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WO2018095386A1 - 稠环化合物、高聚物、混合物、组合物以及有机电子器件 - Google Patents

稠环化合物、高聚物、混合物、组合物以及有机电子器件 Download PDF

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WO2018095386A1
WO2018095386A1 PCT/CN2017/112707 CN2017112707W WO2018095386A1 WO 2018095386 A1 WO2018095386 A1 WO 2018095386A1 CN 2017112707 W CN2017112707 W CN 2017112707W WO 2018095386 A1 WO2018095386 A1 WO 2018095386A1
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atoms
organic
fused ring
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杨曦
潘君友
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Guangzhou Chinaray Optoelectronic Materials Ltd
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Guangzhou Chinaray Optoelectronic Materials Ltd
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Priority to US16/463,277 priority Critical patent/US20190330152A1/en
Priority to CN201780059199.7A priority patent/CN109790177A/zh
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Definitions

  • the present invention relates to the field of organic electroluminescence technology, and in particular to a fused ring compound, a polymer, a mixture and a composition thereof, and its use in the field of organic electroluminescence.
  • OLEDs Organic light-emitting diodes
  • Organic electroluminescence refers to the phenomenon of converting electrical energy into light energy using organic matter.
  • An organic electroluminescence device utilizing an organic electroluminescence phenomenon generally has a structure in which a positive electrode and a negative electrode and an organic layer are contained therebetween.
  • the organic layer has a multilayer structure, and each layer contains a different organic substance. Specifically, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and the like may be included.
  • Such an organic electroluminescence device when a voltage is applied between the two electrodes, holes are injected from the positive electrode into the organic layer, electrons are injected from the negative electrode into the organic layer, and excitons are formed when the injected holes meet the electrons. The excitons emit light when they transition back to the ground state.
  • Such an organic electroluminescence device has characteristics such as self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high responsiveness.
  • the development of a blue fluorescent material having a narrow-band emission spectrum and good stability is advantageous for obtaining a longer-life and higher-efficiency blue light device, and on the other hand, it is advantageous for the improvement of the color gamut, thereby improving the display effect.
  • the conventional blue organic electroluminescent device luminescent layer adopts a host-guest doping structure.
  • ruthenium-based fused ring derivatives are described, for example, in the patents CN1914293B, CN102448945B, US2015287928A1, etc.
  • these compounds have problems of insufficient luminous efficiency and brightness, and poor lifetime of the device.
  • an aryl vinylamine compound (WO 04/013073, WO 04/016575, WO 04/018587) can be used.
  • these compounds have poor thermal stability and are easily decomposed, resulting in poor lifetime of the device, which is currently the most important shortcoming in the industry.
  • the blue light-emitting materials can have deep blue light emission, and they are thermally stable, exhibit good efficiency and longevity in the organic electroluminescence element, are easy to repeat in the manufacture and operation of the device, and have simple material synthesis.
  • the present invention provides a fused ring compound of the formula (I):
  • X 1 , X 2 may be the same or different, CR 21 R 22 , NR 23 , O or S;
  • R 11 -R 16 and R 21 -R 23 are each independently H, or a linear alkyl group having 1 to 20 C atoms, an alkoxy group or a thioalkoxy group, or having 3 to 20 C atoms. a branched or cyclic alkyl, alkoxy or thioalkoxy group, or a substituted or unsubstituted silyl group, or a substituted ketone group having 1 to 20 C atoms, or 2 to 20
  • Unit A is selected from substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 40 ring atoms, or aryloxy or heteroaryloxy groups having 5 to 40 ring atoms, or combination.
  • the unit A is preferably selected from the following structures:
  • X is CR 31 or N, and multiple Xs are the same or different;
  • R 31 -R 36 are a straight-chain alkyl group, an alkoxy group or a thioalkoxy group independently having H or having 1 to 20 C atoms, or a branched or cyclic group having 3 to 20 C atoms.
  • At least one of R 11 -R 16 in formula (I) contains one of the following structures:
  • R 41 -R 49 and R 410 -R 431 are each independently H, or a linear alkyl group having 1 to 20 C atoms, an alkoxy group or a thioalkoxy group, or having 3 to 20 C atoms. a branched or cyclic alkyl, alkoxy or thioalkoxy group, or a substituted or unsubstituted silyl group, or a substituted ketone group having 1 to 20 C atoms, or 2 to 20
  • n is an integer of 0-3, n, p and s are each independently an integer of 0-4, and t and q are each independently an integer of 0-5;
  • Unit P is a saturated cycloalkane having 3 to 8 C atoms
  • L represents a single bond or a linking group
  • the linking group may be a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy group having 5 to 40 ring atoms. Or a heteroaryloxy group, or a combination of these systems;
  • the fused ring compound has a structure as shown in Formula (II):
  • the fused ring compound has a structure as shown in one of the formulae (II-1) to (II-7):
  • the present invention also provides a high polymer, the repeating unit of the high polymer comprising a group formed by the above fused ring compound losing at least one hydrogen atom.
  • the present invention still further provides a mixture comprising the fused ring compound and a second organic functional material, or the high polymer and the second organic functional material, the second organic functional material being selectable in a cavity (also called Holes) Injection or transport materials (HIM/HTM), hole blocking materials (HBM), electron injecting or transporting materials (EIM/ETM), electron blocking materials (EBM), organic matrix materials (Host), singlet luminescence At least one of a body (fluorescent illuminant), a triplet illuminant (phosphorescent illuminant), a thermally excited delayed fluorescent material (TADF material), and an organic dye.
  • a cavity also called Holes
  • Injection or transport materials HIM/HTM
  • HBM hole blocking materials
  • EIM/ETM electron injecting or transporting materials
  • EBM organic matrix materials
  • the present invention also provides a composition comprising the fused ring compound and an organic solvent, or the high polymer and an organic solvent.
  • Another object of the present invention is to provide an organic electronic device comprising the fused ring compound or polymer.
  • the organic electronic device can be selected from an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting battery (OLEEC), and an airport. Effect tube (OFET), organic light-emitting field effect transistor, organic laser, organic spintronic device, organic sensor and organic plasmon emitting diode (Organic Plasmon Emitting Diode).
  • the organic electronic device is an organic electroluminescent device comprising a light-emitting layer comprising the fused ring compound or high polymer.
  • the fused ring compound or polymer according to the present invention has a fluorescence emission having an emission wavelength at a short wavelength, and an emission spectrum thereof exhibits a narrow half width, so that the substance has a deep blue fluorescence emission and has a high Luminous efficiency.
  • Organic electroluminescent elements prepared from such fused ring compounds or polymers have dark blue color coordinates, high luminous efficiency, and long device lifetime.
  • FIG. 1 is a schematic structural view of an organic light emitting device provided by the present invention
  • 101 is a substrate
  • 102 is an anode
  • 103 is a hole injection layer (HIL) or a hole transport layer (HTL)
  • 104 is a light-emitting layer
  • 105 is an electron injection layer (EIL) or an electron transport layer (ETL).
  • 106 is a cathode.
  • 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.
  • composition printing ink, ink, and ink have the same meaning and are interchangeable.
  • the present invention provides a fused ring compound of the formula (I):
  • X 1 and X 2 may be the same or different and are CR 21 R 22 , NR 23 , O or S.
  • Unit A is selected from substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 40 ring atoms, or aryloxy or heteroaryloxy groups having 5 to 40 ring atoms, or Combinations wherein one or more of the groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded.
  • unit A is selected from substituted or unsubstituted aromatic or heteroaromatic ring systems having from 5 to 20 ring atoms, or aryloxy or heteroaryl groups having from 5 to 20 ring atoms.
  • An oxy group, or a combination of these systems, wherein one or more groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded.
  • the unit A is selected from a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 10 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 10 ring atoms, Or a combination of these systems, wherein one or more of the groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded.
  • the aromatic ring system comprises from 5 to 15 carbon atoms, more preferably from 5 to 10 carbon atoms in the ring system;
  • the heteroaromatic ring system contains from 2 to 15 carbon atoms in the ring system, More preferably, it is 2 to 10 carbon atoms, and at least one hetero atom, provided that the total number of carbon atoms and hetero atoms is at least 4.
  • the heteroatoms are preferably selected from Si, N, P, O, S and/or Ge, particularly preferably from Si, N, P, O and/or S, more particularly preferably from N, O and/or S.
  • the above aromatic ring system or aromatic group means a hydrocarbon group containing at least one aromatic ring, and includes a monocyclic group and a polycyclic ring system.
  • the heteroaromatic ring or heteroaromatic group described above refers to a hydrocarbon group (containing a hetero atom) containing at least one heteroaromatic ring, and includes 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 heteroaromatic.
  • aromatic or heteroaromatic ring systems include not only aromatic or heteroaromatic systems, but also multiple aryl or heteroaryl 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 group are: benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, anthracene, benzopyrene, triphenylene, anthracene, anthracene, snail, and derivatives thereof.
  • heteroaromatic groups are: furan, benzofuran, dibenzofuran, thiophene, benzothiophene, dibenzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole , thiazole, tetrazole, anthracene, oxazole, pyrroloimidazole, pyrrolopyrrol, thienopyrrole, thienothiophene, furopyrrol, furanfuran, thienofuran, benzisoxazole, benzisothiazole , benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-naphthyridine, quinoxaline, phenanthridine, pyridine, quinazoline, quinazolinone,
  • the fused ring compound can be used as an organic functional material in electronic devices, particularly OLED devices.
  • Organic 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
  • HBM hole blocking materials
  • Emitter Host and Organic Dyes.
  • the fused ring compound can be used as a host material, or an electron transport material, or a hole transport material.
  • the fused ring compound can act as a singlet emitter (or fluorescent emitter).
  • S 1 As a singlet emitter, there must be an appropriate singlet level, S 1 .
  • S 1 ⁇ 2.2 eV, preferably ⁇ 2.4 eV, more preferably ⁇ 2.6 eV, still more preferably ⁇ 2.7 eV, and most preferably ⁇ 2.8 eV.
  • the singlet energy level S 1 of an organic compound depends on the substructure of the fused ring compound having the largest conjugated system. Generally, S 1 decreases as the conjugated system increases. In certain preferred embodiments, the substructures of formula (Ia) have the largest conjugated system.
