-80° C. under protection and heated to reflux and stirred for 4 h. After the reaction is completed, the solution is cooled to room temperature, dichloromethane and water are added to extract the reaction solution, the organic phases are combined, the organic phase is dried over anhydrous magnesium sulfate, filtered to obtain a filtrate, and concentrated. The crude product was purified by silica gel column chromatography to obtain Intermediate-D-1 (29.79 g, yield 70%).

Intermediate-C-1 (10.00 g, 21.71 mmol), Intermediate-D-1 (8.81 g, 21.52 mmol), Tris(dibenzylideneacetone) dipalladium (0.20 g, 0.22 mmol), 2-Dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.18 g, 0.43 mmol) and sodium t-butoxide (3.13 g, 32.56 mmol) were added to a toluene solvent (260 mL), and the reaction was carried out under nitrogen gas protection. Then, the temperature was raised to 105° C. to 110° C., heated to reflux, and stirred for 10 hours. After the reaction solution is cooled to room temperature, the reaction solution is extracted with dichloromethane and water, the organic layer is dried over anhydrous magnesium sulfate and filtered. After filtration, the filtrate is passed through a short silica column, and the solvent is was removed and the crude was purified by recrystallization using dichloromethane/n-heptane system to give compound 3 (12.11 g, yield 71%). Mass Spec: m/z=793.02(M+H) ⁺ .

９－フェナントレンボロン酸（３０ｇ、１３５．１２ｍｍｏｌ）、４－ブロモアニリン（２８．５７ｇ、１６６．１２ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム（９．５９ｇ、８．３０ｍｍｏｌ）、炭酸カリウム（４５．９２ｇ、３３２．２４ｍｍｏｌ）、テトラブチルアンモニウムクロリド（１．８９ｇ、８．３１ｍｍｏｌ）、トルエン（２４０ｍＬ）、エタノール（１２０ｍＬ）、及び脱イオン水（３６ｍＬ）を三口フラスコに加え、窒素ガス保護下で、７５℃～８０℃に昇温させ、加熱して還流させ４ｈ撹拌した。反応の終了後、溶液を室温に冷却させて、ジクロロメタン及び水を加えて反応液を抽出し、有機相を合併し、無水硫酸マグネシウムで有機相を乾燥させて、ろ過してろ液を得て濃縮させ、シリカゲルカラムクロマトグラフィーにより粗品を精製し、中間体－Ｂ－２（２７．２９ｇ、収率７５％）を得た。

中間体－Ｂ－２（２７．２９ｇ、１０１．３２ｍｍｏｌ）、９－（４－ブロモフェニル）カルバゾール（４０．１２ｇ、１２４．５３ｍｍｏｌ）、トリス（ジベンジリデンアセトン）ジパラジウム（１．１４ｇ、１．２４ｍｍｏｌ）、２－ジシクロヘキシルホスフィノ－２，４，６－トリイソプロピルビフェニル（１．１９ｇ、２．５０ｍｍｏｌ）、ｔ－ブトキシドナトリウム（１７．９５ｇ、１８６．８１ｍｍｏｌ）をトルエン溶媒（２６０ｍＬ）に加え、窒素ガス保護下で、１０５℃～１１０℃に昇温させ、加熱して還流させ１０ｈ撹拌した。反応液を室温に冷却させた後、ジクロロメタン及び水で反応溶液を抽出し、無水硫酸マグネシウムで有機層を乾燥させてろ過し、ろ過後にろ液をショートシリカカラムに通過させて、減圧して溶媒を除去し、ジクロロメタン／ｎ－ヘプタン系を用いて粗品を再結晶させて精製し、中間体－Ｃ－２（３９．１０ｇ、収率７５％）を得た。

中間体－Ｃ－２（１０．００ｇ、１９．４２ｍｍｏｌ）、中間体－Ｄ－１（７．０９ｇ、１９．４３ｍｍｏｌ）、トリス（ジベンジリデンアセトン）ジパラジウム（０．２０ｇ、０．２２ｍｍｏｌ）、２－ジシクロヘキシルホスフィノ－２´，６´－ジメトキシビフェニル（０．１８ｇ、０．４３ｍｍｏｌ）、ｔ－ブトキシドナトリウム（３．１３ｇ、３２．５６ｍｍｏｌ）をトルエン溶媒（２６０ｍＬ）に加え、窒素ガス保護下で、１０５℃～１１０℃に昇温させ、加熱して還流させ１０ｈ撹拌した。反応液を室温に冷却させた後、ジクロロメタン及び水で反応溶液を抽出し、無水硫酸マグネシウムで有機層を乾燥させてろ過し、ろ過後にろ液をショートシリカカラムに通過させて、減圧して溶媒を除去し、ジクロロメタン／ｎ－ヘプタン系を用いて粗品を再結晶させて精製し、化合物４（１２．１１ｇ、収率７１％）を得た。質量分析：m/z=793.02(M+H)⁺。 Synthesis of compound 4:

