WO2017118262A1

WO2017118262A1 - Organic compound and use thereof

Info

Publication number: WO2017118262A1
Application number: PCT/CN2016/109270
Authority: WO
Inventors: 谭甲辉; 黄宏; 潘君友
Original assignee: 广州华睿光电材料有限公司
Priority date: 2016-01-07
Filing date: 2016-12-09
Publication date: 2017-07-13
Also published as: CN108137583B; CN108137583A

Abstract

Disclosed are an organic compound and a use thereof. The organic compound has a general formula (1) as follows: wherein, -X- and -Y- respectively independently represent -O-, -S-, -S＝O-, -SO₂-, -N(R₁₀₀)-, -C(R₂₀₀)(R₂₀₁)- or -Si(R₃₀₀)(R₃₀₁)-; Ar₁ and Ar₂, which are the same or different, represent an aromatic ring having 6-20 carbon atoms, or a heteroaromatic or non-aromatic ring having 2-20 carbon atoms, unsubstituted or substituted with one or more groups R¹; and Ar₃ and Ar₄, which are the same or different, represent an aromatic ring having 6-40 carbon atoms, or a heteroaromatic or non-aromatic ring having 2-40 carbon atoms, unsubstituted or substituted with one or more groups R¹.

Description

Organic compounds and their applications

Technical field:

The present invention relates to the field of organic electroluminescent materials, and more particularly to an organic compound, a high polymer, a mixture, a composition, and an organic electronic device.

Background technique:

Organic semiconductor materials are versatile in synthesis, relatively low in manufacturing cost, and have excellent optical and electrical properties. Organic light-emitting diodes (OLEDs) have great potential for applications in optoelectronic devices such as flat panel displays and lighting.

In order to improve the luminous efficiency of organic light-emitting diodes, various phosphor- and phosphorescent-based luminescent material systems have been developed. Organic light-emitting diodes using fluorescent materials have high reliability, but their internal electroluminescent quantum under electrical excitation The efficiency is limited to 25% because the branch ratio of the singlet excited state to the triplet excited state of the exciton is 1:3. In contrast, organic light-emitting diodes using phosphorescent materials have achieved nearly 100% internal electroluminescence quantum efficiency. However, there is a significant problem with phosphorescent OLEDs, that is, the Roll-off effect, that is, the luminous efficiency rapidly decreases with increasing current or brightness, which is particularly disadvantageous for high brightness applications.

So far, phosphorescent materials with practical use value are mainly rhodium and platinum complexes, which are rare and expensive, and the synthesis of complexes is complicated, so the cost is also quite high. In order to overcome the rarity and high cost of the raw materials of rhodium and platinum complexes, and the complexity of their synthesis, Adachi proposed the concept of reverse intersystem crossing, which can be achieved by using organic compounds, ie without using metal complexes. High efficiency compared to phosphorescent OLEDs. This concept has been achieved through a combination of materials such as: 1) using the exciplex, see Adachi et al., Nature Photonics, Vol 6, p 253 (2012); 2) using thermally excited delayed fluorescence (TADF) Materials, see Adachi et al., Nature, Vol 492, 234, (2012). However, most of the existing organic compounds with TADF are connected by electron donating (Donor) and electron-deficient or acceptor groups, resulting in complete distribution of the highest occupied orbit (HOMO) and the lowest unoccupied orbital (LUMO) electron cloud. Separating and narrowing the energy level difference (Δ(S ₁ -T ₁ )) between the singlet (S ₁ ) and triplet (T ₁ ) of the organic compound, but also causing the resonance factor (f) of the organic compound to decrease, further causing organic The reduced fluorescence quantum efficiency of the compounds results in shorter lifetimes for such OLED devices.

Summary of the invention:

Based on this, it is necessary to provide an organic compound having a high fluorescence quantum efficiency.

An organic compound having the following general formula (1):

Wherein -X- and -Y- respectively represent -O-, -S-, -S=O-, -SO ₂ -, -N(R ₁₀₀ )-, -C(R ₂₀₀ )(R ₂₀₁ )- Or -Si(R ₃₀₀ )(R ₃₀₁ )-;

X and Ar ₁ and the intermediate benzene ring are connected by a single bond or a double bond, and Y and Ar ₂ and the intermediate benzene ring are connected by a single bond or a double bond;

The same or different Ar ₁ and Ar ₂ represent an aromatic having 6 to 20 carbon atoms or a heteroaromatic or non-aromatic having 2 to 20 carbon atoms which are unsubstituted or substituted by one or more groups R ¹ . Ring system

The same or different Ar ₃ and Ar ₄ represent an aromatic having 6 to 40 carbon atoms or a heteroaromatic or non-aromatic having 2 to 40 carbon atoms which are unsubstituted or substituted by one or more groups R ¹ . Ring system

The groups R ¹ may be the same or different when they occur multiple times;

R ₁ , R ₂ , R ₁₀₀ , R ₂₀₀ , R ₂₀₁ , R ₃₀₀ , R ₃₀₁ and R ¹ each independently represent H, F, Cl, Br, I, D, CN, NO ₂ , CF ₃ , B (OR ² ₂ ), Si(R ² ) ₃ , linear alkanes, alkane ethers, alkane sulfides having 1 to 10 carbon atoms, branched paraffins, cycloalkanes, alkane ethers having 3 to 10 carbon atoms or alkane sulfides Group

R ² in each occurrence, the same or different selected from H, D, aliphatic alkanes having 1 to 10 carbon atoms, aromatic hydrocarbons, substituted or unsubstituted aromatic groups having 5 to 10 ring atoms Ring or aromatic hetero group.

A high polymer, the compound corresponding to the repeating unit of the high polymer comprising the above organic compound.

a mixture comprising the above organic compound and an organic functional material, or the mixture comprising the above-mentioned high polymer and an organic functional material;

The organic functional material is selected from at least one of a hole injecting material, a hole transporting material, an electron transporting material, an electron injecting material, an electron blocking material, a hole blocking material, an illuminant, a host material, and an organic dye.

a composition comprising the above organic compound and at least one organic solvent;

Alternatively, the composition comprises the high polymer of any of the above and at least one organic solvent;

Alternatively, the composition comprises the mixture of any of the above and at least one organic solvent.

The use of the above organic compounds or polymers in electronic devices.

An organic electronic device comprising the above organic compound, the above-mentioned high polymer or a mixture of the above.

detailed description

In order to make the objects, technical solutions and effects of the present invention more clear and clear, the present invention will be further described in detail below. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

In this context, the composition and printing ink, or ink, have the same meaning and are interchangeable. In this context, host materials, matrix materials, Host or Matrix materials have the same meaning and are interchangeable. Herein, metal organic complexes, metal organic complexes, and organometallic complexes have the same meaning and are interchangeable.

The organic compound of one embodiment has the following general formula (1):

Wherein -X- and -Y- respectively represent -O-, -S-, -S=O-, -SO ₂ -, -N(R ₁₀₀ )-, -C(R ₂₀₀ )(R ₂₀₁ )- Or -Si(R ₃₀₀ )(R ₃₀₁ )-.

-X- and -Y- are two bridged groups. X is bonded to Ar ₁ and the intermediate benzene ring by a single bond or a double bond, and Y is bonded to Ar ₂ and the intermediate benzene ring by a single bond or a double bond. The intermediate benzene ring specifically refers to a benzene ring having R ₁ and R ₂ substituted.

The same or different Ar ₁ and Ar ₂ represent an aromatic having 6 to 20 carbon atoms or a heteroaromatic or non-aromatic having 2 to 20 carbon atoms which are unsubstituted or substituted by one or more groups R ¹ . Ring system.

The same or different Ar ₃ and Ar ₄ represent an aromatic having 6 to 40 carbon atoms or a heteroaromatic or non-aromatic having 2 to 40 carbon atoms which are unsubstituted or substituted by one or more groups R ¹ . Ring system.

The groups R ¹ may be the same or different when they occur multiple times.

