CN105408333B - Nitrogenous polycyclic compound and use its organic luminescent device - Google Patents

Nitrogenous polycyclic compound and use its organic luminescent device Download PDF

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CN105408333B
CN105408333B CN201380078324.0A CN201380078324A CN105408333B CN 105408333 B CN105408333 B CN 105408333B CN 201380078324 A CN201380078324 A CN 201380078324A CN 105408333 B CN105408333 B CN 105408333B
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CN105408333A (en
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李玹姝
金基龙
吴炯瑄
阴盛镇
李柱东
卢永锡
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LT Materials Co Ltd
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HISUNG MATERIAL CO Ltd
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
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    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom

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Abstract

The present invention relates to the nitrogenous polycyclic compound of following formula 1 and including its organic luminescent device.Compound described in this specification may be used as the material of the organic material layer of organic luminescent device.[formula 1]。

Description

Nitrogenous polycyclic compound and use its organic luminescent device
Technical field
The present invention relates to novel nitrogen-containing polycyclic compound and including its organic luminescent device.
Background technology
Electroluminescent device is a kind of self-luminous display part, and advantage be wide viewing angle, excellent contrast and Rapid response speed.
Organic luminescent device has the following structure：Organic film is wherein set between two electrodes.When to this It is compound with the shape in organic film in the electrons and holes from two electrode injections when the organic luminescent device of structure applies voltage At electron hole pair, shine while then the electron hole pair is quenched.The organic film if necessary can by single layer or Multilayer forms.
Material for the organic film can have lighting function if necessary.For example, the material as organic film Material, can be used alone the compound that may be constructed luminescent layer, or can use can be as the hair based on host-dopant The main body of photosphere or the compound of dopant.In addition to above-mentioned material, as the material of organic film, can also use can inject Hole, transporting holes, blocking electronics, blocking hole, transmission electronics or the compound for injecting electronics.
In order to enhance performance, service life or the efficiency of organic luminescent device, it is constantly needed to the material of exploitation organic film.
Invention content
Technical problem
The present invention provides novel nitrogen-containing polycyclic compound and including its organic luminescent device.
Technical solution
The present invention provides the compounds of the following Expression 1：
[formula 1]
In formula 1,
R1For substituted or unsubstituted C6To C60Monocycle or polyaromatic or substituted or unsubstituted C2To C60Monocycle is more The nitrogenous heteroaryl of ring；
R2For substituted or unsubstituted C1To C60Linear or branched alkyl group or substituted or unsubstituted C6To C60Monocycle is more Cyclophane base；And
R3To R7It is same or different to each other, and is each independently selected from hydrogen, substituted or unsubstituted C1To C60Straight chain or branch Alkyl group, substituted or unsubstituted C2To C60Linear chain or branched chain alkenyl, substituted or unsubstituted C2To C60Linear chain or branched chain alkynyl, Substituted or unsubstituted C3To C60Monocycle or polycyclic naphthene base, substituted or unsubstituted C6To C60Monocycle or polyaromatic and substitution Or unsubstituted C10To C60Tap bolt.
In addition, the present invention provides a kind of organic luminescent device, the organic luminescent device includes：It anode, cathode and sets Set the organic material layer of between the anode and cathode one or more layers, wherein one or more layers in the organic material layer Include the compound of formula 1.
Advantageous effect
Compound described in this specification may be used as the material of the organic material layer of organic luminescent device.The chemical combination Object can be used as hole-injecting material, hole mobile material, luminescent material, electron transport material and electricity in an organic light emitting device Sub- injection material.Particularly, the compound can be effectively used as the hole transmission layer and/or electronics of organic luminescent device The material of transport layer.In addition, the compound is used as luminescent material.For example, the compound is used as phosphorescence Material of main part.
Description of the drawings
Fig. 1 to 3 is the electrode and organic material for illustrating organic luminescent device according to an illustrative embodiment of the invention The diagram of the lamination order of layer.
Figure 4 and 5 are E derived from the CV measurement results that illustrate by compound 16oxThe diagram of value.
Fig. 6 and 7 is E derived from the CV measurement results that illustrate by compound 26oxThe diagram of value.
Fig. 8 and 9 is E derived from the CV measurement results that illustrate by compound 49oxThe diagram of value.
Figure 10 and 11 is E derived from the CV measurement results that illustrate by compound 50oxThe diagram of value.
Figure 12 and 13 is E derived from the CV measurement results that illustrate by compound 89oxThe diagram of value.
Figure 14 and 15 is E derived from the CV measurement results that illustrate by compound 90oxThe diagram of value.
Figure 16 is the UV experiment curv figures of compound 16.
Figure 17 is PL experiment curv figure of the compound 16 relative to 263nm.
Figure 18 is the UV experiment curv figures of compound 26.
Figure 19 is PL experiment curv figure of the compound 26 relative to 327nm.
Figure 20 is LTPL (- 78 DEG C) experiment curv figure of compound 49.
Figure 21 is the UV experiment curv figures of compound 49.
Figure 22 is PL experiment curv figure of the compound 49 relative to 261nm.
Figure 23 is LTPL (- 78 DEG C) experiment curv figure of compound 50.
Figure 24 is the UV experiment curv figures of compound 50.
Figure 25 is PL experiment curv figure of the compound 50 relative to 264nm.
Figure 26 is LTPL (- 78 DEG C) experiment curv figure of compound 89.
Figure 27 is the UV experiment curv figures of compound 89.
Figure 28 is PL experiment curv figure of the compound 89 relative to 259nm.
Figure 29 is LTPL (- 78 DEG C) experiment curv figure of compound 90.
Figure 30 is the UV experiment curv figures of compound 90.
Figure 31 is PL experiment curv figure of the compound 90 relative to 331nm.
Specific implementation mode
Hereinafter, will be described in detail the present invention.
The compound described in the present specification can be indicated by formula 1.Specifically, passing through mother nucleus structure as described above With substituent group (especially R1And R2Substituent group) architectural characteristic, the compound of formula 1 may be used as the organic of organic luminescent device The material of material layer.Particularly, spy of the compound with above structure with the organic luminescent device for being suitable for transmitting electronics Property.
In the present specification, alkyl includes the linear or branched alkyl group with 1 to 60 carbon atom, and can be further Replaced by other substituent groups.The carbon atom number of alkyl can be 1 to 60, especially 1 to 40, and more particularly 1 to 20.
In the present specification, alkenyl includes the linear chain or branched chain alkenyl with 2 to 60 carbon atoms, and can be further Replaced by other substituent groups.The carbon atom number of alkenyl can be 2 to 60, especially 2 to 40, and more particularly 2 to 20.
In the present specification, alkynyl includes the linear chain or branched chain alkynyl with 2 to 60 carbon atoms, and can be further Replaced by other substituent groups.The carbon atom number of alkynyl can be 2 to 60, especially 2 to 40, and more particularly 2 to 20.
In the present specification, naphthenic base includes the monocycle with 3 to 60 carbon atoms or polycyclic alkynyl, and can be into one Step is replaced by other substituent groups.Here, polycyclic to refer to that wherein naphthenic base is connected directly to other ring groups or thick with other ring groups The group of conjunction.Here, other ring groups may be naphthenic base, it is also possible that other kinds of ring group, such as Heterocyclylalkyl, Aryl, heteroaryl etc..The carbon atom number of naphthenic base can be 3 to 60, especially 3 to 40, and more particularly 5 to 20.
In the present specification, aryl includes the monocycle or polyaromatic for having 6 to 60 carbon atoms, and can be further Replaced by other substituent groups.Here, polycyclic to refer to that wherein aryl is connected directly to other ring groups or is condensed with other ring groups Group.Here, other ring groups may be aryl, it is also possible that other kinds of ring group, such as naphthenic base, heterocycle alkane Base, heteroaryl etc..The carbon atom number of aryl can be 6 to 60, especially 6 to 40, and more particularly 6 to 20.Aryl it is specific Example include phenyl, xenyl, triphenyl, naphthalene, anthryl,Base, phenanthryl, base, fluoranthene base, benzo phenanthryl, that non-alkenyl, Pyrenyl, aphthacene base, pentacene, fluorenyl, indenyl, acenaphthylene base or their fused rings, but it is not limited to these.
