CN109790085A - Fused ring compound and preparation method and application - Google Patents

Fused ring compound and preparation method and application Download PDF

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CN109790085A
CN109790085A CN201780059501.9A CN201780059501A CN109790085A CN 109790085 A CN109790085 A CN 109790085A CN 201780059501 A CN201780059501 A CN 201780059501A CN 109790085 A CN109790085 A CN 109790085A
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杨曦
潘君友
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Guangzhou Chinaray Optoelectronic Materials Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/62—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with more than three condensed rings
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/72—Spiro hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/06—Ring systems of three rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials

Abstract

The present invention relates to a kind of fused ring compound and its preparation method and application, the fused ring compound is as shown in logical formula (I).Above-mentioned fused ring compound is located at the fluorescent emission of short wavelength with emission wavelength, and luminescent spectrum shows as the half-peak breadth for having narrow, so that the substance has navy blue fluorescent emission, and has high luminous efficiency.There is dark blue chromaticity coordinates, high luminous efficiency and long device lifetime by the organic electroluminescent device that object is prepared of such aromatic amine derivant.

Description

Fused ring compound and preparation method and application Technical field
The present invention relates to technical field of organic electroluminescence, more particularly to fused ring compound and preparation method and application.
This application claims on November 30th, 2016 submit Patent Office of the People's Republic of China, application No. is a kind of 201611086328.5, priority of the Chinese patent application of entitled " fused ring compound and its application in organic electronic device ", entire contents are hereby incorporated by reference in the application.
Background technique
Due to optics and electric property that organic semiconducting materials have diversity, manufacturing cost relatively low and excellent in synthesis, Organic Light Emitting Diode (OLED) has very big potentiality in the application aspect of photoelectric device (such as flat-panel monitor and illumination).
Organic electroluminescent phenomenon refers to the phenomenon that converting electrical energy into luminous energy using organic substance.Usually there are positive electrode and negative electrode using the organic electroluminescent device of organic electroluminescent phenomenon and among them comprising the structure of organic matter layer.In order to improve efficiency and the service life of organic electroluminescent device, organic matter layer has multilayered structure, and each layer includes different organic substance.Specifically, may include hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer etc..In this organic electroluminescent device, apply voltage between two electrodes, then inject hole from anode to organic matter layer, there is cathode once to inject electronics to organic matter, form exciton when injected holes meets with electronics, which issues light when returning ground state.This organic electroluminescent device has the characteristics such as self-luminous, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, high responsiveness.
In order to improve the luminous efficiency of organic electroluminescent device, the various luminescent material systems based on fluorescence and phosphorescence are developed, regardless of being fluorescent material or phosphor material, the exploitation of outstanding blue light material is all a huge challenge, in general, the organic light emitting diode reliability of blue-light fluorescent material used at present is higher.Nevertheless, the emission spectrum of most of blue-light fluorescent materials is wide at present, excitation purity is poor, it is unfavorable for high-end display, and the synthesis of this kind of fluorescent material is also more complex, is unfavorable for scale of mass production, while the OLED stability of this kind of blue fluorescent material also needs to further increase.Therefore the blue fluorescent material that exploitation has narrow band emission spectra, stability good, is on the one hand conducive to obtain the blue-light device of more long-life higher efficiency, is on the other hand conducive to the raising of colour gamut, and then improve display effect.
The blue-ray organic electroluminescent element luminescent layer of the prior art uses host-guest system structure.It is the condensed ring analog derivative based on anthracene as existing Blue-light emitting host material, as described in patent CN1914293B, CN102448945B, US2015287928A1 etc., however the problem that these compounds have luminous efficiency and brightness is insufficient and device lifetime is poor.As the blue light-emitting guest compound of the prior art, adoptable is aryl vinyl aminated compounds (WO 04/013073, WO 04/016575, WO 04/018587).However, the thermal stability of these compounds is poor, easily decomposes, cause the service life of device poor, be most important disadvantage in current industry.In addition, the excitation purity of these compounds is poor, it is difficult to realize navy blue shine.In addition, the patents such as US 7233019, KR 2006-0006760 disclose the organic electroluminescent device of the pyrene based compound using arylamine substituent group, but because the excitation purity of blue light is low, it is difficult to realize dark blue luminous therefore problematic in terms of the full color display for embodying natural colour.
Therefore, it still needs to be further improved material, especially luminophor, especially blue light-emitting compound.Enable blue light emitting material have navy blue shine, and they be it is heat-staple, good efficiency and service life are embodied in organic electroluminescent device, is easy to repeat in the manufacture and operation of device, and materials synthesis is simple.
Summary of the invention
A kind of application based on this, the object of the present invention is to provide fused ring compound and its in electronic device.
Specific technical solution is as follows:
The present invention provides a kind of fused ring compound as shown in logical formula (I):
Wherein,
X1It is CR1R2、O、S、NR3。
R1、R2Or R3It is each independently selected from: H, or the straight chained alkyl with 1 to 20 C atom, or the alkoxy with 1 to 20 C atom, or the thio alkoxy with 1 to 20 C atom, or branch or cricoid alkyl with 3 to 20 C atoms, or the alkoxy with 3 to 20 C atoms, or the thio alkoxy with 3 to 20 C atoms, either substituted or unsubstituted silicyl, or the substituted ketone group with 1 to 20 C atom, or the alkoxy carbonyl with 2 to 20 C atoms, or the aryloxycarbonyl with 7 to 20 C atoms, cyano, carbamoyl, halogen formoxyl, formoxyl, isocyano group, isocyanates, thiocyanates or isothiocyanates, hydroxyl, nitro, CF3, Cl, Br, F, crosslinkable group, or substituted or unsubstituted aromatics or heteroaromatic ring system with 5 to 40 annular atoms, or aryloxy group or heteroaryloxy group with 5 to 40 annular atoms；
The R1、R2Or R3Middle one or more group can form monocycle or polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding；
R11-R19、R110、R111Or R112In at least one contain the structure as shown in general formula (III), other substituent groups are each independently selected from: H, or the straight chained alkyl with 1 to 20 C atom, or the alkoxy with 1 to 20 C atom, or the thio alkoxy with 1 to 20 C atom, or branch or cricoid alkyl with 3 to 20 C atoms, or the alkoxy with 3 to 20 C atoms, or the thio alkoxy with 3 to 20 C atoms, either substituted or unsubstituted silicyl, or the substituted ketone group with 1 to 20 C atom, or the alkoxy carbonyl with 2 to 20 C atoms, or the aryloxycarbonyl with 7 to 20 C atoms, cyano, carbamoyl, halogen formoxyl, formoxyl, isocyano group, isocyanates, thiocyanates or isothiocyanates, hydroxyl Base, nitro, CF3, Cl, Br, F, crosslinkable group, or substituted or unsubstituted aromatics or heteroaromatic ring system with 5 to 40 annular atoms, or aryloxy group or heteroaryloxy group with 5 to 40 annular atoms；The R11-R19、R110、R111Or R112Middle one or more group can form monocycle or polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding；
The structure of the logical formula (III) are as follows:
Wherein,
R31、R32、R33Or R34It is each independently selected from: the straight chained alkyl with 1 to 20 C atom, or the alkoxy with 1 to 20 C atom, or the thio alkoxy with 1 to 20 C atom, or branch or cricoid alkyl with 3 to 20 C atoms, or the alkoxy with 3 to 20 C atoms, or the thio alkoxy with 3 to 20 C atoms, either substituted or unsubstituted silicyl, or the substituted ketone group with 1 to 20 C atom, or the alkoxy carbonyl with 2 to 20 C atoms, or the aryloxycarbonyl with 7 to 20 C atoms, cyano, carbamoyl, halogen formoxyl, formoxyl, isocyano group, isocyanates, thiocyanates or isothiocyanates, hydroxyl, nitro, CF3, Cl, Br, F, crosslinkable group, or substituted or unsubstituted aromatics or heteroaromatic ring system with 5 to 40 annular atoms, or aryloxy group or heteroaryloxy group with 5 to 40 annular atoms；
The R31、R32、R33Or R34Middle one or more group can form monocycle or polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding；
L indicates that singly-bound or linking group, the linking group are selected from the substituted or unsubstituted aromatics with 5 to 40 annular atoms or heteroaromatic ring system, or aryloxy group or heteroaryloxy group with 5 to 40 annular atoms；
One or more groups can form monocycle or polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding in the L；
M is 0,1,2 or 3；
N is 0,1,2,3 or 4；
Dotted line indicates the singly-bound connecting with other groups.
A kind of high polymer, the repetitive unit formed comprising above-mentioned fused ring compound.
A kind of mixture, include above-mentioned fused ring compound or above-mentioned high polymer and organic functional material, the organic functional material is optional in the injection of: hole or transmission material, hole barrier materials, electron injection or transmission material, electron-blocking materials, organic host materials, singlet emitters, triplet emitters, thermal excitation delayed fluorescence material and organic dyestuff.
A kind of composition includes above-mentioned fused ring compound or above-mentioned high polymer or said mixture and organic solvent.
A kind of organic electronic device, including above-mentioned fused ring compound or above-mentioned high polymer or said mixture.
Above-mentioned fused ring compound is located at the fluorescent emission of short wavelength with emission wavelength, and luminescent spectrum shows as the half-peak breadth for having narrow, so that the substance has navy blue fluorescent emission, and has high luminous efficiency.There is dark blue chromaticity coordinates, high luminous efficiency and long device lifetime by the organic electroluminescent device that object is prepared of such aromatic amine derivant.
Detailed description of the invention: Fig. 1 is the emitting device structure figure of an embodiment.
Specific embodiment:
To facilitate the understanding of the present invention, a more comprehensive description of the invention is given in the following sections with reference to the relevant attached drawings.Presently preferred embodiments of the present invention is given in attached drawing.But the invention can be realized in many different forms, however it is not limited to embodiment described herein.It is made the disclosure of the present invention more thorough and comprehensive on the contrary, purpose of providing these embodiments is.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.Term as used herein in the specification of the present invention, which is only for the purpose of describing specific embodiments, is not intended to limit the present invention.Term as used herein "and/or" includes any and all combinations of one or more related listed items.
In the present invention, material of main part, host material, Host material and Matrix material have the same meaning, and can be interchanged.
In the present invention, metallo-organic complex, metal organic complex, organometallic complex have the same meaning, and can be interchanged.
In the present invention, composition, printing ink, ink and ink have the same meaning, and can be interchanged.
In the present invention, " H " and hydrogen atom are had the same meaning, and " D " and D-atom have the same meaning.
