CN105601570A - Compound containing heterocyclic ligand and preparation method and application thereof - Google Patents

Compound containing heterocyclic ligand and preparation method and application thereof Download PDF

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Publication number
CN105601570A
CN105601570A CN201610117722.4A CN201610117722A CN105601570A CN 105601570 A CN105601570 A CN 105601570A CN 201610117722 A CN201610117722 A CN 201610117722A CN 105601570 A CN105601570 A CN 105601570A
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replacement
unsubstituted
formula
condensed ring
compound
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高春吉
王永光
崔敦洙
尹恩心
李明
王钊
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Jilin Optical and Electronic Materials Co Ltd
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Jilin Optical and Electronic Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/18—Benzimidazoles; Hydrogenated benzimidazoles with aryl radicals directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
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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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/381—Metal complexes comprising a group IIB metal element, e.g. comprising cadmium, mercury or zinc
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/186—Metal complexes of the light metals other than alkali metals and alkaline earth metals, i.e. Be, Al or Mg
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups

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  • Electroluminescent Light Sources (AREA)

Abstract

The invention provides a compound containing a heterocyclic ligand, a preparation method thereof and an electroluminescence device. According to the compound containing the heterocyclic ligand, the specific heterocyclic ligand is selected to be combined with different metals, the wavelength of the compound can be adjusted, and after the obtained organic metal compound is used for the organic electroluminescence device, the luminous efficiency of the device is improved, and the service life is long.

Description

A kind of compound containing heterocyclic ligand and preparation method thereof, application
Technical field
The present invention relates to luminous organic material field, relate in particular to a kind of compound and preparation side thereof containing heterocyclic ligandMethod, application.
Background technology
Organic luminescent device (OLED) is normally made up of the organic matter layer inserting between negative electrode, anode and negative electrode and anode, the composition of device is by transparent ito anode, hole injection layer (TIL), hole transmission layer (HTL), luminescent layer (EL), skyBarrier layer, cave (HBL), electron transfer layer (ETL), electron injecting layer (EIL) and negative electrode form, and can omit on demand 1～2 organicLayer. Its mechanism of action is between two electrodes, to form voltage to inject from cathode electronics on one side, and another side is from anode injected hole, electricitySon and hole are at luminescent layer again in conjunction with forming excitation state, and excitation state is got back to stable ground state, and device is luminous.
Wherein, the luminescent material in luminescent device is divided into fluorescent material and phosphor material, and the formation method of luminescent layer is mainHaving: 1) Doping Phosphorus luminescent material (organic metal) in fluorescence material of main part, 2) fluorescence material of main part doping fluorescent (comprises the organic of nitrogenThing) adulterant, 3) utilize the existing long wavelength of adulterant (DCM, Rubrene, DCJTB etc.) tool in illuminator; And the luminous material of dopingThe emission wavelength of material to luminescent device, efficiency, driving voltage and life-span all have a great impact.
General form luminescent layer material be have the centerbodies such as benzene, naphthalene, fluorenes, spiral shell two fluorenes, anthracene, pyrene, carbazole and benzene, biphenyl,The part such as naphthalene, heterocycle; The replacing structures such as the binding site at contraposition, a position, ortho position and amido, cyano group, fluorine, methyl, the tert-butyl group.
As:
Organic metal part is applied in OLED in various form, and what cyan was luminous has FIrPic and Bepp2, green sending outLight have Zn (BTZ) 2 and an Alq3, electron transport material material has Alq3, electron injection material has Liq etc.
Along with oled panel develops into maximization, need material finer and smoother and that color is distincter and there is better propertyCan, luminous efficiency and life-span also need further raising on the other hand.
But, current disclosed luminescent material, its luminous efficiency and life-span are all poor, therefore, develop a kind of luminous effectRate is high and have the luminescent material of longer life, has become that this area is each to produce and application vendor is urgently that the technology of solution is askedTopic.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide compound and the preparation side thereof containing heterocyclic ligandMethod, organic electroluminescence device, this compound light-emitting efficiency better and long service life.
The invention provides a kind of compound containing heterocyclic ligand, described compound has formula (1) structure,
Wherein, described R1、R2、R3、R4、R5、R6、R7And R8Independently be selected from separately hydrogen, halogen, cyano group, replacement or do not replaceThe cycloalkyl, replacement or not of alkoxyl, replacement or unsubstituted C1～C30 of C1～C30 of alkyl, replacement of C1～C30The aryl of heterocyclic radical, replacement or the unsubstituted C6～C50 of aryl, replacement or the unsubstituted C5～C50 of the C6～C60 replacingThe condensed ring radical of amido, replacement or unsubstituted C8～C60;
Described R9Be selected from replace or the alkyl of unsubstituted C1～C30, aryl replacement or unsubstituted C6～C60,The condensed ring radical of replacement or unsubstituted C8～C60;
Described M is selected from Be, Zn or Al; Described L is integer, when M is selected from Be or Zn, and L=2, when M is selected from Al, L=3;
Described R9During for benzene, described R1～R8Can not be hydrogen simultaneously;
Described R1、R2、R3And R4In the phenyl ring at any two adjacent substituting groups and place form condensed ring structure or non-condensed ringStructure;
Described R5、R6、R7And R8In the phenyl ring at any two adjacent substituting groups and place form condensed ring structure or non-condensed ringStructure.
Preferably, described R1、R2、R3、R4、R5、R6、R7、R8Each group is independently selected from hydrogen, halogen, cyano group, replacement or does not getThe cycloalkyl of alkoxyl, replacement or the unsubstituted C1～C20 of the alkyl of the C3～C20 in generation, the C1～C20 of replacement, replacement orThe virtue of heterocyclic radical, replacement or the unsubstituted C6～C30 of aryl, replacement or the unsubstituted C5～C30 of unsubstituted C6～C30The condensed ring radical of base amido, replacement or unsubstituted C10～C30.
Preferably, described R1、R2、R3、R4、R5、R6、R7、R8Independently be selected from separately methyl, ethyl, propyl group, isopropyl, uncleButyl, normal-butyl, isobutyl group, suc as formula any one shown in (a-1)～formula (a-37),
Wherein, described X, Y be independently selected from separately hydrogen, halogen, cyano group, alkyl replacement or unsubstituted C1～C30,Replace or thiazolinyl, replacement or the unsubstituted C7 of alkoxyl, replacement or the unsubstituted C2～C30 of unsubstituted C1～C30～Aryl, the replacement of aryloxy alkyl, replacement or the unsubstituted C6～C30 of alkaryl, replacement or the unsubstituted C7～C30 of C30Or the heterocyclic radical of the aryloxy group of unsubstituted C6～C30, replacement or unsubstituted C5～C30, replacement or unsubstituted C6～C60The condensed ring radical of arylamine group, replacement or unsubstituted C8～C60.
Preferably, described R9For replacing or the virtue of alkyl, replacement or the unsubstituted C8～C30 of unsubstituted C3～C20The condensed ring radical of base, replacement or unsubstituted C10～C30.
Preferably, described R9For methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, the tert-butyl group, amyl group, hexyl, benzeneThe anthracene of the naphthyl of base, phenyl containing fluorophenyl, cyano-containing, naphthyl, fluorine-containing naphthyl, cyano-containing, anthryl, fluorine-containing anthryl, cyano-containingThe phenanthryl of base, phenanthryl, fluorine-containing phenanthryl, cyano-containing, xenyl, fluorine-containing xenyl or the xenyl of cyano-containing.
Preferably, described compound is suc as formula shown in (G), formula (H) or formula (I) any one,
Wherein, described R1、R2、R3、R4、R6Independently be selected from separately hydrogen, halogen, cyano group, replacement or unsubstituted C1～C30Alkyl, replacement C1～C30 alkoxyl, replacement or unsubstituted C1～C30 cycloalkyl, replacement or unsubstituted C6～Arylamine group, the replacement of heterocyclic radical, replacement or the unsubstituted C6～C50 of aryl, replacement or the unsubstituted C5～C50 of C60Or the condensed ring radical of unsubstituted C8～C60;
Described R9Be selected from replace or the alkyl of unsubstituted C1～C30, aryl replacement or unsubstituted C6～C60,The condensed ring radical of replacement or unsubstituted C8～C60;
Described R9During for benzene, described R1～R4And R6Can not be hydrogen simultaneously;
Described R1、R2、R3And R4In the phenyl ring at any two adjacent substituting groups and place form condensed ring structure or non-condensed ringStructure;
Described R6Adjacent any one the C atom of C atom, described C atom connecting and the benzene at above-mentioned two C atom placesCommon condensed ring structure or the non-condensed ring structure of forming of ring.
