CN107586261A - A kind of organic compound containing spiral shell dibenzocycloheptene fluorenes and its application - Google Patents

A kind of organic compound containing spiral shell dibenzocycloheptene fluorenes and its application Download PDF

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CN107586261A
CN107586261A CN201710909067.0A CN201710909067A CN107586261A CN 107586261 A CN107586261 A CN 107586261A CN 201710909067 A CN201710909067 A CN 201710909067A CN 107586261 A CN107586261 A CN 107586261A
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raw material
mol ratio
fluorenes
dibenzocycloheptene
spiral shell
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CN107586261B (en
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王立春
吴秀芹
张兆超
李崇
张小庆
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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 organic compound containing spiral shell dibenzocycloheptene fluorenes and its application.The compound using spiral shell dibenzocycloheptene fluorenes as core connects nitrogenous side chain by phenyl, xenyl or naphthyl.The compounds of this invention is not easy to crystallize, with good film forming and heat endurance, with higher glass transition temperature, suitable HOMO and lumo energy, optimized by device architecture, the photoelectric properties of OLED and the life-span of OLED can be effectively lifted, so as to preferably adapt to and meet the application requirement of panel manufacturing enterprise.

Description

A kind of organic compound containing spiral shell dibenzocycloheptene fluorenes and its application
Technical field
The present invention relates to technical field of semiconductors, more particularly, to skeleton centered on a kind of dibenzocycloheptene fluorenes by spiral shell Compound-material and its application in OLED fields.
Background technology
Organic electroluminescent (OLED:Organic Light Emission Diodes) device technology both can be used for make New display product is made, can be used for making novel illumination product, be expected to substitute existing liquid crystal display and fluorescent lighting, Application prospect is quite varied.OLED luminescent devices are just as the structure of sandwich, including electrode material film layer, and are clipped in different electricity Organic functional material between the film layer of pole, various difference in functionality materials are overlapped mutually according to purposes collectively constitutes OLED hairs together Optical device.As current device, when the two end electrodes to OLED luminescent devices apply voltage, and pass through electric field action organic layer work( Positive and negative charge in energy film layer, positive and negative charge is further compound in luminescent layer, that is, produces OLED electroluminescent.
Currently, OLED Display Techniques are applied in fields such as smart mobile phone, tablet personal computers, further will also be to electricity Depending on etc. large scale application field extension, still, with reality products application requirement compare, the luminous efficiency of OLED, use The performances such as life-span also need to further be lifted.Proposing high performance research for OLED luminescent devices includes：Reduce the driving of device Voltage, the luminous efficiency of device is improved, improve the service life etc. of device.In order to realize constantly carrying for the performance of OLED Rise, not only need the innovation from OLED structure and manufacture craft, with greater need for the constantly research and wound of oled light sulfate ferroelectric functional material Newly, higher performance OLED functional material is formulated out.
Oled light sulfate ferroelectric functional material applied to OLED can be divided into two major classes, i.e. electric charge injection transmission from purposes Material and luminescent material, further, it can also inject charge into transmission material and be divided into electron injection transmission material, electronic blocking material Luminescent material, can also be divided into main body luminescent material and dopant material by material, hole injection transmission material and hole barrier materials.
In order to make high performance OLED luminescent devices, it is desirable to various organic functional materials possess good photoelectric characteristic, For example, as charge transport materials, it is desirable to there is good carrier mobility, high-vitrification conversion temperature etc., as luminous The material of main part of layer requires that material has good bipolarity, appropriate HOMO/LUMO energy ranks etc..
The oled light sulfate ferroelectric functional material film layer for forming OLED comprises at least more than two layers structure, is applied in industry OLED structure, then passed including hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electronics A variety of film layers such as defeated layer, electron injecting layer, that is to say, that the photoelectric functional material applied to OLED is noted including at least hole Enter material, hole mobile material, luminescent material, electron transport material etc., material type and collocation form have rich and more The characteristics of sample.In addition, for the OLED collocation of different structure, used photoelectric functional material has stronger Selectivity, performance of the identical material in different structure device, it is also possible to completely totally different.
Therefore, for the difference in functionality film layer of the industry application requirement of current OLED, and OLED, device Photoelectric characteristic demand, it is necessary to which selection is more suitable for, and has high performance OLED functional materials or combination of materials, could realize device The overall characteristic of high efficiency, long-life and low-voltage.For the actual demand that current OLED shows Lighting Industry, OLED at present The development of material is also far from enough, lags behind the requirement of panel manufacturing enterprise, as the organic of material enterprise development higher performance Functional material is particularly important.
The content of the invention
In view of the above-mentioned problems existing in the prior art, the invention provides a kind of using spiral shell dibenzocycloheptene fluorenes as core Compound and its applied on organic electroluminescence device.The compound using spiral shell dibenzocycloheptene fluorenes as core passes through benzene Base, xenyl or naphthyl connect nitrogenous side chain.The compounds of this invention is not easy to crystallize, and has good film forming and thermostabilization Property, there is higher glass transition temperature, suitable HOMO and lumo energy are optimized by device architecture, can effectively lift OLED The photoelectric properties of device and the life-span of OLED, so as to preferably adapt to and meet the application requirement of panel manufacturing enterprise.