In the present invention, " Dn" indicate n D, such as " D4" indicate that there are four D-atoms to replace, D1~D4Refer to and optionally contains 1-4 D-atom.
In the present invention, it " is optionally substituted " and is had the same meaning with " can also further be substituted ", be can be interchanged, referring to can be substituted, it can not also be substituted, such as: Ar6In one or more hydrogen atoms optionally replaced by D-atom and refer to Ar6In one or more hydrogen atoms can be replaced by D-atom, can not also be replaced by D-atom.
The present invention provides a kind of fused ring compound as shown in logical formula (I):
Wherein,
X1It is CR1R2、O、S、NR3。
In some preferential embodiments, X1It is CR1R2Or NR3。
In other preferential embodiments, X1It is O or S.
R1、R2Or R3It is each independently selected from: H, or the straight chained alkyl with 1 to 20 C atom, or the alkoxy with 1 to 20 C atom, or the thio alkoxy with 1 to 20 C atom, or branch or cricoid alkyl with 3 to 20 C atoms, or the alkoxy with 3 to 20 C atoms, or the thio alkoxy with 3 to 20 C atoms, either substituted or unsubstituted silicyl, or the substituted ketone group with 1 to 20 C atom, or the alkoxy carbonyl with 2 to 20 C atoms, or the aryloxycarbonyl with 7 to 20 C atoms, cyano (- CN), carbamoyl (- C (=O) NH2), halogen formoxyl (wherein X represents halogen atom to-C (=O)-X), formoxyl (- C (=O)-H), isocyano group, isocyanates, thiocyanates or isothiocyanates, hydroxyl, nitro, CF3, Cl, Br, F, crosslinkable group, or substituted or unsubstituted aromatics or heteroaromatic ring system with 5 to 40 annular atoms, or aryloxy group or heteroaryloxy group with 5 to 40 annular atoms；R1、R2Or R3Middle one or more group can form monocycle or polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding；One or more H in above-described various groups are optionally further replaced D.
In one embodiment, R1、R2Or R3It is each independently selected from: H, or the straight chained alkyl with 1 to 10 C atom, or the alkoxy with 1 to 10 C atom, or the thio alkoxy with 1 to 10 C atom, or branch or cricoid alkyl with 3 to 10 C atoms, or the alkoxy with 3 to 10 C atoms, or the thio alkoxy with 3 to 10 C atoms, either substituted or unsubstituted silicyl, or the substituted ketone group with 1 to 10 C atom, or the alkoxy carbonyl with 2 to 10 C atoms, or the aryloxycarbonyl with 7 to 10 C atoms, cyano (- CN), carbamoyl (- C (=O) NH2), halogen formoxyl (wherein X represents halogen atom to-C (=O)-X), formoxyl (- C (=O)-H), isocyano group, isocyanates, thiocyanates or isothiocyanates, hydroxyl, nitro, CF3, Cl, Br, F, crosslinkable group, or substituted or unsubstituted aromatics or heteroaromatic ring system with 5 to 20 annular atoms, or aryloxy group or heteroaryloxy group with 5 to 20 annular atoms；R1、R2Or R3Middle one or more group can form monocycle or polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding；One or more H in above-described various groups are optionally further replaced D.
R11-R19、R110、R111Or R112In at least one contain the structure as shown in general formula (III), other substituent groups are each independently selected from: H, or the straight chained alkyl with 1 to 20 C atom, or the alkoxy with 1 to 20 C atom, or the thio alkoxy with 1 to 20 C atom, or branch or cricoid alkyl with 3 to 20 C atoms, or the alkoxy with 3 to 20 C atoms, or the thio alkoxy with 3 to 20 C atoms, either substituted or unsubstituted silicyl, or the substituted ketone group with 1 to 20 C atom, or the alkoxy carbonyl with 2 to 20 C atoms, or the aryloxycarbonyl with 7 to 20 C atoms, cyano, carbamoyl, halogen formoxyl, formoxyl, isocyano group, isocyanates, thiocyanates or isothiocyanates, hydroxyl Base, nitro, CF3, Cl, Br, F, crosslinkable group, or substituted or unsubstituted aromatics or heteroaromatic ring system with 5 to 40 annular atoms, or aryloxy group or heteroaryloxy group with 5 to 40 annular atoms；The R11-R19、R110、R111Or R112Middle one or more group can form monocycle or polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding；The R11-R19、R110、R111Or R112One or more of optionally further replaced D；
In one embodiment, R11-R19、R110、R111Or R112In at least one contain the structure as shown in general formula (III), other substituent groups are each independently selected from: H, or the straight chained alkyl with 1 to 10 C atom, or the alkoxy with 1 to 10 C atom, or the thio alkoxy with 1 to 10 C atom, or branch or cricoid alkyl with 3 to 10 C atoms, or the alkoxy with 3 to 10 C atoms, or the thio alkoxy with 3 to 10 C atoms, either substituted or unsubstituted silicyl, or the substituted ketone group with 1 to 10 C atom, or the alkoxy carbonyl with 2 to 10 C atoms, or the aryloxycarbonyl with 7 to 10 C atoms, cyano (- CN), carbamoyl (- C (=O) NH2), halogen formoxyl (wherein X represents halogen atom to-C (=O)-X), formoxyl (- C (=O)-H), isocyano group, isocyanates, thiocyanates or isothiocyanates, hydroxyl, nitro, CF3, Cl, Br, F, crosslinkable group, or substituted or unsubstituted aromatics or heteroaromatic ring system with 5 to 20 annular atoms, or the aryloxy group with 5 to 20 annular atoms or miscellaneous Aryloxy group；R11-R19、R110、R111Or R112Middle one or more group can form monocycle or polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding；One or more H in above-described various groups are optionally further replaced D.
The structure of the logical formula (III) are as follows:
Wherein,
R31、R32、R33Or R34It is each independently selected from: the straight chained alkyl with 1 to 20 C atom, or the alkoxy with 1 to 20 C atom, or the thio alkoxy with 1 to 20 C atom, or branch or cricoid alkyl with 3 to 20 C atoms, or the alkoxy with 3 to 20 C atoms, or the thio alkoxy with 3 to 20 C atoms, either substituted or unsubstituted silicyl, or the substituted ketone group with 1 to 20 C atom, or the alkoxy carbonyl with 2 to 20 C atoms, or the aryloxycarbonyl with 7 to 20 C atoms, cyano (- CN), carbamoyl (- C (=O) NH2), halogen formoxyl (wherein X represents halogen atom to-C (=O)-X), formoxyl (- C (=O)-H), isocyano group, isocyanates, thiocyanates or isothiocyanates, hydroxyl, nitro, CF3, Cl, Br, F, crosslinkable group, or substituted or unsubstituted aromatics or heteroaromatic ring system with 5 to 40 annular atoms, or aryloxy group or heteroaryloxy group with 5 to 40 annular atoms；R31、R32、R33Or R34Middle one or more group can form monocycle or polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding；One or more H in above-described various groups are optionally further replaced D.
In one embodiment, R31、R32、R33Or R34It is each independently selected from the straight chained alkyl with 1 to 10 C atom, or the alkoxy with 1 to 10 C atom, or the thio alkoxy with 1 to 10 C atom, or branch or cricoid alkyl with 3 to 10 C atoms, or the alkoxy with 3 to 10 C atoms, or the thio alkoxy with 3 to 10 C atoms, either substituted or unsubstituted silicyl, or the substituted ketone group with 1 to 10 C atom, or the alkoxy carbonyl with 2 to 10 C atoms, or the aryloxycarbonyl with 7 to 10 C atoms, cyano (- CN), carbamoyl (- C (=O) NH2), halogen formoxyl (wherein X represents halogen atom to-C (=O)-X), formoxyl (- C (=O)-H), isocyano group, isocyanates, thiocyanates or isothiocyanates, hydroxyl, nitro, CF3, Cl, Br, F, crosslinkable group, or substituted or unsubstituted aromatics or heteroaromatic ring system with 5 to 20 annular atoms, or aryloxy group or heteroaryloxy group with 5 to 20 annular atoms；R31、R32、R33Or R34Middle one or more group can form monocycle or polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding；One or more H in above-described various groups can also be further replaced D.
L indicates singly-bound or linking group.Linking group can be substituted or unsubstituted aromatics or heteroaromatic ring system with 5 to 40 annular atoms, or aryloxy group or heteroaryloxy group with 5 to 40 annular atoms；One or more groups can form polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding in the L；One or more H in above-described various groups are optionally further replaced D.
In one embodiment, L is the deuterated or not deuterated substituted or unsubstituted aromatics with 5 to 30 annular atoms or heteroaromatic ring system or the deuterated or not deuterated aryloxy group or heteroaryloxy group with 5 to 30 annular atoms；One or more groups can form polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding in the L.
In another embodiment, L is the deuterated or not deuterated substituted or unsubstituted aromatics with 5 to 20 annular atoms or heteroaromatic ring system or the deuterated or not deuterated aryloxy group or heteroaryloxy group with 5 to 20 annular atoms；One or more groups can form polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding in the L.
In one embodiment, 0,1,2 or 3 m；In one embodiment, 0,1 or 2 m；In one embodiment, m is 0 or 1.
In one embodiment, 0,1,2,3 or 4 n；In one embodiment, 0,1,2 or 3 n；In one embodiment, 0,1 or 2 n；In one embodiment, n is 0 or 1.
Dotted line indicates the singly-bound connecting with other groups.
In one embodiment, R1-R3、R11-R19、R110、R111Or R112In at least one include aromatic ring or miscellaneous aromatic ring.In one embodiment, aromatic ring includes 5~15 carbon atoms in ring system；In one embodiment, aromatic ring includes 5~10 carbon atoms in ring system；In one embodiment, miscellaneous aromatic ring includes 2~15 carbon atoms and at least one hetero atom in ring system, and carbon atom and heteroatomic sum are at least 4.In one embodiment, miscellaneous aromatic ring includes 2~10 carbon atoms and at least one hetero atom in ring system, and carbon atom and heteroatomic sum are at least 4.Hetero atom is selected from Si, N, P, O, S and/or Ge；In one embodiment, hetero atom is selected from Si, N, P, O and/or S；In one embodiment, hetero atom is preferably selected from N, O or S.
