WO2019114765A1 - 双极性化合物、高聚物、混合物、组合物、有机电子器件及应用 - Google Patents

双极性化合物、高聚物、混合物、组合物、有机电子器件及应用 Download PDF

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WO2019114765A1
WO2019114765A1 PCT/CN2018/120702 CN2018120702W WO2019114765A1 WO 2019114765 A1 WO2019114765 A1 WO 2019114765A1 CN 2018120702 W CN2018120702 W CN 2018120702W WO 2019114765 A1 WO2019114765 A1 WO 2019114765A1
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substituted
bipolar compound
unsubstituted
organic
group
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PCT/CN2018/120702
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English (en)
French (fr)
Inventor
何锐锋
林伟杰
吴灿杰
潘君友
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广州华睿光电材料有限公司
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Priority to CN201880070059.4A priority Critical patent/CN111278819A/zh
Publication of WO2019114765A1 publication Critical patent/WO2019114765A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • This invention relates to bipolar compounds, including polymers, mixtures and compositions thereof, organic electronic devices and applications.
  • the invention further relates to an electronic device comprising the bipolar compound and to its use, in particular in an electroluminescent device.
  • Organic semiconductor materials have many advantages such as various structures, relatively low manufacturing cost, and superior photoelectric performance, and have great potential in applications such as organic light-emitting diodes (OLEDs) such as flat panel displays and illumination.
  • OLEDs organic light-emitting diodes
  • the host material plays an important role in energy transfer and exciton dispersion in the light-emitting layer. From the aspect of energy transmission, the host material needs to have suitable HOMO and LUMO energy levels, which can reduce the potential barrier of electron and hole injection; the triplet energy level of the host material is higher than the triplet energy level of the light-emitting guest material, which can prevent The rotation of energy; the host material needs to have a certain charge transfer balance ability, so that the exciton recombination region is concentrated in the center of the luminescent layer to achieve high energy utilization efficiency and device stability. Considering the exciton dispersion, the structure of the host material has suitable sterically hindered structural units, which can effectively prevent dense packing between molecules and act as excitons to reduce the aggregation quenching of triplet excitons.
  • a bipolar compound is often used as a host material.
  • a technique discloses that a compound formed by using a hole transport unit and an electron transport unit as a host material can simultaneously transport holes and electrons, and can obtain good results.
  • Device performance the device performance and lifetime of such host materials still need to be further improved.
  • the new material system needs further development.
  • a bipolar compound as shown in the general formula (1):
  • L represents a single bond, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, and a substituted or unsubstituted aromatic group having 5 to 60 ring atoms. a hydrocarbon group or an aromatic heterocyclic group;
  • Z 1 , Z 2 , and Z 3 each independently represent N or CH, and at least one of Z 1 , Z 2 , and Z 3 is an N atom;
  • Ar 1 and Ar 2 are each independently represented as a substituted or unsubstituted aromatic hydrocarbon group or an aromatic heterocyclic group having 6 to 30 ring atoms, wherein at least one ring atom number of Ar 1 and Ar 2 is more than 6;
  • Ar 3 , Ar 4 and Ar 5 each independently represent a substituted or unsubstituted aromatic hydrocarbon group or an aromatic heterocyclic group having 5 to 60 ring atoms.
  • the above bipolar compounds, Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , L may each independently comprise one or more combinations of the following structural groups:
  • X 1 -X 12 respectively represent CR 3 or N, and X 1 -X 6 are not N at the same time;
  • R 3 represents H, D, F, CN, alkenyl, alkynyl, nitrile, amine, nitro, acyl, alkoxy, carbonyl, sulfone, substituted or unsubstituted alkyl having 1 to 30 carbon atoms a substituted, unsubstituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted ring atom number of 5 to 60 aromatic hydrocarbon groups or an aromatic heterocyclic group; and R 4 and R 5 have the same meanings as R 1 .
  • the above bipolar compound wherein Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , L may each independently comprise one of the following chemical formulas, wherein H on the ring may be optionally substituted:
  • the above bipolar compound comprises a structure represented by any of the formulae (2) to (6):
  • X, L, Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 have the same meanings as described above.
  • the above bipolar compound is preferably one of the following structural formulas:
  • the above bipolar compound is characterized in that the bipolar compound has T 1 ⁇ 2.2 eV, preferably ⁇ 2.3 eV, more preferably ⁇ 2.4 eV, and most preferably ⁇ 2.5 eV.
  • T1 represents the triplet level of the bipolar compound.
  • a high polymer comprising at least one repeating unit comprising a structural unit represented by the chemical formula (1).
  • a mixture comprising a bipolar compound or polymer as described above, and at least one organic functional material, said organic functional material being selected from at least one of the following materials: a hole injecting material ( HIM), hole transport material (HTM), electron transport material (ETM), electron injecting material (EIM), electron blocking material (EBM), hole blocking material (HBM), illuminator (Emitter), host material (Host) ) and organic dyes.
  • HIM hole injecting material
  • HTM hole transport material
  • ETM electron transport material
  • EIM electron injecting material
  • EBM electron blocking material
  • HBM hole blocking material
  • Hos host material
  • a composition comprising a bipolar compound or polymer as described above, and at least one organic solvent.
  • An organic electronic device comprising a functional layer comprising a bipolar compound or polymer as described above.
  • the above organic electronic device can be selected from an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, an organic sensor, and an organic plasma.
  • OLED organic light emitting diode
  • OLED organic photovoltaic cell
  • OEEC organic light emitting cell
  • OFET organic field effect transistor
  • OLED organic light emitting field effect transistor
  • the organic electronic device is an electroluminescent device
  • the functional layer of the electroluminescent device comprises a light-emitting layer and an electron transport layer
  • the light-emitting layer comprises a bipolar compound or a polymer as described above, or a light-emitting layer A bipolar compound or polymer and a phosphorescent emitter as described above, or an electron transport layer comprising a bipolar compound or polymer as described above.
  • the bipolar compound according to the present invention is used in an OLED, particularly as a light-emitting layer material, to provide high luminescent properties and device lifetime.
  • the possible reasons are as follows, but are not limited thereto.
  • the two segments of the phenyl group substituted with an ortho-aryl group are respectively connected to the hole transporting unit and the electron transporting unit, and on the one hand, the spatial structure of the compound can be adjusted.
  • it can significantly improve the resonance factor of the compound, can effectively prevent dense packing between molecules and reduce the concentration of excitons, and can achieve more efficient energy transfer. Thereby effectively improving the luminescent properties and lifetime of the associated organic light emitting diode.
  • the present invention provides a class of bipolar compounds, including mixtures and compositions thereof, and uses thereof.
  • a class of bipolar compounds including mixtures and compositions thereof, and uses thereof.
  • composition and the printing ink, or ink have the same meaning and are interchangeable.
  • the host material, the matrix material, the Host or the Matrix material have the same meaning, and they are interchangeable.
  • metal organic complexes metal organic complexes, metal organic complexes, and organometallic complexes have the same meaning and are interchangeable.
  • substituted in the expression “substituted or unsubstituted” means that the hydrogen atom in the substituent is substituted by a substituent, and "unsubstituted” means that the hydrogen atom on the group is unsubstituted. Replaced.
  • the substituent may be selected from the group consisting of D, F, CN, alkenyl, alkynyl, nitrile, amine, nitro, acyl, alkoxy, carbonyl, sulfone, boron-containing, silicon-containing
  • ⁇ 8 is more preferably a cycloalkyl group of 5 or 6) or an aromatic hydrocarbon group or an aromatic heterocyclic group having 3 to 50 (preferably 3 to 25, more preferably 3 to 18) ring atoms.
  • the "number of ring atoms” means a structural compound (for example, a monocyclic compound, a fused ring compound, a crosslinking compound, a carbocyclic compound, or a heterocyclic compound) obtained by synthesizing a ring bond, which constitutes the ring itself.
  • the number of atoms in an atom When the ring is substituted by a substituent, the atom contained in the substituent is not included in the ring-forming atom.
  • the “number of ring atoms” described below is also the same unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.
  • aromatic hydrocarbon group or “aromatic group” means a hydrocarbon group containing at least one aromatic ring, and includes a monocyclic group and a polycyclic ring system.
  • Aromatic heterocyclic group or “heteroaromatic group” refers to a hydrocarbon group (containing a hetero atom) comprising at least one aromatic heterocyclic ring, including a monocyclic group and a polycyclic ring system. 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 aromatic.
  • an aromatic or aromatic heterocyclic ring system includes not only a system of an aryl or a aryl group, but also a plurality of aryl or aryl groups may also be interrupted by short non-aromatic units ( ⁇ 10%).
  • Non-H atoms preferably less than 5% of non-H atoms, such as C, N or O atoms).
  • 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.
  • examples of the aromatic hydrocarbon group are: benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, anthracene, benzofluorene, triphenylene, anthracene, anthracene, and derivatives thereof.
  • examples of the aromatic heterocyclic group 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-diazepine, quinoxaline, phenanthridine, carbaidine, quinazoline, quinazolinone, and derivatives thereof.
  • the present invention provides a bipolar compound represented by the formula (1),
  • L represents a single bond, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, and a substituted or unsubstituted aromatic group having 5 to 60 ring atoms. a hydrocarbon group or an aromatic heterocyclic group;
  • Z 1, Z 2, Z 3 each independently represent N or CH, and Z 1, Z 2, Z 3 Species at least one N atom;
  • Ar 1 and Ar 2 are each independently represented as a substituted or unsubstituted aromatic hydrocarbon group or an aromatic heterocyclic group having 6 to 30 ring atoms, wherein at least one ring atom number of Ar 1 and Ar 2 is more than 6;
  • Ar 3 , Ar 4 and Ar 5 each independently represent a substituted or unsubstituted aromatic hydrocarbon group or an aromatic heterocyclic group having 5 to 60 ring atoms.
  • X represented by the formula (1) is a single bond, N(R 1 ), C(R 1 R 2 ), O or S; in a more preferred embodiment, X is Single button, O or S.
  • R 1 and R 2 represented by the formula (1) are each independently represented by a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon atom number of 3 ⁇ 20 cycloalkyl, substituted or unsubstituted aromatic hydrocarbon group or aromatic heterocyclic group having 5 to 40 ring atoms; and in a more preferred embodiment, R 1 and R 2 are independently represented as substituted or not a substituted alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 15 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 5 to 30 ring atoms or an aromatic heterocyclic group In a most preferred embodiment, R 1 and R 2 are each independently represented by a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl
  • L represented by the formula (1) is represented by a single bond, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon atom number of 3 to 20 a cycloalkyl group, a substituted or unsubstituted aromatic hydrocarbon group having 5 to 40 ring atoms or an aromatic heterocyclic group; in a more preferred embodiment, L is represented by a single bond, a substituted or unsubstituted carbon atom number of 1 ⁇ 15 alkyl, substituted or unsubstituted cycloalkyl having 3 to 15 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group having 5 to 30 ring atoms or aromatic heterocyclic group; most preferred embodiment In the examples, L represents a single bond, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having
  • At least two of Z 1 , Z 2 , and Z 3 represented by the formula (1) are N atoms, such as the following formulas (4) to (6); more preferred embodiments In the examples, Z 1 , Z 2 and Z 3 are all N atoms, as in the following general formula (6).
  • Ar 1 and Ar 2 represented by the formula (1) are each independently represented by a substituted or unsubstituted aromatic hydrocarbon group or an aromatic heterocyclic group having 6 to 25 ring atoms; In a more preferred embodiment, Ar 1 and Ar 2 are each independently represented by a substituted or unsubstituted aromatic hydrocarbon group or an aromatic heterocyclic group having 6 to 20 ring atoms; in a most preferred embodiment, Ar 1 , Ar 2 is independently represented by a substituted or unsubstituted aromatic hydrocarbon group or an aromatic heterocyclic group having 6 to 15 ring atoms, wherein at least one ring atom number of Ar 1 and Ar 2 is more than 6; more preferred examples In the above, both Ar 1 and Ar 2 have more than 6 ring atoms.
  • Ar 3 , Ar 4 , and Ar 5 represented by the formula (1) are each independently represented by a substituted or unsubstituted aromatic hydrocarbon group or an aromatic heterocyclic ring having 5 to 40 ring atoms.