  • the formula (Ia), in the case of removing a substituent, has no more than 36 ring atoms, preferably no more than 32, more preferably no more than 30, and most preferably no more than 28.
  • the formula (Ia) has S 1 ⁇ 2.3 eV, preferably ⁇ 2.5 eV, more preferably ⁇ 2.7 eV, still more preferably ⁇ 2.8 eV, and most preferably ⁇ 2.85 eV.
  • the unit A is preferably selected from the following structures:
  • X is CR 31 or N, and multiple Xs may be the same or different;
  • R 31 -R 36 may independently of each other be H, or a linear alkyl group having 1 to 20 C atoms, an alkoxy group or a thioalkoxy group, or a branch or ring having 3 to 20 C atoms.
  • R 31 -R 36 may independently of each other be H, or a linear alkyl group having 1 to 10 C atoms, an alkoxy group or a thioalkoxy group, or a branch having 3 to 10 C atoms.
  • unit A is selected from the following structures:
  • At least one of R 11 -R 16 contains one of the following structures:
  • R 41 -R 49 and R 410 -R 433 are each independently H, or a linear alkyl group having 1 to 20 C atoms, an alkoxy group or a thioalkoxy group, or having 3 to 20 C atoms. a branched or cyclic alkyl, alkoxy or thioalkoxy group, or a substituted or unsubstituted silyl group, or a substituted ketone group having 1 to 20 C atoms, or 2 to 20
  • n, p, and s are each independently an integer of 0-4, and t and q are each independently an integer of 0-5.
  • Unit P is a saturated cycloalkane having 3 to 8 C atoms.
  • Preferred are saturated cycloparaffins of 4 to 6 C atoms. More preferably, it is a saturated cycloalkane of 5 to 6 C atoms.
  • L represents a single bond or a linking group.
  • the linking group may be a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or these systems
  • a combination wherein one or more groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded.
  • L represents a single bond
  • L is a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 20 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 20 ring atoms.
  • a group, or a combination of these systems, wherein one or more groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded.
  • L is a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 10 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 10 ring atoms.
  • a group, or a combination of these systems, wherein one or more groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded.
  • the dashed line indicates a single bond attached to other groups.
  • linking group L described above may comprise one or more of the following structural groups:
  • a 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 respectively represent CR 3 or N;
  • R 3 , R 4 , and R 5 are each independently H, or a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branch having 3 to 20 C atoms.
  • a chain or cyclic alkyl, alkoxy or thioalkoxy group is either a silyl group, or a substituted keto group having from 1 to 20 C atoms, or from 2 to 20 C
  • linking group L is preferably one of the following structural groups, wherein H on the ring may be optionally substituted:
  • the fused ring cyclate has a structure as shown in formula (II):
  • X 1 , X 2 , and unit A, R 12 and R 16 are the same as described above.
  • the fused ring compound has a structure as shown in one of the formulae (II-1) to (II-14):
  • X 1 , X 2 , R 12 and R 16 are the same as described above.
  • X 1 and X 2 are preferably independently selected from CR 21 R 22 , respectively, and R 21 , R 22 are the same as described above. More preferably, it is selected from C(CH 3 ) 2 .
  • Z is an O atom.
  • H in the fused ring compound is at least partially deuterated, preferably 10% H is deuterated, more preferably 20% H is deuterated, preferably 30% The H is replaced, preferably 40% of the H is replaced.
  • a specific example of a fused ring compound according to the present invention is as follows, but is not limited thereto
  • the present invention also relates to a method for synthesizing the fused ring compound, which comprises carrying out a reaction using a raw material containing a reactive group.
  • active materials comprise at least one leaving group, for example, bromine, iodine, boric acid or a boronic ester.
  • Suitable reactions to form C-C linkages are well known to those skilled in the art and are described in the literature.
  • Particularly suitable and preferred coupling reactions are SUZUKI, STILLE and HECK coupling reactions.
  • the present invention still further relates to a high polymer, wherein the repeating unit of the high polymer includes a group formed by the above fused ring compound losing at least one hydrogen atom.
  • the high polymer is a non-conjugated high polymer.
  • the group formed after the fused ring compound loses at least one hydrogen atom is on the side chain of the high polymer.
  • the high polymer is a conjugated polymer
  • the invention also provides a mixture comprising a fused ring compound or polymer as described above, and a second organic functional material.
  • the second organic functional material may be selected from 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), an electron blocking material. (EBM), organic matrix material (Host), singlet emitter (fluorescent emitter), triplet emitter (phosphorescent emitter), thermally excited delayed fluorescent material (TADF material) and one or more of organic dyeskind.
  • Various organic functional materials are described in detail in, for example, WO2010135519A1, US20090134784A1, and WO 2011110277A1, the entire disclosure of which is hereby incorporated by reference.
  • the second organic functional material is a fluorescent host material (or a singlet matrix material), the fused ring compound or the high polymer may be used as a guest, and the weight percentage thereof is ⁇ 15 wt%. It is preferably ⁇ 12 wt%, more preferably ⁇ 9 wt%, still more preferably ⁇ 8 wt%, most preferably ⁇ 7 wt%.
  • the second organic functional material is a fluorescent illuminant (or singlet illuminant) and a fluorescent host material.
  • the fused ring compound or the high polymer may serve as a secondary luminescent material having a weight ratio to the fluorescent illuminant of from 1:2 to 2:1.
  • the second organic functional material is a TADF material.
  • the second organic functional material is an HTM material.
  • HTM singlet matrix materials
  • singlet emitters singlet emitters
  • Suitable organic HIM/HTM materials may optionally comprise compounds having the following structural units: phthalocyanine, porphyrin, amine, aromatic amine, biphenyl triarylamine, thiophene, thiophene such as dithienothiophene and thiophene, pyrrole, aniline , carbazole, azide and azepine and their derivatives.
  • suitable HIMs also include self-assembling monomers such as compounds containing phosphonic acid and sliane derivatives; metal complexes and crosslinking compounds and the like.
  • An electron blocking layer is used to block electrons from adjacent functional layers, particularly the luminescent layer.
  • 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 HBM has a larger excited state level than the adjacent luminescent layer, such as a singlet or triplet, depending on the illuminant, while the EBM has a hole transport function.
  • HIM/HTM materials that typically have high LUMO levels can be used as EBMs.
  • cyclic aromatic amine-derived compounds useful as HIM, HTM or EBM 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, phenalrene, phenanthrene, anthracene, anthracene, fluorene, anthracene, anthracene; Heterocyclic compounds such as dibenzothiophene, dibenzofuran, furan, thiophene, benzofuran, benzothiophene, oxazole, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, evil Triazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, acesulfazine, oxadiazine, hydrazine
  • Ar 1 to Ar 9 may be independently selected from the group consisting of:
  • n is an integer from 1 to 20; X 1 to X 8 are CH or N; and Ar 1 is as defined above.
  • metal complexes that can be used as HTM or HIM include, but are not limited to, the following general structures:
  • M is a metal having an atomic weight greater than 40
  • (Y 1 -Y 2 ) is a two-dentate ligand, Y 1 and Y 2 are independently selected from C, N, O, P and S; L is an ancillary ligand; m is an integer from 1 to The maximum coordination number of this metal; m+n is the maximum coordination number of this metal.
  • (Y 1 -Y 2 ) is a 2-phenylpyridine derivative.
  • (Y 1 -Y 2 ) is a carbene ligand.
  • M is selected from Ir, Pt, Os, and Zn.
  • the HOMO of the metal complex is greater than -5.5 eV (relative to the vacuum level).
  • the example of the singlet host material is not particularly limited, and any organic compound may be used as the host as long as its singlet energy is higher than that of the illuminant, particularly the singlet illuminant or the luminescent illuminant.
  • Examples of the organic compound used as the singlet host material may be selected from the group consisting of a cyclic aromatic compound such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, anthracene, phenanthrene, anthracene, anthracene, fluorene, fluorene, fluorene, An aromatic heterocyclic compound such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, oxazole, carbazole, pyridine Anthraquinone, pyrrole dipyridine, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, triazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrim
  • the singlet host material can be selected from compounds comprising at least one of the following groups:
  • R 1 may be independently selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl;
  • Ar 1 is an aryl group Or a heteroaryl group, which has the same meaning as Ar 1 defined in the above HTM;
  • n is an integer from 0 to 20;
  • X 1 -X 8 is selected from CH or N;
  • X 9 and X 10 are selected from CR 1 R 2 Or NR 1 .
  • Singlet emitters tend to have longer conjugated pi-electron systems.
  • styrylamine and its derivatives disclosed in JP 2913116 B and WO 2001021729 A1
  • indenoindenes and derivatives thereof disclosed in WO 2008/006449 and WO 2007/140847.
  • the singlet emitter can be selected from the group consisting of monostyrylamine, dibasic styrylamine, ternary styrylamine, quaternary styrylamine, styrene phosphine, styrene ether and aromatic amine.
  • a monostyrylamine refers to a compound comprising an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine.
  • a dibasic styrylamine refers to a compound comprising two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • a ternary styrylamine refers to a compound comprising three unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • a quaternary styrylamine refers to a compound comprising four unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • a preferred styrene is stilbene, which may be further substituted.
  • the corresponding phosphines and ethers are defined similarly to amines.
  • An arylamine or an aromatic amine refers to a compound comprising three directly linked nitrogen An unsubstituted or substituted aromatic ring or heterocyclic ring system. At least one of these aromatic or heterocyclic ring systems is preferably selected from the fused ring system and preferably has 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.
  • An aromatic amide refers to a compound in which a diaryl arylamine group is attached directly to the oxime, preferably at the position of 9.
  • An aromatic quinone diamine refers to a compound in which two diaryl arylamine groups are attached directly to the oxime, 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 preferably bonded to the 1 or 1,6 position of hydrazine.
  • 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 7250532 B2, DE 102005058557 A1, CN 1583691 A, JP 08053397 A, US 6251531 B1, US 2006/210830 A, EP 1957606 A1 and US 2008/0113101 A1, the entire contents of which are hereby incorporated by reference. This article is incorporated herein by reference.