9-phenanthreneboronic acid (30 g, 135.12 mmol), 4-bromoaniline (28.57 g, 166.12 mmol), tetrakis(triphenylphosphine) palladium (9.59 g, 8.30 mmol), potassium carbonate (45.92 g) , 332.24 mmol), tetrabutylammonium chloride (1.89 g, 8.31 mmol), toluene (240 mL), ethanol (120 mL), and deionized water (36 mL) were added to a three-necked flask and under nitrogen gas protection, 75 C. to 80.degree. C., heated to reflux and stirred for 4 h. After the reaction is completed, the solution is cooled to room temperature, dichloromethane and water are added to extract the reaction solution, the organic phases are combined, the organic phase is dried over anhydrous magnesium sulfate, filtered to obtain a filtrate, and concentrated. The crude product was purified by silica gel column chromatography to obtain Intermediate-B-2 (27.29 g, yield 75%).

Intermediate-B-2 (27.29 g, 101.32 mmol), 9-(4-bromophenyl)carbazole (40.12 g, 124.53 mmol), tris(dibenzylideneacetone) dipalladium (1.14 g, 1. 24 mmol), 2-dicyclohexylphosphino-2,4,6-triisopropylbiphenyl (1.19 g, 2.50 mmol), sodium t-butoxide (17.95 g, 186.81 mmol) were added to toluene solvent (260 mL), Under nitrogen gas protection, the temperature was raised to 105° C.-110° C., heated to reflux and stirred for 10 h. After the reaction solution is cooled to room temperature, the reaction solution is extracted with dichloromethane and water, the organic layer is dried over anhydrous magnesium sulfate and filtered. After filtration, the filtrate is passed through a short silica column, and the solvent is was removed and the crude was purified by recrystallization using a dichloromethane/n-heptane system to give Intermediate-C-2 (39.10 g, yield 75%).

Intermediate-C-2 (10.00 g, 19.42 mmol), Intermediate-D-1 (7.09 g, 19.43 mmol), Tris(dibenzylideneacetone) dipalladium (0.20 g, 0.22 mmol), 2-Dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.18 g, 0.43 mmol) and sodium t-butoxide (3.13 g, 32.56 mmol) were added to a toluene solvent (260 mL), and the reaction was carried out under nitrogen gas protection. Then, the temperature was raised to 105° C. to 110° C., heated to reflux, and stirred for 10 hours. After the reaction solution is cooled to room temperature, the reaction solution is extracted with dichloromethane and water, the organic layer is dried over anhydrous magnesium sulfate and filtered. After filtration, the filtrate is passed through a short silica column, and the solvent is was removed and the crude was purified by recrystallization using dichloromethane/n-heptane system to give compound 4 (12.11 g, yield 71%). Mass Spec: m/z=793.02(M+H) ⁺ .

中間体－Ｃ－２（１０．００ｇ、１９．４２ｍｍｏｌ）、４－ブロモ－ｐ－テルフェニル（６．００ｇ、１９．４２ｍｍｏｌ）、トリス（ジベンジリデンアセトン）ジパラジウム（０．２０ｇ、０．２２ｍｍｏｌ）、２－ジシクロヘキシルホスフィノ－２´，６´－ジメトキシビフェニル（０．１８ｇ、０．４３ｍｍｏｌ）、ｔ－ブトキシドナトリウム（３．１３ｇ、３２．５６ｍｍｏｌ）をトルエン溶媒（２６０ｍＬ）に加え、窒素ガス保護下で、１０５℃～１１０℃に昇温させ、加熱して還流させ、１０ｈ撹拌した。反応液を室温に冷却させた後、ジクロロメタン及び水で反応溶液を抽出し、無水硫酸マグネシウムで有機層を乾燥させてろ過し、ろ過後にろ液をショートシリカカラムに通過させて、減圧して溶媒を除去し、ジクロロメタン／ｎ－ヘプタン系を用いて粗品を再結晶させて精製し、化合物５（１０．２５ｇ、収率７０％）を得た。質量分析：m/z=742.96(M+H)⁺。図３に示すように、化合物５の水素スペクトル：¹H NMR (400MHz,CD₂Cl₂)(ppm):8.81(d,1H),8.75(d,1H),8.16(d,2H),8.10(d,1H),7.94(d,1H),7.77(s,1H),7.75-7.61(m,12H),7.56(d,2H),7.52(t, 4H),7.49-7.44(m,6H),7.42(d,4H),7.37(t,1H),7.30(t,2H)。 Synthesis of compound 5:

Intermediate-C-2 (10.00 g, 19.42 mmol), 4-bromo-p-terphenyl (6.00 g, 19.42 mmol), tris(dibenzylideneacetone) dipalladium (0.20 g, 0.22 mmol) ), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.18 g, 0.43 mmol) and sodium t-butoxide (3.13 g, 32.56 mmol) were added to a toluene solvent (260 mL) and nitrogen gas was added. The temperature was raised to 105-110° C. under protection and heated to reflux and stirred for 10 h. After the reaction solution is cooled to room temperature, the reaction solution is extracted with dichloromethane and water, the organic layer is dried over anhydrous magnesium sulfate and filtered. After filtration, the filtrate is passed through a short silica column, and the solvent is was removed and the crude was purified by recrystallization using dichloromethane/n-heptane system to give compound 5 (10.25 g, yield 70%). Mass Spec: m/z=742.96 (M+H) ⁺ . Hydrogen spectrum of compound 5 as shown in Figure 3: ¹ H NMR (400 MHz, CD ₂ Cl ₂ ) (ppm): 8.81 (d, 1 H), 8.75 (d, 1 H), 8.16 (d, 2 H), 8.10 (d,1H),7.94(d,1H),7.77(s,1H),7.75-7.61(m,12H),7.56(d,2H),7.52(t,4H),7.49-7.44(m,6H) ), 7.42(d,4H), 7.37(t,1H), 7.30(t,2H).

中間体－Ｃ－２（１０．００ｇ、１９．４２ｍｍｏｌ）、中間体－Ａ－１（６．１１ｇ、１９．４２ｍｍｏｌ）、トリス（ジベンジリデンアセトン）ジパラジウム（０．２０ｇ、０．２２ｍｍｏｌ）、２－ジシクロヘキシルホスフィノ－２´，６´－ジメトキシビフェニル（０．１８ｇ、０．４３ｍｍｏｌ）、ｔ－ブトキシドナトリウム（３．１３ｇ、３２．５６ｍｍｏｌ）をトルエン溶媒（２６０ｍＬ）に加え、窒素ガス保護下で、１０５℃～１１０℃に昇温させ、加熱して還流させ、１０ｈ撹拌した。反応液を室温に冷却させた後、ジクロロメタン及び水で反応溶液を抽出し、無水硫酸マグネシウムで有機層を乾燥させてろ過し、ろ過後にろ液をショートシリカカラムに通過させて、減圧して溶媒を除去し、ジクロロメタン／ｎ－ヘプタン系を用いて粗品を再結晶させて精製し、化合物６（１０．９３ｇ、収率７１％）を得た。質量分析：m/z=788.99(M+H)⁺。 Synthesis of compound 6:

Intermediate-C-2 (10.00 g, 19.42 mmol), Intermediate-A-1 (6.11 g, 19.42 mmol), Tris(dibenzylideneacetone) dipalladium (0.20 g, 0.22 mmol), 2-Dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.18 g, 0.43 mmol) and sodium t-butoxide (3.13 g, 32.56 mmol) were added to a toluene solvent (260 mL), and the reaction was carried out under nitrogen gas protection. The temperature was raised to 105° C. to 110° C., heated to reflux, and stirred for 10 h. After the reaction solution is cooled to room temperature, the reaction solution is extracted with dichloromethane and water, the organic layer is dried over anhydrous magnesium sulfate and filtered. After filtration, the filtrate is passed through a short silica column, and the solvent is was removed and the crude was purified by recrystallization using dichloromethane/n-heptane system to give compound 6 (10.93 g, yield 71%). Mass Spec: m/z=788.99 (M+H) ⁺ .