Technical scheme is as follows：
A kind of organic compound containing spiral shell dibenzocycloheptene fluorenes, shown in the structure such as formula (1) of the compound：
Wherein, R1、R2、R3、R4Separately it is expressed as structure shown in formula (2) or formula (3)；R1、R2、R3With R4Phase It is same or different；R1、R2、R3It is also denoted as hydrogen atom；
In formula (2), formula (3), R5、R6Separately it is expressed as substituted or unsubstituted C6-60Aryl, contain one Or multiple heteroatomic substituted or unsubstituted 5-60 unit's heteroaryls；The hetero atom is nitrogen, oxygen or sulphur；R5With R6It is identical or It is different；
In formula (3), Ar1It is expressed as substituted or unsubstituted C6-60Arlydene, contain one or more heteroatomic substitutions Or unsubstituted 5~60 yuan of heteroarylidenes；The hetero atom is nitrogen, oxygen or sulphur；
Preferably, Ar1The one kind being expressed as in phenylene, biphenylene or naphthylene；R5、R6Separately it is expressed as C1-10Straight or branched alkyl, C6-30Aryl is substituted or unsubstituted：Phenyl, pyridine radicals, dibiphenylyl, terphenyl, naphthyl, Anthryl, phenanthryl, triazine radical, pyrimidine radicals, quinolyl, dibenzofuran group, 9,9- dimethyl fluorenyl, 9,9- diphenyl fluorenyl, 9, The fluorenyl of 9- spiral shells two, 9,9- diethyl fluorenyl, carbazyl, benzo carbazole base, dibenzothiophenes base, acridinyl, indolocarbazole base, One kind in phenoxazine group, Sai oxazinyls.
Preferably, the formula (2) is embodied as：
In any one.Preferably, institute Stating compound concrete structure is：
In any one.
The applicant additionally provides a kind of preparation method of the organic compound containing spiral shell dibenzocycloheptene fluorenes, works as R2、 R3、R4When being expressed as hydrogen atom, reaction equation is as shown in 1-1,1-2：
The specific preparation method of above-mentioned reaction is：Weigh raw material I and H-R1, dissolved with toluene；Add Pd2(dba)3、P (t-Bu)3, sodium tert-butoxide；Under an inert atmosphere, it is small that the mixed solution of above-mentioned reactant is reacted to 10~24 at 95~110 DEG C When, cool down and filtering reacting solution, filtrate rotate, cross silicagel column, obtain above-mentioned target product I；The raw material I and H-R1Rub You are than being 1:(1.2~3.0), Pd2(dba)3Mol ratio with raw material I is (0.006~0.02):1, tri-butyl phosphine and raw material I Mol ratio be (0.006~0.02):1, the mol ratio of sodium tert-butoxide and raw material I is (1.0~3.0):1；
The specific preparation method of above-mentioned reaction is：Weigh raw material I, R1-B(OH)2, it is 2 with volume ratio:1 toluene and ethanol Mixed solvent dissolving；Under an inert atmosphere, Na is added2CO3The aqueous solution, Pd (PPh3)4；The mixing of above-mentioned reactant is molten Liquid reacts 10~24 hours in 95~110 DEG C of reaction temperature, cools down and filtering reacting solution, filtrate rotate, cross silicagel column, obtain To target product II；The raw material I and R1-B(OH)2Mol ratio be 1:1.0~2.0；Na2CO3Mol ratio with raw material I is (1.0~3.0):1；Pd(PPh3)4Mol ratio with raw material I is (0.006~0.02):1；
Work as R1、R2、R3When being expressed as hydrogen atom, reaction equation is as shown in 1-3,1-4：
The specific preparation method of above-mentioned reaction is：Weigh raw material II and H-R4, dissolved with toluene；Add Pd2(dba)3、P (t-Bu)3, sodium tert-butoxide；Under an inert atmosphere, it is small that the mixed solution of above-mentioned reactant is reacted to 10~24 at 95~110 DEG C When, cool down and filtering reacting solution, filtrate rotate, cross silicagel column, obtain above-mentioned target product III；The raw material II and H-R4 Mol ratio be 1:(1.2~3.0), Pd2(dba)3Mol ratio with raw material II is (0.006~0.02):1, tri-butyl phosphine with The mol ratio of raw material II is (0.006~0.02):1, the mol ratio of sodium tert-butoxide and raw material II is (1.0~3.0):1；
The specific preparation method of above-mentioned reaction is：Weigh raw material II, R4-B(OH)2, it is 2 with volume ratio:1 toluene and second The mixed solvent dissolving of alcohol；Under an inert atmosphere, Na is added2CO3The aqueous solution, Pd (PPh3)4；By the mixing of above-mentioned reactant Solution rotates in 95~110 DEG C of reaction temperature, reaction 10~24 hours, cooling and filtering reacting solution, filtrate, crosses silicagel column, Obtain target product IV；The raw material II and R4-B(OH)2Mol ratio be 1:1.0~2.0；Na2CO3With mole of raw material II Than for (1.0~3.0):1；Pd(PPh3)4Mol ratio with raw material I is (0.006~0.02):1.
