CN108586368A - A kind of triaizine compounds and its organic luminescent device of the class formation containing fluorenes - Google Patents

A kind of triaizine compounds and its organic luminescent device of the class formation containing fluorenes Download PDF

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CN108586368A
CN108586368A CN201810575407.5A CN201810575407A CN108586368A CN 108586368 A CN108586368 A CN 108586368A CN 201810575407 A CN201810575407 A CN 201810575407A CN 108586368 A CN108586368 A CN 108586368A
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unsubstituted
substituted
base
substitution
triaizine compounds
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刘喜庆
蔡辉
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Changchun Haipurunsi Technology Co Ltd
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Changchun Haipurunsi Technology Co Ltd
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Abstract

The invention discloses the triaizine compounds and its organic luminescent device of a kind of class formation containing fluorenes, are related to organic optoelectronic materials technology.On the one hand, triazine group structure is relatively stablized, and has high glass transition temperature, high electron mobility and lower energy level.On the one hand, fluorenes class group is the space structure of 3 D stereo, can effectively prevent intermolecular aggregation, it is made to be not easy to crystallize；Easily modification, strong rigid advantage make compound structure stablize in fluorenes class group.On the other hand, triazine group is combined with fluorenes class group, is especially connected by phenyl ring or cyclohexyl biphenyl therebetween, is increased conjugated system, and continuous pi-conjugated system brings preferable electron mobility, to have high electron mobility；Also, the combination of the two makes carrier transport balance.It is applied to organic luminescent device, is used as electron transfer layer or hole blocking layer, device shows the advantage that driving voltage is low, luminous efficiency is high, is better than existing common OLED device.

Description

A kind of triaizine compounds and its organic luminescent device of the class formation containing fluorenes
Technical field
The present invention relates to the triaizine compounds of organic photoelectrical material technical field more particularly to a kind of class formation containing fluorenes and its Organic luminescent device.
Background technology
Organic electroluminescent LED (Organic Light Emitting Diode, OLED) is to utilize electrons and holes The recombination luminescence in organic film and the luminescent device prepared, have the following advantages：(1) from main light emission, backlight is not needed； (2) brightness is high, there is high contrast, pure in colour, the problem of almost without visible angle；(3) ultra-thin, by very thin organic Material coating and basis material are constituted, small to be suitable for portable product；(4) power consumption is very small, environmental protection and energy saving；(5) it rings It answers speed fast, is the one thousandth of LCD；(6) use temperature range is wide, remains to normally show at -40 DEG C.
Organic charge transport material is a kind of when there is carrier (electronics or hole) to inject, can be under electric field action Realize the controllable oriented and ordered migration of carrier to realize the organic semiconducting materials of charge transmission.Relative to inorganic material, Organic charge transport material have at low cost, small toxicity, it is easily processed into type and be chemically modified to meet different needs, can The advantages that make Grazing condition device, is widely used to xerography, sensor, electroluminescent, field-effect tube and too at present The numerous areas such as positive energy battery, become one of the hot spot studied both at home and abroad.Organic charge transport material can divide organic hole to transmit (p-type) material and organic electronic transmit (N-shaped) material.Compared with organic p-type material, the development of n-type material is slower, such as 8- Hydroxyquinoline aluminum (Aq3) He oxadiazole derivatives PBD is the relatively early n-type material studied.
The hole mobility of hole mobile material is typically much deeper than the electron mobility of electron transport material in device, this meeting Cause being remarkably decreased for device performance.It is adjusted so how to design the better electron transport material of new performance, is always Those skilled in the art's urgent problem to be solved.
Invention content
The object of the present invention is to provide the triaizine compounds and its organic luminescent device of a kind of class formation containing fluorenes.The present invention carries The triaizine compounds thermal stability height of the class formation containing fluorenes supplied, glass transition temperature are high, are not easy to crystallize, by the compound for electricity Manufactured organic luminescent device in sub- transport layer, shows the advantage that driving voltage is low, luminous efficiency is high, is function admirable Luminous organic material.
The present invention provides a kind of triaizine compounds of class formation containing fluorenes, and general formula of molecular structure is as shown in I：
Wherein, Ar1、Ar2、Ar3It is independent to be selected from substituted or unsubstituted C6~C65Aryl, substituted or unsubstituted C3 ~C65Heteroaryl in one kind, and it is at least one be selected from following group：
Wherein, R1、R2It is independent to be selected from substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C6~C30's Aryl, substituted or unsubstituted C6~C30Heteroaryl in one kind；R3Selected from hydrogen atom, substituted or unsubstituted C1~C10's Alkyl, substituted or unsubstituted C6~C30Aryl in one kind.
Preferably, the Ar1、Ar2、Ar3It is at least one to be selected from following group：
Wherein, R1、R2It is independent to be selected from methyl, ethyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, take Generation or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyrene Base, substituted or unsubstituted base, substituted or unsubstituted ferrosin base, substituted or unsubstituted pyridyl group, substitution do not take The pyrimidine radicals in generation, substituted or unsubstituted pyridazinyl, substituted or unsubstituted triazine radical, takes substituted or unsubstituted pyrazinyl Generation or unsubstituted pyrrole radicals, substituted or unsubstituted benzopyrrole base, substituted or unsubstituted triazolyl, substitution or unsubstituted Thienyl, substituted or unsubstituted furyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted benzofuran Base, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzofuran group, substituted or unsubstituted quinoline One kind in base, substituted or unsubstituted isoquinolyl, substituted or unsubstituted indyl；R3Selected from hydrogen atom, methyl, second Base, isopropyl or tertiary butyl.