Preferably, described compound is suc as formula (G-0), formula (G-00), formula (G-000), formula (G-0000), formula (H-0), formula(H-00), formula (H-000), formula (H-0000), formula (I-0), formula (I-00), formula (I-000) or formula (I-0000) any one instituteShow:
Wherein, described R1、R2、R3、R4Independently be selected from separately hydrogen, halogen, cyano group, replacement or unsubstituted C1～C30Cycloalkyl, replacement or the unsubstituted C6 of alkoxyl, replacement or the unsubstituted C1～C30 of the C1～C30 of alkyl, replacement～Arylamine group, the replacement of heterocyclic radical, replacement or the unsubstituted C6～C50 of aryl, replacement or the unsubstituted C5～C50 of C60Or the condensed ring radical of unsubstituted C8～C60;
Described R9Be selected from replace or the alkyl of unsubstituted C1～C30, aryl replacement or unsubstituted C6～C60,The condensed ring radical of replacement or unsubstituted C8～C60.
Preferably, described compound suc as formula shown in G-1～formula G-30 any one, formula H-1～formula H-30 any one instituteShow or formula I-1～formula I-51 any one shown in,
The invention provides a kind of preparation of the compound containing heterocyclic ligand as described in technique scheme any oneMethod, comprises the following steps:
1) by the compound reaction of the compound of formula (II) structure and formula (III) structure, obtain formula (IV) structureCompound,
2) by compound and the M reactant salt of formula (IV) structure, the compound of (1) structure that obtains thering is formula;
Described R1、R2、R3、R4、R5、R6、R7And R8Independently be selected from separately hydrogen, halogen, cyano group, replacement or unsubstituted C1Cycloalkyl, replacement or the not replacement of alkoxyl, replacement or the unsubstituted C1～C30 of the alkyl of～C30, the C1～C30 of replacementThe arylamine of heterocyclic radical, replacement or unsubstituted C6～C50 of aryl, replacement or unsubstituted C5～C50 of C6～C60The condensed ring radical of base, replacement or unsubstituted C8～C60;
Described R9Be selected from replace or the alkyl of unsubstituted C1～C30, aryl replacement or unsubstituted C6～C60,The condensed ring radical of replacement or unsubstituted C8～C60;
Described M is selected from Be, Zn or Al; Described L is integer, when M is selected from Be or Zn, and L=2, when M is selected from Al, L=3;
Described R1、R2、R3And R4In the phenyl ring at any two adjacent substituting groups and place form condensed ring structure or non-condensed ringStructure;
Described R5、R6、R7And R8In the phenyl ring at any two adjacent substituting groups and place form condensed ring structure or non-condensed ringStructure.
The present invention also provides a kind of organic electroluminescence device, comprises electroluminescent material; Described electroluminescent materialComprise compound or the prepared compound of technique scheme described in technique scheme any one.
The invention provides a kind of compound containing heterocyclic ligand, described compound has formula (1) structure, wherein, described inR1、R2、R3、R4、R5、R6、R7And R8Independently be selected from separately hydrogen, halogen, cyano group, replacement or unsubstituted C1～C30 alkyl,The virtue of cycloalkyl, replacement or the unsubstituted C6～C60 of alkoxyl, replacement or the unsubstituted C1～C30 of the C1～C30 replacingArylamine group, replacement or the not replacement of heterocyclic radical, replacement or the unsubstituted C6～C50 of base, replacement or unsubstituted C5～C50The condensed ring radical of C8～C60; Described R9Be selected from replace or the alkyl of unsubstituted C1～C30, replacement or unsubstituted C6～The condensed ring radical of aryl, replacement or the unsubstituted C8～C60 of C60; Described M is selected from Be, Zn or Al; Described L is integer, and M is selected fromWhen Be or Zn, L=2, when M is selected from Al, L=3; Described R1、R2、R3And R4In the benzene at any two adjacent substituting groups and placeRing forms condensed ring structure or non-condensed ring structure; Described R5、R6、R7And R8In the phenyl ring at any two adjacent substituting groups and placeForm condensed ring structure or non-condensed ring structure. Compared with prior art, the compound containing heterocyclic ligand provided by the invention, by choosingSelect the part of specific heterocycle and different metal combinations, can regulate the wavelength of compound, the organo-metallic compound obtainingAfter for organic electroluminescence device, the luminous efficiency of device is improved, and long service life, experimental result shows,Use the OLED preparing containing the compound of heterocyclic ligand provided by the invention, its luminous efficiency can, up to 22.8cd/A, be used the longevityLife can be up to 9300 hours.
Detailed description of the invention
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, stillShould be appreciated that these describe just as further illustrating the features and advantages of the present invention, instead of to the claims in the present inventionRestriction.
The all raw materials of the present invention, are not particularly limited its source, on market, buy or according to art technology peoplePrepared by the conventional method that member knows.
The all raw materials of the present invention, are not particularly limited its purity, and the present invention preferably adopts analysis pure.
In the present invention, those skilled in the art can correct understanding formula (*) and the culvert of two kinds of form of presentation representatives of formula *Justice is equal to, and has or not bracket not affect its its practical significance.
The invention provides a kind of compound containing heterocyclic ligand, it is characterized in that, described compound has formula (1) knotStructure,
Wherein, described R1、R2、R3、R4、R5、R6、R7And R8Independently be selected from separately hydrogen, halogen, cyano group, replacement or do not replaceThe cycloalkyl, replacement or not of alkoxyl, replacement or unsubstituted C1～C30 of C1～C30 of alkyl, replacement of C1～C30The aryl of heterocyclic radical, replacement or the unsubstituted C6～C50 of aryl, replacement or the unsubstituted C5～C50 of the C6～C60 replacingThe condensed ring radical of amido, replacement or unsubstituted C8～C60;
Described R9Be selected from replace or the alkyl of unsubstituted C1～C30, aryl replacement or unsubstituted C6～C60,The condensed ring radical of replacement or unsubstituted C8～C60;
Described M is selected from Be, Zn or Al; Described L is integer, when M is selected from Be or Zn, and L=2, when M is selected from Al, L=3;
Described R9During for benzene, described R1～R8Can not be hydrogen simultaneously;
Described R1、R2、R3And R4In the phenyl ring at any two adjacent substituting groups and place form condensed ring structure or non-condensed ringStructure;
Described R5、R6、R7And R8In the phenyl ring at any two adjacent substituting groups and place form condensed ring structure or non-condensed ringStructure.