R ₁ , R ₂ , R ₁₀₀ , R ₂₀₀ , R ₂₀₁ , R ₃₀₀ , R ₃₀₁ and R ¹ each independently represent H, F, Cl, Br, I, D, CN, NO ₂ , CF ₃ , B, respectively. (OR ² ) ₂ , Si(R ² ) ₃ , linear alkane, alkane ether, alkane sulfide having 1 to 10 carbon atoms, branched alkane, cycloalkane, alkane ether having 3 to 10 carbon atoms or Alkane thioether group;

In certain embodiments, each of R ₁ , R ₂ , R ₁₀₀ , R ₂₀₀ , R ₂₀₁ , R ₃₀₀ , R _{301 ,} and R ¹ may be substituted with one or more reactive groups R ² . And one or more non-adjacent methylene groups (CH ₂ ) may be replaced by the group consisting of R ² C=CR ² , C=C, Si(R ² ) ₂ , Ge(R ² ) ₂ , Sn(R ² ) ₂ , C=O, C=S, C=Se, C=N(R ² ), O, S, -COO-, or CONR ² , wherein one or more H atoms can be D, Substituting F, Cl, Br, I, CN, or N ₂ , or replacing it with one or more active R ² or an aromatic group and a heteroaromatic substituted aromatic amine, or substituted or unsubstituted anthracene The azole is replaced.

In some embodiments, -X- and -Y- are each independently selected from one of the following structural groups:

Wherein R ₃ , R ₄ , R ₅ and R ₆ independently represent H, F, Cl, Br, I, D, CN, NO ₂ , CF ₃ , B(OR ² ) ₂ , Si (R ² ), respectively. ₃ ) a linear alkane, an alkane ether, an alkane sulfide having 1 to 10 carbon atoms, a branched alkane, a cycloalkane, an alkane ether having 3 to 10 carbon atoms or an alkane sulfide group;

The dotted line bond in the above structural group represents a bond in which X or Y is bonded to Ar ₁ , Ar ₂ or an intermediate benzene ring.

In some embodiments, -X- and -Y- are independently selected from the group consisting of -O-, -S-, -S=O-, -SO ₂ -, -N(R ₁₀₀ ), -C(R ₂₀₀ ). (R ₂₀₁ )- or -Si(R ₃₀₀ )(R ₃₀₁ )-.

In each occurrence, Ar ¹ to Ar ⁴ may be the same or different heteroaromatic groups having 6 to 20 carbon atoms or heteroaroms having 2 to 20 carbon atoms which are unsubstituted or substituted by R ₁ . ring.

In some embodiments, the aromatic ring system comprises from 5 to 18 carbon atoms in the ring system, and the heteroaromatic ring system comprises from 2 to 8 carbon atoms and at least one hetero atom in the ring system, provided that the carbon atom and the hetero atom are The total number is at least 4. In some embodiments, the aromatic ring system contains from 5 to 16 carbon atoms in the ring system, and the heteroaromatic ring system contains from 2 to 16 carbon atoms and at least one hetero atom in the ring system. In some embodiments, the aromatic ring system contains from 5 to 13 carbon atoms in the ring system, and the heteroaromatic ring system contains from 2 to 13 carbon atoms and at least one hetero atom in the ring system. The hetero atom may be selected from the group consisting of Si, N, P, O, S, and/or Ge. In some embodiments, the hetero atom is selected from the group consisting of Si, N, P, O, and/or S.

An aromatic ring system or aromatic group refers to a hydrocarbon group containing at least one aromatic ring, including a monocyclic group and a polycyclic ring system. A heteroaromatic or heteroaromatic group refers to a hydrocarbyl group (containing heteroatoms) comprising at least one heteroaromatic ring, including monocyclic groups and polycyclic ring systems. These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, a fused ring. At least one of these rings of the polycyclic ring is aromatic or heteroaromatic. For the purposes of the present invention, aromatic or heteroaromatic ring systems include not only aromatic or heteroaromatic systems, but also wherein multiple aryl or heteroaryl groups may also be interrupted by short non-aromatic units (eg, <10). % of non-H atoms, 5% of non-H atoms, such as C, N or O atoms). Thus, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, etc., are also considered to be aromatic ring systems for the purposes of the present invention.

Specifically, examples of the aromatic group are: benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, anthracene, benzofluorene, triphenylene, anthracene, anthracene, and derivatives thereof.

Specifically, examples of heteroaromatic groups are: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, anthracene, anthracene Oxazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrol, furanfuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, Pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-diazine, quinoxaline, phenanthridine, carbaidine, quinazoline, quinazolinone, and derivatives thereof.

In certain embodiments, at least one of Ar ¹ -Ar ⁴ comprises a non-aromatic ring system having from 2 to 20 carbon atoms unsubstituted or substituted with R ₁ .

For the purposes of the present invention, a non-aromatic ring system contains from 1 to 10 carbon atoms in the ring system, for example from 1 to 6 carbon atoms, and includes not only saturated but also partially unsaturated cyclic systems, which may or may not It is substituted or substituted by the group R ₁ . The groups R ₁ may be the same or different in each occurrence, and may also contain one or more heteroatoms, for example Si, N, P, O, S and/or Ge, in some embodiments The atom is selected from the group consisting of Si, N, P, O, and/or S. These may, for example, be cyclohexyl- or piperidine-like systems or ring-like octadiene ring systems. The term also applies to fused non-aromatic ring systems.

For the purposes of the present invention, wherein the H atom or the bridging group CH ₂ group on NH may be substituted by an R ¹ group, R ¹ may be selected from, (1) a C ₁ - C ₁₀ alkyl group, for example, a methyl group, Ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, n-hexyl, cyclo Hexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoromethyl, 2,2,2-trifluoroethyl, vinyl, propenyl , butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butyne a group, a pentynyl group, a hexynyl group and an octynyl group; (2) a C ₁ -C ₁₀ alkoxy group, for example: a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group , isobutoxy, sec-butoxy, tert-butoxy or 2-methylbutoxy; (3) C ₂ -C ₁₀ aryl or heteroaryl, which may be monovalent or divalent depending on the use In each case, it can also be substituted by the above mentioned group R ¹ and can be passed through any desired position. Aromatic or heteroaromatic ring linkages, for example: benzene, naphthalene, anthracene, phthalocyanine, dihydroanthracene, fluorene, fluorene, fluoranthene, butyl, pentacene, benzopyrene, furan, benzofuran, isobenzo Furan, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, thiopurine, pyrrole, hydrazine, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo -5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, oxazole, imidazole, benzimidazole, naphtho Imidazole, phenamimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, indoloxazole, phenanthroxazole, isoxazole, 1, 2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzoxazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, diazonium, 1,5-naphthyridine, hydrazine Oxazole, benzoporphyrin, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4- Oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5- Thiadiazole, 1,3,4-thiadiazole, 1,3,5- Triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole. 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, anthracene, pteridine, guanidinium and benzothiadiazole. For the purposes of the present invention, aromatic and heteroaromatic ring systems are considered to be especially in addition to the above-mentioned aryl and heteroaryl groups, but also to biphenylene, benzene terphenyl, anthracene, spirobifluorene, dihydrogen. Phenanthrene, tetrahydroanthracene and cis or trans fluorene.

In certain embodiments, the compound according to formula (1) wherein Ar ¹ is the same or different from Ar ² is selected from the group consisting of an aromatic having 6 to 10 carbon atoms and 2 to 10 carbon atoms in each occurrence. Heteroaromatic or non-aromatic ring systems which may be unsubstituted or substituted by one or more R ₁ groups. Specifically, the aromatic group or heteroaryl group may be selected from benzene, naphthalene, anthracene, phenanthrene, pyridine, perylene or thiophene.

