WO2016112762A1 - 化合物、包含其的混合物、组合物和有机电子器件 - Google Patents

化合物、包含其的混合物、组合物和有机电子器件 Download PDF

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WO2016112762A1
WO2016112762A1 PCT/CN2015/097193 CN2015097193W WO2016112762A1 WO 2016112762 A1 WO2016112762 A1 WO 2016112762A1 CN 2015097193 W CN2015097193 W CN 2015097193W WO 2016112762 A1 WO2016112762 A1 WO 2016112762A1
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organic
compound
carbon atoms
aromatic
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潘君友
何锐锋
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Guangzhou Chinaray Optoelectronic Materials Ltd
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Guangzhou Chinaray Optoelectronic Materials Ltd
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Priority to CN201580068615.0A priority Critical patent/CN107001380B/zh
Priority to KR1020177022531A priority patent/KR20170102014A/ko
Priority to US15/543,227 priority patent/US20170365789A1/en
Priority to EP15877673.2A priority patent/EP3246326A4/en
Publication of WO2016112762A1 publication Critical patent/WO2016112762A1/zh
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Definitions

  • This invention relates to the field of electroluminescent materials, and more particularly to a compound (deuterated indolocarbazole compound), mixtures, compositions and organic electronic devices therefor.
  • organic light-emitting diodes Due to the synthetic diversity of organic semiconductor materials, the possibility of implementing large-area flexible devices, low manufacturing costs and high-performance optical and electrical properties, organic light-emitting diodes (OLEDs) are realized in novel optoelectronic devices, for example, There is great potential in flat panel display and lighting applications.
  • OLEDs organic light-emitting diodes
  • various systems based on fluorescent and phosphorescent materials have been developed.
  • An organic light-emitting diode using a fluorescent material has high reliability, but its internal electroluminescence quantum efficiency is limited to 25% under electric field excitation because the branch ratio of the singlet excited state and the triplet excited state of the exciton is 1: 3.
  • organic light-emitting diodes using phosphorescent materials have achieved nearly 100% internal luminescence quantum efficiency.
  • the stability of phosphorescent OLEDs needs to be improved.
  • the stability of the phosphorescent OLED, in addition to the illuminant itself, the host material is critical.
  • a compound deuterated indolocarbazole compound
  • organic electronic devices which can solve the existing problems And the stability of carbazole compound materials and related organic electronic devices and low device lifetime.
  • X may be an aromatic ring or an aromatic heterocyclic ring.
  • R, R 1 - R 8 may be independently or differently selected from -H, -F, -Cl, Br, I, -D, -CN, -NO 2 , -CF 3 , B in each occurrence.
  • One or more H atoms of R, R 1 - R 8 may be optionally substituted by D, F, Cl, Br, I, CN, NO 2 , one or more active R 0 , an aromatic group or a heteroaromatic ring.
  • R 0 in each occurrence may be independently or differently selected from H, D, an aliphatic alkane having 1 to 10 carbon atoms, an aromatic hydrocarbon, an aromatic ring or a aryl group having 5 to 10 carbon atoms. group.
  • Ar may be an alkyl group having 1 to 17 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 3 to 60 carbon atoms.
  • M may be an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 3 to 60 carbon atoms.
  • R and R 1 to R 8 may be a D atom.
  • X when multiple occurrences, may be the same or differently selected from the group consisting of:
  • the compound may have a structure represented by any of the following formulas (2) to (7):
  • Y 1 and Y 2 may be C or N, and when Y 1 and Y 2 are N, R may be unoptionally substituted.
  • Ar may be an alkyl group having 1 to 17 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 3 to 60 carbon atoms.
  • M may be an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 3 to 60 carbon atoms.
  • n may be an integer of 1 to 10.
  • the compound may have a structure represented by the following chemical formula
  • the compound may comprise a group having hole transport and/or electron transport properties.
  • a mixture comprising an organic compound according to one aspect of the invention, and at least one organic functional material, said organic functional material being selected from the group consisting of hole injection materials (HIM), hole transport materials (HTM), any of electron injecting material (EIM), electron transporting material (ETM), hole blocking (HBM), electron blocking (EBM), luminescent material (Emitter) or host material (Host) or the like or combination.
  • organic functional material being selected from the group consisting of hole injection materials (HIM), hole transport materials (HTM), any of electron injecting material (EIM), electron transporting material (ETM), hole blocking (HBM), electron blocking (EBM), luminescent material (Emitter) or host material (Host) or the like or combination.
  • a composition may comprise a compound according to the invention, and with at least one organic solvent.
  • An organic electronic device which may comprise at least one organic compound according to one aspect of the invention and mixtures thereof.
  • the organic electronic device may be selected from the group consisting of 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 laser, and an organic laser.
  • OLED organic light emitting diode
  • OCV organic photovoltaic cell
  • OEEC organic light emitting cell
  • OFET organic field effect transistor
  • an organic light emitting field effect transistor an organic laser
  • an organic laser and an organic laser.
  • the compounds described in accordance with one aspect of the invention are useful in OLEDs, particularly as host materials, to provide a longer lifetime.
  • the possible mechanism is as follows, but is not limited to, the mass of the ytterbium (D) atom is twice the mass of the H atom, and the CD bond has a relatively low reaction free energy, a reaction rate, and a osmotic barrier with respect to the CH bond, so that the CD bond It has a lower reactivity with respect to the CH bond (Chem. Rev. 1955, 55, 713-743), which opens up the possibility of improving the chemical/environmental stability of the indolocarbazole compounds and photovoltaic devices.
  • a deuterated indolocarbazole compound comprising related mixtures and compositions, and their use in organic electronic devices, in order to make the technical solutions and effects of the present invention clearer It is clear that 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.
  • X is an aromatic ring or an aromatic heterocyclic ring.
  • R, R 1 - R 8 may be independently or differently selected from -H, -F, -Cl, Br, I, -D, -CN, -NO 2 , -CF 3 , B in each occurrence.
  • One or more H atoms of R, R 1 - R 8 may be optionally substituted by D, F, Cl, Br, I, CN, NO 2 , one or more active R 0 , an aromatic group or a heteroaromatic ring.
  • R 0 in each occurrence may be independently or differently selected from H, D, an aliphatic alkane having 1 to 10 carbon atoms, an aromatic hydrocarbon, an aromatic ring or a aryl group having 5 to 10 carbon atoms. group.
  • Ar may be an alkyl group having 1 to 17 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 3 to 60 carbon atoms.
  • M may be an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 3 to 60 carbon atoms.
  • n may be an integer of 1 to 10.
  • R and R 1 to R 8 is a D atom.
  • n is an integer of 1 to 4, more preferably an integer of 1 to 3, more preferably an integer of 1 to 3, and most preferably an integer of 1 to 2.
  • the organic compound according to one aspect of the invention is a small molecule material.
  • 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, more preferably ⁇ 2000 g/mol, most preferably ⁇ 1500 g/mol.
  • polymer ie, Polymer, as defined herein, includes homopolymers, copolymers, block copolymers. Also in the present invention, the 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.].
  • conjugated polymer as defined herein is a polymer whose backbone backbone consists primarily of sp2 hybrid orbitals of C atoms, notable examples of which are: polyacetylene polyacetylene and poly ( Phenylene vinylene), the C atom in its main chain may also be optionally substituted by other non-C atoms, and is still considered to be a conjugated polymer when the sp2 hybridization in the main chain is interrupted by some natural defects. Further, in the present invention, the conjugated polymer may also include an aryl amine, an aryl phosphine and other heteroarmotics, and an organometallic complexes in the main chain. )Wait.
  • a first feature of the compound according to one aspect of the invention is that at least one H atom of the organic compound is optionally substituted by hydrazine.
  • at least one of R, R 1 - R 8 is a D atom.
  • the present invention shows that the post-deuterated compound has a more preferable stability, and the OLED containing the post-deuterated compound has a long life.
  • the possible mechanism is, but is not limited to, due to the isotope effect of kinetics, a reaction rate involving a CH bond is usually 6-10 times faster than the corresponding CD bond, and therefore, after the OLED is operated, the compound containing the deuteration is contained. There is a relatively slow decay in the kinetics of decay.
  • those H with higher reactivity can be optionally substituted with hydrazine.
  • the organic compound, wherein the H atom of at least one of Ar may be optionally substituted by hydrazine.
  • the organic compound, wherein the H atom of at least one of M, is optionally substituted by hydrazine.
  • the abundance in the ocean is 0.0156%, that is, one of the 6420 hydrogen atoms is helium.
  • the amount of ruthenium in the compound according to one aspect of the invention may be much greater than the natural abundance.
  • at least 1% of the H atoms may be optionally substituted by ruthenium, more preferably at least 10% of the H atom. Replaced by the election.
  • the deuterated organic compound wherein more than 20%, more preferably 30% or more, more preferably 40% or more, and most preferably 50% or more of the H atom may be used Optional replacement.
  • the compound according to formula (1), wherein X, when multiple occurrences, may be the same or differently selected from the group consisting of:
  • the compound according to one aspect of the present invention may comprise a structure having a chemical formula represented by any one of the following (2) to (7):
  • Y 1 and Y 2 may be C and N. When Y 1 and Y 2 are N, Y 1 and Y 2 do not contain a substituent, and preferably Y 1 and Y 2 are C.
  • R, R 1 - R 8 may each independently be H, D, alkyl, arylalkyl, alkenyl, alkynyl, nitrile, amine, nitro, acyl, alkoxy, carbonyl, sulfone, ring An alkyl group or a hydroxyl group; at least one of which is a D atom.
  • the alkyl group may represent an alkyl group having 1 to 17 carbon atoms or a cycloalkyl group having 3 to 18 carbon atoms, and a preferred alkyl group may be a methyl group or a t-butyl group;
  • the aromatic alkyl group may be Examples of the aromatic hydrocarbon group having 6 to 60 carbon atoms or the aromatic heterocyclic group having 3 to 60 carbon atoms include the following non-limiting examples: benzene, naphthalene, anthracene, phenanthrene, anthracene, pyridine, pyrimidine, and the like.
  • the preferred aromatic alkyl group is phenyl, Triazine, carbazole, pyridyl.
  • the number of ruthenium atoms is an integer of from 1 to 10
  • a preferred optional substitution position is an ortho and para position of the indolocarbazole nitrogen atom
  • a preferred number of optional substitutions is an integer of from 1 to 6.
  • Ar can be represented by an alkyl group having 1 to 17 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 3 to 60 carbon atoms.
  • Preferred examples include non-limiting examples of methyl, benzene, naphthalene, anthracene, phenanthrene, anthracene, pyridine, pyrimidine, triazine, anthracene, thioindigo, silicon germanium, oxazole, thiophene, furan, and thiazole.
  • a group such as triphenylamine, triphenylphosphine oxide, tetraphenyl silicon, snail, or spirosilicone, and more preferably a group such as benzene, pyridine, pyrimidine, triazine or carbazole.
  • One or more carbon atoms of the alkyl or cycloalkyl group may be optionally substituted by a hetero atom such as nitrogen, oxygen, sulfur or silicon.
  • the aromatic hydrocarbon group or the aromatic heterocyclic group may have a plurality of aromatic groups linked thereto and may have a substituent.
  • a plurality of preferred aromatic groups are biphenyl, terphenyl, phenylpyridine, and Phenyltriazine, phenylcarbazole, pyridylcarbazole, and the like. More preferred substituents are fluorine, methyl, t-butyl, methoxy, acetyl and the like.
  • M may be an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 3 to 60 carbon atoms.
  • Preferred examples include benzene, naphthalene, anthracene, phenanthrene, and the like.
  • the aromatic hydrocarbon group or the aromatic heterocyclic group may have a substituent, and among them, a more preferable substituent is fluorine, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 2 carbon atoms.
  • n may be an integer of 1 to 10, and preferably n is an integer of 1 to 4.
  • the compound according to one aspect of the invention may have a structure represented by the following chemical formula
  • the compound according to one aspect of the invention may comprise a structure having the chemical formula represented by any one of the following (2a) to (7a):
  • the compound according to one aspect of the invention wherein at least one M or one Ar may comprise a group having a hole transporting property.
  • Groups of suitable hole transport properties will be illustrated in the underlying hole transport material (HTM).
  • the compound according to one aspect of the invention, wherein at least one M or one Ar may contain a group having electron transporting properties.
  • Groups of suitable electron transport characteristics will be described in the following electron transport materials (ETM).