The H-R1、H-R2With B (OH)2-R1、B(OH)2-R4Synthesis step respectively such as reaction equation 2-1 and reaction equation 2-2 It is shown：
Intermediate B I in above-mentioned reaction represents H-R1、H-R2；
The specific preparation method of above-mentioned reaction is：Weigh raw material O and raw material P is dissolved with toluene, add Pd2(dba)3、P (Ph)3And sodium tert-butoxide；Under an inert atmosphere, the mixed solution of above-mentioned reactant is reacted at 90~110 DEG C of reaction temperature 10~24 hours, cooling, filtering reacting solution, filtrate revolving, silicagel column is crossed, obtains intermediate B I；The raw material O and raw material P Mol ratio be 1:(1.0~1.5)；Pd2(dba)3Mol ratio with raw material O is (0.006~0.02):1, sodium tert-butoxide with it is former The mol ratio for expecting O is (2.0~3.0):1；P(Ph)3Mol ratio with raw material O is (2.0~3.0):1；
Intermediate B II in above-mentioned reaction represents B (OH)2-R1、B(OH)2-R4；
The specific preparation method of above-mentioned reaction is：Intermediate B I and raw material N are weighed, is dissolved with toluene；Add Pd2 (dba)3、P(Ph)3, sodium tert-butoxide；Under an inert atmosphere, the mixed solution of above-mentioned reactant is reacted 10 at 95~110 DEG C ~24 hours, cool down and filtering reacting solution, filtrate rotate, cross silicagel column, obtain intermediate C；The intermediate B I and raw material N Mol ratio be 1:(1.0~1.5), Pd2(dba)3Mol ratio with intermediate B I is (0.006~0.02):1, P (Ph)3With in Mesosome BI mol ratio is (0.006~0.02):1, the mol ratio of sodium tert-butoxide and intermediate B I is (1.0~3.0):1；
Under the atmosphere of nitrogen, intermediate C, double (pinacol conjunctions) two boron, Pd (dppf) Cl are weighed2, potassium acetate be dissolved in first In benzene, reacted 12~24 hours at 100~120 DEG C, sample point plate, reaction is complete, natural cooling, filtering, filtrate revolving, obtains Crude product, cross neutral silica gel post and obtain intermediate B II；The mol ratio of intermediate C and double (pinacol conjunction) two boron is 2:(1~ 1.5), intermediate C and Pd (dppf) Cl2Mol ratio be 1:The mol ratio of (0.01~0.05), intermediate C and potassium acetate is 1: (2~2.5).
The applicant additionally provides the organic compound containing spiral shell dibenzocycloheptene fluorenes and is used to prepare organic electroluminescent The application of device.
The applicant additionally provides a kind of organic electroluminescence device, and the organic electroluminescence device includes at least one layer Functional layer contains the described organic compound containing spiral shell dibenzocycloheptene fluorenes.
The applicant additionally provides a kind of organic electroluminescence device, including hole transmission layer or electronic barrier layer, described Hole transmission layer or electronic blocking layer material are the organic compound containing spiral shell dibenzocycloheptene fluorenes.The applicant is also Provide a kind of organic electroluminescence device, including luminescent layer, the luminescent layer, which contains, described contains spiral shell dibenzocycloheptene The organic compound of fluorenes.
The present invention is beneficial to be had technical effect that：
The pi-conjugated effects of p- in the compounds of this invention cause it to have very strong cavity transmission ability, high hole transport speed Rate can improve the efficiency of organic electroluminescence device；Low molecular crystallization can drop in asymmetric tertiary aromatic amine structure in compound Property, low molecular flatness is dropped, prevents molecule from moving in the plane so as to improve the heat endurance of molecule.The chemical combination of the present invention Thing using spiral shell dibenzocycloheptene fluorenes as parent nucleus, connect nitrogenous side chain, the structure has higher dielectric constant, makes compound With higher refractive index.
The structure of the compound of the present invention causes electronics and hole more to be balanced in the distribution of luminescent layer, in appropriate HOMO Under energy level, hole injection and transmission performance are improved；Under suitable lumo energy, the effect of electronic blocking is served again, is carried Rise combined efficiency of the exciton in luminescent layer；During light emitting functional layer materials'use as OLED luminescent devices, spiral shell dibenzo ring Side chain in the heptene fluorenes collocation scope of the invention can effectively improve exciton utilization rate and high fluorescent radiation efficiency, and it is close to reduce high current Efficiency roll-off under degree, device voltage is reduced, improve current efficiency and the life-span of device.
The compound of the present invention is optimized by device architecture when OLED is applied, can keep high membranous layer stability, The photoelectric properties of OLED and the life-span of OLED can effectively be lifted.Compound of the present invention is in OLED luminescent devices In there is good application effect and industrialization prospect.
Brief description of the drawings
Fig. 1 is the materials application cited by the present invention in the structural representation of OLED；Wherein, 1, transparent substrate layer, 2nd, ito anode layer, 3, hole injection layer, 4, hole transmission layer 5, electronic barrier layer, 6, luminescent layer, 7, hole blocking layer/electronics Transport layer, 8, electron injecting layer, 9, negative electrode reflection electrode layer.
Fig. 2 is the efficiency curve diagram that device measures at different temperatures.
Embodiment
Embodiment 1：Intermediate B I synthesis：
Weigh raw material O and raw material P is dissolved with toluene, add Pd2(dba)3、P(Ph)3And sodium tert-butoxide；In inert atmosphere Under, the mixed solution of above-mentioned reactant is reacted 10~24 hours at 90~110 DEG C of reaction temperature, cooling, filtering reaction are molten Liquid, filtrate revolving, crosses silicagel column, obtains intermediate B I；The raw material O and raw material P mol ratio is 1:(1.0~1.5)；Pd2 (dba)3Mol ratio with raw material O is (0.006~0.02):1, the mol ratio of sodium tert-butoxide and raw material P is (2.0~3.0):1； P(Ph)3Mol ratio with raw material O is (2.0~3.0):1；
By taking the synthesis of intermediate B 1 as an example：
In 250ml there-necked flask, lead under nitrogen protection, add 0.01mol raw materials O1,0.012mol raw material P1,150ml Toluene is stirred, and then adds 5 × 10-5molPd2(dba)3, 5 × 10-5mol P(Ph)3, 0.03mol sodium tert-butoxides, heating To 105 DEG C, back flow reaction 24 hours, sample point plate, show that no bromo-derivative is remaining, reaction is complete；Naturally cool to room temperature, mistake Filter, filtrate rotate to without cut, cross neutral silica gel post, obtain target product intermediate B 1；HPLC purity 99.53%, yield 75.5%；Elementary analysis structure (molecular formula C21H19N)：Theoretical value C, 88.38；H,6.71；N,4.91；Test value：C,88.37； H,6.71；N,4.92.ESI-MS(m/z)(M+)：Theoretical value 285.39, measured value 285.36.