R of the present invention1、R2、R3、R4、R5、R6、R7And R8Separately independently preferably from hydrogen, halogen, cyano group, replacement or notCycloalkyl, the replacement of alkoxyl, replacement or the unsubstituted C1～C30 of the alkyl of the C1～C30 replacing, the C1～C30 of replacementOr the heterocyclic radical of the aryl of unsubstituted C6～C60, replacement or unsubstituted C5～C50, replacement or unsubstituted C6～C50The condensed ring radical of arylamine group, replacement or unsubstituted C8～C60, more separately independently preferably from hydrogen, halogen, cyano group, replacement orThe cycloalkyl of alkoxyl, replacement or the unsubstituted C3～C20 of the alkyl of unsubstituted C3～C20, the C3～C20 of replacement, getHeterocyclic radical, replacement or the unsubstituted C8～C30 of aryl, replacement or the unsubstituted C8～C30 of generation or unsubstituted C8～C30The condensed ring radical of arylamine group, replacement or unsubstituted C10～C30, more separately independently preferably from hydrogen, halogen, cyano group, replacementOr the cycloalkyl of alkoxyl, replacement or the unsubstituted C5～C10 of the C5～C10 of the alkyl of unsubstituted C5～C10, replacement,Heterocyclic radical, replacement or the unsubstituted C10 of aryl, replacement or the unsubstituted C10～C20 of replacement or unsubstituted C10～C20The condensed ring radical of arylamine group, replacement or the unsubstituted C14～C20 of～C20; More separately independently preferably from hydrogen, halogen, cyanogenAny one in base, methyl, ethyl, propyl group, isopropyl, the tert-butyl group, normal-butyl, isobutyl group, formula (a-1)～formula (a-37),
In the above-mentioned formula of the present invention (a-1)～formula (a-37), described X, Y separately independently preferably from hydrogen, halogen, cyano group, getAlkoxyl, replacement or the unsubstituted C2 of alkyl generation or unsubstituted C1～C30, replacement or unsubstituted C1～C30～Aryloxy alkyl, the replacement of alkaryl, replacement or the unsubstituted C7～C30 of thiazolinyl, replacement or the unsubstituted C7～C30 of C30Or the aryloxy group of the aryl of unsubstituted C6～C30, replacement or unsubstituted C6～C30, replacement or unsubstituted C5～C30The condensed ring radical of arylamine group, replacement or the unsubstituted C8～C60 of heterocyclic radical, replacement or unsubstituted C6～C60, more independentlyPreferably the do for oneself alkyl, the alkyl of unsubstituted C3～C20, the C3～C20 of replacement of C3～C20 of hydrogen, halogen, cyano group, replacementThe alkoxyl, the alcoxyl of unsubstituted C3～C20 of C3～C20 of cycloalkyl, replacement of cycloalkyl, unsubstituted C3～C20The arylamine group of the C8～C30 of the heterocyclic radical of the C8～C30 of base, replacement, the heterocyclic radical of unsubstituted C8～C30, replacement, do not getThe C10 of the aryl of the arylamine group of the C8～C30 in generation, the C8～C30 of replacement, the aryl of unsubstituted C8～C30, replacement～The condensed ring radical of C30 or the condensed ring radical of unsubstituted C10～C30; The more preferred C5 from hydrogen, halogen, cyano group, replacement～The cycloalkyl of the C5～C10 of the alkyl of C10, the alkyl of unsubstituted C5～C10, replacement, the cycloalkanes of unsubstituted C5～C10The heterocyclic radical of the C10～C15 of the alkoxyl of the C5～C10 of base, replacement, the alkoxyl of unsubstituted C5～C10, replacement, do not getThe arylamine group of the heterocyclic radical of the C10～C15 in generation, the C10～C18 of replacement, the arylamine group of unsubstituted C10～C18, replacementThe condensed ring radical of C14～C18 of aryl, replacement of aryl, unsubstituted C10～C16 of C10～C16 or unsubstituted C14～The condensed ring radical of C18; Most preferably be hydrogen, fluorine, cyano group, methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, the tert-butyl group, amyl group,The naphthyl of hexyl, phenyl, phenyl containing fluorophenyl, cyano-containing, naphthyl, fluorine-containing naphthyl, cyano-containing, anthryl, fluorine-containing anthryl, containing cyanogenThe phenanthryl of the anthryl of base, phenanthryl, fluorine-containing phenanthryl, cyano-containing, xenyl, fluorine-containing xenyl or the xenyl of cyano-containing.
In substituting group of the present inventionRepresent connecting key ,-X and-Y represent substituting group can place aromatic rings appointMeaning position.
The present invention is not particularly limited described alkyl, with alkyl well known to those skilled in the art, and institute of the present inventionState that alkyl is preferably direct-connected alkyl that straight chained alkyl, branched alkyl, at least 1 substituting group replace, at least 1 substituting group replacesBranched alkyl; Wherein, described substituting group is independently selected from one or more in halogen and cyano group, substituent on described alkylNumber is preferably 1～5, and more preferably 2,3 or 4.
The present invention is not particularly limited described cycloalkyl, with cycloalkyl well known to those skilled in the art, described inCycloalkyl is preferably unsubstituted cycloalkyl or at least 1 cycloalkyl that substituting group replaces; Wherein, described substituting group independently selectsOne or more in halogen and cyano group, in described cycloalkyl, substituent number is preferably 1～5, and more preferably 2,3 or 4.
The present invention is not particularly limited described alkoxyl, with alkoxyl well known to those skilled in the art, described inAlkoxyl is preferably unsubstituted alkoxyl or at least 1 alkoxyl that substituting group replaces; Wherein, described substituting group independently selectsOne or more in halogen and cyano group, on described alkoxyl, substituent number is preferably 1～5, and more preferably 2,3 or 4.
The present invention is not particularly limited described thiazolinyl, with thiazolinyl well known to those skilled in the art, and institute of the present inventionState thiazolinyl and be preferably straight-chain alkenyl, branched-chain alkenyl, cycloalkenyl group, at least 1 direct-connected thiazolinyl, at least 1 replacement that substituting group replacesThe branched-chain alkenyl that base replaces or at least 1 cycloalkenyl group that substituting group replaces; Wherein, described substituting group is independently selected from halogen and cyanogenOne or more in base, on described thiazolinyl, substituent number is preferably 1～5, and more preferably 2,3 or 4.
The present invention is not particularly limited described alkaryl, with alkaryl well known to those skilled in the art, thisBright described alkaryl is preferably unsubstituted alkaryl or at least 1 alkaryl that substituting group replaces; Wherein, described substituting group is onlyVertical selection halogen and/or cyano group; On described alkaryl, substituent number is preferably 1～5, and more preferably 2,3 or 4.
The present invention is not particularly limited described aryloxy alkyl, with aryloxy alkyl well known to those skilled in the art,Aryloxy alkyl of the present invention is preferably unsubstituted alkaryl or at least 1 aryloxy alkyl that substituting group replaces; Wherein, described inSubstituting group is independently selected halogen and/or cyano group; On described aryloxy alkyl, substituent number is preferably 1～5, more preferably 2,3 or 4.
The present invention is not particularly limited described aryl, with aryl well known to those skilled in the art, and institute of the present inventionState aryl and be preferably unsubstituted aryl or at least 1 aryl that substituting group replaces; Wherein, described substituting group is independently selected halogenElement and/or cyano group; On described aryl, substituent number is preferably 1～5, and more preferably 2,3 or 4.
The present invention is not particularly limited described aryloxy group, with aryloxy group well known to those skilled in the art, thisBright described aryloxy group is preferably unsubstituted aryl or at least 1 aryloxy group that substituting group replaces; Wherein, described substituting group is independentSelection halogen and/or cyano group; On described aryloxy group, substituent number is preferably 1～5, and more preferably 2,3 or 4.
The present invention is not particularly limited described heterocyclic radical, with heterocyclic radical well known to those skilled in the art, thisBright described heterocyclic radical is preferably unsubstituted heterocyclic radical or at least 1 heterocyclic radical that substituting group replaces; Wherein, mixing in heterocyclic radicalAtom is nitrogen, sulphur or oxygen; Described substituting group is independently selected halogen and/or cyano group; On described heterocyclic radical, substituent number is excellentElect 1～5 as, more preferably 2,3 or 4.
The present invention is not particularly limited described arylamine group, with arylamine group well known to those skilled in the art,Arylamine group of the present invention is preferably unsubstituted arylamine group or at least 1 arylamine group that substituting group replaces; Wherein, instituteState substituting group and independently select halogen and/or cyano group; In described arylamine group, substituent number is preferably 1～5, more preferably2,3 or 4.
The present invention is not particularly limited described condensed ring radical, with condensed ring radical well known to those skilled in the art, thisBright described condensed ring radical is preferably unsubstituted condensed ring radical or at least 1 condensed ring radical that substituting group replaces; Wherein, described substituting group is onlyVertical selection halogen and/or cyano group; On described condensed ring radical, substituent number is preferably 1～5, and more preferably 2,3 or 4.