Above-described aromatic ring or aromatic group refer to the alkyl for containing at least one aromatic ring, including monocyclic groups and polycyclic loop system.Above-described miscellaneous aromatic ring or heteroaromatic group refer to the alkyl (containing hetero atom) comprising at least one hetero-aromatic ring, including monocyclic groups and polycyclic loop system.These polycyclic rings can have two or more rings, and two of them carbon atom is shared by two adjacent rings, i.e. condensed ring.These polycyclic ring species, at least one is aromatics or heteroaromatic.For the purpose of the present invention, aromatic series or heteroaromatic ring system not only include the system of aromatic radical or heteroaryl perfume base, moreover, plurality of aryl or heteroaryl can also be interrupted (< 10% non-H atom by short non-aromatic unit, preferably smaller than 5% non-H atom, such as C, N or O atom)., two fluorenes of 9'- spiral shell, 9,9- diaryl fluorenes, triaryl amine, the systems such as diaryl ether, for the goal of the invention it also hold that being aromatic ring system.
Specifically, the example of aromatic group has: benzene, naphthalene, anthracene, phenanthrene, perylene, aphthacene, pyrene, BaP, triphenylene, acenaphthene, fluorenes, spiro fluorene and its derivative.
Specifically, the example of heteroaromatic group has: furans, benzofuran, dibenzofurans, thiophene, benzothiophene, dibenzothiophenes, pyrroles, pyrazoles, triazole, imidazoles, oxazole, oxadiazoles, thiazole, tetrazolium, indoles, carbazole, pyrrolo- imidazoles, pyrrolopyrrole, Thienopyrroles, thienothiophene, furans and pyrroles, furans and furans, thienofuran, benzo isoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinolin, cinnoline, quinoxaline, phenanthridines, primary pyridine, quinazoline, quinazolinone, and its derivative.
In one embodiment, according to the compound of logical formula (I), the R11-R19、R110、R111Or R112In at least one contain the structure as shown in general formula (III), other substituent groups are each independently selected from flowering structure:
R41-R49Or R410-R431It is each independently selected from: H, or the straight chained alkyl with 1 to 20 C atom, or the alkoxy with 1 to 20 C atom, or the thio alkoxy with 1 to 20 C atom, or branch or cricoid alkyl with 3 to 20 C atoms, or the alkoxy with 3 to 20 C atoms, or the thio alkoxy with 3 to 20 C atoms, either substituted or unsubstituted silicyl, or the substituted ketone group with 1 to 20 C atom, or the alkoxy carbonyl with 2 to 20 C atoms, or the aryloxycarbonyl with 7 to 20 C atoms, cyano (- CN), carbamoyl (- C (=O) NH2), halogen formoxyl (wherein X represents halogen atom to-C (=O)-X), formoxyl (- C (=O)-H), isocyano group, isocyanates, thiocyanates or isothiocyanates, hydroxyl, nitro, CF3Cl, Br, F, crosslinkable group, or substituted or unsubstituted aromatics or heteroaromatic ring system with 5 to 40 annular atoms, or aryloxy group or heteroaryloxy group with 5 to 40 annular atoms, wherein one or more groups can form monocycle or polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding；One or more H in above-described various groups are optionally further replaced D.
In one embodiment, R41-R49Or R410-R431It is each independently selected from: H, or the straight chained alkyl with 1 to 10 C atom, or the alkoxy with 1 to 10 C atom, or the thio alkoxy with 1 to 10 C atom, or branch or cricoid alkyl with 3 to 10 C atoms, or the alkoxy with 3 to 10 C atoms, or the thio alkoxy with 3 to 10 C atoms, either substituted or unsubstituted silicyl, or the substituted ketone group with 1 to 10 C atom, or the alkoxy carbonyl with 2 to 10 C atoms, or the aryloxycarbonyl with 7 to 10 C atoms, cyano (- CN), carbamoyl (- C (=O) NH2), halogen formoxyl (wherein X represents halogen atom to-C (=O)-X), formoxyl (- C (=O)-H), isocyano group, isocyanates, thiocyanates or isothiocyanates, hydroxyl, nitro, CF3Cl, Br, F, crosslinkable group, or substituted or unsubstituted aromatics or heteroaromatic ring system with 5 to 20 annular atoms, or aryloxy group or heteroaryloxy group with 5 to 20 annular atoms, wherein one or more groups can form monocycle or polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding；One or more H in above-described various groups are optionally further replaced D.
In one embodiment, 0,1,2 or 3 m；In one embodiment, 0,1 or 2 m；In one embodiment, m is 0 or 1.
In one embodiment, n, p or s are each independently 0,1,2,3 or 4；In one embodiment, n, p or s are each independently 0,1,2 or 3；In one embodiment, n, p or s are each independently 0,1 or 2；In one embodiment, n, p or s are each independently 0 or 1.
In one embodiment, t or q is 0,1,2,3,4 or 5；In one embodiment, t or q is 0,1,2 or 3；In one embodiment, t or q is 0,1 or 2；In one embodiment, t or q is 0 or 1.
A is the saturation cycloalkane with 3 to 8 C atoms.In one embodiment, A is the saturation cycloalkane with 4 to 6 C atoms.In one embodiment, A is the saturation cycloalkane with 5 to 6 C atoms.
In one embodiment, the structure for leading to formula (III) can be selected from:
R55-R59Or R511-R548It is independently selected from: the straight chained alkyl with 1 to 20 C atom, or the alkoxy with 1 to 20 C atom, or the thio alkoxy with 1 to 20 C atom, or branch or cricoid alkyl with 3 to 20 C atoms, or the alkoxy with 3 to 20 C atoms, or the thio alkoxy with 3 to 20 C atoms, either substituted or unsubstituted silicyl, or the substituted ketone group with 1 to 20 C atom, or the alkoxy carbonyl with 2 to 20 C atoms, or the aryloxycarbonyl with 7 to 20 C atoms, cyano (- CN), carbamoyl (- C (=O) NH2), halogen formoxyl (wherein X represents halogen atom to-C (=O)-X), formoxyl (- C (=O)-H), isocyano group, isocyanates, thiocyanates or isothiocyanates, hydroxyl, nitro, CF3, Cl, Br, F, crosslinkable group, or substituted or unsubstituted aromatics or heteroaromatic ring system with 5 to 40 annular atoms, or aryloxy group or heteroaryloxy group with 5 to 40 annular atoms；R55-R59Or R511-R548Middle one or more group can form monocycle or polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding；One or more H in above-described various groups are optionally further replaced D.
M is 0,1,2 or 3；In one embodiment, 0,1 or 2 m；In one embodiment, m is 0 or 1.
N is 0,1,2,3 or 4；In one embodiment, 0,1,2 or 3 n；In one embodiment, 0,1 or 2 n；In one embodiment, n is 0 or 1.
S is 1,2,3,4 or 5；In one embodiment, 0,1,2 or 3 s；In one embodiment, 0,1 or 2 s；In one embodiment, s is 0 or 1.
U is 0,1,2,3,4,5 or 6；In one embodiment, 0,1,2,3,4 or 5 u；In one embodiment, 0,1,2 or 3 u；In one embodiment, 0,1 or 2 u；In one embodiment, u is 0 or 1.
V is 0,1,2,3,4,5,6 or 7；In one embodiment, v is 0,1,2 or 3；In one embodiment, v is 0,1 or 2；In one embodiment, v is 0 or 1.
L indicates singly-bound or linking group.Linking group can be substituted or unsubstituted aromatics or heteroaromatic ring system with 5 to 40 annular atoms, or aryloxy group or heteroaryloxy group with 5 to 40 annular atoms；One or more groups can form polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding in the L；One or more H in above-described various groups are optionally further replaced D.
Dotted line indicates the singly-bound connecting with other groups.
In one embodiment, R55-R59Or R511-R548It is independently selected from: the straight chained alkyl with 1 to 10 C atom, or the alkoxy with 1 to 10 C atom, or the thio alkoxy with 1 to 10 C atom, or branch or cricoid alkyl with 3 to 10 C atoms, or the alkoxy with 3 to 10 C atoms, or the thio alkoxy with 3 to 10 C atoms, either substituted or unsubstituted silicyl, or the substituted ketone group with 1 to 10 C atom, or the alkoxy carbonyl with 2 to 10 C atoms, or the aryloxycarbonyl with 7 to 10 C atoms, cyano (- CN), carbamoyl (- C (=O) NH2), halogen formoxyl (wherein X represents halogen atom to-C (=O)-X), formoxyl (- C (=O)-H), isocyano group, isocyanates, thiocyanates or isothiocyanates, hydroxyl, nitro, CF3, Cl, Br, F, crosslinkable group, or substituted or unsubstituted aromatics or heteroaromatic ring system with 5 to 20 annular atoms, or aryloxy group or heteroaryloxy group with 5 to 20 annular atoms；R55-R59Or R511-R548Middle one or more group can form monocycle or polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding；One or more H in above-described various groups are optionally further replaced D.
In another embodiment, L is the deuterated or not deuterated substituted or unsubstituted aromatics with 5 to 30 annular atoms or heteroaromatic ring system, or the deuterated or not deuterated aryloxy group or heteroaryloxy group with 5 to 30 annular atoms, or the combination of these systems, wherein one or more groups can form polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding.
In another embodiment, L is the deuterated or not deuterated substituted or unsubstituted aromatics with 10 to 25 annular atoms or heteroaromatic ring system, or the deuterated or not deuterated aryloxy group or heteroaryloxy group with 10 to 25 annular atoms, or the combination of these systems, wherein one or more groups can form polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding.
In one embodiment, L linking group described in above each general formula structure is preferably selected from singly-bound.
In certain embodiments, above-mentioned linking group L includes following structural formula:
Wherein:
X1It is CR61Or N；
Y is selected from CR62R63, SiR64R65, NR66Or, C (=O), S or O；
R61-R66It is each independently selected from: H, or the straight chained alkyl with 1 to 20 C atom, or the alkoxy with 1 to 20 C atom, or the thio alkoxy with 1 to 20 C atom, or branch or cricoid alkyl with 3 to 20 C atoms, or the alkoxy with 3 to 20 C atoms, or the thio alkoxy with 3 to 20 C atoms, either substituted or unsubstituted silyl-group, or the substituted keto group with 1 to 20 C atom, or the alkoxycarbonyl groups with 2 to 20 C atoms, or the aryloxycarbonyl group with 7 to 20 C atoms, cyano group (- CN), carbamoyl group (- C (=O) NH2), halogen formyl group (wherein X represents halogen atom to-C (=O)-X), formyl group (- C (=O)-H); isocyano group group, isocyanate groups, thiocyanates group or isothiocyanates group; hydroxyl group, nitryl group, CF3Group, Cl, Br, F, crosslinkable group or substituted or unsubstituted aromatics or heteroaromatic ring system with 5 to 40 annular atoms, or aryloxy group or heteroaryloxy group with 5 to 40 annular atoms；R61-R66Middle one or more group R61, R62, R63, R64, R65, R66Monocycle or polycyclic aliphatic series or aromatic ring can be formed each other and/or with the ring of the group bonding.