  • Ar 3 , Ar 4 and Ar 5 are each independently represented by a substituted or unsubstituted aromatic hydrocarbon group or an aromatic heterocyclic group having 5 to 30 ring atoms; the most preferred embodiment
  • Ar 3 , Ar 4 and Ar 5 each independently represent a substituted or unsubstituted aromatic hydrocarbon group or an aromatic heterocyclic group having 5 to 20 ring atoms.
  • the above bipolar compound, Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , L may each independently comprise one or more combinations of the following structural groups:
  • X 1 -X 12 respectively represent CR 3 or N, and X 1 -X 6 are not N at the same time;
  • R 3 represents H, D, F, CN, alkenyl, alkynyl, nitrile, amine, nitro, acyl, alkoxy, carbonyl, sulfone, substituted or unsubstituted alkyl having 1 to 30 carbon atoms a substituted, unsubstituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted ring atom number of 5 to 60 aromatic hydrocarbon groups or an aromatic heterocyclic group; and R 4 and R 5 have the same meanings as R 1 .
  • the above bipolar compound wherein Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , L may each independently comprise one of the following chemical formulas, wherein H can be arbitrarily replaced:
  • the above bipolar compound wherein Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , L may each independently comprise one of the following chemical formulas, wherein H can be arbitrarily replaced:
  • the bipolar compound comprises a structure represented by any of the formulae (2)-(6):
  • the energy level structure of the organic material the triplet energy levels T 1 , LUMO, HOMO, and the resonance factor f (S1) play a key role.
  • the following is an introduction to the determination of these energy levels.
  • the LUMO and HOMO levels can be measured by photoelectric effects such as XPS (X-ray photoelectron spectroscopy) and UPS (UV photoelectron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV).
  • photoelectric effects such as XPS (X-ray photoelectron spectroscopy) and UPS (UV photoelectron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV).
  • CV cyclic voltammetry
  • quantum chemical methods such as density functional theory (hereinafter referred to as DFT) have also become effective methods for calculating molecular orbital energy levels.
  • the triplet level T 1 of the organic material can be measured by low temperature time-resolved luminescence spectroscopy or by quantum simulation calculations (eg by Time-dependent DFT), such as by the commercial software Gaussian 09W (Gaussian Inc.), a specific simulation method. See WO2011141110 or as described below in the examples.
  • the absolute values of LUMO, HOMO, T 1 depend on the measurement method or calculation method used, and even for the same method, different evaluation methods, such as starting point and peak point on the CV curve, can give different LUMO/ HOMO value. Therefore, reasonable and meaningful comparisons should be made using the same measurement method and the same evaluation method.
  • the values of HOMO, LUMO, T 1 , and f(S1) are simulations based on Time-dependent DFT, but do not affect the application of other measurement or calculation methods.
  • the above bipolar compound has a resonance factor f(S1) ⁇ 0.001, preferably f(S1) ⁇ 0.005, more preferably f(S1) ⁇ 0.04, and most preferably f(S1) ⁇ 0.08.
  • the bipolar compound according to the present invention can be used as a functional material in an electronic device.
  • Functional materials can be classified into hole injection materials (HIM), hole transport materials (HTM), electron transport materials (ETM), electron injecting materials (EIM), electron blocking materials (EBM), and hole blocking materials (HBM).
  • HIM hole injection materials
  • HTM hole transport materials
  • ETM electron transport materials
  • EIM electron injecting materials
  • EBM electron blocking materials
  • HBM hole blocking materials
  • Emitter host material.
  • the bipolar compound according to the invention may be used as a host material, or an electron transport material, or a hole transport material.
  • the bipolar compound according to the invention can be used as a phosphorescent host material.
  • T1 As a phosphorescent host material, there must be an appropriate triplet level, T1.
  • T1 ⁇ 2.3 eV, preferably ⁇ 2.4 eV, more preferably ⁇ 2.5 eV, still more preferably ⁇ 2.6 eV, and most preferably ⁇ 2.7 eV.
  • the above bipolar compound has ((LUMO+1)-LUMO) ⁇ 0.1 eV, preferably ⁇ 0.15 eV, more preferably ⁇ 0.20 eV, still more preferably ⁇ 0.25.
  • eV is preferably ⁇ 0.30 eV.
  • the above bipolar compound (HOMO-(HOMO-1)) ⁇ 0.2 eV, preferably ⁇ 0.25 eV, more preferably ⁇ 0.30 eV, more preferably ⁇ 0.35 eV, preferably ⁇ 0.40 eV.
  • the compounds according to the present invention the bipolar, the glass transition temperature T g ⁇ 100 °C, in a preferred embodiment, its T g ⁇ 120 °C, in a more preferred embodiment its T g ⁇ 140 °C, in a more preferred embodiment, its T g ⁇ 160 °C, in a most preferred embodiment, its T g ⁇ 180 °C.
  • the hydrogen atom may be partially deuterated, preferably 10% of H is deuterated, more preferably 20% of H is deuterated, Fortunately, 30% of H is destroyed, and preferably 40% of H is deuterated.
  • the bipolar compound according to the invention is a small molecule material.
  • the bipolar compound according to the invention is used in an evaporated OLED device.
  • the compounds according to the invention have a molecular weight of ⁇ 1000 g/mol, preferably ⁇ 900 g/mol, very preferably ⁇ 850 g/mol, more preferably ⁇ 800 g/mol, most preferably ⁇ 700 g/mol.
  • the bipolar compound according to the present invention has luminescent properties with an emission wavelength between 300 and 1000 nm, preferably between 350 and 900 nm, more preferably between 400 and 800 nm, more More preferably it is between 400 and 600 nm, preferably between 400 and 500 nm.
  • the luminescence referred to herein means photoluminescence or electroluminescence.
  • the bipolar compound according to the present invention has a photo or electroluminescence efficiency of ⁇ 30%, preferably ⁇ 40%, more preferably ⁇ 50%, and most preferably ⁇ 60%. .
  • the present invention also relates to a high polymer in which at least one repeating unit contains the structure represented by the general formula (1).
  • 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.
  • the high polymer is a conjugated high polymer.
  • small molecule 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 ⁇ 3000 g/mol, preferably ⁇ 2000 g/mol, preferably ⁇ 1500 g/mol.
  • the polymer that is, the polymer, includes a homopolymer, a copolymer, and a block copolymer. Further, in the present invention, the high polymer also includes a dendrimer.
  • 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.].
  • the conjugated polymer is a high polymer, and its backbone backbone is mainly composed of sp2 hybrid orbitals of C atoms.
  • Famous examples are: polyacetylene polyacetylene and poly(phenylene vinylene), the main chain thereof.
  • the C atom on it can also be replaced by other non-C atoms, and when the sp2 hybrid on the main chain is interrupted by some natural defects, it is still considered to be a conjugated polymer.
  • 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 method for synthesizing the high polymer is selected from the group consisting of SUZUKI-, YAMAMOTO-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD- and ULLMAN.
  • the polymer according to the invention has a glass transition temperature (Tg) ⁇ 100 ° C, preferably ⁇ 120 ° C, more preferably ⁇ 140 ° C, more preferably ⁇ 160 ° C, optimal. It is ⁇ 180 °C.
  • the polymer according to the present invention preferably has a molecular weight distribution (PDI) in the range of from 1 to 5; more preferably from 1 to 4; more preferably from 1 to 3, still more preferably 1 ⁇ 2 is most preferably 1 to 1.5.
  • PDI molecular weight distribution
  • the weight average molecular weight (Mw) of the high polymer according to the present invention preferably ranges from 10,000 to 1,000,000; more preferably from 50,000 to 500,000; more preferably from 100,000 to 40. More preferably, it is 150,000 to 300,000, and most preferably 200,000 to 250,000.
  • the invention further relates to a mixture comprising, for example, one of the above bipolar compounds or polymers, and at least one other organic functional material.
  • the other organic functional material includes hole (also called hole) injection or transport material (HIM/HTM), hole blocking material (HBM), electron injection or transport material (EIM/ETM), electron Barrier material (EBM), organic host material (Host), singlet illuminant (fluorescent illuminant), organic thermal excitation delayed fluorescent material (TADF material), triplet illuminant (phosphorescent illuminant), especially luminescent organic metal Complexes, and organic dyes.
  • organic functional materials are described in detail in, for example, WO2010135519A1, US20090134784A1, and WO 2011110277A1, the entire contents of which are hereby incorporated by reference.
  • the organic functional material may be a small molecule and a high polymer material.
  • the mixture comprises a bipolar compound or polymer according to the invention, and a phosphorescent emitter.
  • the bipolar compound according to the present invention may be used as a host, and the phosphorescent illuminant is ⁇ 30% by weight, preferably ⁇ 25% by weight, more preferably ⁇ 20% by weight.
  • the mixture comprises a bipolar compound or polymer according to the invention, another host material and a phosphorescent emitter.
  • the bipolar compound according to the invention herein as a co-host material has a weight percentage of ⁇ 10% by weight, preferably ⁇ 20% by weight, more preferably ⁇ 30% by weight, most preferably ⁇ 40% by weight.
  • the mixture comprises a bipolar compound or polymer according to the invention, a phosphorescent emitter and a host material.
  • the bipolar 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.
  • the organic compound according to the present invention a T 1 higher than the phosphorescent emitter.
  • the mixture comprises a bipolar compound or polymer according to the invention, and another TADF material.
  • the mixture comprises a bipolar compound or polymer according to the invention, and another ETM material.
  • Triplet Host Material (Triplet Host):
  • 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 level is higher than that of the illuminant, particularly the triplet illuminant or the phosphorescent illuminant.
  • metal complexes that can be used as a 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 is from 1 to the maximum coordination number of the metal; in a preferred 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 a metal is coordinated to an O and N atom.
  • m is an integer whose value ranges from 1 to the maximum coordination number of the metal;
  • M is optional for 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, triphenylbenzene, benzindene; compounds containing an aromatic heterocyclic group such as dibenzothiophene, Dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, oxazole, dibenzoxazole, carbazole, pyridinium, pyrrole dipyridine, Pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxazine , oxadiazin
  • each Ar may be further substituted, and the substituent may be hydrogen, hydrazine, cyano, halogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl. base.
  • the triplet host material can be selected from compounds comprising at least one of the following groups:
  • R 2 -R 7 have the same meaning as R 1
  • X 9 is selected from CR 1 R 2 or NR 1
  • Y is selected from CR 1 R 2 or NR 1 or O or S.
  • R 1 , n,, X 1 -X 8 , and Ar 1 to Ar 3 have the same meanings as described above.
  • triplet host materials examples include:
  • Phosphorescent emitters are also referred to as triplet emitters.
  • 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.
  • these metal complexes are coupled to a polymer by one or more positions, preferably by an organic ligand.
  • 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, with Os, Ir, Ru, Rh, Re, Pd, Au or Pt being particularly preferred.
  • 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.
  • the metal complex that can be used as the triplet emitter has the following form:
  • M is a metal selected from a transition metal element or a lanthanide or actinide element, particularly preferably Ir, Pt, Au;
  • Ar1 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.
  • Ar2 may be the same or different at each occurrence, and is a cyclic group containing at least one C atom through which a cyclic group is bonded to a metal; Ar1 and Ar2 are linked by a covalent bond, respectively Carrying one or more substituent groups, which may also be linked together by a substituent group; each occurrence of L' may be the same or different and is a bidentate chelate auxiliary ligand, preferably a monoanion pair Teeth chelating ligand; q1 may be 0, 1, 2 or 3, preferably 2 or 3; q2 may be 0, 1, 2 or 3, preferably 1 or 0.
  • triplet emitters Some examples of suitable triplet emitters are listed in the table below:
  • 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 ( ⁇ E st ), and triplet excitons can be converted into singlet exciton luminescence by inter-system 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%.
  • 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 ⁇ Est ⁇ 0.3 eV, and secondly ⁇ Est ⁇ 0.2 eV, preferably ⁇ Est ⁇ 0.1 eV.
  • the TADF material has a relatively small ⁇ Est, and in another preferred embodiment, the TADF has a better fluorescence quantum efficiency.