  • Further preferred singlet emitters can be selected from indenoindole-amines and indenofluorene-diamines, as disclosed in WO 2006/122630, benzoindoloindole-amines and benzoindenoindole-diamines , as disclosed in WO 2008/006449, dibenzoindolo-amine and dibenzoindeno-diamine, as disclosed in WO 2007/140847.
  • polycyclic aromatic hydrocarbon compounds in particular derivatives of the following compounds: for example, 9,10-bis(2-naphthoquinone), naphthalene, tetraphenyl, xanthene, phenanthrene , ⁇ (such as 2,5,8,11-tetra-t-butyl fluorene), anthracene, phenylene such as (4,4'-bis(9-ethyl-3-carbazolevinyl)-1 , 1 '-biphenyl), indenyl hydrazine, decacycloolefin, hexacene benzene, anthracene, spirobifluorene, aryl hydrazine (such as US20060222886), arylene vinyl (such as US5121029, US5130603), cyclopentane Alkene such as tetraphenylcyclopentadiene, rub
  • 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 ( ⁇ Est), and triplet excitons can be converted into singlet exciton luminescence by anti-intersystem crossing. This can make full use of the singlet excitons and triplet excitons formed under electrical excitation.
  • the quantum efficiency in the device can reach 100%.
  • 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:
  • the fused ring compound or polymer is used in an evaporated OLED device.
  • the fused ring compound or polymer has 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.
  • Another object of the invention is to provide a material solution for printing OLEDs.
  • the fused ring compound or polymer has a molecular weight of ⁇ 700 g/mol, preferably ⁇ 800 g/mol, very preferably ⁇ 900 g/mol, more preferably ⁇ 1000 g/mol, most preferably ⁇ 1100 g/mol.
  • the fused ring compound or polymer has a solubility in toluene of > 2 mg/ml, preferably > 3 mg/ml, most preferably > 5 mg/ml at 25 °C.
  • the invention also provides a composition comprising the fused ring compound or polymer, and a first organic solvent.
  • composition according to the invention wherein the fused ring compound is useful as a singlet emitter material.
  • composition in accordance with the present invention further comprises a host material.
  • composition in accordance with the present invention further comprises a host material and a singlet emitter.
  • composition according to the invention further comprises at least two host materials.
  • composition in accordance with the present invention further comprises a host material and a thermally activated delayed fluorescent luminescent material.
  • a composition in accordance with the present invention further comprises a hole transporting material (HTM), and more preferably, said HTM comprises a crosslinkable group.
  • HTM hole transporting material
  • 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 0.01 to 20% by weight of a fused ring compound, preferably 0.1 to 15% by weight, more preferably 0.2 to 10% by weight, most preferably 0.25 to 5% by weight of a fused ring compound. .
  • the first organic solvent is selected from the group consisting of an aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, an aliphatic ketone or an aliphatic ether, an alicyclic or olefinic compound, or An inorganic ester compound such as a boric acid ester or a phosphate ester, or a mixture of two or more solvents.
  • a composition according to the invention comprises at least 50% by weight of an aromatic or heteroaromatic solvent; preferably at least 80% by weight of an aromatic or heteroaromatic solvent; particularly preferably at least 90% by weight Aromatic or heteroaromatic solvents.
  • aromatic or heteroaromatic-based first organic solvent examples include, but not limited to, 1-tetralone, 3-phenoxytoluene, acetophenone, 1-methoxynaphthalene, p- Diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, o-di Ethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, ten Dialkylbenzene, 1-methylnaphthalene, 1,2,4-t
  • suitable and preferred first organic solvents are aliphatic, cycloaliphatic or aromatic hydrocarbons, amines, thiols, amides, nitriles, esters, ethers, polyethers, alcohols, glycols or polyols. .
  • the alcohol represents a suitable class of first organic solvent.
  • Preferred alcohols include alkylcyclohexanols, especially methylated aliphatic alcohols, naphthols and the like.
  • the first organic solvent may be a cycloalkane such as decalin.
  • the first organic solvent may be used singly or as a mixture of two or more organic solvents.
  • the composition according to the present invention may further comprise a second organic solvent, an example of the second organic solvent , including but not limited to: methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, Meta-xylene, p-xylene, 1,4 dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1,1,1-trichloroethane Alkane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene,
  • a second organic solvent including but not limited to: methanol, ethanol, 2-methoxy
  • the first organic solvent and the second organic solvent particularly suitable for the present invention are solvents having a Hansen solubility parameter in the following ranges:
  • ⁇ d (dispersion force) is in the range of 17.0 to 23.2 MPa 1/2 , especially in the range of 18.5 to 21.0 MPa 1/2 ;
  • ⁇ p polar forces in the range of 0.2 ⁇ 12.5MPa 1/2, especially in the 2.0 ⁇ 6.0MPa 1/2;
  • the composition according to the present invention wherein the first organic solvent and the second organic solvent are selected in consideration of their boiling point parameters.
  • the first organic solvent and the second organic solvent have a boiling point of ⁇ 150 ° C; preferably ⁇ 180 ° C; more preferably ⁇ 200 ° C; more preferably ⁇ 250 ° C; optimally ⁇ 275 °C or ⁇ 300 °C.
  • the boiling points within these ranges are beneficial for preventing nozzle clogging of the inkjet printhead.
  • the first organic solvent and the second organic solvent may be evaporated from the composition system to form a film comprising a functional material.
  • composition according to the invention is characterized in that
  • the surface tension is at 25 ° C, in the range of 19 dyne / cm (dyne / cm) to 50 dyne / cm.
  • composition according to the present invention wherein the first organic solvent and the second organic solvent are selected in consideration of their surface tension parameters.
  • Suitable ink surface tension parameters are suitable for a particular substrate and a particular printing method.
  • the surface tension of the first organic solvent and the second organic solvent at 25 ° C It is in the range of about 19 dyne/cm to 50 dyne/cm; more preferably in the range of 22 dyne/cm to 35 dyne/cm; most preferably in the range of 25 dyne/cm to 33 dyne/cm.
  • the ink according to the invention has a surface tension 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; preferably in 25 dyne/ Cm to the 33dyne/cm range.
  • compositions according to the present invention wherein the first organic solvent and the second organic solvent are selected in consideration of viscosity parameters of the ink.
  • the viscosity can be adjusted by different methods, such as by the selection of a suitable organic solvent and the concentration of the functional material in the ink.
  • the first organic solvent and the second organic solvent have a viscosity of less than 100 cps; more preferably less than 50 cps; and most preferably from 1.5 to 20 cps.
  • the viscosity herein refers to the viscosity at ambient temperature at the time of printing, and is usually 15 to 30 ° C, preferably 18 to 28 ° C, more preferably 20 to 25 ° C, and most preferably 23 to 25 ° C.
  • Compositions so formulated will be particularly suitable for ink jet printing.
  • the composition according to the invention has a viscosity at 25 ° C in the range of from about 1 cps to about 100 cps; more preferably in the range of from 1 cps to 50 cps; more preferably in the range of from 1.5 cps to 20 cps.
  • the ink obtained by the organic solvent satisfying the above boiling point and surface tension parameters and viscosity parameters can form a functional material film having uniform thickness and composition properties.
  • Another object of the present invention is to provide the use of the above fused ring compounds or polymers in organic electronic devices.
  • the 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 laser, and an organic spintronic device.
  • OLED organic light emitting diode
  • OCV organic photovoltaic cell
  • OEEC organic light emitting cell
  • OFET organic field effect transistor
  • OLED organic light emitting field effect transistor
  • Another object of the present invention is to provide a method of producing the above organic electronic device.
  • the method comprises: forming a functional layer on a substrate by evaporation of the above fused ring compound, high polymer or mixture; or mixing the fused ring compound, high polymer or mixture with the second by co-evaporation
  • the organic functional materials together form a functional layer on a substrate; or the above composition is applied to a substrate by printing or coating to form a functional layer.
  • the printing or coating method can be selected from, but 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, slit-type extrusion coating, and the like.
  • the invention further relates to the use of the composition as a printing ink in the preparation of an organic electronic device, particular preference being given to a preparation process by printing or coating.
  • suitable printing or coating techniques include, but are not limited to, inkjet printing, typography, screen printing, dip coating, spin coating, blade coating, roller printing, twist roll printing, lithography, flexography Printing, rotary printing, spraying, brushing or pad printing, slit-type extrusion coating, etc.
  • Preferred are gravure, screen printing and inkjet printing. Gravure printing It will be applied in embodiments of the invention.
  • 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 functional layer may have a thickness between 5 nm and 1000 nm.
  • the invention further relates to an organic electronic device comprising the fused ring compound or polymer; or at least a functional layer prepared using the fused ring compound or polymer.
  • the organic electronic device comprises at least one cathode, an anode and a functional layer between the cathode and the anode, wherein the functional layer comprises a fused ring compound or polymer as described above.
  • the organic electronic device described above is an electroluminescent device, in particular an OLED.
  • the organic electronic device includes a substrate (101), an anode (102), at least one light emitting layer (104), and a cathode (106).
  • the substrate (101) may 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-
  • the anode (102) may 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 (106) 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.
  • EIL electron injection layer
  • the absolute value of the difference between the LUMO level or the conduction band level of the n-type semiconductor material of the electron transport layer (ETL) or the hole blocking layer (HBL) is less than 0.5 eV, preferably less than 0.3 eV, 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 comprise other functional layers such as a hole injection layer (HIL) or a hole transport layer (HTL) (103), an electron blocking layer (EBL), an electron injection layer (EIL) or an electron transport layer (ETL) (105). ), 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 (104) is vacuum-deposited, and the evaporation source thereof contains the fused ring compound or high polymer.
  • the luminescent layer (104) is prepared by printing the composition.
  • the electroluminescent device according to the invention 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 also relates to the use of the organic electronic device in various electronic devices, including, but not limited to, display devices, illumination devices, light sources, sensors, and the like.
  • the invention further relates to an electronic device incorporating the organic electronic device, including, but not limited to, a display device, a lighting device, a light source, a sensor, and the like.