In the present specification, nitrogenous heteroaryl includes N as hetero atom and the monocycle with 2 to 60 carbon atoms or more Ring, and can further be replaced by other substituent groups.In the present specification, unless other specifically mentioned, nitrogenous heteroaryl packet S, O or N are included as hetero atom and the monocycle with 2 to 60 carbon atoms or polycyclic, and can be further by other substituent groups Substitution.Here, the polycyclic group for referring to that wherein heteroaryl is connected directly to other ring groups or is condensed with other ring groups.Here, Other ring groups may be heteroaryl, it is also possible that other kinds of ring group, such as naphthenic base, Heterocyclylalkyl, aryl etc.. The carbon atom number of heteroaryl can be 2 to 60, especially 2 to 40, and more particularly 3 to 20.The specific example of heteroaryl includes Pyridyl group, pyrrole radicals, pyrimidine radicals, pyridazinyl, furyl, thienyl, imidazole radicals, pyrazolyl, oxazolyl, isoxazolyls, thiazole Base, isothiazolyl, triazolyl, furazanyl, oxadiazolyls, thiadiazolyl group, dithiazole base, tetrazole radical, pyranose, thiapyran base, two Piperazine Ji, oxazinyls, thiazinyl, dioxin base, triazine radical, tetrazine base, quinolyl, isoquinolyl, quinazolyl, isoquinoline oxazoline Base, acridinyl, phenanthridinyl, imidazopyridyl, phthalazinyl, benzotriazole base, indyl, benzothiazolyl, Ben Bing Evil Oxazolyl, benzimidazolyl, benzothienyl, benzofuranyl, dibenzothiophene, dibenzofuran group, carbazyl, benzo click Oxazolyl, phenazinyl or their fused rings, but it is not limited to these.
In the present specification, tap bolt is the group for including spiro structure, and can have 15 to 60 carbon atoms.Example Such as, tap bolt may include wherein 2,3- dihydro -1H- indenyls or cyclohexane group is screw-coupled to structure on fluorenyl.Specifically, spiral shell Base includes the group of following structural.
In the present specification, " substituted or unsubstituted " refer to it is unsubstituted or by one in following groups or Multiple substituent group substitutions：C1To C60Linear or branched alkyl group, C2To C60Linear chain or branched chain alkenyl, C2To C60Linear chain or branched chain alkynes Base, C3To C60Monocycle or polycyclic naphthene base, C2To C60Monocycle or polycyclic Heterocyclylalkyl, C6To C60Monocycle or polyaromatic, C2Extremely C60Monocycle or polyheteroaromatic, C2To C60Monocycle or polycyclic Heterocyclylalkyl, C10To C60Tap bolt and unsubstituted or by C1To C20 Alkyl, substituted or unsubstituted C6To C60Monocycle or polyaromatic or substituted or unsubstituted C2To C60Monocycle or polyheteroaromatic Substituted amido.The additional substituent group can be further substituted.
Property embodiment according to an example of the present invention, the R in formula 11Including nitrogenous heteroaryl.Term " including it is nitrogenous Heteroaryl " refers to R1The virtue replaced for substituted or unsubstituted nitrogenous heteroaryl or with substituted or unsubstituted nitrogenous heteroaryl Base.Here, aryl includes the group for combining two or more aromatic groups.
Property embodiment according to an example of the present invention, the R in formula 11Including nitrogenous bicyclic heteroaryl.Term " including Nitrogenous bicyclic heteroaryl " refers to R1For substituted or unsubstituted nitrogenous bicyclic heteroaryl or with substituted or unsubstituted nitrogenous list The aryl of ring heteroaryl substitution.
The nitrogenous heteroaryl may include 1 to 3 nitrogen-atoms.The nitrogenous heteroaryl can be pyridyl group, pyrimidine radicals, Triazine radical, quinolyl or isoquinolyl.
The nitrogenous bicyclic heteroaryl may include 1 to 3 nitrogen-atoms.
The nitrogenous heteroaryl is unsubstituted or is replaced by additional substituent group.When the nitrogenous heteroaryl is substituted When, the nitrogenous heteroaryl can be by C6To C60Aryl is unsubstituted or by C2To C60The C of heteroaryl substitution6To C60Aryl takes Generation.
Property embodiment according to an example of the present invention, the R in formula 11Including nitrogenous bicyclic heteroaryl, and described contain Nitrogen bicyclic heteroaryl can be pyridyl group, pyrimidine radicals or triazine radical.
Property embodiment according to an example of the present invention, the R in formula 11For substituted or unsubstituted pyridyl group, substitution or Unsubstituted pyrimidine radicals either substituted or unsubstituted triazine radical or for be substituted or unsubstituted pyridyl group, substitution or not The aryl of one or two of substituted pyrimidine radicals and substituted or unsubstituted triazine radical or more substitution.
Property embodiment according to an example of the present invention, the R in formula 11For substituted or unsubstituted pyridyl group, substitution or Unsubstituted pyrimidine radicals either substituted or unsubstituted triazine radical or for be substituted or unsubstituted pyridyl group, substitution or not The phenyl of one or two of substituted pyrimidine radicals and substituted or unsubstituted triazine radical or more substitution.
In an exemplary embodiment of the present invention, formula 1 can be expressed as following formula 2.
[formula 2]
In formula 2,
L is substituted or unsubstituted C6To C60Monocycle or polycyclic arlydene,
Het is substituted or unsubstituted C2To C60Monocycle or polycyclic nitrogenous heteroaryl,
The integer that n is 0 to 2, p are 1 or 2, and
R2To R7It is identical as the definition in formula 1.
Property embodiment according to an example of the present invention, in formula 2, n 0,1 or 2, and L is phenylene.
Property embodiment according to an example of the present invention, in formula 2, Het is substituted or unsubstituted pyridyl group, substitution Or unsubstituted pyrimidine radicals or substituted or unsubstituted triazine radical.
Property embodiment according to an example of the present invention, in formula 2, Het is substituted or unsubstituted pyridyl group, substitution Or unsubstituted pyrimidine radicals or substituted or unsubstituted triazine radical, and when Het is substituted, substituent group is substitution or unsubstituted C6To C60Monocycle or polyaromatic.
Property embodiment according to an example of the present invention, in formula 2, Het is substituted or unsubstituted pyridyl group, substitution Or unsubstituted pyrimidine radicals or substituted or unsubstituted triazine radical, and when Het is substituted, substituent group be it is unsubstituted or By C6To C60Aryl or C2To C60The C of heteroaryl substitution6To C60Monocycle or polyaromatic.
Property embodiment according to an example of the present invention, in formula 2, Het is substituted or unsubstituted pyridyl group, substitution Or unsubstituted pyrimidine radicals or substituted or unsubstituted triazine radical, and when Het is substituted, substituent group be phenyl, xenyl, Terphenyl, naphthalene or phenanthryl, and can by phenyl, xenyl, terphenyl, naphthalene, phenanthryl, pyridyl group, pyrimidine radicals or Triazine radical is further substituted with.
Another illustrative embodiments according to the present invention, formula 1 can be expressed as following formula 3.
[formula 3]
In formula 3,
R8For substituted or unsubstituted C6To C60Monocycle or polyaromatic or substituted or unsubstituted C2To C60Monocycle is more The nitrogenous heteroaryl of ring, and the integer that m is 0 to 9,
R2To R7It is identical as the definition in formula 1, and
L and n is identical as the definition in formula 2.
Property embodiment according to an example of the present invention, in formula 3, n 0,1 or 2, and L is phenylene.
Property embodiment according to an example of the present invention, in formula 3, m is 1 or 2, and R8For with 1 to 3 ring Aryl or nitrogenous heteroaryl.
Property embodiment according to an example of the present invention, in formula 3, m is 1 or 2, and R8For phenyl, naphthalene, phenanthrene Base, terphenyl, pyridyl group, bipyridyl, pyrimidine radicals, connection pyrimidine radicals, triazine radical, connection triazine radical, quinolyl, isoquinolyl or Phenanthridinyl.
Another illustrative embodiments according to the present invention, formula 1 can be expressed as following formula 4.
[formula 4]
In formula 4,
X1 and X2 is substituted or unsubstituted C6To C60Monocycle or Ppolynuclear aromatic hydrocarbon ring or substituted or unsubstituted C2Extremely C60Monocycle or Ppolynuclear aromatic heterocycle；
R2To R7It is identical as the definition in formula 1, and
L and n is identical as the definition in formula 2.
Property embodiment according to an example of the present invention, in formula 4, n 0,1 or 2, and L is phenylene.
Property embodiment according to an example of the present invention, in formula 4,Including having structure.
In the structural formula, Y1To Y6Respectively CRR ', NR, S or O,
Z1To Z3Respectively S or O, and
R and R' are same or different to each other, and respectively hydrogen, substituted or unsubstituted C1To C60Linear or branched alkyl group, Or substituted or unsubstituted C6To C60Monocycle or polyaromatic.
Property embodiment according to an example of the present invention, the R in formula 12For substituted or unsubstituted C1To C20Straight chain or Branched alkyl or substituted or unsubstituted C6To C20Monocycle or polyaromatic.