  • the compound according to one aspect of the invention wherein at least one of M or Ar may comprise a group having electron transport properties and the other comprises a hole transporting property. Group.
  • deuterated indolocarbazole compound according to one aspect of the present invention is exemplified below, but the deuterated indolocarbazole compound of the present invention is not limited thereto.
  • One may be an indole carbazole precursor with a halogen atom, and then a functional group may be optionally substituted on the NH bond of the group, and a halogen atom may be substituted with a D atom; First, the functional group is optionally substituted with an NH bond of an indolocarbazole, and then halogen substitution is carried out on the unit, and finally the halogen atom thereon is replaced with a D atom to form a final deuterated indolocarbazole.
  • the invention further relates to a mixture which may comprise at least one organic compound according to one aspect of the invention, and at least one other organic functional material.
  • Another organic functional material described herein may comprise a hole (also called a hole) injection or transport material (HIM/HTM), a hole blocking material (HBM), an electron injecting or transporting material (EIM/ETM), Any one or a combination of an electron blocking material (EBM), an organic matrix material (Host), a singlet illuminant (fluorescent illuminant), a triplet illuminant (phosphorescent illuminant), particularly a luminescent metal organic complex .
  • HIM/HTM hole injection or transport material
  • HBM hole blocking material
  • EIM/ETM electron injecting or transporting material
  • Non-limiting examples of various organic functional materials are described in detail in, for example, WO
  • the organic functional material can be a small molecule or a polymeric material.
  • the host material In the present invention, the host material, the matrix material, the Host material, and the Matrix material have the same meaning and are interchangeable.
  • metal organic complexes metal organic complexes, metal organic complexes, and organometallic complexes have the same meaning and are interchangeable.
  • Suitable organic HIM/HTM materials for use in one aspect of the invention may optionally comprise a compound having the following structural units: phthalocyanine, porphyrin, amine, aromatic amine, biphenyl triarylamine, thiophene, and thiophene such as dithiophene. And any one or a combination of thiophene and thiophene, pyrrole, aniline, carbazole, aziridine and aziridine, and derivatives thereof.
  • HIMs also comprise fluorocarbon-containing polymers; conductively doped polymers; conductive polymers such as PEDOT/PSS; self-assembling monomers such as compounds containing phosphonic acid and sliane derivatives; metal oxides, Any one or a combination of, for example, MoOx; a metal complex, and a crosslinking compound.
  • An electron blocking layer (EBL) used in one aspect of the invention is typically used to block electrons from adjacent functional layers, particularly luminescent layers.
  • the electron blocking material (EBM) of the electron blocking layer (EBL) requires a higher LUMO than an adjacent functional layer such as a light emitting layer.
  • the EBM has a larger excited state level than the adjacent luminescent layer, such as a singlet or triplet level, depending on the illuminant.
  • the EBM has a hole transport function. HIM/HTM materials that typically have high LUMO levels can be used as EBM.
  • cyclic aromatic amine-derived compounds that can be used as HIM or HTM include, but are not limited to, the following general structures:
  • Each of Ar 1 to Ar 9 may be independently selected from the group consisting of a cyclic aromatic hydrocarbon compound such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenalene, phenanthrene, anthracene, anthracene, fluorene, anthracene, anthracene; aromatic heterocyclic ring Compounds such as dibenzothiophene, dibenzofuran, furan, thiophene, benzofuran, benzothiophene, oxazole, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, oxatriazole, Oxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, hydr
  • Ar 1 to Ar 9 may be independently selected from the group consisting of:
  • n 1 is an integer from 1 to 20; X 1 to X 8 are CH or N; and Ar 1 is as defined above.
  • Non-limiting examples of metal complexes that can be used as HTM or HIM include, but are not limited to, the following general structures:
  • M can be a metal having an atomic weight greater than 40;
  • (Y 3 -Y 4 ) may be a two-dentate ligand, Y 3 and Y 4 may be independently selected from C, N, O, P, and S; L is an ancillary ligand; m may be an integer, The value is from 1 to the maximum coordination number of this metal; m+h is the maximum coordination number of this metal.
  • (Y 3 -Y 4 ) may be a 2-phenylpyridine derivative.
  • (Y 3 -Y 4 ) may be a carbene ligand.
  • M can be selected from the group consisting of Ir, Pt, Os, and Zn.
  • the HOMO of the metal complex that can be used as HTM or HIM can be greater than -5.5 eV (relative to the vacuum level).
  • HIM/HTM/EBM compounds are listed in the table below:
  • EIM/ETM material used in one aspect of the present invention are not particularly limited, and any metal complex or organic compound may be used as the EIM/ETM as long as they can transport electrons.
  • Preferred organic EIM/ETM materials may be selected from the group consisting of tris(8-hydroxyquinoline)aluminum (AlQ3), phenazine, phenanthroline, anthracene, phenanthrene, anthracene, diterpene, spirobifluorene, p-phenylacetylene, triazine, Triazole, imidazole, hydrazine, hydrazine, ruthenium fluorene, hydrazine, dibenzo-indenoindole, anthracene naphthalene, benzindene and derivatives thereof.
  • the hole blocking layer (HBL) used in one aspect of the invention is typically used to block cavities from adjacent functional layers, particularly luminescent layers. In contrast to a light-emitting device without a barrier layer, the presence of HBL typically results in an increase in luminous efficiency.
  • the hole blocking material (HBM) of the hole blocking layer (HBL) needs to have a lower HOMO than an adjacent functional layer such as a light emitting layer.
  • the HBM has a larger excited state level than the adjacent luminescent layer, such as a singlet or triplet, depending on the illuminant.
  • the HBM has an electron transport function. . . . EIM/ETM materials, which typically have deep HOMO levels, can be used as HBM.
  • the compound useful as EIM/ETM/HBM can be a molecule comprising at least one of the following groups:
  • R 9 may be selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl when they are aryl or heteroaryl , which may be the same meaning Ar 1 and Ar 2 in the HTM above;
  • Ar 1 -Ar 5 and X 1 -X 8 may be the same meaning 8 Ar 1 -Ar 5 and X 1 -X in the HTM described;
  • n 1 can be an integer from 1 to 20;
  • examples of metal complexes that can be used as EIM/ETM may include, but are not limited to, the following general structure:
  • (ON) or (NN) is a two-tooth ligand in which the metal is coordinated to O, N or N, N; L is an ancillary ligand; m is an integer from 1 to the maximum coordination of the metal number.
  • ETM compounds are listed in the table below:
  • an organic alkali metal compound can be used as the EIM.
  • an organic alkali metal compound is understood to be a compound having at least one alkali metal, that is, lithium, sodium, potassium, rubidium, cesium, and further comprising at least one organic ligand.
  • Non-limiting examples of suitable organic alkali metal compounds may include the compounds described in US Pat. No. 7,776,317 B2, EP 1 194 562 B1 and EP 1 144 543 B1.
  • Preferred organic alkali metal compounds may be compounds of the formula:
  • R 9 has the meaning as described above, the arc represents two or three atoms and a bond, so as to form a 5- or 6-membered ring with the metal M if necessary, wherein the atom may also be selected by one or more R 9 Alternatively, M may be an alkali metal selected from the group consisting of lithium, sodium, potassium, rubidium, and cesium.
  • the organobase metal compound may be in the form of a monomer, as described above, or in the form of an aggregate, for example, a two alkali metal ion with two ligands, a tetra alkali metal ion and a tetraligand, a hexametal ion and Six ligands or in other forms.
  • Preferred organic alkali metal compounds may be compounds of the formula:
  • each occurrence may be the same or differently selected from 0, 1, 2, 3 or 4;
  • each occurrence may be the same or differently selected from 0, 1, 2 or 3;
  • the alkali metal M may be selected from the group consisting of lithium, sodium, potassium, more preferably lithium or sodium, and most preferably lithium.
  • the electron injecting layer may contain an organic alkali metal compound. More preferably, the electron injecting layer is composed of an organic alkali metal compound.
  • the organoalkali metal compound can be doped into other ETMs to form an electron transport layer or an electron injection layer. More preferably, it is an electron transport layer.
  • Non-limiting examples of suitable organic alkali metal compounds as EIM are listed in the table below:
  • the example of the triplet matrix material used in one aspect of the present invention is not particularly limited, and any metal complex or organic compound may be used as a matrix as long as its triplet energy ratio is an illuminant, particularly a triplet state.
  • the illuminant or phosphorescent emitter is higher.
  • the general structure used in one aspect of the invention includes, but is not limited to, the following:
  • M may be a metal
  • (Y 5 -Y 6 ) may be a two-dentate ligand, Y 5 and Y 6 may be independently selected from C, N, O, P and S
  • L may be an ancillary ligand; It can be an integer with a value from 1 to the maximum coordination number of the metal; m+h is the maximum coordination number of the metal.
  • the metal complex that can be used as the triplet matrix can have the following form:
  • (O-N) is a two-tooth ligand in which the metal is coordinated to the O and N atoms.
  • M can be selected from the group consisting of Ir and Pt.
  • Non-limiting examples of organic compounds that can be used as the triplet matrix used in one aspect of the invention are selected from compounds containing a cyclic aromatic hydrocarbon group, such as benzene, biphenyl, triphenyl, benzo, anthracene; a compound containing an aromatic heterocyclic group such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, Triazoles, oxazoles, thiazoles, oxadiazoles, oxatriazoles, dioxins, thiadiazoles, pyridines, pyridazines, pyrimidines, pyrazines, triazines, oxazines, o
  • each of Ar may be further optionally substituted, and the substituent may be hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.
  • the triplet matrix material can be selected from compounds comprising at least one of the following groups:
  • R 9 -R 15 are each independently the same meaning of R 9 above; X 1 -X 8 1 -X 8 and X is the same as defined above; X 9 is selected from CR 9 R 10 or NR 9; n 1 may be from a 1 An integer of up to 20.
  • the example of the singlet matrix material used in one aspect of the present invention is not particularly limited, and any organic compound may be used as a matrix as long as it has a singlet energy ratio illuminant, particularly a singlet illuminant. Or the fluorescent illuminant is higher.
  • Non-limiting examples of the organic compound used as the singlet matrix material may be selected from the group consisting of a cyclic aromatic compound such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenalene, phenanthrene, anthracene, anthracene, quinone , anthracene, anthracene; aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, Pyrrolodipyridine, pyrazole, imidazole , triazole, isoxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyr
  • the singlet matrix material can be selected from compounds comprising at least one of the following groups:
  • X 10 is selected from CR 9 R 10 or NR 9 ; R 9 , Ar 1 , X 1 -X 8 , X 9 and n 1 have the same meanings as defined above.
  • Singlet emitters tend to have longer conjugated pi-electron systems. To date, there have been many examples such as, but not limited to, styrylamine and its derivatives, and indenofluorene and its derivatives.
  • the singlet emitter can be selected from the group consisting of monostyrylamines, distyrylamines, tristyrylamines, tetrastyrylamines. , styryl phosphines, styryl ethers and arylamines.
  • the monostyrylamine refers to a compound comprising an optionally substituted or optionally substituted styryl group and at least one amine, most preferably an aromatic amine.
  • the distyrylamine refers to a compound comprising two unsubstituted or optionally substituted styryl groups and at least one amine, most preferably an aromatic amine.
  • Ternary styrylamine refers to a compound comprising three unsubstituted or optionally substituted styryl groups and at least one amine, most preferably an aromatic amine.
  • Tetrastyrylamine refers to a compound comprising four unsubstituted or optionally substituted styryl groups and at least one amine, most preferably an aromatic amine.
  • Preferred styrene is Styrene, which may be further optionally substituted.
  • the corresponding phosphines and ethers are defined similarly to amines.
  • An arylamine or an aromatic amine refers to a compound comprising three unsubstituted or optionally substituted aromatic ring or heterocyclic systems directly bonded to the nitrogen. At least one of these aromatic or heterocyclic ring systems is preferably selected from the group consisting of fused ring systems, and most preferably at least 14 aromatic ring atoms.
  • Preferred examples thereof are aromatic decylamine, aromatic quinone diamine, aromatic decylamine, aromatic quinone diamine, aromatic thiamine and aromatic quinone diamine.
  • Aromatic guanamine refers to a compound in which a diarylamino group is directly attached to the oxime, most preferably at the position of 9.
  • Aromatic quinone diamine refers to a compound in which two diarylamino groups are directly attached to the oxime, most preferably at the 9,10 position.