In another embodiment, L linking group described in above each general formula structure is selected from flowering structure:
Wherein, dotted line indicates the singly-bound connecting with other groups.
In one embodiment, the compound has structure shown in logical formula (IV):
Wherein,
X1It is CR1R2、O、S、NR3。
In some preferential embodiments, X1It is CR1R2。
In other preferential embodiments, X1It is O or S.
R1、R2Or R3It is each independently selected from: H, or the straight chained alkyl with 1 to 20 C atom, or the alkoxy with 1 to 20 C atom, or the thio alkoxy with 1 to 20 C atom, or branch or cricoid alkyl with 3 to 20 C atoms, or the alkoxy with 3 to 20 C atoms, or the thio alkoxy with 3 to 20 C atoms, either substituted or unsubstituted silicyl, or the substituted ketone group with 1 to 20 C atom, or the alkoxy carbonyl with 2 to 20 C atoms, or the aryloxycarbonyl with 7 to 20 C atoms, cyano (- CN), carbamoyl (- C (=O) NH2), halogen formoxyl (wherein X represents halogen atom to-C (=O)-X), formoxyl (- C (=O)-H), isocyano group, isocyanates, thiocyanates or isothiocyanates, hydroxyl, nitro, CF3, Cl, Br, F, crosslinkable group, or substituted or unsubstituted aromatics or heteroaromatic ring system with 5 to 40 annular atoms, or aryloxy group or heteroaryloxy group with 5 to 40 annular atoms；R1、R2Or R3Middle one or more group can form monocycle or polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding；One or more H in above-described various groups are optionally further replaced D.
In one embodiment, lead in formula (IV), R1、R2Or R3It is each independently selected from: the straight chained alkyl with 1 to 10 C atom, or the alkoxy with 1 to 10 C atom, or the thio alkoxy with 1 to 10 C atom, or branch or cricoid alkyl with 3 to 10 C atoms, or the alkoxy with 3 to 10 C atoms, or the thio alkoxy with 3 to 10 C atoms, either substituted or unsubstituted silicyl, or the substituted ketone group with 1 to 10 C atom, or the alkoxy carbonyl with 2 to 10 C atoms, or the aryloxycarbonyl with 7 to 10 C atoms, cyano (- CN), carbamoyl (- C (=O) NH2), halogen formoxyl (wherein X represents halogen atom to-C (=O)-X), formoxyl (- C (=O)-H), isocyano group, isocyanates, thiocyanates or isothiocyanates, hydroxyl, nitro, CF3, Cl, Br, F, crosslinkable group, or substituted or unsubstituted aromatics or heteroaromatic ring system with 5 to 20 annular atoms, or aryloxy group or heteroaryloxy group with 5 to 20 annular atoms；R1、R2Or R3Middle one or more group can form monocycle or polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding；One or more H in above-described various groups are optionally further replaced D.
R13、R15Or R111As logical formula (I) defines.
In one embodiment, lead in formula (IV), R13、R15Or R111It is each independently selected from: H, or the straight chained alkyl with 1 to 10 C atom, or the alkoxy with 1 to 10 C atom, or the thio alkoxy with 1 to 10 C atom, or branch or cricoid alkyl with 3 to 10 C atoms, or the alkoxy with 3 to 10 C atoms, or the thio alkoxy with 3 to 10 C atoms, either substituted or unsubstituted silicyl, or the substituted ketone group with 1 to 10 C atom, or the alkoxy carbonyl with 2 to 10 C atoms, or the aryloxycarbonyl with 7 to 10 C atoms, cyano (- CN), carbamoyl (- C (=O) NH2), halogen formoxyl (wherein X represents halogen atom to-C (=O)-X), formoxyl (- C (=O)-H), isocyano group, isocyanates, thiocyanates or isothiocyanates, hydroxyl, nitro, CF3, Cl, Br, F, crosslinkable group, or substituted or unsubstituted aromatics or heteroaromatic ring system with 5 to 20 annular atoms, or aryloxy group or heteroaryloxy group with 5 to 20 annular atoms；R13、R15Or R111Middle one or more group can form monocycle or polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding；One or more H in above-described various groups are optionally further replaced D.
In one embodiment, the R13、R15Or R111At least one contains:
Other are each independently selected from hydrogen atom ,-NR21R22Or following group:
Wherein, the R21Or R22It is each independently selected from hydrogen atom or following group:
In one embodiment, the R21Or R22It is each independently selected from following group:
A kind of fused ring compound according to the invention, specific example is as follows, but is not limited only to this:
In certain embodiments, fused ring compound according to the invention, emission wavelength 300 between 800nm, preferably 350 between 600nm, preferably 400 between 500nm.
In one embodiment, fused ring compound according to the invention photoluminescence quantum efficiencies with higher, general >=15%, more excellent >=25%, more excellent >=35%, optimal >=50%.
In some preferential embodiments, glass transition temperature >=100 DEG C of fused ring compound according to the invention, preferably >=110 DEG C, more preferably >=120 DEG C, preferably >=140 DEG C.
In one embodiment, compound according to the invention is at least partly deuterated, and preferably 10% H is deuterated, and more preferably 20% H is deuterated, is that 30% H is deuterated very well, preferably 40% H is deuterated.
The invention further relates to a kind of high polymer, wherein at least one repetitive unit, which includes above-mentioned fused ring compound.In certain embodiments, the high polymer is non-conjugated highpolymer, wherein the structural unit as shown in logical formula (I) or (IV) is on side chain.In another embodiment, the high polymer is conjugated highpolymer.
The invention further relates to one kind according to the synthetic method of the organic compound of logical formula (I)-(IV), wherein the raw material containing active group is used to be reacted.These activated feedstocks include at least one leaving group, for example, bromine, iodine, boric acid or borate.The reaction appropriate for forming C-C connection is well known to those skilled in the art and is described in document that especially appropriate and preferred coupling reaction is SUZUKI, STILLE and HECK coupling reaction.
The present invention also provides a kind of mixtures, it include above-mentioned fused ring compound or high polymer and organic functional material, the organic functional material it is optional in: hole (also referred to as electric hole) injection or transmission material (HIM/HTM), hole barrier materials (HBM), electron injection or transmission material (EIM/ETM), electron-blocking materials (EBM), organic host materials (Host), singlet emitters (fluorescent illuminant), triplet emitters (phosphorescent emitter), thermal excitation delayed fluorescence material (TADF material) and organic dyestuff.Such as various organic functional materials are described later in detail in WO2010135519A1, US20090134784A1 and WO 2011110277A1, the full content in this 3 patent document is incorporated herein by reference hereby.
In one embodiment, the mixture includes above-mentioned fused ring compound or high polymer and fluorescent host material (or singlet state host material).Here above-mentioned fused ring compound or high polymer can be used as object, weight percent≤15wt%, preferably≤12wt%, more preferably≤9wt%, more more preferably≤8wt%, preferably≤7wt%.
In one embodiment, the mixture includes a kind of organic compound according to the invention or high polymer, another fluorescent illuminant (or singlet emitters) and a kind of fluorescent host material.In such an embodiment, organic compound according to the invention can be used as auxiliary light emission material, and the weight ratio with another fluorescent illuminant is from 1:2 to 2:1.
In some embodiments, the mixture includes a kind of organic compound according to the invention or high polymer and a kind of TADF material.
In further embodiments, the mixture includes above-mentioned fused ring compound or high polymer and a kind of HTM material.
Some more detailed descriptions (but not limited to this) are made to HTM, singlet state host material, singlet emitters and TADF material below.
1.HIM/HTM/EBM
Suitable organic HIM/HTM material is optional include following structural unit compound: phthalocyanine, porphyrin, amine, aromatic amine, biphenyl class triaryl amine, thiophene, bithiophene such as dithienothiophene and bithiophene, pyrroles, aniline, carbazole, indolocarbazole and their derivative.In addition, suitable HIM also includes self assembly monomer, such as compound containing phosphonic acids and sliane derivative；Metal complex and cross-linking compounds etc..
Electronic barrier layer (EBL) is used to stop the electronics from successive functional layers, especially luminescent layer.Comparison one does not have barrier layer Luminescent device, the presence of EBL normally results in the raising of luminous efficiency.The electron-blocking materials (EBM) of electronic barrier layer (EBL) are needed than successive functional layers, such as the higher LUMO of luminescent layer.In a preferential embodiment, HBM has the excited level bigger than adjacent emissive layers, such as singlet state or triplet, depends on illuminator, meanwhile, EBM has hole transfer function.Usually the HIM/HTM material with high lumo energy can be used as EBM.
The example that can be used as the cyclophane perfume (or spice) amine derivative compounds of HIM, HTM or EBM includes but is not limited to following general structure:
Each Ar1To Ar9Aromatic hydrocarbon ring compound can be independently selected from, such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, that non-alkene, phenanthrene, fluorenes, pyrene, bend, Azulene；Heteroaromatic compound, such as dibenzothiophenes, dibenzofurans, furans, thiophene, benzofuran, benzothiophene, carbazole, pyrazoles, imidazoles, triazole, isoxazole, thiazole, oxadiazoles, dislike triazole, dioxazole, thiadiazoles, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazines, dislike thiazine, oxadiazines, indoles, benzimidazole, indazole, indolizine, benzoxazoles, benzisoxazole, benzothiazole, quinoline, isoquinolin, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, azophenlyene, phenthazine, phenoxazine, dibenzo selenophen, benzo selenophen, benzofuran pyridine, indole carbazole, pyridine indoles, two pyridine of pyrroles, two pyridine of furans, benzothiophene pyridine, thiophene pyridine, two pyridine of benzo selenophen pyridine and selenophen；It include the group of 2 to 10 ring structures, they can be the aromatic hydrocarbon ring group or aromatic heterocycle group of identical or different type, and link together directly with one another or by least one group below, such as oxygen atom, nitrogen-atoms, sulphur atom, silicon atom, phosphorus atoms, boron atom, chain structural unit and aliphatic cyclic group.Wherein, each Ar can be further substituted, and substituent group is chosen as hydrogen, alkyl, alkoxy, amino, alkene, alkynes, aralkyl, miscellaneous alkyl, aryl and heteroaryl.
In one aspect, Ar1To Ar9It can be independently selected from comprising the group such as the following group:
N is 1 to 20 integer；X1To X8It is CH or N；Ar1As defined above.