Property embodiment according to an example of the present invention, the R in formula 12For methyl, phenyl or naphthyl.
Property embodiment according to an example of the present invention, the R in formula 13To R7It is each independently hydrogen, substitution or does not take The C in generation1To C60Linear or branched alkyl group or substituted or unsubstituted C6To C60Monocycle or polyaromatic.
Property embodiment according to an example of the present invention, the R in formula 13To R7For hydrogen.
Property embodiment according to an example of the present invention, formula 1 can be selected from following compounds.
Above compound can be prepared according to following preparation embodiments.According to following preparation embodiment, art technology Personnel can add or remove if necessary substituent group.Furthermore it is possible to differently select position and the type of substituent group.In addition, Starting material, reaction material, reaction condition etc. can be changed according to technology as known in the art.
The present invention another exemplary embodiment provides a kind of organic luminescent devices, it includes the changes of above-mentioned formula 1 Close object.Specifically, organic luminescent device according to the present invention includes：Anode, cathode and with setting anode and cathode it Between one or more layers organic material layer, wherein one or more layers in the organic material layer includes the compound of formula 1.
Fig. 1 to 3 illustrates the electrode and organic material of organic luminescent device according to an illustrative embodiment of the invention The lamination order of layer.But the scope of the present invention is not intended to be limited by these attached drawings, and it is well known in the prior art The structure of organic luminescent device can also be applied to the present invention.
According to Fig. 1, it is illustrated that a kind of organic luminescent device, wherein anode 200, organic has sequentially been laminated on the substrate 100 Material layer 300 and cathode 400.But the organic luminescent device is not limited in the structure, and as shown in Fig. 2, can be with Realize the organic luminescent device that cathode, organic material layer and anode are sequentially laminated wherein on substrate.
Fig. 3 illustrates the case where organic material layer is multilayer.Organic luminescent device according to fig. 3 includes hole injection layer 301, hole transmission layer 302, luminescent layer 303, electron transfer layer 304 and electron injecting layer 305.But the scope of the present invention is not It is limited to the stepped construction, can be omitted other layers other than luminescent layer if necessary, and if necessary can be further Add other functional layers.
Other than one or more layers of organic material layer includes the compound of formula 1, organic luminescent device according to the present invention It can be prepared with material as known in the art and method.
The compound of formula 1 can be separately formed one or more layers of the organic material layer of organic luminescent device.But in necessity Shi Suoshu compounds can be mixed with other materials to form organic material layer.
The compound of formula 1 can be used as hole-injecting material, hole mobile material, luminous material in an organic light emitting device Material, electron transport material, electron injection material etc..
According to an illustrative embodiments, the compound of formula 1 is used as the hole transmission layer of organic luminescent device And/or the material of electron transfer layer.As specific illustrative embodiments, including the organic material layer of the compound of formula 1 can Think the electron transfer layer of organic luminescent device.
According to another illustrative embodiments, the compound of formula 1 may be used as the luminescent material of organic luminescent device.Make Organic material layer for specific illustrative embodiments, including the compound of formula 1 can be the luminescent layer of organic luminescent device.
The compound of formula 1 is used as phosphorescent light body material.In this case, the compound and luminescent dopant of formula 1 Agent is used together.As luminescent dopant material, those materials as known in the art can be used.
It is, for example, possible to use by LL'MX, LL'L " M, LMXX', L2MX and L3The phosphorescence dopant material that M is indicated, but this The range of invention is not limited to these examples.
Here, L, L', L ", X and X' are bidentate ligand different from each other, and M is the metal to form Octahedral Complexes.
M can be iridium, platinum, osmium etc..
L is that can play capture electronics or sky through sp2 carbon and hetero atom and the anionic bidentate ligand and X of M coordinations The effect in cave.The non-limiting examples of L include 2- (1- naphthalene) benzoxazoles, 2- Ben bases benzoxazole, 2- phenylbenzothiazols, 2- phenylbenzothiazols, 7,8- benzoquinolines, thienylpyridine, phenylpyridine, benzothiophene yl pyridines, 3- methoxyl group -2- benzene Yl pyridines, thienylpyridine, tolylpyridine etc..The non-limiting examples of X include acetylacetone,2,4-pentanedione (acetylacetonate, Acac), hexafluoroacetylacetone (hexafluoroacetylacetonate), salicylidene (salicylidene), pyridine carboxylic acid (picolinate), 8-hydroxyquinoline (8-hydroxyquinolinate) etc..
Their more specific examples will be shown below, but X is not limited to these instances.
In organic luminescent device according to the present invention, the material other than the compound of formula 1 is illustrated below Illustrate, but be to provide these purposes for being only used for illustrating, is not meant to limit the scope of the present disclosure, and can be with existing Well known material substitution in technology.
As anode material, the material with relatively large work content can be used, and transparent conductive oxide can be used Object, metal or conducting polymer.
As cathode material, the material with relatively small work content can be used, and metal, metal can be used to aoxidize Object or conducting polymer.
As hole-injecting material, hole-injecting material commonly known in the art can also be used, it is, for example, possible to use The phthalocyanine compound disclosed in United States Patent (USP) No.4,356,429, such as copper phthalocyanine, or in document [Advanced Material, 6, p.677 (1994)] star burst type amine derivative disclosed in, such as TCTA, m-MTDATA, m-MTDAPB, it is solvable Property conducting polymer Pani/DBSA (polyaniline/dodecyl benzene sulfonic acid) or PEDOT/PSS (poly- (3,4- ethylidene dioxy thiophenes Pheno)/poly- (4- styrene sulfonic acids)), Pani/CSA (polyaniline/camphorsulfonic acid) or PANI/PSS (polyaniline/poly- (4- styrene Sulfonic acid)) etc..
As hole mobile material, pyrazoline derivative, the derivative based on arylamine, stilbene derivatives, three can be used Phenylenediamine derivative etc., and low molecule or high molecular material can also be used.
It, can be to use oxadiazole derivative, anthraquinone bismethane and its derivative, benzoquinones and its spread out as electron transport material Biology, naphthoquinones and its derivative, anthraquinone and its derivative, four cyano anthraquinone bismethane and its derivative, fluorenone derivatives, hexichol The metal complex etc. of base dicyanoethylene and its derivative, diphenoquinone, 8-hydroxyquinoline and its derivative, and High molecular material and low molecule material can be used.
As electron injection material, for example, LiF is usually used in the art, still, the invention is not limited thereto.
As luminescent material, red, green or blue emitting material can be used, and if necessary, can mix makes With two or more luminescent materials.In addition, as luminescent material, fluorescent material can be used, but phosphorescence material can also be used Material.As luminescent material, can use it is compound respectively individually from anode and cathode injected holes and electronics and luminous material, But it is also possible to use the material for being related to material of main part and dopant material simultaneously in shining.
Organic luminescent device according to the present invention can include additionally hole blocking layer and/or electronic barrier layer.As this A little materials can use those materials as known in the art.
Property embodiment according to an example of the present invention, the organic luminescent device include the compound containing formula 1 Luminescent layer, and further comprise being arranged the hole blocking layer between luminescent layer and cathode.In this case, the luminescent layer Light-emitting dopant can be further included.
Embodiment
Hereinafter, the present invention will be more fully described by embodiment, but it is to provide these embodiments and is only used for illustrating The purpose of the present invention is not meant to limit the scope of the present disclosure.
Compound experiment embodiment 1) with the following table 1 substituent group compound preparation
The preparation of compound 1-1
The 2- methyl-bromobenzoates of 20g (93mmol, 1 equivalent) are dissolved in the THF of 180ml, then by 7.44g's NaH is added in solution, and gained mixture is stirred 30 minutes.After stirring, being slowly added to 11.17g thereto, (93mmol, 1 works as Amount) acetophenone.Gained mixture is stirred 2 hours at normal temperatures, is then heated 16 hours at 100 DEG C.After the completion of reaction, Temperature is cooled to room temperature, then sequence ethyl acetate, 1N HCl, NaHCO3Aqueous solution and H2O extracts products therefrom.Extraction Afterwards, extract obtains the compound 1-1 of 25.6g (90%) with column chromatography separating purification.
The preparation of compound 1-2
The compound 1-1 of 25.6g (84mmol, 1 equivalent) is dissolved in the DMF of 160ml, is then added into the solution The H of 6ml (92.4mmol, 1.1 equivalents)2NNH2·H2O, and gained mixture is stirred 6 hours at normal temperatures.When reaction is completed Afterwards, with ethyl acetate and H2O extracts products therefrom.After extraction, extract obtains the change of 20g (79%) with column chromatography separating purification Close object 1-2.