  • HIL a triarylamine derivative
  • HTL a triarylamine derivative
  • a, cleaning of the conductive glass substrate when used for the first time, can be washed with a variety of solvents, such as chloroform, ketone, isopropyl alcohol, and then UV ozone plasma treatment;
  • HIL 50 nm
  • HTL 35 nm
  • EML 25 nm
  • ETL 28 nm
  • cathode LiQ / Al (1nm / 150nm) in a high vacuum (1 ⁇ 10 -6 mbar) in the thermal evaporation;
  • 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. It has been found that the color coordinates of the blue light device prepared by using Compound 1 - Compound 10 as the EML layer illuminant are better than that of Comparative Compound 1, for example, the color coordinates of the device prepared by Compound 7 are (0.148, 0.077); The luminous efficiency of the blue light device prepared by the compound 10 as the EML layer illuminant is in the range of 6-8 cd/A, which has more excellent luminous efficiency; in terms of device lifetime, the blue light device is prepared by using the compound 1 - compound 10 as the EML layer illuminant. The lifetime is much better than that of Comparative Compound 1, for example, the device prepared by Compound 7 has a T95 of more than 1500 hours at 1000 nits.

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Abstract

本发明公开了一种稠环化合物，及其在有机电子器件的应用，特别是在有机电致发光二极管中的应用。本发明还公开了包含有所述稠环化合物的有机电子器件，特别是有机电致发光二极管，及其在显示及照明技术中的应用。本发明还进一步公开了一种包含所述稠环化合物的组合物，及其在制备有机电子器件中的应用。通过器件结构优化，可达到较佳的器件性能，特别是可实现高性能的OLED器件，对全彩显示和照明应用提供了较好的材料和制备技术选项。

Description

稠环化合物、高聚物、混合物、组合物以及有机电子器件
相关申请
本发明申请要求2016年11月23日申请的，申请号为201611051634.5，名称为“稠环化合物及其在有机电子器件的应用”的中国专利申请的优先权，在此将其全文引入作为参考。
技术领域
本发明涉及有机电致发光技术领域，特别是涉及一种稠环化合物，高聚物，混合物及组合物，及其在有机电致发光领域的应用。
背景技术
由于有机半导体材料在合成上具有多样性、制造成本相对较低和优良的光学与电学性能，有机发光二极管(OLED)在光电器件(例如平板显示器和照明)的应用方面具有很大的潜力。
有机电致发光现象是指利用有机物质将电能转化为光能的现象。利用有机电致发光现象的有机电致发光元件通常具有正极与负极以及在它们中间包含有机物层的结构。为了提高有机电致发光元件的效率与寿命，有机物层具有多层结构，每一层包含有不同的有机物质。具体的，可以包括空穴注入层、空穴传输层、发光层、电子传输层、电子注入层等。在这种有机电致发光元件中，在两个电极之间施加电压，则由正极向有机物层注入空穴，由负极向有机物层注入电子，当注入的空穴与电子相遇时形成激子，该激子跃迁回基态时发出光。这种有机电致发光元件具有自发光、高亮度、高效率、低驱动电压、广视角、高对比度、高响应性等特性。
为了提高有机电致发光元件的发光效率，各种基于荧光和磷光的发光材料体系已被开发出来，而无论是荧光材料还是磷光材料，优秀蓝光材料的开发都是一个巨大的挑战，总体而言，目前使用的蓝光荧光材料的有机发光二级管可靠性更高。尽管如此，目前大多数蓝光荧光材料的发射光谱过宽，色纯度较差，不利于高端显示，并且这类荧光材料的合成也较复杂，不利于大规模量产，同时这类蓝色荧光材料的OLED稳定性还需进一步提高。因此开发具有窄带发射光谱、稳定性好的蓝色荧光材料，一方面有利于得到更长寿命更高效率的蓝光器件，另一方面有利于色域的提高，进而改善显示效果。
传统的的蓝光有机电致发光元件发光层采用主客体掺杂结构。作为传统蓝光主体材料的是基于蒽的稠环类衍生物，如专利CN1914293B、CN102448945B、US2015287928A1等所述，然而这些化合物存在发光效率和亮度不充分的问题，及器件寿命较差的问题。作为传统发蓝光客体化合物，可采用的是芳基乙烯基胺类化合物(WO 04/013073,WO 04/016575,WO 04/018587)。然而，这些化合物的热稳定性差，易分解，导致器件的寿命差，是目前产业上最主要的缺点。此 外，这些化合物的色纯度差，难以实现深蓝色的发光。另外，US 7233019、KR 2006-0006760等专利公开了利用芳基胺取代基的芘系化合物的有机电致发光元件，但是因为蓝光的色纯度低，很难实现深蓝发光，因此在体现天然颜色的全彩色显示器方面有问题。
因此，仍需进一步改进材料，特别是发光化合物，尤其是蓝色发光化合物。使蓝光发光材料能具有深蓝色发光，且它们是热稳定的，在有机电致发光元件中体现良好的效率和寿命，在器件的制造与操作中易于重复，且材料合成简单。
发明内容
基于此，本发明的目的是提供一种稠环化合物，高聚物，混合物及组合物及其在电子器件中的应用。
具体技术方案如下：
本发明提供一种如通式(I)所示的稠环化合物：
Figure PCTCN2017112707-appb-000001
其中，
X1、X2可以相同或不同的是CR21R22、NR23、O或S；
R11-R16和R21-R23分别独立地是H、或者具有1至20个C原子的直链烷基、烷氧基或硫代烷氧基，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，或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，或氰基(-CN)，或氨基甲酰基(-C(＝O)NH2)，或卤甲酰基(-C(＝O)-X，其中，X代表卤素原子)，或甲酰基(-C(＝O)-H)，或异氰基，或异氰酸酯，或硫氰酸酯或异硫氰酸酯，或羟基，或硝基，或CF3，或Cl，或Br，或F，或可交联的基团，或者具有5至40个环原子的取代或未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；
单元A选自具有5至40个环原子的取代或未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。
在其中一些实施例中，所述的单元A优先选自以下结构：
Figure PCTCN2017112707-appb-000002
其中，
X是CR31或N，多个X相同或不同；
Y选自CR32R33，SiR34R35，NR36，C(＝O)，S，S(＝O)2或O；
R31-R36是分别独立地H、或者具有1至20个C原子的直链烷基、烷氧基或硫代烷氧基，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，或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，或氰基(-CN)，或氨基甲酰基(-C(＝O)NH2)，或卤甲酰基(-C(＝O)-X，其中，X代表卤素原子)，或甲酰基(-C(＝O)-H)，或异氰基，或异氰酸酯，或硫氰酸酯或异硫氰酸酯，或羟基，或硝基，或CF3，或Cl，或Br，或F，或可交联的基团，或者具有5至40个环原子的取代或未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。
在其中一些实施例中，通式(I)中R11-R16中至少一个含有一个以下结构中的一种：
Figure PCTCN2017112707-appb-000003
其中，
R41-R49和R410-R431分别独立地是H，或者具有1至20个C原子的直链烷基、烷氧基或硫代烷氧基，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，或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，或氰基(-CN)，或氨基甲酰基(-C(＝O)NH2)，或卤甲酰基(-C(＝O)-X，其中，X代表卤素原子)，或甲酰基(-C(＝O)-H)，或异氰基，或异氰酸酯，或硫氰酸酯或异硫氰酸酯，或羟基，或硝基，或CF3，或Cl，或Br，或F，或可交联的基团，或者具有5至40个环原子的取代或未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；
m为0-3的整数，n、p和s分别独立地为0-4的整数，t和q分别独立地为0-5的整数；
单元P是具有3到8个C原子的饱和环烷烃；
L表示单键或连接基团，所述连接基团可以是具有5至40个环原子的取代或未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；
L与通式(I)的稠环连接。
在其中一些实施例中，所述稠环化合物具有如通式(II)所示的结构：
Figure PCTCN2017112707-appb-000004
在其中一些较为优先的实施例中，所述稠环化合物具有如通式(II-1)-(II-7)之一所示的结构：
Figure PCTCN2017112707-appb-000005
本发明还提供一种高聚物，所述高聚物的重复单元包括上述稠环化合物失去至少一个氢原子后形成的基团。本发明还进一步提供一种混合物，包括所述稠环化合物和第二有机功能材料，或者所述高聚物和第二有机功能材料，所述第二有机功能材料可选于空穴(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)、热激发延迟荧光材料(TADF材料)及有机染料中的至少一种。
本发明还提供一种组合物，包括所述稠环化合物和有机溶剂，或者所述高聚物和有机溶剂。
本发明的另一目的是提供一种包含有所述稠环化合物或高聚物的有机电子器件。所述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)。
在其中一些实施例中，所述的有机电子器件是有机电致发光器件，包括发光层，所述发光层包括所述稠环化合物或高聚物。
有益效果：
按照本发明的所述稠环化合物或高聚物，具有发光波长位于短波长的荧光发射，其发光光谱表现为具有窄的半峰宽，从而该类物质具有深蓝色的荧光发射，且具有高的发光效率。以此类稠环化合物或高聚物制备得到的有机电致发光元件具有深蓝的色坐标、高的发光效率、及长的器件寿命。