The other example of cyclophane perfume (or spice) amine derivative compounds can be found in US3567450, US4720432, US5061569, US3615404, and US5061569.
The example that can be used as the metal complex of HTM or HIM includes but is not limited to following general structure:
M is a metal, there is the atomic weight greater than 40；
(Y1-Y2) it is one liang of tooth ligand, Y1And Y2Independently selected from C, N, O, P and S；L is an assistant ligand；M is an integer, value from 1 to this metal maximum coordination number；M+n is the maximum coordination number of this metal.
In one embodiment, (Y1-Y2) it is 2- phenylpyridine derivative
In another embodiment, (Y1-Y2) it is a carbenes
In another embodiment, M choosing is in Ir, Pt, Os and Zn.
On the other hand, the HOMO of metal complex is greater than -5.5eV (relative to vacuum level)
The example that suitably can be used as HIM/HTM compound is listed in following table:
2. singlet state host material (Singlet Host):
The example of singlet state material of main part is not particularly limited, and any organic compound may all be used as main body, as long as its singlet energy is higher than illuminator, especially singlet emitters or fluorescent illuminant.
The example of the organic compound used as singlet state material of main part can be selected from containing aromatic hydrocarbon ring compound, such as benzene, biphenyl, triphenyl, benzo, naphthalene, En, Fu, phenanthrene, fluorenes, pyrene, bend, Azulene；Heteroaromatic compound, such as dibenzothiophenes, dibenzofurans, dibenzo selenophen, furans, thiophene, benzofuran, benzothiophene, benzo selenophen, carbazole, indole carbazole, pyridine indoles, two pyridine of pyrroles, pyrazoles, imidazoles, triazole, isoxazole, thiazole, oxadiazoles, dislike triazole, dioxazole, thiadiazoles, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazines, dislike thiazine, oxadiazines, indoles, benzimidazole, indazole, indolizine, benzoxazoles, benzisoxazole, benzothiazole, quinoline, isoquinolin, cinnolines, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, azophenlyene, phenthazine, phenoxazine, benzofuran pyridine, two pyridine of furans, benzothiophene pyridine, two pyridine of thiophene, two pyridine of benzo selenophen pyridine and selenophen；Include the group of 2 to 10 ring structures, they can be it is identical or Different types of aromatic hydrocarbon ring group or aromatic heterocycle group, and link together directly with one another or by least one group below, such as oxygen atom, nitrogen-atoms, sulphur atom, silicon atom, phosphorus atoms, boron atom, chain structural unit and aliphatic cyclic group.
In one embodiment, singlet state material of main part is optional in the compound comprising at least one following group:
Wherein, R1It can select independently of each other in following group: hydrogen, alkyl, alkoxy, amino, alkene, alkynes, aralkyl, miscellaneous alkyl, aryl and heteroaryl；Ar1It is aryl or heteroaryl, Ar defined in it and above-mentioned HTM1Meaning is identical；N is an integer from 0 to 20；X1-X8It selects in CH or N；X9And X10It selects in CR1R2Or NR1。
The example of some anthryl singlet state material of main parts is listed in following table:
3. singlet emitters (Singlet Emitter)
Singlet emitters often have longer conjugated pi electron system.So far, there are many examples, such as the styrylamine disclosed in JP2913116B and WO2001021729A1 and its derivative, and the indenofluorene disclosed in WO2008/006449 and WO2007/140847 and its derivative.
In a preferential embodiment, singlet emitters can be selected from unitary styrylamine, binary styrylamine, ternary styrylamine, quaternary styrylamine, styrene phosphine, styrene ether and arylamine.
One unitary styrylamine refers to a compound, it includes a styryl group and at least one amine, preferably aromatic amine unsubstituted or replace.One binary styrylamine refers to a compound, it is comprising two unsubstituted or substitution styryl groups and extremely Few amine, preferably aromatic amine.One ternary styrylamine refers to a compound, it includes three styryl groups and at least one amine, preferably aromatic amine unsubstituted or replace.One quaternary styrylamine refers to a compound, it includes four styryl groups and at least one amine, preferably aromatic amine unsubstituted or replace.One preferred styrene is talan, may be further substituted.The definition of corresponding phosphine and ethers is similar to amine.Arylamine or aromatic amine refer to a kind of compound, the aromatic rings or heterocyclic ring system for directly coupling the unsubstituted of nitrogen comprising three or replacing.At least one in the loop system of these aromatic series or heterocycle is preferentially selected in fused ring system, and is preferably formed at least 14 aromatic ring atoms.Wherein preferred example has fragrant anthranylamine, fragrant anthradiamine, fragrant pyrene amine, fragrant pyrene diamines, fragrance amine in the wrong and fragrance diamines in the wrong.One fragrant anthranylamine refers to a compound, and one of binary arylamine group is directly linked on anthracene, preferably on 9 position.One fragrant anthradiamine refers to a compound, and wherein two binary arylamine group is directly linked on anthracene, preferably on 9,10 position.Fragrant pyrene amine, fragrant pyrene diamines, fragrance amine in the wrong is similar with the fragrance definition of diamines in the wrong, and wherein binary arylamine group is preferably linked to the 1 or 1 of pyrene, on 6 positions
The example of singlet emitters based on vinylamine and arylamine, it is also preferred example, it can be found in following patent documents: WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549, WO 2007/115610, US 7250532B2, DE 102005058557A1, CN 1583691A, JP 08053397A, the full content of US 6251531B1, US 2006/210830A, EP 1957606A1 and US 2008/0113101A1 hereby in the above-mentioned patent document listed is incorporated herein by reference.
The example of singlet emitters based on stibene extremely derivative has US 5121029.
Further preferred singlet emitters are optional in indenofluorene-amine and indenofluorene-diamines, as disclosed in WO 2006/122630, benzo indenofluorene-amine and benzo indenofluorene-diamines, as disclosed in WO 2008/006449, dibenzo indenofluorene-amine and dibenzo indenofluorene-diamines, as disclosed in WO2007/140847.
Other materials that can be used as singlet emitters have polycyclic aromatic hydrocarbon compounds, the derivative of especially following compound: anthracene such as 9, 10- bis- (2- naphthanthracene), naphthalene, four benzene, xanthene, it is luxuriant and rich with fragrance, pyrene (such as 2, 5, 8, tetra--t- butyl of 11-), indeno pyrene, penylene such as (4, 4 '-bis- (9- ethyl -3- carbazole vinyl) -1, 1 '-biphenyl), two indeno pyrenes, decacyclene, coronene, fluorenes, two fluorenes of spiral shell, aryl pyrene (such as US20060222886), arylene ethylene (such as US5121029, US5130603), cyclopentadiene such as tetraphenyl cyclopentadiene, rubrene, cumarin, rhodamine, quinacridone, pyrans such as 4 (dicyano methylene) -6- (4- is to dimethylaminostyryl -2- methyl) -4 H- pyrans (DCM), thiapyran, bis- (azine) imines boron compounds (US 2007/0092753A1), bis- (azine) methylene compounds, carbostyryl compound, oxazinone, benzoxazoles, benzothiazole, benzimidazole and pyrrolo-pyrrole-dione.The material of some singlet emitters can be found in following patent documents: US 20070252517A1, US 4769292, US 6020078, US 2007/0252517A1, US 2007/0252517A1.The full content in the above-mentioned patent document listed is incorporated herein by reference hereby.
The example of some suitable singlet emitters is listed in following table:
4. thermal excitation delayed fluorescence luminescent material (TADF material)
Traditional organic fluorescence materials can only be shone using 25% singlet exciton to be formed is electrically excited, and the internal quantum efficiency of device is lower (up to 25%).Although phosphor material passes through between being since the strong SO coupling in heavy atom center enhances, it can efficiently use and be electrically excited the singlet exciton to be formed and Triplet exciton, the internal quantum efficiency of device is made to reach 100%.But phosphor material is expensive, and stability of material is poor, and device efficiency the problems such as serious of roll-offing limits its application in OLED.Hot activation delayed fluorescence luminescent material is the third generation luminous organic material developed after organic fluorescence materials and organic phosphorescent material.Such material generally has small singlet-triplet poor (Δ Est), triplet excitons can by it is counter be between pass through be transformed into singlet exciton shine.This can make full use of the singlet exciton and triplet excitons that are electrically excited lower formation.Device internal quantum efficiency can reach 100%.Material structure is controllable simultaneously, and property is stablized, cheap woth no need to noble metal, in having a extensive future for the field OLED.
TADF material needs to have lesser singlet-triplet poor, preferably Δ Est < 0.3eV, and secondary is Δ Est < 0.2eV well, preferably Δ Est < 0.1eV.In a preferential embodiment, TADF material has smaller Δ Est, and in another preferential embodiment, TADF has preferable fluorescence quantum efficiency.Some TADF luminous material can be found in following patent documents: CN103483332 (A), TW201309696 (A), TW201309778 (A), TW201343874 (A), TW201350558 (A), US20120217869 (A1), WO2013133359 (A1), WO2013154064 (A1), Adach i, et.al.Adv.Mater., 21,2009,4802, Adachi, et.al.Appl.Phys.Lett., 98,2011,083302, Adachi, et.al.Appl.Phys.L Ett., 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, the full content in the above-mentioned patent listed or article file is incorporated herein by reference hereby.
The example of some suitable TADF luminescent materials is listed in following table:
The organic functional material publication appeared above is that disclosed purpose is incorporated herein in way of reference.
In one embodiment, above-mentioned pyrene class organic compound is for being deposited type OLED device.For this purpose, molecular weight≤1000g/mol of above-mentioned pyrene class organic compound.In one embodiment, molecular weight≤900g/mol of above-mentioned fused ring compound；In one embodiment, molecular weight≤850g/mol of above-mentioned fused ring compound；In one embodiment, molecular weight≤800g/mol of above-mentioned fused ring compound；In one embodiment, molecular weight≤700g/mol of above-mentioned fused ring compound.
Another object of the present invention is to provide material solution for printing OLED.
For this purpose, in one embodiment, molecular weight >=700g/mol of above-mentioned fused ring compound；In one embodiment, molecular weight >=800g/mol of above-mentioned fused ring compound；In one embodiment, molecular weight >=900g/mol of above-mentioned fused ring compound；In one embodiment, molecular weight >=1000g/mol of above-mentioned fused ring compound；In one embodiment, molecular weight >=1100g/mol of above-mentioned fused ring compound.
The present invention also provides a kind of compositions, include above-mentioned fused ring compound or high polymer or said mixture and organic solvent.
In some embodiments, a kind of composition according to the invention, wherein the fused ring compound can be used as singlet emitters material.
