CN106467531B - It is a kind of using nitrogenous five-ring heterocycles as the compound of core and its application - Google Patents

It is a kind of using nitrogenous five-ring heterocycles as the compound of core and its application Download PDF

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CN106467531B
CN106467531B CN201610692025.1A CN201610692025A CN106467531B CN 106467531 B CN106467531 B CN 106467531B CN 201610692025 A CN201610692025 A CN 201610692025A CN 106467531 B CN106467531 B CN 106467531B
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compound
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core
nitrogenous
molar ratio
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CN106467531A (en
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唐丹丹
张兆超
李崇
张小庆
王立春
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Jiangsu Sunera Technology Co Ltd
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Jiangsu Sanyue Optoelectronic Technology Co Ltd
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Abstract

The invention discloses a kind of using nitrogenous five-ring heterocycles as the compound of core and its application, which has the characteristics that intermolecular be not easy to crystallize, be not easy to assemble, have good filming using nitrogenous five-ring heterocycles as core.It is applied to the compounds of this invention as emitting layer material on organic electroluminescence device, is showed using the organic electroluminescence device of the compounds of this invention with good photoelectric properties, can preferably adapt to and meet the application requirement of panel manufacturing enterprise.

Description

It is a kind of using nitrogenous five-ring heterocycles as the compound of core and its application
Technical field
The present invention relates to technical field of semiconductors, are the compound of core more particularly, to a kind of nitrogenous five-ring heterocycles, with And its application as emitting layer material on Organic Light Emitting Diode.
Background technique
Organic electroluminescent (OLED:Organic Light Emission Diodes) device technology can both be used to make New display product is made, production novel illumination product is can be used for, is expected to substitute existing liquid crystal display and fluorescent lighting, Application prospect is very extensive.
Structure of the OLED luminescent device like sandwich, including electrode material film layer, and be clipped in Different electrodes film layer it Between organic functional material, various different function materials are overlapped mutually depending on the application collectively constitutes OLED luminescent device together. As current device, when the two end electrodes application voltage to OLED luminescent device, and pass through electric field action organic layer functional material Positive and negative charge in film layer, positive and negative charge is further compound in luminescent layer, i.e. generation OLED electroluminescent.
Application of the Organic Light Emitting Diode (OLEDs) in terms of large-area flat-plate is shown and is illuminated causes industry and The extensive concern of art circle.However, traditional organic fluorescence materials can only be shone using 25% singlet exciton to be formed is electrically excited, device The internal quantum efficiency of part is lower (up to 25%).External quantum efficiency is generally lower than 5%, and there are also very big with the efficiency of phosphorescent devices Gap.Although phosphor material can efficiently use electricity since the strong SO coupling in heavy atom center enhances intersystem crossing The singlet exciton formed and Triplet exciton are excited, makes the internal quantum efficiency of device up to 100%.But phosphor material exists Expensive, stability of material is poor, and device efficiency tumbles the problems such as serious and limits it in the application of OLEDs.Hot activation is prolonged Slow fluorescence (TADF) material is the third generation luminous organic material developed after organic fluorescence materials and organic phosphorescent material.It should Class material generally has poor (the △ E of small singlet-tripletST), triplet excitons can be changed by anti-intersystem crossing It shines at singlet exciton.This can make full use of the singlet exciton and triplet excitons that are electrically excited lower formation, device it is interior Quantum efficiency can achieve 100%.Meanwhile material structure is controllable, and property is stablized, and it is cheap to be not necessarily to precious metal, in OLEDs Field has a extensive future.
Although theoretically 100% exciton utilization rate may be implemented in TADF material, following problem there are in fact: (1) T1 the and S1 state for designing molecule has strong CT feature, very small S1-T1 state energy gap, although can realize by TADF process High T1→S1State exciton conversion ratio, but low S1 state radiation transistion rate is also resulted in, consequently it is difficult to have both (or realizing simultaneously) High exciton utilization rate and high fluorescent radiation efficiency；(2) even if having used doping device to mitigate T exciton concentration quenching effect, greatly Efficiency roll-off is serious at higher current densities for the device of most TADF materials.
For current OLED shows the actual demand of Lighting Industry, the development of OLED material is also far from enough at present, falls Afterwards in the requirement of panel manufacturing enterprise, the organic functional material as material enterprise development higher performance is particularly important.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, the applicant provides a kind of using nitrogenous five-ring heterocycles as the change of core Close object and its application on organic electroluminescence device.The compounds of this invention is based on TADF mechanism using nitrogenous five-ring heterocycles as core The heart is applied to Organic Light Emitting Diode as emitting layer material, and the device that the present invention makes has good photoelectric properties, can Meet the requirement of panel manufacturing enterprise.