Embodiment 2：Intermediate B II synthesis：
The specific preparation method of above-mentioned reaction is：Intermediate B I and raw material N are weighed, is dissolved with toluene；Add Pd2 (dba)3、P(Ph)3, sodium tert-butoxide；Under an inert atmosphere, the mixed solution of above-mentioned reactant is reacted 10 at 95~110 DEG C ~24 hours, cool down and filtering reacting solution, filtrate rotate, cross silicagel column, obtain intermediate C；The intermediate B I and raw material N Mol ratio be 1:(1.0~1.5), Pd2(dba)3Mol ratio with intermediate B I is (0.006~0.02):1, P (Ph)3With in Mesosome BI mol ratio is (0.006~0.02):1, the mol ratio of sodium tert-butoxide and intermediate B I is (1.0~3.0):1.
Under the atmosphere of nitrogen, intermediate C, double (pinacol conjunctions) two boron, Pd (dppf) Cl are weighed2, potassium acetate be dissolved in first In benzene, reacted 12~24 hours at 100~120 DEG C, sample point plate, reaction is complete, natural cooling, filtering, filtrate revolving, obtains Crude product, cross neutral silica gel post and obtain intermediate B II；The mol ratio of intermediate C and double (pinacol conjunction) two boron is 2:(1~ 1.5), intermediate C and Pd (dppf) Cl2Mol ratio be 1:The mol ratio of (0.01~0.05), intermediate C and potassium acetate is 1: (2~2.5).
By taking the synthesis of intermediate B 10 as an example：
In 250ml there-necked flask, lead under nitrogen protection, add 0.01mol intermediate B I-n, 0.012mol raw material N1,150ml toluene are stirred, and then add 5 × 10-5molPd2(dba)3, 5 × 10-5mol P(Ph)3, the tertiary fourths of 0.03mol Sodium alkoxide, 105 DEG C are heated to, back flow reaction 24 hours, sample point plate, shows that no bromo-derivative is remaining, reaction is complete；Naturally cool to Room temperature, filtering, filtrate rotate to without cut, cross neutral silica gel post, obtain target product intermediate C1；
Under the atmosphere of nitrogen, 0.02mol intermediates C1,0.012mol double (pinacol conjunction) two boron, 0.0002mol are weighed Pd(dppf)Cl2, 0.05mol potassium acetates be dissolved in toluene, reacted 12~24 hours at 100~120 DEG C, sample point plate, react Completely, natural cooling, filtering, filtrate revolving, crude product is obtained, crosses neutral silica gel post and obtain intermediate B 10；HPLC purity 99.35%, yield 76.3%；Elementary analysis structure (molecular formula C33H26BNO3)：Theoretical value C, 80.01；H,5.29；B,2.18； N,2.83；O,9.69；Test value：C,80.01；H,5.28；B,2.18；N,2.84；O,9.69.ESI-MS(m/z)(M+)：It is theoretical It is worth for 495.38, measured value 495.29.The synthesis material such as table 1 of intermediate B I and intermediate B II needed for embodiment：
Table 1
Embodiment 3：Intermediate A I synthesis：
In the flask of drying, 0.01mol raw materials N is dissolved in 500mL anhydrous THF, reactant mixture is cooled down To -78 DEG C, then, 34.3mL n-BuLi (2.5mol/L, hexane solution) is slowly added dropwise, 1h is stirred, then by 0.01mol's Raw material M is dissolved in THF, and is added dropwise at -70 DEG C.After the end of the addition, reactant mixture is gradually heated to room temperature, uses chlorine Change ammonium to extract and concentrated on a rotary evaporator, 500mL acetic acid is carefully added into concentrate solution, and is subsequently added into 100mL fuming hydrochloric acid.75 DEG C are heated the mixture to, and keeps 5h, white solid is during which had and comes out, then by mixture Room temperature is cooled to, and is filtered out the solid of precipitation with suction strainer, is washed with methanol, under reduced pressure in 40 DEG C of dried residues.
Embodiment 4：Intermediate A II synthesis：
Intermediate A II is prepared by the synthetic method of the intermediate A I in embodiment 1, difference is to replace original with raw material K Expect that M, raw material L replace raw material N.The synthesis material such as table 2 of intermediate A I and intermediate A II needed for embodiment:
Table 2
Embodiment 5：The synthesis of compound 3：
In 250ml there-necked flask, lead under nitrogen protection, addition 0.01mol intermediate As 6,0.012mol intermediate Bs 1, 150ml toluene is stirred, and then adds 5 × 10-5molPd2(dba)3, 5 × 10-5mol P(t-Bu)3, the 0.03mol tert-butyl alcohols Sodium, 105 DEG C are heated to, back flow reaction 24 hours, sample point plate, shows that no bromo-derivative is remaining, reaction is complete；Naturally cool to room Temperature, filtering, filtrate rotate to without cut, cross neutral silica gel post, obtain target product, HPLC purity 99.76%, yield 75.3%.Elementary analysis structure (molecular formula C48H35N)：Theoretical value:C,92.12；H,5.64；N,2.24；Test value：C, 92.13；H,5.65；N,2.23.HPLC-MS：Material molecule amount is 625.81, surveys molecular weight 625.60.