In other embodiments, above-mentioned composition further includes a material of main part.
In one embodiment, a kind of composition includes a kind of material of main part and a kind of singlet emitters.
In another embodiment, above-mentioned composition further includes at least two material of main parts.
In another embodiment, above-mentioned composition further includes a kind of material of main part and a kind of hot activation delayed fluorescence luminescent material.
In another embodiment, above-mentioned composition further includes a kind of hole mobile material (HTM), and more preferential, the HTM includes a crosslinkable groups.
In one embodiment, composition according to the invention is a solution.
In another embodiment, composition according to the invention is a suspension.
It may include 0.01 to 20wt% fused ring compound in above-mentioned composition；In one embodiment, in above-mentioned composition include 0.1 to 15wt% fused ring compound；In one embodiment, in above-mentioned composition include 0.2 to 10wt% fused ring compound；In one embodiment, in above-mentioned composition include 0.25 to 5wt% fused ring compound.
In one embodiment, a kind of composition, wherein the solvent is selected from aromatics or heteroaromatic, ester, aromatic ketone or aromatic oxide, aliphatic ketone or fatty ether, alicyclic or alkenes compounds, or the mixture of the inorganic ester type compound such as borate or phosphate or two kinds and two or more solvents.
In another embodiment, a kind of composition according to the invention, wherein including at least aromatics of 50wt% or heteroaromatic solvent；The preferably at least aromatics of 80wt% or heteroaromatic solvent；The particularly preferred at least aromatics of 90wt% or heteroaromatic solvent.
Example based on aromatics or heteroaromatic solvent has, but is not limited to: 1-tetralone, 3- phenoxytoluene, acetophenone, 1- methoxynaphthalene, to diisopropyl benzene, penta benzene, naphthane, cyclohexyl benzene, chloronaphthalene, Isosorbide-5-Nitrae-dimethylnaphthalene, 3- isopropyl biphenyl, right Cymene, diamyl benzene, adjacent diethylbenzene, NSC 62102, p-Diethylbenzene, 1, 2, 3, 4- durene, 1, 2, 3, 5- durene, 1, 2, 4, 5- durene, butylbenzene, detergent alkylate, 1- methyl naphthalene, 1, 2, 4- trichloro-benzenes, 1, 3- dipropoxy benzene, 4, 4- difluoro-diphenylmethane, diphenyl ether, 1, 2- dimethoxy-4 '-(1- acrylic) benzene, diphenyl-methane, 2- phenylpyridine, 3- phenylpyridine, 2- phenoxy group methyl ether, 2- phenoxy group tetrahydrofuran, ethyl -2- naphthyl ether, N- methyldiphenylamine, 4- isopropyl biphenyl, α, α-dichloro diphenyl methane, 4- (3- phenyl propyl) pyridine, Ergol, 1, 1- bis- (3, 4- 3,5-dimethylphenyl) ethane, 2- isopropyl naphthalene, benzyl ether etc..
In further embodiments, solvent appropriate and preferred be aliphatic, alicyclic or aromatic hydrocarbons race, amine, mercaptan, amide, nitrile, ester, ether, polyethers, alcohol, glycol or polyalcohol.
In further embodiments, alcohol represents the solvent of appropriate classification.Preferred alcohol includes alkyl cyclohexanol, the aliphatic alcohol especially to methylate, naphthols etc..
The solvent can be cycloalkane, such as decahydronaphthalenes.
The solvent can be single use, and be also possible to use as the mixture of two or more organic solvents.
In certain embodiments, composition according to the invention, it include a kind of organic functions chemical combination object as described above and at least one organic solvent, it also can further include another organic solvent, another example of organic solvent, including but not limited to: methanol, ethyl alcohol, 2-methyl cellosolve, methylene chloride, chloroform, chlorobenzene, o-dichlorohenzene, tetrahydrofuran, methyl phenyl ethers anisole, morpholine, toluene, ortho-xylene, meta-xylene, paraxylene, 1, 4 dioxanes, acetone, methyl ethyl ketone, 1, 2 dichloroethanes, 3- phenoxytoluene, 1, 1, 1- trichloroethanes, 1, 1, 2, 2- tetrachloroethanes, ethyl acetate, butyl acetate, dimethylformamide, dimethyl acetamide, dimethyl sulfoxide, naphthane, naphthalane, indenes and/or their mixture.
In some preferred embodiments, being particularly suitable for solvent of the invention is solvent of Hansen (Hansen) solubility parameter in following range:
δd(dispersion force) is in 17.0~23.2MPa1/2Range, especially in 18.5~21.0MPa1/2Range；
δp(polar forces) are in 0.2~12.5MPa1/2Range, especially in 2.0~6.0MPa1/2Range；
δh(hydrogen bond force) is in 0.9~14.2MPa1/2Range, especially in 2.0~6.0MPa1/2Range.
Composition according to the invention, wherein organic solvent need to consider its boiling point parameter when choosing.In the present invention, boiling point >=150 DEG C of the organic solvent；Preferably >=180 DEG C；It is more preferably >=200 DEG C；More excellent is >=250 DEG C；Optimal is >=275 DEG C or >=300 DEG C.Boiling point within the scope of these is beneficial to the spray nozzle clogging of ink jet printing head is prevented.The organic solvent can be evaporated from dicyandiamide solution, include functional membranes to be formed.
In one embodiment, a kind of viscosity of composition and surface tension parameter are as follows:
1) 25 DEG C of its viscosity@, in 1cPs to 100cPs range, and/or
2) 25 DEG C of its surface tension@, in 19dyne/cm to 50dyne/cm range.
Its surface tension parameter need to be considered when choosing the organic solvent in above-mentioned composition.Suitable ink surface tension parameter is suitable for specific substrate and specific printing process.Such as to ink jet printing, in a preferred embodiment, surface tension of the organic solvent at 25 DEG C is about in 19dyne/cm to 50dyne/cm range；More excellent is in 22dyne/cm to 35dyne/cm range；Optimal is in 25dyne/cm to 33dyne/cm range.
In one embodiment, surface tension of the ink according to the invention at 25 DEG C is about in 19dyne/cm to 50dyne/cm range；More preferably in 22dyne/cm to 35dyne/cm range；Preferably in 25dyne/cm to 33dyne/cm range.
In addition, need to consider the viscosity parameter of its ink when choosing the organic solvent in above-mentioned composition.Viscosity can be adjusted by different methods, such as pass through the concentration of functional material in the selection of suitable organic solvent and ink.In one embodiment, the viscosity of the organic solvent is lower than 100cps；In one embodiment, the viscosity of the organic solvent is lower than 50cps；
In one embodiment, the viscosity of the organic solvent arrives 20cps lower than 1.5.
Here viscosity refers to the viscosity under the environment temperature in printing, generally at 15-30 DEG C, preferably 18-28 DEG C, more preferably 20-25 DEG C, preferably 23-25 DEG C.The composition so prepared will be particularly suitable for ink jet printing.
In one embodiment, at 25 DEG C, the viscosity of above-mentioned composition is about in 1cps to 100cps range；
In one embodiment, at 25 DEG C, the viscosity of above-mentioned composition is in 1cps to 50cps range；
In one embodiment, at 25 DEG C, the viscosity of above-mentioned composition is in 1.5cps to 20cps range.
The ink for meeting the organic solvent acquisition of above-mentioned boiling point and surface tension parameter and viscosity parameter is capable of forming with uniform thickness And the functional membranes of composition and property.
It is a further object of the present invention to provide application of the upper compound in organic electronic device.
In some embodiments, the organic electronic device is optional in Organic Light Emitting Diode (OLED), organic photovoltaic battery (OPV), organic light emission battery (OLEEC), organic field-effect tube (OFET), organic light-emitting field effect pipe, organic laser, organic spin electric device, organic sensor and organic phasmon emitting diode (Organic Plasmon Emitting Diode).
It is a further object of the present invention to provide the preparation methods of above-mentioned electronic device.
Specific technical solution is as follows:
A kind of preparation method, by above compound in the method that is deposited in forming a functional layer on a substrate, or it arises from the method for total vapor deposition and at least one another organic functional material one and forms a functional layer on a substrate, or the method that combinations of the above object is printed or is coated with is coated on a substrate and forms a functional layer, the method wherein printed or be coated with is optional in (but being not limited to) inkjet printing, spray printing (Nozzle Printing), typographic printing, silk-screen printing, dip-coating, rotary coating, blade coating, roller printing, reverse roller printing, lithographic printing, flexographic printing, rotary printing, spraying, brushing or bat printing, slit-type squash type coating etc..
Purposes the invention further relates to the composition as printing ink when preparing organic electronic device, particularly preferably passes through the preparation method of printing or coating.
Wherein, suitable printing or coating technique include but is not limited to inkjet printing, typographic printing, silk-screen printing, dip-coating, roller printing, lithographic printing are reversed in rotary coating, blade coating, roller printing, flexographic printing, rotary printing, spraying, brushing or bat printing, slit-type squash type coating etc..It is preferred that intaglio printing, silk-screen printing and ink jet printing.Intaglio printing, ink jet printing will apply in an embodiment of the present invention.Solution or suspension can also comprise one or more components such as surface active cpd, and lubricant, wetting agent, dispersing agent, hydrophobing agent, bonding agent etc., for adjusting viscosity, filming performance improves adhesion etc..Related printing technique, and its to the related request in relation to solution, such as solvent and concentration, viscosity etc., details refer to Helmut Kipphan chief editor " print media handbook: technology and production method " (Handbook of Print Media:Technologies and Production Methods), ISBN 3-540-67326-1.
Preparation method as described above, a functional layer of the formation, thickness is in 5nm-1000nm.
The invention further relates to a kind of organic electronic device, the organic electronic device is organic electroluminescence device, includes luminescent layer, and the luminescent layer is formed by above-mentioned fused ring compound or above-mentioned high polymer or above-mentioned mixture.In general, such organic electronic device contains at least one cathode, an anode and a functional layer between cathode and anode, wherein including at least above-mentioned fused ring compound or above-mentioned high polymer or above-mentioned mixture in the functional layer.
In one embodiment, above-described organic electronic device is electroluminescent device, especially OLED (as shown in Figure 1), including substrate 101, anode 102, luminescent layer 104, cathode 106.