ｐ－フェニルアニリン（３０．３９ｇ、１７９．５９ｍｍｏｌ）、９－（４－ブロモフェニル）カルバゾール（４０．１２ｇ、１２４．５３ｍｍｏｌ）、トリス（ジベンジリデンアセトン）ジパラジウム（１．１４ｇ、１．２４ｍｍｏｌ）、２－ジシクロヘキシルホスフィノ－２，４，６－トリイソプロピルビフェニル（１．１９ｇ、２．５０ｍｍｏｌ）、ｔ－ブトキシドナトリウム（１７．９５ｇ、１８６．８１ｍｍｏｌ）をトルエン溶媒（２６０ｍＬ）に加え、窒素ガス保護下で、１０５～１１０℃に昇温させ、加熱して還流させ、１０ｈ撹拌した。反応液を室温に冷却させた後、ジクロロメタン及び水で反応溶液を抽出し、無水硫酸マグネシウムで有機層を乾燥させてろ過し、ろ過後にろ液をショートシリカカラムに通過させて、減圧して溶媒を除去し、ジクロロメタン／ｎ－ヘプタン系を用いて粗品を再結晶させて精製し、中間体－Ｃ－３（５０．６２ｇ、収率６９％）を得た。

中間体－Ｃ－３（６．１１ｇ、１９．４２ｍｍｏｌ）、中間体－Ａ－１（６．８３ｇ、２１．７１ｍｍｏｌ）、トリス（ジベンジリデンアセトン）ジパラジウム（０．２０ｇ、０．２２ｍｍｏｌ）、２－ジシクロヘキシルホスフィノ－２´，６´－ジメトキシビフェニル（０．１８ｇ、０．４３ｍｍｏｌ）、ｔ－ブトキシドナトリウム（３．１３ｇ、３２．５６ｍｍｏｌ）をトルエン溶媒（２６０ｍＬ）に加え、窒素ガス保護下で、１０５℃～１１０℃に昇温させ、加熱して還流させ、１０ｈ撹拌した。反応液を室温に冷却させた後、ジクロロメタン及び水で反応溶液を抽出し、無水硫酸マグネシウムで有機層を乾燥させてろ過し、ろ過後にろ液をショートシリカカラムに通過させて、減圧して溶媒を除去し、ジクロロメタン／ｎ－ヘプタン系を用いて粗品を再結晶させて精製し、化合物７（１１．６９ｇ、収率７０％）を得た。質量分析：m/z=692.90(M+H)⁺。 Synthesis of compound 7:

p-phenylaniline (30.39 g, 179.59 mmol), 9-(4-bromophenyl)carbazole (40.12 g, 124.53 mmol), tris(dibenzylideneacetone) dipalladium (1.14 g, 1.24 mmol) , 2-dicyclohexylphosphino-2,4,6-triisopropylbiphenyl (1.19 g, 2.50 mmol), sodium t-butoxide (17.95 g, 186.81 mmol) were added to a toluene solvent (260 mL) and nitrogen gas was added. The temperature was raised to 105-110° C. under protection, heated to reflux and stirred for 10 h. After the reaction solution is cooled to room temperature, the reaction solution is extracted with dichloromethane and water, the organic layer is dried over anhydrous magnesium sulfate and filtered. After filtration, the filtrate is passed through a short silica column, and the solvent is was removed and the crude was purified by recrystallization using dichloromethane/n-heptane system to give Intermediate-C-3 (50.62 g, 69% yield).

Intermediate-C-3 (6.11 g, 19.42 mmol), Intermediate-A-1 (6.83 g, 21.71 mmol), Tris(dibenzylideneacetone) dipalladium (0.20 g, 0.22 mmol), 2-Dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.18 g, 0.43 mmol) and sodium t-butoxide (3.13 g, 32.56 mmol) were added to a toluene solvent (260 mL), and the reaction was carried out under nitrogen gas protection. The temperature was raised to 105° C. to 110° C., heated to reflux, and stirred for 10 h. After the reaction solution is cooled to room temperature, the reaction solution is extracted with dichloromethane and water, the organic layer is dried over anhydrous magnesium sulfate and filtered. After filtration, the filtrate is passed through a short silica column, and the solvent is was removed and the crude was purified by recrystallization using dichloromethane/n-heptane system to give compound 7 (11.69 g, yield 70%). Mass Spec: m/z=692.90 (M+H) ⁺ .