Embodiment 6：The synthesis of compound 6：
Being prepared by the synthetic method of compound 3 in embodiment 5, difference is to replace intermediate A 6 with intermediate A 3, in Mesosome B2 replaces intermediate B 1；Elementary analysis structure (molecular formula C52H37N)：Theoretical value:C,92.41；H,5.52；N,2.07；Survey Examination value：C,92.43；H,5.51；N,2.06.HPLC-MS：Material molecule amount is 675.88, surveys molecular weight 675.35.
Embodiment 7：The synthesis of compound 12：
Being prepared by the synthetic method of compound 3 in embodiment 5, difference is to replace intermediate A 6 with intermediate A 1, in Mesosome B3 replaces intermediate B 1；Elementary analysis structure (molecular formula C54H39N)：Theoretical value:C,92.40；H,5.60；N,2.00；Survey Examination value：C,92.41；H,5.61；N,1.99.HPLC-MS：Material molecule amount is 701.91, surveys molecular weight 701.38.
Embodiment 8:The synthesis of compound 20：
Being prepared by the synthetic method of compound 3 in embodiment 5, difference is to replace intermediate A 6 with intermediate A 5, in Mesosome B4 replaces intermediate B 1；Elementary analysis structure (molecular formula C54H39N)：Theoretical value:C,92.40；H,5.60；N,2.00；Survey Examination value：C,92.39；H,5.60；N,2.01.HPLC-MS：Material molecule amount is 701.91, surveys molecular weight 701.80.
Embodiment 9：The synthesis of compound 31：
Being prepared by the synthetic method of compound 3 in embodiment 5, difference is to replace intermediate A 6 with intermediate A 2, in Mesosome B5 replaces intermediate B 1；Elementary analysis structure (molecular formula C54H37NO)：Theoretical value：C,90.60；H,5.21；N,1.96； O,2.23；Test value：C,90.61；H,5.19；N,1.96；O,2.24.HPLC-MS：Material molecule amount is 715.90, actual measurement point Son amount 715.71.
Embodiment 10：The synthesis of compound 38：
Being prepared by the synthetic method of compound 3 in embodiment 5, difference is to replace intermediate A 6 with intermediate A 4, in Mesosome B6 replaces intermediate B 1；Elementary analysis structure (molecular formula C51H33NO)：Theoretical value：C,90.64；H,4.92；N,2.07； O,2.37；Test value：C,90.65；H,4.92；N,2.06.HPLC-MS：Material molecule amount is 675.83, surveys molecular weight 675.55。
Embodiment 11：The synthesis of compound 48：
Being prepared by the synthetic method of compound 3 in embodiment 5, difference is to replace intermediate A 6 with intermediate A 3, in Mesosome B7 replaces intermediate B 1；Elementary analysis structure (molecular formula C51H33NO)：Theoretical value:C,90.64；H,4.92；N,2.07； O,2.37；Test value：C,90.63；H,4.93；N,2.07；O,2.37.HPLC-MS：Material molecule amount is 675.83, actual measurement point Son amount 675.71.
Embodiment 12：The synthesis of compound 61：
Prepared by the synthetic method of compound 3 in embodiment 5, difference is to replace intermediate B 1 with intermediate B 8；Member Plain analytical structure (molecular formula C57H39N3)：Theoretical value:C,89.38；H,5.13；N,5.49；Test value：C,89.39；H,5.14； N,5.47.HPLC-MS：Material molecule amount is 765.96, surveys molecular weight 765.09.
Embodiment 13：The synthesis of compound 76：
Being prepared by the synthetic method of compound 3 in embodiment 5, difference is to replace intermediate A 6 with intermediate A 4, in Mesosome B9 replaces intermediate B 1；Elementary analysis structure (molecular formula C49H31NO)：Theoretical value:C,90.57；H,4.81；N,2.16； O,2.46；Test value：C,90.55；H,4.82；N,2.15；O,2.48.HPLC-MS：Material molecule amount is 649.79, actual measurement point Son amount 649.75.
Embodiment 14：The synthesis of compound 111：
In 250ml there-necked flask, intermediate 0.01mol intermediate As 5,0.015mol intermediate Bs 10 are added, uses volume Than for 2:1 toluene and the mixed solvent of ethanol dissolve；Under an inert atmosphere, 0.02mol Na are added2CO3The aqueous solution (2M), 0.0001mol Pd(PPh3)4；By the mixed solution of above-mentioned reactant in 95~110 DEG C of reaction temperature, react 10~24 hours, Cool down and filtering reacting solution, filtrate rotate, cross silicagel column, obtain target product, HPLC purity 99.80%, yield 74.3%. Elementary analysis structure (molecular formula C60H41NO)：Theoretical value:C,90.99；H,5.22；N,1.77；O,2.02；Test value：C, 90.98；H,5.21；N,1.78；O,2.03.HPLC-MS：Material molecule amount is 791.99, surveys molecular weight 791.80.