Preferably, the Ar1、Ar2、Ar3It is at least one to be selected from following group：
Wherein, R1、R2It is independent to be selected from methyl, ethyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, take It is generation or unsubstituted anthryl, substituted or unsubstituted ferrosin base, substituted or unsubstituted pyridyl group, substituted or unsubstituted phonetic Piperidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substitution or One kind in unsubstituted indyl；R3Selected from hydrogen atom, methyl, ethyl, isopropyl or tertiary butyl.
Preferably, the Ar2、Ar3It is identical, it is selected from following group：
Wherein, R1、R2It is independent to be selected from methyl, ethyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, take Generation or unsubstituted anthryl, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted pyrazine One kind in base；R3Selected from hydrogen atom, methyl, ethyl, isopropyl or tertiary butyl.
Further preferably, the Ar1It does not take selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, substitution or The anthryl in generation, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted acridinyl, substitution Or unsubstituted phenoxazine base, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted phenoxazine thiophene base, substitution or unsubstituted Fluorenyl, substituted or unsubstituted carbazyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted ferrosin base, substitution or Unsubstituted base, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine radicals, takes substituted or unsubstituted acenaphthenyl Generation or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted triazine radical, substituted or unsubstituted pyrrole Cough up base, substituted or unsubstituted benzopyrrole base, substituted or unsubstituted triazolyl, substituted or unsubstituted thienyl, substitution Or it unsubstituted furyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted benzofuranyl, substitution or does not take One kind in the dibenzothiophene in generation, substituted or unsubstituted dibenzofuran group.
Most preferably, a kind of triaizine compounds of class formation containing fluorenes are arbitrary in chemical constitution as follows It is a kind of：
The present invention also provides a kind of organic luminescent device, including first electrode, second electrode and it is placed in two electrode Between one or more organic compound layers, the organic compound layer contains any one of them one kind class formation containing fluorenes Triaizine compounds.
Preferably, organic compound layer includes electron transfer layer, contains one kind knot of class containing fluorenes in electron transfer layer The triaizine compounds of structure.
Preferably, organic compound layer includes hole blocking layer, contains one kind knot of class containing fluorenes in hole blocking layer The triaizine compounds of structure.
Beneficial effects of the present invention：
The present invention provides a kind of triaizine compounds of class formation containing fluorenes, on the one hand, triazine group especially 1,3,5- tri- Piperazine unit structure is relatively stablized, acid and alkali-resistance and high temperature resistant, has high glass transition temperature；Triazine group is as typical strong electrophilic Group, compound of structure has high electron mobility and lower energy level centered on it.On the one hand, fluorenes class group is three Three-dimensional space structure is tieed up, intermolecular aggregation is can effectively prevent, it is made to be not easy to crystallize；It is easily modified in fluorenes class group, is strong The advantage of rigidity makes compound structure stablize.On the other hand, triazine group is combined one kind knot of class containing fluorenes to be formed with fluorenes class group The triaizine compounds of structure are especially connected therebetween by phenyl ring or cyclohexyl biphenyl, increase conjugated system, possess extensible three Structure is tieed up, continuous pi-conjugated system brings preferable electron mobility, to have high electron mobility；Also, the two It is balanced in conjunction with carrier transport is made.
Meanwhile the substituent group of fluorenes class group is alkyl substituent, especially methyl, ethyl, isopropyl or tertiary fourth in structure Base, the dissolubility of the triaizine compounds for being added to increase the class formation containing fluorenes of alkyl.
It is applied to organic luminescent device, is used as electron transfer layer or hole blocking layer, device shows to drive The advantage that voltage is low, luminous efficiency is high is better than existing common OLED device.What is shown in OLED luminescent devices good answers With effect, this point shows it with good industrialization prospect.
Specific implementation mode：
It is clearly and completely described below in conjunction with the technical solution of the embodiment of the present invention, it is clear that described implementation Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, art technology The every other embodiment that personnel are obtained without making creative work, belongs to protection scope of the present invention.
Alkyl of the present invention refers to alkyl made of minusing a hydrogen atom in alkane molecule, can be straight chain alkane Base, branched alkyl, naphthenic base, example may include methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary fourth Base, amyl, isopentyl, cyclopenta, cyclohexyl etc., but not limited to this.
Aryl of the present invention refer to aromatic hydrocarbon molecule aromatic core carbon on remove a hydrogen atom after, be left univalent perssad it is total Claiming, can be monocyclic aryl or fused ring aryl, example may include phenyl, xenyl, naphthalene, anthryl, phenanthryl or pyrenyl etc., but It is without being limited thereto.
Heteroaryl of the present invention refers to the group that one or more of aryl aromatic core carbon is substituted by hetero atom General name, the hetero atom include but not limited to oxygen, sulphur or nitrogen-atoms, and the heteroaryl can be bicyclic heteroaryl or condensed ring heteroaryl Base, example may include pyridyl group, pyrrole radicals, pyridyl group, thienyl, furyl, indyl, quinolyl, isoquinolyl, benzo thiophene Pheno base, benzofuranyl, dibenzofuran group, dibenzothiophene, carbazyl etc., but not limited to this.
The present invention provides a kind of triaizine compounds of class formation containing fluorenes, and general formula of molecular structure is as shown in I：
Wherein, Ar1、Ar2、Ar3It is independent to be selected from substituted or unsubstituted C6~C65Aryl, substituted or unsubstituted C3 ~C65Heteroaryl in one kind, and it is at least one be selected from following group：
Wherein, R1、R2It is independent to be selected from substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C6~C30's Aryl, substituted or unsubstituted C6~C30Heteroaryl in one kind；R3Selected from hydrogen atom, substituted or unsubstituted C1~C10's Alkyl, substituted or unsubstituted C6~C30Aryl in one kind.