  • the definitions of aromatic decylamine, aromatic quinone diamine, aromatic thiamine and aromatic quinone diamine are similar, wherein the diaryl aryl group is most preferably bonded to the 1 or 1,6 position of hydrazine.
  • Non-limiting examples of singlet emitters based on vinylamines and arylamines are also preferred examples and can be found in the following patent documents: WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549 , WO 2007/115610, US Pat. No. 7,250,532, B2, DE 102005058557 A1, CN 1583691 A, JP 08053397 A, US Pat. No. 6,215, 531, B1, US 2006/210830 A, EP 1957606 A1 and US 2008/0113101 A1.
  • a non-limiting example of a singlet emitter based on a distyrylbenzene extreme derivative is US 5121029.
  • Further preferred singlet emitters may be selected from the group consisting of an indeno-amine and an indeno-diamine, as disclosed in WO 2006/122630, benzoindenofluorene-amine and benzindene Benzoindenofluorene-diamine, as disclosed in WO 2008/006449, dibenzoindenofluorene-amine and dibenzoindenofluorene-diamine, such as Published in WO2007/140847.
  • polycyclic aromatic hydrocarbon compounds in particular derivatives of the following compounds: for example, 9,10-di(2-naphthoquinone) (9,10-di(2-naphthylanthracene) ), naphthalene, tetraphenyl, xanthene, phenanthrene, perylene such as 2,5,8,11-tetra-t-butylperylene, indenoperylene, phenylenes such as (4) , 4'-(bis(9-ethyl-3-carbazovinylene)-1,1'-biphenyl), periflanthene, decacyclene, coronene, sputum, spirofluorene, Arylpyrene (such as US20060222886), arylenevinylene (such as US5121029, US5130603), cyclopentadiene such as tetraphenylcyclopen
  • Non-limiting examples of some suitable singlet emitters are listed in the table below:
  • the triplet emitters used in one aspect of the invention are also referred to as phosphorescent emitters.
  • the triplet emitter may be a metal complex having the formula M(L)n, wherein M is a metal atom, and L may be the same or different organic ligand each time it appears. It is attached to the metal atom M by one or more position linkages or coordination, n being an integer greater than 1, more preferably 1, 2, 3, 4, 5 or 6.
  • these metal complexes are coupled to one polymer by one or more positions, most preferably by an organic ligand.
  • the metal atom M may be selected from transition metal elements or lanthanides or actinides, preferably Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy Re, Cu or Ag, particularly preferably Os, Ir, Ru, Rh, Re, Pd, Pt.
  • the triplet emitter may comprise a chelating ligand, ie a ligand, coordinated to the metal by at least two bonding sites, it being particularly preferred to consider that the triplet emitter comprises two or three identical or different Double or multidentate ligand.
  • Chelating ligands are beneficial for increasing the stability of metal complexes.
  • Non-limiting examples of organic ligands may be selected from the group consisting of phenylpyridine derivatives, 7,8-benzoquinoline derivatives, 2(2-thienyl)pyridine (2 (2) a -thienyl) pyridine) derivative, a 2 (1-naphthyl) pyridine derivative, or a 2 phenylquinoline derivative. All of these organic ligands may be optionally substituted, for example by fluorine or trifluoromethyl.
  • the ancillary ligand may preferably be selected from the group consisting of acetoacetate or picric acid.
  • the metal complex that can be used as the triplet emitter can have the following form:
  • M is a metal selected from the group consisting of transition metal elements or lanthanides or actinides; each occurrence of Ar 10 may be the same or different cyclic group containing at least one donor atom, ie, a lone pair of electrons An atom, such as nitrogen or phosphorus, is coordinated to the metal through its cyclic group; each occurrence of Ar 11 may be the same or a different cyclic group containing at least one C atom through which a cyclic group The group is attached to the metal; Ar 10 and Ar 11 are linked together by a covalent bond, each of which may carry one or more substituent groups, which may also be linked together by a substituent group; L may be the same each time it occurs or Different ancillary ligands, preferably from a bidentate chelate ligand, most preferably a monoanionic bidentate chelate ligand; m is 1, 2 or 3, preferably 2 or 3, particularly preferably 3; 0, 1 or 2, preferably 0 or 1, particularly preferably preferably
  • Non-limiting examples of materials for some triplet emitters and their use 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.
  • triplet emitters Some non-limiting examples of suitable triplet emitters are listed in the table below:
  • the organic functional materials described above including HIM, HTM, ETM, EIM, Host, fluorescent emitters, phosphorescent emitters, may all be in the form of a polymer.
  • the polymer suitable for the present invention may be a conjugated polymer.
  • conjugated polymers have the following general formula:
  • A can independently select the same or different structural units when multiple occurrences
  • B a ⁇ -conjugated structural unit having a large energy gap, also called a Backbone Unit, selected from a monocyclic or polycyclic aryl or heteroaryl group, and the preferred unit form may be benzene, bis. Biphenylene, naphthalene, anthracene, phenanthrene, dihydrophenanthrene, 9,10-dihydrophenanthrene, anthracene, diterpene, spirobifluorene, p-phenylacetylene, ruthenium, fluorene, dibenzo-indole And hydrazine, hydrazine and their derivatives.
  • a Backbone Unit selected from a monocyclic or polycyclic aryl or heteroaryl group, and the preferred unit form may be benzene, bis. Biphenylene, naphthalene, anthracene, phenanthrene, dihydrophenanthrene, 9,10-dihydrophenanthrene
  • a ⁇ -conjugated structural unit having a small energy gap may be selected from hole injection or transport materials (HIM/HTM) containing the above-described functions according to different functional requirements. , hole blocking material (HBM), electron injecting or transporting material (EIM/ETM), electron blocking material (EBM), organic matrix material (Host), singlet illuminant (fluorescent illuminant), heavy illuminant ( A structural unit of a phosphorescent emitter.
  • HBM hole blocking material
  • EIM/ETM electron injecting or transporting material
  • EBM electron blocking material
  • organic matrix material Host
  • singlet illuminant fluorescent illuminant
  • heavy illuminant A structural unit of a phosphorescent emitter.
  • the polymeric HTM material may be a homopolymer, and preferred homopolymers are selected from the group consisting of polythiophenes, polypyrroles, polyanilines, polybiphenyl triarylamines, polyvinylcarbazoles, and derivatives thereof. Things.
  • the polymer HTM material may be a conjugated copolymer represented by Chemical Formula 1, wherein
  • A a functional group having a hole transporting ability, which may be selected from structural units containing the hole injection or transport material (HIM/HTM) described above; in a preferred embodiment, A may be selected from an amine, Biphenyl triarylamine, thiophene, and thiophene such as dithienothiophene and thiophene, pyrrole, aniline, carbazole, indenocarbazole, indole carbazide, pentacene, phthalocyanine, porphyrin and their derivatives.
  • HIM/HTM hole injection or transport material
  • Non-limiting examples of suitable conjugated polymers that can serve as HTM are listed below:
  • R o , R r and R s may each independently be a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branch having 3 to 20 C atoms. Or a cyclic alkyl, alkoxy or thioalkoxy group or a silyl group, or an optionally substituted keto group having 1 to 20 C atoms, having 2 to 20 C
  • organic ETM materials are polymers having electron transport capabilities, including conjugated polymers and non-conjugated polymers.
  • Preferred polymeric ETM materials are homopolymers, and preferred homopolymers are selected from the group consisting of polyphenanthrene, polyphenanthroline, polyfluorene, polyspiroquinone, polyfluorene, and derivatives thereof.
  • a preferred polymer ETM material is a conjugated copolymer represented by Chemical Formula 1, wherein A can independently select the same or different forms in multiple occurrences:
  • A a functional group having an electron transporting ability, preferably selected from the group consisting of tris(8-hydroxyquinoline)aluminum (AlQ 3 ), benzene, diphenylene, naphthalene, anthracene, phenanthrene, Dihydrophenanthrene, anthracene, diterpene, snail ⁇ , p-phenylacetylene, anthracene, anthracene, 9,10-Dihydrophenanthrene, phenazine, phenanthroline, ruthenium, fluorene, dibenzo-indenoindole, anthracene naphthalene, benzopyrene and their derivative
  • the luminescent polymer may be a conjugated polymer having the general formula of the formula:
  • a 1 a functional group having a hole or electron transporting ability, which may be selected from a structural unit comprising the hole injection or transport material (HIM/HTM) described above, or an electron injecting or transporting material (EIM/ETM). .
  • HIM/HTM hole injection or transport material
  • EIM/ETM electron injecting or transporting material
  • a 2 a group having a light-emitting function, which may be selected from structural units including the above-described singlet light emitter (fluorescent light emitter) and heavy light emitter (phosphorescent light emitter).
  • Non-limiting examples of luminescent polymers are disclosed in the following patent applications:
  • WO2003099901 WO2003051092
  • WO2003020790 WO2003020790, US2020040076853, US2020040002576, US2007208567, US2005962631, EP201345477, EP2001344788, DE102004020298.
  • the polymer suitable for the present invention may be a non-conjugated polymer.
  • This can be that all functional groups are on the side chain and the backbone is a non-conjugated polymer.
  • Some non-limiting examples of such non-conjugated polymers useful as phosphorescent or phosphorescent materials are disclosed in U.S. Patent Nos. 7,250,226, B2, JP 2007 059 939 A, JP 2007 211 243 A2, and JP 2007 1975 074 A2, et al.
  • Non-limiting examples of conjugated polymers are disclosed in patent applications such as JP2005108556, JP2005285661, and JP2003338375.
  • non-conjugated polymer may also be a polymer, and the functional units conjugated to the main chain are linked by non-conjugated linking units.
  • Non-limiting examples of such polymers are in DE102009023154.4 and DE102009023156.0. There is publicity in it.
  • the organic compound according to one aspect of the invention may be present in an amount of from 0.01 to 90% by weight, more preferably from 1 to 80% by weight, in a mixture according to one aspect of the invention. More preferably, it is 10 to 80% by weight, and most preferably 20 to 70% by weight.
  • the mixture according to one aspect of the invention may comprise an organic compound and a triplet emitter according to one aspect of the invention.
  • the mixture according to one aspect of the invention may comprise an organic compound according to one aspect of the invention, a triplet emitter and another triplet Body material.
  • the mixture according to one aspect of the invention may comprise an organic compound according to one aspect of the invention and two other triplet emitters.
  • the invention further relates to a composition, which may comprise the organic compound or a mixture as described above, and at least one organic solvent.
  • the invention further provides a film prepared from a solution comprising an organic compound according to one aspect of the invention.
  • Non-limiting examples of organic solvents may include, but are not limited to, methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, Porphyrin, 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, four Hydronaphthalene, decalin, hydrazine and/or mixtures thereof.
  • composition according to one aspect of the invention may be a solution.
  • composition according to one aspect of the invention may be a suspension.
  • composition in the examples of the present invention may comprise 0.01 to 20% by weight of the organic compound or a mixture thereof according to an aspect of the invention, more preferably 0.1 to 15% by weight, still more preferably 0.2 to 10% by weight, Most preferred is 0.25 to 5% by weight of the organic compound of the invention 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 may include, but are not limited to, inkjet printing, nozzle printing, typography, screen printing, dip coating, spin coating, blade coating, roller printing, twisting. Roll 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.
  • the present invention also provides the use of an organic compound as described above in an organic electronic device.
  • 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), especially OLEDs.
  • the organic compound is preferably used for a hole transport layer, an electron blocking layer, a light emitting layer, an exciton blocking layer, an electron transport layer, and a hole transport layer of an OLED device, and particularly preferably, the light is emitted.
  • the layer is preferably used for a hole transport layer, an electron blocking layer, a light emitting layer, an exciton blocking layer, an electron transport layer, and a hole transport layer of an OLED device, and particularly preferably, the light is emitted.
  • the layer is preferably used for a hole transport layer, an electron blocking layer, a light emitting layer, an exciton blocking layer, an electron transport layer, and a hole transport layer of an OLED device, and particularly preferably, the light is emitted.
  • the invention further relates to an organic electronic device which may comprise at least one organic compound as described above.
  • an organic electronic device may comprise at least one cathode, an anode and a functional layer between the cathode and the anode, wherein the functional layer contains at least one organic compound 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).
  • the organic electronic device may be an electroluminescent device, in particular an OLED, comprising a substrate, an anode, at least one luminescent layer, and a cathode.
  • an electroluminescent device in particular an OLED, comprising a substrate, an anode, at least one luminescent layer, and a cathode.