The preparation of compound 1-3
The compound 1-2 of 20g (66mmol, 1 equivalent) is dissolved in the DMF of 240ml, is then added into the solution The 4- bromobenzaldehydes of the CuI and 14.8g (80.4mmol, 1.2 equivalents) of 1.25g (6.6mmol, 0.1 equivalent), and gained is mixed Object stirs 30 minutes.After stirring, the NH of 66ml is added into solution3·H2O, and it is small that gained mixture is stirred at 100 DEG C to 24 When.After the completion of reaction, with ethyl acetate and H2O extracts products therefrom.After extraction, extract is obtained with column chromatography separating purification The compound 1-3 of 15g (56%).
The preparation of compound 1-4
The compound 1-3 of 15g (37mmol, 1 equivalent) is dissolved in the DMF of 60ml, is then added into the solution The CuI of 1.25g (6.6mmol, 0.1 equivalent), and gained mixture is stirred 24 hours at 100 DEG C.After the completion of reaction, second is used Acetoacetic ester and H2O extracts products therefrom.After extraction, extract obtains the compound 1-4 of 10g (80%) with column chromatography separating purification.
The preparation of compound S-1
S-2 (1 equivalent) is dissolved in Isosorbide-5-Nitrae-dioxane of 300ml, 2,2,3,3,7 are then added into the solution, 7,8,8- prestoxs -1,4,6,9- four oxa- -514- boron spiral shell [4.4] nonane (2 equivalent), PdCl2(dppf) (0.05 equivalent) and KOAc (3 equivalent), and gained mixture is stirred 24 hours at 80 DEG C.After the completion of reaction, with dichloromethane and H2O extracts institute Obtain product.After extraction, extract obtains S-1 with column chromatography separating purification.
The preparation of compound P1
Compound 1-4 (1 equivalent) is dissolved in mixing ratio 5:1:1 toluene/ethanol/H2In O, then add into the solution Enter Pd (PPh3)4(0.05 equivalent), K2CO3(3 equivalent) and compound S-1 (1.3 equivalent), and the heating 4 of gained mixture is small When.After the completion of reaction, with dichloromethane and H2O extracts products therefrom.After extraction, extract is obtained with column chromatography separating purification Target compound P-1.
[table 1]
Compound experiment embodiment 2) with the following table 2 substituent group compound preparation
The preparation of compound 1-1
By with it is identical in compound 1-1 in compound experiment embodiment 1 in a manner of prepare the compound.
The preparation of compound 1-2
By with it is identical in compound 1-2 in compound experiment embodiment 1 in a manner of prepare the compound.
The preparation of compound S-3
S-4 (1 equivalent) is dissolved in THF, temperature is then cooled to -78 DEG C, n-BuLi is added into the solution, and Gained mixture is stirred 1 hour.After stirring 1 hour, DMF (5 equivalent) is added into the mixture, and gained mixture is stirred It mixes 24 hours.After the completion of reaction, with dichloromethane and H2O extracts products therefrom.After extraction, extract pillar layer separation is pure Change obtains S-3.
The preparation of compound 2-3
The compound 1-2 of 20g (66mmol, 1 equivalent) is dissolved in the DMF of 240ml, is then added into the solution The CuI and compound S-3 (1.2 equivalent) of 1.25g (6.6mmol, 0.1 equivalent), and gained mixture is stirred 30 minutes.Stirring Afterwards, the NH of 66ml is added into solution3·H2O, and gained mixture is stirred 24 hours at 100 DEG C.After the completion of reaction, use Ethyl acetate and H2O extracts products therefrom.After extraction, extract obtains compound 2-3 with column chromatography separating purification.
The preparation of compound P2
Compound 2-3 (1 equivalent) is dissolved in the DMF of 60ml, CuI (0.1 equivalent) is then added into the solution, and Gained mixture is stirred 24 hours at 100 DEG C.After the completion of reaction, with ethyl acetate and H2O extracts products therefrom.Extraction Afterwards, extract obtains target compound P2 with column chromatography separating purification.
[table 2]
Compound experiment embodiment 3) with the following table 3 substituent group compound preparation
The preparation of compound 3-1
The 2- methyl-bromobenzoates of 20g (93mmol, 1 equivalent) are dissolved in the THF of 180ml, then by 7.44g's NaH is added in solution, and gained mixture is stirred 30 minutes.After stirring, being slowly added to 5.4g thereto, (93mmol, 1 works as Amount) acetone.Gained mixture is stirred 2 hours at normal temperatures, is then heated 16 hours at 100 DEG C.It, will after the completion of reaction Temperature is cooled to room temperature, then sequence ethyl acetate, 1N HCl, NaHCO3Aqueous solution and H2O extracts products therefrom.After extraction, Extract obtains the compound 3-1 of 22g (98%) with column chromatography separating purification.
The preparation of compound 3-2
The compound 3-1 of 22g (91mmol, 1 equivalent) is dissolved in the DMF of 180ml, is then added into the solution The H of 12ml (100.1mmol, 1.1 equivalents)2NNH2·H2O, and gained mixture is stirred 6 hours at normal temperatures.When having reacted Cheng Hou, with ethyl acetate and H2O extracts products therefrom.After extraction, extract obtains 19g's (88%) with column chromatography separating purification Compound 3-2.
The preparation of compound 3-3
The compound 3-2 of 19g (80mmol, 1 equivalent) is dissolved in the DMF of 160ml, is then added into the solution The 4- bromobenzaldehydes of the CuI and 17.7g (96mmol, 1.2 equivalents) of 1.5g (8mmol, 0.1 equivalent), and gained mixture is stirred It mixes 30 minutes.After stirring, the NH of 80ml is added into solution3·H2O, and gained mixture is stirred 24 hours at 100 DEG C.When After the completion of reaction, with ethyl acetate and H2O extracts products therefrom.After extraction, extract obtains 20g with column chromatography separating purification (73%) compound 3-3.
The preparation of compound 3-4
The compound 3-3 of 20g (59mmol, 1 equivalent) is dissolved in the DMF of 120ml, is then added into the solution The CuI of 1.14g (6mmol, 0.1 equivalent), and gained mixture is stirred 24 hours at 100 DEG C.After the completion of reaction, acetic acid is used Ethyl ester and H2O extracts products therefrom.After extraction, extract obtains the compound 3-4 of 17g (85%) with column chromatography separating purification.
The preparation of compound S-5
S-6 (1 equivalent) is dissolved in Isosorbide-5-Nitrae-dioxane of 300ml, 2,2,3,3,7 are then added into the solution, 7,8,8- prestoxs -1,4,6,9- four oxa- -514- boron spiral shell [4.4] nonane (2 equivalent), PdCl2(dppf) (0.05 equivalent) and KOAc (3 equivalent), and gained mixture is stirred 24 hours at 80 DEG C.After the completion of reaction, with dichloromethane and H2O extracts institute Obtain product.After extraction, extract obtains S-5 with column chromatography separating purification.
The preparation of compound P3
Compound 3-4 (1 equivalent) is dissolved in mixing ratio 5:1:1 toluene/ethanol/H2In O, then add into the solution Enter Pd (PPh3)4(0.05 equivalent), K2CO3(3 equivalent) and compound S-5 (1.3 equivalent), and the heating 4 of gained mixture is small When.After the completion of reaction, with dichloromethane and H2O extracts products therefrom.After extraction, extract is obtained with column chromatography separating purification Target compound P3.
[table 3]
Compound experiment embodiment 4) with the following table 4 substituent group compound preparation
The preparation of compound S-7
Other than using S-8 to replace the S-4 in compound experiment embodiment 2, with the compound with compound experiment embodiment 2 Identical mode synthesizes the compound in S-3.
The preparation of compound 4-3
Other than using 3-2 to replace the 2-2 in compound experiment embodiment 2, with the compound with compound experiment embodiment 2 Identical mode synthesizes the compound in 2-3.
The preparation of compound P4
Other than using 4-3 to replace the 2-3 in compound experiment embodiment 2, with the compound with compound experiment embodiment 2 Identical mode synthesizes the compound in P2.
[table 4]
Compound experiment embodiment 5) compound 49 preparation
The preparation of compound 49-1
By (9,9- dimethyl -9H- fluorenes -2- bases) boric acid (25.9g, 108mmol), the bromo- 2- of 1- in single necked round bottom flask Nitrobenzene (20g, 99mmol), Pd (PPh3)4(5.7g, 4.95mmol), K2CO3(27.3g, 198mmol) and THF (250ml)/ H2The mixture of O (50ml) flows back 24 hours at 110 DEG C.Water layer is removed, then organic layer MgSO4It is dry.It is organic after concentration Layer column chromatography (SiO2, hexane:Dichloromethane=2:1) isolated yellow solid compound 49-1 (21g, 61%).