According to the present invention, the substituted alkyl, substituted aryl, substituted heterocycle, the independent choosing of substituent group From methyl, ethyl, isopropyl, tertiary butyl, phenyl, naphthalene, anthryl, phenanthryl, benzo phenanthryl, base, pyrenyl, benzyl, methoxy Base, methyl mercapto, phenoxy group, thiophenyl, fluorenyl, 9,9- dimethyl fluorenyl, hexichol amido, dimethylamino, carbazyl, 9- phenyl clicks Oxazolyl, furyl, thienyl, cyano, fluorine-based, deuterium base, triphenyl silicon substrate, trimethyl silicon substrate, phenothiazinyl, phenoxazine group, a word used for translation Piperidinyl, piperidyl, pyridyl group, pyrimidine radicals, xenyl, terphenyl, nitro etc., but not limited to this.
Preferably, the Ar1、Ar2、Ar3It is at least one to be selected from following group：
Wherein, R1、R2It is independent to be selected from methyl, ethyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, take Generation or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyrene Base, substituted or unsubstituted base, substituted or unsubstituted ferrosin base, substituted or unsubstituted pyridyl group, substitution do not take The pyrimidine radicals in generation, substituted or unsubstituted pyridazinyl, substituted or unsubstituted triazine radical, takes substituted or unsubstituted pyrazinyl Generation or unsubstituted pyrrole radicals, substituted or unsubstituted benzopyrrole base, substituted or unsubstituted triazolyl, substitution or unsubstituted Thienyl, substituted or unsubstituted furyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted benzofuran Base, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzofuran group, substituted or unsubstituted quinoline One kind in base, substituted or unsubstituted isoquinolyl, substituted or unsubstituted indyl；R3Selected from hydrogen atom, methyl, second Base, isopropyl or tertiary butyl.
Preferably, the Ar1、Ar2、Ar3It is at least one to be selected from following group：
Wherein, R1、R2It is independent to be selected from methyl, ethyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, take It is generation or unsubstituted anthryl, substituted or unsubstituted ferrosin base, substituted or unsubstituted pyridyl group, substituted or unsubstituted phonetic Piperidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substitution or One kind in unsubstituted indyl；R3Selected from hydrogen atom, methyl, ethyl, isopropyl or tertiary butyl.
Preferably, the Ar2、Ar3It is identical, it is selected from following group：
Wherein, R1、R2It is independent to be selected from methyl, ethyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, take Generation or unsubstituted anthryl, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted pyrazine One kind in base；R3Selected from hydrogen atom, methyl, ethyl, isopropyl or tertiary butyl.
Preferably, the Ar1It does not take selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, substitution or The anthryl in generation, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted acridinyl, substitution Or unsubstituted phenoxazine base, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted phenoxazine thiophene base, substitution or unsubstituted Fluorenyl, substituted or unsubstituted carbazyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted ferrosin base, substitution or Unsubstituted base, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine radicals, takes substituted or unsubstituted acenaphthenyl Generation or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted triazine radical, substituted or unsubstituted pyrrole Cough up base, substituted or unsubstituted benzopyrrole base, substituted or unsubstituted triazolyl, substituted or unsubstituted thienyl, substitution Or it unsubstituted furyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted benzofuranyl, substitution or does not take One kind in the dibenzothiophene in generation, substituted or unsubstituted dibenzofuran group.
Further preferably, the triaizine compounds of a kind of class formation containing fluorenes, it is arbitrary in chemical constitution as follows It is a kind of：
A kind of triaizine compounds of class formation containing fluorenes of the present invention, specific synthetic route are as follows：
Wherein, Ar1、Ar2、Ar3It is independent to be selected from substituted or unsubstituted C6~C65Aryl, substituted or unsubstituted C3 ~C65Heteroaryl in one kind, and it is at least one be selected from following group：
Wherein, R1、R2It is independent to be selected from substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C6~C30's Aryl, substituted or unsubstituted C6~C30Heteroaryl in one kind；R3Selected from hydrogen atom, substituted or unsubstituted C1~C10's Alkyl, substituted or unsubstituted C6~C30Aryl in one kind.
Above-mentioned synthesis is to be coupled to obtain target via a series of C-C for starting material with 2,4,6- tri- chloro-1,3,5-triazines Product I, it is recommended to use Suzuki coupling reactions, under nitrogen protection, using tetra-triphenylphosphine palladium as catalyst, potassium carbonate is alkali, four Hydrogen furans is solvent, and reflux is reacted.
The present invention does not have coupling reaction special limitation, is using popular response well-known to those skilled in the art Can, the preparation method is easy to operate, is readily produced.
The present invention also provides a kind of organic luminescent device, including first electrode, second electrode and it is placed in two electrode Between one or more organic compound layers, organic compound layer include hole injection layer, hole transmission layer, electronic blocking At least one layer of layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer；At least one in the organic compound layer Layer includes a kind of triaizine compounds of the class formation containing fluorenes of the present invention.
Preferably, a kind of triaizine compounds of class formation containing fluorenes can be used as the electron-transport in organic luminescent device Material.The device architecture of use is preferably specially：NPB-DPA is used as hole injection layer substance, and NPB is used as hole transmission layer object Matter, AND are used as main substance, and DPAVBi is used as dopant, and the triaizine compounds and Liq of a kind of class formation containing fluorenes are total With electron-transporting material is used as, to manufacture the organic luminescent device of construction same as below：ITO/NPB-DPA/NPB/AND： A kind of triaizine compounds of DPAVBi (doping concentration 2wt%)/class formation containing fluorenes：Liq/LiF/Al.It is described organic Electroluminescent device can be used for the application fields such as flat-panel monitor, lighting source, direction board, signal lamp.