Technical scheme is as follows:
The applicant provides a kind of using nitrogenous five-ring heterocycles as the compound of core, the compound structure such as general formula (1) It is shown:
In general formula (1), X is expressed as oxygen atom, sulphur atom, C1-10Alkylidene, the aryl of linear or branched alkyl group substitution take One of the tertiary amine groups that alkylidene, the alkyl or aryl in generation replace；
In general formula (1), Ar indicates phenyl, xenyl, naphthalene, anthryl, phenanthryl, pyrenyl, furyl, thienyl or pyridine Base；
In general formula (1), R1、R2Independently be expressed as structure shown in hydrogen atom, general formula (2) or general formula (3), and R1、R2 Simultaneously it is not hydrogen atom:
Wherein, X1It is expressed as oxygen atom, sulphur atom, C1-10The Asia of alkylidene, aryl substitution that linear or branched alkyl group replaces One of the tertiary amine groups that alkyl, alkyl or aryl replace；
R3It is expressed as structure shown in hydrogen atom, general formula (4) or general formula (5)
Wherein, a isX2、X3、X4、X5Independently be expressed as oxygen atom, Sulphur atom, C1-10The tertiary amine groups that alkylidene, the alkyl or aryl of alkylidene, aryl substitution that linear or branched alkyl group replaces replace One of；General formula (4) or general formula (5) pass through CL1-CL2Key, CL2-CL3Key, CL3-CL4Key or CL4-CL5Key and general formula (2) are even It connects；
R4、R5Independently be expressed as phenyl, naphthalene, xenyl, general formula (6), general formula (7), general formula (8) or general formula (9) Shown structure；R5It is also denoted as hydrogen atom:
Wherein, X6For oxygen atom, sulphur atom, C1-10The alkylene of alkylidene, aryl substitution that linear or branched alkyl group replaces One of the tertiary amine groups that base, alkyl or aryl replace；
R6、R7Expression phenyl independently, naphthalene, dibiphenylyl, terphenyl, dibenzofurans, dibenzothiophenes, 9,9- dimethyl fluorene or carbazole.
Particularly, when X is expressed as oxygen atom or sulphur atom, the R3 in general formula (2) is not expressed as general formula (5).
Preferably, the general formula (2) indicates are as follows:
Any one of.
Preferably, general formula (3) indicates are as follows:
Any one of.
It is preferably, described using nitrogenous five-ring heterocycles as the concrete structure formula of the compound of core are as follows:
Any one of.
The applicant additionally provides a kind of method of compound, and the reaction equation occurred in preparation process is:
Work as R1When for hydrogen atom,
It is specific the preparation method comprises the following steps:
It weighs using nitrogenous five-ring heterocycles as the bromo compound of core and R2- H is dissolved with toluene；Add Pd2(dba)3、 Tri-tert-butylphosphine, sodium tert-butoxide；Under an inert atmosphere, by the mixed solution of above-mentioned reactant in 95~110 DEG C of reaction temperature, instead It answers 10~24 hours, cooling and filtering reacting solution, filtrate revolving crosses silicagel column, obtains target product；
It is described using nitrogenous five-ring heterocycles as the bromo compound of core and R2The molar ratio of-H is 1:1.0~1.5, Pd2 (dba)3Be 0.006~0.02:1 using nitrogenous five-ring heterocycles as the molar ratio of the bromo compound of core, tri-tert-butylphosphine with Be 0.006~0.02:1 using nitrogenous five-ring heterocycles as the molar ratio of the bromo compound of core, sodium tert-butoxide with nitrogenous five yuan Heterocycle is that the molar ratio of the bromo compound of core is 2.0~3.0:1；
Work as R1It is not hydrogen atom and R1And R2When identical,
It is specific the preparation method comprises the following steps:
It weighs using nitrogenous five-ring heterocycles as the bromo compound of core and R1- H or R2- H is dissolved with toluene；Add Pd2 (dba)3, tri-tert-butylphosphine, sodium tert-butoxide；Under an inert atmosphere, by the mixed solution of above-mentioned reactant in reaction temperature 95~ It 110 DEG C, reacts 10~24 hours, cooling and filtering reacting solution, filtrate revolving crosses silicagel column, obtains target product；
It is described using nitrogenous five-ring heterocycles as the bromo compound of core and R1- H or R2The molar ratio of-H is 1:2.0~3.0, Pd2(dba)3Be 0.006~0.02:1, tri-tert-butylphosphine by the molar ratio of the bromo compound of core of nitrogenous five-ring heterocycles Be 0.006~0.02:1 using nitrogenous five-ring heterocycles as the molar ratio of the bromo compound of core, sodium tert-butoxide with nitrogenous five Circle heterocyclic ring is that the molar ratio of the bromo compound of core is 3.0~5.0:1；
Work as R1It is not hydrogen atom and R1And R2When different,
It is specific the preparation method comprises the following steps:
It weighs using nitrogenous five-ring heterocycles as the halogenated compound of core and R2- H is dissolved with toluene；CuCl, 1 are added, 10- phenanthroline, potassium hydroxide；Under an inert atmosphere, by the mixed solution of above-mentioned reactant in 100~140 DEG C of reaction temperature, 1mol/L dilute hydrochloric acid is added after reaction and neutralizes for reaction 8~20 hours, and mixed liquor, which is adopted, to be extracted with dichloromethane, organic phase point Not Yong ammonium hydroxide and water washing, revolving, cross silicagel column, obtain intermediate product；
It is described using nitrogenous five-ring heterocycles as the halogenated compound of core and R2The molar ratio of-H be 1:1.0~1.5, CuCl with Be 0.05~0.15:1 using nitrogenous five-ring heterocycles as the molar ratio of the halogenated compound of core, 1,10- phenanthroline with nitrogenous Five-ring heterocycles are that the molar ratio of the halogenated compound of core is 0.05~0.15:1, potassium hydroxide with using nitrogenous five-ring heterocycles as core The molar ratio of the halogenated compound of the heart is 3.0~5.0:1；
Weigh intermediate product and R1- H is dissolved with toluene；Add Pd2(dba)3, tri-tert-butylphosphine, sodium tert-butoxide；Lazy Property atmosphere under, by the mixed solution of above-mentioned reactant in 95~110 DEG C of reaction temperature, react 10~24 hours, it is cooling simultaneously to filter Reaction solution, filtrate revolving, crosses silicagel column, obtains target product；
The intermediate product and R1The molar ratio of-H is 1:1.0~1.5, Pd2(dba)3Molar ratio with intermediate product is The molar ratio of 0.006~0.02:1, tri-tert-butylphosphine and intermediate product is 0.006~0.02:1, sodium tert-butoxide and intermediate product Molar ratio be 2.0~3.0:1.
The applicant additionally provides a kind of luminescent device containing the compound, and the compound is as luminescent layer material Material is applied to Organic Light Emitting Diode.
The present invention is beneficial to be had the technical effect that
The compounds of this invention is a kind of luminescent material, such material with it is intermolecular be not easy to crystallize, be not easy to assemble, have it is good The thermal stability of material, the compound can be improved in the characteristics of good film forming, the rigid radical in the compounds of this invention molecule Combination comprising electron donor (donor, D) and electron acceptor (acceptor, A) in structural molecule can increase Orbital Overlap, Luminous efficiency is improved, while connecting aromatic heterocycle group to obtain the charge transfer state material that HOMO, LUMO are spatially separating, is realized The energy level difference of small S1 state and T1 state is suitable as the layer main body that shines to realize reversed intersystem crossing under the conditions of thermostimulation Materials'use.
Compound of the present invention can be used as emitting layer material and make applied to OLED luminescent device, can obtain good Device performance, the current efficiency of device, power efficiency and external quantum efficiency are greatly improved；Meanwhile for device lifetime It is promoted clearly.
Compound of the present invention has good application effect in OLED luminescent device, before having good industrialization Scape.
Detailed description of the invention
Fig. 1 is the structural schematic diagram that the compounds of this invention is applied to OLED device；
Wherein, 1 is transparent substrate layer, and 2 be ito anode layer, and 3 be hole injection layer, and 4 be hole transmission layer, and 5 be luminous Layer, 6 be electron transfer layer, and 7 be electron injecting layer, and 8 be cathode reflection electrode layer.
Specific embodiment
With reference to the accompanying drawings and examples, the present invention is specifically described.
Embodiment 1: the synthesis of compound 11
Synthetic route:
0.01mol 3- (4- bromophenyl) -4,4- dimethyl-is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 250ml 5- phenyl -4H- pyrazoles, 0.012mol intermediate A 1,0.03mol sodium tert-butoxide, 5 × 10-5mol Pd2(dba)3, 5 × 10-5mol Tri-tert-butylphosphine, 150ml toluene are heated to reflux 24 hours, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, Silicagel column is crossed, target product, purity 98.9%, yield 75.6% are obtained.
Elemental analysis structure (molecular formula C45H32N4O): theoretical value C, 83.83；H,5.00；N,8.69；O,2.48；Test Value: C, 83.85；H,5.00；N,8.68；O,2.47.
HPLC-MS: material molecule amount 644.76 surveys molecular weight 618.95.
Embodiment 2: the synthesis of compound 19
Synthetic route:
0.01mol 3- (4- bromophenyl) -4,4- dimethyl-is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 250ml 5- phenyl -4H- pyrazoles, 0.012mol intermediate A 2,0.03mol sodium tert-butoxide, 5 × 10-5mol Pd2(dba)3, 5 × 10-5mol Tri-tert-butylphosphine, 150ml toluene are heated to reflux 24 hours, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, Silicagel column is crossed, target product, purity 98.7%, yield 72.7% are obtained.