  • 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. Most preferably, the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice.
  • the substrate may be flexible and may be selected from polymeric films or plastics having a glass transition temperature Tg of 150 ° C or higher, more preferably more than 200 ° C, more preferably more than 250 ° C, most preferably It is over 300 °C.
  • 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.
  • 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, more preferably less than 0.3 eV, most preferably less than 0.2 eV.
  • anode materials 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
  • the absolute value of the difference in conduction band energy levels may be less than 0.5 eV, more 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.
  • Non-limiting examples of cathode materials may include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloys, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc.
  • 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
  • the light-emitting layer thereof may comprise the organic compound of the invention.
  • the light-emitting device may have an emission wavelength of between 300 and 1000 nm, more preferably between 350 and 900 nm, and even more preferably between 400 and 800 nm.
  • the invention further relates to the use of an organic electronic device according to one aspect of the invention in various electronic devices, including, but not limited to, display devices, illumination devices, light sources, sensors, and the like.
  • 1,2, cyclohexanedione 56g (0.5mol), 2-bromophenylhydrazine hydrochloride 224g (1mol) and ethanol 700mL were added to a 1000mL three-necked flask, mechanically stirred for 5min, slowly drip Concentrated sulfuric acid 10mL. After stirring at room temperature for 15 min, the reaction was heated to 65 ° C and allowed to react for 6 hours. The reaction was stopped, and the reaction solution was allowed to cool to room temperature, and a large amount of solid was precipitated. The reaction solution was suction filtered, and the filter residue was washed with ethanol several times.
  • 1,10-dibromo-indolo[2,3a]carbazole 31 g, 75 mmol
  • 250 mL of anhydrous THF 250 mL was added to a 500 mL three-necked flask, stirred and dissolved, and cooled to -78 with liquid nitrogen.
  • n-butyl lithium 375 mmol, 150 mL, 2.5 M in n-hexane
  • D 2 O deuterated water
  • N,N'-dipyrimidinium[3,2a]carbazole solid add 8 mL of anhydrous THF, stir to dissolve, and slowly add in ice bath (3.6 g, 20 mmol) of a solution of N-bromosuccinimide (NBS) in THF (50 mL) was added dropwise and the reaction was allowed to slowly warm to room temperature.
  • NBS N-bromosuccinimide
  • 1,2-cyclohexanedione 56g (0.5mol), phenylhydrazine hydrochloride 144g (1mol) and ethanol 700mL were added to a 1000mL three-necked flask, mechanically stirred for 5min, and the concentrated sulfuric acid was slowly added dropwise. 10mL. After stirring at room temperature for 15 min, the reaction was heated to 65 ° C and allowed to react for 6 hours. The reaction was stopped, and the reaction solution was allowed to cool to room temperature, and a large amount of solid was precipitated. The reaction solution was suction filtered, and the filter residue was washed with ethanol several times.
  • 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 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.
  • 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
  • HOMO(G) and LUMO(G) are direct calculation results of Gaussian 03W, and the unit is Hartree.
  • the results are shown in Table 1:
  • Ref1 The energy level of Ref1 is the same as (2-6), and Ref2 is the same as (3-1).
  • compounds (2-6), (3-1), Ref1 and Ref2 are used as host materials
  • Ir(ppy) 3 is used as a light-emitting material
  • HATCN is used as a hole injecting material
  • NPB and TCTA are used as hole transporting.
  • the material, B3PYMPM was used as an electron transporting material to construct an electroluminescent device having a device structure of ITO/HATCN/NPB/TCTA/host material: Ir(ppy) 3 (15%)/B3PYMPM/LiF/Al.
  • 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/NPB/TCTA/body material: Ir(ppy) 3 /B3PYMPM/LiF/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;
  • HATCN 5nm
  • NPB 40nm
  • TCTA 10nm
  • host material 15% Ir(ppy) 3 (15nm)
  • B3PYMPM 40nm
  • LiF 1nm
  • Al 100nm
  • high vacuum (1 ⁇ 10 -6 mbar
  • the device is encapsulated in a nitrogen glove box with an ultraviolet curable resin.
  • the current-voltage (J-V) characteristics of each OLED device are characterized by characterization equipment while recording important parameters such as efficiency, lifetime and external quantum efficiency.
  • the luminous efficiency of OLED1 is similar to that of RefOELD1, but the lifetime is more than twice that of RefOELD1.
  • the luminous efficiency of OLED2 is similar to that of RefOLED2, and the lifetime is three times. It can be seen that the lifetime of the OLED device prepared by using the organic compound of the invention is greatly improved.

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Abstract

本发明公开一种氘代的吲哚并咔唑类化合物，及包含其的组合物和有机电子器件。所述氘代的吲哚并咔唑类化合物，在吲哚并咔唑共轭结构中，用C-D键任选取代C-H键，可以降低反应活性，赋予该基团更优选的化学和环境稳定性。本发明将氘代的吲哚并咔唑类化合物应用到有机电子器件中，提供了一种提高器件稳定性和寿命的解决方案。

Description

化合物、包含其的混合物、组合物和有机电子器件 技术领域
本发明涉及电致发光材料领域，尤其涉及一种化合物(氘代的吲哚并咔唑类化合物)，包含其的混合物，组合物和有机电子器件。
背景技术
因为有机半导体材料的在合成上的多样性，实现大面积柔性器件的可能，低的制造成本和高性能的光学和电学性能，有机发光二极管(OLED)在新颖的光电器件的实现中，例如，在平板显示器和照明应用，有很大的潜力。为了提高有机发光二极管的发光效率，各种基于荧光和磷光发光材料体系已被开发出来。使用荧光材料的有机发光二极管，已具有可靠性高，但在电场激发下其内部电致发光量子效率被限制为25％，因为激子的单重激发态和三重激发态的分支比为1∶3。与此相反，使用磷光材料的有机发光二极管已经取得了几乎100％的内部发光量子效率。然而，磷光OLED的稳定性还需提高。磷光OLED的稳定性，除了发光体本身，主体材料是关键。
吲哚并咔唑类化合物由于具有较高的载流子传输能力、光电响应性质和热稳定性等优点，成为学术界和产业界关注的焦点，并广泛应用于有机发光二极管中。但目前开发的大部分吲哚并咔唑类衍生物仍然存在着化学/环境稳定性较差的不足，主要是因为这类材料结构中氮原子的孤对电子，共轭到苯环中，形成电子云密度较大、反应活性较高的C-H键，致使这类型化合物的化学/环境稳定性较差、器件寿命较短。
为了提高吲哚并咔唑类化合物的稳定性及器件寿命，人们寻求降低C-H键的反应活性的方法。一种方案是引入缺电子单元，使得电子云向缺电子单元的方向转移，降低C-H的电子云密度及反应活性。但缺电子的引入同时可能会带来电化学能级的变化等问题(Adv.Funct.Mater.，2014，24，3551-3561)。
对材料的稳定性和器件寿命不断提高的需求，迫使人们寻求更稳定的光电性能材料。
发明内容
本发明的各方面中提供了一种化合物(氘代的吲哚并咔唑类化合物)，包含相关的混合物和组合物、及其在有机电子器件中的应用，其可以解决现有的吲哚并咔唑类化合物材料及相关的有机电子器件稳定性及器件寿命低的问题。
本发明的一个方面中所提供的技术方案如下：
一种化合物，包括如下所示的通式(1)：
Figure PCTCN2015097193-appb-000001
其中，
X可以为芳香环或芳杂环，
R，R1-R8在每一次出现中，可以相同或不同地独立选自-H，-F，-Cl，Br，I，-D，-CN，-NO2，-CF3，B(OR0)2，Si(R0)3，直链烷烃，烷烃醚，含1～10个碳原子烷烃硫醚，支链烷烃，环烷烃，含有3～10个碳原子的烷烃醚基团。R，R1-R8可被一个或多个活性基团R0任选取代，且其中一个或多个非相邻的亚甲基(CH2)可以被以下基团任选取代，它们包括R0C＝CR0，C＝C，Si(R0)2，Ge(R0)2，Sn(R0)2，C＝O，C＝S，C＝Se，C＝N(R0)，O，S，-COO-，或CONR2。R，R1-R8中一个或多个H原子可被D，F，Cl，Br，I，CN，NO2，一个或多个活性R0，芳香基团或杂芳香环任选取代。
R0在每一次出现中，可以相同或不同地独立选自H，D，含1～10个碳原子脂肪族烷烃，芳香碳氢化合物，含5～10个碳原子的芳香环或芳杂基团。
Ar可以为碳原子数1-17的烷基、碳原子数3～18的环烷基、碳原子数6～60的芳香族烃基或碳原子数3～60的芳香族杂环基。