The synthesis of [embodiment 1] compound A1
The synthesis of intermediate a1-1
3,5- dichlorobenzenes (9.4g, 42.4mmol) are taken to be added in there-necked flask, addition THF 100mL, nitrogen protection ,- 78 DEG C are stirred 30 minutes, and n-BuLi (2.5M) 21mL is then added, reacts 1 hour, adds triisopropyl borate ester 14g, low Temperature reaction 1 hour, gradually restores room temperature.Last handling process, 2M hydrochloric acid is added in system makes solution pH value be 4-5, stands liquid separation, Aqueous layer with ethyl acetate extracts, and merges organic layer, is spin-dried for, obtains intermediate a1-1 (8.2g, yield 80%).
Mass spectrum m/z：242.16 (calculated values：242.09).Theoretical elemental content (%) C12H12B2O4：C,59.60；H, 5.00；B,8.94；O, 26.46 actual measurement constituent contents (%)：C,59.61；H,5.02；B,8.94；O,26.43.The above results are demonstrate,proved The real product that obtains is target product.
The synthesis of intermediate a1-2
Tetra-triphenylphosphine palladium (2.1g, 1.83mmol) and potassium carbonate (75.7g, 549mmol) are added to intermediate a1-1 Bromo- 9, the 9- dimethyl fluorenes (50.3g, 185mmol) of (44.3g, 183mmol) and 2- are molten in degassing tetrahydrofuran (500mL) Liquid, and the mixture is heated 4 hours under reflux.It filters while hot, obtains a large amount of solids, with solvent dissolved solid, later Concentration, intermediate a1-2 (50.0g, theoretical value 70%) is obtained via silica gel column chromatography.
Mass spectrum m/z：390.25 (calculated values：390.28).Theoretical elemental content (%) C27H23BO2：C,83.09；H,5.94； B,2.77；O, 8.20 actual measurement constituent contents (%)：C,83.07；H,5.94；B,2.77；O,8.22.The above results confirmation is produced Object is target product.
The synthesis of compound A1
Tetra-triphenylphosphine palladium (2.1g, 1.83mmol) and potassium carbonate (75.7g, 549mmol) are added to intermediate a1-2 (150g, 384mmol) and 2, bis- bromo- 6- phenyl of 4- -1,3,5-triazines (41.3g, 183mmol) is in degassing tetrahydrofuran Solution in (500mL), and the mixture is heated 4 hours under reflux.It filters while hot, obtains a large amount of solids, use solvent Dissolved solid concentrates later, and compound A1 (92.9g, theoretical value 60%) is obtained via silica gel column chromatography.
Mass spectrum m/z：846.05 (calculated values：846.07).Theoretical elemental content (%) C63H47N3：C,89.43；H,5.60； N, 4.97 actual measurement constituent contents (%)：C,89.43；H,5.63；N,4.94.The above results confirm that it is target product to obtain product.
The synthesis of [embodiment 2] compound A40
Change 2,4-, bis- bromo- 6- phenyl -1,3,5-triazines in embodiment 1 into equimolar compound d, other steps are equal It is identical as the synthesis of embodiment 1, obtain target product compound A40.Mass spectrum m/z：936.26 (calculated values：936.15).It is theoretical Constituent content (%) C69H49N3O：C,88.53；H,5.28；N,4.49；O, 1.71 actual measurement constituent contents (%)：C,88.53；H, 5.26；N,4.49；O,1.73.The above results confirm that it is target product to obtain product.
The synthesis of [embodiment 3] compound B-11
The synthesis of intermediate b1-1
It after penta phenanthrene of 4H- rings is replaced by iodomethane, is reacted with bromine, it is luxuriant and rich with fragrance to obtain bromo- 4, the 4- diformazans basic rings penta of 8-.Take 8- bromo- 4,4- diformazan basic ring penta luxuriant and rich with fragrance (12.6g, 42.4mmol) is added in there-necked flask, THF 100mL is added, nitrogen protection, -78 DEG C are stirred It mixes 30 minutes, n-BuLi (2.5M) 21mL is then added, react 1 hour, add triisopropyl borate ester 7g, low-temp reaction 1 Hour, gradually restore room temperature.Last handling process, 2M hydrochloric acid is added in system makes solution pH value be 4-5, stands liquid separation, water layer is used Ethyl acetate extracts, and merges organic layer, is spin-dried for, obtains intermediate b1-1 (8.3g, yield 75%).
Mass spectrum m/z：262.16 (calculated values：262.11).Theoretical elemental content (%) C17H15BO2：C,77.90；H,5.77； B,4.12；O, 12.21 actual measurement constituent contents (%)：C,77.92；H,5.74；B,4.12；O,12.22.The above results confirm to obtain Product is target product.
The synthesis of compound B-11
Tetra-triphenylphosphine palladium (2.1g, 1.83mmol) and potassium carbonate (75.7g, 549mmol) are added to intermediate b1-1 (100.6g, 384mmol) and 2, bis- bromo- 6- phenyl of 4- -1,3,5-triazines (41.3g, 183mmol) is in degassing tetrahydrofuran Solution in (500mL), and the mixture is heated 4 hours under reflux.It filters while hot, obtains a large amount of solids, use solvent Dissolved solid concentrates later, and compound B-11 (70.0g, theoretical value 65%) is obtained via silica gel column chromatography.