  • 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.
  • TADF luminescent materials are listed in the table below:
  • Another object of the invention is to provide a material solution for printing OLEDs.
  • the bipolar compounds according to the invention have a molecular weight of ⁇ 700 g/mol, preferably ⁇ 900 g/mol, very preferably ⁇ 900 g/mol, more preferably ⁇ 1000 g/mol, most preferably ⁇ 1100 g/mol.
  • the bipolar compound or polymer according to the invention has a solubility in toluene of > 10 mg/ml, preferably > 15 mg/ml, most preferably > 20 mg/ml at 25 °C.
  • the invention still further relates to a composition or ink comprising a bipolar compound or polymer according to the invention and at least one organic solvent.
  • 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.
  • the ink according to the 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; more preferably in the range of from 22 dyne/cm to 35 dyne/cm; In the range of 25dyne/cm to 33dyne/cm.
  • the ink according to the present invention has a viscosity at an operating temperature or 25 ° C in the range of about 1 cps to 100 cps; preferably in the range of 1 cps to 50 cps; more preferably in the range of 1.5 cps to 20 cps; It is in the range of 4.0cps to 20cps.
  • the composition so formulated will facilitate 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 metal organic complex 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.
  • the composition according to the present invention comprises a functional material (i.e., a bipolar compound or a high polymer) in a weight ratio of from 0.3% to 30% by weight, preferably from 0.5% to 20% by weight, more preferably. It is in the range of 0.5% to 15% by weight, more preferably in the range of 0.5% to 10% by weight, most preferably in the range of 1% to 5% by weight.
  • 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 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 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 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 is selected from the
  • 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, di
  • 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.
  • an aliphatic ketone for example, 2-nonan
  • the printing ink further comprises another organic solvent.
  • 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, tetrahydronaphthalene , decalin, hydrazine and/or mixtures thereof.
  • the composition according to the invention is a solution.
  • composition according to the invention is a suspension.
  • composition in the examples of the present invention may comprise from 0.01 to 20% by weight of the bipolar compound according to the invention or a mixture thereof, preferably from 0.1 to 15% by weight, more preferably from 0.2 to 10% by weight, most preferably 0.25 to 5 wt% of a bipolar compound or a mixture thereof.
  • the invention further relates to the use of the composition as a coating or printing ink in the preparation of an organic electronic device, particularly preferably by a printing or coating process.
  • 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 rolls. Printing, lithography, flexographic printing, rotary printing, spraying, brushing or pad printing, slit-type extrusion coating, etc. Preferred are inkjet printing, jet printing and gravure printing.
  • the solution or suspension may additionally comprise 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.
  • the invention further relates to the use of a bipolar compound or polymer according to any of the preceding claims in an organic electronic device.
  • the invention further relates to an organic electronic device comprising a functional layer comprising a bipolar compound or polymer as described above.
  • the organic electronic device may be selected from, but not limited to, an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, and an organic Lasers, organic spintronic devices, organic sensors and organic plasmon emitting diodes (Organic Plasmon Emitting Diode), etc., particularly preferred are organic electroluminescent devices such as OLED, OLEEC, organic light-emitting field effect transistors.
  • the organic electroluminescent device comprises at least one luminescent layer comprising a bipolar compound or polymer as described above.
  • the organic electroluminescent device comprises a substrate, an anode, at least one luminescent layer, a cathode, and optionally a hole transport layer or an electron transport layer.
  • a compound or polymer according to the invention is included in the hole transport layer.
  • a compound or polymer according to the invention is included in the luminescent layer, more preferably a compound or polymer according to the invention is included in the luminescent layer, and at least one luminescent material, which may be preferably a fluorescent illuminant, a phosphorescent illuminant, or a TADF material.
  • the device structure of the electroluminescent device will be described below, but is not limited thereto.
  • 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.
  • the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice.
  • 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).
  • PET poly(ethylene terephthalate)
  • PEN polyethylene glycol (2,6-na
  • 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.
  • HIL hole injection layer
  • HTL hole transport layer
  • 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.
  • anode material examples 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.
  • 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.
  • 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 comprise a conductive metal or metal oxide.
  • the cathode can easily inject electrons into the EIL or ETL or directly into the luminescent layer.
  • 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
  • EIL electron injection layer
  • ETL electron transport layer
  • HBL hole blocking layer
  • 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.