In some embodiments, Ar ₁ in the chemical formula (1) may be the same as or different from Ar ₂ and may be selected from one of the following structural groups:

Wherein X ₁ is C(R ₆ ) or N; Y _{1 is} selected from C(R ₇ R ₈ ), Si(R ₉ R ₁₀ ), N(R ₁₁ ) or, C(=O), S, or O ;

R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ are H, or D, or a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms or a silyl group or a substituted ketone group having 1 to 20 C atoms a group, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, a cyano group (-CN), a carbamoyl group (- C(=O)NH ₂ ), haloformyl group (-C(=O)-X wherein X represents a halogen atom), formyl group (-C(=O)-H), isocyanato group , isocyanate group, thiocyanate group or isothiocyanate group, hydroxyl group, nitro group, CF ₃ group, Cl, Br, F, crosslinkable group or having 5 to a substituted or unsubstituted aromatic or heteroaromatic ring system of 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems, one or more of which radicals _{_{_{R 6, R 7, R 8}}} , R 9, R 10, R 11 may be and / or the group bonded to each other in the ring To aliphatic monocyclic or polycyclic aromatic or aromatic ring.

In certain embodiments, Ar ₁ in the formula (1) is the same as or different from Ar ₂ and is selected from the group consisting of the following: or one of the substituent units in which the structural unit is further substituted:

In certain embodiments, the organic compound as shown in structural formula (1) has a higher triplet energy level T ₁ , typically T ₁ ≥ 2.0 eV. In some embodiments T ₁ ≥ 2.2 eV. In some embodiments T ₁ ≥ 2.4 eV. In some embodiments T ₁ ≥ 2.6 eV. In some embodiments T ₁ ≥ 2.8 eV.

Generally, the triplet level T ₁ of an organic compound depends on the substructure of the compound having the largest conjugated system. Generally, T ₁ decreases as the conjugated system increases. In certain embodiments, the organic compound has a larger conjugated system with a substructure of the organic compound represented by the following formula (1a).

In certain embodiments, the formula (1a) has no more than 32 ring atoms in the case of removing the substituent, and in one embodiment, the number of ring atoms is not more than 28. In one embodiment, the number of ring atoms does not exceed 25, and in one embodiment, the number of ring atoms does not exceed 22.

In some embodiments, the sub-structure according to formula (1a) in the case of removal of a substituent, T ₁ which is no greater than any other sub-structures of the remaining T _1.

In other embodiments, the sub-structure according to formula (1a) has a higher triplet energy level T ₁ , typically T ₁ ≥ 2.0 eV, in the removal of substituents, in some embodiments, T ₁ ≥ 2.2 eV, in some embodiments, T ₁ ≥ 2.4 eV, in some embodiments, T ₁ ≥ 2.6 eV, and in some embodiments, T ₁ ≥ 2.8 eV.

In certain embodiments, the organic compound has the formula shown by any one of the following formulas (2) to (8):

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₀₀ , R ₂₀₀ , R ₂₀₁ , R ₃₀₀ and R ₃₀₁ are each independently represented independently H, F, Cl, Br, I, D, CN, NO ₂ , CF ₃ , B(OR ² ) ₂ , Si(R ² ) ₃ , linear alkane, alkane ether, alkane having 1 to 10 carbon atoms a thioether, a branched alkane, a cycloalkane, an alkane ether having 3 to 10 carbon atoms or an alkane sulfide group. Each of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₀₀ , R ₂₀₀ , R ₂₀₁ , R ₃₀₀ and R ₃₀₁ Each is substituted with one or more reactive groups R ² and one or more non-adjacent methylene groups (CH ₂ ) may be replaced by the group consisting of R ² C=CR ² , C=C, Si (R ² ) ₂ , Ge(R ² ) ₂ , Sn(R ² ) ₂ , C=O, C=S, C=Se, C=N(R ² ), O, S, -COO-, or CONR ² , wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or N ₂ or by one or more active R ² or an aromatic group and a heteroaromatic ring Aromatic amine substitution, or replacement of substituted or unsubstituted carbazole.

In some embodiments, R ₃ and R ₄ , R ₄ and R ₅ , R ₅ and R ₆ , R ₇ and R ₈ , R ₈ and R ₉ , R ₉ and R ₁₀ may also be bonded to each other to form a cyclic structure. .

L ₁ is a substituted or unsubstituted aliphatic alkyl chain having 2 to 60 carbon atoms or an aromatic ring having 6 to 60 carbon atoms or a heterocyclic ring having 2 to 60 carbon atoms. For example, L ₁ may be an aromatic or heteroaromatic ring having 5 to 24 aromatic ring atoms, which ring system may in each case be substituted by one or more groups R ² . For example, it may be a phenyl group, an ortho, meta or para biphenyl group, an ortho, meta, para or branched triphenyl group, an ortho, meta, para or branched tetraphenyl group. , 1-indenyl, 2-indenyl or 3-indenyl, 1-spirobi-yl, 2-spirobi-yl, 3-spirobi-yl or 4-spirobi-yl, 1-naphthyl or 2 -naphthyl, pyrrole, furan, thiophene, anthracene, benzofuran, benzothiophene, 1-oxazole, 2-oxazole or 3-oxazole, 1-dibenzofuran, 2-dibenzofuran or 3-dibenzofuran, 1-dibenzothiophene, 2-dibenzothiophene or 3-dibenzothiophene, indolocarbazole, indolocarbazole, 2-pyridine, 3-pyridine or 4-pyridine , 2-pyrimidine, 4-pyrimidine or 5-pyrimidine, pyrazine, pyridazine, triazine, anthracene, phenanthrene, triphenylene, anthracene, benzofluorene, or a combination of two or three of these groups. Each of the groups may be substituted with one or more groups R ² . In particular, the above groups may also pass through a substituted or unsubstituted aliphatic alkyl chain having from 2 to 60 carbon atoms, including a C ₁ -C ₁₀ alkyl group, for example, a methyl group, an ethyl group, a n-propyl group, Isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, ring Heptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoromethyl, 2,2,2-trifluoroethyl, vinyl, propenyl, butenyl, pentene Base, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexyl Alkynyl and octynyl; C ₁ -C ₁₀ alkoxy, particularly preferred are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butyl Oxy, tert-butoxy or 2-methylbutoxy.

Although this is obvious from the description, it should be clearly pointed out once again that in addition to the general formulae (7) and (8), any two of the (2) to (6) units may be used, and the same or different units may pass. L _{1 is} connected.

In certain embodiments, according to the compound of the formula (1), wherein Ar ₃ and Ar _{4 are} present multiple times, they may have the structure represented by the following formula (2):

Wherein Ar _{6 is} as defined above for Ar ₁ or Ar ₂ .

In certain embodiments, wherein Ar ₃ , Ar ₄ , Ar ₆ may, when present multiple times, comprise the following structural units or combinations thereof, or a combination unit in which the following structural units or combinations thereof are further substituted; .

Specifically, the energy level difference Δ(S ₁ -T ₁ ) of the singlet state (S ₁ ) and the triplet state (T ₁ ) of the organic compound represented by the structural formula ( ₁ ) is ≤0.30 eV. In some embodiments, Δ(S ₁ -T ₁ )≤0.25eV, in some embodiments, Δ(S ₁ -T ₁ )≤0.20eV, in some embodiments, Δ(S ₁ -T ₁ ) ≤0.10eV. In some embodiments, Δ(S ₁ -T ₁ )≤0.05eV

According to the principle of thermal excitation delayed fluorescent TADF material (see Adachi et al., Nature Vol 492, 234, (2012)), when the Δ(S ₁ -T ₁ ) of the organic compound is sufficiently small, the triplet excitons of the organic compound can pass. Reverse internal conversion to singlet excitons for efficient illumination. In general, TADF materials are obtained by electron donating (Donor) to electron-deficient or acceptor groups, i.e., having a distinct DA structure. The organic compounds of the above examples facilitate the obtaining of thermally excited delayed fluorescent TADF properties.

In certain embodiments, the compound according to formula (1) does not have a distinct D-A structure, and its HOMO, LUMO orbitals at least partially overlap, preferably most overlap.

In certain embodiments, according to the compound of formula (1) wherein Ar ₃ and Ar _{4 are} present multiple times, at least one Ar ₃ or Ar ₄ comprises an electron donating group, and/or at least one Ar ₃ or Ar ₄ contains an electron withdrawing group.

In some embodiments, the organic compound has the structural formula of the formula (1a), and has an electron withdrawing property, at least one of Ar ³ or Ar ⁴ contains an electron donating group, and further, both Ar ³ and Ar ⁴ contain one Electronic basis.