Mass spectrum m/z：589.75 (calculated values：589.73).Theoretical elemental content (%) C43H31N3：C,87.58；H,5.30； N, 7.13 actual measurement constituent contents (%)：C,87.56；H,5.31；N,7.13.The above results confirm that it is target product to obtain product.
The synthesis of [embodiment 4] compound B-11 2
Change the bis- bromo- 6- phenyl -1,3,5- triazines of 2,4- in embodiment 1 into equimolar 2,4- bis- bromo- 6- (9- anthracenes Base) -1,3,5-triazines, other steps are identical as the synthesis of embodiment 1, obtain target product compound B-11 2.Mass spectrum m/z： 689.86 (calculated values：689.84).Theoretical elemental content (%) C51H35N3：C,88.79；H,5.11；N, 6.09 actual measurement elements contain It measures (%)：C,88.53；H,5.26；N,4.49；O,1.73.The above results confirm that it is target product to obtain product.
The synthesis of [embodiment 5] compound B23
The synthesis of intermediate b23-1
After penta phenanthrene of 4H- rings is restored by Pd/C, bromo compound is obtained by the reaction with bromine, then it is bromo- to obtain 2- for oxidative cyclization 4H- rings penta are luxuriant and rich with fragrance, and iodomethane reacts with it to obtain bromo- 4,4- diformazans basic ring, penta phenanthrene of 2-.Take the bromo- 4,4- diformazans basic rings penta of 2- luxuriant and rich with fragrance (12.6g, 42.4mmol) is added in there-necked flask, THF 100mL is added, nitrogen protection, -78 DEG C are stirred 30 minutes, are then added Enter n-BuLi (2.5M) 21mL, reacts 1 hour, add triisopropyl borate ester 7g, low-temp reaction 1 hour, gradual recovery room Temperature.Last handling process, 2M hydrochloric acid is added in system makes solution pH value be 4-5, stands liquid separation, and aqueous layer with ethyl acetate extraction is closed And organic layer, it is spin-dried for, obtains intermediate b23-1 (8.3g, yield 75%).
Mass spectrum m/z：262.16 (calculated values：262.11).Theoretical elemental content (%) C17H15BO2：C,77.90；H,5.77； B,4.12；O, 12.21 actual measurement constituent contents (%)：C,77.92；H,5.75；B,4.11；O,12.22.The above results confirm to obtain Product is target product.
The synthesis of compound B23
Tetra-triphenylphosphine palladium (2.1g, 1.83mmol) and potassium carbonate (75.7g, 549mmol) are added to intermediate b23-1 The solution of (100.6g, 384mmol) and compound d (57.6g, 183mmol) in degassing tetrahydrofuran (500mL), and will The mixture heats 4 hours under reflux.It filters while hot, obtains a large amount of solids, with solvent dissolved solid, concentrate later, via Silica gel column chromatography obtains compound B23 (74.5g, theoretical value 60%).
Mass spectrum m/z：679.75 (calculated values：679.81).Theoretical elemental content (%) C49H33N3O：C,86.57；H,4.89； N,6.18；O, 2.35 actual measurement constituent contents (%)：C,86.56；H,4.89；N,6.19；O,2.36.The above results confirmation is produced Object is target product.
The synthesis of [embodiment 6] compound B27
Change the compound d in embodiment 5 into equimolar compound e, other steps with the synthesis phase of embodiment 5 Together, target product compound B27 is obtained.Mass spectrum m/z：754.86 (calculated values：754.92).Theoretical elemental content (%) C55H38N4：C,87.50；H,5.07；N, 7.42 actual measurement constituent contents (%)：C,87.53；H,5.05；N,7.42.The above results are demonstrate,proved The real product that obtains is target product.
The synthesis of [embodiment 7] compound D1
Tetra-triphenylphosphine palladium (2.1g, 1.83mmol) and potassium carbonate (75.7g, 549mmol) are added to intermediate a1-2 (71.4g, 183mmol) and the chloro- 4- of 2- (biphenyl -4- bases) -6- phenyl -1,3,5-triazines (63.6g, 185mmol) is in degassing four Solution in hydrogen furans (500mL), and the mixture is heated 4 hours under reflux.It filters while hot, obtains a large amount of solids, It with solvent dissolved solid, concentrates later, compound D1 (71.8g, theoretical value 60%) is obtained via silica gel column chromatography.
Mass spectrum m/z：653.85 (calculated values：653.81).Theoretical elemental content (%) C48H35N3：C,88.18；H,5.40； N, 6.43 actual measurement constituent contents (%)：C,88.16；H,5.41；N,6.43.The above results confirm that it is target product to obtain product.
[the synthesis of 8 compound D7 of embodiment
It takes bromo- 9,9- spiral shells, two fluorenes (16.7g, 42.4mmol) of 2- to be added in there-necked flask, THF 100mL is added, nitrogen is protected Shield, -78 DEG C are stirred 30 minutes, and n-BuLi (2.5M) 21mL is then added, reacts 1 hour, adds triisopropyl borate ester 7g, Low-temp reaction 1 hour, gradually restores room temperature.Last handling process, 2M hydrochloric acid is added in system makes solution pH value be 4-5, stands point Liquid, aqueous layer with ethyl acetate extraction, merges organic layer, is spin-dried for, obtains two fluorenes of 2- boric acid -9,9- spiral shell (12.2g, yield 80%).