附图说明
图1是本发明提供的一种有机发光器件的结构示意图，
图中，101是基板，102是阳极，103是空穴注入层(HIL)或空穴传输层(HTL)，104是发光层，105是电子注入层(EIL)或电子传输层(ETL)，106是阴极。
具体实施方式
为了便于理解本发明，下面将参照相关附图对本发明进行更全面的描述。附图中给出了本发明的较佳实施例。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。本文所使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。
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。
在本发明中，组合物、印刷油墨、油墨、和墨水具有相同的含义，可以互换。
本发明提供一种如通式(I)所示的稠环化合物：
Figure PCTCN2017112707-appb-000006
其中，
X1、X2可以相同或不同的是CR21R22、NR23、O或S。
R11-R16和R21-R23可以分别独立地是氢(H)、或者具有1至20个C原子的直链烷基、烷氧基或硫代烷氧基，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，或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，或氰基(-CN)，或氨基甲酰基(-C(＝O)NH2)，或卤甲酰基(-C(＝O)-X，其中，X代表卤素原子)，或甲酰基(-C(＝O)-H)，或异氰基，或异氰酸酯，或硫氰酸酯或异硫氰酸酯，或羟基，或硝基，或CF3，或Cl，或Br，或F，或可交联的基团，或者具有5至40个环原子的取代或未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，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。
单元A选自具有5至40个环原子的取代或未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，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。
在一个优先的实施例中，R11-R16和R21-R23分别独立地是H、或者具有1至10个C原子的直链烷基、烷氧基或硫代烷氧基，或者具有3至10个C原子的支链或环状的烷基、烷氧基或硫代烷氧基，或者是取代或无取代的甲硅烷基，或具有1至10个C原子的取代的酮基，或具有2至10个C原子的烷氧基羰基，或具有7至10个C原子的芳氧基羰基，或氰基(-CN)，或氨基甲酰基(-C(＝O)NH2)，或卤甲酰基(-C(＝O)-X，其中，X代表卤素原子)，或甲酰基(-C(＝O)-H)，或异氰基，或异氰酸酯，或硫氰酸酯或异硫氰酸酯，或羟基，或硝基，或CF3，或Cl，或Br，或F，或可交联的基团，或者具有5至20个环原子的取代或未取代的芳族或杂芳族环系，或具有5至20个环原子的芳氧基或杂芳氧基基团，或这些体系的组合，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。
在另一个优先的实施例中，单元A选自具有5至20个环原子的取代或未取代的芳族或杂芳族环系，或具有5至20个环原子的芳氧基或杂芳氧基基团，或这些体系的组合，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。
更优地，单元A选自具有5至10个环原子的取代或未取代的芳族或杂芳族环系，或具有5至10个环原子的芳氧基或杂芳氧基基团，或这些体系的组合，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。
在一些较为优先的实施例中，芳香环系在环系中包含5至15个碳原子，更优是5至10个碳原子；杂芳香环系在环系中包含2至15个碳原子，更优是2至10个碳原子，和至少一个杂原子，条件是碳原子和杂原子的总数至少为4。杂原子优选选自Si、N、P、O、S和/或Ge，特别优选选自Si、N、P、O和/或S，更加特别优选选自N、O和/或S。
以上所述的芳香环系或芳族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系统。以上所述的杂芳香环系或杂芳族基团指包含至少一个杂芳环的烃基(含有杂原子)，包括单环基团和多环的环系统。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，至少一个是芳族的或杂芳族的。对于本发明的目的，芳香族或杂芳香族环系不仅包括芳香基或杂芳香基的体系，而且，其中多个芳基或杂芳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，芳族基团的例子有：苯、萘、蒽、菲、二萘嵌苯、并四苯、芘、苯并芘、三亚苯、苊、芴、螺芴及其衍生物。
具体地，杂芳族基团的例子有：呋喃、苯并呋喃、二苯并呋喃、噻吩、苯并噻吩、二苯并噻吩、吡咯、吡唑、三唑、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。
所述稠环化合物可以作为有机功能材料应用于电子器件，特别是OLED器件中。有机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)和有机染料。在一个优先的实施例中，所述稠环化合物可作为主体材料，或电子传输材料，或空穴传输材料。在一个优先的实施例中，所述稠环化合物可作为单重态发光体(或荧光发光体)。
作为单重态发光体必须有适当的单线态能级，即S1。在某些实施例中，按照发明的稠环化合物，其S1≥2.2eV，较好是≥2.4eV，更好是≥2.6eV，更更好≥2.7eV，最好是≥2.8eV。
通常，有机化合物的单线态能级S1取决于稠环化合物中具有最大共轭体系的分结构。一般地，S1随共轭体系的增大而递减。在某些优先的实施方案中，如通式(Ia)所示的分结构具有最 大的共轭体系。
Figure PCTCN2017112707-appb-000007
在某些实施例中，通式(Ia)在去除取代基的情况下，其环原子数不超过36个，较好为不超过32个，更好为不超过30个，最好为不超过28个。
在某些优选的实施例中，通式(Ia)其S1≥2.3eV，较好是≥2.5eV，更好是≥2.7eV，更更好≥2.8eV，最好是≥2.85eV。
在其中某些实施例中，所述单元A优先选自以下结构：
Figure PCTCN2017112707-appb-000008
其中，
X是CR31或N，多个X可以相同，也可以不同；
Y选自CR32R33，SiR34R35，NR36，C(＝O)，S，S(＝O)2，或O；
R31-R36可以相互独立地是H、或者具有1至20个C原子的直链烷基、烷氧基或硫代烷氧基，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，或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，或氰基(-CN)，或氨基甲酰基(-C(＝O)NH2)，或卤甲酰基(-C(＝O)-X，其中，X代表卤素原子)，或甲酰基(-C(＝O)-H)，或异氰基，或异氰酸酯，或硫氰酸酯或异硫氰酸酯，或羟基，或硝基，或CF3，或Cl，或Br，或F，或可交联的基团，或者具有5至40个环原子的取代或未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，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。
更优地，R31-R36可以相互独立地是H、或者具有1至10个C原子的直链烷基、烷氧基或硫代烷氧基，或者具有3至10个C原子的支链或环状的烷基、烷氧基或硫代烷氧基，或者是取代或无取代的甲硅烷基，或具有1至10个C原子的取代的酮基，或具有2至10个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，或氰基(-CN)，或氨基甲酰基(-C(＝O)NH2)，或卤甲酰基(-C(＝O)-X，其中，X代表卤素原子)，或甲酰基(-C(＝O)-H)，或异氰基，或异氰酸酯，或硫氰酸酯或异硫氰酸酯，或羟基，或硝基，或CF3，或Cl，或Br，或F，或可交联的基团，或者具有5至20个环原子的取代或未取代的芳族或杂芳族环系，或具有5至20个环原子的芳氧基或杂芳氧基基团，或这些体系的组合，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。
在一些较为优先的实施例中，单元A选自以下结构：
Figure PCTCN2017112707-appb-000009
在其中一些实施例中，R11-R16中至少一个含有以下结构中的一个：
Figure PCTCN2017112707-appb-000010
其中，
R41-R49和R410-R433分别独立地是H，或者具有1至20个C原子的直链烷基、烷氧基或硫代烷氧基，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，或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，或氰基(-CN)，或氨基甲酰基(-C(＝O)NH2)，或卤甲酰基(-C(＝O)-X，其中，X代表卤素原子)，或甲酰基(-C(＝O)-H)，或异氰基，或异氰酸酯，或硫氰酸酯或异硫氰酸酯，或羟基，或硝基，或CF3，或Cl，或Br，或F，或可交联的基团，或者具有5至40个环原子的取代或未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，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。
更优地，R41-R49和R410-R431分别独立地是H，或者具有1至10个C原子的直链烷基、烷氧基或硫代烷氧基，或者具有3至10个C原子的支链或环状的烷基、烷氧基或硫代烷氧基，或者是取代或无取代的甲硅烷基，或具有1至10个C原子的取代的酮基，或具有2至10个C原子的烷氧基羰基，或具有7至10个C原子的芳氧基羰基，或氰基(-CN)，或氨基甲酰基(-C(＝O)NH2)，或卤甲酰基(-C(＝O)-X，其中，X代表卤素原子)，或甲酰基(-C(＝O)-H)，或异氰基，或异氰酸酯，或硫氰酸酯或异硫氰酸酯，或羟基，或硝基，或CF3，或Cl，或Br，或F，或可交联的基团，或者具有5至20个环原子的取代或未取代的芳族或杂芳族环系，或具有5至20个环原子的芳氧基或杂芳氧基基团，或这些体系的组合，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。
m为0-3的整数，n、p、s分别独立地为0-4的整数，t、q分别独立地为0-5的整数。
单元P是具有3到8个C原子的饱和环烷烃。优选为4到6个C原子的饱和环烷烃。更优为5到6个C原子的饱和环烷烃。
L表示单键或连接基团。连接基团可以是具有5至40个环原子的取代或未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，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。
在一个优先的实施例中，L表示单键。
在另一个优先的实施例中，L是具有5至20个环原子的取代或未取代的芳族或杂芳族环系，或具有5至20个环原子的芳氧基或杂芳氧基基团，或这些体系的组合，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。