R of the present invention9Preferably from replacing or the alkyl of unsubstituted C1～C30, replacement or unsubstituted C6～C60The condensed ring radical of aryl, replacement or unsubstituted C8～C60, more preferably from replacing or alkyl, the replacement of unsubstituted C3～C20Or the condensed ring radical of the aryl of unsubstituted C8～C30, replacement or unsubstituted C10～C30, more preferably from replacement or unsubstitutedThe condensed ring radical of aryl, replacement or the unsubstituted C14～C20 of alkyl, replacement or the unsubstituted C10～C20 of C5～C10, moreSpecifically preferably from methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, the tert-butyl group, amyl group, hexyl, phenyl, containing fluorophenyl, containThe phenyl of cyano group, naphthyl, fluorine-containing naphthyl, the naphthyl of cyano-containing, anthryl, fluorine-containing anthryl, the anthryl of cyano-containing, phenanthryl, fluorine-containing phenanthreneThe phenanthryl of base, cyano-containing, xenyl, fluorine-containing xenyl or the xenyl of cyano-containing.
The present invention is special, as described R9While being preferably benzene, described R1～R8Can not be preferably hydrogen, i.e. simultaneously described R1～R8Preferably having one is not hydrogen.
In the structure shown in formula of the present invention (1), preferred described R1、R2、R3And R4In any two adjacent substituting groups withThe phenyl ring at place forms condensed ring structure or non-condensed ring structure, i.e. preferred described R1、R2、R3And R4In any two adjacent replacementsThe phenyl ring at base and place can form condensed ring structure; The present invention refers to, described R1、R2、R3And R4In any two adjacent replacementsBase, and the C atom that is connected respectively of these two adjacent substituting groups, then and the phenyl ring at above-mentioned these two C atom places (R in formula (1)1、R2、R3And R4This phenyl ring at place), can jointly form condensed ring structure; That is to say described R1、R2、R3And R4In any two adjacent substituting groups, and the C atom that these two adjacent substituting groups are connected respectively can form benzene jointlyRing structure or condensed ring structure.
In the structure shown in formula of the present invention (1), preferred described R5、R6、R7And R8In any two adjacent substituting groups withThe phenyl ring at place forms condensed ring structure or non-condensed ring structure, i.e. preferred described R5、R6、R7And R8In any two adjacent replacementsThe phenyl ring at base and place can form condensed ring structure; The present invention refers to, described R5、R6、R7And R8In any two adjacent replacementsBase, and the C atom that is connected respectively of these two adjacent substituting groups, then and the phenyl ring at above-mentioned these two C atom places (R in formula (1)5、R6、R7And R8This phenyl ring at place), can jointly form condensed ring structure; That is to say described R5、R6、R7And R8In any two adjacent substituting groups, and the C atom that these two adjacent substituting groups are connected respectively can form benzene jointlyRing structure or condensed ring structure.
M of the present invention is preferably from Be, Zn or Al; Described L is preferably integer, when M is during preferably from Be, and L=2; When M preferredIn the time of Zn, L=2; When M is during preferably from Al, L=3.
More specifically, described M is preferably in the time of Be, and the described compound containing heterocyclic ligand is preferably formula (G),
The described compound containing heterocyclic ligand is preferably formula (G), wherein, and described R1、R2、R3、R4、R6Or R9SubstituentAs hereinbefore, this is no longer going to repeat them for range of choice and optimum principle scope;
Described R6Adjacent any one the C atom of C atom, described C atom connecting and the benzene at above-mentioned two C atom placesCommon condensed ring structure or non-condensed ring structure, the i.e. preferred described R of forming of ring6Connect C atom, described C atom adjacent any oneThe phenyl ring at individual C atom and above-mentioned two C atom places can form condensed ring structure; The present invention refers to, described R6The C connecting is formerSon, and any one adjacent C atom of this C atom, then and the phenyl ring at above-mentioned these two C atom places (be in formula (1)R5、R6、R7And R8This phenyl ring at place), can jointly form condensed ring structure; That is to say described R6The C atom connecting, andCan form benzene ring structure or condensed ring structure with any one adjacent C atom of this C atom.
Described M preferably in the time of Be, described more preferably formula (G-0), formula (G-00), the formula (G-of compound containing heterocyclic ligand000) or formula (G-0000),
Wherein, described R1、R2、R3、R4Or R9Substituent range of choice and optimum principle scope as hereinbefore, at thisRepeat no longer one by one;
Described M is preferably in the time of Be, and the described compound containing heterocyclic ligand is more preferably in formula G-1～formula G-30 any one,
More specifically, described M is preferably in the time of Zn, and the described compound containing heterocyclic ligand is preferably formula (H),
The described compound containing heterocyclic ligand is preferably formula (H), wherein, and described R1、R2、R3、R4、R6Or R9SubstituentAs hereinbefore, this is no longer going to repeat them for range of choice and optimum principle scope;
Described R6Adjacent any one the C atom of C atom, described C atom connecting and the benzene at above-mentioned two C atom placesCommon condensed ring structure or non-condensed ring structure, the i.e. preferred described R of forming of ring6Connect C atom, described C atom adjacent any oneThe phenyl ring at individual C atom and above-mentioned two C atom places can form condensed ring structure; The present invention refers to, described R6The C connecting is formerSon, and any one adjacent C atom of this C atom, then and the phenyl ring at above-mentioned these two C atom places (be in formula (1)R5、R6、R7And R8This phenyl ring at place), can jointly form condensed ring structure; That is to say described R6The C atom connecting, andCan form benzene ring structure or condensed ring structure with any one adjacent C atom of this C atom.
Described M preferably in the time of Zn, described more preferably formula (H-0), formula (H-00), the formula (H-of compound containing heterocyclic ligand000) or formula (H-0000),
Wherein, described R1、R2、R3、R4Or R9Substituent range of choice and optimum principle scope as hereinbefore, at thisRepeat no longer one by one;
Described M is preferably in the time of Zn, and the described compound containing heterocyclic ligand is more preferably in formula H-1～formula H-30 any one,
More specifically, described M is preferably in the time of Al, and the described compound containing heterocyclic ligand is preferably formula (I),
The described compound containing heterocyclic ligand is preferably formula (I), wherein, and described R1、R2、R3、R4、R6Or R9SubstituentAs hereinbefore, this is no longer going to repeat them for range of choice and optimum principle scope;
Described R6Adjacent any one the C atom of C atom, described C atom connecting and the benzene at above-mentioned two C atom placesCommon condensed ring structure or non-condensed ring structure, the i.e. preferred described R of forming of ring6Connect C atom, described C atom adjacent any oneThe phenyl ring at individual C atom and above-mentioned two C atom places can form condensed ring structure; The present invention refers to, described R6The C connecting is formerSon, and any one adjacent C atom of this C atom, then and the phenyl ring at above-mentioned these two C atom places (be in formula (1)R5、R6、R7And R8This phenyl ring at place), can jointly form condensed ring structure; That is to say described R6The C atom connecting, andCan form benzene ring structure or condensed ring structure with any one adjacent C atom of this C atom.
Described M preferably in the time of Al, described more preferably formula (I-0), formula (I-00), the formula (I-of compound containing heterocyclic ligand000) or formula (I-0000),
Wherein, described R1、R2、R3、R4Or R9Substituent range of choice and optimum principle scope as hereinbefore, at thisRepeat no longer one by one;
Described M is preferably in the time of Zn, and the described compound containing heterocyclic ligand is more preferably in formula I-1～formula I-51 any one,
The present invention also provides the preparation of the compound containing heterocyclic ligand described in a kind of above-mentioned any one technical schemeMethod, comprises the following steps:
1) by the compound reaction of the compound of formula (II) structure and formula (III) structure, obtain formula (IV) structureCompound,
2) by compound and the M reactant salt of formula (IV) structure, the compound of (1) structure that obtains thering is formula;
Described R1、R2、R3、R4、R5、R6、R7And R8Independently be selected from separately hydrogen, halogen, cyano group, replacement or unsubstituted C1Cycloalkyl, replacement or the not replacement of alkoxyl, replacement or the unsubstituted C1～C30 of the alkyl of～C30, the C1～C30 of replacementThe arylamine of heterocyclic radical, replacement or unsubstituted C6～C50 of aryl, replacement or unsubstituted C5～C50 of C6～C60The condensed ring radical of base, replacement or unsubstituted C8～C60;
Described R9Be selected from replace or the alkyl of unsubstituted C1～C30, aryl replacement or unsubstituted C6～C60,The condensed ring radical of replacement or unsubstituted C8～C60;
Described M is selected from Be, Zn or Al; Described L is integer, when M is selected from Be or Zn, and L=2, when M is selected from Al, L=3;
Described R1、R2、R3And R4In the phenyl ring at any two adjacent substituting groups and place form condensed ring structure or non-condensed ringStructure;
Described R5、R6、R7And R8In the phenyl ring at any two adjacent substituting groups and place form condensed ring structure or non-condensed ringStructure.