M可以为碳原子数6～60的芳香族烃基或碳原子数3～60的芳香族杂环基。
其中，R、R1-R8中可以至少一个为D原子。
在一个优选实施例中，X在多次出现时，可相同或不同地选自包含有如下结构的基团：
Figure PCTCN2015097193-appb-000002
在另一个优选的实施例中，所述的化合物可以具有下述(2)-(7)中之任一化学式表示的结构：
Figure PCTCN2015097193-appb-000003
其中：
Y1、Y2可以为C或N，当Y1、Y2为N时，R可以为未任选取代。
Ar可以为碳原子数1-17的烷基、碳原子数3～18的环烷基、碳原子数6～60的芳香族烃基或碳原子数3～60的芳香族杂环基。
M可以为碳原子数6～60的芳香族烃基或碳原子数3～60的芳香族杂环基。
n可以为1～10的整数。
在一个特别优选的实施例中，所述的化合物可以具有下述化学式表示的结构
Figure PCTCN2015097193-appb-000004
所述的化合物，可以包含具有空穴传输和/或电子传输特性的基团。
一种混合物，可以包括一种按照本发明的一个方面中所述的有机化合物，及至少一种有机功能材料，所述的有机功能材料可选自空穴注入材料(HIM)，空穴传输材料(HTM)，电子注入材料(EIM)，电子传输材料(ETM)，空穴阻挡(HBM)，电子阻挡(EBM)，发光材料(Emitter)或主体材料(Host)等中的任一种或其组合。
一种组合物，可以包括一种按照本发明的化合物，及与至少一种有机溶剂。
一种按照本发明的一个方面中所述的有机化合物在有机电子器件中的应用。
一种有机电子器件，其中，可以至少包括一种按照本发明的一个方面中所述的有机化合物及其混合物。
所述的有机电子器件可选自为有机发光二极管(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)。
按照本发明的一个方面中所述的化合物用于OLED中，特别是作为主体材料，能提供较长的寿命。其可能的机理如下，但不限于，氘(D)原子的质量是H原子质量的两倍，C-D键相对于C-H键具有相对较低的反应自由能、反应速率和渗透势垒，使得C-D键的相对于C-H键具有较低的反应活性(Chem.Rev.1955，55，713-743)，这为提高吲哚并咔唑类化合物及光电器件的化学/环境稳定性提供了可能。
具体实施方式
本发明的一个方面中，提供一种氘代的吲哚并咔唑类化合物，包含相关的混合物和组合物、及其在有机电子器件中的应用，为使本发明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仅用以解释本发明，并不用于限定本发明。
本发明的一个方面中，提供一种具有如下结构式(1)的有机化合物：
Figure PCTCN2015097193-appb-000005
其中，
X为芳香环或芳杂环，
R，R1-R8在每一次出现中，可以相同或不同地独立选自-H，-F，-Cl，Br，I，-D，-CN，-NO2，-CF3，B(OR0)2，Si(R0)3，直链烷烃，烷烃醚，含1～10个碳原子烷烃硫醚，支链烷烃，环烷烃，含有3～10个碳原子的烷烃醚基团。R，R1-R8可被一个或多个活性基团R0任选取代，且其中一个或多个非相邻的亚甲基(CH2)可以被以下基团任选取代，它们包括R0C＝CR0，C＝C，Si(R0)2，Ge(R0)2，Sn(R0)2，C＝O，C＝S，C＝Se，C＝N(R0)，O，S，-COO-，或CONR2。R，R1-R8中一个或多个H原子可被D，F，Cl，Br，I，CN，NO2，一个或多个活性R0，芳香基团或杂芳香环任选取代。
R0在每一次出现中，可以相同或不同地独立选自H，D，含1～10个碳原子脂肪族烷烃，芳香碳氢化合物，含5～10个碳原子的芳香环或芳杂基团。
Ar可以为碳原子数1-17的烷基、碳原子数3～18的环烷基、碳原子数6～60的芳香族烃基或碳原子数3～60的芳香族杂环基。
M可以为碳原子数6～60的芳香族烃基或碳原子数3～60的芳香族杂环基。
n可以为1～10的整数。
其中，R、R1-R8中至少一个为D原子。
在一个优选的实施例中，n为1～4的整数，较优选是为1～3的整数，更优选是为1～3的整数，最优选是为1～2的整数。
在一个优选的实施例中，按照本发明的一个方面中所述的有机化合物是一种小分子材料。
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，较优选是≤2000克/摩尔，最优选是≤1500克/摩尔。
本文中所定义的术语聚合物，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，聚合物也包括树状物(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.】。
本文中所定义的术语共轭聚合物(conjugated polymer)是一聚合物，它的主链backbone主要是由C原子的sp2杂化轨道构成，著名的非限制性例子有：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原子任选取代，而且当主链上的sp2杂化被一些自然的缺陷打断时，仍然被认为是共轭聚合物。另外在本发明中共轭聚合物也可以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。
按照本发明的一个方面中所述的化合物的第一个特征是，该有机化合物至少有一个H原子被氘任选取代。优选的，R、R1-R8中至少一个为D原子。
本发明显示，氘代后的化合物具有较优选的稳定性，含有氘代后的化合物的OLED具有较长的寿命。其可能的机理是，但不限于，由于动力学的同位素效应，一个涉及C-H键的反应率通常比是相应的C-D键快6-10倍，因此，在OLED工作时，含有氘代后的化合物在衰变的动力学过程中有比较慢的衰变。
在某些实施例中，那些反应活性较高的H可以被氘任选取代。
在某些实施例中，所述的有机化合物，其中Ar中至少一个的H原子可以被氘任选取代。
在某些实施例中，所述的有机化合物，其中M中至少一个的H原子可以被氘任选取代。
在自然界中氘在海洋中的丰度为0.0156％，即6420个氢原子中有一个是氘。按照本发明的一个方面中所述的化合物中氘的含量可以远远大于自然丰度，一般来说可以至少有1％的H原子被氘任选取代，较优选是至少有10％的H原子被氘任选取代。
在一个优选的实施例中，所述的氘化的有机化合物，其中，20％以上，较优选是30％以上，更优选是40％以上，最优选是50％以上的H原子可以被氘任选取代。
在一个优选的实施例中，按照结构式(1)的化合物，其中X在多次出现时，可相同或不同地选自包含有如下结构的基团：
Figure PCTCN2015097193-appb-000006
在一个优选的实施例中，按照本发明的一个方面中所述的化合物，可以包含有具有下述(2)-(7)中之任一化学式表示的结构：
Figure PCTCN2015097193-appb-000007
其中：
Y1、Y2可以为C、N，当Y1、Y2为N时，Y1、Y2上不含取代基，优选的Y1、Y2为C。
R、R1-R8分别可以为独立的H、D、烷基、芳香烷基、烯基、炔基、腈基、胺基、硝基、酰基、烷氧基、羰基、砜基、环烷基或羟基；其中，至少一个为D原子。所述的烷基，可以表示碳原子数1-17的烷基、碳原子数3～18的环烷基，优选的烷基可以为甲基、叔丁基；所述的芳香烷基，可以表示碳原子数6～60的芳香族烃基或碳原子数3～60的芳香族杂环基，可以举出如下的非限制性例子：苯、萘、蒽、菲、芘、吡啶、嘧啶、三嗪、芴、硫芴、硅芴、咔唑、噻吩、呋喃、噻唑、三苯胺、三苯基氧磷，四苯基硅、螺芴、螺硅芴等，优选的芳香烷基为苯基、三嗪、咔唑、吡啶基。氘原子数为1～10的整数，优选的任选取代位置是吲哚并咔唑氮原子的邻位和对位，优选的任选取代数为1～6的整数。
Ar可以表示为碳原子数1-17的烷基、碳原子数3～18的环烷基、碳原子数6～60的芳香族烃基或碳原子数3～60的芳香族杂环基，作为优选的方案，可以举出如下的非限制性例子：甲基、苯、萘、蒽、菲、芘、吡啶、嘧啶、三嗪、芴、硫芴、硅芴、咔唑、噻吩、呋喃、噻唑、三苯胺、三苯基氧磷，四苯基硅、螺芴、螺硅芴等基团，更优的为苯、吡啶、嘧啶、三嗪、咔唑等基团。所述的烷基、环烷基的其中一个或多个碳原子可被氮、氧、硫、硅等杂原子任选取代。所述的芳香族烃基、芳香族杂环基可有多个芳香族基团链接而成，可以具有取代基，其中比较优选的多个芳香族基为联苯、三联苯、苯基吡啶、二苯基三嗪、苯基咔唑、吡啶基咔唑等。比较优选的取代基为氟、甲基、叔丁基、甲氧基、乙酰基等。
M可以为碳原子数6～60的芳香族烃基或碳原子数3～60的芳香族杂环基，作为优选的方案，可以举出如下的非限制性例子：苯、萘、蒽、菲、芘、吡啶、嘧啶、三嗪、芴、硫芴、硅芴、咔唑、噻吩、呋喃、噻唑、三苯胺、三苯基氧磷，四苯基硅、螺芴、螺硅芴等，所述的芳香族烃基或芳香族杂环基可以具有取代基，其中比较优选的取代基，为氟、碳数1～4的烷基、碳数为1～2的烷氧基。
n可以为1～10的整数，优选n为1～4的整数。
在一个较为优选的实施例中，按照本发明的一个方面中所述的化合物可以具有下述化学式表示的结构
Figure PCTCN2015097193-appb-000008
在一个特别优选的实施例中，按照本发明的一个方面中所述的化合物，可以包含有具有下述(2a)-(7a)中之任一化学式表示的结构：
Figure PCTCN2015097193-appb-000009
其中的符号的定义如同(2)-(7)中的定义。
在一个优选的实施例中，按照本发明的一个方面中所述的化合物，其中，可以至少有一个M或一个Ar包含有一个具有空穴传输特性的基团。合适的空穴传输特性的基团将在下面的空穴传输材料(HTM)中说明。
在另一个优选的实施例中，按照本发明的一个方面中所述的化合物，其中，可以至少有一个M或一个Ar包含有一个具有电子传输特性的基团。合适的电子传输特性的基团将在下面的电子传输材料(ETM)中说明。
在一个特别优选的实施例中，按照本发明的一个方面中所述的化合物，其中，M或Ar中可以至少有一个包含有具有电子传输特性的基团，另一个包含有具有空穴传输特性的基团。
下面举例按照本发明的一个方面中所述的氘代吲哚并咔唑类化合物的具体例子，但本发明的氘代吲哚并咔唑类化合物并不限定于这些。
Figure PCTCN2015097193-appb-000010
Figure PCTCN2015097193-appb-000011
Figure PCTCN2015097193-appb-000012
Figure PCTCN2015097193-appb-000013
按照本发明的一个方面中所述的氘代吲哚并咔唑类化合物，D原子引入到吲哚并咔唑共轭骨架的合成方法一般可以有两种。
一种可以是先做成带卤素原子的吲哚并咔唑前驱体，再在该基团的N-H键上进行官能团任选取代，再用D原子置换其上的卤素原子；另一种是可以先在吲哚并咔唑的N-H键进行官能团任选取代，再在该单元上进行卤素任选取代，最后再用D原子置换其上的卤素原子，生成最终的氘代吲哚并咔唑类化合物。
本发明还涉及一种混合物，可以包含至少一种按照本发明的一个方面中所述的有机化合物，及至少另一种的有机功能材料。
这里所述另一种的有机功能材料，可以包含空穴(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)，有机基质材料(Host)，单重态发光体(荧光发光体)，三重态发光体(磷光发光体)中的任一种或其组合，特别是发光金属有机配合物。各种有机功能材料的非限制性例子例如在WO2010135519A1，US20090134784A1和WO 2011110277A1中有详细的描述。
有机功能材料可以是小分子或聚合物材料。
在本发明中，主体材料、基质材料、Host材料和Matrix材料具有相同的含义，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。
下面对有机功能材料作一些较详细的描述(但不限于此)。
1.HIM/HTM/EBM
本发明的一个方面中所使用的合适的有机HIM/HTM材料可选包含有如下结构单元的化合物：酞菁，卟啉，胺，芳香胺，联苯类三芳胺，噻吩，并噻吩如二噻吩并噻吩和并噻吩，吡咯，苯胺，咔唑，氮茚并氮芴，及它们的衍生物中的任一种或其组合。另外合适的HIM也包含含有氟烃的聚合物；含有导电掺杂的聚合物；导电聚合物，如PEDOT/PSS；自组装单体，如含有膦酸和sliane衍生物的化合物；金属氧化物，如MoOx；金属络合物，和交联化合物等中的任一种或其组合。
本发明的一个方面中所使用的电子阻挡层(EBL)通常用来阻挡来自相邻功能层，特别是发光层的电子。对比一个没有阻挡层的发光器件，EBL的存在通常会导致发光效率的提高。电子阻挡层(EBL)的电子阻挡材料(EBM)需要有比相邻功能层，如发光层更高的LUMO。在一个优选的实施方案中，EBM有比相邻发光层更大的激发态能级，如单重态或三重态能级，取决于发光体。在另一个优选的实施方案中，EBM有空穴传输功能。通常具有高的LUMO能级的HIM/HTM材料可以做为EBM。
可用作HIM或HTM的环芳香胺衍生化合物的例子包含(但不限于)如下的一般结构：
Figure PCTCN2015097193-appb-000014
每个Ar1到Ar9可独立选自环芳香烃化合物，如苯，联苯，三苯基，苯并，萘，蒽，phenalene，菲，芴，芘，屈，苝，薁；芳香杂环化合物，如二苯并噻吩，二苯并呋喃，呋喃，噻吩，苯并呋喃，苯并噻吩，咔唑，吡唑，咪唑，三氮唑，异恶唑，噻唑，恶二唑，oxatriazole，二恶唑，噻二唑，吡啶，哒嗪，嘧啶，吡嗪，三嗪，恶嗪，oxathiazine，oxadiazine，吲哚，苯并咪唑，吲唑，indoxazine，苯并恶唑，benzisoxazole，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，dibenzoselenophene，benzoselenophene，benzofuropyridine，indolocarbazole，pyridylindole，pyrrolodipyridine，furodipyridine，benzothienopyridine，thienodipyridine，benzoselenophenopyridine和selenophenodipyridine；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可以进一步被任选取代，取代基可选为氢，烷基，烷氧基，氨基，烯，炔，芳烷基，杂烷基，芳基和杂芳基。
在一个方面，Ar1到Ar9可独立选自包含如下组的基团：
Figure PCTCN2015097193-appb-000015
n1是1-20的整数；X1到X8是CH或N；Ar1如以上所定义。
环芳香胺衍生化合物的另外的非限制性例子可参见US3567450，US4720432，US5061569，US3615404和US5061569。
可用作HTM或HIM的金属络合物的非限制性例子包含(但不限于)如下的一般结构：
Figure PCTCN2015097193-appb-000016
M可以是金属，有大于40的原子量；
(Y3-Y4)可以是一两齿配体，Y3和Y4可以独立地选自C，N，O，P，和S；L是一个辅助配体；m可以是一整数，其值从1到此金属的最大配位数；m+h是此金属的最大配位数。
在一个实施例中，(Y3-Y4)可以是一2-苯基吡啶衍生物。
在另一个实施例中，(Y3-Y4)可以是一卡宾配体。
在另一个实施例中，M可以选自Ir，Pt，Os和Zn。
在另一个方面，可用作HTM或HIM的金属络合物的HOMO可以大于-5.5eV(相对于真空能级).