在另一个更优的实施例中，L是具有5至10个环原子的取代或未取代的芳族或杂芳族环系，或具有5至10个环原子的芳氧基或杂芳氧基基团，或这些体系的组合，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。
虚线表示与其它基团连接的单键。
在某些优选的实施例中，上述的连接基团L可包含如下结构基团中的一种或多种组合：
Figure PCTCN2017112707-appb-000011
其中，
A1、A2、A3、A4、A5、A6、A7、A8分别独立表示CR3或N；
Y1选自CR4R5、SiR4R5、NR3、C(＝O)、S或O；
R3、R4、R5分别独立地是H、或具有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原子的取代的酮基基团，或具有2至20个C原子的烷氧基羰基基团，或具有7至20个C原子的芳氧基羰基基团，或氰基基团(-CN)，或氨基甲酰基基团(-C(＝O)NH2)，或卤甲酰基基团(-C(＝O)-X，其中，X代表卤素原子)，或甲酰基基团(-C(＝O)-H)，或异氰基基团，或异氰酸酯基团，或硫氰酸酯基团或异硫氰酸酯基团，或羟基基团，或硝基基团，或CF3基团，或Cl，或Br，或F，或可交联的基团或者具有5至40个环原子的取代或未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，其中一个或多个基团R3，R4，R5可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环。
在一个更加优选的实施例中，所述的连接基团L优选自如下结构基团中的一种，其中环上的H可以被任意取代：
Figure PCTCN2017112707-appb-000012
在一些较为优先的实施例中，所述稠环环合物具有如通式(II)所示的结构：
Figure PCTCN2017112707-appb-000013
其中，
X1、X2、单元A，R12、R16与上述相同。
在另一个更加优先的实施例中，所述的稠环化合物，具有如通式(II-1)-(II-14)之一所示的结构：
Figure PCTCN2017112707-appb-000014
其中，
X1、X2、R12、R16与上述相同。
Z选自CR32R33，SiR34R35，NR36，C(＝O)，S，S(＝O)2，或O，且R32-R36与上述相同。
在其中一些实施例中，所述X1和X2优先分别独立地选自CR21R22，且R21、R22与上述相同。更优地是选自C(CH3)2。
在优先的一个实施例中，通式(II-6)-(II-12)中，Z为O原子。
在一个比较优先的实施例中，所述稠环化合物中的H至少部分被氘代，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。
按照本发明的一种稠环化合物，其具体的例子如下，但不仅限于此
Figure PCTCN2017112707-appb-000015
Figure PCTCN2017112707-appb-000016
Figure PCTCN2017112707-appb-000017
Figure PCTCN2017112707-appb-000018
本发明还涉及一种所述稠环化合物的合成方法，包括使用含有活性基团的原料进行反应。这些活性原料包含至少一种离去基团，例如，溴，碘，硼酸或硼酸酯。形成C-C连接的适当的反应是本领域技术人员熟知的并描述于文献中，特别适当和优选的偶联反应是SUZUKI，STILLE和HECK偶联反应。
本发明还进一步涉及一种高聚物，其中，所述高聚物的重复单元包括上述稠环化合物失去至少一个氢原子后形成的基团。在某些实施例中，所述的高聚物是非共轭高聚物。在某些实施例中，所述稠环化合物失去至少一个氢原子后形成的基团在所述高聚物的侧链上。在另一个优选的实施例中，所述的高聚物是共轭高聚物
本发明还提供一种混合物，包括如上所述稠环化合物或高聚物，和第二有机功能材料。所述第二有机功能材料可选于空穴(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)、热激发延迟荧光材料(TADF材料)及有机染料中的一种或多种。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。
在一个优先优选的实施例中，所述第二有机功能材料是荧光主体材料(或单重态基质材料)所述稠环化合物或所述高聚物可以作为客体，其重量百分比≤15wt％，较好是≤12wt％，更好是≤9wt％，更更好是≤8wt％，最好是≤7wt％。
在一个较为优先优选的实施例中，所述第二有机功能材料为荧光发光体(或单重态发光体)和荧光主体材料。在这种实施例中，所述稠环化合物或所述高聚物可以作为辅助发光材料，其与所述荧光发光体的重量比为从1:2到2:1。
某些实施例中，所述第二有机功能材料是TADF材料。
在另一些优选的实施例中，所述第二有机功能材料是HTM材料。
下面对HTM，单重态基质材料，单重态发光体和TADF材料作一些较详细的描述(但不限于此)。
1.HIM/HTM/EBM
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。另外，合适的HIM也包括自组装单体,如含有膦酸和sliane衍生物的化合物；金属络合物和交联化合物等。
电子阻挡层(EBL)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。在一个优先的实施方案中，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，同时，EBM有空穴传输功能。通常具有高的LUMO能级的HIM/HTM材料可以作为EBM。
可用作HIM，HTM或EBM的环芳香胺衍生化合物的例子包括(但不限于)如下的一般结构：
Figure PCTCN2017112707-appb-000019
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、非那烯、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、恶三唑、二恶唑、噻二唑、吡啶、哒嗪、嘧啶、吡嗪、三嗪、恶嗪、恶噻嗪、恶二嗪、吲哚、苯并咪唑、吲唑、吲哚嗪、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、二苯并硒吩、苯并硒吩、苯并呋喃吡啶、吲哚咔唑、吡啶吲哚、吡咯二吡啶、呋喃二吡啶、苯并噻吩吡啶、噻吩吡啶、苯并硒吩吡啶和硒吩二吡啶；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、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 PCTCN2017112707-appb-000020
n是1到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例子可参见US3567450,US4720432,US5061569,US3615404,和US5061569.
可用作HTM或HIM的金属络合物的例子包括(但不限于)如下的一般结构:
Figure PCTCN2017112707-appb-000021
M是一金属,有大于40的原子量；
(Y1-Y2)是一两齿配体,Y1和Y2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；m+n是此金属的最大配位数。
在一个实施例中，(Y1-Y2)是2-苯基吡啶衍生物.
在另一个实施例中,(Y1-Y2)是一卡宾配体.
在另一个实施例中,M选于Ir、Pt、Os和Zn.
在另一个方面，金属络合物的HOMO大于-5.5eV(相对于真空能级).
下面列出合适的可作为HIM/HTM化合物的例子:
Figure PCTCN2017112707-appb-000022
Figure PCTCN2017112707-appb-000023
2.单重态基质材料(Singlet Host)
单重态主体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主体,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。
作为单重态主体材料使用的有机化合物的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、萉、菲、芴、芘、屈、苝、薁；芳香杂环化合物，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、吲哚咔唑、吡啶吲哚、吡咯二吡啶、吡唑、咪唑、三氮唑、异恶唑、噻唑、恶二唑、恶三唑、二恶唑、噻二唑、吡啶、哒嗪、嘧啶、吡嗪、三嗪、恶嗪、恶噻嗪、恶二嗪、吲哚、苯并咪唑、吲唑、吲哚嗪、苯并恶唑、苯异恶唑、苯并噻唑、喹啉、异喹啉、噌啉、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、呋喃二吡啶、苯并噻吩吡啶、噻吩二吡啶、苯并硒吩吡啶和硒吩二吡啶；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。
在一个优先的实施方案中，单重态主体材料可选于包含至少一个以下基团的化合物：
Figure PCTCN2017112707-appb-000024
Figure PCTCN2017112707-appb-000025
其中，R1可相互独立地选于如下的基团：氢、烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基和杂芳基；Ar1是芳基或杂芳基，它与上述的HTM中定义的Ar1意义相同；n是一个从0到20的整数；X1-X8选于CH或N；X9和X10选于CR1R2或NR1。
在下面的表中列出一些蒽基单重态主体材料的例子：
Figure PCTCN2017112707-appb-000026
3.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，例如在JP2913116B和WO2001021729A1中公开的苯乙烯胺及其衍生物，和在WO2008/006449和WO2007/140847中公开的茚并芴及其衍生物。
在一个优先的实施方案中,单重态发光体可选自一元苯乙烯胺，二元苯乙烯胺，三元苯乙烯胺，四元苯乙烯胺，苯乙烯膦，苯乙烯醚和芳胺。
一个一元苯乙烯胺是指一化合物,它包含一个无取代或取代的苯乙烯基组和至少一个胺，最好是芳香胺。一个二元苯乙烯胺是指一化合物,它包含二个无取代或取代的苯乙烯基组和至少一个胺，最好是芳香胺。一个三元苯乙烯胺是指一化合物,它包含三个无取代或取代的苯乙烯基组和至少一个胺，最好是芳香胺。一个四元苯乙烯胺是指一化合物,它包含四个无取代或取代的苯乙烯基组和至少一个胺，最好是芳香胺。一个优选的苯乙烯是二苯乙烯,其可能会进一步被取代。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 的无取代或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先选于稠环系统，并最好有至少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。一个芳香蒽胺是指一化合物，其中一个二元芳基胺基团直接联到蒽上,最好是在9的位置上。一个芳香蒽二胺是指一化合物，其中二个二元芳基胺基团直接联到蒽上,最好是在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好联到芘的1或1,6位置上.