中間体－Ｃ－３（６．１１ｇ、１９．４２ｍｍｏｌ）、中間体－Ｄ－１（８．８８ｇ、２４．１２ｍｍｏｌ）、トリス（ジベンジリデンアセトン）ジパラジウム（０．２０ｇ、０．２２ｍｍｏｌ）、２－ジシクロヘキシルホスフィノ－２´，６´－ジメトキシビフェニル（０．１８ｇ、０．４３ｍｍｏｌ）、ｔ－ブトキシドナトリウム（３．１３ｇ、３２．５６ｍｍｏｌ）をトルエン溶媒（２６０ｍＬ）に加え、窒素ガス保護下で、１０５℃～１１０℃に昇温させ、加熱して還流させ、１０ｈ撹拌した。反応液を室温に冷却させた後、ジクロロメタン及び水で反応溶液を抽出し、無水硫酸マグネシウムで有機層を乾燥させてろ過し、ろ過後にろ液をショートシリカカラムに通過させて、減圧して溶媒を除去し、ジクロロメタン／ｎ－ヘプタン系を用いて粗品を再結晶させて精製し、化合物８（１２．７２ｇ、収率７１％）を得た。質量分析：m/z=742.96(M+H)⁺。 Synthesis of compound 8:

Intermediate-C-3 (6.11 g, 19.42 mmol), Intermediate-D-1 (8.88 g, 24.12 mmol), Tris(dibenzylideneacetone) dipalladium (0.20 g, 0.22 mmol), 2-Dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.18 g, 0.43 mmol) and sodium t-butoxide (3.13 g, 32.56 mmol) were added to a toluene solvent (260 mL), and the reaction was carried out under nitrogen gas protection. The temperature was raised to 105° C. to 110° C., heated to reflux, and stirred for 10 h. After the reaction solution is cooled to room temperature, the reaction solution is extracted with dichloromethane and water, the organic layer is dried over anhydrous magnesium sulfate and filtered. After filtration, the filtrate is passed through a short silica column, and the solvent is was removed and the crude was purified by recrystallization using dichloromethane/n-heptane system to give compound 8 (12.72 g, yield 71%). Mass Spec: m/z=742.96 (M+H) ⁺ .

The present application further provides a photoelectric conversion device, as shown in FIG. 3, and this functional layer 3 may comprise the nitrogen-containing compound of any one of the above embodiments.

The anode 1 may be a material that contributes to the injection of holes into the functional layer 3, and this material may have a large work function. For example, the material of the anode 1 may be metal, alloy or metal oxide, such as nickel, platinum, vanadium, chromium, copper, zinc, gold or alloys thereof, zinc oxide, It may be indium oxide, indium tin oxide (ITO) and indium zinc oxide (IZO). Of course, the material of the anode 1 can be other, for example ZnO:Al, SnO ₂ :Sb, conductive polymers (poly(3-methylthiophene), poly[3,4-(ethylene-1 ,2-dioxy)thiophene] (PEDT), polypyrrole, and polyaniline). Of course, the materials of the anode 1 are not limited to these, and other materials may be used, and they are not mentioned here one by one. Preferably, the material of the anode 1 may be indium tin oxide (ITO).

Cathode 5 may be a material that contributes to electron injection into functional layer 3, and this material may have a low work function. For example, the material of the cathode 5 may be a metal or alloy material, such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead or alloys thereof. or multiple layers of materials such as LiF/Al, Liq/Al, _LiO2 /Al, LiF/Ca, LiF/Al, and _BaF2 /Ca. Of course, the materials of the cathode 5 are not limited to these, and other materials may be used, which are not mentioned here one by one. Preferably, the material of cathode 5 may be aluminum. For example, the photoelectric conversion device may be a solar cell, an organic electroluminescence device, or, of course, other photoelectric conversion devices, which are not listed here one by one.

The functional layer 3 can be used to transport electrons and holes and can provide sites for recombination or separation of electrons and holes, which recombine in the functional layer 3 to generate excitons. can be used to achieve the effect of luminescence.

In one embodiment, the nitrogen-containing compound of any embodiment of the present application is used to form one or more of the functional layers 3 to reduce the operating voltage of the photovoltaic device, increase the luminous efficiency, It can extend the life of the device. For example, functional layer 3 may include electron barrier layer 32, which may include the nitrogen-containing compound of any one embodiment of the present application. This nitrogen-containing compound may be used to barrier electron transport to the anode 1, ie the nitrogen-containing compound of any one embodiment of the present application may also be used as an electron barrier material.

The functional layer 3 may further comprise a light-emitting layer 33, a hole-transporting layer 31 and an electron-transporting layer 34, provided that the light-emitting layer 33 may be provided on the side of the electron barrier layer 32 remote from said anode 1. Well, the hole transport layer 31 may be provided on the side of the electron barrier layer 32 remote from the light emitting layer 33 and the electron transport layer 34 is provided between the light emitting layer 33 and the cathode 5. good too. The photoelectric conversion device may comprise an anode 1, a hole-transporting layer 31, a light-emitting layer 33, an electron-transporting layer 34 and a cathode 5 which are stacked.