Embodiment 15：The synthesis of compound 118：
Being prepared by the synthetic method of compound 111 in embodiment 14, difference is to replace intermediate A 5 with intermediate A 1, Intermediate B 11 replaces intermediate B 10；Elementary analysis structure (molecular formula C57H37NO)：Theoretical value；C,91.05；H,4.96；N, 1.86；O,2.13；Test value：C,91.04；H,4.95；N,1.87；O,2.14.HPLC-MS：Material molecule amount is 751.93, real Survey molecular weight 751.58.
Embodiment 16：The synthesis of compound 124：
Being prepared by the synthetic method of compound 111 in embodiment 14, difference is to replace intermediate A 5 with intermediate A 6, Intermediate B 12 replaces intermediate B 10；Elementary analysis structure (molecular formula C63H41NO)：Theoretical value:C,91.39；H,4.99；N, 1.69；O,1.93；Test value：C,91.37；H,4.98；N,1.71；O,1.94.HPLC-MS：Material molecule amount is 828.03, real Survey molecular weight 827.90.
The compounds of this invention uses in luminescent device, can be used as electronic blocking layer material, can also be used as luminescent layer Subjective and Objective materials'use.To the above embodiment of the present invention prepare compound carry out respectively hot property, T1 energy levels, HOMO energy levels and The test of fluorescence quantum efficiency (PLQY) and the test of refractive index, testing result are as shown in table 3.
Table 3
Note："/" in upper table is expressed as not carrying out this test (height of the fluorescence quantum efficiency of electronic blocking layer material Influence to OLED performance is smaller)；Glass transition temperature Tg is by differential scanning calorimetry (DSC, German Nai Chi companies DSC204F1 differential scanning calorimeters) measure, 10 DEG C/min of heating rate；Thermal weight loss temperature Td is weightless in nitrogen atmosphere 1% temperature, it is measured on the TGA-50H thermogravimetric analyzers of Japanese Shimadzu Corporation, nitrogen flow 20mL/min；Three lines State energy level T1 is the F4600 XRFs test by Hitachi, and the test condition of material is 2*10-5Toluene solution；Refractive index It is by ellipsometer (U.S.'s J.A.Woollam Co. models：ALPHA-SE) measured under atmospheric environment；Fluorescence quantum efficiency uses The Quantaurus-QY (C13534-11) of Japanese HAMAMATSU companies is identified；Highest occupied molecular orbital HOMO energy levels And minimum occupied molecular orbital lumo energy is tested by photoelectron emissions spectrometer (AC-2 type PESA), is tested as atmospheric environment.
From upper table data, organic compound of the invention has high glass transition temperature, can improve material membrane phase State stability, further improve device service life；With high T1 energy levels, luminescent layer energy loss can be stopped, so as to carry Rise device light emitting efficiency；Suitable HOMO energy levels can solve the problems, such as the injection of carrier, can reduce device voltage；Higher is glimmering Photo-quantum efficiency and refractive index, the luminous efficiency of OLED can be improved.Therefore, the present invention is using spiral shell dibenzocycloheptene fluorenes as core The compound of the heart can effectively improve the luminous efficiency and service life of device after the difference in functionality layer applied to OLED.
The OLED material of the invention synthesized is described in detail below by way of device embodiments 1~12 and comparative example 1 in the devices Application effect.The complete phase of manufacture craft of the device compared with device embodiments 1 of device embodiments 1~12 of the present invention Together, and employed identical baseplate material and electrode material, the thickness of electrode material are also consistent, except that right The material of main part or electronic blocking layer material of luminescent layer in device are changed.The performance test knot of each embodiment obtained device Fruit is as shown in table 4.
Device embodiments 1
As shown in figure 1, a kind of electroluminescent device, its preparation process includes：A) the ITO sun cleaned on transparent substrate layer 1 Pole layer 2, cleaned each 15 minutes with deionized water, acetone, EtOH Sonicate respectively, 2 points are then handled in plasma cleaner Clock；B) on ito anode layer 2, hole injection layer material HAT-CN, thickness 10nm, this layer are deposited by vacuum evaporation mode As hole injection layer 3；C) on hole injection layer 3, the defeated layer material NPB in hole is deposited by vacuum evaporation mode, thickness is 60nm, the layer are hole transmission layer 4；D) on hole transport layer material 4, NPB, thickness are deposited by way of vacuum evaporation For 20nm, the layer is electronic barrier layer 5；E) luminescent layer 6 is deposited on electronic barrier layer 5, is made using the compounds of this invention 12 For material of main part, Ir (ppy)3As dopant material, Ir (ppy)3Mass ratio with compound 12 is 1:9, thickness 30nm；f) On luminescent layer 6, electron transport material TPBI, thickness 40nm are deposited by vacuum evaporation mode, this layer of organic material is made Used for hole barrier/electron transfer layer 7；G) on hole blocking layer/electron transfer layer 7, vacuum evaporation electron injecting layer LiF, thickness 1nm, the layer are electron injecting layer 8；H) on electron injecting layer 8, vacuum evaporation negative electrode Al (100nm) should Layer is negative electrode reflection electrode layer 9；According to above-mentioned steps complete electroluminescent device making after, the current efficiency of measurement device and In the life-span, it the results are shown in Table shown in 4.The molecular structural formula of associated materials is as follows：