The present invention, to substituent range of choice and optimum principle in described raw material, as without dated especially, mixes with aforementioned containingThe range of choice of the compound of ring part is all consistent with optimum principle, and this is no longer going to repeat them.
First the present invention by the compound reaction of the compound of formula (II) structure and formula (III) structure, obtains formula(IV) compound of structure; The reaction equation of described reaction is suc as formula shown in A,
The present invention does not have particular/special requirement to the ratio of described raw material, normal with this type of reaction well known to those skilled in the artRule ratio, those skilled in the art can select and adjust according to practical condition, product requirement or quality requirementWhole. The present invention does not have particular/special requirement to the condition of described reaction, with the conventional bar of this type of reaction well known to those skilled in the artPart, those skilled in the art can select and adjust according to practical condition, product requirement or quality requirement, thisInvent described solvent and be preferably DMF, described catalyst is preferably sodium pyrosulfite.
In addition the not special limit in the source of the compound of the compound of the present invention to formula (II) structure and formula (III) structure,System, makes or commercially available purchase by preparation method well known in the art.
The present invention is also by compound and the M reactant salt of formula (IV) structure, (1) structure that obtains thering is formula containing heterocyclic ligandCompound; Described M is selected from Be, Zn or Al, and described M salt is more preferably from BeSO44H2O、ZnCl2Or Al2(SO4)3; Described reactionFormula is suc as formula shown in B,
The present invention does not have particular/special requirement to the ratio of above-mentioned reaction Raw, and this type of is anti-with well known to those skilled in the artThe conventional ratio of answering, those skilled in the art can select according to practical condition, product requirement or quality requirementSelect and adjust. The present invention does not have particular/special requirement to the condition of described reaction, with this type of reaction well known to those skilled in the artNormal condition, those skilled in the art can select according to practical condition, product requirement or quality requirement andAdjust, the solvent of reaction of the present invention is preferably methyl alcohol, and the alkali that reacts required is preferably the aqueous solution of NaOH.
The present invention obtains intermediate by aldehyde compound and amines through magically change reaction, has formula (IV) structureHeterocyclic compound, then the hydroxyl of this heterocyclic compound and metallic compound are formed to the new heterocyclic ligand with formula (1) structureCompound.
The present invention also provides a kind of organic electroluminescence device, comprises electroluminescent material; Described electroluminescent materialComprise the compound containing heterocyclic ligand described in technique scheme any one or technique scheme prepared containing heterocycleThe compound of part.
Organic electroluminescence device of the present invention preferably includes:
The first electrode, the second electrode and be placed in the organic matter layer between described two electrodes, wherein, wrap in described organic matter layerThe compound that contains structure shown in formula (1); The compound of structure shown in formula (1) can be single form or mix with other materialBe present in organic matter layer.
Wherein, described organic matter layer at least comprises hole injection layer, hole transmission layer, not only possesses hole injection but also possess skyCave transmission technical ability layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer and both possessed electronics and passDefeated one or more that possess again in electronic injection technical ability layer.
Described hole injection layer, described hole transmission layer, describedly not only possessed hole and inject but also possess hole transport technical ability layerIn to have one at least be conventional hole injected material, hole transport material or not only possessed hole and inject but also possess hole transportTechnical ability material is likely also the material that electric transmission material generates.
In this patent, " organic matter layer " refers to dispose between organic electronic device the first electrode and the second electrode wholeThe term of layer.
Such as, above-mentioned organic matter layer comprises luminescent layer, above-mentioned organic matter layer comprises phosphorescence main body, fluorescence main body, phosphorescenceIn doping and fluorescence doping more than one, wherein above-mentioned luminescent layer comprises the heterocyclic ligand of above-mentioned formula (1) structure, i) above-mentionedFluorescence main body can be above-mentioned formula (1) structure heterocyclic ligand ii) doping of above-mentioned fluorescence can be the assorted of above-mentioned formula (1) structureRing part iii) above-mentioned fluorescence main body and fluorescence doping can be the heterocyclic ligand of above-mentioned formula (1) structure.
Concrete, in the time that the compound of formula (1) structure is present in the luminescent layer in described organic layer, described formula (1) structureCompound can be used as the luminous main body of electroluminescent material or be entrained in other fluorescence main body; For example: luminescent layer canTo be redness, yellow or cyan luminescent layer. And compound doped in cyan main body by formula (1) structure can be improved luminousEfficiency, brightness, resolution ratio and the long-life of device.
When the compound of formula (1) structure is present in electron transfer layer, described electron transfer layer also comprises and contains metalCompound.
When described organic layer comprises luminescent layer and electron transfer layer, the compound of described formula (1) structure may reside inWherein one deck or two-layer.
Device prepared by the compound that includes formula (I) structure of the present invention can be for organic luminescent device(OLED), organic photovoltaic cell (OSC), Electronic Paper (e-Paper), Organophotoreceptor (OPC) or OTFT(OTFT)。
Device of the present invention can pass through the methods such as film vapor deposition, electron beam evaporation, physical vapour deposition (PVD) at substrateUpper evaporation metal and have the oxide of electric conductivity and their alloy forms anode, also can adopt spin-coating (spin-Coating) or strip take the lead evaporation; Can also adopt moulding (tape-casting), scraping blade method (doctor-blading), silkThe methods such as reticulated printing (Screen-Printing), ink jet printing or thermal imaging (Thermal-Imaging) reduce number of plies manufacture.
The invention provides a kind of compound containing heterocyclic ligand and preparation method thereof, organic electroluminescence device, thisThe bright compound containing heterocyclic ligand providing, is combined with specific metal by the part of selecting specific heterocycle, and what obtain hasMachine metallic compound after for organic electroluminescence device, improves the luminous efficiency of device, and long service life.
Technical scheme below in conjunction with the embodiment of the present invention is clearly and completely described, obviously, and described enforcementExample is only the present invention's part embodiment, instead of whole embodiment. Based on the embodiment in the present invention, this area is commonTechnical staff is not making the every other embodiment obtaining under creative work prerequisite, all belongs to the model of the present invention's protectionEnclose.
Embodiment 1
The manufacture of intermediate
The preparation of intermediate 5-fluoro-2-nitro-N-phenylaniline (A-1)
By 15.6 grams of fluoro-5-2-aminonitrobenzenes, join in reaction bulb, add 300ML dry toluene, stir, add19.2 grams of sodium tert-butoxides, nitrogen protection, reacts 1 hour. Add successively again 30 grams of iodobenzenes, three (dibenzalacetone) two palladiums 2.8Gram, injection adds 4 grams of part tri-butyl phosphines, and reaction is warmed up to 60 DEG C and spends the night. After reaction finishes, system cooling, 100ML adds waterWashing, extract and separate, toluene layer is used anhydrous magnesium sulfate drying 30 minutes. Steaming desolventizes toluene, obtains dark grease, silica gel column chromatographyPost separates, carrene: benzinum=1:4 rinses, and the monitoring of some plate, collects RF=0.3 product point. Steaming desolventizes, and obtains off-white colorSolid, with PE washing, 16.3 grams of dry products, productive rate 71%.
The preparation method of intermediate A-2～A-28 is with the preparation method of above-mentioned A-1.
The compound of [table 1] below obtaining according to the preparation method of described intermediate A-1.