Tetra-triphenylphosphine palladium (2.1g, 1.83mmol) and potassium carbonate (75.7g, 549mmol) are added to 2- boric acid -9,9- Two fluorenes of spiral shell (65.8g, 183mmol) and the chloro- 4- of 2- (biphenyl -4- bases) -6- phenyl -1,3,5-triazines (63.6g, 185mmol) exist Solution in degassing tetrahydrofuran (500mL), and the mixture is heated 4 hours under reflux.It filters, obtains a large amount of while hot Solid is concentrated later with solvent dissolved solid, and compound D7 (71.8g, theoretical value 60%) is obtained via silica gel column chromatography.
Mass spectrum m/z：623.74 (calculated values：623.74).Theoretical elemental content (%) C46H29N3：C,88.58；H,4.69； N, 6.74 actual measurement constituent contents (%)：C,88.54；H,4.69；N,6.77.The above results confirm that it is target product to obtain product.
The synthesis of [embodiment 9] compound D20
Tetra-triphenylphosphine palladium (2.1g, 1.83mmol) and potassium carbonate (75.7g, 549mmol) are added to compound b23-1 (148.6g, 183mmol) and 2,4,6- tri- chloro-1,3,5-triazines (33.6g, 183mmol) are in degassing tetrahydrofuran (500mL) Solution, and the mixture is heated 4 hours under reflux.It filters while hot, obtains a large amount of solids, with solvent dissolved solid, It concentrates later, compound D20 (71.8g, theoretical value 60%) is obtained via silica gel column chromatography.
Mass spectrum m/z：731.94 (calculated values：731.92).Theoretical elemental content (%) C54H41N3：C,88.61；H,5.65； N, 5.74 actual measurement constituent contents (%)：C,88.62；H,5.66；N,5.72.The above results confirm that it is target product to obtain product.
The synthesis of [embodiment 10] compound D23
The synthesis of intermediate d23-1
Tetra-triphenylphosphine palladium (2.1g, 1.83mmol) and potassium carbonate (75.7g, 549mmol) are added to compound 3,3 '- Xenyl hypoboric acid (44.2g, 183mmol) and bromo- 9, the 9- dimethyl fluorenes (50.0g, 183mmol) of 2- are in degassing tetrahydrofuran Solution in (500mL), and the mixture is heated 4 hours under reflux.It filters while hot, obtains a large amount of solids, use solvent Dissolved solid concentrates later, and midbody compound d23-1 (72.8g, theoretical value 60%) is obtained via silica gel column chromatography.
Mass spectrum m/z：390.24 (calculated values：390.28).Theoretical elemental content (%) C27H23BO2：C,83.09；H,5.94； B,2.77；O, 8.20 actual measurement constituent contents (%)：C,83.09；H,5.94；B,2.75；O,8.22.The above results confirmation is produced Object is target product.
The synthesis of compound D23
Tetra-triphenylphosphine palladium (2.1g, 1.83mmol) and potassium carbonate (75.7g, 549mmol) are added to intermediate d23-1 (148.6g, 183mmol) and the chloro- 4- of 2- (biphenyl -4- bases) -6- phenyl -1,3,5-triazines (63.6g, 185mmol) is in degassing four Solution in hydrogen furans (500mL), and the mixture is heated 4 hours under reflux.It filters while hot, obtains a large amount of solids, It with solvent dissolved solid, concentrates later, compound D20 (71.8g, theoretical value 60%) is obtained via silica gel column chromatography.
Mass spectrum m/z：731.94 (calculated values：731.92).Theoretical elemental content (%) C54H41N3：C,88.61；H,5.65； N, 5.74 actual measurement constituent contents (%)：C,88.62；H,5.66；N,5.72.The above results confirm that it is target product to obtain product.
[comparison Application Example]
Transparent anode electrode ito substrate is cleaned by ultrasonic 15 minutes in isopropanol, and is exposed 30 minutes under ultraviolet light, Then handled 10 minutes with plasma.Then by treated, ito substrate is put into evaporated device.One layer of 60nm's of vapor deposition first The NPB of 20nm is deposited as hole transmission layer, vapor deposition as hole injection layer, evaporation rate 0.1nm/s in NPB-DPA later Speed is 0.1nm/s, followed by ADN/DPAVBi, doping concentration 2wt%, host material is deposited in the vapor deposition of luminescent layer, mixing Evaporation rate be 0.1nm/s, dopant material evaporation rate is 0.002nm/s, evaporation thickness 35nm, and 30nm is then deposited Alq3As electron transfer layer, evaporation rate 0.1nm/s, vacuum evaporation LiF and Al is used as the moon successively on the electron transport layer Pole, thickness 200nm.
[Application Example 1]
Transparent anode electrode ito substrate is cleaned by ultrasonic 15 minutes in isopropanol, and is exposed 30 minutes under ultraviolet light, Then handled 10 minutes with plasma.Then by treated, ito substrate is put into evaporated device.One layer of 60nm's of vapor deposition first The NPB of 20nm is deposited as hole transmission layer, vapor deposition as hole injection layer, evaporation rate 0.1nm/s in NPB-DPA later Speed is 0.1nm/s, followed by ADN/DPAVBi, doping concentration 2wt%, host material is deposited in the vapor deposition of luminescent layer, mixing Evaporation rate be 0.1nm/s, dopant material evaporation rate is 0.002nm/s, evaporation thickness 35nm, and 30nm is then deposited Compound A1 is as electron transfer layer, and evaporation rate 0.05nm/s, vacuum evaporation LiF and Al makees successively on the electron transport layer For cathode, thickness 200nm.