Device embodiments 2：The difference of the present embodiment and device embodiments 1 is：The luminescent layer of electroluminescent device Material of main part is changed into compound 20 prepared by the present invention, and dopant material is Ir (ppy)3, compound 20 and Ir (ppy)3Mass ratio For 90:10.Device embodiments 3：The luminescent layer material of main part of electroluminescent device is changed into compound 31 prepared by the present invention, doping Material is Ir (ppy)3, compound 31 and Ir (ppy)3Mass ratio be 92:8.Device embodiments 4：Electroluminescent device lights Layer main body material is changed into compound 38 prepared by the present invention, and dopant material is Ir (ppy)3, compound 38 and Ir (ppy)3Quality Than for 88:12.Device embodiments 5：The luminescent layer material of main part of electroluminescent device is changed into the He of compound 48 prepared by the present invention Compound GH, dopant material are Ir (ppy)3, compound 48 and GH and Ir (ppy)3Three's mass ratio is 60:30:10.Device is real Apply example 6：The luminescent layer material of main part of electroluminescent device is changed into compound 61 and compound GH prepared by the present invention, dopant material For Ir (ppy)3, compound 61, GH and Ir (ppy)3Three's mass ratio is 60:30:10.Device embodiments 7：Electroluminescent device Luminescent layer material of main part to be changed into the compound 76 for preparing of the present invention and compound GH, dopant material be Ir (ppy)3, compound 76th, GH and Ir (ppy)3Three's mass ratio is 60:30:10.Device embodiments 8：The electronic blocking layer material of electroluminescent device For the compounds of this invention 3, the luminescent layer material of main part of electroluminescent device is changed into CBP, CBP and Ir (ppy)3Mass ratio be 90:10.Device embodiments 9：The electronic blocking layer material of electroluminescent device is the compounds of this invention 6, electroluminescent device Luminescent layer material of main part is changed into CBP, CBP and Ir (ppy)3Mass ratio be 88:12.Device embodiments 10：Electroluminescent device Electronic blocking layer material be the compounds of this invention 111, the luminescent layer material of main part of electroluminescent device is changed into CBP, CBP and Ir (ppy)3Mass ratio be 90:10.Device embodiments 11：The electronic blocking layer material of electroluminescent device is the compounds of this invention 118, the luminescent layer material of main part of electroluminescent device is changed into CBP, CBP and Ir (ppy)3Mass ratio be 80:20.Device is implemented Example 12：The electronic blocking layer material of electroluminescent device is the compounds of this invention 124, the luminous layer main body material of electroluminescent device Material is changed into CBP, CBP and Ir (ppy)3Mass ratio be 80:20.Device comparative example 1：The electronic barrier layer material of electroluminescent device Expect that for NPB, the luminescent layer material of main part of electroluminescent device is CBP, and the detection data of gained electroluminescent device are shown in Table 4 institutes Show.
Table 4
Note：Life-span test system is owner of the present invention and the OLED life test of Shanghai University's joint research Instrument.
The compound containing spiral shell dibenzocycloheptene fluorenes that it can be seen from the result of table 4 prepared by the present invention can be applied to OLED luminescent devices make, and compared with device comparative example, either efficiency or life-span obtain than known OLED material The life time decay of larger change, particularly device obtains larger lifting.
Work limitation rate is also more stable at low temperature for OLED prepared by further material of the present invention, and device is real Apply example 1,5,11 and device comparative example 1 and carry out efficiency test in -10~80 DEG C of sections, acquired results are as shown in table 5 and Fig. 2.
Table 5
It was found from table 5 and Fig. 2 data, device embodiments 1,5,11 are material of the present invention and the device of known materials collocation Structure, compared with device comparative example 1, not only Efficiency at Low Temperature is high, and in temperature elevation process, efficiency steadily raises.
To sum up, presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, all essences in the present invention God any modification, equivalent substitution and improvements made etc., should be included in the scope of the protection with principle.

Claims (10)

  1. A kind of 1. organic compound containing spiral shell dibenzocycloheptene fluorenes, it is characterised in that the structure of the compound such as formula (1) shown in：
    Wherein, R1、R2、R3、R4Separately it is expressed as structure shown in formula (2) or formula (3)；R1、R2、R3With R4It is identical or Person is different；R1、R2、R3It is also denoted as hydrogen atom；
    In formula (2), formula (3), R5、R6Separately it is expressed as substituted or unsubstituted C6-60Aryl, contain one or more Individual heteroatomic substituted or unsubstituted 5-60 unit's heteroaryls；The hetero atom is nitrogen, oxygen or sulphur；R5With R6It is identical or different；
    In formula (3), Ar1It is expressed as substituted or unsubstituted C6-60Arlydene, containing one or more heteroatomic substitutions or not 5~60 yuan of heteroarylidenes of substitution；The hetero atom is nitrogen, oxygen or sulphur.
  2. 2. the organic compound according to claim 1 containing spiral shell dibenzocycloheptene fluorenes, it is characterised in that Ar1It is expressed as One kind in phenylene, biphenylene or naphthylene；R5、R6Separately it is expressed as C1-10Straight or branched alkyl, C6-30Virtue Base is substituted or unsubstituted：Phenyl, pyridine radicals, dibiphenylyl, terphenyl, naphthyl, anthryl, phenanthryl, triazine radical, pyrimidine radicals, Quinolyl, dibenzofuran group, 9,9- dimethyl fluorenyl, 9,9- diphenyl fluorenyl, the fluorenyl of 9,9- spiral shells two, 9,9- diethyl fluorenes One in base, carbazyl, benzo carbazole base, dibenzothiophenes base, acridinyl, indolocarbazole base, phenoxazine group, Sai oxazinyls Kind.