在下面的表中列出合适的可作为HIM/HTM/EBM化合物的非限制性例子：
Figure PCTCN2015097193-appb-000017
2.EIM/ETM/HBM
本发明的一个方面中所使用的EIM/ETM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EIM/ETM，只要它们可以传输电子。优选的有机EIM/ETM材料可选自三(8-羟基喹啉)铝(AlQ3)，吩嗪，菲罗啉，蒽，菲，芴，二芴，螺二芴，对苯乙炔，三嗪，三唑，咪唑，芘，苝，反茚并芴，顺茚并，二苯并-茚并芴，茚并萘，苯并蒽及它们的衍生物。
本发明的一个方面中所使用的空穴阻挡层(HBL)通常用来阻挡来自相邻功能层，特别是发光层的空穴。对比一个没有阻挡层的发光器件，HBL的存在通常会导致发光效率的提高。空穴阻挡层(HBL)的空穴阻挡材料(HBM)需要有比相邻功能层，如发光层更低的HOMO。在一个优选的实施方案中，HBM有比相邻发光层更大的激发态能级，如单重态或三重态，取决于发光体.在另一个优选的实施方案中，HBM有电子传输功能.。通常具有深的HOMO能级的EIM/ETM材料可以作为HBM。
另一方面，可用作EIM/ETM/HBM的化合物可以是至少包含一个以下基团的分子：
Figure PCTCN2015097193-appb-000018
R9可选自如下的基团：氢，烷基，烷氧基，氨基，烯，炔，芳烷基，杂烷基，芳基和杂芳基，当它们是芳基或杂芳基时，它们可以与上述HTM中的Ar1和Ar2意义相同；Ar1-Ar5和X1-X8可以与在HTM中所描述的Ar1-Ar5和X1-X8意义相同；
n1可以是一个从1到20的整数；
另一方面，可用作EIM/ETM的金属络合物的例子可以包含(但不限于)如下的一般结构：
Figure PCTCN2015097193-appb-000019
(O-N)或(N-N)是一两齿配体，其中金属与O，N或N，N配位；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。
在下面的表中列出合适的可作ETM化合物的非限制性例子：
Figure PCTCN2015097193-appb-000020
在另一个优选的实施方案中，有机碱金属化合物可用作EIM。在本发明中，有机碱金属化合物可以理解为如下的化合物，其中至少有一个碱金属，即锂，钠，钾，铷，铯，并进一步包含至少一个有机配体。
合适的有机碱金属化合物的非限制性示例，可以包含US7767317B2，EP1941562B1和EP 1144543B1中所描述的化合物。
优选的有机碱金属化合物可以是下列化学式的化合物：
Figure PCTCN2015097193-appb-000021
其中R9的含义如上所述，弧线代表两个或三个原子及键接，以便必要时的与金属M形成5元或六元环，其中原子也可以由一个或多个R9任选取代，M可以为碱金属，选自锂，钠，钾，铷，铯。
有机碱金属化合物可以有单体的形式，如以上所述的，或有聚集体的形式，例如，两碱金属离子与两个配体，四碱金属离子和四配体，六碱金属离子和六配体或在其他的形式。
优选的有机碱金属化合物可以是下列化学式的化合物：
Figure PCTCN2015097193-appb-000022
其中使用的符号有上述定义相同，另外：
o，每次出现时可以是相同或不同地选自0，1，2，3或4；
p，每次出现时可以是相同或不同地选自0，1，2或3；
在一个优选的实施方案中，碱金属M可以选自锂，钠，钾，更优选是锂或钠，最优选是锂。
在一个优选的实施方案中，电子注入层中可以包含有有机碱金属化合物.更优选地，电子注入层由有机碱金属化合物组成。
在另一个优选的实施方案中，有机碱金属化合物可以掺杂到其他ETM中形成电子传输层或电子注入层中。更优选地，是电子传输层。
在下面的表中列出合适作为EIM的有机碱金属化合物的非限制性例子：
Figure PCTCN2015097193-appb-000023
3.三重态基质材料(TripletHost)：
本发明的一个方面中所使用的三重态基质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基质，只要其三重态能量比发光体，特别是三重态发光体或磷光发光体更高。
可用作三重态基质(Host)的金属络合物的例子本发明的一个方面中所使用的包含(但不限于)如下的一般结构：
Figure PCTCN2015097193-appb-000024
M可以是一金属；(Y5-Y6)是可以一两齿配体，Y5和Y6可以独立地选自C，N，O，P和S；L可以是一个辅助配体；m可以是一整数，其值从1到此金属的最大配位数；m+h是此金属的最大配位数。
在一个优选的实施方案中，可用作三重态基质的金属络合物可以有如下形式：
Figure PCTCN2015097193-appb-000025
(O-N)是一两齿配体，其中金属与O和N原子配位。
在某一个实施方案中，M可选自Ir和Pt。
本发明的一个方面中所使用的可作为三重态基质的有机化合物的非限制性例子选自包含有环芳香烃基的化合物，碍如苯，联苯，三苯基，苯并，芴；测试；包含有芳香杂环基的化合物，如二苯并噻吩，二苯并呋喃，dibenzoselenophene，呋喃，噻吩，苯并呋喃，苯并噻吩，benzoselenophene，咔唑，indolocarbazole，pyridylindole，pyrrolodipyridine，吡唑，咪唑，三唑类，恶唑，噻唑，恶二唑，oxatriazole，二恶唑，噻二唑，吡啶，哒嗪，嘧啶，吡嗪，三嗪类，oxazines，oxathiazines，oxadiazines，吲哚，苯并咪唑，吲唑，indoxazine，bisbenzoxazoles，benzisoxazole，苯并噻唑，喹啉，异喹啉，cinnoline，喹唑啉，喹喔啉，萘，酞，蝶啶，氧杂蒽，吖啶，吩嗪，吩噻嗪，phenoxazines，benzofuropyridine，furodipyridine，benzothienopyridine，thienodipyridine，benzoselenophenopyridine和selenophenodipyridine；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可以进一步被任选取代，取代基可选为氢，烷基，烷氧基，氨基，烯，炔，芳烷基，杂烷基，芳基和杂芳基。
在一个优选的实施方案中，三重态基质材料可选自包含至少一个以下基团的化合物：
Figure PCTCN2015097193-appb-000026
R9-R15分别独立与上述的R9意义相同；X1-X8与上述的X1-X8意义相同；X9选自CR9R10或NR9；n1可以是一个从1到20的整数。
在下面的表中列出合适的三重态基质材料的非限制性例子：
Figure PCTCN2015097193-appb-000027
Figure PCTCN2015097193-appb-000028
4.单重态基质材料(Singlet Host)：
本发明的一个方面中所使用的单重态基质材料的例子并不受特别的限制，任何有机化合物都可能被用作为基质，只要其单重态能量比发光体，特别是单重态发光体或荧光发光体更高。
作为单重态基质材料使用的有机化合物的非限制性例子可选自含有环芳香烃化合物，如苯，联苯，三苯基，苯并，萘，蒽，phenalene，菲，芴，芘，屈，苝，薁；芳香杂环化合物，如二苯并噻吩，二苯并呋喃，dibenzoselenophene，呋喃，噻吩，苯并呋喃，苯并噻吩，benzoselenophene，咔唑，indolocarbazole，pyridylindole，Pyrrolodipyridine，吡唑，咪唑，三氮唑，异恶唑，噻唑，恶二唑，oxatriazole，二恶唑，噻二唑，吡啶，哒嗪，嘧啶，吡嗪，三嗪，恶嗪，oxathiazine，oxadiazine，吲哚，苯并咪唑，吲唑，indoxazine，苯并恶唑，benzisoxazole，苯并噻唑，喹啉，异喹啉，cinnoline，喹唑啉，喹喔啉，萘，酞，蝶啶，氧杂蒽，吖啶，吩嗪，吩噻嗪，吩恶嗪，benzofuropyridine，furodipyridine，benzothienopyridine，thienodipyridine，benzoselenophenopyridine和selenophenodipyridine；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。
在一个优选的实施方案中，单重态基质材料可选自包含至少一个以下基团的化合物：
Figure PCTCN2015097193-appb-000029
X10选自CR9R10或NR9；R9、Ar1、X1-X8、X9和n1与上述的定义意义相同。
在下面的表中列出合适的单重态基质材料的非限制性例子：
Figure PCTCN2015097193-appb-000030
5.单重态发光体(Singlet Emitter)
单重态发光体往往有较长的共轭π电子系统。迄今，已有许多例子，例如但不限于苯乙烯胺(styrylamine)及其衍生物，和茚并芴(indenofluorene)及其衍生物。
在一个优选的实施方案中，单重态发光体可选自一元苯乙烯胺(monostyrylamines)，二元苯乙烯胺(distyrylamines)，三元苯乙烯胺(tristyrylamines)，四元苯乙烯胺(tetrastyrylamines)，苯乙烯膦(styrylphosphines)，苯乙烯醚(styryl ethers)和芳胺(arylamines)。
一元苯乙烯胺是指一化合物，它包含无任选取代或任选取代的苯乙烯基组和至少一个胺，最优选是芳香胺。二元苯乙烯胺是指一化合物，它包含二个无任选取代或任选取代的苯乙烯基组和至少一个胺，最优选是芳香胺。三元苯乙烯胺是指一化合物，它包含三个无任选取代或任选取代的苯乙烯基组和至少一个胺，最优选是芳香胺。四元苯乙烯胺是指一化合物，它包含四个无任选取代或任选取代的苯乙烯基组和至少一个胺，最优选是芳香胺。优选的苯乙烯是 二苯乙烯，其可能会进一步被任选取代。相应的膦类和醚类的定义与胺类相似。芳基胺或芳香胺是指一种化合物，包含三个直接联接氮的无任选取代或任选取代的芳香环或杂环系统。这些芳香族或杂环的环系统中至少有一个优选选自稠环系统，并最优选有至少14个芳香环原子。其中优选的例子有芳香蒽胺，芳香蒽二胺，芳香芘胺，芳香芘二胺，芳香屈胺和芳香屈二胺。芳香蒽胺是指一化合物，其中一个二元芳基胺基团(diarylamino)直接联到蒽上，最优选是在9的位置上。芳香蒽二胺是指一化合物，其中二个二元芳基胺基团(diarylamino)直接联到蒽上，最优选是在9，10的位置上。芳香芘胺，芳香芘二胺，芳香屈胺和芳香屈二胺的定义类似，其中二元芳基胺基团最优选联到芘的1或1，6位置上。
基于乙烯胺及芳胺的单重态发光体的非限制性示例，也是优选的例子，可在下述专利文件中找到：WO 2006/000388，WO 2006/058737，WO 2006/000389，WO 2007/065549，WO 2007/115610，US 7250532 B2，DE 102005058557 A1，CN 1583691 A，JP 08053397 A，US 6251531 B1，US 2006/210830 A，EP 1957606 A1和US 2008/0113101 A1。
基于均二苯乙烯(distyrylbenzene)极其衍生物的单重态发光体的非限制性例子有US 5121029。
进一步的优选的单重态发光体可选自茚并芴-胺和茚并芴-二胺，如WO 2006/122630所公开的，苯并茚并芴-胺(benzoindenofluorene-amine)和苯并茚并芴-二胺(benzoindenofluorene-diamine)，如WO 2008/006449所公开的，二苯并茚并芴-胺(dibenzoindenofluorene-amine)和二苯并茚并芴-二胺(dibenzoindenofluorene-diamine)，如WO2007/140847所公开的。
其他可用作单重态发光体的材料有多环芳烃化合物，特别是如下化合物的衍生物：蒽如9，10-二(2-萘并蒽)(9，10-di(2-naphthylanthracene))，萘，四苯，氧杂蒽，菲(phenanthrene)，芘(perylene)如2，5，8，11-tetra-t-butylperylene，茚并芘(indenoperylene)，苯撑(phenylenes)如(4，4’-(bis(9-ethyl-3-carbazovinylene)-1，1’-biphenyl)，periflanthene，十环烯(decacyclene)，六苯并苯(coronene)，芴，螺二芴(spirofluorene)，芳基芘(arylpyrene)(如US20060222886)，亚芳香基乙烯(arylenevinylene)(如US5121029，US5130603)，环戊二烯如四苯基环戊二烯(tetraphenylcyclopentadiene)，红荧烯(rubrene)，香豆素(coumarine)，若丹明(rhodamine)，喹吖啶酮(quinacridone)，吡喃(pyrane)如4(dicyanoethylene)-6-(4-dimethylaminostyryl-2-methyl)-4H-pyrane(DCM)，噻喃(thiapyran)，bis(azinyl)imine-boron化合物(US 2007/0092753 A1)，bis(azinyl)methene化合物，carbostyryl化合物，噁嗪酮(oxazone)，苯并恶唑(benzoxazole)，苯并噻唑(benzothiazole)，苯并咪唑(benzimidazole)及diketopyrrolopyrrole。一些单重态发光体的材料的非限制性示例可在下述专利文件中找到：US 20070252517 A1，US 4769292，US 6020078，US 2007/0252517 A1，US 2007/0252517  A1。