[table 1]
Embodiment 2
The fluoro-N1-phenyl of intermediate 5-benzene-1, the preparation of 2-diamines (B-1)
20 grams of (5 fluoro-2-nitrobenzene) aniline are added in 300ML autoclave, add absolute ethyl alcohol 200ML, add5% 1 gram of palladium-carbon catalyst, is filled with high pressure hydrogen 5MPa, 50 DEG C of reactions of oil bath 4 hours. Reactant liquor cooling, suction filtration, removes catalysisAgent, filtrate is revolved steaming, obtains approximately 20 grams of solids, productive rate 88%.
The preparation method of intermediate B-2～B-20 is with the preparation method of above-mentioned B-1.
Obtain the compound of [table 2] according to the preparation method of described intermediate B-1.
[table 2]
Embodiment 3
The manufacture of the fluoro-2-of intermediate 4-(1-phenyl-1H-benzo [d] imidazoles-2-yl) phenol (C-1)
By 8.36 grams of adjacent aminodiphenylamines, 10 grams of the fluoro-Benzaldehyde,2-hydroxies of 5-, 13 grams of sodium pyrosulfites, dimethyl formylAmine 200mL joins in reaction bulb, is heated to the reaction overnight that refluxes. System cooling, is poured into 500mL cold water by reactant liquor, noStop stirring, have solid to separate out. First use alcohol flushing, then with benzinum flushing, after being dried, obtain 16 grams of intermediate C-1, productive rate 97%.
The manufacture of intermediate C-2～C-48 is with the preparation method of above-mentioned C-1.
Obtain the compound of [table 3] according to the preparation method of described intermediate C-1.
[table 3]
Embodiment 4
The manufacture of intermediate 3-(1-methyl isophthalic acid H-benzo [d] imidazoles-2-yl) biphenyl-2-alcohol (D-1)
Process feeds intake:
By 15 grams of-phenol of bromo-2-6-(1-methyl isophthalic acid H-phenylimidazole-2-yl), 7.2 grams of phenyl boric acids, four triphenyl phasphine palladiums 1.8Gram, 13.6 grams, potash, 500ML (toluene: water=4:1) mixed solvent, nitrogen protection. Be heated to 80 DEG C of reactions 24 hours. InsteadAnswer system cooling, washing, extraction, separatory, toluene is dried and is spin-dried for, and obtains dark solid. Add carrene to dissolve, cross pillar,Obtain 14 grams of white solids, productive rate 93%.
The preparation of intermediate D-2～D-51 is with the preparation method of above-mentioned D-1
Obtain the compound of [table 4] according to the preparation method of described intermediate D-1:
[table 4]
Embodiment 5
The manufacture of intermediate 3-(1-methyl-6-phenyl-1H-benzo [d] imidazoles-2-yl) biphenyl-4-alcohol (E-1)
By 20 grams of-phenol of bromo-4-2-(the bromo-1-methyl isophthalic acid of 6-H-benzimidazolyl-2 radicals-yl), 7.7 grams of phenyl boric acids, four triphenyls1.8 grams of phosphine palladiums, 14.2 grams, potash, 500ML (toluene: water=4:1) mixed solvent, nitrogen protection. Be heated to 80 DEG C of reactions 24Hour. Reaction system cooling, separatory, toluene are dried and are spin-dried for, and obtain dark solid, add carrene to dissolve, and cross pillar, obtain whiteLook solid 16.8g, productive rate 85%.
The preparation method of intermediate E-2～E-9 is with the preparation method of above-mentioned E-1.
Obtain the compound of [table 5] according to the preparation method of described intermediate E-1.
[table 5]
Embodiment 6
The manufacture of intermediate 3-(1-methyl-6-phenyl-1H-benzo [d] imidazoles-2-yl) biphenyl-4-alcohol (F-1)
4.5 grams of dimethylamine, 9.6 grams of sodium tert-butoxides, toluene 500ML are joined in reaction bulb, nitrogen protection, reaction 1 is littleTime. Again by 20 grams of-phenol of bromo-4-2-(1-phenyl-1H-naphtho-[2,3-d] imidazoles-2-yl), three (dibenzalacetone) two palladiums4 grams of 2.8 grams, tri-butyl phosphine. Be warmed up to 90 DEG C, react 24 hours. Processing method is with the fluoro-2-nitro-N-of intermediate 5-phenylAniline (A-1), obtains 15.8 grams of solids, productive rate 83%.
The preparation of intermediate F-2～F-4 is with the preparation method of above-mentioned F-1.
Obtain the compound of [table 6] according to the manufacture method of described intermediate F-1.
[table 6]
Embodiment 7
(G-1) manufacture
By 14.2 grams of upper step raw materials, methyl alcohol 300ML joins in reaction bulb, then adds 2 grams of NaOH and 40ML water to joinThe mixed liquor becoming, 65 DEG C are reacted 30 minutes. The mixed liquor that finally adds 3 gram of four water beryllium sulfate and 30ML water to be made into, reaction is spent the night,Suction filtration obtains white solid, and first water rinses, then uses washed with methanol, finally rinses and is dried with PE, obtains 11 grams of white solids, productive rate77％。
1HNMR(500MHz,Chloroform)δ8.10(s,2H),7.99(s,2H),7.84(s,4H),7.61(d,J＝10.0Hz,4H),7.48(s,8H),7.38(s,4H),7.29(s,2H),7.06(s,2H).
The preparation of embodiment G-2～G-30 and the preparation method of above-mentioned G-1.
Obtain the compound of [table 7] according to the manufacture method of described embodiment G-1.
[table 7]
The nuclear magnetic data of G-21HNMR(500MHz,Chloroform)δ8.55(s,1H),8.22(s,1H),8.09(s,1H),7.85(s,1H),7.65(dd,J＝37.5,12.5Hz,4H),7.48(s,2H),7.38(s,2H),7.29(s,1H),7.06(s,1H),6.97(s,1H).
The nuclear magnetic data of G-31HNMR(500MHz,Chloroform)δ8.51(s,1H),8.11(s,1H),7.85(s,1H),7.77–7.24(m,10H),7.01(d,J＝45.0Hz,2H).
The nuclear magnetic data of G-41HNMR(500MHz,Chloroform)δ8.98(s,1H),8.11(s,1H),7.63(t,J＝20.0Hz,3H),7.51–7.25(m,3H),7.01(d,J＝45.0Hz,1H).
The nuclear magnetic data of G-51HNMR(500MHz,Chloroform)δ7.66–7.44(m,1H),7.34(d,J＝45.0Hz,1H),7.06(t,J＝41.8Hz,1H).
Embodiment 8
The preparation of H-1
By 10 grams of upper step raw materials, be dissolved in 150ML methyl alcohol, add the mixed liquor of 1.7 grams of NaOH and 20ML water, heat up60 degree stir 1 hour. Add the mixture of 1.9 grams of zinc chloride and 30ML water again, have soon solid to separate out, reaction is spent the night. Take outFilter to obtain white solid, first water rinses, then uses washed with methanol, finally rinses and is dried with PE, obtains 6.5 grams of solids, and productive rate 74% is surveyedPurity is 99.5%.
1HNMR(500MHz,Chloroform)δ7.84(s,1H),7.61(d,J＝10.0Hz,1H),7.48(s,2H),7.38(s,1H),7.29(s,1H),7.06(s,1H),6.97(s,1H).
The preparation method of embodiment H-2～H-30 is with the preparation method of above-mentioned H-1.
According to the compound that obtains [table 8] by the manufacture method of above-described embodiment H-1.
[table 8]
The nuclear magnetic data of H-21HNMR(500MHz,Chloroform)δ8.55(s,1H),8.22(s,1H),8.09(s,1H),7.85(s,1H),7.65(dd,J＝37.5,12.5Hz,4H),7.51–7.26(m,5H),7.01(d,J＝45.0Hz,2H).
The nuclear magnetic data of H-31HNMR(500MHz,Chloroform)δ8.51(s,1H),8.11(s,1H),7.85(s,1H),7.76–7.54(m,5H),7.50–7.26(m,5H),7.01(d,J＝45.0Hz,2H).