[Application Example 2]
Transparent anode electrode ito substrate is cleaned by ultrasonic 15 minutes in isopropanol, and is exposed 30 minutes under ultraviolet light, Then handled 10 minutes with plasma.Then by treated, ito substrate is put into evaporated device.One layer of 60nm's of vapor deposition first The NPB of 20nm is deposited as hole transmission layer, vapor deposition as hole injection layer, evaporation rate 0.1nm/s in NPB-DPA later Speed is 0.1nm/s, followed by ADN/DPAVBi, doping concentration 2wt%, host material is deposited in the vapor deposition of luminescent layer, mixing Evaporation rate be 0.1nm/s, dopant material evaporation rate is 0.002nm/s, evaporation thickness 35nm, and 30nm is then deposited Compound A1 and Liq co-evaporates (50:50wt%) it is used as electron transfer layer, evaporation rate 0.05nm/s, in electron transfer layer On successively vacuum evaporation LiF and Al as cathode, thickness 200nm.
[Application Example 3]
The electron transfer layer in Application Example 2 is changed into compound B-11 to co-evaporate with Liq.
[Application Example 4]
The electron transfer layer in Application Example 2 is changed into compound B23 and Liq to co-evaporate.
[Application Example 5]
The electron transfer layer in Application Example 2 is changed into compound B27 and Liq to co-evaporate.
[Application Example 6]
The electron transfer layer in Application Example 2 is changed into compound D1 and Liq to co-evaporate.
[Application Example 7]
The electron transfer layer in Application Example 2 is changed into compound D7 and Liq to co-evaporate.
[Application Example 8]
The electron transfer layer in Application Example 2 is changed into compound D20 and Liq to co-evaporate.
[Application Example 9]
The electron transfer layer in Application Example 2 is changed into compound D23 and Liq to co-evaporate.
[Application Example 10]
Transparent anode electrode ito substrate is cleaned by ultrasonic 15 minutes in isopropanol, and is exposed 30 minutes under ultraviolet light, Then handled 10 minutes with plasma.Then by treated, ito substrate is put into evaporated device.One layer of 60nm's of vapor deposition first The NPB of 20nm is deposited as hole transmission layer, vapor deposition as hole injection layer, evaporation rate 0.1nm/s in NPB-DPA later Speed is 0.1nm/s, followed by ADN/DPAVBi, doping concentration 2wt%, host material is deposited in the vapor deposition of luminescent layer, mixing Evaporation rate be 0.1nm/s, dopant material evaporation rate is 0.002nm/s, evaporation thickness 35nm, and 30nm is then deposited Alq is as electron transfer layer, evaporation rate 0.05nm/s, then the compound A1 of 10nm is deposited as hole blocking layer, in sky On the barrier layer of cave successively vacuum evaporation LiF and Al as cathode, thickness 200nm.
[Application Example 11]
Transparent anode electrode ito substrate is cleaned by ultrasonic 15 minutes in isopropanol, and is exposed 30 minutes under ultraviolet light, Then handled 10 minutes with plasma.Then by treated, ito substrate is put into evaporated device.One layer of 60nm's of vapor deposition first The NPB of 20nm is deposited as hole transmission layer, vapor deposition as hole injection layer, evaporation rate 0.1nm/s in NPB-DPA later Speed is 0.1nm/s, followed by ADN/DPAVBi, doping concentration 2wt%, host material is deposited in the vapor deposition of luminescent layer, mixing Evaporation rate be 0.1nm/s, dopant material evaporation rate is 0.002nm/s, evaporation thickness 35nm, and 30nm is then deposited Compound A1 is as electron transfer layer and hole blocking layer, evaporation rate 0.05nm/s, in electron transfer layer and hole barrier On layer successively vacuum evaporation LiF and Al as cathode, thickness 200nm.
[Application Example 12]
By in Application Example 11 electron transfer layer and hole blocking layer change compound B-11 into.
[Application Example 13]
Change the electron transfer layer in Application Example 11 into compound B23.
[Application Example 14]
Change the electron transfer layer in Application Example 11 into compound B27.
[Application Example 15]
Change the electron transfer layer in Application Example 11 into compound D1.
[Application Example 16]
Change the electron transfer layer in Application Example 11 into compound D7.
[Application Example 17]
Change the electron transfer layer in Application Example 11 into compound D20.
[Application Example 18]
Change the electron transfer layer in Application Example 11 into compound D23.
The electron luminescence characteristic of the organic luminescent device of above method manufacture indicates in the following table：
The above result shows that a kind of triaizine compounds of class formation containing fluorenes of the invention are applied in organic luminescent device, It as electron transport layer materials, hole barrier layer material or can be both electron transfer layer and hole blocking layer, show The advantage that driving voltage is low, luminous efficiency is high is luminous organic material of good performance.
Obviously, the explanation of above example is only intended to facilitate the understanding of the method and its core concept of the invention.It should refer to Go out, it, without departing from the principle of the present invention, can also be to this hair for the those of ordinary skill of the technical field Bright some improvement and modification can also be carried out, these improvement and modification are also fallen within the protection scope of the claims of the present invention.

Claims (9)

1. a kind of triaizine compounds of class formation containing fluorenes, which is characterized in that its general formula of molecular structure is as shown in I：
Wherein, Ar1、Ar2、Ar3It is independent to be selected from substituted or unsubstituted C6~C65Aryl, substituted or unsubstituted C3~C65 Heteroaryl in one kind, and it is at least one be selected from following group：
Wherein, R1、R2It is independent to be selected from substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C6~C30Aryl, Substituted or unsubstituted C6~C30Heteroaryl in one kind；R3Selected from hydrogen atom, substituted or unsubstituted C1~C10Alkyl, Substituted or unsubstituted C6~C30Aryl in one kind.