Elemental analysis structure (molecular formula C60H46N4O): theoretical value C, 85.89；H,5.53；N,6.68；O,1.91；Test Value: C, 85.88；H,5.52；N,6.70；O,1.90.
HPLC-MS: material molecule amount 839.03 surveys molecular weight 839.19.
Embodiment 3: the synthesis of compound 29
Synthetic route:
0.01mol3- (4- bromophenyl) -4,4- dimethyl-is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 250ml 5- phenyl -4H- pyrazoles, 0.012mol intermediate A 3,0.03mol sodium tert-butoxide, 5 × 10-5mol Pd2(dba)3, 5 × 10-5mol Tri-tert-butylphosphine, 150ml toluene are heated to reflux 24 hours, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, Silicagel column is crossed, target product, purity 99.1%, yield 78.5% are obtained.
Elemental analysis structure (molecular formula C48H38N4O): theoretical value C, 83.94；H,5.58；N,8.16；O,2.33；Test Value: C, 83.92；H,5.60；N,8.14；O,2.34.
HPLC-MS: material molecule amount 686.84 surveys molecular weight 687.06.
Embodiment 4: the synthesis of compound 47
Synthetic route:
0.01mol 3- (the bromo- 1- naphthalene of 4-) 4,4- diformazan is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 250ml Base -5- (1- naphthalene) -4H- pyrazoles, 0.012mol intermediate B 1,0.03mol sodium tert-butoxide, 5 × 10-5mol Pd2(dba)3, 5 ×10-5Mol tri-tert-butylphosphine, 150ml toluene are heated to reflux 24 hours, sample contact plate, fully reacting；Natural cooling, filtering, Filtrate revolving, crosses silicagel column, obtains target product, purity 99.4%, yield 76.1%.
Elemental analysis structure (molecular formula C56H42N4O): theoretical value C, 85.47；H,5.38；N,7.12；O,2.03；Test Value: C, 85.48；H,5.39；N,7.11；O,2.02.
HPLC-MS: material molecule amount 786.96 surveys molecular weight 787.25.
Embodiment 5: the synthesis of compound 51
Synthetic route:
0.01mol 3- (the bromo- 2- furyl of 5-) -4,4- bis- is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 250ml Methyl -5- (2- furyl) -4H- pyrazoles, 0.012mol intermediate C1,0.03mol sodium tert-butoxide, 5 × 10-5mol Pd2 (dba)3, 5 × 10-5Mol tri-tert-butylphosphine, 150ml toluene are heated to reflux 24 hours, sample contact plate, fully reacting；Naturally cold But, it filters, filtrate revolving crosses silicagel column, obtains target product, purity 98.7%, yield 68.8%.
Elemental analysis structure (molecular formula C53H44N4O2): theoretical value C, 82.78；H,5.77；N,7.29；O,4.16；Test Value: C, 82.77；H,5.75；N,7.30；O,4.18.
HPLC-MS: material molecule amount 768.94 surveys molecular weight 769.10.
Embodiment 6: the synthesis of compound 87
Synthetic route:
0.01mol 2- (4- bromophenyl) -5- phenyl -1,3 is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 250ml, 4- oxadiazoles, 0.012mol intermediate D1,0.03mol sodium tert-butoxide, 5 × 10-5mol Pd2(dba)3, 5 × 10-5The tertiary fourth of mol tri- Base phosphine, 150ml toluene are heated to reflux 24 hours, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving cross silica gel Column obtains target product, purity 99.2%, yield 75.4%.
Elemental analysis structure (molecular formula C53H37N5O2): theoretical value C, 82.04；H,4.81；N,9.03；O,4.12；Test Value: C, 82.05；H,4.80；N,9.04；O,4.11.
HPLC-MS: material molecule amount 775.89 surveys molecular weight 776.12.
Embodiment 7: the synthesis of compound 91
Synthetic route:
0.01mol 3- (4- bromophenyl) -4,4- dimethyl-is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 250ml 5- phenyl -4H- pyrazoles, 0.012mol intermediate E 1,0.03mol sodium tert-butoxide, 5 × 10-5mol Pd2(dba)3, 5 × 10-5mol Tri-tert-butylphosphine, 150ml toluene are heated to reflux 24 hours, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, Silicagel column is crossed, target product, purity 99.5%, yield 77.3% are obtained.
Elemental analysis structure (molecular formula C50H38N4O): theoretical value C, 84.48；H,5.39；N,7.88；O,2.25；Test Value: C, 84.46；H,5.40；N,7.87；O,2.27.
HPLC-MS: material molecule amount 710.86 surveys molecular weight 711.03.