The nuclear magnetic data of H-41HNMR(500MHz,Chloroform)δ8.98(s,1H),8.11(s,1H),7.63(t,J＝20.0Hz,3H),7.52–7.25(m,3H),7.01(d,J＝45.0Hz,1H).
The nuclear magnetic data of H-51HNMR(500MHz,Chloroform)δ7.61(d,J＝10.0Hz,1H),7.55(s,1H),7.48(s,1H),7.38(s,1H),7.29(s,1H),7.01(d,J＝45.0Hz,1H),4.91(s,1H),3.63(s,1H).
Embodiment 9
(I-1) manufacture
By 34 grams of upper step raw materials, methyl alcohol 500ML joins in reaction bulb, adds 4.8 grams, NaOH and 50ML water to be made intoSolution, 60 DEG C are reacted 1 hour. The aqueous solution that adds 16.2 grams of aluminum sulfate and 80ML water to be made into, 60 DEG C of reactions are spent the night, and have solid to analyseGo out. Suction filtration obtains white solid, by washed with methanol, then washes with ethanol, finally rinses dry with PE. Obtain 5.5 grams of solids, productive rate71%, surveying purity is 99.95%.
Mass spectrum: 1033.34.
The preparation of example I-2～I-51 is with the preparation method of above-mentioned I-1.
Obtain the compound of [table 9] according to the manufacture method of described example I-1.
[table 9]
The mass spectrometry value of I-2 is mass spectrum: 1033.34.
The mass spectrometry value of I-3 is mass spectrum: 1033.34.
The mass spectrometry value of I-4 is mass spectrum: 1082.36.
The mass spectrometry value of I-5 is mass spectrum: 1033.34.
Embodiment 10
Device preparation
By Fisher Co., Ltd's coating layer thickness beIto glass substrate be placed in distilled water and clean 2 times, ultrasonic wave is washedWash 30 minutes, repeatedly clean 2 times with distilled water, ultrasonic washing 10 minutes, after distilled water cleans and finishes, isopropyl alcohol, acetone, firstAlcohol equal solvent in order ultrasonic washing is later dry, transfers in plasma clean machine, and by aforesaid substrate washing 5 minutes,Deliver in evaporator. By evaporation hole injection layer 2-TNATA evaporation on ready ito transparent electrodeHole passesDefeated layer a-NPD evaporationIn table 10, cyan is mixed and compares material mCP (N, N '-dicarbazolyl-3,5-benzene)And FIrpic (Iridium (III) bis[(4,6-difluorophenyl)-pyridinato-N, C2'] picolinate and realityExecute routine compound (10%)Thickness evaporation, hole blocking layer and electron transfer layerNegative electrode Said process organic matter vaporization plating speed is to keep Al is
The luminescent device that the present invention is prepared adopts KEITHLEY Keithley 2400 type source measuring units, CS-2000Spectroradio luminance meter is tested, to evaluate driving voltage, luminosity, luminous efficiency and the glow color of luminescent device;To the performance characteristics of luminescence test of the device obtaining, the results are shown in Table 10, the part of compounds that table 10 is prepared for the embodiment of the present inventionAnd the characteristics of luminescence test result of the luminescent device that relatively prepared by material.
[table 10]
From above-mentioned table 10 result, can find out the compound system containing heterocyclic ligand that the invention provides (1) structure that there is formulaLuminous efficiency and the life characteristic of standby organic electroluminescence device all increase significantly.
Utilization of the present invention can obtain luminous efficiency containing the organic luminescent device of the compound of heterocyclic ligand and the life-span goodResult, therefore can be applicable to the OLED industry that practicality is high. Organic electroluminescence device of the present invention is applicable to plane faceFace illuminating OLED illuminator for plate demonstration, flat luminous body, illumination, flexible illuminator, duplicator, printer, LCD backlight orThe light source of dosing machine class, display board, mark etc.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof. It is right to it should be pointed out thatIn those skilled in the art, under the premise without departing from the principles of the invention, can also carry out the present inventionSome improvement and modification, these improvement and modification also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, make professional and technical personnel in the field can realize or use the present invention.To be apparent, as defined herein for those skilled in the art to the multiple amendment of these embodimentGeneral Principle can, in the situation that not departing from the spirit or scope of the present invention, realize in other embodiments. Therefore, the present inventionTo can not be restricted to these embodiment shown in this article, but will meet and principle disclosed herein and features of novelty phase oneThe widest scope causing.

Claims (10)

1. containing a compound for heterocyclic ligand, it is characterized in that, described compound has formula (1) structure,
Wherein, described R1、R2、R3、R4、R5、R6、R7And R8Independently be selected from separately hydrogen, halogen, cyano group, replacement or unsubstituted C1Cycloalkyl, replacement or the not replacement of alkoxyl, replacement or the unsubstituted C1～C30 of the alkyl of～C30, the C1～C30 of replacementThe arylamine of heterocyclic radical, replacement or unsubstituted C6～C50 of aryl, replacement or unsubstituted C5～C50 of C6～C60The condensed ring radical of base, replacement or unsubstituted C8～C60;
Described R9Be selected from replace or the alkyl of unsubstituted C1～C30, aryl replacement or unsubstituted C6～C60, replacement orThe condensed ring radical of unsubstituted C8～C60;
Described M is selected from Be, Zn or Al; Described L is integer, when M is selected from Be or Zn, and L=2, when M is selected from Al, L=3;
Described R9During for benzene, described R1～R8Can not be hydrogen simultaneously;
Described R1、R2、R3And R4In the phenyl ring at any two adjacent substituting groups and place form condensed ring structure or non-condensed ring structure;
Described R5、R6、R7And R8In the phenyl ring at any two adjacent substituting groups and place form condensed ring structure or non-condensed ring structure.
2. compound according to claim 1, is characterized in that, described R1、R2、R3、R4、R5、R6、R7、R8Each group independentlyBe selected from alkyl, the replacement of hydrogen, halogen, cyano group, replacement or unsubstituted C3～C20 C1～C20 alkoxyl, replacement or do not getThe heterocycle of aryl, replacement or the unsubstituted C5～C30 of cycloalkyl, replacement or the unsubstituted C6～C30 of the C1～C20 in generationThe condensed ring radical of arylamine group, replacement or the unsubstituted C10～C30 of base, replacement or unsubstituted C6～C30.
3. compound according to claim 1, is characterized in that, described R1、R2、R3、R4、R5、R6、R7、R8Separately independentlyBe selected from methyl, ethyl, propyl group, isopropyl, the tert-butyl group, normal-butyl, isobutyl group, suc as formula shown in (a-1)～formula (a-37) arbitrarilyOne,
Wherein, described X, Y are independently selected from hydrogen, halogen, cyano group, alkyl replacement or unsubstituted C1～C30, replacement separatelyOr the thiazolinyl of the alkoxyl of unsubstituted C1～C30, replacement or unsubstituted C2～C30, replacement or unsubstituted C7～C30Aryl, the replacement of aryloxy alkyl, replacement or the unsubstituted C6～C30 of alkaryl, replacement or unsubstituted C7～C30 or do not getThe aryl of heterocyclic radical, replacement or the unsubstituted C6～C60 of aryloxy group, replacement or the unsubstituted C5～C30 of the C6～C30 in generationThe condensed ring radical of amido, replacement or unsubstituted C8～C60.
4. compound according to claim 1, is characterized in that, described R9For the alkane of replacement or unsubstituted C3～C20The condensed ring radical of aryl, replacement or the unsubstituted C10～C30 of base, replacement or unsubstituted C8～C30.
5. compound according to claim 1, is characterized in that, described R9For methyl, ethyl, propyl group, isopropyl, butyl,The naphthalene of isobutyl group, the tert-butyl group, amyl group, hexyl, phenyl, the phenyl that contains fluorophenyl, cyano-containing, naphthyl, fluorine-containing naphthyl, cyano-containingThe phenanthryl of the anthryl of base, anthryl, fluorine-containing anthryl, cyano-containing, phenanthryl, fluorine-containing phenanthryl, cyano-containing, xenyl, fluorine-containing xenylOr the xenyl of cyano-containing.