基于乙烯胺及芳胺的单重态发光体的例子,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特此上述列出的专利文件中的全部内容并入本文作为参考。
基于均二苯乙烯极其衍生物的单重态发光体的例子有US 5121029。
进一步的优选的单重态发光体可选于茚并芴-胺和茚并芴-二胺，如WO 2006/122630所公开的，苯并茚并芴-胺和苯并茚并芴-二胺，如WO 2008/006449所公开的，二苯并茚并芴-胺和二苯并茚并芴-二胺，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)，萘,四苯，氧杂蒽，菲,芘(如2,5,8,11-四-t-丁基苝)，茚并芘，苯撑如(4,4’-双(9-乙基-3-咔唑乙烯基)-1,1’-联苯)，二茚并芘,十环烯,六苯并苯,芴，螺二芴,芳基芘(如US20060222886)，亚芳香基乙烯(如US5121029，US5130603),环戊二烯如四苯基环戊二烯,红荧烯，香豆素，若丹明，喹吖啶酮，吡喃如4(二氰基亚甲基)-6-(4-对二甲氨基苯乙烯基-2-甲基)-4H-吡喃(DCM),噻喃,双(吖嗪基)亚胺硼化合物(US 2007/0092753 A1),双(吖嗪基)亚甲基化合物,carbostyryl化合物,噁嗪酮,苯并恶唑,苯并噻唑,苯并咪唑及吡咯并吡咯二酮。一些单重态发光体的材料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。特此将上述列出的专利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单重态发光体的例子:
Figure PCTCN2017112707-appb-000027
4.热激发延迟荧光发光材料(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(ΔEst)，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 PCTCN2017112707-appb-000028
Figure PCTCN2017112707-appb-000029
出现以上有机功能材料的出版物为公开的目的以参考方式并入本申请。
在一个优选的实施方案中，所述稠环化合物或高聚物用于蒸镀型OLED器件。用于这个目的，所述稠环化合物或高聚物的分子量≤1000g/mol，优选≤900g/mol，很优选≤850g/mol，更优选800≤g/mol，最优选≤700g/mol。
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，所述稠环化合物或高聚物的分子量≥700g/mol，优选≥800g/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，所述稠环化合物或高聚物在25℃时，在甲苯中的溶解度≥2mg/ml，优选≥3mg/ml，最优选≥5mg/ml。
本发明还提供一种组合物，包括所述稠环化合物或高聚物，及第一有机溶剂。
在一些实施方案中，按照本发明的一种组合物，其中所述的稠环化合物可作为单重态发光体材料。
在另一些实施方案中，按照本发明的一种组合物，进一步包含一主体材料。
在一个优先的实施例中，按照本发明的一种组合物进一步包含有一种主体材料和一种单重态发光体。
在另一个优先的实施例中，按照本发明的一种组合物进一步包含有至少两种主体材料。
在另一个优先的实施例中，按照本发明的一种组合物进一步包含有一种主体材料和一种热激活延迟荧光发光材料。
在另一些优先的实施方案中，按照本发明的一种组合物进一步包含有一种空穴传输材料(HTM)，更加优先的，所述的HTM包含有一可交联基团。
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％的稠环化合物，较好的是0.1至15wt％，更好的是0.2至10wt％，最好的是0.25至5wt％的稠环化合物。
在一些优先的实施方案中，所述第一有机溶剂选自芳族或杂芳族、酯、芳族酮或芳族醚、脂肪族酮或脂肪族醚、脂环族或烯烃类化合物，或硼酸酯或磷酸酯等无机酯类化合物，或两种及两种以上溶剂的混合物。
在另一些优先的实施方案中，按照本发明的一种组合物，其中包含至少50wt％的芳族或杂芳族溶剂；优选至少80wt％的芳族或杂芳族溶剂；特别优选至少90wt％的的芳族或杂芳族溶剂。
按照本发明的基于芳族或杂芳族的第一有机溶剂的例子有，但不限于：1-四氢萘酮、3-苯氧基甲苯、苯乙酮、1-甲氧基萘、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、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、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、二苯醚、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、2-苯氧基甲醚、2-苯氧基四氢呋喃、乙基-2-萘基醚、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。
在另一些实施例中，适当的和优选的第一有机溶剂是脂肪族、脂环族或芳烃族，胺，硫醇，酰胺，腈，酯，醚，聚醚，醇，二醇或多元醇。
在另一些实施例中，醇代表适当类别的第一有机溶剂。优选的醇包括烷基环己醇，特别是甲基化的脂肪族醇，萘酚等。
所述的第一有机溶剂可以是环烷烃，例如十氢化萘。
所述的第一有机溶剂可以是单独使用，也可以是作为两种或多种有机溶剂的混合物使用。
在某些实施例中，按照本发明的组合物，包括所述稠环化合物或高聚物，及至所述第一有机溶剂，还可进一步包括第二有机溶剂，所述第二有机溶剂的例子，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。
一些优选的实施例中，特别适合本发明的第一有机溶剂和第二有机溶剂是汉森(Hansen)溶解度参数在以下范围内的溶剂：
δd(色散力)在17.0～23.2MPa1/2的范围，尤其是在18.5～21.0MPa1/2的范围；
δp(极性力)在0.2～12.5MPa1/2的范围，尤其是在2.0～6.0MPa1/2的范围；
δh(氢键力)在0.9～14.2MPa1/2的范围，尤其是在2.0～6.0MPa1/2的范围。
按照本发明的组合物，其中所述第一有机溶剂和所述第二有机溶剂在选取时需考虑其沸点参数。在一个实施例中，所述第一有机溶剂和所述第二有机溶剂的沸点≥150℃；优选为≥180℃；较优选为≥200℃；更优为≥250℃；最优为≥275℃或≥300℃。这些范围内的沸点对防止喷墨印刷头的喷嘴堵塞是有益的。所述第一有机溶剂和所述第二有机溶剂可从组合物体系中蒸发，以形成包含功能材料薄膜。
在一些优先的实施方案中，按照本发明的一种组合物，其特征在于
1)其粘度在25℃时，在1cPs(毫帕·秒)到100cPs范围，和/或
2)其表面张力在25℃时，在19dyne/cm(达因/厘米)到50dyne/cm范围。
按照本发明的组合物，其中所述第一有机溶剂和所述第二有机溶剂在选取时需考虑其表面张力参数。合适的油墨表面张力参数适合于特定的基板和特定的印刷方法。例如对喷墨印刷，在一个优选的实施例中，所述的所述第一有机溶剂和所述第二有机溶剂在25℃下的表面张力 约在19dyne/cm到50dyne/cm范围；更优为在22dyne/cm到35dyne/cm范围；最优为在25dyne/cm到33dyne/cm范围。
在一个优选的实施例中，按照本发明的油墨在25℃下的表面张力约在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。
按照本发明的组合物，其中所述第一有机溶剂和所述第二有机溶剂在选取时需考虑其油墨的粘度参数。粘度可以通过不同的方法调节，如通过合适的有机溶剂的选取和油墨中功能材料的浓度。在一个优选的实施例中，所述的所述第一有机溶剂和所述第二有机溶剂的粘度低于100cps；更优为低于50cps；最优为为1.5到20cps。这里的粘度是指在印刷时的环境温度下的粘度，一般在15-30℃，较好的是18-28℃，更好是20-25℃，最好是23-25℃。如此配制的组合物将特别适合于喷墨印刷。
在一个优选的实施例中，按照本发明的组合物，在25℃下的粘度约在1cps到100cps范围；更好是在1cps到50cps范围；最好是在1.5cps到20cps范围。
满足上述沸点及表面张力参数及粘度参数的有机溶剂获得的油墨能够形成具有均匀厚度及组成性质的功能材料薄膜。
本发明的另一目的是提供上述稠环化合物或高聚物在有机电子器件中的应用。
所述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)。
本发明的另一目的是提供上述有机电子器件的制备方法。
包括：将上述稠环化合物、高聚物或混合物以蒸镀的方法于一基板上形成一功能层；或以共蒸镀的方法将上述稠环化合物、高聚物或混合物与所述第二有机功能材料一起于一基板上形成一功能层；或将上述的组合物用印刷或涂布的方法涂布于一基板上形成一功能层。其中，印刷或涂布的方法可选于(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。
本发明还涉及所述组合物作为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，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。首选的是凹版印刷，丝网印刷及喷墨印刷。凹版印刷，喷墨印刷 将在本发明的实施例中应用。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。
在一个实施例中，所述功能层的厚度可以在5nm-1000nm。
本发明进一步涉及一种有机电子器件，包括所述稠环化合物或高聚物；或至少包括一功能层，所述功能层是使用所述稠环化合物或高聚物制备而成。一般的，所述有机电子器件至少包含一个阴极，一个阳极及位于阴极和阳极之间的一个功能层，其中所述功能层包括如上所述的稠环化合物或高聚物。
在一个更为优选的实施例中，以上所述的有机电子器件是电致发光器件，特别是OLED。如图1所示，所述有机电子器件包括一基片(101)，一阳极(102)，至少一发光层(104)，和一阴极(106)。
基片(101)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(102)可包括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。阳极材料的例子包括但不限于：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，包括射频磁控溅射，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(106)可包括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。阴极材料的例子包括但不限于：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，包括射频磁控溅射，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)或空穴传输层(HTL)(103)、电子阻挡层(EBL)、电子注入层(EIL)或电子传输层(ETL)(105)、空穴阻挡层(HBL)。适合用于这些功能层中的材料在WO2010135519A1、US20090134784A1和WO2011110277A1中有详细的描述，特此将此3篇专利文件中的全部内容并入本文作为参考。
在一个优选的实施例中，按照本发明的发光器件中，其发光层(104)是通过真空蒸镀，其蒸镀源包含有所述稠环化合物或高聚物。
在另一个优选的实施例中，所述发光层(104)是通过打印所述组合物制备而成。
按照本发明的电致发光器件，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。
本发明还涉及所述有机电子器件在各种电子设备中的应用，包括，但不限于，显示设备，照明设备，光源，传感器等等。
本发明还涉及包含有所述有机电子器件的电子设备，包括，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。
实施例1：化合物1的合成
Figure PCTCN2017112707-appb-000030
在氮气流下带有冷凝管的500mL三口烧瓶中，加入5,11-二溴-7,7,9,9-四甲基-苯并茚并芴(5.2g,10mmol)、N-苯基-二苯并呋喃-4-胺(5.2g,20mmol)、Pd(dba)2(345mg,0.6mmol)、NaOtBu(5.76g,60mmol)、(tBu)3P(360mg,1.8mmol)和无水甲苯100mL，100℃搅拌过夜。 反应结束后，柱色谱纯化得淡黄色固体粉末(6.3g,72％)。
实施例2：化合物2的合成
Figure PCTCN2017112707-appb-000031
在氮气流下带有冷凝管的500mL三口烧瓶中，加入5,11-二溴-7,7,9,9-四甲基-苯并茚并芴(7.8g,15mmol)、N-(2,6二甲基苯基)-二苯并呋喃-4-胺(8.6g,30mmol)、Pd(dba)2(320mg,0.9mmol)、NaOtBu(8.6g,90mmol)、(tBu)3P(540mg,2.7mmol)和无水甲苯150mL，100℃搅拌过夜。反应结束后，柱色谱纯化得淡黄色固体粉末(10.7g,77％)。