  • all materials which can be used as cathodes for OLEDs are possible as cathode materials for the devices of the invention.
  • cathode material examples include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2/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).
  • HIL hole injection layer
  • HTL hole transport layer
  • EBL electron blocking layer
  • EIL electron injection layer
  • ETL electron transport layer
  • HBL hole blocking layer
  • an electron transport layer (ETL) or a hole blocking layer (HBL) comprises an organic compound or polymer according to the invention, and a method of processing by solution Prepared.
  • the light-emitting device has an emission wavelength of between 300 and 1000 nm, preferably between 350 and 900 nm, more preferably between 400 and 800 nm.
  • the invention further relates to the use of an electroluminescent device according to the invention in various electronic devices, including, but not limited to, display devices, illumination devices, light sources, sensors and the like.
  • a method of synthesizing a compound according to the present invention is exemplified, but the present invention is not limited to the following examples.
  • 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.
  • TD-DFT time-dependent density functional theory
  • Gaussian 03W Gaussian Inc.
  • the specific simulation method can be found in WO2011141110.
  • the energy structure of the organic molecule is determined by TD-DFT.
  • the method (inclusive time density functional theory) calculates "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
  • HOMO(eV) ((HOMO(G) ⁇ 27.212)-0.9899)/1.1206
  • HOMO(G) and LUMO(G) are direct calculation results of Gaussian 03W, and the unit is Hartree.
  • the compounds (6-16), (6-21), (6-35), (6-37), Ref-1 and Ref-2 were used as the host materials, respectively, as shown in the following figure Ir(mphq) 2 acac as a luminescent material, HATCN as a hole injecting material, SFNFB as a hole transporting material, NaTzF 2 as an electron transporting material, Liq as an electron injecting material, and a device structure of ITO/HATCN/SFNFB/host material: Emitter ( 3%)/NaTzF 2 : Liq/Liq/Al electroluminescent device.
  • the preparation process of the OLED device described above will be described in detail below through specific embodiments.
  • the structure of the OLED device (such as Table 2) is: ITO/HATCN/SFNFB/body material: Emitter (3%)/NaTzF 2 : Liq/Liq/ Al, the preparation steps are as follows:
  • ITO indium tin oxide
  • a conductive glass substrate cleaning using a variety of solvents (such as one or several of chloroform, acetone or isopropanol) cleaning, and then UV ozone treatment;
  • the device is encapsulated in a nitrogen glove box with an ultraviolet curable resin.
  • J-V current-voltage

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Abstract

本发明涉及一种双极性化合物，包含其的高聚物、混合物、组合物及其应用，其中，所述的双极性化合物中，通过含空穴传输单元和电子传输单元分别连接在含邻位基团取代的苯基上，可有效提高双极性化合物的谐振因子，同时进一步调节分子的空间结构，从而有利于提高化合物的器件性能和稳定性，为提高有机电子器件的性能和寿命提供一种行之有效的方案。

Description

双极性化合物、高聚物、混合物、组合物、有机电子器件及应用
本申请要求于2017年12月14日提交中国专利局、申请号为201711341843.8发明名称为“一类双极性化合物、混合物、组合物及其在有机电子器件中的应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及双极性化合物，包含其的高聚物、混合物和组合物，有机电子器件及应用。本发明还涉及包含所述双极性化合物的电子器件及其应用，特别是在电致发光器件中的应用。
背景技术
有机半导体材料具有结构多样、制造成本相对较低、光电性能优越等特性，在有机发光二极管(OLED)等光电器件(例如平板显示器和照明)方面的应用具有巨大的潜力。
为了提高有机发光二极管的发光性能，推进有机发光二极管大范围产业化进程，各类有机光电性能材料体系已被广泛地开发。但OLED的性能，特别是性能和寿命仍有待进一步提高。高效稳定的有机光电性能材料急需被开发出来。
就主体材料而言，主体材料在发光层中发挥着能量传输和激子分散等重要作用。从能量传输方面考虑，主体材料需要有合适的HOMO和LUMO能级，能够降低电子和空穴注入的势垒；主体材料的三线态能级要高于发光客体材料的三线态能级，可防止能量的回转；主体材料需要有一定的电荷传输平衡能力，让激子复合区域集中在发光层中心，实现高的能量利用效率和器件稳定性。从激子分散方面考虑，主体材料结构上有合适的空间位阻结构单元，可有效防止分子间的密堆积，起到激子分散的作用，从而降低三线态激子的聚集淬灭。
在现有技术中，多以双极性化合物作为主体材料，如一种技术公开了利用空穴传输单元和电子传输单元进行搭配形成的化合物作为主体材料能够同时传输空穴和电子，能够获得不错的器件性能。但这类主体材料的器件性能和寿命方面仍需进一步的提高。新的材料体系还需进一步开发。
发明内容
鉴于上述现有技术的不足，本发明的目的在于提供一种双极性化合物，包含其的高聚物、混合物和组合物及其应用，旨在解决现有的有机电子器件性能及寿命偏低的问题。
本发明的技术方案如下：
一种双极性化合物，如通式(1)所示：
Figure PCTCN2018120702-appb-000001
其中，
X分别独立表示单键、N(R 1)、C(R 1R 2)、Si(R 1R 2)、O、C＝N(R 1)、C＝C(R 1R 2)、P(R 1)、P(＝O)R 1、S、S＝O或SO 2；其中，R 1、R 2每次出现时，分别独立表示H、D、取代或未取代的碳原子数1～30的烷基、取代或未取代的碳原子数3～30的环烷基、取代或未取代的环原子数为5～60的芳香族烃基或芳香族杂环基；
L表示单键、取代或未取代的碳原子数1～30的烷基、取代或未取代的碳原子数3～30 的环烷基、取代或未取代的环原子数为5～60的芳香族烃基或芳香族杂环基；
Z 1、Z 2、Z 3分别独立表示N或CH，且Z 1、Z 2、Z 3中至少一个为N原子；
Ar 1、Ar 2分别独立表示为取代或未取代的环原子数为6～30的芳香族烃基或芳香族杂环基，其中Ar 1和Ar 2至少一个环原子数大于6；
Ar 3、Ar 4、Ar 5分别独立表示为取代或未取代的环原子数为5～60的芳香族烃基或芳香族杂环基。
上述的双极性化合物，Ar 1、Ar 2、Ar 3、Ar 4、Ar 5、L可分别独立地包含如下结构基团中的一种或多种组合：
Figure PCTCN2018120702-appb-000002
其中，
X 1-X 12分别独立表示CR 3或N，且X 1-X 6不同时为N；
Y选自N(R 4)、C(R 4R 5)、Si(R 4R 5)、C(＝O)、S或O；
R 3表示H、D、F、CN、烯基、炔基、腈基、胺基、硝基、酰基、烷氧基、羰基、砜基、取代或未取代的碳原子数1～30的烷基、取代或未取代的碳原子数3～30的环烷基、取代或未取代的环原子数为5～60芳香族烃基或芳香族杂环基；R 4、R 5的含义同R 1。
优选的，上述的双极性化合物，其中Ar 1、Ar 2、Ar 3、Ar 4、Ar 5、L可分别独立地包含如下的化学式中的一种，其中环上的H可以被任意取代：
Figure PCTCN2018120702-appb-000003
上述的双极性化合物，包含通式(2)-(6)中任一化学式表示的结构：
Figure PCTCN2018120702-appb-000004
Figure PCTCN2018120702-appb-000005
其中，X、L、Ar 1、Ar 2、Ar 3、Ar 4、Ar 5的含义如上。
上述的双极性化合物，优选自如下结构式中的一种：
Figure PCTCN2018120702-appb-000006
上述的双极性化合物，其特征在于，此双极性化合物的T 1≥2.2eV，较好≥2.3eV，更好≥2.4eV，最好≥2.5eV。T1表示双极性化合物的三线态能级。
一种高聚物，包含至少一个重复单元，该重复单元包含化学式(1)所示的结构单元。
一种混合物，包括一种如上所述的双极性化合物或高聚物，及至少一种有机功能材料，所述的有机功能材料可选自以下材料中的至少一种：空穴注入材料(HIM),空穴传输材料(HTM),电子传输材料(ETM),电子注入材料(EIM),电子阻挡材料(EBM),空穴阻挡材料(HBM),发光体(Emitter),主体材料(Host)和有机染料。
一种组合物，包括如上所述的双极性化合物或高聚物，及至少一种有机溶剂。
一种如上所述的双极性化合物或高聚物在有机电子器件中的应用。
一种有机电子器件，包括功能层，所述功能层包括如上所述的双极性化合物或高聚物。
上述的有机电子器件，可选于有机发光二极管(OLED)、有机光伏电池(OPV)、有机发光电池(OLEEC)、有机场效应管(OFET)、有机发光场效应管、有机传感器及有机等离激元发射二极管(Organic Plasmon Emitting Diode)。
优选的，有机电子器件是一种电致发光器件，该电致发光器件的功能层包括发光层和电子传输层，其中发光层包含如上所述的双极性化合物或高聚物，或发光层包含如上所述的双极性化合物或高聚物和磷光发光体，或电子传输层包含如上所述的双极性化合物或高聚物。
有益效果：按照本发明的双极性化合物用于OLED中，特别是作为发光层材料，能提供较高的发光性能和器件寿命。其可能的原因如下，但不限于此，利用一个含邻位芳香基团取代的苯基两段分别连接空穴传输单元和电子传输单元，一方面能够对化合物的空间结构有一定的调节作用，另一方面能明显提高化合物的谐振因子，能有效防止分子间的密堆积和降低激子的浓度，并能实现更高效的能量传输。从而有效地提高相关有机发光二极管的发光性能和寿命。
具体实施方式
本发明提供一类双极性化合物，包含其的混合物和组合物及其应用。为使本发明的目的、技术方案及效果更加清楚、明确，以下对本发明进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。
在本发明中，组合物和印刷油墨，或油墨具有相同的含义，它们之间可以互换。