The preparation of compound 49-2
Under a nitrogen by compound 49-1 (20g, 63.4mmol), PPh in single necked round bottom flask3(49.8g, 190mmol) flow back 1 hour at 180 DEG C with the mixture of 1,2- dichloro-benzenes (300ml).1,2- dichloro-benzenes is removed by distillation, so Gained mixture column chromatography (SiO afterwards2, hexane:Dichloromethane=3:1) isolated compound as white solid 49-2 (6.6g, And compound 74-1 (7.5g, 41%) 36%).
The preparation of compound 49
By compound 49-2 (4.8g, 16.9mmol), compound experiment embodiment under nitrogen charging in single necked round bottom flask Compound 1-4 (6.4g, 16mmol), Cu (1g, 16.9mmol), 18- crown- 6- ethers (550mg, 1.69mmol), K2CO3(7g, 50.7mmol) flow back 60 hours at 180 DEG C with the mixture of o-DCB (130ml).1,2- dichloro-benzenes is removed by distillation, then Gained mixture column chromatography (SiO2, hexane:Dichloromethane=2:1) isolated compound as white solid 49 (3.8g, 37%).
Compound experiment embodiment 6) compound 50 preparation
The preparation of compound 50-1
Flow back in single necked round bottom flask bromo- 9, the 9- diphenyl -9H- fluorenes (40g, 100.67mmol) of 2-, two boron (51.1g, 201.34mmol)、PdCl2(dppf) (2.2g, 3.02mmol), KOAc (29.6g, 302.01mmol) and DMF's (400ml) is mixed Close object.The mixture is extracted with MC and uses MgSO4It is dry, then DMF is removed with vacuum rotary evaporator.Concentrate column color Compose (SiO2, hexane:Dichloromethane=1:1) isolated compound as white solid 50-1 (41g, 91%).
The preparation of compound 50-2
In single necked round bottom flask by the bromo- 2- nitrobenzenes of compound 50-1 (41g, 92.26mmol), 1- (18.6g, 92.26mmol)、Pd(PPh3)4(10.6g, 9.2mmol), K2CO3(26.6g, 192.5mmol) and THF (500ml)/H2O The mixture of (100ml) flows back 24 hours at 110 DEG C.Water layer is removed, then organic layer MgSO4It is dry.Organic layer concentrates, so Column chromatography (SiO is used afterwards2, hexane:Dichloromethane=1:1) isolated yellow solid compound 50-2 (26.3g, 65%).
The preparation of compound 50-3
Under a nitrogen by compound 50-2 (26.3g, 59.8mmol), PPh in single necked round bottom flask3(47g, 179.4mmol) flow back 18 hours at 180 DEG C with the mixture of 1,2- dichloro-benzenes (300ml).1,2- dichloros are removed by distillation Benzene, then gained mixture column chromatography (SiO2, hexane:Dichloromethane=3:1) isolated compound as white solid 50-3 (9g, 37%).
The preparation of compound 50
In single necked round bottom flask under a nitrogen by compound 50-3 (5.1g, 12.5mmol), compound 1-4 (5g, 12.5mmol)、Pd(OAc)2(280mg, 1.25mmol), K3PO4(5.3g, 25mmol), P (t-Bu)3(6ml, 3.75mmol) and Toluene/H2The mixture of O (120ml/30ml) flows back 24 hours at 110 DEG C.Reactant is extracted with MC, uses MgSO4It is dry, then Concentration.Concentrate is purified with MC/MeOH, is filtered at high temperature with ACN, is then dissolved in MC, and by filtering concentrate It pours into the crystal generated in excessive hexane and obtains compound 50 (6.7g, 73%).
Compound experiment embodiment 7) compound 59 preparation
The preparation of compound 59-1
Under a nitrogen by bromo- 9, the 9- dimethyl -9H- fluorenes (15g, 54.91mmol) of 2-, benzo in single necked round bottom flask [b]-thiophene -2- bases tributyl stannane (34.8g, 82.3mmol), Pd (PPh3)4Mixture with toluene (350ml) is at 110 DEG C Reflux 12 hours.After concentration, the mixture is filtered with silica gel, then will use CH2Cl2The compound EtOH of/MeOH precipitations Opaque compound as white solid 59-1 (15.7g, 87%) is obtained by filtration at high temperature.
The preparation of compound 59-2
Under a nitrogen by compound 59-1 (15.7g, 48mmol), AcOH (260ml) solution, HNO3(6ml, 143mmol) It is slowly added in single necked round bottom flask, is then heated to 60 DEG C and stirs 30 minutes with the mixture of AcOH (260ml) solution.It will Mixture is cooled to room temperature, filters, and is then washed with distilled water (500ml).Resulting materials are in vacuum drying oven in 50 DEG C of dryings 12 hours, then obtain yellow solid compound 59-2 (16.1g, 90%).
The preparation of compound 59-3
Under a nitrogen by compound 59-2 (16.1g, 43mmol), PPh in single necked round bottom flask3(33.8g, 129mmol) flow back 18 hours at 200 DEG C with the mixture of 1,2- dichloro-benzenes (250ml).1,2- dichloro-benzenes is removed by distillation, Then gained mixture column chromatography (SiO2, hexane:Dichloromethane=2:1) isolated pale red brown solid compound 59-3 (3.0g, 20%).
The preparation of compound 59
By the change of compound 59-3 (2g, 5.85mmol), compound experiment embodiment 1 under nitrogen charging in single necked round bottom flask Close object 1-4 (2.59g, 6.45mmol), Cu (374mg, 5.85mmol), 18- crown- 6- ethers (191mg, 0.58mmol), K2CO3 The mixture of (1.6g, 11.78mmol) and o-DCB (25ml) flow back 60 hours at 180 DEG C.1,2- dichloros are removed by distillation Benzene, then gained mixture column chromatography (SiO2, hexane:Dichloromethane=3:1) isolated solid chemical compound 59 (2.8g, 72%).
Compound experiment embodiment 8) compound 64 preparation
The preparation of compound 64-1
By 9,9- dimethyl -9H- fluorenes -2- ylboronic acids (25.95g, 109mmol), 3- bromines benzo-thiophene (10ml, 72.5mmol), Pd(PPh3)4(4.189g, 3.625mmol), K2CO3(30.06g, 217.5mmol), toluene (200ml), ethyl alcohol (40ml) and H2O The mixture of (40ml) flows back.Mixture stirs 4 hours in reflux temperature, then concentrated solvent is extracted with MC.Solid methanol It washs and filters.Obtain compound as white solid 64-1 (30g, 87%).
The preparation of compound 64-2
Under a nitrogen by compound 64-1 (21.3g, 65.3mmol), AcOH (1,260ml) solution, HNO3(5.9ml, It 130mmol) is slowly added in single necked round bottom flask with the mixture of AcOH (12ml), is then heated to 60 DEG C and stirs 30 points Clock.Mixture is cooled to room temperature, is filtered, is then washed with distilled water (400ml).Resulting materials are in vacuum drying oven at 50 DEG C It is 12 hours dry, then obtain bright yellow solid compound 64-2 (21.0g, 95%).
The preparation of compound 64-3
Under a nitrogen by compound 64-2 (29.5g, 79.4mmol), PPh in single necked round bottom flask3(54.8g, 198.5mmol) flow back 4 hours at 180 DEG C with the mixture of 1,2- dichloro-benzenes (450ml).1,2- dichloro-benzenes is removed by distillation, Then gained mixture column chromatography (SiO2, hexane:Dichloromethane=4:1) isolated yellow solid compound 64-3 (15g, 55%).
The preparation of compound 64
By the change of compound 64-3 (4g, 11.7mmol), compound experiment embodiment 1 under nitrogen charging in single necked round bottom flask Close object 1-4 (5.18g, 12.9mmol), Cu (748mg, 11.7mmol), 18- crown- 6- ethers (383mg, 1.17mmol), K2CO3 The mixture of (3.2g, 23.56mmol) and o-DCB (50ml) flow back 60 hours at 180 DEG C.1,2- dichloros are removed by distillation Benzene, then gained mixture column chromatography (SiO2, hexane:Dichloromethane=3:1) isolated solid chemical compound 64 (5.2, 67%).
Compound experiment embodiment 9) compound 70 preparation
The preparation of compound 70-1
In single necked round bottom flask simultaneously [b] by dibenzo [b, d] thiophene -4- ylboronic acids (23g, 107.9mmol), 3- bromobenzenes Thiophene (27g, 118.7mmol), K2CO3(10g, 10.8mmol), H2O (90ml) and 1,4- dioxane (360ml) solution it is mixed Object is closed to flow back 12 hours at 110 DEG C.After concentration, mixture CH2Cl2(3 × 300ml) and distilled water (150ml) extract, and are used in combination Silica gel filters.After concentration, mixture is stirred 1 hour with MeOH (400ml), uses CH2Cl2/ MeOH is precipitated, and palm fibre is then obtained by filtration Color solid chemical compound 70-1 (26.5g, 77%).