Embodiment 8: the synthesis of compound 95
Synthetic route:
0.01mol 2- (4- bromophenyl) -5- phenyl -1,3 is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 250ml, 4- oxadiazoles, 0.012mol intermediate E 2,0.03mol sodium tert-butoxide, 5 × 10-5mol Pd2(dba)3, 5 × 10-5The tertiary fourth of mol tri- Base phosphine, 150ml toluene are heated to reflux 24 hours, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving cross silica gel Column obtains target product, purity 99.2%, yield 78.2%.
Elemental analysis structure (molecular formula C50H38N4O2): theoretical value C, 82.62；H,5.27；N,7.71；O,4.40；Test Value: C, 82.62；H,5.27；N,7.71；O,4.40.
HPLC-MS: material molecule amount 726.86 surveys molecular weight 727.08.
Embodiment 9: the synthesis of compound 98
Synthetic route:
The preparation method of compound 98 is with embodiment 6, the difference is that replacing intermediate D1 with intermediate F1.
Elemental analysis structure (molecular formula C47H32N4O2): theoretical value C, 82.44；H,4.71；N,8.18；O,4.67；Test Value: C, 82.46；H,4.72；N,8.17；O,4.65.
HPLC-MS: material molecule amount 684.78 surveys molecular weight 684.95.
Embodiment 10: the synthesis of compound 120
Synthetic route:
The preparation method of compound 120 is with embodiment 6, the difference is that replacing intermediate D1 with intermediate G1.
Elemental analysis structure (molecular formula C47H34N4O2): theoretical value C, 82.19；H,4.99；N,8.16；O,4.66；Test Value: C, 82.20；H,5.00；N,8.15；O,4.65.
HPLC-MS: material molecule amount 686.80 surveys molecular weight 686.98.
Embodiment 11: the synthesis of compound 162
Synthetic route:
The preparation method of compound 162 is with embodiment 6, the difference is that replacing intermediate D1 with intermediate H1.
Elemental analysis structure (molecular formula C44H28N4O4): theoretical value C, 78.09；H,4.17；N,8.28；O,9.46；Test Value: C, 78.07；H,4.19；N,8.26；O,9.48.
HPLC-MS: material molecule amount 676.72 surveys molecular weight 676.90.
Embodiment 12: the synthesis of compound 170
Synthetic route:
The preparation method of compound 170 is with embodiment 6, the difference is that replacing intermediate D1 with intermediate compound I 1.
Elemental analysis structure (molecular formula C50H38N4O3): theoretical value C, 80.84；H,5.16；N,7.54；O,6.46；Test Value: C, 80.83；H,5.17；N,7.53；O,6.47.
HPLC-MS: material molecule amount 742.86 surveys molecular weight 743.06.
Embodiment 13: the synthesis of compound 198
Synthetic route:
The preparation method of compound 198 is with embodiment 6, the difference is that replacing intermediate D1 with intermediate J1.
Elemental analysis structure (molecular formula C53H38N4O2): theoretical value C, 83.44；H,5.02；N,7.34；O,4.19；Test Value: C, 83.42；H,5.03；N,7.35；O,4.20.
HPLC-MS: material molecule amount 762.89 surveys molecular weight 763.14.
Embodiment 14: the synthesis of compound 200
Synthetic route:
The preparation method of compound 200 is with embodiment 6, the difference is that replacing intermediate D1 with intermediate K1.
Elemental analysis structure (molecular formula C53H35N3O3): theoretical value C, 83.55；H,4.63；N,5.52；O,6.30；Test Value: C, 83.56；H,4.61；N,5.54；O,6.29.
HPLC-MS: material molecule amount 761.86 surveys molecular weight 762.03.
Embodiment 15: the synthesis of compound 210
Synthetic route:
0.01mol 3- (4- bromophenyl) -4- methyl -4,5- is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 250ml Diphenyl -4H- pyrazoles, 0.012mol intermediate J2,0.03mol sodium tert-butoxide, 5 × 10-5mol Pd2(dba)3, 5 × 10-5mol Tri-tert-butylphosphine, 150ml toluene are heated to reflux 24 hours, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, Silicagel column is crossed, target product, purity 99.3, yield 76.4% are obtained.
Elemental analysis structure (molecular formula C58H41N5O): theoretical value C, 84.54；H,5.02；N,8.50；O,1.94；Test Value: C, 84.56H, 5.00；N,8.49；O,1.95.
HPLC-MS: material molecule amount 823.98 surveys molecular weight 824.19.
Embodiment 16: the synthesis of compound 212
Synthetic route:
The preparation method of compound 212 is with embodiment 6, the difference is that replacing intermediate D1 with intermediate J3.
Elemental analysis structure (molecular formula C50H31N5O3): theoretical value C, 80.09；H,4.17；N,9.34；O,6.40；Test Value: C, 80.08H, 4.15N, 9.35O, 6.42.
HPLC-MS: material molecule amount 749.81 surveys molecular weight 749.97.
Embodiment 17: the synthesis of compound 216
Synthetic route:
The preparation method of compound 216 is with embodiment 6, the difference is that replacing intermediate D1 with intermediate K2.