在本发明中，主体材料，基质材料，Host或Matrix材料具有相同的含义，它们之间可以互换。
在本发明中，金属有机络合物，金属有机配合物，有机金属配合物具有相同的含义，可以互换。
在本发明中，“取代或未取代”这一表达方式中的“取代”表示被取代基中的氢原子被取代基所取代，“未取代”则表示基团上的氢原子未被取代基所取代。其中，取代基可选自如下基团：D、F、CN、烯基、炔基、腈基、胺基、硝基、酰基、烷氧基、羰基、砜基、含硼基团、含硅基团、碳原子数为1～50(优选的为1～18，更优选的为1～8)的烷基、环原子数为3～50(优选的为3～10，更优选的为3～8，进一步优选的为5或6)的环烷基、环原子数为3～50(优选的为3～25，更优选的为3～18)的芳香族烃基或芳香族杂环基。
在本发明中，“环原子数”表示原子键合成环状而得到的结构化合物(例如，单环化合物、稠环化合物、交联化合物、碳环化合物、杂环化合物)的构成该环自身的原子之中的原子数。该环被取代基所取代时，取代基所包含的原子不包括在成环原子内。关于以下所述的“环原子数”，在没有特别说明的条件下也是同样的。例如，苯环的环原子数为6，萘环的环原子数为10，噻吩基的环原子数为5。
在本发明中，“芳香族烃基”或“芳香基团”指至少包含一个芳环的烃基，包括单环基团和多环的环***。“芳香族杂环基”或“杂芳香基团”指包含至少一个芳杂环的烃基(含有杂原子)，包括单环基团和多环的环***。这些多环的环可以具有两个或多个环，其中两个碳原子被两个相邻的环共用，即稠环。多环的这些环种，至少一个是芳香族的或芳杂族的。对于本发明的目的，芳香族或芳杂族环系不仅包括芳香基或芳杂基的体系，而且，其中多个芳香基或芳杂基也可以被短的非芳族单元间断(<10％的非H原子，优选小于5％的非H原子，比如C、N或O原子)。因此，比如9，9'-螺二芴，9，9-二芳基芴，三芳胺，二芳基醚等体系，对于该发明目的同样认为是芳香族环系。
具体地，芳香族烃基的例子有：苯、萘、蒽、菲、二萘嵌苯、并四苯、芘、苯并芘、三亚苯、苊、芴、及其衍生物。
具体地，芳香族杂环基的例子有：呋喃、苯并呋喃、噻吩、苯并噻吩、吡咯、吡唑、***、咪唑、噁唑、噁二唑、噻唑、四唑、吲哚、咔唑、吡咯并咪唑、吡咯并吡咯、噻吩并吡咯、噻吩并噻吩、呋喃并吡咯、呋喃并呋喃、噻吩并呋喃、苯并异噁唑、苯并异噻唑、苯并咪唑、吡啶、吡嗪、哒嗪、嘧啶、三嗪、喹啉、异喹啉、邻二氮萘、喹喔啉、菲啶、 伯啶、喹唑啉、喹唑啉酮、及其衍生物。
本发明提供一种如通式(1)所示的双极性化合物，
Figure PCTCN2018120702-appb-000007
其中，
X分别独立表示单键、N(R 1)、C(R 1R 2)、Si(R 1R 2)、O、C＝N(R 1)、C＝C(R 1R 2)、P(R 1)、P(＝O)R 1、S、S＝O或SO 2；其中，R 1、R 2每次出现时，分别独立表示H、D、取代或未取代的碳原子数1～30的烷基、取代或未取代的碳原子数3～30的环烷基、取代或未取代的环原子数为5～60的芳香族烃基或芳香族杂环基；
L表示单键、取代或未取代的碳原子数1～30的烷基、取代或未取代的碳原子数3～30的环烷基、取代或未取代的环原子数为5～60的芳香族烃基或芳香族杂环基；
Z 1、Z 2、Z 3分别独立表示N或CH，且Z 1、Z 2、Z 3种至少一个为N原子；
Ar 1、Ar 2分别独立表示为取代或未取代的环原子数为6～30的芳香族烃基或芳香族杂环基，其中Ar 1和Ar 2至少一个环原子数大于6；
Ar 3、Ar 4、Ar 5分别独立表示为取代或未取代的环原子数为5～60的芳香族烃基或芳香族杂环基。
在一些优选的实施方案中，通式(1)中所示的X为单键、N(R 1)、C(R 1R 2)、O或S；在更加优选的实施例中，X为单键、O或S。
在一些优选的实施方案中，通式(1)中所示的R 1、R 2分别独立表示为取代或未取代的碳原子数1～20的烷基、取代或未取代的碳原子数3～20的环烷基、取代或未取代的环原子数为5～40的芳香族烃基或芳香族杂环基；在更加优选的实施例中，R 1、R 2分别独立表示为取代或未取代的碳原子数1～15的烷基、取代或未取代的碳原子数3～15的环烷基、取代或未取代的环原子数为5～30的芳香族烃基或芳香族杂环基；在最为优选的实施例中，R 1、R 2分别独立表示为取代或未取代的碳原子数1～10的烷基、取代或未取代的碳原子数3～10的环烷基、取代或未取代的环原子数为5～20的芳香族烃基或芳香族杂环基。
在一些优选的实施方案中，通式(1)中所示的L表示为单键、取代或未取代的碳原子数1～20的烷基、取代或未取代的碳原子数3～20的环烷基、取代或未取代的环原子数为5～40的芳香族烃基或芳香族杂环基；在更加优选的实施例中，L表示为单键、取代或未取代的碳原子数1～15的烷基、取代或未取代的碳原子数3～15的环烷基、取代或未取代的环原子数为5～30的芳香族烃基或芳香族杂环基；在最为优选的实施例中，L表示为单键、取代或未取代的碳原子数1～10的烷基、取代或未取代的碳原子数3～10的环烷基、取代或未取代的环原子数为5～20的芳香族烃基或芳香族杂环基。
在一些优选的实施方案中，通式(1)中所示的Z 1、Z 2、Z 3中至少两个为N原子，如下述的通式(4)-(6)；更优选的实施例中，Z 1、Z 2、Z 3全为N原子，如下述的通式(6)。
在一些优选的实施方案中，通式(1)中所示的Ar 1、Ar 2分别独立表示为取代或未取代的环原子数为6～25的芳香族烃基或芳香族杂环基；在更加优选的实施例中，Ar 1、Ar 2分别独立表示为取代或未取代的环原子数为6～20的芳香族烃基或芳香族杂环基；在最为优选的实施例中，Ar 1、Ar 2分别独立表示为取代或未取代的环原子数为6～15的芳香族烃基或芳香族杂环基，其中，Ar 1和Ar 2至少一个环原子数大于6；在更加优选的实施例中，Ar 1和Ar 2两个环原子数都大于6。
在一些优选的实施方案中，通式(1)中所示的Ar 3、Ar 4、Ar 5分别独立表示为取代或未取代的环原子数为5～40的芳香族烃基或芳香族杂环基；在更加优选的实施例中，Ar 3、Ar 4、Ar 5分别独立表示为取代或未取代的环原子数为5～30的芳香族烃基或芳香族杂环基；在最 为优选的实施例中，Ar 3、Ar 4、Ar 5分别独立表示为取代或未取代的环原子数为5～20的芳香族烃基或芳香族杂环基。
在一些优选的实施例中，上述的双极性化合物，Ar 1、Ar 2、Ar 3、Ar 4、Ar 5、L可分别独立地包含如下结构基团中的一种或多种组合：
Figure PCTCN2018120702-appb-000008
其中，
X 1-X 12分别独立表示CR 3或N，且X 1-X 6不同时为N；
Y选自N(R 4)、C(R 4R 5)、Si(R 4R 5)、C(＝O)、S或O；
R 3表示H、D、F、CN、烯基、炔基、腈基、胺基、硝基、酰基、烷氧基、羰基、砜基、取代或未取代的碳原子数1～30的烷基、取代或未取代的碳原子数3～30的环烷基、取代或未取代的环原子数为5～60芳香族烃基或芳香族杂环基；R 4、R 5的含义同R 1。
在一些更加优选的实施例中，上述的双极性化合物，其中Ar 1、Ar 2、Ar 3、Ar 4、Ar 5、L可分别独立的包含如下的化学式中的一种，其中环上的H可以被任意取代：
Figure PCTCN2018120702-appb-000009
在一些最为优选的实施例中，上述的双极性化合物，其中Ar 1、Ar 2、Ar 3、Ar 4、Ar 5、L可分别独立的包含如下的化学式中的一种，其中环上的H可以被任意取代：
Figure PCTCN2018120702-appb-000010
在某些较为优选的实施例中，所述的双极性化合物，包含通式(2)-(6)中任一化学式表示的结构：
Figure PCTCN2018120702-appb-000011
其中，X、L、Ar 1、Ar 2、Ar 3、Ar 4、Ar 5的含义如上所述。
下面按照通式(1)所示的化合物举例如下，但并不限定于此:
Figure PCTCN2018120702-appb-000012
Figure PCTCN2018120702-appb-000013
Figure PCTCN2018120702-appb-000014
Figure PCTCN2018120702-appb-000015
Figure PCTCN2018120702-appb-000016
Figure PCTCN2018120702-appb-000017
Figure PCTCN2018120702-appb-000018
Figure PCTCN2018120702-appb-000019
在本发明实施例中，有机材料的能级结构，三线态能级T 1、LUMO、HOMO、谐振因子f(S1)起着关键的作用。以下对这些能级的确定做一介绍。
LUMO和HOMO能级可以通过光电效应进行测量，例如XPS(X射线光电子光谱法)和UPS(紫外光电子能谱)或通过循环伏安法(以下简称CV)。最近，量子化学方法，例如密度泛函理论(以下简称DFT)，也成为行之有效的计算分子轨道能级的方法。
有机材料的三线态能级T 1可通过低温时间分辨发光光谱来测量，或通过量子模拟计算(如通过Time-dependent DFT)得到，如通过商业软件Gaussian 09W(Gaussian Inc.)，具体的模拟方法可参见WO2011141110或如下在实施例中所述。
应该注意，LUMO、HOMO、T 1的绝对值取决于所用的测量方法或计算方法，甚至对 于相同的方法，不同评价的方法，例如在CV曲线上起始点和峰点可给出不同的LUMO/HOMO值。因此，合理有意义的比较应该用相同的测量方法和相同的评价方法进行。本发明实施例的描述中，HOMO、LUMO、T 1、f(S1)的值是基于Time-dependent DFT的模拟，但不影响其他测量或计算方法的应用。
优先的，上述的双极性化合物，其谐振因子f(S1)≥0.001，较好f(S1)≥0.005，更好f(S1)≥0.04，最好f(S1)≥0.08。
按照本发明的双极性化合物，可以作为功能材料用于电子器件中。功能材料可分为空穴注入材料(HIM),空穴传输材料(HTM),电子传输材料(ETM),电子注入材料(EIM),电子阻挡材料(EBM),空穴阻挡材料(HBM),发光体(Emitter),主体材料(Host)。在一个优选的实施例中，按照本发明的双极性化合物可作为主体材料，或电子传输材料，或空穴传输材料。在一个更加优选的实施例中，按照发明的双极性化合物可作为磷光主体材料。
作为磷光主体材料必须有适当的三线态能级，即T1。在某些实施例中，按照发明的双极性化合物，其T1≥2.3eV，较好≥2.4eV，更好≥2.5eV，更更好≥2.6eV，最好≥2.7eV。
在一个较为优先的实施例中，上述的双极性化合物，其((LUMO+1)-LUMO)≥0.1eV，较好是≥0.15eV，更好是≥0.20eV，更更好是≥0.25eV，最好是≥0.30eV。
在另一个较为优先的实施例中，上述的双极性化合物，其(HOMO-(HOMO-1))≥0.2eV，较好是≥0.25eV，更好是≥0.30eV，更更好是≥0.35eV，最好是≥0.40eV。
在一个优选的实施例中，按照本发明的双极性化合物，其玻璃化温度T g≥100℃，在一个优选的实施例中，其T g≥120℃，在一个较为优选的实施例中，其T g≥140℃，在一个更为优选的实施例中，其T g≥160℃，在一个最为优选的实施例中，其T g≥180℃。
在一个较为优选的实施例中，按照本发明的双极性化合物，其氢原子可部分被氘代，较好是10％的H被氘代，更好是20％的H被氘代，很好是30％的H被氘代，最好是40％的H被氘代。
在一个优选的实施例中，按照本发明的双极性化合物是一种小分子材料。
在一个优选的实施方案中，按照本发明的双极性化合物用于蒸镀性OLED器件。用于这个目的，按照本发明的化合物，其分子量≤1000g/mol，优选≤900g/mol，很优选≤850g/mol，更优选≤800g/mol，最优选≤700g/mol。
在某些实施例中，按照本发明的双极性化合物具有发光性能，其发光波长在300到1000nm之间，较好是在350到900nm之间，更好是在400到800nm之间，更更好是在400到600nm之间，最好是在400到500nm之间。这里指的发光是指光致发光或电致发光。
在某些优选的实施例中，按照本发明的双极性化合物，其光致或电致发光效率≥30％，较优是≥40％，更优是≥50％，最优是≥60％。
本发明还涉及一种高聚物，其中至少有一个重复单元包含通式(1)所示的结构。在某些实施例中，所述的高聚物是非共轭高聚物，其中如通式(1)所示的结构单元在侧链上。在另一个优选的实施例中，所述的高聚物是共轭高聚物。
本文中所定义的术语“小分子”是指不是聚合物，低聚物，树枝状聚合物，或共混物的分子。特别是，小分子中没有重复结构。小分子的分子量≤3000克/摩尔，较好是≤2000克/摩尔，最好是≤1500克/摩尔。
高聚物，即Polymer，包括均聚物(homopolymer)，共聚物(copolymer)，镶嵌共聚物(block copolymer)。另外在本发明中，高聚物也包括树状物(dendrimer)，有关树状物的合成及应用请参见[Dendrimers and Dendrons，Wiley-VCH Verlag GmbH&Co.KGaA，2002，Ed.George R.Newkome，Charles N.Moorefield，Fritz Vogtle.]。
共轭高聚物(conjugated polymer)是一高聚物，它的主链backbone主要是由C原子的sp2杂化轨道构成，著名的例子有：聚乙炔polyacetylene和poly(phenylene vinylene)，其 主链上的C原子的也可以被其他非C原子取代，而且当主链上的sp2杂化被一些自然的缺陷打断时，仍然被认为是共轭高聚物。另外在本发明中共轭高聚物也包括主链上包含有芳基胺(aryl amine)、芳基磷化氢(aryl phosphine)及其他杂环芳烃(heteroarmotics)、有机金属络合物(organometallic complexes)等。