The preparation of compound 70-2
Under a nitrogen by compound 70-1 (26g, 82.1mmol), AcOH (400ml) solution, HNO3(10ml, It 246.4mmol) is slowly added in single necked round bottom flask with the mixture of AcOH (400ml) solution, is then heated to 60 DEG C and stirs It mixes 30 minutes.Mixture is cooled to room temperature, is filtered, is then washed with distilled water (800ml).Obtained solid compound is dissolved in CH2Cl2In (200ml), water layer is removed, organic layer is then concentrated under reduced pressure.Then Adsorption Concentration liquid uses column chromatography (SiO2, hexane: Dichloromethane=3:1) isolated yellow solid compound 70-2 (19.6g, 66%).
The preparation of compound 70-3
Under a nitrogen by compound 70-2 (17.9g, 49.6mmol), PPh in single necked round bottom flask3(38.7g, 148.4mmol) flow back 12 hours at 180 DEG C with the mixture of 1,2- dichloro-benzenes (500ml).1,2- dichloros are removed by distillation Benzene, then gained mixture CH2Cl2/ MeOH is precipitated and is filtered, and then uses column chromatography (SiO2, hexane:Dichloromethane=2:1) Isolated opaque compound as white solid 70-3 (10g, 61%).
The preparation of compound 70
By compound 70-3 (10g, 30.35mmol), compound experiment embodiment 1 under nitrogen charging in single necked round bottom flask Compound 1-4 (13.34g, 33.38mmol), Cu (1.9mg, 30.35mmol), 18- crown- 6- ethers (987mg, 3.03mmol), K2CO3The mixture of (8.3g, 60.7mmol) and o-DCB (100ml) flow back 60 hours at 180 DEG C.1,2- bis- is removed by distillation Chlorobenzene, then gained mixture column chromatography (SiO2, hexane:Dichloromethane=3:1) isolated solid chemical compound 70 (13.6g, 69%).
Compound experiment embodiment 10) compound 73 preparation
The preparation of compound 73-1
Sulfuric acid (1.4ml, 0.1 equivalent) is slowly added into 1,2-, bis- cyclohexanone under nitrogen charging in single necked round bottom flask In (30.0g, 1.0 equivalents), phenylhydrazine hydrochloride (77.37g, 2.0 equivalents) and the mixture of ethyl alcohol (1,000ml), then by gained Mixture stirs 4 hours at 60 DEG C.Khaki solid 73-1 (69g, 93%) is obtained by filtration in the solution that will be cooled to room temperature.
The preparation of compound 73-2
Compound 73-1 (68.9g, 1.0 equivalents), acetic acid (700ml) and trifluoroacetic acid (46.5ml, 2.4 equivalents) are added In single necked round bottom flask, then stirred 15 hours at 100 DEG C.The solution acetic acid and hexane that will be cooled to room temperature are washed and are filtered Obtain Off-white solid 73-2 (27.3g, 42%).
The preparation of compound 73-3
In single necked round bottom flask under nitrogen charging by compound 73-2 (2.1g, 1.0 equivalents), (2.5g, 1.5 work as iodobenzene Amount), Cu (0.312g, 0.6 equivalent), 18- crown- 6- ethers (0.433g, 0.2 equivalent), K2CO3(3.397g, 3.0 equivalents) and 1,2- The mixture of dichloro-benzenes (20ml) stirs 16 hours at a reflux temperature.The solution MC/H being cooled to room temperature2O extractions are simultaneously dense Then column chromatography (SiO is used in contracting2, hexane:Ethyl acetate=10:1) isolated compound as white solid 73-3 (1.76g, 64%).
The preparation of compound 73
By compound 73-3 (1.7g, 5.11mmol), compound experiment embodiment 1 under nitrogen charging in single necked round bottom flask Compound 1-4 (2g, 5.11mmol), Cu (324mg, 5.11mmol), 18- crown- 6- ethers (166mg, 0.51mmol), K2CO3 The mixture of (1.4g, 0.22mmol) and o-DCB (10ml) flow back 60 hours at 180 DEG C.1,2- dichloro-benzenes is removed by distillation, Then gained mixture column chromatography (SiO2, hexane:Dichloromethane=2:1) isolated solid chemical compound 73 (1.1g, 33%).
Compound experiment embodiment 11) compound 74 preparation
By compound 74-1 (1g, 3.53mmol), the compound 1-4 of compound experiment embodiment 1 in single necked round bottom flask (1.2g, 3.53mmol), Pd (OAc)2(80mg, 0.353mmol), K3PO4(1.4g, 7.06mmol), P (t-Bu)3(1.5ml, 1mmol) flow back 24 hours at 100 DEG C with the mixture of o-DCB (10ml).The mixture is extracted with MC, uses MgSO4It is dry, Then column chromatography (SiO is used2, hexane:Dichloromethane=2:1) isolated solid chemical compound 74 (1.35g, 64%).
Compound experiment embodiment 12) compound 79 preparation
The preparation of compound 79-1
By dibenzo [b, d] furans -2- ylboronic acids (20g, 94.33mmol), the bromo- 2- nitros of 1- in single necked round bottom flask Benzene (19g, 94.33mmol), K2CO3(26g, 188mmol), H2The solution of O (45ml) and 1,4- dioxane (300ml) is 110 DEG C reflux 12 hours.After concentration, mixture CH2Cl2(3 × 200ml) and distilled water (120ml) extract, and silica gel is used in combination to filter. After concentration, mixture column chromatography (SiO2, hexane:Dichloromethane=8:1) isolated Off-white solid compound 79-1 (18.2g, 67%).
The preparation of compound 79-2
By compound 79-1 (19g, 65.6mmol), PPh under nitrogen charging in single necked round bottom flask3(51.6g, 197mmol) flow back 12 hours at 180 DEG C with the mixture of 1,2- dichloro-benzenes (400ml).1,2- dichloro-benzenes is removed by distillation, Then gained mixture CH2Cl2/ MeOH is precipitated and is filtered, and then uses column chromatography (SiO2, hexane:Dichloromethane=2:1) divide From obtaining compound as white solid 79-2.(6.7g, 39%)
The preparation of compound 79
By the change of compound 79-2 (6.7g, 26mmol), compound experiment embodiment 1 under nitrogen charging in single necked round bottom flask Close object 1-4 (10.4g, 26mmol), Cu (1.6g, 26mmol), 18- crown- 6- ethers (847mg, 2.6mmol), K2CO3(7.1g, 52mmol) flow back 48 hours at 180 DEG C with the mixture of o-DCB (100ml).1,2- dichloro-benzenes is removed by distillation, then institute Obtain mixture column chromatography (SiO2, hexane:Dichloromethane=3:1) isolated compound as white solid 79 (7.2g, 48%).
Compound experiment embodiment 13) compound 89 preparation
Other than using the compound 3-4 of compound experiment embodiment 3 to replace the compound 1-4 of compound experiment embodiment 1, The compound is synthesized in a manner of identical in the preparation with compound 49.
Compound experiment embodiment 14) compound 90 preparation
Other than using the compound 3-4 of compound experiment embodiment 3 to replace the compound 1-4 of compound experiment embodiment 1, The compound is synthesized in a manner of identical in the preparation with compound 50.
Compound experiment embodiment 15) compound 99 preparation
Other than using the compound 3-4 of compound experiment embodiment 3 to replace the compound 1-4 of compound experiment embodiment 1, The compound is synthesized in a manner of identical in the preparation with compound 60.
Compound experiment embodiment 16) compound 104 preparation
Other than using the compound 3-4 of compound experiment embodiment 3 to replace the compound 1-4 of compound experiment embodiment 1, The compound is synthesized in a manner of identical in the preparation with compound 64.
Compound experiment embodiment 17) compound 110 preparation
Other than using the compound 3-4 of compound experiment embodiment 3 to replace the compound 1-4 of compound experiment embodiment 1, The compound is synthesized in a manner of identical in the preparation with compound 70.
Compound experiment embodiment 18) compound 113 preparation
Other than using the compound 3-4 of compound experiment embodiment 3 to replace the compound 1-4 of compound experiment embodiment 1, The compound is synthesized in a manner of identical in the preparation with compound 73.
Compound experiment embodiment 19) compound 119 preparation
Other than using the compound 3-4 of compound experiment embodiment 3 to replace the compound 1-4 of compound experiment embodiment 1, The compound is synthesized in a manner of identical in the preparation with compound 79.