Substrate 101 can be opaque or transparent.One transparent substrate can be used to manufacture a transparent light emitting component.It see, for example, the Nature such as Bulovic 1996,380, p29 and Gu etc., Appl.Phys.Lett.1996,68, p2606.Substrate can be rigid or elasticity.Substrate can be plastics, metal, semiconductor wafer or glass.Preferably substrate has a smooth surface.Substrate free of surface defects is especially desirable selection.In a preferred embodiment, substrate is flexible, optional in thin polymer film or plastics, and glass transition temperature Tg is 150 DEG C or more, preferably more than 200 DEG C, more preferably more than 250 DEG C, preferably more than 300 DEG C.The example of suitable flexible base board has poly- (ethylene glycol terephthalate) (PET) and polyethylene glycol (2,6- naphthalene) (PEN).
Anode 102 may include a conductive metal or metal oxide or conducting polymer.Anode can be easily injected into hole into hole injection layer (HIL) or hole transmission layer (HTL) or luminescent layer.In one embodiment, the absolute value of the difference of the HOMO energy level or valence-band level of illuminator in the work function and luminescent layer of anode or the p-type semiconductor material as HIL or HTL or electronic barrier layer (EBL) is less than 0.5eV, preferably it is less than 0.3eV, preferably less than 0.2eV.The example of anode material includes but is not limited to: Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminium-doped zinc oxide (AZO) etc..Other suitable anode materials be it is known, those of ordinary skill in the art are readily able to select use.Any suitable technology deposition, such as a suitable physical vaporous deposition, including rf magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam) etc. can be used in anode material.In certain embodiments, anode is patterning.Patterned ITO electrically-conductive backing plate is commercially available, and can be used to prepare device according to the present invention.
Cathode 106 may include a conductive metal or metal oxide.Cathode can be easily injected into electronics to EIL or ETL or straight It is connected in luminescent layer.In one embodiment, the absolute value of the difference of the lumo energy or conduction level of illuminator or the n-type semiconductor as electron injecting layer (EIL) or electron transfer layer (ETL) or hole blocking layer (HBL) is less than 0.5eV in the work function and luminescent layer of cathode, preferably it is less than 0.3eV, preferably less than 0.2eV.In principle, the material of all cathodes that can be used as OLED all may be as the cathode material of device of the present invention.The example of cathode material includes but is not limited to: Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO etc..Any suitable technology deposition, such as a suitable physical vaporous deposition, including rf magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam) etc. can be used in cathode material.
OLED can also include other function layer, such as hole injection layer (HIL) or hole transmission layer (HTL) (103), electronic barrier layer (EBL), electron injecting layer (EIL) or electron transfer layer (ETL) (105), hole blocking layer (HBL).It is described later in detail in WO2010135519A1, US20090134784A1 and WO2011110277A1 suitable for the material in these functional layers, is hereby incorporated herein by reference the full content in this 3 patent documents.
In a preferred embodiment, in luminescent device according to the invention, luminescent layer 104 is by vacuum evaporation, and evaporation source includes a compound according to the invention.
In another more preferred embodiment, in luminescent device according to the invention, luminescent layer 104 is prepared by printing composition according to the invention.
Electroluminescent device according to the invention, emission wavelength 300 between 1000nm, preferably 350 between 900nm, preferably 400 between 800nm.
The invention further relates to the application of organic electronic device according to the invention in electronic equipment of various, include, but are not limited to show equipment, lighting apparatus, light source, sensor etc..
The invention further relates to the electronic equipment for including organic electronic device according to the invention, include, but are not limited to show equipment, lighting apparatus, light source, sensor etc..
Below in conjunction with preferred embodiment, the present invention is described, but the present invention is not limited to the following examples, it should be understood that, appended claims summarise the scope of the present invention under the guidance of present inventive concept it should be appreciated by one skilled in the art that, to certain change that various embodiments of the present invention are carried out, will all be covered by the spirit and scope of claims of the present invention.
Synthesis example 1: the synthesis of compound 1
Under nitrogen flowing in the 250mL three-necked flask with condenser pipe, 3- bromo- 7 is added, 7- dimethyl-indeno [1,2-a] pyrene (5.9g, 15mmol), (2 N-, 6- dimethyl benzene -1- base) -9,9- dimethyl-fluorenes -3- amine (4.7g, 15mmol), Pd (dba)2(260mg,0.45mmol)、NaOtBu(4.3g,45mmol)、(tBu)3P (270mg, 1.35mmol) and dry toluene 100mL, 100 DEG C are stirred overnight.After reaction, column chromatography purifies to obtain faint yellow solid powder (7.8g, 83%).
Synthesis example 2: the synthesis of compound 2
Under nitrogen flowing in the 250mL three-necked flask with condenser pipe, 3- bromo- 7 is added, 7- dimethyl-indeno [1,2-a] pyrene (7.9g, 20mmol), (9 N-, 9- dimethyl fluorene -3- base) dibenzofurans -4- amine (7.5g, 20mmol), Pd (dba)2(340mg,0.6mmol)、NaOtBu(5.7g,60mmol)、(tBu)3P (360mg, 1.8mmol) and dry toluene 150mL, 100 DEG C are stirred overnight.After reaction, column chromatography purifies to obtain faint yellow solid powder (10.6g, 77%).
Synthesis example 3: the synthesis of compound 3
Under nitrogen flowing in the 250mL three-necked flask with condenser pipe, 3,9- bis- bromo- 7 is added, 7- dimethyl-indeno [1,2-a] pyrene (4.8g, 10mmol), (9,9- dimethyl fluorene -3- base) boric acid (4.8g, 20mmol), Pd (PPh3)4(690mg, 0.6mmol), potassium carbonate (8.3g, 60mmol), toluene 100mL and water 30mL, 90 DEG C are stirred overnight.After reaction, column chromatography purifies to obtain faint yellow solid powder (5.7g, 81%).
Synthesis example 4: the synthesis of compound 4
Under nitrogen flowing in the 250mL three-necked flask with condenser pipe, the bromo- 3- of 9- (9,9- dimethyl fluorene -3- base) -7 is added, 7- dimethyl-indeno [1,2-a] pyrene (5.9g, 10mmol), N- (3,5- 3,5-dimethylphenyl)-[1,1'；4', 1 "-terphenyl] -4- amine (3.5g, 10mmol), Pd (dba)2(170mg,0.3mmol)、NaOtBu(2.9g,30mmol)、(tBu)3P (180mg, 0.9mmol) and dry toluene 100mL, 100 DEG C are stirred overnight.After reaction, the solid of precipitation is filtered out, toluene and methanol wash to obtain faint yellow solid powder (6.6g, 64%).
Compare synthesis example 1: the synthesis of control compounds 1
Under nitrogen flowing in the 500mL three-necked flask with condenser pipe, 1,6- dibromo pyrene (7.2g, 20mmol), di-o-tolyl amine (7.9g, 40mmol), Pd (dba) is added2(690mg,1.2mmol)、NaOtBu(11.5g,120mmol)、(tBu)3P (730mg, 3.6mmol) and dry toluene 150mL, 100 DEG C are stirred overnight.After reaction, the solid for filtering out precipitation washs to obtain faint yellow solid powder (10.7g, 90%) with toluene and methanol.
The preparation and representation of embodiment 1:OLED device:
The used material of each layer of OLED device:
A kind of HIL: triarylamine derivative；
A kind of HTL: triarylamine derivative；
Host: anthracene derivant；
Dopant: compound 1- compound 4, control compounds 1.
It is as follows with ITO/HIL (50nm)/HTL (35nm)/Host:5%Dopant (25nm)/ETL (28nm)/LiQ (1nm)/Al (150nm)/cathode OLED device preparation step:
A, the cleaning of electro-conductive glass substrate: for the first time in use, can be cleaned with multi-solvents, such as chloroform, ketone, isopropanol are cleaned, and then carry out UV ozone plasma treatment；
B, HIL (50nm), HTL (35nm), EML (25nm), ETL (28nm): in high vacuum (1 × 10-6Millibar, mbar) in hot evaporation form.
C, cathode: LiQ/Al (1nm/150nm) is in high vacuum (1 × 10-6Millibar) in hot evaporation form；
D, encapsulate: device is encapsulated in nitrogen glove box with ultraviolet hardening resin.
Current Voltage (J-V) characteristic of each OLED device is characterized by characterization equipment, while recording important parameter such as efficiency, service life and external quantum efficiency.Through detecting, control compounds 1 are better than as the chromaticity coordinates of blue-light device prepared by EML layers of illuminator using compound 1- compound 4, such as the chromaticity coordinates of device prepared by compound 3 is (0.149,0.078)；In addition, using compound 1- compound 4 as blue-light device prepared by EML layers of illuminator luminous efficiency all in 6-8cd/A range, there is more excellent luminous efficiency；In terms of device lifetime, control compounds 1 are more better than as the service life of blue-light device prepared by EML layers of illuminator using compound 1- compound 4, such as T95 of the device prepared by compound 3 at 1000nits is that 1.7 times of control compounds 1 are.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, combination not all possible to each technical characteristic in above-described embodiment is all described, however, as long as there is no contradiction in the combination of these technical features, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, and but it cannot be understood as the limitations to patent of invention range.It should be pointed out that for those of ordinary skill in the art, without departing from the inventive concept of the premise, various modifications and improvements can be made, and these are all within the scope of protection of the present invention.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.