In addition, the photoelectric conversion device of the embodiment of the present application may further include a hole injection layer 2 and an electron injection layer 4, provided that the hole injection layer 2 is provided between the anode 1 and the hole transport layer 31. The electron injection layer 4 may be provided between the cathode 5 and the electron transport layer 34 . For example, the photoelectric conversion device may be an organic electroluminescent device.

Hereinafter, the organic electroluminescent device of the present application will be described in detail by way of examples, taking the organic electroluminescent device as an example. However, the following examples are only examples of the present application and are not intended to limit the present application.

Examples of preparation and evaluation of organic electroluminescent devices

Example 1 Fabrication of Blue Organic Electroluminescent Device Anode 1 was fabricated by the following process. An ITO substrate with an ITO thickness of 1500 angstroms is cut into a size of 40 mm (length) x 40 mm (width) x 0.7 mm (thickness), and has a pattern of cathode 5, anode 1 and insulating layer by photolithography process. An experimental substrate may be prepared, and the surface treatment may be performed using ultraviolet rays, ozone and O ₂ :N ₂ plasma to increase the work function of the anode 1, and the surface of the ITO substrate may be cleaned using an organic solvent. , foreign matter and oil stains on the surface of the ITO substrate may be removed. It should be noted that the ITO substrate may be cut into other sizes according to actual needs, and the size of the ITO substrate in the present application is not specifically limited herein.
m-MTDATA (4,4′,4″-tris(N-3-methylphenyl-N-phenylamino)triphenylamine) (structural formula shown below) was vacuum-coated onto the experimental substrate (anode 1). vapor deposition to form a hole injection layer 2 (HIL) with a thickness of 100 angstroms; 1,1'-biphenyl-4,4'-diamine) (structural formula shown below) was vacuum evaporated to form a hole transport layer 31 (HTL) with a thickness of 800 Angstroms.
Compound 1 was evaporated onto the hole transport layer 31 (HTL) to form an electron barrier layer 32 (EBL) with a thickness of 100-350 Angstroms. For example, the electron barrier layer 32 (EBL) may have a thickness of 100 Angstroms, 150 Angstroms, 200 Angstroms, 250 Angstroms, 300 Angstroms, or 350 Angstroms, or of course other thicknesses, herein. I can't list them one by one.
α,β-ADN (structural formula shown below) as body, doped with BD-1 (structural formula shown below) at a film thickness ratio of 100:3, 200-450 Å thick emission A layer 33 (EML) was formed. For example, the thickness of the light-emitting layer 33 (EML) may be 200 Angstroms, 250 Angstroms, 300 Angstroms, 350 Angstroms, 400 Angstroms, or 450 Angstroms, and of course other thicknesses, here only one. I can't list them one by one.
DBimiBphen (structural formula shown below) and LiQ (structural formula shown below) are mixed in a 1:1 weight ratio to form a 200-400 Angstrom thick electron transport layer 34 (ETL) through a vapor deposition process. You may For example, the thickness of the electron transport layer 34 may be 200 Angstroms, 250 Angstroms, 300 Angstroms, 350 Angstroms, or 400 Angstroms, or of course other thicknesses, listed here individually. do not have. Next, LiQ is evaporated on the electron transport layer 34 to form an electron injection layer 4 (EIL) with a thickness of 5-20 angstroms, for example, the thickness of the electron injection layer 4 is 5 angstroms, 10 angstroms, 15 angstroms. or 20 Angstroms, or of course other thicknesses, not listed individually here. Next, magnesium (Mg) and silver (Ag) were mixed at a deposition rate of 1:9 and vacuum deposited onto the electron injection layer 4 (EIL) to form a cathode 5 with a thickness of 120 angstroms.
Also, CP-1 (structural formula is shown below) was vapor-deposited on the cathode 5 to a thickness of 650 angstroms to form a coating layer (CPL), thereby manufacturing an organic light-emitting device.