Elemental analysis structure (molecular formula C53H37N5O): theoretical value C, 83.77；H,4.91；N,9.22；O,2.11；Test Value: C, 83.76；H,4.93；N,9.21；O,2.10.
HPLC-MS: material molecule amount 759.89 surveys molecular weight 760.10.
Embodiment 18: the synthesis of compound 225
Synthetic route:
0.01mol2- (5- bromo-2-pyridyl base) -5- (2- pyrrole is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 250ml Piperidinyl) -1,3,4- thiadiazoles, 0.012mol intermediate L1,0.03mol sodium tert-butoxide, 5 × 10-5mol Pd2(dba)3, 5 × 10-5Mol tri-tert-butylphosphine, 150ml toluene are heated to reflux 24 hours, sample contact plate, fully reacting；Natural cooling, filtering, filtrate Revolving crosses silicagel column, obtains target product, purity 98.5, yield 73.3%.
Elemental analysis structure (molecular formula C48H29N7S2): theoretical value C, 75.07；H,3.81；N,12.77；S,8.35；Test Value: C, 75.06；H,3.82；N,12.76；S,8.36.
HPLC-MS: material molecule amount 767.92 surveys molecular weight 768.09.
Embodiment 19: the synthesis of compound 250
Synthetic route:
The preparation method of compound 250 is with embodiment 6, the difference is that changing intermediate D1 with intermediate K3.
Elemental analysis structure (molecular formula C53H41N5O): theoretical value C, 83.33；H,5.41；N,9.17；O,2.09；Test Value: C, 83.32；H,5.42；N,9.18；O,2.08.
HPLC-MS: material molecule amount 763.93 surveys molecular weight 764.16.
Embodiment 20: the synthesis of compound 255
Synthetic route:
0.01mol 2,5- bis- (4- bromophenyl) -1,3,4- is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 250ml Oxadiazoles, 0.025mol intermediate J4,0.04mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert Phosphine, 150ml toluene are heated to reflux 24 hours, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving cross silica gel Column obtains target product, purity 98.8%, yield 62.4%.
Elemental analysis structure (molecular formula C62H38N6O3): theoretical value C, 81.38；H,4.19；N,9.18；O,5.25；Test Value: C, 81.37；H,4.21；N,9.16；O,5.26.
HPLC-MS: material molecule amount 915.00 surveys molecular weight 915.17.
The compounds of this invention can be used as the use of luminescent layer material of main part, to the compounds of this invention 48, compound 173, change It closes object 216 and current material CBP carries out the test of hot property, luminescent spectrum and cyclic voltammetric stability, test result such as 1 institute of table Show.
Table 1
Compound Td(℃) λPL(nm) Cyclic voltammetric stability
Compound 48 421 471 It is excellent
Compound 173 436 460 It is excellent
Compound 216 443 475 It is excellent
Material C BP 353 369 Difference
Note: thermal weight loss temperature Td is the temperature of the weightlessness 1% in nitrogen atmosphere, in the TGA-50H heat of Japanese Shimadzu Corporation It is measured on weight analysis instrument, nitrogen flow 20mL/min；λPLIt is sample solution fluorescence emission wavelengths, opens up Pu Kang using Japan The measurement of SR-3 spectroradiometer；Cyclic voltammetric stability be by cyclic voltammetry observe material redox characteristic come into Row identification；Test condition: test sample is dissolved in the methylene chloride and acetonitrile mixed solvent that volume ratio is 2:1, concentration 1mg/mL, electricity Solving liquid is the tetrabutyl ammonium tetrafluoroborate of 0.1M or the organic solution of hexafluorophosphate.Reference electrode is Ag/Ag+ electricity Pole is titanium plate to electrode, and working electrode is ITO electrode, and cycle-index is 20 times.
By upper table data it is found that the compounds of this invention has preferable oxidation-reduction stability, higher thermal stability is closed Suitable luminescent spectrum, so that getting a promotion using the compounds of this invention as the OLED device efficiency of emitting layer material and service life.
The 21-30 and comparative example 1-3 OLED material that the present invention will be described in detail synthesizes is made in the devices by the following examples For the application effect of luminescent layer material of main part.The production of 22-30, comparative example 1-3 device compared with embodiment 21 of the present invention Technique is identical, and uses identical baseplate material and electrode material, and the film thickness of electrode material is also consistent, institute The difference is that being converted to the material of main part and dopant material of the luminescent layer 5 in device.The structure of each embodiment obtained device Composition is as shown in table 2.The test result of obtained device is shown in Table 3.