Claims (16)

  1. A kind of fused ring compound, which is characterized in that as shown in logical formula (I):
    Wherein,
    X1It is CR1R2、O、S、NR3；
    R1、R2Or R3It is each independently selected from: H, or the straight chained alkyl with 1 to 20 C atom, or the alkoxy with 1 to 20 C atom, or the thio alkoxy with 1 to 20 C atom, or branch or cricoid alkyl with 3 to 20 C atoms, or the alkoxy with 3 to 20 C atoms, or the thio alkoxy with 3 to 20 C atoms, either substituted or unsubstituted silicyl, or the substituted ketone group with 1 to 20 C atom, or the alkoxy carbonyl with 2 to 20 C atoms, or the aryloxycarbonyl with 7 to 20 C atoms, cyano, carbamoyl, halogen formoxyl, formoxyl, isocyano group, isocyanates, thiocyanates or isothiocyanates, hydroxyl, nitro, CF3, Cl, Br, F, crosslinkable group, or substituted or unsubstituted aromatics or heteroaromatic ring system with 5 to 40 annular atoms, or aryloxy group or heteroaryloxy group with 5 to 40 annular atoms；
    The R1、R2Or R3Middle one or more group can form monocycle or polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding；
    R11-R19、R110、R111Or R112In at least one contain the structure as shown in general formula (III), other substituent groups are each independently selected from: H, or the straight chained alkyl with 1 to 20 C atom, or the alkoxy with 1 to 20 C atom, or the thio alkoxy with 1 to 20 C atom, or branch or cricoid alkyl with 3 to 20 C atoms, or the alkoxy with 3 to 20 C atoms, or the thio alkoxy with 3 to 20 C atoms, either substituted or unsubstituted silicyl, or the substituted ketone group with 1 to 20 C atom, or the alkoxy carbonyl with 2 to 20 C atoms, or the aryloxycarbonyl with 7 to 20 C atoms, cyano, carbamoyl, halogen formoxyl, formoxyl, isocyano group, isocyanates, thiocyanates or isothiocyanates, hydroxyl Base, nitro, CF3, Cl, Br, F, crosslinkable group, or substituted or unsubstituted aromatics or heteroaromatic ring system with 5 to 40 annular atoms, or aryloxy group or heteroaryloxy group with 5 to 40 annular atoms；
    The R11-R19、R110、R111Or R112Middle one or more group can form monocycle or polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding；
    The structure of the logical formula (III) are as follows:
    Wherein,
    R31、R32、R33Or R34It is each independently selected from: the straight chained alkyl with 1 to 20 C atom, or the alkoxy with 1 to 20 C atom, or the thio alkoxy with 1 to 20 C atom, or branch or cricoid alkyl with 3 to 20 C atoms, or the alkoxy with 3 to 20 C atoms, or the thio alkoxy with 3 to 20 C atoms, , either substituted or unsubstituted silicyl, or the substituted ketone group with 1 to 20 C atom, or the alkoxy carbonyl with 2 to 20 C atoms, or the aryloxycarbonyl with 7 to 20 C atoms, cyano, carbamoyl, halogen formoxyl, formoxyl, isocyano group, isocyanates, thiocyanates or isothiocyanates, hydroxyl, nitro, CF3, Cl, Br, F, crosslinkable group, or substituted or unsubstituted aromatics or heteroaromatic ring system with 5 to 40 annular atoms, or aryloxy group or heteroaryloxy group with 5 to 40 annular atoms；
    The R31、R32、R33Or R34Middle one or more group can form monocycle or polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding；
    L indicates that singly-bound or linking group, the linking group are selected from the substituted or unsubstituted aromatics with 5 to 40 annular atoms or heteroaromatic ring system, or aryloxy group or heteroaryloxy group with 5 to 40 annular atoms；
    One or more groups can form polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding in the L；
    M is 0,1,2 or 3；
    N is 0,1,2,3 or 4；
    Dotted line indicates the singly-bound connecting with other groups.
  2. Fused ring compound according to claim 1, which is characterized in that the logical formula (III)) structure be selected from flowering structure:
    Wherein,
    R55-R59Or R511-R548It is independently selected from: the straight chained alkyl with 1 to 20 C atom, or the alkoxy with 1 to 20 C atom, or the thio alkoxy with 1 to 20 C atom, or branch or cricoid alkyl with 3 to 20 C atoms, or the alkoxy with 3 to 20 C atoms, or the thio alkoxy with 3 to 20 C atoms, , either substituted or unsubstituted silicyl, or the substituted ketone group with 1 to 20 C atom, or the alkoxy carbonyl with 2 to 20 C atoms, or the aryloxycarbonyl with 7 to 20 C atoms, cyano, carbamoyl, halogen formoxyl, formoxyl, isocyano group, isocyanates, thiocyanates or isothiocyanates, hydroxyl, nitro, CF3, Cl, Br, F, crosslinkable group, or substituted or unsubstituted aromatics or heteroaromatic ring system with 5 to 40 annular atoms, or aryloxy group or heteroaryloxy group with 5 to 40 annular atoms；
    The R55-R59Or R511-R548Middle one or more group can form monocycle or polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding；
    M is 0,1,2 or 3；
    N is 0,1,2,3 or 4；
    S is 0,1,2,3,4 or 5；
    U is 0,1,2,3,4,5 or 6；
    V is 0,1,2,3,4,5,6 or 7；
    L such as right wants 1 to be defined.
  3. Fused ring compound according to claim 2, which is characterized in that the R11-R19、R110、R111Or R112In at least one contain the structure as shown in general formula (III), other substituent groups are each independently selected from flowering structure
    Wherein,
    R41-R49Or R410-R431It is each independently selected from: the straight chained alkyl with 1 to 20 C atom, or the alkoxy with 1 to 20 C atom, or the thio alkoxy with 1 to 20 C atom, or branch or cricoid alkyl with 3 to 20 C atoms, or the alkoxy with 3 to 20 C atoms, or the thio alkoxy with 3 to 20 C atoms, , either substituted or unsubstituted silicyl, or the substituted ketone group with 1 to 20 C atom, or the alkoxy carbonyl with 2 to 20 C atoms, or the aryloxycarbonyl with 7 to 20 C atoms, cyano, carbamoyl, halogen formoxyl, formoxyl, isocyano group, isocyanates, thiocyanates or isothiocyanates, hydroxyl, nitro, CF3, Cl, Br, F, crosslinkable group, or substituted or unsubstituted aromatics or heteroaromatic ring system with 5 to 40 annular atoms, or aryloxy group or heteroaryloxy group with 5 to 40 annular atoms；
    The R41-R49Or R410-R431Middle one or more group can form monocycle or polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding；
    M is 0,1,2 or 3；
    N, p or s is each independently 0,1,2,3 or 4；
    T or q is 0,1,2,3,4 or 5；
    A is the saturation cycloalkane with 3 to 8 C atoms；
    L indicates singly-bound or linking group, and the linking group can be substituted or unsubstituted aromatics or heteroaromatic ring system with 5 to 40 annular atoms, or aryloxy group or heteroaryloxy group with 5 to 40 annular atoms；One or more groups can form polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding in the linking group；
    Dotted line indicates the singly-bound connecting with other groups.
  4. Fused ring compound according to claim 1-3, which is characterized in that there is structure shown in logical formula (IV):
    Wherein,
    X1It is CR1R2、O、S、NR3；
    R1、R2Or R3It is each independently selected from: H, or the straight chained alkyl with 1 to 20 C atom, or the alkoxy with 1 to 20 C atom, or the thio alkoxy with 1 to 20 C atom, or branch or cricoid alkyl with 3 to 20 C atoms, or the alkoxy with 3 to 20 C atoms, or the thio alkoxy with 3 to 20 C atoms, , either substituted or unsubstituted silicyl, or the substituted ketone group with 1 to 20 C atom, or the alkoxy carbonyl with 2 to 20 C atoms, or the aryloxycarbonyl with 7 to 20 C atoms, cyano, carbamoyl, halogen formoxyl, formoxyl, isocyano group, isocyanates, thiocyanates or isothiocyanates, hydroxyl, nitro, CF3, Cl, Br, F, crosslinkable group, or substituted or unsubstituted aromatics or heteroaromatic ring system with 5 to 40 annular atoms, or aryloxy group or heteroaryloxy group with 5 to 40 annular atoms；
    The R1、R2Or R3Middle one or more group can form monocycle or polycyclic aliphatic series or aromatics ring system each other and/or with the ring of the group bonding；
    R13、R15Or R111As defined in claim 1.
  5. Fused ring compound according to claim 4, which is characterized in that the linking group L is selected from:
    Wherein:
    X1It is CR61Or N；
    Y is selected from CR62R63, SiR64R65, NR66Or, C (=O), S or O；
    R61-R66It is each independently selected from: H, or the straight chained alkyl with 1 to 20 C atom, or the alkoxy with 1 to 20 C atom, or the thio alkoxy with 1 to 20 C atom, or branch or cricoid alkyl with 3 to 20 C atoms, or the alkoxy with 3 to 20 C atoms, or the thio alkoxy with 3 to 20 C atoms, either substituted or unsubstituted silyl-group, or the substituted keto group with 1 to 20 C atom, or the alkoxycarbonyl groups with 2 to 20 C atoms, or the aryloxycarbonyl group with 7 to 20 C atoms, cyano group, carbamoyl group, halogen formyl group, formyl group, isocyano group group, isocyanate groups, thiocyanates group or isothiocyanates group, hydroxyl base Group, nitryl group, CF3Group, Cl, Br, F, crosslinkable group or substituted or unsubstituted aromatics or heteroaromatic ring system with 5 to 40 annular atoms, or aryloxy group or heteroaryloxy group with 5 to 40 annular atoms；
    R61, R62, R63, R64, R65Or R66Middle one or more group can form monocycle or polycyclic aliphatic series or aromatic ring each other and/or with the ring of the group bonding.
  6. Fused ring compound according to claim 5, which is characterized in that the linking group L is selected from:
  7. Fused ring compound according to claim 4, which is characterized in that the R13、R15Or R111At least one containsOther are each independently selected from: hydrogen atom ,-NR21R22Or following group:
    Wherein, the R21Or R22It is each independently selected from: hydrogen atom or following group:
  8. Fused ring compound according to claim 7, which is characterized in that the R21Or R22It is each independently selected from following group:
  9. Fused ring compound according to claim 1-8, which is characterized in that the X1It is-C (CH3)2。
  10. - 9 described in any item fused ring compounds according to claim 1, which is characterized in that the fused ring compound at least contains a D-atom.
  11. A kind of high polymer, which is characterized in that the repetitive unit comprising the described in any item fused ring compound compositions of claim 1-10.
  12. A kind of mixture, it is characterized in that, it include high polymer and organic functional material described in the described in any item fused ring compounds of claim 1-10 or claim 11, organic functional material choosing is in hole injection or transmission material, hole barrier materials, electron injection or transmission material, electron-blocking materials, organic host materials, singlet emitters, triplet emitters, thermal excitation delayed fluorescence material and organic dyestuff.
  13. A kind of composition, which is characterized in that include mixture and organic solvent described in high polymer described in the described in any item fused ring compounds of claim 1-10 or claim 11 or claim 12.
  14. A kind of organic electronic device, which is characterized in that include mixture described in high polymer described in the described in any item fused ring compounds of claim 1-10 or claim 11 or claim 12.
  15. Organic electronic device according to claim 14, it is characterized in that, organic electronic device choosing is in Organic Light Emitting Diode, organic photovoltaic battery, organic light emission battery, organic field-effect tube, organic light-emitting field effect pipe, organic laser, organic spin electric device, organic sensor and organic phasmon emitting diode.
  16. Organic electronic device according to claim 14, it is characterized in that, the organic electronic device is organic electroluminescence device, comprising luminescent layer, luminescent layer mixture as described in the described in any item fused ring compounds of claim 1-10 or high polymer as claimed in claim 11 or claim 12 is formed.
CN201780059501.9A 2016-11-30 2017-11-30 Fused ring compound and preparation method and application Pending CN109790085A (en)

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