In certain embodiments, the organic compound having electron withdrawing properties is selected from one of the following structural groups:

In certain embodiments, the organic compound has an electron withdrawing property, wherein at least one of -X-, -Y- is selected from the group consisting of:

In another embodiment, the organic compound has the structural formula of the formula (1a), and has electron donating characteristics. At least one of Ar ³ or Ar ⁴ contains an electron donating group, and more preferably, both Ar ³ and Ar ⁴ contain one. Electronic basis.

In certain embodiments, the organic compound having an electron donating property is selected from one of the following structural groups:

In certain embodiments, according to the compound of formula (1), one of Ar ³ , Ar ⁴ contains at least one electron-donating group and the other contains at least one electron-withdrawing group.

In some embodiments, the electron donating group is selected from one of the following groups D1 to D10:

In some embodiments, the electron withdrawing group is selected from the group consisting of F, cyano, or the structure of the electron withdrawing group comprises one of the following structural groups:

Wherein a is 1, 2, 3 or 4; X ² to X ^{9 are} selected from C(R) or N, and at least one is N;

-Z ₁ -, -Z ₂ -, -Z ₃ - optionally represent -N(R)-, -C(R) ₂ -, -Si(R) ₂ -, -O-, -C=N ( R)-, -C=C(R) ₂ -, -P(R)-, -P(=O)R-, -S-, -S=O- or -SO ₂ -; wherein R may be selected from One of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl. The positions corresponding to Z ₁ , Z ₂ , and Z ₃ may also have no connection of keys, but at least one is not absent.

According to the general formula (1), the following are non-limiting specific examples of organic compounds which may also be substituted at all possible substitution points.

In one embodiment, the above organic compound is a small molecule material.

The term "small molecule" as defined herein refers to a molecule that is not a polymer, oligomer, dendrimer, or blend. In particular, there are no repeating structures in small molecules. The molecular weight of the small molecule is ≤4000 g/mol, such as ≤3000 g/mol, and further, for example, ≤2000 g/mol.

The polymer, that is, the polymer, includes a homopolymer, a copolymer, and a block copolymer. In addition, in the present invention, the high polymer also includes a dendrimer. For the synthesis and application of the tree, see [Dendrimers and Dendrons, Wiley-VCH Verlag GmbH & Co. KGaA, 2002, Ed. George R. Newkome, Charles N. Moorefield, Fritz Vogtle.].

Conjugated polymer (conjugated polymer) is a polymer whose main chain is mainly composed of a backbone atoms of sp C ² hybrid orbital, well-known examples are: polyacetylene, polyacetylene and poly (phenylene vinylene), the main The C atom on the chain can also be substituted by other non-C atoms, and is still considered a conjugated polymer when the sp ² hybrid on the backbone is interrupted by some natural defects. Further, in the present invention, the conjugated high polymer also includes an aryl amine, an aryl phosphine and other heteroarmotics, and an organometallic complexes in the main chain. )Wait.

The polymer of an embodiment comprising a repeating unit, wherein the compound corresponding to the repeating unit comprises a structural unit as shown in the formula (1). In certain embodiments, the high polymer is a non-conjugated high polymer wherein the structural unit as shown in the general formula (1) is on the side chain of the high polymer. In another embodiment, the high polymer is a conjugated high polymer.

A mixture of an embodiment comprising at least one organic compound according to the invention, and at least one other organic functional material. Alternatively, the mixture comprises at least one of the polymers of the invention and an organic functional material.

Organic functional materials, available from HIM, HTM, ETM, EIM, EBM, HBM, Emitter, Host and organic dyes Wait. These organic functional materials are described in detail in, for example, WO2010135519A1, US20090134784A1, and WO 2011110277A1, the entire contents of each of which are incorporated herein by reference. The organic functional material may be a small molecule and a high polymer material.

In one embodiment, the mixture comprises an organic compound or polymer according to the invention, and a phosphorescent emitter. The organic compound according to the invention here can be used as the host, the phosphorescent emitter weight percentage ≤ 30% by weight, for example ≤25% by weight, or ≤20% by weight.

In another embodiment, the mixture comprises an organic compound or polymer according to the invention, and a host material. The organic compound according to the invention here can be used as a luminescent material in a weight percentage ≤ 30% by weight, for example ≤25% by weight, or ≤20% by weight, or ≤15% by weight.

In one embodiment, the mixture comprises an organic compound or polymer according to the invention, a phosphorescent emitter and a host material. In one embodiment, the organic compound according to the invention may be used as an auxiliary luminescent material in a weight ratio to phosphorescent emitter of from 1:2 to 2:1. In another embodiment, the organic compound according to the present invention a T ₁ higher than the phosphorescent emitter.

In certain embodiments, the mixture comprises an organic compound or polymer according to the invention, and another TADF material.

In other embodiments, the mixture comprises an organic compound or polymer according to the invention, and another HTM material.

The HTM, host material, phosphorescent material and TADF material are described in more detail below (but are not limited thereto).

1. HIM/HTM

HTM is sometimes referred to as a p-type organic semiconductor material. Suitable HIM/HTM materials may optionally comprise compounds having the following structural units: phthalocyanine, porphyrin, amine, aromatic amine, biphenyl triarylamine, thiophene, and thiophene such as dithienothiophene and thiophene, pyrrole, aniline, Carbazole, azepine and azepine, and their derivatives. Suitable suitable HIMs also include fluorocarbon-containing polymers; conductively doped polymers; conductive polymers such as PEDOT/PSS; self-assembling monomers such as compounds containing phosphonic acid and silane derivatives; a substance such as MoO _x ; a metal complex, and a crosslinking compound.

Examples of cyclic aromatic amine-derived compounds that can be used as HIM or HTM include, but are not limited to, the following general structures:

Wherein each of Ar ¹ to Ar ⁹ may be independently selected from a cyclic aromatic hydrocarbon group such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenalrene, phenanthrene, anthracene, anthracene, pyrene, anthracene, anthracene Aromatic heterocyclic groups such as dibenzothiophene, dibenzofuran, furan, thiophene, benzofuran, benzothiophene, oxazole, pyrazole, imidazole, triazole, isoxazole, thiazole, dioxin Azole, triazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazole, dioxazin, hydrazine, benzimidazole, carbazole, guanamine , benzoxazole, benzoxazole, benzothiazole, quinoline, isoquinoline, o-diaza(hetero)naphthalene, quinazoline, quinoxaline, naphthalene, anthracene, pteridine, xanthene, anthracene Pyridine, phenazine, phenothiazine, phenoxazine, diphenylselenophene, benzoselenophene, quinoline, carbazole, pyridinium, dipyridylpyrrole, dipyridylfuran, phenylthienopyridine, dipyridine Thiophene, phenylpyridine selenium and dipyridyl selenophene; groups containing a 2 to 10 ring structure, which may be the same or different types of cyclic aromatic hydrocarbon groups or aromatic heterocyclic groups, and are directly related to each other Or linked together by at least one of the following groups, such as an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit, and an aliphatic ring group. Wherein each of Ar may be further substituted, and the substituent may be hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl or heteroaryl.

In one aspect, Ar ¹ to Ar ⁹ may be independently selected from the group consisting of:

Wherein n is an integer from 1 to 20; X ¹ to X ⁸ are CH or N; and Ar ^{1 is} as defined above. Further examples of cyclic aromatic amine-derived compounds can be found in US Pat. No. 3,567,450, US Pat. No. 4,724, 432, US Pat. No. 5,061,569, US Pat.

Examples of metal complexes that can be used as HTM or HIM include, but are not limited to, the following general structures:

Wherein M is a metal having an atomic weight greater than 40; (Y ¹ -Y ² ) is a bidentate ligand, and Y ¹ and Y ^{2 are} independently selected from C, N, O, P, and S; L is an auxiliary Ligand; m is an integer whose value ranges from 1 to the maximum coordination number of the metal; m+n is the maximum coordination number of the metal. In one embodiment, (Y ¹ -Y ² ) is a 2-phenylpyridine derivative. In another embodiment, (Y ¹ -Y ² ) is a carbene ligand. In another embodiment, M is selected from the group consisting of Ir, Pt, Os, and Zn. In another aspect, the HOMO of the metal complex is greater than -5.5 eV (relative to the vacuum level).