Embodiment 21
2/ hole injection layer of ito anode layer, 2 (molybdenum trioxide MoO3, thickness 10nm) and/hole transmission layer 4 (TAPC, thickness 80nm)/luminescent layer 5 (the weight ratio blending of compound 200 and GD19 according to 100:5, thickness 30nm)/electron transfer layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/Al
Specific preparation process is as follows:
Transparent substrate layer 1 is transparent substrate, such as transparent PI film, glass.
Ito anode layer 2 (film thickness 150nm) is washed, i.e., successively carry out neutralizing treatment, pure water, drying, then into Row ultraviolet-ozone is washed to remove the organic residue on the transparent surface ITO.
On having carried out the ito anode layer 2 after above-mentioned washing, using vacuum deposition apparatus, it is 10nm's that film thickness, which is deposited, Molybdenum trioxide MoO3It is used as hole injection layer 3.And then the TAPC of 80nm thickness is deposited as hole transmission layer 4.
After above-mentioned hole mobile material vapor deposition, the luminescent layer 5 of OLED luminescent device is made, structure includes OLED hair The used material compound 200 of photosphere 5 is used as material of main part, and for GD19 as dopant material, dopant material doping ratio is 5% weight Ratio is measured, luminescent layer film thickness is 30nm.
After above-mentioned luminescent layer 5, continuation vacuum evaporation electron transport layer materials are TPBI.The vacuum evaporation coating of the material Thickness is 40nm, this layer is electron transfer layer 6.
On electron transfer layer 6, by vacuum deposition apparatus, lithium fluoride (LiF) layer that film thickness is 1nm is made, this layer is Electron injecting layer 7.
On electron injecting layer 7, by vacuum deposition apparatus, aluminium (Al) layer that film thickness is 80nm is made, this layer is cathode Reflection electrode layer 8 uses.
After completing OLED luminescent device as described above, anode and cathode is connected with well known driving circuit, is surveyed The current efficiency of metering device and the service life of device.The test result of made OLED luminescent device is shown in Table 3.
Table 2
Table 3
Embodiment 21-23 is compound of the present invention as luminescent layer TADF material of main part and is applied to OLED luminescent device Production；Embodiment 24-28 is that compound of the present invention is applied to as luminescent layer material of main part collocation TADF dopant material The production of OLED luminescent device；Embodiment 29-30 is compound of the present invention as luminescent layer Co-host material and is applied to OLED Luminescent device production；The test result of table 3 shows: compared with Comparative Examples 1 and 2,3；Either efficiency or service life obtain larger Take on a new look, the especially driving service life of device obtains biggish promotion.It is of the present invention that there is TADF from the point of view of above data application The emitting layer material of characteristic has good application effect in OLED luminescent device, has good industrialization prospect.
Although disclosing the present invention by embodiment and preferred embodiment, it should be appreciated that it is public that the present invention is not limited to institutes The embodiment opened.On the contrary, it will be understood by those skilled in the art that it is intended to various modifications and similar arrangement.Therefore, institute Attached the scope of the claims should be consistent with widest explanation to cover all such modifications and similar arrangement.

Claims (7)

1. a kind of using nitrogenous five-ring heterocycles as the compound of core, it is characterised in that shown in the compound structure such as general formula (1):
In general formula (1), X is expressed as methylene, the benzene that methylene, the aminomethyl phenyl that oxygen atom, sulphur atom, dimethyl replace replace One of the tertiary amine groups that base replaces；
In general formula (1), Ar indicates phenyl；
In general formula (1), R1、R2Independently be expressed as structure shown in hydrogen atom, general formula (2) or general formula (3), and R1、R2It is different When be hydrogen atom, and R1、R2One must be hydrogen:
Wherein, X1It is expressed as one of the tertiary amine groups that methylene, the phenyl that oxygen atom, sulphur atom, dimethyl replace replace；
R3It is expressed as structure shown in hydrogen atom, general formula (4) or general formula (5)
Wherein, a isX2、X3、X4、X5Independently to be expressed as oxygen atom, sulphur former One of the tertiary amine groups that son, the methylene of dimethyl substitution, phenyl replace；General formula (4) or general formula (5) pass through CL1-CL2Key, CL2-CL3Key, CL3-CL4Key or CL4-CL5Key is connect with general formula (2)；
R4、R5Independently be expressed as phenyl, naphthalene, xenyl, general formula (6), general formula (7), shown in general formula (8) or general formula (9) Structure；
Wherein, X6One of the tertiary amine groups that methylene, the phenyl replaced for oxygen atom, sulphur atom, dimethyl replaces；
R6、R7Expression phenyl, naphthalene, dibiphenylyl, terphenyl, dibenzofurans, dibenzothiophenes, 9,9- independently Dimethyl fluorene or carbazole.
2. compound according to claim 1, it is characterised in that in the general formula (1), X is expressed as oxygen atom or sulphur atom When, the R3 in general formula (2) is not expressed as general formula (5).
3. compound according to claim 1, it is characterised in that the general formula (2) indicates are as follows:
Any one of.