6. compound according to claim 1, is characterized in that, described compound is any suc as formula (G), formula (H) or formula (I)Shown in one,
Wherein, described R1、R2、R3、R4、R6Independently be selected from separately the alkane of hydrogen, halogen, cyano group, replacement or unsubstituted C1～C30Cycloalkyl, replacement or the unsubstituted C6～C60 of alkoxyl, replacement or the unsubstituted C1～C30 of the C1～C30 of base, replacementThe arylamine group, replacement or not of heterocyclic radical, replacement or unsubstituted C6～C50 of aryl, replacement or unsubstituted C5～C50The condensed ring radical of the C8～C60 replacing;
Described R9Be selected from replace or the alkyl of unsubstituted C1～C30, aryl replacement or unsubstituted C6～C60, replacement orThe condensed ring radical of unsubstituted C8～C60;
Described R9During for benzene, described R1～R4And R6Can not be hydrogen simultaneously;
Described R1、R2、R3And R4In the phenyl ring at any two adjacent substituting groups and place form condensed ring structure or non-condensed ring structure;
Described R6Adjacent any one the C atom of C atom, described C atom connecting and the phenyl ring at above-mentioned two C atom places are altogetherWith forming condensed ring structure or non-condensed ring structure.
7. compound according to claim 1, is characterized in that, described compound is suc as formula (G-0), formula (G-00), formula (G-000), formula (G-0000), formula (H-0), formula (H-00), formula (H-000), formula (H-0000), formula (I-0), formula (I-00), formula (I-000) or shown in formula (I-0000) any one:
Wherein, described R1、R2、R3、R4Independently be selected from separately hydrogen, halogen, cyano group, replacement or unsubstituted C1～C30 alkyl,The virtue of cycloalkyl, replacement or the unsubstituted C6～C60 of alkoxyl, replacement or the unsubstituted C1～C30 of the C1～C30 replacingArylamine group, replacement or the not replacement of heterocyclic radical, replacement or the unsubstituted C6～C50 of base, replacement or unsubstituted C5～C50The condensed ring radical of C8～C60;
Described R9Be selected from replace or the alkyl of unsubstituted C1～C30, aryl replacement or unsubstituted C6～C60, replacement orThe condensed ring radical of unsubstituted C8～C60.
8. compound according to claim 1, is characterized in that, described compound is suc as formula G-1～formula G-30 any oneShown in, shown in formula H-1～formula H-30 any one or shown in formula I-1～formula I-51 any one,
9. a preparation method for the compound containing heterocyclic ligand as described in claim 1～8 any one, its feature existsIn, comprise the following steps:
1), by the compound reaction of the compound of formula (II) structure and formula (III) structure, obtain the chemical combination of formula (IV) structureThing,
2) by compound and the M reactant salt of formula (IV) structure, the compound of (1) structure that obtains thering is formula;
Described R1、R2、R3、R4、R5、R6、R7And R8Independently be selected from separately hydrogen, halogen, cyano group, replacement or unsubstituted C1～C30Alkyl, replacement C1～C30 alkoxyl, replacement or unsubstituted C1～C30 cycloalkyl, replacement or unsubstituted C6～Arylamine group, the replacement of heterocyclic radical, replacement or the unsubstituted C6～C50 of aryl, replacement or the unsubstituted C5～C50 of C60Or the condensed ring radical of unsubstituted C8～C60;
Described R9Be selected from replace or the alkyl of unsubstituted C1～C30, aryl replacement or unsubstituted C6～C60, replacement orThe condensed ring radical of unsubstituted C8～C60;
Described M is selected from Be, Zn or Al; Described L is integer, when M is selected from Be or Zn, and L=2, when M is selected from Al, L=3;
Described R1、R2、R3And R4In the phenyl ring at any two adjacent substituting groups and place form condensed ring structure or non-condensed ring structure;
Described R5、R6、R7And R8In the phenyl ring at any two adjacent substituting groups and place form condensed ring structure or non-condensed ring structure.
10. an organic electroluminescence device, is characterized in that, comprises electroluminescent material; Described electroluminescent material comprisesThe compound that compound described in claim 1～8 any one or claim 9 are prepared.
CN201610117722.4A 2016-03-02 2016-03-02 Compound containing heterocyclic ligand and preparation method and application thereof Pending CN105601570A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018021406A1 (en) * 2016-07-29 2018-02-01 大電株式会社 Metal complex and electron-transporting material using same
CN109470671A (en) * 2018-11-30 2019-03-15 齐齐哈尔大学 One kind being used for H2The fluorescent test paper strip and its preparation and application of S detection
CN112979683A (en) * 2021-03-09 2021-06-18 电子科技大学 Phenanthroimidazole-based zinc complex and preparation method and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09328678A (en) * 1996-06-10 1997-12-22 Toyo Ink Mfg Co Ltd Organic electroluminescent element material and organic electroluminescent element using the same
JPH10265478A (en) * 1997-03-25 1998-10-06 Mitsubishi Chem Corp Imidazole metal complex and organic electric field luminous element using the same
JP2007157899A (en) * 2005-12-02 2007-06-21 Toyo Ink Mfg Co Ltd Organic electroluminescence element
CN101468973A (en) * 2007-09-07 2009-07-01 葛来西雅帝史派有限公司 Organometallic compounds for electroluminescence and organic electroluminescent device using the same
CN102731406A (en) * 2012-07-05 2012-10-17 吉林大学 Phenanthroimidazole derivatives and application of phenanthroimidazole derivatives in preparation of electroluminescent device
WO2015019725A1 (en) * 2013-08-09 2015-02-12 国立大学法人九州大学 Organic metal complex, luminescent material, delayed phosphor and organic light emitting element
CN105503736A (en) * 2015-12-08 2016-04-20 华南理工大学 N-type compound containing naphthyl[1,2]imidazole as well as preparation and application thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09328678A (en) * 1996-06-10 1997-12-22 Toyo Ink Mfg Co Ltd Organic electroluminescent element material and organic electroluminescent element using the same
JPH10265478A (en) * 1997-03-25 1998-10-06 Mitsubishi Chem Corp Imidazole metal complex and organic electric field luminous element using the same
JP2007157899A (en) * 2005-12-02 2007-06-21 Toyo Ink Mfg Co Ltd Organic electroluminescence element
CN101468973A (en) * 2007-09-07 2009-07-01 葛来西雅帝史派有限公司 Organometallic compounds for electroluminescence and organic electroluminescent device using the same
CN102731406A (en) * 2012-07-05 2012-10-17 吉林大学 Phenanthroimidazole derivatives and application of phenanthroimidazole derivatives in preparation of electroluminescent device
WO2015019725A1 (en) * 2013-08-09 2015-02-12 国立大学法人九州大学 Organic metal complex, luminescent material, delayed phosphor and organic light emitting element
CN105503736A (en) * 2015-12-08 2016-04-20 华南理工大学 N-type compound containing naphthyl[1,2]imidazole as well as preparation and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HUI XU等: "A Novel Deep Blue-Emitting ZnII Complex Based on Carbazole-Modified 2-(2-Hydroxyphenyl)benzimidazole: Synthesis, Bright Electroluminescence, and Substitution Effect on Photoluminescent, Thermal, and Electrochemical Properties", 《JOURNAL OF PHYSICAL CHEMISTRY C》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018021406A1 (en) * 2016-07-29 2018-02-01 大電株式会社 Metal complex and electron-transporting material using same
CN109689665A (en) * 2016-07-29 2019-04-26 大电株式会社 Metal complex and the electron transport material for using the metal complex
CN112961102A (en) * 2016-07-29 2021-06-15 大电株式会社 Metal complex and electron transport material using the same
CN109689665B (en) * 2016-07-29 2021-10-01 大电株式会社 Metal complex and electron transport material using the same
CN112961102B (en) * 2016-07-29 2024-03-12 大电株式会社 Metal complex and electron transport material using the same
CN109470671A (en) * 2018-11-30 2019-03-15 齐齐哈尔大学 One kind being used for H2The fluorescent test paper strip and its preparation and application of S detection
CN112979683A (en) * 2021-03-09 2021-06-18 电子科技大学 Phenanthroimidazole-based zinc complex and preparation method and application thereof

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