Compound experiment embodiment 20) compound 129 preparation
The preparation of compound S9
The preparation of compound S9-1
The 2- methyl-bromobenzoates of 20g (93mmol, 1 equivalent) are dissolved in the THF of 180ml, then by 7.44g's NaH is added in solution, and gained mixture is stirred 30 minutes.After stirring, being slowly added to 11.17g thereto, (93mmol, 1 works as Amount) acetophenone.Gained mixture is stirred 2 hours at normal temperatures, is then heated 16 hours at 100 DEG C.After the completion of reaction, Temperature is cooled to room temperature, then sequence ethyl acetate, 1N HCl, NaHCO3Aqueous solution and H2O extracts products therefrom.Extraction Afterwards, extract obtains the S9-1 of 25.6g (90%) with column chromatography separating purification.
The preparation of compound S9-2
The compound S9-1 of 25.6g (84mmol, 1 equivalent) is dissolved in the DMF of 160ml, is then added into the solution Enter the H of 6ml (92.4mmol, 1.1 equivalents)2NNH2·H2O, and gained mixture is stirred 6 hours at normal temperatures.When having reacted Cheng Hou, with ethyl acetate and H2O extracts products therefrom.After extraction, extract obtains 20g's (79%) with column chromatography separating purification S9-2。
The preparation of compound S9-3
The compound S9-2 of 20g (66mmol, 1 equivalent) is dissolved in the DMF of 240ml, is then added into the solution The 4- bromobenzaldehydes of the CuI and 14.8g (80.4mmol, 1.2 equivalents) of 1.25g (6.6mmol, 0.1 equivalent), and gained is mixed Object stirs 30 minutes.After stirring, the NH of 66ml is added into solution3·H2O, and it is small that gained mixture is stirred at 100 DEG C to 24 When.After the completion of reaction, with ethyl acetate and H2O extracts products therefrom.After extraction, extract is obtained with column chromatography separating purification The S9-3 of 15g (56%).
The preparation of compound S9
The compound S9-3 of 15g (37mmol, 1 equivalent) is dissolved in the DMF of 60ml, is then added into the solution The CuI of 1.25g (6.6mmol, 0.1 equivalent), and gained mixture is stirred 24 hours at 100 DEG C.After the completion of reaction, second is used Acetoacetic ester and H2O extracts products therefrom.After extraction, extract obtains the S9 of 10g (80%) with column chromatography separating purification.
The preparation of compound 129
Other than using the compound 1-4 that compound S9 replaces compound experiment embodiment 1, with the preparation with compound 49 In identical mode synthesize the compound.
Compound experiment embodiment 21) compound 139 preparation
Other than using the compound 1-4 that compound S9 replaces compound experiment embodiment 1, with the preparation with compound 59 In identical mode synthesize the compound.
Compound experiment embodiment 22) compound 144 preparation
Other than using the compound 1-4 that compound S9 replaces compound experiment embodiment 1, with the preparation with compound 64 In identical mode synthesize the compound.
The prepare compound in a manner of identical with compound experiment embodiment, and will confirm that the result of synthesis includes in table 5 In.
[table 5]
Test example 1：
It (is manufactured by Princeton Applied Research Inc., model using CV measuring instruments：Parstat2273) Measure in the following method compound 16, compound 26, compound 49, compound 50, compound 89 and compound 90 HOMO, LUMO and band gap, and the results are shown in the following table 7 to 12.
1, the preparation of electrolyte solution, standard solution and testing liquid
1) electrolyte solution：The tetrabutyl ammonium tetrafluoroborate of accurate weighing 3.3g is simultaneously added in the volumetric flask of 100ml, so Dichloromethane is added to the electrolyte solution that 100ml is prepared in the volumetric flask afterwards.
2) standard solution：The NPB of accurate weighing 1mg is simultaneously added in the volumetric flask of 10ml, then adds electrolyte solution Enter the solution for preparing 10ml into the volumetric flask, the solution is then used as standard solution.
3) testing liquid：Using compound as sample, the compound of accurate weighing 1mg and the appearance for being added to 10ml In measuring bottle, then electrolyte solution is added to the solution that 10ml is prepared in the volumetric flask, then by the solution with being tested Solution.
2, analysis condition
[table 6]
Parameter Value
Reference electrode type Ag.AgCl/NaCl (saturation)
Initial potential (E0) 0.00 volt
Spike potential (E1) 1.5 to 2.5 volts
Final potential (E2) 0.00 volt
Sweep speed 50 to 100 volts
3, CV measurement methods
1) NPB and electrolyte solution is used to prepare the standard solution of 6ml.
2) installment work electrode, reference electrode and auxiliary electrode.
3) it carries out nitrogen to be bubbled about 30 seconds, then starts to measure.
4) when the measurement is finished, using MC and acetone that electrode clean is clean, then prepare the experiment of compound to be measured Solution simultaneously measures in aforementioned manners.
4, calculation formula
Homo=-5.5- (Eox(to measure compound)-Eox(NPB))eV
Band gap (HOMO-LUMO)=1240/UV absorbs limit
[table 7]
[table 8]
[table 9]
[table 10]
[table 11]
[table 12]
Figure 4 and 5 show E derived from the CV measurement results by compound 16oxValue.
E derived from CV measurement results of the displays of Fig. 6 and 7 by compound 26oxValue.
E derived from CV measurement results of the displays of Fig. 8 and 9 by compound 49oxValue.
E derived from CV measurement results of the displays of Figure 10 and 11 by compound 50oxValue.
E derived from CV measurement results of the displays of Figure 12 and 13 by compound 89oxValue.
E derived from CV measurement results of the displays of Figure 14 and 15 by compound 90oxValue.
In Fig. 4 to 15, y-axis refers to electric current (unit：A), and x-axis refers to potential (unit：V).
Meanwhile compound 49, compound 50, the T1 values of compound 89 and compound 90 are shown in the following table 13.T1 values are Derived from low temperature PL nmax values.Specifically, T1 values be by instrument HITACHI-F7000, -196 DEG C of temperature (77K), What diluent 2- methyltetrahydrofurans and calculation formula [T1 (eV)=1240/PL most short-crested waves length (nm)] obtained.
[table 13]
Compound 49 Compound 50 Compound 89 Compound 90
T1 2.60eV 2.59eV 2.60eV 2.60eV
Meanwhile Figure 16 shows the UV experiment curv figures of compound 16.
Figure 17 shows PL experiment curv figure of the compound 16 relative to 263nm.
Figure 18 shows the UV experiment curv figures of compound 26.
Figure 19 shows PL experiment curv figure of the compound 26 relative to 327nm.
Figure 20 shows LTPL (- 78 DEG C) experiment curv figure of compound 49.
Figure 21 shows the UV experiment curv figures of compound 49.
Figure 22 shows PL experiment curv figure of the compound 49 relative to 261nm.
Figure 23 shows LTPL (- 78 DEG C) experiment curv figure of compound 50.
Figure 24 shows the UV experiment curv figures of compound 50.
Figure 25 shows PL experiment curv figure of the compound 50 relative to 264nm.
Figure 26 shows LTPL (- 78 DEG C) experiment curv figure of compound 89.
Figure 27 shows the UV experiment curv figures of compound 89.
Figure 28 shows PL experiment curv figure of the compound 89 relative to 259nm.
Figure 29 shows LTPL (- 78 DEG C) experiment curv figure of compound 90.
Figure 30 shows the UV experiment curv figures of compound 90.
Figure 31 shows PL experiment curv figure of the compound 90 relative to 331nm.
The y-axis and x-axis of Figure 16 to 31 is respectively intensity and wavelength (unit：nm).
Comparing embodiment 1：The manufacture of OLED device
First, by for the transparent electrode ito thin film of OLED obtained by glass (by Samsung Corning Co., Ltd (Samsung-Corning Co., Ltd.) is manufactured) it is washed using trichloro ethylene, acetone, ethyl alcohol and distilled water ultrasound by sequence It washs, is washed in isopropanol, then used.
Then, ITO substrate is mounted on the substrate folder of vacuum deposition instrument, vacuum deposition instrument is vacuumized until vacuum is sunk Vacuum degree in product instrument reaches 10-7Then support passes through 4,4', 4 following "-three (N, N- (2- the naphthalenes)-phenylaminos that are vapor-deposited Base) triphenylamine (2-TNATA) deposition thickness in ITO substrate isHole injection layer.
Then, by the way that by following N, it is heavy that N'- bis- (Alpha-Naphthyl)-N, N'- diphenyl -4,4'- diamines (NPB) is put into vacuum Another interior of product instrument applies electric current to the room and evaporates compound deposition thickness on hole injection layer and be's Hole transmission layer.