在下面的表中列出一些合适的单重态发光体的非限制性例子：
Figure PCTCN2015097193-appb-000031
6.三重态发光体(Triplet Emitter)
本发明的一个方面中所使用的三重态发光体也称磷光发光体。在一个优选的实施方案中，三重态发光体可以是有通式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的有机配体，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，较优选选是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，最优选是通过有机配体。
在一个优选的实施方案中，金属原子M可以选自过渡金属元素或镧系元素或锕系元素，优选Ir，Pt，Pd，Au，Rh，Ru，Os，Sm，Eu，Gd，Tb，Dy，Re，Cu或Ag，特别优选Os，Ir，Ru，Rh，Re，Pd，Pt。
优选地，三重态发光体可以包含有螯合配体，即配体，通过至少两个结合点与金属配位，特别优选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。
有机配体的非限制性例子可选自苯基吡啶(phenylpyridine)衍生物，7，8-苯并喹啉(7，8-benzoquinoline)衍生物，2(2-噻吩基)吡啶(2(2-thienyl)pyridine)衍生物，2(1-萘基)吡啶(2(1-naphthyl)pyridine)衍生物，或2苯基喹啉(2phenylquinoline)衍生物。所有这些有机配体都可能被任选取代，例如被含氟或三氟甲基任选取代。辅助配体可优选选自乙酸丙酮(acetylacetonate)或苦味酸。
在一个优选的实施方案中，可用作三重态发光体的金属络合物可以有如下形式：
Figure PCTCN2015097193-appb-000032
其中M是一金属，选自过渡金属元素或镧系元素或锕系元素；Ar10每次出现时可以是相同或不同的环状基团，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；Ar11每次出现时可以是相同或不同的环状基团，其中至少包含有一个C原子，通过它环状基团与金属连接；Ar10和Ar11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的辅助配体，优选自双齿螯合配体，最优选是单阴离子双齿螯合配体；m是1，2或3，优选地是2或3，特别优选地是3；h是0，1或2，优选地是0或1，特别优选地是0；
一些三重态发光体的材料及其应用的非限制性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 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。
在下面的表中列出一些合适的三重态发光体的非限制性例子：
Figure PCTCN2015097193-appb-000033
Figure PCTCN2015097193-appb-000034
Figure PCTCN2015097193-appb-000035
Figure PCTCN2015097193-appb-000036
Figure PCTCN2015097193-appb-000037
Figure PCTCN2015097193-appb-000038
Figure PCTCN2015097193-appb-000039
Figure PCTCN2015097193-appb-000040
Figure PCTCN2015097193-appb-000041
Figure PCTCN2015097193-appb-000042
Figure PCTCN2015097193-appb-000043
Figure PCTCN2015097193-appb-000044
Figure PCTCN2015097193-appb-000045
Figure PCTCN2015097193-appb-000046
7.聚合物
在某些实施例中，以上所述的有机功能材料，包含HIM，HTM，ETM，EIM，Host，荧光发光体，磷光发光体都可以是聚合物的形式。
在一个优选的实施例中，适合于本发明的聚合物可以是共轭聚合物。一般地，共轭聚合物有如下通式：
Figure PCTCN2015097193-appb-000047
其中B，A可以在多次出现时可独立选择相同或不同的结构单元
B：具有较大的能隙的π-共轭结构单元，也称骨干单元(Backbone Unit)，选自单环或多环芳基或杂芳基，优选的单元形式可以为苯，联二亚苯(Biphenylene)，萘，蒽，菲，二氢菲，9，10-二氢菲，芴，二芴，螺二芴，对苯乙炔，反茚并芴，顺茚并，二苯并-茚并芴，茚并萘及它们的衍生物。
A：具有较小能隙的π-共轭结构单元，也称功能单元(Functional Unit)，按照不同的功能要求，可选自包含有以上所述的空穴注入或传输材料(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)，有机基质材料(Host)，单重态发光体(荧光发光体)，重态发光体(磷光发光体)的结构单元。
x，y：＞0，且x+y＝1；
在一个优选的实施例中，聚合物HTM材料可以为均聚物，优选的均聚物选自聚噻吩，聚吡咯，聚苯胺，聚联苯类三芳胺，聚乙烯基咔唑及它们的衍生物。
在另一个优选的实施例中，聚合物HTM材料可以为化学式1表示的共轭共聚物，其中
A：具有空穴输运能力的功能基，可选自包含有以上所述的空穴注入或传输材料(HIM/HTM)的结构单元；在一个优选的实施例中，A可以选自胺，联苯类三芳胺，噻吩，并噻吩如二噻吩并噻吩和并噻吩，吡咯，苯胺，咔唑，indenocarbazole，氮茚并氮芴，并五苯，酞菁，卟啉及它们的衍生物。
x，y：＞0，且x+y＝1；通常y≥0.10，比较优选为≥0.15，更优选为≥0.20，最优选为x＝y＝0.5。
在下面列出合适的可作为HTM的共轭聚合物的非限制性例子：
Figure PCTCN2015097193-appb-000048
其中
Ro、Rr和Rs可以各自彼此独立地是具有1至20个C原子的直链烷基、烷氧基或硫代烷氧基基团，或者具有3至20个C原子的支链或环状的烷基、烷氧基或硫代烷氧基基团或者是甲硅烷基基团，或具有1至20个C原子的任选取代的酮基基团，具有2至20个C原子的烷氧基羰基基团，具有7至20个C原子的芳氧基羰基基团，氰基基团(-CN)，氨基甲酰基基团(-C(＝O)NH2)，卤甲酰基基团(-C(＝O)-X其中X代表卤素原子)，甲酰基基团(-C(＝O)-H)，异氰基基团，异氰酸酯基团，硫氰酸酯基团或异硫氰酸酯基团，羟基基团，硝基基团，CF3基团，Cl，Br，F，可交联 的基团或者具有5至40个环原子的任选取代或未任选取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团，或这些体系的组合；
x，y：＞0，且x+y＝1；通常y≥0.10，比较优选为≥0.15，更优选为≥0.20，最优选为x＝y＝0.5。
另一类优选的有机ETM材料是具有电子传输能力的聚合物，包含共轭聚合物和非共轭聚合物。
优选的聚合物ETM材料为均聚物，优选的均聚物选自聚菲，聚菲罗啉，聚茚并芴，聚螺二芴，聚芴及它们的衍生物。
优选的聚合物ETM材料为化学式1表示的共轭共聚物，其中A在多次出现时可独立选择相同或不同的形式：
A：具有电子输运能力的功能基，优选选自三(8-羟基喹啉)铝(AlQ3)，苯，联二亚苯，萘，蒽，菲，Dihydrophenanthrene，芴，二芴，螺二芴，对苯乙炔，芘，苝，9，10-Dihydrophenanthrene，吩嗪，菲罗啉，反茚并芴，顺茚并，二苯并-茚并芴，茚并萘，苯并蒽及它们的衍生物
x，y：＞0，且x+y＝1.通常y≥0.10，比较优选为≥0.15，更优选为≥0.20，最优选为x＝y＝0.5.
在一个优选的实施例中，发光聚合物可以是有如下通式的共轭聚合物聚合物有如下通式：
Figure PCTCN2015097193-appb-000049
B：与化学式1的定义相同。
A1：具有空穴或电子输运能力的功能基，可选自包含有以上所述的空穴注入或传输材料(HIM/HTM)，或电子注入或传输材料(EIM/ETM)的结构单元。
A2：具有发光功能的基团，可选自包含有以上所述的单重态发光体(荧光发光体)，重态发光体(磷光发光体)的结构单元。
x，y，z：＞0，且x+y+z＝1；
发光聚合物的非限制性例子在如下的专利申请中公开：
WO2007043495，WO2006118345，WO2006114364，WO2006062226，WO2006052457，WO2005104264，WO2005056633.WO2005033174，WO2004113412，WO2004041901，
WO2003099901，WO2003051092，WO2003020790，WO2003020790，US2020040076853，US2020040002576，US2007208567，US2005962631，EP201345477，EP2001344788，DE102004020298。
在另一个的实施例中，适合于本发明的聚合物可以是非共轭聚合物。这可以是所有功能基团都在侧链上，而主链是非共轭的聚合物。一些用作磷光主体或磷光发光材料的这类非共轭聚合物的非限制性示例在US 7250226 B2，JP2007059939A，JP2007211243A2和JP2007197574A2等专利申请中有公开，一些用作荧光发光材料的这类非共轭聚合物的非限制性示例在JP2005108556，JP2005285661和JP2003338375等专利申请中有公开。另外，非共轭聚合物也可以是一种聚合物，主链上共轭的功能单元通过非共轭的链接单元链接起来，这种聚合物的非限制性例子在DE102009023154.4和DE102009023156.0中有公开。
在某些实施例中，按照本发明的一个方面中所述的混合物中，按照本发明的一个方面中所述的有机化合物的含量可以为0.01至90wt％，较优选的是1至80wt％，更优选的是10至80wt％，最优选的是20至70wt％。
在一个优选的实施方案中，按照本发明的一个方面中所述的混合物可以包含一种按照本发明的一个方面中所述的有机化合物和一种三重态发光体。
在另一个优选的实施方案中，按照本发明的一个方面中所述的混合物可以包含一种按照本发明的一个方面中所述的有机化合物，一种三重态发光体和另一种的三重态主体材料。
在一个优选的实施方案中，按照本发明的一个方面中所述的混合物可以包含一种按照本发明的一个方面中所述的有机化合物和另外两种的三重态发光体。
本发明进一步涉及一种组合物，其中，可以包含所述的有机化合物或者如上所述的混合物，以及至少一种有机溶剂。本发明进一步提供一种从溶液中制备包含有按照本发明的一个方面中所述的有机化合物的薄膜。
有机溶剂的非限制性例子，可以包含(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，按照本发明的一个方面中所述的组合物可以是一溶液。
在另一个优选的实施方案中，按照本发明的一个方面中所述的组合物可以是一悬浮液。
本发明实施例中的组合物中可以包含0.01至20wt％的按照本发明的一个方面中所述的有机化合物或其混合物，较优选的是0.1至15wt％，更优选的是0.2至10wt％，最优选的是0.25至5wt％的本发明的有机化合物或其混合物。
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可以包含(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，喷印刷(Nozzle printing)，狭缝型挤压式涂布等。首选的是喷墨印刷，狭缝型挤压式涂布，喷印刷及凹版印刷。溶液或悬浮液可以另外包含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。
基于上述有机化合物，本发明还提供一种如上所述的有机化合物在有机电子器件的应用。所述的有机电子器件可选自，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，特别是OLED。
本发明实施例中，优选地将所述有机化合物用于OLED器件的空穴传输层，电子阻挡层，发光层，激子阻挡层，电子传输层，空穴传输层中，特别优选的是发光层中。
本发明进一步涉及一种有机电子器件，可以至少包含一种如上所述的有机化合物。一般的，此种有机电子器件可以至少包含一个阴极，一个阳极及位于阴极和阳极之间的一个功能层，其中所述的功能层中至少包含一种如上所述的有机化合物。所述的有机电子器件可选自，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)。
在一个特别优选的实施例中，所述的有机电子器件可以是电致发光器件，特别是OLED，其中包含一基片，一阳极，至少一发光层，一阴极。
基片可以是不透明或透明。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。最优选是基片有平滑的表面。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，基片可以是柔性的，可选自聚合物薄膜或塑料，其玻璃化温度Tg为150℃以上，较优选是超过200℃，更优选是超过250℃，最优选是超过300℃。合适的柔性基板的非限制性例子有聚(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，较优选是小于0.3eV，最优选是小于0.2eV。阳极材料的非限制性例子包含但不限于：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可以小于0.5eV，较优选是小于0.3eV，最优选是小于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。阴极材料的非限制性例子可以包含但不限于：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。