在一个优选的实施例中，其中的高聚物的合成方法选自SUZUKI-,YAMAMOTO-,STILLE-,NIGESHI-,KUMADA-,HECK-,SONOGASHIRA-,HIYAMA-,FUKUYAMA-,HARTWIG-BUCHWALD-和ULLMAN。
在一个优先的实施例中，按照本发明的高聚物，其玻璃化温度(Tg)≥100℃，优选为≥120℃，更优为≥140℃，更更优为≥160℃，最优为≥180℃。
在一个优先的实施例中，按照本发明的高聚物，其分子量分布(PDI)取值范围优选为1～5；较优选为1～4；更优选为1～3，更更优选为1～2，最优选为1～1.5。
在一个优先的实施例中，按照本发明的高聚物，其重均分子量(Mw)取值范围优选为1万～100万；较优选为5万～50万；更优选为10万～40万，更更优选为15万～30万，最优选为20万～25万。
本发明还涉及一种混合物，包括如一种上述的双极性化合物或高聚物，以及至少另一种有机功能材料。所述的另一种的有机功能材料，包括空穴(也称电洞)注入或传输材料(HIM/HTM)、空穴阻挡材料(HBM)、电子注入或传输材料(EIM/ETM)、电子阻挡材料(EBM)、有机主体材料(Host)、单重态发光体(荧光发光体)、有机热激发延迟荧光材料(TADF材料)、三重态发光体(磷光发光体)，特别是发光有机金属络合物，和有机染料。例如在WO2010135519A1、US20090134784A1和WO 2011110277A1中对各种有机功能材料有详细的描述，特此将此3专利文件中的全部内容并入本文作为参考。有机功能材料可以是小分子和高聚物材料。
在一个优选的实施例中，所述的混合物包含一种按照本发明的双极性化合物或高聚物，和一种磷光发光体。这里按照本发明的双极性化合物可以作为主体，磷光发光体重量百分比≤30wt％,较好是≤25wt％,更好是≤20wt％。
在另一个优选的实施例中，所述的混合物包含一种按照本发明的双极性化合物或高聚物，另一种主体材料和一种磷光发光体。这里按照本发明的双极性化合物作为共主体材料，其重量百分比≥10wt％,较好是≥20wt％,更好是≥30wt％，最好是≥40wt％。
在一个较为优选的实施例中，所述的混合物包含一种按照本发明的双极性化合物或高聚物，一种磷光发光体和一种主体材料。在这种实施例中，按照本发明的双极性化合物可以作为辅助发光材料，其与磷光发光体的重量比为从1:2到2:1。在另一种优选的实施例中，按照本发明的有机化合物的T 1高于所述的磷光发光体。
在某些实施例中，所述的混合物包含一种按照本发明的双极性化合物或高聚物，和另一种TADF材料。
在另一些优选的实施例中，所述的混合物包含一种按照本发明的双极性化合物或高聚物，和另一种ETM材料。
下面对主体材料，磷光发光材料及TADF材料作一些较详细的描述(但不限于此)。1.三重态主体材料(Triplet Host):
三重态主体材料的例子并不受特别的限制，任何金属络合物或有机化合物都可能被用作为主体,只要其三重态能级比发光体,特别是三重态发光体或磷光发光体更高，可用作三重态主体(Host)的金属络合物的例子包括(但不限于)如下的一般结构:
Figure PCTCN2018120702-appb-000020
M是一金属；(Y 3-Y 4)是一两齿配体,Y 3和Y 4独立地选自C,N,O,P,和S；L是一个 辅助配体；m是一整数，其值从1到此金属的最大配位数；在一个优先的实施方案中，可用作三重态主体的金属络合物有如下形式：
Figure PCTCN2018120702-appb-000021
(O-N)是一两齿配体,其中金属与O和N原子配位.m是一整数，其值从1到此金属的最大配位数；
在某一个实施方案中,M可选于Ir和Pt.
可作为三重态主体的有机化合物的例子选自包含有环芳香烃基的化合物，例如苯、联苯、三苯基苯、苯并芴；包含有芳香杂环基的化合物，如二苯并噻吩、二苯并呋喃、二苯并硒吩、呋喃、噻吩、苯并呋喃、苯并噻吩、苯并硒吩、咔唑、二苯并咔唑，吲哚咔唑、吡啶吲哚、吡咯二吡啶、吡唑、咪唑、***类、恶唑、噻唑、恶二唑、恶***、二恶唑、噻二唑、吡啶、哒嗪、嘧啶、吡嗪、三嗪类、恶嗪、恶噻嗪、恶二嗪、吲哚、苯并咪唑、吲唑、恶唑、二苯并恶唑、苯异恶唑、苯并噻唑、喹啉、异喹啉、邻二氮杂萘、喹唑啉、喹喔啉、萘、酞、蝶啶、氧杂蒽、吖啶、吩嗪、吩噻嗪、吩恶嗪、苯并呋喃吡啶、呋喃并吡啶、苯并噻吩吡啶、噻吩吡啶、苯并硒吩吡啶和硒吩苯并二吡啶；包含有2至10环结构的基团，它们可以是相同或不同类型的环芳香烃基团或芳香杂环基团，并彼此直接或通过至少一个以下的基团连结在一起,如氧原子、氮原子、硫原子、硅原子、磷原子、硼原子、链结构单元和脂肪环基团。其中，每个Ar可以进一步被取代，取代基可选为氢、氘、氰基、卤素、烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基和杂芳基。
在一个优先的实施方案中,三重态主体材料可选于包含至少一个以下基团的化合物:
Figure PCTCN2018120702-appb-000022
。R 2-R 7的含义同R 1，X 9选于CR 1R 2或NR 1，Y选自CR 1R 2或NR 1或O或S。R 1，n,，X 1-X 8，Ar 1～Ar 3的含义同上所述。
在下面的表中列出合适的三重态主体材料的例子但不局限于此:
Figure PCTCN2018120702-appb-000023
2.磷光发光材料
磷光发光体也称三重态发光体。在一个优先的实施方案中，三重态发光体是有通式M(L)n的金属络合物,其中M是一金属原子，L每次出现时可以是相同或不同，是一有机配体，它通过一个或多个位置键接或配位连接到金属原子M上,n是一个大于1的整数，较好选是1，2，3，4，5或6。可选地，这些金属络合物通过一个或多个位置联接到一个聚合物上，最好是通过有机配体。
在一个优先的实施方案中,金属原子M选于过渡金属元素或镧系元素或锕系元素,优先选择Ir,Pt,Pd,Au,Rh,Ru,Os,Sm,Eu,Gd,Tb,Dy,Re,Cu或Ag，特别优先选择Os,Ir,Ru,Rh,Re,Pd,Au或Pt。
优先地,三重态发光体包含有螯合配体，即配体，通过至少两个结合点与金属配位，特别优先考虑的是三重态发光体包含有两个或三个相同或不同的双齿或多齿配体。螯合配体有利于提高金属络合物的稳定性。
有机配体的例子可选自苯基吡啶衍生物，7,8-苯并喹啉衍生物，2(2-噻吩基)吡啶衍生物，2(1-萘基)吡啶衍生物，或2苯基喹啉衍生物。所有这些有机配体都可能被取代，例如被含氟或三氟甲基取代。辅助配体可优先选自乙酸丙酮或苦味酸。
在一个优先的实施方案中，可用作三重态发光体的金属络合物有如下形式：
Figure PCTCN2018120702-appb-000024
其中M是一金属,选于过渡金属元素或镧系或锕系元素,特别优先的是Ir,Pt,Au；
Ar1每次出现时可以是相同或不同,是一个环状基团,其中至少包含有一个施主原子，即有一孤对电子的原子，如氮或磷，通过它环状基团与金属配位连接；Ar2每次出现时可以是相同或不同,是一个环状基团,其中至少包含有一个C原子,通过它环状基团与金属连接；Ar1和Ar2由共价键联接在一起,可各自携带一个或多个取代基团，它们也可再通过取代基团联接在一起；L’每次出现时可以是相同或不同,是一个双齿螯合的辅助配体,最好是单阴离子双齿螯合配体；q1可以是0,1,2或3,优先地是2或3；q2可以是0,1,2或3,优先地是1或0。
一些三重态发光体的材料极其应用的例子可在下述专利文件和文献中找到: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 20070087219A1,US 20090061681A1,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 20010053462A1,WO 2007095118A1,US 2012004407A1,WO 2012007088A1,WO2012007087A1,WO 2012007086A1,US 2008027220A1,WO 2011157339A1,CN 102282150A,WO 2009118087A1,WO 2013107487A1,WO 2013094620A1,WO 2013174471A1,WO 2014031977A1,WO 2014112450A1,WO 2014007565A1,WO 2014038456A1,WO 2014024131A1,WO 2014008982A1,WO2014023377A1。特此将上述列出的专利文件和文献中的全部内容并入本文作为参考。
在下面的表中列出一些合适的三重态发光体的例子:
Figure PCTCN2018120702-appb-000025
Figure PCTCN2018120702-appb-000026
3.TADF材料
传统有机荧光材料只能利用电激发形成的25％单线态激子发光，器件的内量子效率较低(最高为25％)。尽管磷光材料由于重原子中心强的自旋-轨道耦合增强了系间穿越，可以有效利用电激发形成的单线态激子和三线态激子发光，使器件的内量子效率达到100％。但磷光材料昂贵，材料稳定性差，器件效率滚降严重等问题限制了其在OLED中的应用。热激活延迟荧光发光材料是继有机荧光材料和有机磷光材料之后发展的第三代有机发光材料。该类材料一般具有小的单线态-三线态能级差(ΔE st)，三线态激子可以通过反系间穿越转变成单线态激子发光。这可以充分利用电激发下形成的单线态激子和三线态激子。器件内量子效率可达到100％。同时材料结构可控，性质稳定，价格便宜无需要贵金属，在OLED领域的应用前景广阔。
TADF材料需要具有较小的单线态-三线态能级差，较好是ΔEst<0.3eV，次好是ΔEst<0.2eV，最好是ΔEst<0.1eV。在一个优先的实施方案中，TADF材料有比较小的ΔEst，在 另一个优先的实施方案中,TADF有较好的荧光量子效率。一些TADF发光的材料可在下述专利文件中找到: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.al.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，特此将上述列出的专利或文章文件中的全部内容并入本文作为参考。
在下面的表中列出一些合适的TADF发光材料的例子:
Figure PCTCN2018120702-appb-000027
Figure PCTCN2018120702-appb-000028
本发明的另一个目的是为印刷OLED提供材料解决方案。
用于这个目的，按照本发明的双极性化合物，其分子量≥700g/mol，优选≥900g/mol，很优选≥900g/mol，更优选≥1000g/mol，最优选≥1100g/mol。
在另一些优选的实施例中，按照本发明的双极性化合物或高聚物，在25℃时，在甲苯中的溶解度≥10mg/ml，优选≥15mg/ml，最优选≥20mg/ml。
本发明还进一步涉及一种组合物或油墨，包含有一种按照本发明的双极性化合物或高聚物及至少一种有机溶剂。
用于印刷工艺时，油墨的粘度，表面张力是重要的参数。合适的油墨的表面张力参数适合于特定的基板和特定的印刷方法。
在一个优选的实施例中，按照本发明的油墨在工作温度或在25℃的表面张力约在19dyne/cm到50dyne/cm范围；更好是在22dyne/cm到35dyne/cm范围；最好是在25dyne/cm到33dyne/cm范围。
在另一个优选的实施例中，按照本发明的油墨在工作温度或25℃的粘度约在1cps到100cps范围；较好是在1cps到50cps范围；更好是在1.5cps到20cps范围；最好是在4.0cps到20cps范围。如此配制的组合物将便于喷墨印刷。
粘度可以通过不同的方法调节，如通过合适的溶剂选取和油墨中功能材料的浓度。按照本发明的包含有所述地金属有机配合物或高聚物的油墨可方便人们将印刷油墨按照所用的印刷方法在适当的范围调节。一般地，按照本发明的组合物，包含的功能材料(即双极性化合物或高聚物)的重量比为0.3％～30wt％范围，较好的为0.5％～20wt％范围，更好的为0.5％～15wt％范围，更更好的为0.5％～10wt％范围，最好的为1％～5wt％范围。
在一些实施例中，按照本发明的油墨，所述的至少一种的有机溶剂选自基于芳族或杂芳族的溶剂，特别是脂肪族链/环取代的芳族溶剂、或芳族酮溶剂，或芳族醚溶剂。
适合本发明的溶剂的例子有，但不限于：基于芳族或杂芳族的溶剂:对二异丙基苯、戊苯、四氢萘、环己基苯、氯萘、1,4-二甲基萘、3-异丙基联苯、对甲基异丙苯、二戊苯、三戊苯、戊基甲苯、邻二甲苯、间二甲苯、对二甲苯、邻二乙苯、间二乙苯、对二乙苯、1,2,3,4-四甲苯、1,2,3,5-四甲苯、1,2,4,5-四甲苯、丁苯、十二烷基苯、二己基苯、二丁基苯、对二异丙基苯、1-甲氧基萘、环己基苯、二甲基萘、3-异丙基联苯、对甲基异丙苯、1-甲基萘、1,2,4-三氯苯、1,3-二丙氧基苯、4,4-二氟二苯甲烷、1,2-二甲氧基-4-(1-丙烯基)苯、二苯甲烷、2-苯基吡啶、3-苯基吡啶、N-甲基二苯胺、4-异丙基联苯、α,α-二氯二苯甲烷、4-(3-苯基丙基)吡啶、苯甲酸苄酯、1,1-双(3,4-二甲基苯基)乙烷、2-异丙基萘、二苄醚等；基于酮的溶剂:1-四氢萘酮，2-四氢萘酮，2-(苯基环氧)四氢萘酮，6-(甲氧基)四氢萘酮，苯乙酮、苯丙酮、二苯甲酮、及它们的衍生物，如4-甲基苯乙酮、3-甲基苯乙酮、2-甲基苯乙酮、4-甲基苯丙酮、3-甲基苯丙酮、2-甲基苯丙酮，异佛尔酮、2,6,8-三甲基-4-壬酮、葑酮、2-壬酮、3-壬酮、5-壬酮、2-癸酮、2,5-己二酮、佛尔酮、二正戊基酮；芳族醚溶剂：3-苯氧基甲苯、丁氧基苯、苄基丁基苯、对茴香醛二甲基乙缩醛、四氢-2-苯氧基-2H-吡喃、1,2-二甲氧基-4-(1-丙烯基)苯、1,4-苯并二噁烷、1,3-二丙基苯、2,5-二甲氧基甲苯、4-乙基本***、1,2,4-三甲氧基苯、4-(1-丙烯基)-1,2-二甲氧基苯、1,3-二甲氧基苯、缩水甘油基苯基醚、二苄基醚、4-叔丁基茴香醚、反式-对丙烯基茴香醚、1,2-二甲氧基苯、1-甲氧基萘、二苯醚、2-苯氧基甲醚、2-苯氧基四氢呋喃、乙基-2-萘基醚、戊醚c己醚、二辛醚、乙二醇二丁醚、二乙二醇二***、二乙二醇丁基甲醚、二乙二醇二丁醚、三乙二醇二甲醚、三乙二醇乙基甲醚、三乙二醇丁基甲醚、三丙二醇二甲醚、四乙二醇二甲醚；酯溶剂：辛酸烷酯、癸二酸烷酯、硬脂酸烷酯、苯甲酸烷酯、苯乙酸烷酯、肉桂酸烷酯、草酸烷酯、马来酸烷酯、烷内酯、油酸烷酯等。