After forming hole injection layer and hole transmission layer, depositing light emitting layer on it as follows.By following main body (α- AND an interior of vacuum deposition instrument) is put into as luminescent material, and following dopant (BD1) is put into another interior.
Then, by heating the two rooms together, and with deposition velocity ratio (main body:Dopant=95:5) 5wt% is deposited Dopant on the hole transport layer withThickness depositing light emitting layer.Then, with Thickness deposit it is following Three (8-hydroxyquinoline) aluminium (III) (Alq3) it is used as electron transfer layer.
Later, withThe depositing fluorinated lithium of thickness (LiF) be used as electron injecting layer.In addition, by with 1's Thickness depositing Al cathode manufactures OLED.
Meanwhile for manufacturing all organic compounds of OLED device for each material all 10-6To 10-8Under support into Row vacuum sublimation and purifying, and for manufacturing OLED.
Embodiment 1：The manufacture of OLED device
In addition to using the compound prepared in compound 1 to 38 to replace three (8-hydroxyquinoline) aluminium in comparative example (III)(Alq3) as the material of electron transfer layer outside, by with it is identical in comparative example in a manner of manufacture OLED.
Test example 2：The evaluation of OLED characteristics
In 1,000cd/m2The OLED device manufactured as described above driving voltage (Op.V) and efficiency (cd/A) and Until time when efficiency is down to 50% describes in the following table 14.
[table 14]
Compound number Op.V Cd/A T50
1 4.46 4.8 430
2 4.44 5.0 440
3 4.46 4.8 450
4 4.48 4.7 430
5 4.46 4.8 440
6 4.46 4.7 440
7 4.39 5.0 450
8 4.35 5.3 480
9 4.39 5.1 460
10 4.42 5.0 450
11 4.43 4.9 440
12 4.43 5.0 440
13 1.45 5.0 440
14 4.43 5.0 450
15 4.44 5.1 440
16 4.21 5.6 550
17 4.30 5.3 500
18 4.29 5.5 520
19 4.30 5.4 500
20 4.40 4.9 440
21 4.39 5.0 450
22 4.40 5.0 440
26 4.31 5.6 540
27 4.38 5.1 480
28 4.30 5.3 500
29 4.35 5.3 480
30 4.43 4.9 430
31 4.40 4.9 440
32 4.41 4.9 440
33 4.43 5.0 450
34 4.42 5.0 450
35 4.43 5.1 440
36 4.47 5.0 450
37 4.43 5.0 450
38 4.45 5.0 440
1 (Alq of comparing embodiment3) 6.73 4.3 350
Comparing embodiment 2：The manufacture of OLED device
By for the transparent electrode ito thin film (Co., Ltd manufactures by Samsung Corning) of OLED obtained by glass by suitable Sequence uses trichloro ethylene, acetone, ethyl alcohol and distilled water supersound washing, is stored in isopropanol, then uses.
Then, ITO substrate is mounted on the substrate folder of vacuum deposition instrument, and by following 4,4', 4 "-three (N, N- (2- Naphthalene)-phenyl amino) triphenylamine (2-TNATA) is put into an interior of vacuum deposition instrument.
Then, room is vacuumized until the vacuum degree in the room reaches 10-6Support, then by applying electric current to the room and steaming Sending out 2-TNATA deposition thickness in ITO substrate isHole injection layer.By by following N, N'- bis- (Alpha-Naphthyl)- N, N'- diphenyl -4,4'- diamines (NPB) are put into another interior of vacuum deposition instrument, and described to evaporate to room application electric current Compound come on hole injection layer deposition thickness be Hole transmission layer.
After as formed above hole injection layer and hole transmission layer, phosphorescence green of the deposition with following structure is sent out on it Luminescent material is as luminescent layer.An interior of vacuum deposition instrument withThickness vacuum deposition as green emitting main body 4,4'- bis- (carbazole -9- bases) biphenyl (CBP) of material, and together with the material of main part, with based on the material of main part amount 10% amount vacuum deposition three (2- phenylpyridines) iridium (III) (Ir (ppy)3)。
Then, withThickness deposit the following 2,9- dimethyl -4,7- hexichol as hole barrier layer material Base -1,10- phenanthroline (BCP) be used as hole blocking layer, and withThickness deposit three following (8- Hydroxy-quinolins Close) aluminium (Alq3) it is used as electron transfer layer.
Later, withThe depositing fluorinated lithium of thickness (LiF) be used as electron injecting layer.In addition, by withThickness It spends depositing Al cathode and manufactures OLED.
Meanwhile for manufacturing all organic compounds of OLED device for each material all 10-6To 10-8Under support into Row vacuum sublimation and purifying, and for manufacturing OLED.
Embodiment 2
In addition to use the following table 15 material replace CBP as the material of green light emitting layer other than, with in comparing embodiment 2 Identical mode manufactures device by using other materials.
Test example 3：The evaluation of OLED characteristics
In 1,000cd/m2The OLED manufactured as described above driving voltage (Op.V) and efficiency (cd/A) and until Time when efficiency is down to 50% describes in the following table 15.
[table 15]
Compound number Op.V Cd/A T50
49 4.65 42.3 410
50 4.63 43.1 400
59 4.69 45.2 400
64 4.68 44.9 410
70 4.58 44.2 420
73 4.62 43.1 380
74 4.64 42.2 410
79 4.62 44.3 370
89 4.59 42.2 380
90 4.60 42.8 370
99 4.61 43.2 380
104 4.62 43.3 380
110 4.59 43.1 400
113 4.61 43.0 370
119 4.58 42.7 350
129 4.65 42.4 430
139 4.64 44.1 430
144 4.65 44.3 430
Comparing embodiment 2 (CBP) 6.71 35.3 260
[reference numeral]
100:Substrate
200：Anode
300 organic material layers
301 hole injection layers
302 hole transmission layers
303 luminescent layers
304 electron transfer layers
305 electron injecting layers
400：Cathode

Claims (13)

1. the compound of following formula 2：
[formula 2]
Wherein, in formula 2,
L is C6To C20Arlydene,
Het is pyridyl group, substituted or unsubstituted pyrimidine radicals or the substituted or unsubstituted triazine radical of substitution, and works as Het When substituted, substituent group is phenyl, naphthalene or phenanthryl, and is unsubstituted or pyridyl is further substituted with,
The integer that n is 0 to 2, p are 1 or 2,
R2For C1To C20Linear or branched alkyl group or C6To C20Aryl；And
R3To R7For hydrogen.
2. the compound of formula 3 below：
[formula 3]
Wherein, in formula 3,
R2For C1To C20Linear or branched alkyl group or C6To C20Aryl；
R3To R7For hydrogen；
R8It is unsubstituted or use C6To C20The C of aryl substitution6To C20Aryl, and the integer that m is 0 to 9,
L is C6To C20Arlydene, and
The integer that n is 0 to 2.
3. the compound of formula 4 below：
[formula 4]
Wherein, in formula 4,
R2For C1To C20Linear or branched alkyl group or C6To C20Aryl；
R3To R7For hydrogen；
X1 and X2 is unsubstituted or uses C1To C20Linear or branched alkyl group and C6To C20The C of at least one of aryl substitution6Extremely C20Aromatic series hydrocarbon ring is unsubstituted or use C1To C20Linear or branched alkyl group and C6To C20The substitution of at least one of aryl C2To C20Heteroaromatic,
L is C6To C20Arlydene, and
The integer that n is 0 to 2.
4. compound according to claim 3, whereinSelected from following structural：
In the structural formula, Y1To Y6Respectively CRR ', NR, S or O,
Z1To Z3Respectively S or O, and
R and R' are same or different to each other, and respectively hydrogen, C1To C20Linear or branched alkyl group or C6To C20Aryl.
5. compound according to claim 1, wherein 2 compound of formula is selected from following compounds：
6. the compound selected from following compounds：
7. compound according to claim 3, wherein the compound of formula 4 is selected from following compounds：
8. a kind of organic luminescent device comprising：
Anode；
Cathode；With
One or more layers organic material layer between the anode and cathode is set,
Wherein, one or more layers in the organic material layer includes chemical combination according to any one of claim 1 to 7 Object.
9. organic luminescent device according to claim 8 is comprising the organic material layer of the compound is selected from sky One or more layers in cave implanted layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer.
10. organic luminescent device according to claim 8 is comprising the organic material layer of the compound is electronics Transport layer.
11. organic luminescent device according to claim 8 is comprising the organic material layer of the compound is luminous Layer.
12. organic luminescent device according to claim 11, wherein the luminescent layer also includes light-emitting dopant.
13. organic luminescent device according to claim 11 further comprises being arranged between luminescent layer and cathode Hole blocking layer.
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