Examples of suitable HTM compounds are listed in the table below:

2. Triplet Body Material (TripletHost):

The example of the triplet host material is not particularly limited, and any metal complex or organic compound may be used as the host as long as its triplet energy is higher than that of the illuminant, particularly the triplet illuminant or the phosphorescent illuminant. Examples of metal complexes that can be used as the triplet host include, but are not limited to, the following general structure:

M is a metal; (Y ³ -Y ⁴ ) is a bidentate ligand, Y ³ and Y ^{4 are} independently selected from C, N, O, P, and S; L is an ancillary ligand; m is an integer , the value from 1 to the maximum coordination number of this metal; m + n is the maximum coordination number of this metal.

In one embodiment, the metal complex that can be used as the triplet host has the following form:

(O-N) is a two-tooth ligand in which the metal is coordinated to the O and N atoms.

In a certain embodiment, M can be selected from Ir and Pt.

Examples of the organic compound which can be used as the host of the triplet state are selected from compounds containing a cyclic aromatic hydrocarbon group such as benzene, biphenyl, triphenyl, benzo, anthracene; compounds containing an aromatic heterocyclic group such as dibenzothiophene, Dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, carbazole, pyridinium, pyrrole dipyridine, pyrazole, imidazole, three Azole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, thiazide, dioxazin, hydrazine Anthracene, benzimidazole, oxazole, oxazole, dibenzoxazole, benzoisoxazole, benzothiazole, quinoline, isoquinoline, o-naphthyridine, quinazoline, quinoxaline, naphthalene, Anthraquinone, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranpyridine, furopyridine, benzothienopyridine, thienopyridine, benzoselenopyridine and selenophene a dipyridine; a group containing a 2 to 10 ring structure, which may be the same or different types of a cyclic aromatic hydrocarbon group or an aromatic heterocyclic group And coupled to each other directly or through at least one of the following groups together, such as an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, chain structural unit and the aliphatic cyclic group. Wherein each of Ar may be further substituted, and the substituent may be hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl or heteroaryl.

In one embodiment, the triplet host material can be selected from compounds comprising at least one of the following groups:

R ¹ -R ⁷ may be independently of one another selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl, when they are aromatic Or a heteroaryl group, they have the same meaning as Ar ¹ and Ar ² described above;

n is an integer from 0 to 20; X ¹ -X ^{8 is} selected from CH or N; and X ^{9 is} selected from CR ¹ R ² or NR ¹ .

Examples of suitable triplet host materials are listed in the table below:

3. Phosphorescent materials

Phosphorescent materials are also called triplet emitters. In a preferred embodiment, the triplet emitter is a metal complex of the formula M(L)n, wherein M is a metal atom, and each occurrence of L may be the same or different and is an organic ligand. It is bonded to the metal atom M by one or more positional bonding or coordination, and n is an integer greater than 1, preferably 1, 2, 3, 4, 5 or 6. Alternatively, these metal complexes are coupled to a polymer by one or more positions, preferably by an organic ligand.

In one embodiment, the metal atom M is selected from a transition metal element or a lanthanide or a lanthanide element, preferably Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy, Re , Cu or Ag, particularly preferred Os, Ir, Ru, Rh, Re, Pd or Pt.

In particular, the triplet emitter comprises a chelating ligand, ie a ligand, coordinated to the metal by at least two bonding sites, with particular preference being given to the triplet emitter comprising two or three identical or different pairs Tooth or multidentate ligand. Chelating ligands are beneficial for increasing the stability of metal complexes.

Examples of the organic ligand may be selected from a phenylpyridine derivative, a 7,8-benzoquinoline derivative, a 2(2-thienyl)pyridine derivative, a 2(1-naphthyl)pyridine derivative, or a 2 benzene. A quinolinol derivative. All of these organic ligands may be substituted, for example by fluorine or trifluoromethyl. The ancillary ligand may preferably be selected from the group consisting of acetone acetate or picric acid.

In one embodiment, the metal complex that can be used as the triplet emitter has the following form:

Wherein M is a metal selected from transition metal elements or lanthanides or actinides;

Ar ¹ may be the same or different at each occurrence, and is a cyclic group containing at least one donor atom, that is, an atom having a lone pair of electrons, such as nitrogen or phosphorus, through which a cyclic group is coordinated to a metal. Connection; Ar ² may be the same or different each time it appears, is a cyclic group containing at least one C atom through which a cyclic group is attached to the metal; Ar ¹ and Ar ² are bonded by a covalent bond Together, each may carry one or more substituent groups which may also be joined together by a substituent group; each occurrence of L may be the same or different and is an ancillary ligand, preferably a bidentate chelate ligand Preferred is a monoanionic bidentate chelate ligand; m is 1, 2 or 3, preferably 2 or 3, particularly preferably 3; n is 0, 1, or 2, preferably 0 or 1, Particularly preferred is 0;

Triplet emitters are also known as phosphorescent emitters. In one embodiment, the triplet emitter is a metal complex of the formula M(L)n, wherein M is a metal atom, and each occurrence of L may be the same or different and is an organic ligand. It is bonded to the metal atom M by one or more positional bonding or coordination, and n is an integer greater than 1, preferably 1, 2, 3, 4, 5 or 6. Alternatively, these metal complexes are coupled to a polymer by one or more positions, preferably by an organic ligand.

Specifically, the triplet emitter comprises a chelating ligand, ie, a ligand, coordinated to the metal by at least two bonding sites, and it is particularly preferred that the triplet emitter comprises two or three identical or different pairs Tooth or multidentate ligand. Chelating ligands are beneficial for increasing the stability of metal complexes.

Examples of the application of materials for some triplet emitters can be found in the following patent documents and documents: WO 200070655, WO 200141512, WO 200202714, WO 200215645, EP 1191613, EP 1191612, EP 1191614, WO 2005033244, WO 2005019373, US 2005 /0258742, WO 2009146770, WO 2010015307, WO 2010031485, WO 2010054731, WO 2010054728, WO 2010086089, WO 2010099852, WO 2010102709, US 20070087219 A1, US 20090061681 A1, US 20010053462 A1, Baldo, Thompson et al. Nature 403, (2000) ), 750-753, US 20090061681 A1, US 20090061681 A1, Adachi et al. Appl. Phys. Lett. 78 (2001), 1622-1624, J. Kido et al. Appl. Phys. Lett. 65 (1994), 2124, Kido et al. Chem. Lett. 657, 1990, US 2007/0252517 A1, Johnson Et al., JACS 105, 1983, 1795, Wrighton, JACS 96, 1974, 998, Ma et al., Synth. Metals 94, 1998, 245, US 6824895, US 7029766, US 6835469, US 6830828, US 20010053462 A1, WO 2007095118 A1, US 2012004407A1, WO 2012007088A1, WO2012007087A1, WO 2012007086A1, US 2008027220A1, WO 2011157339A1, CN 102282150A, WO 2009118087A1. The entire contents of the above-listed patent documents and documents are hereby incorporated by reference.

4.TADF material

Traditional organic fluorescent materials can only use 25% singlet excitons formed by electrical excitation, and the internal quantum efficiency of the device is low (up to 25%). Although the phosphorescent material enhances the inter-system traversal due to the strong spin-orbit coupling of the center of the heavy atom, it can effectively utilize the singlet excitons and triplet exciton luminescence formed by electrical excitation, so that the internal quantum efficiency of the device reaches 100%. However, the problems of expensive phosphorescent materials, poor material stability, and severe roll-off of device efficiency limit their application in OLEDs. The thermally activated delayed fluorescent luminescent material is a third generation organic luminescent material developed after organic fluorescent materials and organic phosphorescent materials. Such materials generally have a small singlet-triplet energy level difference (ΔEst), and triplet excitons can be converted into singlet exciton luminescence by anti-intersystem crossing. This can make full use of the singlet excitons and triplet excitons formed under electrical excitation. The quantum efficiency in the device can reach 100%. At the same time, the material structure is controllable, the property is stable, the price is cheap, no precious metal is needed, and the application prospect in the OLED field is broad.