4. compound according to claim 1, it is characterised in that general formula (3) indicates are as follows:
In appoint It is a kind of.
5. compound according to claim 1, it is characterised in that described using nitrogenous five-ring heterocycles as the compound of core Concrete structure formula are as follows:
Any one of.
6. a kind of method for preparing any one of Claims 1 to 5 compound, it is characterised in that is occurred in preparation process is anti- Answering equation is:
Work as R1When for hydrogen atom,
It is specific the preparation method comprises the following steps:
It weighs using nitrogenous five-ring heterocycles as the bromo compound of core and R2- H is dissolved with toluene；Add Pd2(dba)3, three uncles Butyl phosphine, sodium tert-butoxide；Under an inert atmosphere, by the mixed solution of above-mentioned reactant in 95~110 DEG C of reaction temperature, reaction 10 ~24 hours, cooling and filtering reacting solution, filtrate revolving crossed silicagel column, obtains target product；
It is described using nitrogenous five-ring heterocycles as the bromo compound of core and R2The molar ratio of-H is 1:1.0~1.5, Pd2(dba)3With Be 0.006~0.02:1 using nitrogenous five-ring heterocycles as the molar ratio of the bromo compound of core, tri-tert-butylphosphine with nitrogenous five Circle heterocyclic ring is that the molar ratio of the bromo compound of core is 0.006~0.02:1, sodium tert-butoxide with using nitrogenous five-ring heterocycles as core The molar ratio of the bromo compound of the heart is 2.0~3.0:1；
Work as R1It is not hydrogen atom and R1And R2When identical,
It is specific the preparation method comprises the following steps:
It weighs using nitrogenous five-ring heterocycles as the bromo compound of core and R1- H or R2- H is dissolved with toluene；Add Pd2 (dba)3, tri-tert-butylphosphine, sodium tert-butoxide；Under an inert atmosphere, by the mixed solution of above-mentioned reactant in reaction temperature 95~ It 110 DEG C, reacts 10~24 hours, cooling and filtering reacting solution, filtrate revolving crosses silicagel column, obtains target product；
It is described using nitrogenous five-ring heterocycles as the bromo compound of core and R1- H or R2The molar ratio of-H is 1:2.0~3.0, Pd2 (dba)3Be 0.006~0.02:1 using nitrogenous five-ring heterocycles as the molar ratio of the bromo compound of core, tri-tert-butylphosphine with Be 0.006~0.02:1 using nitrogenous five-ring heterocycles as the molar ratio of the bromo compound of core, sodium tert-butoxide with nitrogenous five yuan Heterocycle is that the molar ratio of the bromo compound of core is 3.0~5.0:1；
Work as R1It is not hydrogen atom and R1And R2When different,
It is specific the preparation method comprises the following steps:
It weighs using nitrogenous five-ring heterocycles as the halogenated compound of core and R2- H is dissolved with toluene；It is adjacent luxuriant and rich with fragrance to add CuCl, 1,10- Hello quinoline, potassium hydroxide；Under an inert atmosphere, by the mixed solution of above-mentioned reactant in 100~140 DEG C of reaction temperature, reaction 8~ 20 hours, 1mol/L dilute hydrochloric acid is added after reaction and neutralizes, mixed liquor, which is adopted, to be extracted with dichloromethane, and organic phase uses ammonium hydroxide respectively And water washing, revolving cross silicagel column, obtain intermediate product；
It is described using nitrogenous five-ring heterocycles as the halogenated compound of core and R2The molar ratio of-H be 1:1.0~1.5, CuCl with to contain Nitrogen five-ring heterocycles are that the molar ratio of the halogenated compound of core is 0.05~0.15:1,1,10- phenanthroline with nitrogenous five yuan Heterocycle is that the molar ratio of the halogenated compound of core is 0.05~0.15:1, potassium hydroxide with using nitrogenous five-ring heterocycles as core The molar ratio of halogenated compound is 3.0~5.0:1；
Weigh intermediate product and R1- H is dissolved with toluene；Add Pd2(dba)3, tri-tert-butylphosphine, sodium tert-butoxide；In indifferent gas It under atmosphere, by the mixed solution of above-mentioned reactant in 95~110 DEG C of reaction temperature, reacts 10~24 hours, cooling simultaneously filters reaction Solution, filtrate revolving, crosses silicagel column, obtains target product；
The intermediate product and R1The molar ratio of-H is 1:1.0~1.5, Pd2(dba)3Molar ratio with intermediate product is 0.006 The molar ratio of~0.02:1, tri-tert-butylphosphine and intermediate product is 0.006~0.02:1, mole of sodium tert-butoxide and intermediate product Than for 2.0~3.0:1.
7. a kind of luminescent device containing any one of Claims 1 to 5 compound, it is characterised in that the compound conduct Emitting layer material is applied to Organic Light Emitting Diode.
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