实施例3：化合物3的合成
Figure PCTCN2017112707-appb-000032
在氮气流下装有冷凝管的500mL三口烧瓶中，加入5,11-二溴-7,7,9,9-四甲基-苯并茚并芴(6.2g,12mmol)、(9,9-二甲基芴-3-基)硼酸(5.7g,24mmol)、碳酸钾(9.9g,72mmol)、Pd(PPh3)4(800mg,0.7mmol)、150mL甲苯和35mL水，90℃搅拌过夜。反应结束后，水洗有机相，收集有机相旋干柱色谱纯化得白色固体产物(7.4g,83％)。
实施例4：化合物4的合成
Figure PCTCN2017112707-appb-000033
在氮气流下装有冷凝管的500mL三口烧瓶中，加入5,11-二溴-7,7,9,9-四甲基-苯并茚并芴(7.8g,15mmol)、(9,9-二甲基芴-2-基)硼酸(7.1g,30mmol)、碳酸钾(12.4g,90mmol)、Pd(PPh3)4(1.04g,0.9mmol)、150mL甲苯和45mL水，90℃搅拌过夜。反应结束后，水洗有机相，收集有机相旋干柱色谱纯化得白色固体产物(8.9g,80％)。
实施例5：化合物5的合成
Figure PCTCN2017112707-appb-000034
在氮气流下装有冷凝管的500mL三口烧瓶中，加入5,11-二溴-7,7,9,9-四甲基-苯并茚并芴(6.2g,12mmol)、(5a,8a-二甲基-9-苯基-5,5a,6,7,8,8a六氢-咔唑-6-基)硼酸(7.7g,24mmol)、碳酸钾(9.9g,72mmol)、Pd(PPh3)4(800mg,0.7mmol)、150mL甲苯和35mL水，90℃搅拌过夜。反应结束后，水洗有机相，收集有机相旋干柱色谱纯化得白色固体产物(8.4g,77％)。
实施例6：化合物6的合成
Figure PCTCN2017112707-appb-000035
在氮气流下带有冷凝管的500mL三口烧瓶中，加入7,13-二溴-9,9,11,11-四甲基-苯并二茚并菲(5.7g,10mmol)、N-苯基-二苯并呋喃-4-胺(5.2g,20mmol)、Pd(dba)2(345mg,0.6mmol)、NaOtBu(5.76g,60mmol)、(tBu)3P(360mg,1.8mmol)和无水甲苯100mL，100℃搅拌过夜。反应结束后，柱色谱纯化得淡黄色固体粉末(7.3g,79％)。
实施例7：化合物7的合成
Figure PCTCN2017112707-appb-000036
在氮气流下带有冷凝管的500mL三口烧瓶中，加入5,11-二溴-7,7,9,9-四甲基-茚并芴并苯并呋喃(5.6g,10mmol)、N-苯基-二苯并呋喃-4-胺(5.2g,20mmol)、Pd(dba)2(345mg,0.6mmol)、NaOtBu(5.76g,60mmol)、(tBu)3P(360mg,1.8mmol)和无水甲苯100mL，100℃搅拌过夜。反应结束后，柱色谱纯化得淡黄色固体粉末(7.8g,85％)。
实施例8：化合物8的合成
Figure PCTCN2017112707-appb-000037
在氮气流下带有冷凝管的500mL三口烧瓶中，加入5,11-二溴-7,7,9,9-四甲基-茚并芴并苯并呋喃(8.4g,15mmol)、N-苯基-二苯并呋喃-4-胺(7.8g,30mmol)、Pd(dba)2(520mg,0.9mmol)、NaOtBu(8.6g,90mmol)、(tBu)3P(540mg,2.7mmol)和无水甲苯150mL，100℃搅拌过夜。反应结束后，柱色谱纯化得淡黄色固体粉末(9.6g,70％)。
实施例9：化合物9的合成
Figure PCTCN2017112707-appb-000038
在氮气流下带有冷凝管的500mL三口烧瓶中，加入5,11-二溴-7,7,9,9-四甲基-茚并芴并苯并呋喃(5.6g,10mmol)、(5a,8a-二甲基-9-苯基-5,5a,6,7,8,8a六氢-咔唑-6-基)硼酸(6.4g,20mmol)、碳酸钾(8.2g,60mmol)、Pd(PPh3)4(690mg,0.6mmol)、120mL甲苯和30mL水，90℃搅拌过夜。反应结束后，水洗有机相，收集有机相旋干柱色谱纯化得白色固体产物(7.6g,80％)。
实施例10：化合物10的合成
Figure PCTCN2017112707-appb-000039
在氮气流下带有冷凝管的500mL三口烧瓶中，加入5,11-二溴-7,7,9,9-四甲基-茚并芴并苯并呋喃(5.6g,10mmol)、(9,9-二甲基芴-3-基)硼酸(4.7g,20mmol)、碳酸钾(8.2g,60mmol)、Pd(PPh3)4(690mg,0.6mmol)、100mL甲苯和30mL水，90℃搅拌过夜。反应结束后，水洗有机相，收集有机相旋干柱色谱纯化得白色固体产物(5.9g,75％)。
对比实施例1：对比化合物1的合成
Figure PCTCN2017112707-appb-000040
在氮气流下带有冷凝管的500mL三口烧瓶中，加入5,11-二溴7,7,13,13-四甲基-苯并茚并芴(7.8g,15mmol)、二苯胺(5.1g,30mmol)、Pd(dba)2(320mg,0.9mmol)、NaOtBu(8.6g,90mmol)、(tBu)3P(540mg,2.7mmol)和无水甲苯150mL，100℃搅拌过夜。反应结束后， 柱色谱纯化得淡黄色固体粉末(8.3g,80％)。
实施例11：OLED器件的制备与表征：
OLED器件各层所使用材料：
HIL：一种三芳胺衍生物；
HTL：一种三芳胺衍生物；
Host:蒽衍生物；
Dopant：化合物1-化合物10、对比化合物1。
具有ITO/HIL(50nm)/HTL(35nm)/Host：5％Dopant(25nm)/ETL(28nm)/LiQ(1nm)/Al(150nm)/阴极的OLED器件的制备步骤如下:
a、导电玻璃基片的清洗:首次使用时，可用多种溶剂进行清洗，例如氯仿、酮、异丙醇进行清洗，然后进行紫外臭氧等离子处理；
b、HIL(50nm)，HTL(35nm)，EML(25nm)、ETL(28nm)：在高真空(1×10-6毫巴，mbar)中热蒸镀而成。
c、阴极:LiQ/Al(1nm/150nm)在高真空(1×10-6毫巴)中热蒸镀而成；
d、封装:器件在氮气手套箱中用紫外线硬化树脂封装。
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，采用化合物1-化合物10作为EML层发光体所制备蓝光器件的色坐标更优于对比化合物1，例如化合物7所制备器件的色坐标为(0.148,0.077)；此外，采用化合物1-化合物10作为EML层发光体所制备蓝光器件的发光效率都在6-8cd/A范围，具有更加优异的发光效率；在器件寿命方面，采用化合物1-化合物10作为EML层发光体所制备蓝光器件的寿命更加优于对比化合物1，例如化合物7所制备器件在1000nits下的T95大于1500小时。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (13)

  1. 一种如通式(I)所示的稠环化合物：
    Figure PCTCN2017112707-appb-100001
    其中，
    X1和X2相同或不同的是CR21R22、NR23、O或S；
    R11-R16、R21-R23是H或者具有1至20个C原子的直链烷基、烷氧基或硫代烷氧基，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，或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，或氰基(-CN)，或氨基甲酰基(-C(＝O)NH2)，或卤甲酰基(-C(＝O)-X，其中，X代表卤素原子)，或甲酰基(-C(＝O)-H)，或异氰基，或异氰酸酯，或硫氰酸酯或异硫氰酸酯，或羟基，或硝基，或CF3，或Cl，或Br，或F，或可交联的基团，或者具有5至40个环原子的取代或未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；
    单元A选自具有5至40个环原子的取代或未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。
  2. 根据权利要求1所述的稠环化合物，其特征在于，所述单元A选自以下结构中的一种：
    Figure PCTCN2017112707-appb-100002
    其中，
    X是CR31或N，多个X相同或不同；
    Y选自CR32R33，SiR34R35，NR36，C(＝O)，S，S(＝O)2，或O；
    R31-R36分别独立地是H或者具有1至20个C原子的直链烷基、烷氧基或硫代烷氧基，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，或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，或氰基(-CN)，或氨基甲酰基(-C(＝O)NH2)，或卤甲酰基(-C(＝O)-X，其中，X代表卤素原子)，或甲酰基(-C(＝O)-H)，或异氰基，或异氰酸酯，或硫氰酸酯或异硫氰酸酯，或羟基，或硝基，或CF3，或Cl，或Br，或F，或可交联的基团，或者具有5至40个环原子的取代或未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。
  3. 根据权利要求1所述的稠环化合物，其特征在于，R11-R16中至少一个含有以下结构的一个：
    Figure PCTCN2017112707-appb-100003
    其中，
    R41-R49和R410-R433分别独立地是H或者具有1至20个C原子的直链烷基、烷氧基或硫代烷氧基，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，或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，或氰基(-CN)，或氨基甲酰基(-C(＝O)NH2)，或卤甲酰基(-C(＝O)-X，其中，X代表卤素原子)，或甲酰基(-C(＝O)-H)，或异氰基，或异氰酸酯，或硫氰酸酯或异硫氰酸酯，或羟基，或硝基，或CF3，或Cl，或Br，或F，或可交联的基团，或者具有5至40个环原子的取代或未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；
    m为0-3的整数，n、p和s分别独立地为0-4的整数，t和q分别独立地为0-5的整数；
    P是具有3到8个C原子的饱和环烷烃；
    L表示单键或连接基团，所述连接基团是具有5至40个环原子的取代或未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；
    L与通式(I)的稠环连接。
  4. 根据权利要求1-3任一项所述的稠环化合物，其特征在于，具有如通式(II)所示的结构：
    Figure PCTCN2017112707-appb-100004
  5. 根据权利要求1-4任一项所述的稠环化合物，其特征在于，具有如通式(II-1)-(II-7)之一所示的结构：
    Figure PCTCN2017112707-appb-100005
    Figure PCTCN2017112707-appb-100006
  6. 根据权利要求1-5任一项所述的稠环化合物，其特征在于，X1和X2分别独立地为CR21R22。
  7. 根据权利要求1-6任一项所述的稠环化合物，其特征在于，至少部分H被氘代。
  8. 一种高聚物，其特征在于，所述重复单元包含有如权利要求1至7任一项所述的稠环化合物失去至少一个氢原子后形成的基团。
  9. 一种混合物，其特征在于，包括如权利要求1至7任一项所述的稠环化合物和第二有机功能材料，或包括如权利要求8所述的高聚物和第二有机功能材料；所述第二有机功能材料选于空穴(也称电洞)注入或传输材料，空穴阻挡材料，电子注入或传输材料，电子阻挡材料，有机基质材料，单重态发光体(荧光发光体)，三重态发光体(磷光发光体)，热激发延迟荧光材料及有机染料中的至少一种。
  10. 一种组合物，其特征在于，包括如权利要求1至7任一项所述的稠环化合物和有机溶剂，或者包括如权利要求8所述的高聚物和有机溶剂，或者包括如权利要求9所述的混合物和有机溶剂。。
  11. 一种有机电子器件，包括如权利要求1至7任一项所述的稠环化合物或者包括如权利要求8所述的高聚物或者包括如权利要求9所述的混合物。
  12. 根据权利要求11所述的有机电子器件，其特征在于，所述有机电子器件为有机发光二极管、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、有机传感器或有机等离激元发射二极管。
  13. 根据权利要求11或12所述的有机电子器件，其特征在于，是有机电致发光器件，包括发光层，所述发光层包括如权利要求1至7任一项所述的稠环化合物或者包括如权利要求8所述的高聚物或者包括如权利要求9所述的混合物。
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