进一步，按照本发明的油墨，所述的至少一种的有溶剂可选自：脂肪族酮，例如，2-壬酮、3-壬酮、5-壬酮、2-癸酮、2,5-己二酮、2,6,8-三甲基-4-壬酮、佛尔酮、二正戊基酮 等；或脂肪族醚，例如，戊醚、己醚、二辛醚、乙二醇二丁醚、二乙二醇二***、二乙二醇丁基甲醚、二乙二醇二丁醚、三乙二醇二甲醚、三乙二醇乙基甲醚、三乙二醇丁基甲醚、三丙二醇二甲醚、四乙二醇二甲醚等。
在另一些实施例中，所述的印刷油墨进一步包含有另一种有机溶剂。另一种有机溶剂的例子包括(但不限于)：甲醇、乙醇、2-甲氧基乙醇、二氯甲烷、三氯甲烷、氯苯、邻二氯苯、四氢呋喃、苯甲醚、吗啉、甲苯、邻二甲苯、间二甲苯、对二甲苯、1,4二氧杂环己烷、丙酮、甲基乙基酮、1,2二氯乙烷、3-苯氧基甲苯、1,1,1-三氯乙烷、1,1,2,2-四氯乙烷、醋酸乙酯、醋酸丁酯、二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、四氢萘、萘烷、茚和/或它们的混合物。
在一个优选的实施方案中，按照本发明的组合物是一溶液。
在另一个优选的实施方案中，按照本发明的组合物是一悬浮液。
本发明实施例中的组合物中可以包括0.01至20wt％的按照本发明的双极性化合物或其混合物，较好的是0.1至15wt％，更好的是0.2至10wt％，最好的是0.25至5wt％的双极性化合物或其混合物。
本发明还涉及所述组合物作为涂料或印刷油墨在制备有机电子器件时的用途，特别优选的是通过打印或涂布的制备方法。
其中，适合的打印或涂布技术包括(但不限于)喷墨打印，喷印(Nozzle Printing)，活版印刷，丝网印刷，浸涂，旋转涂布，刮刀涂布，辊筒印花，扭转辊印刷，平版印刷，柔版印刷，轮转印刷，喷涂，刷涂或移印，狭缝型挤压式涂布等。首选的是喷墨印刷，喷印及凹版印刷。溶液或悬浮液可以另外包括一个或多个组份例如表面活性化合物，润滑剂，润湿剂，分散剂，疏水剂，粘接剂等，用于调节粘度，成膜性能，提高附着性等。有关打印技术，及其对有关溶液的相关要求，如溶剂及浓度，粘度等，的详细信息请参见Helmut Kipphan主编的《印刷媒体手册:技术和生产方法》(Handbook of Print Media:Technologies and Production Methods),ISBN 3-540-67326-1。
如上所述的制备方法，其特征在于，所述的形成的一功能层，其厚度在5nm-1000nm。
本发明还涉及如上任一项所述的双极性化合物或高聚物在有机电子器件中的应用。
本发明进一步涉及一种有机电子器件，该有机电子器件的功能层包含如上所述的双极性化合物或高聚物。
所述的有机电子器件可选于，但不限于，有机发光二极管(OLED)，有机光伏电池(OPV)，有机发光电池(OLEEC)，有机场效应管(OFET)，有机发光场效应管，有机激光器，有机自旋电子器件，有机传感器及有机等离激元发射二极管(Organic Plasmon Emitting Diode)等，特别优选的是有机电致发光器件，如OLED，OLEEC，有机发光场效应管。
在某些特别优先的实施例中，所述的有机电致发光器件，至少包含有一发光层，所述的发光层包含一种如上所述的双极性化合物或高聚物。
所述的有机电致发光器件，包含一基片，一阳极，至少一发光层，一阴极，选择性的还可包含一空穴传输层或电子传输层。在某些实施例中，在所述的空穴传输层中包含一按照本发明的化合物或高聚物。在一个优选的实施方案中，在所述的发光层中包含一按照本发明的化合物或高聚物，更加优选的，在所述的发光层中包含一按照本发明的化合物或高聚物，及至少一种发光材料，发光材料可优选于荧光发光体，磷光发光体，TADF材料。
下面对电致发光器件的器件结构做一描述，但不限于。
基片可以是不透明或透明。一个透明的基板可以用来制造一个透明的发光元器件。例如可参见，Bulovic等Nature 1996,380,p29，和Gu等，Appl.Phys.Lett.1996,68,p2606。基片可以是刚性的或弹性的。基片可以是塑料，金属，半导体晶片或玻璃。最好是基片有一个平滑的表面。无表面缺陷的基板是特别理想的选择。在一个优选的实施例中，基片是柔性的，可选于聚合物薄膜或塑料，其玻璃化温度Tg为150℃以上，较好是超过200℃， 更好是超过250℃，最好是超过300℃。合适的柔性基板的例子有聚(对苯二甲酸乙二醇酯)(PET)和聚乙二醇(2,6-萘)(PEN)。
阳极可包含一导电金属或金属氧化物，或导电聚合物。阳极可以容易地注入空穴到空穴注入层(HIL)或空穴传输层(HTL)或发光层中。在一个的实施例中，阳极的功函数和发光层中的发光体或作为HIL或HTL或电子阻挡层(EBL)的p型半导体材料的HOMO能级或价带能级的差的绝对值小于0.5eV，较好是小于0.3eV，最好是小于0.2eV。阳极材料的例子包含但不限于：Al、Cu、Au、Ag、Mg、Fe、Co、Ni、Mn、Pd、Pt、ITO、铝掺杂氧化锌(AZO)等。其他合适的阳极材料是已知的，本领域普通技术人员可容易地选择使用。阳极材料可以使用任何合适的技术沉积，如一合适的物理气相沉积法，包含射频磁控溅射，真空热蒸发，电子束(e-beam)等。在某些实施例中，阳极是图案结构化的。图案化的ITO导电基板可在市场上买到，并且可以用来制备根据本发明的器件。
阴极可包含一导电金属或金属氧化物。阴极可以容易地注入电子到EIL或ETL或直接到发光层中。在一个的实施例中，阴极的功函数和发光层中发光体或作为电子注入层(EIL)或电子传输层(ETL)或空穴阻挡层(HBL)的n型半导体材料的LUMO能级或导带能级的差的绝对值小于0.5eV，较好是小于0.3eV，最好是小于0.2eV。原则上，所有可用作OLED的阴极的材料都可能作为本发明器件的阴极材料。阴极材料的例子包含但不限于：Al、Au、Ag、Ca、Ba、Mg、LiF/Al、MgAg合金、BaF2/Al、Cu、Fe、Co、Ni、Mn、Pd、Pt、ITO等。阴极材料可以使用任何合适的技术沉积，如一合适的物理气相沉积法，包含射频磁控溅射，真空热蒸发，电子束(e-beam)等。
OLED还可以包含其他功能层，如空穴注入层(HIL)、空穴传输层(HTL)、电子阻挡层(EBL)、电子注入层(EIL)、电子传输层(ETL)、空穴阻挡层(HBL)。适合用于这些功能层中的材料在前面有详细的描述。
在另一个优选的实施例中，按照本发明的发光器件中，其电子传输层(ETL)或空穴阻挡层(HBL)包含按照本发明的有机化合物或高聚物，并且通过溶液加工的方法制备而成。
按照本发明的发光器件，其发光波长在300到1000nm之间，较好的是在350到900nm之间，更好的是在400到800nm之间。
本发明还涉及按照本发明的电致发光器件在各种电子设备中的应用，包含，但不限于，显示设备，照明设备，光源，传感器等等。
下面将结合优选实施例对本发明进行了说明，但本发明并不局限于下述实施例，应当理解，所附权利要求概括了本发明的范围在本发明构思的引导下本领域的技术人员应意识到，对本发明的各实施例所进行的一定的改变，都将被本发明的权利要求书的精神和范围所覆盖。
具体实施例
1.按照本发明的化合物的合成方法举例，但本发明并不局限于下述实施例。
(1)化合物(2-2)的合成：
Figure PCTCN2018120702-appb-000029
Figure PCTCN2018120702-appb-000030
氮气环境下，将(17.4g,80mmol)的化合物2-2-1、(20.1g,80mmol)的化合物2-2-2、(39.1g,120mmol)的碳酸铯和200mL N,N-二甲基甲酰胺加入到500mL的三口瓶中，加热到150℃反应12小时，待反应完毕，将反应液冷却到室温，旋走大部分溶剂后，将反应液倒置400mL的纯净水中，将析出固体进行抽滤，收集滤渣进行重结晶提纯，产率90％。
Figure PCTCN2018120702-appb-000031
氮气环境下，将(17.9g,40mmol)的化合物2-2-3和150mL无水四氢呋喃加入到250mL的三口瓶中，降温到-78℃，缓慢滴加45mmol正丁基锂，反应2小时，一次性注入50mmol异丙醇频哪醇硼酸酯，让反应自然升到室温，继续反应12小时，加入纯净水淬灭反应，旋走大部分溶剂后，用二氯甲烷萃取并水洗3遍，收集有机相，旋干后重结晶，产率85％。
Figure PCTCN2018120702-appb-000032
氮气环境下，将(9.9g,20mmol)的化合物2-2-4和(5.3g,20mmol)的化合物2-2-5，(1.15g,1mmol)四(三苯基磷)钯，(1.3g,4mmol)四丁基溴化铵，(1.6g,40mmol)氢氧化钠，(10mL)水和(60mL)甲苯加入150mL的三口瓶中，加热80℃搅拌反应12小时，结束反应，将反应液旋转蒸发掉大部分溶剂，用二氯甲烷溶解水洗3遍，收集有机液拌硅胶过柱进行纯化，产率70％。
(2)化合物(4-12)的合成：
Figure PCTCN2018120702-appb-000033
氮气环境下，将(22.6g,80mmol)的化合物4-12-1、(20.1g,80mmol)的化合物2-2-2、 (39.1g,120mmol)的碳酸铯和200mL N,N-二甲基甲酰胺加入到500mL的三口瓶中，加热到150℃反应12小时，待反应完毕，将反应液冷却到室温，旋走大部分溶剂后，将反应液倒置400mL的纯净水中，将析出固体进行抽滤，收集滤渣进行重结晶提纯，产率85％。
Figure PCTCN2018120702-appb-000034
氮气环境下，将(20.6g,40mmol)的化合物4-12-2和150mL无水四氢呋喃加入到250mL的三口瓶中，降温到-78℃，缓慢滴加45mmol正丁基锂，反应2小时，一次性注入50mmol异丙醇频哪醇硼酸酯，让反应自然升到室温，继续反应12小时，加入纯净水淬灭反应，旋走大部分溶剂后，用二氯甲烷萃取并水洗3遍，收集有机相，旋干后重结晶，产率80％。
Figure PCTCN2018120702-appb-000035
氮气环境下，将(10.3g,20mmol)的化合物4-12-3和(5.3g,20mmol)的化合物4-12-4，(1.15g,1mmol)四(三苯基磷)钯，(1.3g,4mmol)四丁基溴化铵，(1.6g,40mmol)氢氧化钠，(10mL)水和(60mL)甲苯加入150mL的三口瓶中，加热80℃搅拌反应12小时，结束反应，将反应液旋转蒸发掉大部分溶剂，用二氯甲烷溶解水洗3遍，收集有机液拌硅胶过柱进行纯化，产率65％。
(3)化合物(5-8)的合成：
Figure PCTCN2018120702-appb-000036
氮气环境下，将(26.6g,80mmol)的化合物5-8-1、(20.1g,80mmol)的化合物2-2-2、(39.1g,120mmol)的碳酸铯和200mL N,N-二甲基甲酰胺加入到500mL的三口瓶中，加热到150℃反应12小时，待反应完毕，将反应液冷却到室温，旋走大部分溶剂后， 将反应液倒置400mL的纯净水中，将析出固体进行抽滤，收集滤渣进行重结晶提纯，产率85％。
Figure PCTCN2018120702-appb-000037
氮气环境下，将(22.6g,40mmol)的化合物5-8-2和150mL无水四氢呋喃加入到250mL的三口瓶中，降温到-78℃，缓慢滴加45mmol正丁基锂，反应2小时，一次性注入50mmol异丙醇频哪醇硼酸酯，让反应自然升到室温，继续反应12小时，加入纯净水淬灭反应，旋走大部分溶剂后，用二氯甲烷萃取并水洗3遍，收集有机相，旋干后重结晶，产率80％。
Figure PCTCN2018120702-appb-000038
氮气环境下，将(12.2g,20mmol)的化合物5-8-3和(5.3g,20mmol)的化合物5-8-4，(1.15g,1mmol)四(三苯基磷)钯，(1.3g,4mmol)四丁基溴化铵，(1.6g,40mmol)氢氧化钠，(10mL)水和(60mL)甲苯加入150mL的三口瓶中，加热80℃搅拌反应12小时，结束反应，将反应液旋转蒸发掉大部分溶剂，用二氯甲烷溶解水洗3遍，收集有机液拌硅胶过柱进行纯化，产率70％。
(4)化合物(6-16)的合成：
Figure PCTCN2018120702-appb-000039
氮气环境下，将(21.4g,80mmol)的化合物6-16-1、(20.1g,80mmol)的化合物2-2-2、(39.1g,120mmol)的碳酸铯和200mL N,N-二甲基甲酰胺加入到500mL的三口瓶中，加热到150℃反应12小时，待反应完毕，将反应液冷却到室温，旋走大部分溶剂后，将反应液倒置400mL的纯净水中，将析出固体进行抽滤，收集滤渣进行重结晶提纯，产率85％。
Figure PCTCN2018120702-appb-000040
Figure PCTCN2018120702-appb-000041
氮气环境下，将(19.9g,40mmol)的化合物6-16-2和150mL无水四氢呋喃加入到250mL的三口瓶中，降温到-78℃，缓慢滴加45mmol正丁基锂，反应2小时，一次性注入50mmol异丙醇频哪醇硼酸酯，让反应自然升到室温，继续反应12小时，加入纯净水淬灭反应，旋走大部分溶剂后，用二氯甲烷萃取并水洗3遍，收集有机相，旋干后重结晶，产率80％。
Figure PCTCN2018120702-appb-000042