The TADF material needs to have a small singlet-triplet energy level difference, preferably ΔEst < 0.3 eV, and secondly ΔEst < 0.2 eV, preferably ΔEst < 0.1 eV. In a preferred embodiment, the TADF material has a relatively small ΔEst, and in another preferred embodiment, the TADF has a better fluorescence quantum efficiency. Some TADF luminescent materials can be found in the following patent documents: CN103483332(A), TW201309696(A), TW201309778(A), TW201343874(A), TW201350558(A), US20120217869(A1), WO2013133359(A1), WO2013154064( A1), Adachi, et.al. Adv. Mater., 21, 2009, 4802, Adachi, et. al. Appl. Phys. Lett., 98, 2011, 083302, Adachi, et. al. Appl. Phys. Lett ., 101, 2012, 093306, Adachi, et. al. Chem. Commun., 48, 2012, 11392, Adachi, et. al. Nature Photonics, 6, 2012, 253, Adachi, et. al. Nature, 492, 2012,234,Adachi,et.al.J.Am.Chem.Soc,134,2012,14706,Adachi,et.al.Angew.Chem.Int.Ed,51,2012,11311,Adachi,et.al. Chem. Commun., 48, 2012, 9580, Adachi, et. al. Chem. Commun., 48, 2013, 10385, Adachi, et. al. Adv. Mater., 25, 2013, 3319, Adachi, et. .Adv. Mater., 25, 2013, 3707, Adachi, et. al. Chem. Mater., 25, 2013, 3038, Adachi, et. al. Chem. Mater., 25, 2013, 3766, Adachi, et. Al.J. Mater. Chem. C., 1, 2013, 4599, Adachi, et. al. J. Phys. Chem. A., 117, 2013, 5607, hereby incorporated by reference to The entire contents are incorporated herein by reference.

Some examples of suitable TADF luminescent materials are listed in the table below:

Another object of the invention is to provide a material solution for printing OLEDs.

In certain embodiments, the organic compound according to the present invention has a molecular weight of ≥ 700 g/mol, in some embodiments, a molecular weight of ≥ 800 g/mol, and in some embodiments, a molecular weight of ≥ 900 g/mol, in some embodiments. In the examples, the molecular weight is ≥1000 g/mol.

In other embodiments, the organic compound according to the present invention has a solubility in toluene of > 10 mg/ml at 25 ° C, and in some embodiments, a solubility of > 15 mg/ml, in some embodiments, its solubility. ≥20mg/ml.

The invention further relates to a composition or ink comprising the above organic compound and at least one organic solvent. Alternatively, the composition comprises the above high polymer and at least one organic solvent. Still alternatively, the composition comprises the above mixture and at least one organic solvent. The invention further provides a film comprising a compound or polymer according to the invention prepared from a solution.

The viscosity and surface tension of the ink are important parameters when used in the printing process. Suitable surface tension parameters for the ink are suitable for the particular substrate and the particular printing method.

In one embodiment, the ink according to the present invention has a surface tension at an operating temperature or at 25 ° C in the range of from about 19 dyne/cm to 50 dyne/cm. In some embodiments, the surface tension is in the range of 22 dyne/cm to 35 dyne/cm. In some embodiments, the surface tension is in the range of 25 dyne/cm to 33 dyne/cm.

In another embodiment, the ink according to the present invention has a viscosity at an operating temperature or 25 ° C in the range of from about 1 cps to about 100 cps. In some embodiments, the viscosity is in the range of 1 cps to 50 cps. In some embodiments, the viscosity is in the range of 1.5 cps to 20 cps. In some embodiments, the viscosity is in the range of 4.0 cps to 20 cps. The composition so formulated will be suitable for ink jet printing.

The viscosity can be adjusted by different methods, such as by selection of a suitable solvent and concentration of the functional material in the ink. The ink containing the compound or polymer according to the present invention can facilitate the adjustment of the printing ink to an appropriate range in accordance with the printing method used. In general, the composition according to the invention comprises a functional material in a weight ratio ranging from 0.3% to 30% by weight, preferably from 0.5% to 20% by weight, more preferably from 0.5% to 15% by weight, even more preferably. It is in the range of 0.5% to 10% by weight, preferably in the range of 1% to 5% by weight.

In some embodiments, the at least one organic solvent is selected from the group consisting of aromatic or heteroaromatic based solvents, particularly aliphatic chain/ring substituted aromatic solvents, or aromatic ketones, in accordance with the inks of the present invention. Solvent, or aromatic ether solvent.

Examples of solvents suitable for the present invention are, but are not limited to, aromatic or heteroaromatic based solvents: p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethyl Naphthalene, 3-isopropylbiphenyl, p-methyl cumene, dipentylbenzene, triphenylbenzene, pentyltoluene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethyl Benzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, two Hexylbenzene, dibutylbenzene, p-diisopropylbenzene, 1-methoxynaphthalene, cyclohexylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methyl Naphthalene, 1,2,4-trichlorobenzene, 1,3-dipropoxybenzene, 4,4-difluorodiphenylmethane, 1,2-dimethoxy-4-(1-propenyl)benzene , diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α,α-dichlorodiphenylmethane, 4-(3-phenylpropane Pyridine, benzyl benzoate, 1,1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, dibenzyl ether, etc.; ketone-based solvent: 1-tetrahydronaphthalene Ketone, 2-tetralone, 2-(phenyl epoxy) tetralone, 6-(methoxy)tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methyl Acetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, isophorone, 2,6,8-trimethyl-4-indanone, anthrone, 2 - anthrone, 3-fluorenone, 5-fluorenone, 2-nonanone, 2,5-hexanedione, phorone, di-n-pentyl ketone; aromatic ether solvent: 3-phenoxytoluene, butyl Oxybenzene, benzylbutylbenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy -2H-pyran, 1,2-dimethoxy-4-(1-propenyl)benzene, 1,4-benzodioxane, 1,3-dipropylbenzene, 2,5-di Methoxytoluene, 4-ethylbenethyl ether, 1,2,4-trimethoxybenzene, 4-(1-propenyl)-1,2-dimethoxybenzene, 1,3-dimethoxybenzene , glycidyl phenyl ether, dibenzyl ether, 4-tert-butyl anisole, trans-p-propenyl anisole, 1,2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether , 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether, pentyl ether c-hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, two Ethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether Ether; ester solvent: alkyl octanoate, alkyl sebacate, alkyl stearate, alkyl benzoate, alkyl phenylacetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkanolactone, An alkyl oleate or the like.

Further, according to the ink of the present invention, the at least one solvent may be selected from the group consisting of: an aliphatic ketone, for example, 2-nonanone, 3-fluorenone, 5-nonanone, 2-nonanone, 2, 5 -hexanedione, 2,6,8-trimethyl-4-indolone, phorone, di-n-pentyl ketone, etc.; or an aliphatic ether, for example, pentyl ether, hexyl ether, dioctyl ether, ethylene Dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether , tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and the like.

In other embodiments, the printing ink further comprises another organic solvent. Examples of another organic solvent include, but are not limited to, methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine , toluene, o-xylene, m-xylene, p-xylene, 1,4 dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1, 1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrogen Naphthalene, decalin, hydrazine and/or mixtures thereof.

In one embodiment, the composition according to the invention is a solution.

In another embodiment, the composition according to the invention is a suspension.

The composition in the examples of the invention may comprise from 0.01 to 20% by weight of the organic compound according to the invention or a mixture thereof, in one embodiment from 0.1 to 15% by weight, in one embodiment from 0.2 to 10% by weight, in one In the examples, it is 0.25 to 5% by weight of an organic compound or a mixture thereof.

The invention further relates to the use of the composition as a printing ink in the preparation of an organic electronic device, particular preference being given to a preparation process by printing or coating.