2. a kind of triaizine compounds of class formation containing fluorenes according to claim 1, which is characterized in that Ar1、Ar2、Ar3At least One is selected from following group：
Wherein, R1、R2It is independent selected from methyl, ethyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, substitution or Unsubstituted anthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyrenyl, takes substituted or unsubstituted phenanthryl It is generation or unsubstituted base, substituted or unsubstituted ferrosin base, substituted or unsubstituted pyridyl group, substituted or unsubstituted phonetic Piperidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted triazine radical, substitution or not Substituted pyrrole radicals, substituted or unsubstituted benzopyrrole base, substituted or unsubstituted triazolyl, substituted or unsubstituted thiophene Base, substituted or unsubstituted benzothienyl, substituted or unsubstituted benzofuranyl, takes substituted or unsubstituted furyl Generation or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzofuran group, substituted or unsubstituted quinolyl, substitution Or one kind in unsubstituted isoquinolyl, substituted or unsubstituted indyl；R3Selected from hydrogen atom, methyl, ethyl, isopropyl Or tertiary butyl.
3. a kind of triaizine compounds of class formation containing fluorenes according to claim 1, which is characterized in that Ar1、Ar2、Ar3At least One is selected from following group：
Wherein, R1、R2It is independent selected from methyl, ethyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, substitution or Unsubstituted anthryl, substituted or unsubstituted ferrosin base, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine Base, substituted or unsubstituted pyrazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substitution or not One kind in substituted indyl；R3Selected from hydrogen atom, methyl, ethyl, isopropyl or tertiary butyl.
4. a kind of triaizine compounds of class formation containing fluorenes according to claim 1, which is characterized in that Ar2、Ar3It is identical, choosing From following group：
Wherein, R1、R2It is independent selected from methyl, ethyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, substitution or In unsubstituted anthryl, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted pyrazinyl One kind；R3Selected from hydrogen atom, methyl, ethyl, isopropyl or tertiary butyl.
5. a kind of triaizine compounds of class formation containing fluorenes according to claim 1, which is characterized in that Ar1Selected from substitution or not Substituted phenyl, substituted or unsubstituted naphthalene, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substitution or not Substituted triphenylene, substituted or unsubstituted acridinyl, substituted or unsubstituted phenoxazine base, substituted or unsubstituted pheno thiophene Piperazine base, substituted or unsubstituted phenoxazine thiophene base, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazyl, substitution or not Substituted pyrenyl, substituted or unsubstituted ferrosin base, substituted or unsubstituted base, substituted or unsubstituted acenaphthenyl, substitution Or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazine Base, substituted or unsubstituted triazine radical, substituted or unsubstituted pyrrole radicals, substituted or unsubstituted benzopyrrole base, substitution or Unsubstituted triazolyl, substituted or unsubstituted thienyl, substituted or unsubstituted furyl, substituted or unsubstituted benzo thiophene Pheno base, substituted or unsubstituted benzofuranyl, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzo One kind in furyl.
6. a kind of triaizine compounds of class formation containing fluorenes according to claim 1, which is characterized in that be selected from as followsization Learn any one in structure：
7. a kind of organic luminescent device, which is characterized in that the organic luminescent device include cathode, anode and be placed in it is described two electricity One or more organic compound layers between pole, the organic compound layer contain claim 1~6 any one of them A kind of triaizine compounds of the class formation containing fluorenes.
8. according to a kind of organic luminescent device described in claim 7, which is characterized in that the organic compound layer includes electricity Sub- transport layer, the triaizine compounds containing a kind of class formation containing fluorenes of claim 1~6 any one of them in electron transfer layer.
9. according to a kind of organic luminescent device described in claim 7, which is characterized in that the organic compound layer includes sky Cave barrier layer, the triaizine compounds containing a kind of class formation containing fluorenes of claim 1~6 any one of them in hole blocking layer.
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WO2019112214A1 (en) * 2017-12-08 2019-06-13 덕산네오룩스 주식회사 Compound for organic electric element, organic electric element using same, and electronic device thereof
CN111233832A (en) * 2020-01-08 2020-06-05 上海传勤新材料有限公司 Organic electronic material containing fluorene and triazine and application thereof
WO2020162156A1 (en) * 2019-02-08 2020-08-13 住友化学株式会社 Compound and light emitting element using same
CN111747951A (en) * 2020-05-30 2020-10-09 浙江华显光电科技有限公司 Triazine compound and organic light-emitting device thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019112214A1 (en) * 2017-12-08 2019-06-13 덕산네오룩스 주식회사 Compound for organic electric element, organic electric element using same, and electronic device thereof
US11807630B2 (en) 2017-12-08 2023-11-07 Duk San Neolux Co., Ltd. Compound for organic electronic element, organic electronic element comprising the same, and electronic device thereof
WO2020162156A1 (en) * 2019-02-08 2020-08-13 住友化学株式会社 Compound and light emitting element using same
CN113365971A (en) * 2019-02-08 2021-09-07 住友化学株式会社 Compound and light-emitting element using same
CN113365971B (en) * 2019-02-08 2024-04-30 住友化学株式会社 Compound and light-emitting element using same
CN111233832A (en) * 2020-01-08 2020-06-05 上海传勤新材料有限公司 Organic electronic material containing fluorene and triazine and application thereof
CN111233832B (en) * 2020-01-08 2023-12-01 上海传勤新材料有限公司 Organic electronic material containing fluorene and triazine and application thereof
CN111747951A (en) * 2020-05-30 2020-10-09 浙江华显光电科技有限公司 Triazine compound and organic light-emitting device thereof

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