在一个优选的实施例中，按照本发明的一个方面中所述的发光器件中，其发光层可以包含本发明的有机化合物。
按照本发明的一个方面中所述的发光器件，其发光波长可以在300到1000nm之间，较优选的是在350到900nm之间，更优选的是在400到800nm之间。
本发明还涉及按照本发明的一个方面中所述的有机电子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.按照本发明的一个方面中所述的化合物的合成
1)化合物(2-6)的合成：
①
Figure PCTCN2015097193-appb-000050
在氩气气氛下，将1，2-环己二酮56g(0.5mol)、2-溴苯肼盐酸盐224g(1mol)和乙醇700mL加入到1000mL的三口烧瓶中，机械搅拌5min，缓慢滴加浓硫酸10mL。室温下搅拌15min后，将反应加热到65℃，反应6小时。停止反应，让反应液冷却到室温，有大量固体析出。将反应液进行抽滤，用乙醇洗滤渣数次，滤渣烘干后，将其加入到1000mL的三口烧瓶中，加入乙酸600mL，三氟乙酸150mL，在100℃下反应加热反应20小时，将反应液冷却到室温，抽滤，用乙酸进行清洗。旋转蒸发所得的滤液，得到淡黄色固体。用四氢呋喃/石油醚混合溶液重结晶，得到62g 1，10-二溴-吲哚并[2，3a]咔唑，产率约30％。
②
Figure PCTCN2015097193-appb-000051
在氩气气氛下，将1，10-二溴-吲哚并[2，3a]咔唑(31g，75mmol)，250mL无水THF加入500mL三口烧瓶中，搅拌溶解，用液氮降温到-78℃，缓慢滴加正丁基锂(375mmol，150mL，2.5M的正己烷溶液)，保持温度搅拌1.5小时，一次性加入氘代水(D2O)(9g，450mmol)，让反应自然升温，室温下搅拌1小时，终止反应，旋转蒸发掉大部分溶剂，抽滤，滤渣用四氢呋喃/石油醚混合溶液重结晶，得到17.5g N，N-二氘-1，10-二氘-吲哚并[2，3a]咔唑，产率约90％。
③
Figure PCTCN2015097193-appb-000052
在氩气保护下，将(13g，50mmol)的N，N-二氘-1，10-二氘-吲哚并[2，3a]咔唑、(10.2g，50mmol)的碘苯、(29g，150mmol)的碘化亚酮、(21g，150mmol)的无水碳酸钾和100mL的邻二氯苯加入到250mL的三口烧瓶中， 加入到180℃下反应12小时，让反应液降到室温，抽滤，取滤液进行减压蒸馏。得到淡黄色固体，用石油醚/二氯甲烷进行柱层析，后用四氢呋喃/乙醇混合溶液重结晶。得到13.4g产物N-苯基-N’-氘-1，10-二氘-吲哚并[2，3a]咔唑，产率约80％。
④
Figure PCTCN2015097193-appb-000053
在氩气保护下，将(3.6g，150mmol)NaH固体加入250mL三空瓶中，加入150mL的无水THF，搅拌10min，缓慢加入(10g，30mmol)的N-苯基-N’-氘-1，10-二氘-吲哚并[2，3a]咔唑，常温搅拌1小时，一次性加入(4.5g，15mmol)3，5-二氯-1-联苯基-三嗪，继续反应3日。将反应液倒置冰水中，搅拌，加入300mL氯仿搅拌，萃取产物，有泡沫状不溶物，抽滤除去，将滤液水洗三遍，有机相用无水硫酸镁干燥，过滤旋干，用四氢呋喃/乙醇重结晶，得到目标化合物(2-3)，产率60％。
2)化合物(3-1)的合成：
①
Figure PCTCN2015097193-appb-000054
在氩气保护下，将(3.6g，150mmol)NaH固体加入250mL三空瓶中，加入150mL的无水THF，搅拌10min，缓慢加入(7.7g，30mmol)的吲哚并[3，2a]咔唑，常温搅拌1小时，一次性加入(4.5g，40mmol)2-氯嘧啶，继续反应2日。将反应液倒置冰水中，搅拌，加入300mL氯仿搅拌，萃取产物，有泡沫状不溶物，抽滤除去，将滤液水洗三遍，有机相用无水硫酸镁干燥，过滤旋干，用四氢呋喃/乙醇重结晶，得到N，N’-二嘧啶基吲哚并[3，2a]咔唑，产率80％。
②
Figure PCTCN2015097193-appb-000055
将(8.2g，20mmol)N，N’-二嘧啶基吲哚并[3，2a]咔唑固体加入150mL三空瓶中，加入50mL的无水THF，搅拌溶解，冰浴下缓慢加入(3.6g，20mmol)的N-溴代丁二酰亚胺(NBS)的THF溶液(50mL)，滴加完毕，让反应缓慢升至室温。将反应液倒置水中，用乙酸乙酯萃取，水洗3次，有机相用无水硫酸镁干燥，过滤旋干，用四氢呋喃/乙醇重结晶，得到5-溴-N，N’-二嘧啶基吲哚并[3，2a]咔唑，产率85％。
③
Figure PCTCN2015097193-appb-000056
在氩气气氛下，将5-溴-N，N’-二嘧啶基吲哚并[3，2a]咔唑(4.9g，10mmol)，500mL无水THF加入150mL三口烧瓶中，搅拌溶解，用液氮降温到-78℃，缓慢滴加正丁基锂(15mmol，6mL，2.5M的正己烷溶液)，保持温度搅拌1.5小时，一次性加入氘代水(D2O)(0.4g，20mmol)，让反应自然升温，室温下搅拌1小时，终止反应，旋转蒸发掉大部分溶剂，抽滤，滤渣用四氢呋喃/石油醚混合溶液重结晶，得到3，7g 5-氘-N，N’-二嘧啶基吲哚并[3，2a]咔唑，产率约90％。
3)作为比较，以下为化合物Ref1的合成：
Figure PCTCN2015097193-appb-000057
①
Figure PCTCN2015097193-appb-000058
在氩气气氛下，将1，2-环己二酮56g(0.5mol)、苯肼盐酸盐144g(1mol)和乙醇700mL加入到1000mL的三口烧瓶中，机械搅拌5min，缓慢滴加浓硫酸10mL。室温下搅拌15min后，将反应加热到65℃，反应6小时。停止反应，让反应液冷却到室温，有大量固体析出。将反应液进行抽滤，用乙醇洗滤渣数次，滤渣烘干后，将其加入到1000mL的三口烧瓶中，加入乙酸600mL，三氟乙酸150mL，在100℃下反应加热反应20小时，将反应液冷却到室温，抽滤，用乙酸进行清洗。旋转蒸发所得的滤液，得到黄色固体。用四氢呋喃/石油醚混合溶液重结晶，得到45g吲哚并[2，3a]咔唑，产率约35％。
②
Figure PCTCN2015097193-appb-000059
在氩气保护下，将(12.8g，50mmol)的N，N-二氘-吲哚并[2，3a]咔唑、(10.2g，50mmol)的碘苯、(29g，150mmol)的碘化亚酮、(21g，150mmol)的无水碳酸钾和100mL的邻二氯苯加入到250mL的三口烧瓶中，加入到180℃下反应12小时，让反应液降到室温，抽滤，取滤液进行减压蒸馏。得到淡黄色固体，用石油醚/二氯甲烷进行柱层析，后用四氢呋喃/乙醇混合溶液重结晶。得到14.1g产物N-苯基-吲哚并[2，3a]咔唑，产率约85％。
③
Figure PCTCN2015097193-appb-000060
在氩气保护下，将(3.6g，150mmol)NaH固体加入250mL三空瓶中，加入150mL的无水THF，搅拌10min，缓慢加入(9.9g，30mmol)的N-苯基-吲哚并[2，3a]咔唑，常温搅拌1小时，一次性加入(4.5g，15mmol)3，5-二氯-1-联苯基-三嗪，继续反应3日。将反应液倒置冰水中，搅拌，加入300mL氯仿搅拌，萃取产物，有泡沫状不溶物， 抽滤除去，将滤液水洗三遍，有机相用无水硫酸镁干燥，过滤旋干，用四氢呋喃/乙醇重结晶，得到目标化合物，产率55％。
4)作为比较，化合物Ref2的合成参见实施例2)中的合成步骤①。
Figure PCTCN2015097193-appb-000061
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/Semi-empirical/Default Spin/AM1”(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：
表一
Figure PCTCN2015097193-appb-000062
Figure PCTCN2015097193-appb-000063
Ref1的能级与(2-6)相同，Ref2于(3-1)相同。
3.OLED器件的制备及表征
在本实施例中，用化合物(2-6)，(3-1)，Ref1和Ref2作为主体材料，Ir(ppy)3作为发光材料，HATCN作为空穴注入材料，NPB和TCTA作为空穴传输材料，B3PYMPM作为电子传输材料，构造成器件结构为ITO/HATCN/NPB/TCTA/主体材料：Ir(ppy)3(15％)/B3PYMPM/LiF/Al的电致发光器件。
Figure PCTCN2015097193-appb-000064
上述材料HATCN、NPB、TCTA、B3PYMPM、Ir(ppy)3的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/NPB/TCTA/主体材料：Ir(ppy)3/B3PYMPM/LiF/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(5nm)，NPB(40nm)，TCTA(10nm)，主体材料：15％Ir(ppy)3(15nm)，B3PYMPM(40nm)，LiF(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
OLED1 (2-6)
OLED2 (3-1)
RefOLED1 Ref1
RefOLED2 Ref2
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，OLED1的发光效率和RefOELD1相似，但寿命是RefOELD1的2倍以上，OLED2的发光效率和RefOLED2相似，而寿命是3倍。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 (11)

  1. 一种化合物，具有如下所示的通式(1)，
    Figure PCTCN2015097193-appb-100001
    其中，
    X为芳香环或芳杂环，
    R，R1-R8在每一次出现中，相同或不同地独立选自-H，-F，-Cl，Br，I，-D，-CN，-NO2，-CF3，B(OR0)2，Si(R0)3，直链烷烃，烷烃醚，含1～10个碳原子的烷烃硫醚，支链烷烃，环烷烃，含有3～10个碳原子的烷烃醚基团；R，R1-R8可被一个或多个活性基团R0任选取代，且其中一个或多个非相邻的亚甲基可被以下基团任选取代：R0C＝CR0，C＝C，Si(R0)2，Ge(R0)2，Sn(R0)2，C＝O，C＝S，C＝Se，C＝N(R0)，O，S，-COO-，或CONR2；R，R1-R8中一个或多个H原子可被D，F，Cl，Br，I，CN，NO2，一个或多个活性基团R0，芳香基团，杂芳香环基团任选取代；
    R0在每一次出现中，相同或不同地独立选自H，D，含1～10个碳原子的脂肪族烷烃，芳香碳氢化合物，含5～10个碳原子的芳香环或芳杂基团；
    Ar为碳原子数1-17的烷基、碳原子数3～18的环烷基、碳原子数6～60的芳香族烃基或碳原子数3～60的芳香族杂环基；
    M为碳原子数6～60的芳香族烃基或碳原子数3～60的芳香族杂环基；
    n为1～10的整数；
    其中，R、R1-R8中至少一个为D原子。
  2. 根据权利要求1所述的化合物，其特征在于，X在多次出现时，相同或不同地选自包含有如下结构的基团：
    Figure PCTCN2015097193-appb-100002
  3. 根据权利要求1所述的化合物，其特征在于，所述化合物具有下述(2)-(7)中之任一化学式表示的结构：
    Figure PCTCN2015097193-appb-100003
    其中：
    Y1、Y2为C或N，当Y1、Y2为N时，R为无基团；
    其中，R、R1-R8中至少一个为D原子，较优选是至少两个为D原子，更优选是至少三个为D原子，最优选至少是四个为D原子。
  4. 根据权利要求1所述的化合物，其特征在于，所述化合物具有下述化学式表示的结构：
    Figure PCTCN2015097193-appb-100004
  5. 根据权利要求1所述的化合物，其特征在于，所述M或Ar包含具有空穴传输特性的基团。
  6. 根据权利要求1所述的化合物，其特征在于，所述M或Ar包含具有电子传输特性的基团。
  7. 根据权利要求1所述的化合物，其特征在于，所述M和Ar中的其中一个包含有具有电子传输特性的基团，另一个包含有具有空穴传输特性的基团。
  8. 一种混合物，包括一种如权利要求1～7任一项所述的化合物，及至少一种有机功能材料，所述有机功能材料选自空穴注入材料，空穴传输材料，电子注入材料，电子传输材料，空穴阻挡材料，电子阻挡材料，发光材料或主体材料中的任一种或其组合。
  9. 一种组合物，包括一种如权利要求1-7任一项所述的化合物，及至少一种有机溶剂。
  10. 一种有机电子器件，其特征在于，包括如权利要求1至7任一项所述的化合物或其组合。
  11. 根据权利要求10所述的有机电子器件，其特征在于，所述的有机电子器件选自有机发光二极管、有机光伏电池、有机发光电池、有机场效应管、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。
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