Among them, suitable printing or coating techniques include, but are not limited to, inkjet printing, Nozzle Printing, typography, screen printing, dip coating, spin coating, blade coating, roller printing, torsion roller Printing, lithography, flexographic printing, rotary printing, spraying, brushing or pad printing, spray printing (Nozzle printing), slit type extrusion coating, and the like. Preferred are ink jet printing, slit type extrusion coating, jet printing and gravure printing. The solution or suspension may additionally contain one or more components such as surface active compounds, lubricants, wetting agents, dispersing agents, hydrophobic agents, binders and the like for adjusting viscosity, film forming properties, adhesion, and the like. For information on printing techniques and their requirements for solutions, such as solvents and concentrations, viscosity, etc., please refer to Helmut Kipphan's "Printing Media Handbook: Techniques and Production Methods" (Handbook of Print Media: Technologies and Production Methods). ), ISBN 3-540-67326-1.

Based on the above organic compounds, the present invention also provides the use of an organic compound or a polymer as described above. For example, the organic compound is applied to an organic electronic device, which is selectable from, but not limited to, an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), and an airport effect. Tube (OFET), organic light-emitting field effect transistor, organic laser, organic spintronic device, organic sensor and organic plasmon emitting diode (Organic Plasmon Emitting Diode), especially OLED. In an embodiment of the invention, the organic compound can be used, for example, in a light-emitting layer of an OLED device.

The invention further relates to an organic electronic device comprising at least one organic compound, polymer or mixture as described above. Typically, such an organic electronic device comprises at least one cathode, an anode and a functional layer between the cathode and the anode, wherein the functional layer comprises at least one organic compound or polymer as described above.

In the above light-emitting device, particularly an OLED, a substrate, an anode, at least one light-emitting layer, and a cathode are included.

The substrate can be opaque or transparent. A transparent substrate can be used to make a transparent light-emitting component. See, for example, Bulovic et al. Nature 1996, 380, p29, and Gu et al, Appl. Phys. Lett. 1996, 68, p2606. The substrate can be rigid or elastic. The substrate can be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice. In a preferred embodiment, the substrate is flexible, optionally in the form of a polymer film or plastic, having a glass transition temperature Tg of 150 ° C or higher, preferably more than 200 ° C, more preferably more than 250 ° C, preferably More than 300 ° C. Examples of suitable flexible substrates are poly(ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).

The anode can comprise a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into a hole injection layer (HIL) or a hole transport layer (HTL) or a light-emitting layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or the valence band level of the illuminant in the luminescent layer or the p-type semiconductor material as the HIL or HTL or electron blocking layer (EBL) is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. Examples of the anode material include, but are not limited to, Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices in accordance with the present invention.

The cathode can include a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the luminescent layer. In one embodiment, the work function of the cathode and the LUMO level of the illuminant or the n-type semiconductor material as an electron injection layer (EIL) or electron transport layer (ETL) or hole blocking layer (HBL) in the luminescent layer or The absolute value of the difference in conduction band energy levels is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. In principle, all materials which can be used as cathodes for OLEDs are possible as cathode materials for the devices of the invention. Examples of the cathode material include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF ₂ /Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, and the like. The cathode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.

The OLED may further include other functional layers such as a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer. (HBL). Materials suitable for use in these functional layers are described in detail above and in WO2010135519A1, US20090134784A1, and WO2011110277A1, the entire contents of each of which are hereby incorporated by reference.

In one embodiment, in the light-emitting device according to the invention, the luminescent layer thereof is prepared by the composition according to the invention.

The light-emitting device according to the present invention has been tested to have an emission wavelength between 300 and 1000 nm, and in some embodiments, an emission wavelength between 350 and 900 nm, and in some embodiments, an emission wavelength between 400 and 800 nm.

The invention further relates to the use of an organic electronic device according to the invention in various electronic devices, including, but not limited to, display devices, illumination devices, light sources, sensors and the like.

The invention further relates to an electronic device comprising an organic electronic device according to the invention, including, but not limited to, a display device, a lighting device, a light source, a sensor and the like.

The present invention will be described with reference to the preferred embodiments thereof, but the present invention is not limited to the embodiments described below. It is to be understood that the scope of the invention is intended to be It is to be understood that the modifications of the various embodiments of the invention are intended to be covered by the spirit and scope of the appended claims.

Specific embodiment

1. Preparation of organic compounds

Example 1 Preparation of Organic Compounds (1)

In a 100 ml single-mouth flask, reactant 1 and reactant 2 (9,9-dimethyl-2-indoleboronic acid) and 2 m of K ₂ CO ₃ aqueous solution were sequentially added while dissolving 1,4-dioxane. Under the protection of nitrogen, the catalyst Pd(PPh ₃ ) _{4 was added} , and the reaction was heated to 100 ° C for 10 hours. The reaction solution was cooled to room temperature, and the reaction was stopped by adding water, and the organic phase was combined and dried over sodium sulfate. Filtration and evaporation of the solvent gave a crude product which was purified using flash column. Yield: 80%. MS (APCI) = 877.1. The reaction formula is as follows:

Example 2 Preparation of Organic Compounds (2)

The synthesis process of compound (2) is similar to the synthesis process of compound (1), except that 9-phenyl-3-borate oxazole is substituted for 9,9-dimethyl-2-indole boronic acid in the above reaction. Things. Yield: 70%. MS (APCI) = 975.2. The reaction formula is as follows:

Example 3 Preparation of Organic Compounds (3)

In a dry single-mouth flask, reactant 3 and reactant 4 and K ₂ CO ₃ powder, cuprous iodide, 18-crown-6 were added in sequence, and a small amount of o-dichlorobenzene was added to dissolve the reactant, nitrogen protection. The reaction is heated to 180 ° C for 20 hours, the reaction solution is cooled to room temperature, the reaction is quenched with water, extracted with dichloromethane, and the organic phase is combined, dried over sodium sulfate, filtered and evaporated to give a crude product. Purify by flash column. Yield: 60%. MS (APCI) = 907.1. The reaction formula is as follows:

2. Energy structure of organic compounds

The energy level of the organic material can be obtained by quantum calculation, for example, by TD-DFT (time-dependent density functional theory) by Gaussian 03W (Gaussian Inc.), and the specific simulation method can be found in WO2011141110. First, the semi-empirical method "Ground State/Semi-empirical/Default Spin/AM1" (Charge 0/Spin Singlet) is used to optimize the molecular geometry, and then the energy structure of the organic molecule is determined by TD-DFT (time-dependent density functional theory) method. Calculated "TD-SCF/DFT/Default Spin/B3PW91" and the base group "6-31G(d)" (Charge 0/Spin Singlet). The HOMO and LUMO levels are calculated according to the following calibration formula, and S1 and T1 are used directly.

HOMO(eV)=((HOMO(G)×27.212)-0.9899)/1.1206

LUMO(eV)=((LUMO(G)×27.212)-2.0041)/1.385

Among them, HOMO(G) and LUMO(G) are direct calculation results of Gaussian 03W, and the unit is Hartree. The results of the materials (1a) to (3a) prepared in Examples 1 to 3 are shown in Table 1:

Table 1: Energy structure of organic compounds

Device Example 1:

An OLED device is prepared using the organic electroluminescent compound of the present invention. The transparent electrode indium tin oxide (ITO) film (15 Ω/sq) on the glass substrate was ultrasonically washed with acetone, ethanol, and isopropyl alcohol, and dried by nitrogen gas, followed by oxygen plasma treatment. The ITO substrate was transferred to a vacuum vapor deposition apparatus and the chamber vacuum was controlled to 10 ^-6 Torr. Subsequently, 35 nm N,N'-bis(1-naphthyl)-N,N'-diphenyl-4,4'-diamine (NPD) was evaporated as a hole transport layer, followed by evaporation of 10 nm 9,9'- (1,3-phenyl)di-9H-carbazole (mCP) as an exciton blocking layer, and then using mCP as a host material, the material (1a) prepared in Example 1 was used as a dopant, and the two materials were Evaporation at different rates and deposition with a doping amount of 6% by weight of dopant (based on the total weight of the matrix material and the dopant) to form a 20 nm luminescent layer, followed by evaporation of 60 nm 1,3, 5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi) was used as an electron transport layer, and then 1 nm of LiF was vapor-deposited as an electron injecting layer, and finally a 150 nm Al cathode was vapor-deposited. Thereafter, the device was packaged with a UV curable resin in a nitrogen glove box. All materials used to prepare the OLED device were purified by vacuum sublimation prior to use.