Examples 2-8
An organic electroluminescent device was fabricated in the same manner as in Example 1, except that Compounds 2 to 8 were used instead of Compound 1 in forming the electron barrier layer 32 (EBL).
That is, in Example 2, the compound 2 was used as one or more layers of the functional layer 3 to produce an organic electroluminescence device, and in Example 3, the compound 3 was used as one or more layers of the functional layer 3. In Example 4, an organic electroluminescence device was produced by using compound 4 as one or more layers of functional layer 3, and in Example 5, compound 5 was used as functional layer 3. An organic electroluminescence device was produced as one or more layers of the functional layer 3, and in Example 6, an organic electroluminescence device was produced using the compound 6 as one or more layers of the functional layer 3. In Example 8, compound 7 was used as one or more layers in the functional layer 3 to produce an organic electroluminescence device, and in Example 8, compound 8 was used as one or more layers in the functional layer 3 to produce an organic electroluminescence device. Devices were fabricated and performance parameters for each device are detailed in Table 1.

即ち、比較例１では、化合物Ａを用いて有機エレクトロルミネッセンスデバイスを製造し、比較例２では、化合物Ｂを用いて有機エレクトロルミネッセンスデバイスを製造し、比較例３では、化合物Ｃを用いて有機エレクトロルミネッセンスデバイスを製造し、比較例４では、化合物Ｄを用いて有機エレクトロルミネッセンスデバイスを製造し、製造した各デバイスの性能について、詳細に表１に示す。ここで、ＩＶＬ（電流、電圧、輝度）のデータは、１０ｍＡ／ｃｍ^２でのテスト結果を比較したものであり、Ｔ９５寿命は２０ｍＡ／ｃｍ^２電流密度でのテスト結果である。

Comparative Examples 1 to 4
In Comparative Examples 1 to 4, organic electroluminescence devices were manufactured in the same manner as in Example 1, except that Compound A to Compound D were used as substitute compounds for the electron barrier layer 32 (EBL), respectively. Here, the structures of compound A to compound D are shown below.

That is, in Comparative Example 1, the compound A was used to produce an organic electroluminescence device, in Comparative Example 2, the compound B was used to produce an organic electroluminescence device, and in Comparative Example 3, the compound C was used to produce an organic electroluminescence device. A luminescence device was manufactured, and in Comparative Example 4, an organic electroluminescence device was manufactured using compound D, and the performance of each manufactured device is shown in Table 1 in detail. Here, the IVL (current, voltage, luminance) data compare the test results at 10 mA/cm ² and the T95 life is the test results at 20 mA/cm ² current density.

As can be seen from the results in Table 1 above, Examples 1, 2, 3, 4, 5, 6, 6, 6, 7, 8, 9, 10, 10, 11, 12, 13, 14, 14, and 14 each used the compounds 1 to 8 as the electron barrier layer 32 (EBL). In Examples 7 and 8, compared to Comparative Examples 1, 2, 3 and 4 using Compounds A to D, both luminous efficiency and device life were significantly improved. In the present application, the organic electroluminescent device manufactured using compound 5 as the electron barrier layer 32 (EBL) in Example 5 has a 54.7% improvement in luminous efficiency (Cd/A) compared to Comparative Example 1. However, the external quantum efficiency improved by at least 56.5% and the lifetime increased by 42 hours, which is a 75.4% improvement. From this, it was found that the organic electroluminescence device of the embodiment of the present application has clearly improved luminous efficiency and lifetime performance.

As shown in Table 1, compared to Compound A, Compound C and Compound D, Compounds 1 to 8 of the present application all showed clear improvements in both efficiency and lifetime. Specifically, by connecting the nitrogen atom of the carbazole and the nitrogen atom of the triarylamine with a phenylene group, the distance between the nitrogen atoms can be reduced, thereby making the angle between the triarylamine and the carbazole plane can be reduced. This allows the HOMO energy levels of the material to be distributed simultaneously to the triarylamine and carbazole groups by conjugation. Thereby, the hole mobility of the material can be increased and the photoelectric conversion efficiency of the device can be improved. Also, the asymmetrical triarylamine branch chain length, combined with the sterically hindered naphthalene/phenanthryl groups, significantly reduced the crystallinity of the compound and significantly enhanced the film deposition uniformity. In the above results, compound 1 and compound 5 are particularly excellent.

Compared to compound B, compounds 1 to 8 of the present application all show clear improvements in both efficiency and lifetime. Compounds 1 to 8 of the present application introduce a large planar condensed ring group into another two branches of triarylamine, thereby effectively dispersing the electron cloud density for the triarylamine and Disconnection can be avoided. In addition, the condensed ring connection method of vertical configuration can increase the molecular space volume, reduce the crystallization effect due to intermolecular stacking, further reduce the operating voltage of the device, and extend the device life.