氮气环境下，将(10.9g,20mmol)的化合物6-16-3和(5.4g,20mmol)的化合物6-16-4，(1.15g,1mmol)四(三苯基磷)钯，(1.3g,4mmol)四丁基溴化铵，(1.6g,40mmol)氢氧化钠，(10mL)水和(60mL)甲苯加入150mL的三口瓶中，加热80℃搅拌反应12小时，结束反应，将反应液旋转蒸发掉大部分溶剂，用二氯甲烷溶解水洗3遍，收集有机液拌硅胶过柱进行纯化，产率65％。
(5)化合物(6-21)的合成：
Figure PCTCN2018120702-appb-000043
氮气环境下，将(21.4g,80mmol)的化合物6-21-1、(20.1g,80mmol)的化合物6-21-2、(39.1g,120mmol)的碳酸铯和200mL N,N-二甲基甲酰胺加入到500mL的三口瓶中，加热到150℃反应12小时，待反应完毕，将反应液冷却到室温，旋走大部分溶剂后，将反应液倒置400mL的纯净水中，将析出固体进行抽滤，收集滤渣进行重结晶提纯，产率90％。
Figure PCTCN2018120702-appb-000044
Figure PCTCN2018120702-appb-000045
氮气环境下，将(19.9g,40mmol)的化合物6-21-3和150mL无水四氢呋喃加入到250mL的三口瓶中，降温到-78℃，缓慢滴加45mmol正丁基锂，反应2小时，一次性注入50mmol异丙醇频哪醇硼酸酯，让反应自然升到室温，继续反应12小时，加入纯净水淬灭反应，旋走大部分溶剂后，用二氯甲烷萃取并水洗3遍，收集有机相，旋干后重结晶，产率80％。
Figure PCTCN2018120702-appb-000046
氮气环境下，将(10.9g,20mmol)的化合物6-21-4和(5.4g,20mmol)的化合物6-16-4，(1.15g,1mmol)四(三苯基磷)钯，(1.3g,4mmol)四丁基溴化铵，(1.6g,40mmol)氢氧化钠，(10mL)水和(60mL)甲苯加入150mL的三口瓶中，加热80℃搅拌反应12小时，结束反应，将反应液旋转蒸发掉大部分溶剂，用二氯甲烷溶解水洗3遍，收集有机液拌硅胶过柱进行纯化，产率65％。
(6)化合物(6-35)的合成：
Figure PCTCN2018120702-appb-000047
氮气环境下，将(26.6g,80mmol)的化合物6-35-1、(24.1g,80mmol)的化合物6-21-2、(39.1g,120mmol)的碳酸铯和200mL N,N-二甲基甲酰胺加入到500mL的三口瓶中，加热到150℃反应12小时，待反应完毕，将反应液冷却到室温，旋走大部分溶剂后，将反应液倒置400mL的纯净水中，将析出固体进行抽滤，收集滤渣进行重结晶提纯，产率80％。
Figure PCTCN2018120702-appb-000048
Figure PCTCN2018120702-appb-000049
氮气环境下，将(24.6g,40mmol)的化合物6-35-3和150mL无水四氢呋喃加入到250mL的三口瓶中，降温到-78℃，缓慢滴加45mmol正丁基锂，反应2小时，一次性注入50mmol异丙醇频哪醇硼酸酯，让反应自然升到室温，继续反应12小时，加入纯净水淬灭反应，旋走大部分溶剂后，用二氯甲烷萃取并水洗3遍，收集有机相，旋干后重结晶，产率85％。
Figure PCTCN2018120702-appb-000050
氮气环境下，将(13.2g,20mmol)的化合物6-35-4和(5.4g,20mmol)的化合物6-16-4，(1.15g,1mmol)四(三苯基磷)钯，(1.3g,4mmol)四丁基溴化铵，(1.6g,40mmol)氢氧化钠，(10mL)水和(60mL)甲苯加入150mL的三口瓶中，加热80℃搅拌反应12小时，结束反应，将反应液旋转蒸发掉大部分溶剂，用二氯甲烷溶解水洗3遍，收集有机液拌硅胶过柱进行纯化，产率65％。
(7)化合物(6-37)的合成：
Figure PCTCN2018120702-appb-000051
氮气环境下，将(17.4g,80mmol)的化合物2-2-1、(20.1g,80mmol)的化合物2-2-2、(39.1g,120mmol)的碳酸铯和200mL N,N-二甲基甲酰胺加入到500mL的三口瓶中，加热到150℃反应12小时，待反应完毕，将反应液冷却到室温，旋走大部分溶剂后，将反应液倒置400mL的纯净水中，将析出固体进行抽滤，收集滤渣进行重结晶提纯，产率90％。
Figure PCTCN2018120702-appb-000052
Figure PCTCN2018120702-appb-000053
氮气环境下，将(17.9g,40mmol)的化合物6-37-1和150mL无水四氢呋喃加入到250mL的三口瓶中，降温到-78℃，缓慢滴加45mmol正丁基锂，反应2小时，一次性注入50mmol异丙醇频哪醇硼酸酯，让反应自然升到室温，继续反应12小时，加入纯净水淬灭反应，旋走大部分溶剂后，用二氯甲烷萃取并水洗3遍，收集有机相，旋干后重结晶，产率85％。
氮气环境下，将(9.9g,20mmol)的化合物6-37-2和(6.4g,20mmol)的化合物6-37-3，(1.15g,1mmol)四(三苯基磷)钯，(1.3g,4mmol)四丁基溴化铵，(1.6g,40mmol)氢氧化钠，(10mL)水和(60mL)甲苯加入150mL的三口瓶中，加热80℃搅拌反应12小时，结束反应，将反应液旋转蒸发掉大部分溶剂，用二氯甲烷溶解水洗3遍，收集有机液拌硅胶过柱进行纯化，产率65％。
对比实施例Ref-1和Ref-2(WO)：
Figure PCTCN2018120702-appb-000055
2.有机化合物的能量结构
有机材料的能级可通过量子计算得到，比如利用TD-DFT(含时密度泛函理论)通过Gaussian03W(Gaussian Inc.)，具体的模拟方法可参见WO2011141110。首先用半经验方法“Ground State/DFT/Default Spin/B3LYP”与基组“6-31G(d)”(Charge 0/Spin Singlet)来优化分子几何结构，然后有机分子的能量结构由TD-DFT(含时密度泛函理论)方法算得“TD-SCF/DFT/Default Spin/B3PW91”与基组“6-31G(d)”(Charge 0/Spin Singlet)。HOMO和LUMO能级按照下面的校准公式计算，S1和T1直接使用。
HOMO(eV)＝((HOMO(G)×27.212)-0.9899)/1.1206
LUMO(eV)＝((LUMO(G)×27.212)-2.0041)/1.385
其中HOMO(G)和LUMO(G)是Gaussian 03W的直接计算结果，单位为Hartree。结果如表一所示，其中ΔHOMO＝HOMO-(HOMO-1)，ΔLUMO＝(LUMO+1)-LUMO：
表一
Figure PCTCN2018120702-appb-000056
3.OLED器件的制备及表征
在本实施例中，分别用化合物(6-16)、(6-21)、(6-35)、(6-37)、Ref-1和Ref-2作为主体材料，如下图的Ir(mphq) 2acac作为发光材料，HATCN作为空穴注入材料，SFNFB作为空穴传输材料，NaTzF 2作为电子传输材料，Liq作为电子注入材料，构造成器件结构为ITO/HATCN/SFNFB/主体材料:Emitter(3％)/NaTzF 2:Liq/Liq/Al的电致发光器件。
Figure PCTCN2018120702-appb-000057
上述材料HATCN、SFNFB、Ir(mphq) 2acac、NaTzF 2、Liq均是可商业购得，比如吉林奥莱德(Jilin OLED Material Tech Co.,Ltd，www.jl-oled.com)，或其合成方法均为现有技术，详见现有技术中的参考文献，在此不再赘述。
下面通过具体实施例来详细说明采用上述的OLED器件的制备过程，OLED器件(如表2)的结构为：ITO/HATCN/SFNFB/主体材料:Emitter(3％)/NaTzF 2:Liq/Liq/Al，制备步骤如下：
a、ITO(铟锡氧化物)导电玻璃基片的清洗：使用各种溶剂(例如氯仿、丙酮或异丙醇中的一种或几种)清洗，然后进行紫外臭氧处理；
b、HATCN(30nm),SFNFB(50nm),主体材料:3％Emitter(40nm)，NaTzF 2:Liq(30nm)，Liq(1nm)，Al(100nm)在高真空(1×10 -6毫巴)中热蒸镀而成；
c、封装:器件在氮气手套箱中用紫外线硬化树脂封装。
表2
OLED器件 主体材料 T90@1000nits
OLED1 (6-16) 3.2
OLED2 (6-21) 4.2
OLED3 (6-35) 3.8
OLED4 (6-37) 3.5
RefOLED-1 Ref-1 1.5
RefOLED-2 Ref-2 1
各OLED器件的电流电压(J-V)特性通过表征设备来表征，同时记录重要的参数如效率，寿命及外部量子效率。经检测，以本发明的邻位取代基团的双极性化合物作为主体的发光寿命在同类型器件中是相对较高的，比是RefOELD的2倍以上。可见，采用本发明的有机化合物制备的OLED器件，其寿命得到大大提高。

Claims (12)

  1. 一种双极性化合物，所述双极性化合物如通式(1)所示：
    Figure PCTCN2018120702-appb-100001
    其中，
    X分别独立表示单键、N(R 1)、C(R 1R 2)、Si(R 1R 2)、O、C＝N(R 1)、C＝C(R 1R 2)、P(R 1)、P(＝O)R 1、S、S＝O或SO 2；其中，R 1、R 2每次出现时，分别独立表示H、D、取代或未取代的碳原子数1～30的烷基、取代或未取代的碳原子数3～30的环烷基、取代或未取代的环原子数为5～60的芳香族烃基或芳香族杂环基；
    L表示单键、取代或未取代的碳原子数1～30的烷基、取代或未取代的碳原子数3～30的环烷基、取代或未取代的环原子数为5～60的芳香族烃基或芳香族杂环基；
    Z 1、Z 2、Z 3分别独立表示N或CH，且Z 1、Z 2、Z 3中至少一个为N原子；
    Ar 1、Ar 2分别独立表示为取代或未取代的环原子数为6～30的芳香族烃基或芳香族杂环基，其中Ar 1和Ar 2至少一个环原子数大于6；
    Ar 3、Ar 4、Ar 5分别独立表示为取代或未取代的环原子数为5～60的芳香族烃基或芳香族杂环基。
  2. 根据权利要求1所述的双极性化合物，其特征在于，所述Ar 1、Ar 2、Ar 3、Ar 4、Ar 5、L可分别独立地包含如下结构基团中的一种或多种组合：
    Figure PCTCN2018120702-appb-100002
    其中，
    X 1-X 12分别独立表示CR 3或N；
    Y选自N(R 4)、C(R 4R 5)、Si(R 4R 5)、C(＝O)、S或O；
    R 3表示H、D、F、CN、烯基、炔基、腈基、胺基、硝基、酰基、烷氧基、羰基、砜基、取代或未取代的碳原子数1～30的烷基、取代或未取代的碳原子数3～30的环烷基、取代或未取代的环原子数为5～60芳香族烃基或芳香族杂环基；
    R 4和R 5分别独立表示H、D、取代或未取代的碳原子数1～30的烷基、取代或未取代的碳原子数3～30的环烷基、取代或未取代的环原子数为5～60的芳香族烃基或芳香族杂环基。
  3. 根据权利要求1所述的双极性化合物，其特征在于，所述Ar 1、Ar 2、Ar 3、Ar 4、Ar 5、L可分别独立地包含如下的化学式中的一种，其中环上的H可以被任意取代：
    Figure PCTCN2018120702-appb-100003
    Figure PCTCN2018120702-appb-100004
  4. 根据权利要求1所述的双极性化合物，其特征在于，所述双极性化合物包含通式(2)-(6)中任一化学式表示的结构：
    Figure PCTCN2018120702-appb-100005
  5. 根据权利要求1至5任一项所述的双极性化合物，其特征在于，所述双极性化合物选自如下结构式中的一种：
    Figure PCTCN2018120702-appb-100006
    Figure PCTCN2018120702-appb-100007
  6. 根据权利要求1至5任一项所述的双极性化合物，其特征在于，所述双极性化合物的T 1≥2.3eV，所述T 1表示双极性化合物的三线态能级。
  7. 一种高聚物，包含至少一个重复单元，所述重复单元包含如权利要求1所述的化学式(1)所示的结构单元。
  8. 一种混合物，包括如权利要求1至6任一项所述的双极性化合物或权利要求7所述的高聚物，及至少一种有机功能材料，所述的有机功能材料可选自以下材料中的至少一种：空穴注入材料空穴传输材料,电子传输材料电子注入材料,电子阻挡材料,空穴阻挡材料,发光体,主体材料和有机染料。
  9. 一种组合物，包括如权利要求1至6任一项所述的双极性化合物或权利要求7所述的高聚物，及至少一种有机溶剂。
  10. 一种有机电子器件，包括一种如权利要求1至6任一项所述的双极性化合物或权利要求7所述的高聚物或权利要求8所述的混合物或权利要求9所述的组合物。
  11. 根据权利要求10所述的有机电子器件，所述有机电子器件为电致发光器件，其特征在于，所述电致发光器件包括功能层，所述功能层包含一种按照权利要求1至6任一项所述的双极性化合物或权利要求7所述的高聚物。
  12. 根据权利要求11所述的有机电子器件，其特征在于，所述功能层包括发光层和电子传输层，所述发光层包含一种按照权利要求1至6任一项所述的双极性化合物或权利要求7所述的高聚物，或所述发光层包含一种按照权利要求1至6任一项所述的双极性化合物或权利要求7所述的高聚物和一种磷光发光体，或所述电子传输层包含一种按照权利要求1至6任一项所述的双极性化合物或权利要求7所述的高聚物。
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