The prepared OLED device had a luminance of 1261 cd/m ² at 4.8 V and a main emission wavelength of 481 nm.

Device Example 2:

An OLED device was produced in the same manner as in Device Example 1, except that the material (3a) prepared in Example 3 was used as a dopant as a dopant.

The prepared OLED device had a luminance of 1138 cd/m ² at 5.0 V and a main emission wavelength of 463 nm.

It is to be understood that the application of the present invention is not limited to the above-described examples, and those skilled in the art can make modifications and changes in accordance with the above description, all of which are within the scope of the appended claims.

Claims

An organic compound having the following general formula (1):

Wherein -X- and -Y- respectively represent -O-, -S-, -S=O-, -SO 2 -, -N(R 100 )-, -C(R 200 )(R 201 )- Or -Si(R 300 )(R 301 )-;

X and Ar 1 and the intermediate benzene ring are connected by a single bond or a double bond, and Y and Ar 2 and the intermediate benzene ring are connected by a single bond or a double bond;

The same or different Ar 1 and Ar 2 represent an aromatic having 6 to 20 carbon atoms or a heteroaromatic or non-aromatic having 2 to 20 carbon atoms which are unsubstituted or substituted by one or more groups R 1 . Ring system

The same or different Ar 3 and Ar 4 represent an aromatic having 6 to 40 carbon atoms or a heteroaromatic or non-aromatic having 2 to 40 carbon atoms which are unsubstituted or substituted by one or more groups R 1 . Ring system

The groups R 1 may be the same or different when they occur multiple times;

R 1 , R 2 , R 100 , R 200 , R 201 , R 300 , R 301 and R 1 each independently represent H, F, Cl, Br, I, D, CN, NO 2 , CF 3 , B (OR 2 2 ), Si(R 2 ) 3 , linear alkanes, alkane ethers, alkane sulfides having 1 to 10 carbon atoms, branched paraffins, cycloalkanes, alkane ethers having 3 to 10 carbon atoms or alkane sulfides Group

R 2 in each occurrence, the same or different selected from H, D, aliphatic alkanes having 1 to 10 carbon atoms, aromatic hydrocarbons, substituted or unsubstituted aromatic groups having 5 to 10 ring atoms Ring or aromatic hetero group.
The organic compound according to claim 1, wherein -X- and -Y- are each independently one selected from the group consisting of:

Wherein R 3 , R 4 , R 5 and R 6 each independently represent H, F, Cl, Br, I, D, CN, NO 2 , CF 3 , B(OR 2 ) 2 , Si(R 2 ) 3 , a linear alkane, an alkane ether, an alkane sulfide having 1 to 10 carbon atoms, a branched alkane, a cycloalkane, an alkane ether having 3 to 10 carbon atoms or an alkane sulfide group;

R 2 in each occurrence, the same or different selected from H, D, aliphatic alkanes having 1 to 10 carbon atoms, aromatic hydrocarbons, substituted or unsubstituted aromatic groups having 5 to 10 ring atoms Ring or aromatic hetero group;

The dotted line bond in the above structural group represents a bond in which X or Y is bonded to Ar 1 , Ar 2 or an intermediate benzene ring.
The organic compound according to claim 1, wherein Ar 1 and Ar 2 are the same or different ones selected from the group consisting of the following structural units or the substituent units further substituted by the following structural units:
The organic compound according to claim 1, wherein the organic compound has a formula represented by any one of the following formulae (2) to (8):

R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 100 , R 200 , R 201 , R 300 and R 301 each independently represent H, F , Cl, Br, I, D, CN, NO 2 , CF 3 , B(OR 2 ) 2 , Si(R 2 ) 3 , linear alkane, alkane ether, alkane sulfide containing 1 to 10 carbon atoms, a branched alkane, a cycloalkane, an alkane ether having 3 to 10 carbon atoms or an alkane sulfide group;

R 2 in each occurrence, the same or different selected from H, D, aliphatic alkanes having 1 to 10 carbon atoms, aromatic hydrocarbons, substituted or unsubstituted aromatic groups having 5 to 10 ring atoms Ring or aromatic hetero group;

L 1 is a substituted or unsubstituted aliphatic alkyl chain having 2 to 60 carbon atoms or an aromatic ring having 6 to 60 carbon atoms or a heterocyclic ring having 2 to 60 carbon atoms.
The organic compound according to claim 1, wherein Ar 3 and Ar 4 are the same or different ones selected from the following structural units or any two or more of the following structural units; :
The organic compound according to any one of claims 1 to 5, wherein, when Ar 3 and Ar 4 are present multiple times, at least one of Ar 3 or Ar 4 contains an electron-donating group, and/or at least One Ar 3 or Ar 4 contains an electron withdrawing group.
The organic compound according to claim 6, wherein the electron-donating group is selected from one of the following groups D1 to D10:
The organic compound according to claim 6 or 7, wherein the electron withdrawing group is selected from the group consisting of F, cyano, or the electron withdrawing group, and one of the following structural groups:

Where a is 1, 2, 3 or 4;

X 2 to X 9 are selected from C(R) or N, and at least one is N;

-Z 1 -, -Z 2 -, -Z 3 - optionally represent -N(R)-, -C(R) 2 -, -Si(R) 2 -, -O-, -C=N ( R)-, -C=C(R) 2 -, -P(R)-, -P(=O)R-, -S-, -S=O- or -SO 2 -;

Wherein R may be selected from one of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.
The organic compound according to any one of claims 1 to 5, wherein the singlet state and the triplet energy level difference ΔE(S 1 -T 1 ) of the organic compound are ≤0.30 eV.
The organic compound according to any one of claims 1 to 5, wherein the singlet and triplet energy level difference ΔE(S 1 -T 1 ) of the organic compound is ≤0.10 eV.
A high polymer characterized in that the compound corresponding to the repeating unit of the high polymer comprises the organic compound according to any one of claims 1 to 10.
The high polymer according to claim 11, wherein the high polymer is a non-conjugated high polymer, and the organic compound according to any one of claims 1 to 10 is located in the high polymer. On the side chain.
The high polymer according to claim 11, wherein the high polymer is a conjugated high polymer.
A mixture, characterized in that the mixture comprises the organic compound according to any one of claims 1 to 10 and an organic functional material, or the mixture comprises the method according to any one of claims 11 to 13 High polymer and organic functional materials;

The organic functional material is selected from at least one of a hole injecting material, a hole transporting material, an electron transporting material, an electron injecting material, an electron blocking material, a hole blocking material, an illuminant, a host material, and an organic dye.
A composition comprising the organic compound according to any one of claims 1 to 10 and at least one organic solvent;

Alternatively, the composition comprises the high polymer according to any one of claims 11 to 13 and at least one organic solvent;

Alternatively, the composition comprises the mixture of claim 14 and at least one organic solvent.
Use of an organic compound according to any one of claims 1 to 10 or a high polymer according to any one of claims 11 to 13 in an electronic device.
An organic electronic device comprising the organic compound according to any one of claims 1 to 10, the high polymer according to any one of claims 11 to 13 or the method according to claim 14. mixture.
The organic electronic device according to claim 17, wherein the organic electronic device is selected from the group consisting of an organic light emitting diode, an organic photovoltaic cell, an organic light emitting battery, an organic field effect transistor, an organic light emitting field effect transistor, an organic sensor, and an organic device. At least one of the exciter emission diodes.
The organic electronic device according to claim 17, wherein the organic electronic device is an electroluminescent device, and the light-emitting layer of the electroluminescent device comprises at least one organic compound according to claims 1 to 10. And a luminescent material;

Or the luminescent layer comprises at least one high polymer according to any one of claims 11 to 13 and a luminescent material;

Or the luminescent layer comprises at least one mixture according to claim 14 and a luminescent material;

The luminescent material is selected from the group consisting of a fluorescent illuminant, a phosphorescent illuminant, a TADF material or a luminescent quantum dot.