Figures 4 and 5 are HOMO energy level diagrams calculated for compound 1 and compound A of the present application. As can be seen from the figure, the HOMO energy levels of compound 1 of the present application are simultaneously distributed to the triarylamine and carbazole groups by conjugation, the nitrogen atom of carbazole and the nitrogen atom of triarylamine are linked by a phenylene group, The reduced spacing between nitrogen atoms increased the hole mobility of the material, further improving the photoelectric conversion efficiency of the device. The present application further provides an electronic device, which may include the photoelectric conversion device of any of the above embodiments, the beneficial effects and details of which can be referred to the photoelectric conversion device and will be described in detail herein. do not do. For example, the electronic device may be a display, an array substrate, a photovoltaic module, etc., but of course it may be other devices, which are not listed here one by one.

Other embodiments of the present application will readily occur to those skilled in the art upon consideration of the specification and practice of the invention disclosed herein. This application is intended to cover all variations, uses, and adaptations of this application which are subject to the general principles of this application and may be incorporated herein by reference. It also includes common knowledge or common technical means in the relevant technical field that are not disclosed. It is intended that the specification and examples be considered as exemplary, with a true scope and spirit of the application being determined by the following claims.

1, anode 2, hole injection layer 3, functional layer 31, hole transport layer 32, electron barrier layer 33, light emitting layer 34, electron transport layer 4, electron injection layer 5, cathode

Claims (11)

Nitrogen-containing compounds whose general structural formula is shown in Formula I.

(wherein Ar ₁ and Ar ₂ are each independently selected from the group consisting of the following structures,

each of A ₁ to A ₁₉ is independently deuterium, tritium, fluorine, chlorine, bromine, cyano group, alkyl group having 1 to 4 carbon atoms, cycloalkyl group having 3 to 10 carbon atoms, carbon atom selected from aryl groups of numbers 6 to 15,
b ₁ to b ₁₉ are represented by b _k , A ₁ to A ₁₉ are represented by A _k , k is a variable representing an arbitrary integer from 1 to 19, b _k represents the number of substituents A _k Where indicated, when b _k is greater than 1, the corresponding substituents A _k are the same or different,
wherein b _k is selected from 0, 1, 2, 3, 4 or 5 when k is selected from 1, 3, 6, 14, 15, 17 or 19;
b _k is selected from 0, 1, 2, 3 or 4 when k is selected from 2, 4, 9, 11, 13 or 18;
when k is chosen from 5, 12, 16, b _k is chosen from 0, 1, 2 or 3;
when k is chosen from 10, b _k is chosen from 0, 1, 2, 3, 4, 5 or 6;
when k is selected from 7, b _k is selected from 0, 1, 2, 3, 4, 5, 6 or 7;
When _k is chosen from 8, bk is chosen from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9. ) 2. The nitrogen-containing compound according to claim 1 , wherein said Ar ₁ and said Ar ₂ are each independently selected from the following groups.

3. A nitrogen-containing compound according to claim 1 or 2 , wherein said Ar ₁ and said Ar ₂ are the same or different and are each independently selected from the following groups.

(Wherein, * indicates that the above group is

Indicates that it is intended to be attached to a group. ) Said Ar ₁ and said Ar ₂ are simultaneously

The nitrogen-containing compound according to any one of claims 1 to 3 , which does not become
(Wherein, * indicates that the above group is

Indicates that it is intended to be attached to a group. ) The nitrogen-containing compound according to any one of claims 1 to 4 , wherein the nitrogen-containing compound is selected from the following compounds.

A photoelectric conversion device comprising an anode and a cathode facing each other, and a functional layer provided between the anode and the cathode,
A photoelectric conversion device, wherein the functional layer contains the nitrogen-containing compound according to any one of claims 1 to 5 . 7. The photoelectric conversion device according to claim 6 , wherein said functional layer comprises an electron barrier layer, said electron barrier layer comprising said nitrogen-containing compound. The functional layer is
a light-emitting layer provided on a side of the electron barrier layer remote from the anode;
a hole transport layer provided on the side of the electron barrier layer remote from the light emitting layer;
8. The photoelectric conversion device according to claim 6 , further comprising an electron transport layer provided between said light emitting layer and said cathode. The photoelectric conversion device according to any one of claims 6 to 8 , wherein the photoelectric conversion device is an organic electroluminescence device. The photoelectric conversion device according to any one of claims 6 to 9 , wherein the photoelectric conversion device is a solar cell. An electronic device comprising the photoelectric conversion device according to any one of claims 6 to 10 .

Images