  3. 3. the organic compound according to claim 1 containing spiral shell dibenzocycloheptene fluorenes, it is characterised in that the formula (2) it is embodied as：
    In any one.
  4. 4. the organic compound according to claim 1 containing spiral shell dibenzocycloheptene fluorenes, it is characterised in that the chemical combination Thing concrete structure is：
    In any one.
  5. 5. a kind of preparation method of the organic compound containing spiral shell dibenzocycloheptene fluorenes described in any one of Claims 1 to 4, Characterized in that,
    Work as R2、R3、R4When being expressed as hydrogen atom, reaction equation is as shown in 1-1,1-2：
    The specific preparation method of above-mentioned reaction is：Weigh raw material I and H-R1, dissolved with toluene；Add Pd2(dba)3、P(t- Bu)3, sodium tert-butoxide；Under an inert atmosphere, the mixed solution of above-mentioned reactant is reacted 10~24 hours at 95~110 DEG C, Cool down and filtering reacting solution, filtrate rotate, cross silicagel column, obtain above-mentioned target product I；The raw material I and H-R1Mole Than for 1:(1.2~3.0), Pd2(dba)3Mol ratio with raw material I is (0.006~0.02):1, tri-butyl phosphine is with raw material I's Mol ratio is (0.006~0.02):1, the mol ratio of sodium tert-butoxide and raw material I is (1.0~3.0):1；
    The specific preparation method of above-mentioned reaction is：Weigh raw material I, R1-B(OH)2, it is 2 with volume ratio:1 toluene and ethanol it is mixed Bonding solvent dissolves；Under an inert atmosphere, Na is added2CO3The aqueous solution, Pd (PPh3)4；By the mixed solution of above-mentioned reactant in 95~110 DEG C of reaction temperature, react 10~24 hours, cool down and filtering reacting solution, filtrate rotate, cross silicagel column, obtain mesh Mark product II；The raw material I and R1-B(OH)2Mol ratio be 1:1.0~2.0；Na2CO3Mol ratio with raw material I is (1.0 ~3.0):1；Pd(PPh3)4Mol ratio with raw material I is (0.006~0.02):1；
    Work as R1、R2、R3When being expressed as hydrogen atom, reaction equation is as shown in 1-3,1-4：
    The specific preparation method of above-mentioned reaction is：Weigh raw material II and H-R4, dissolved with toluene；Add Pd2(dba)3、P(t- Bu)3, sodium tert-butoxide；Under an inert atmosphere, the mixed solution of above-mentioned reactant is reacted 10~24 hours at 95~110 DEG C, Cool down and filtering reacting solution, filtrate rotate, cross silicagel column, obtain above-mentioned target product III；The raw material II and H-R4Rub You are than being 1:(1.2~3.0), Pd2(dba)3Mol ratio with raw material II is (0.006~0.02):1, tri-butyl phosphine and raw material II mol ratio is (0.006~0.02):1, the mol ratio of sodium tert-butoxide and raw material II is (1.0~3.0):1；
    The specific preparation method of above-mentioned reaction is：Weigh raw material II, R4-B(OH)2, it is 2 with volume ratio:1 toluene and ethanol Mixed solvent dissolves；Under an inert atmosphere, Na is added2CO3The aqueous solution, Pd (PPh3)4；By the mixed solution of above-mentioned reactant In 95~110 DEG C of reaction temperature, react 10~24 hours, cool down and filtering reacting solution, filtrate rotate, cross silicagel column, obtain Target product IV；The raw material II and R4-B(OH)2Mol ratio be 1:1.0~2.0；Na2CO3Mol ratio with raw material II is (1.0~3.0):1；Pd(PPh3)4Mol ratio with raw material I is (0.006~0.02):1.
  6. 6. preparation method according to claim 5, it is characterised in that：The H-R1、H-R2With B (OH)2-R1、B(OH)2-R4 Synthesis step respectively as shown in reaction equation 2-1 and reaction equation 2-2：
    Intermediate B I in above-mentioned reaction represents H-R1、H-R2；
    The specific preparation method of above-mentioned reaction is：Weigh raw material O and raw material P is dissolved with toluene, add Pd2(dba)3、P(Ph)3 And sodium tert-butoxide；Under an inert atmosphere, the mixed solution of above-mentioned reactant is reacted 10~24 at 90~110 DEG C of reaction temperature Hour, cooling, filtering reacting solution, filtrate revolving, silicagel column is crossed, obtains intermediate B I；The raw material O and raw material P mole Than for 1:(1.0~1.5)；Pd2(dba)3Mol ratio with raw material O is (0.006~0.02):1, sodium tert-butoxide rubs with raw material O's Your ratio is (2.0~3.0):1；P(Ph)3Mol ratio with raw material O is (2.0~3.0):1；
    Intermediate B II in above-mentioned reaction represents B (OH)2-R1、B(OH)2-R4；
    The specific preparation method of above-mentioned reaction is：Intermediate B I and raw material N are weighed, is dissolved with toluene；Add Pd2(dba)3、P (Ph)3, sodium tert-butoxide；Under an inert atmosphere, it is small that the mixed solution of above-mentioned reactant is reacted to 10~24 at 95~110 DEG C When, cool down and filtering reacting solution, filtrate rotate, cross silicagel column, obtain intermediate C；The intermediate B I and raw material N mole Than for 1:(1.0~1.5), Pd2(dba)3Mol ratio with intermediate B I is (0.006~0.02):1, P (Ph)3With intermediate B I Mol ratio be (0.006~0.02):1, the mol ratio of sodium tert-butoxide and intermediate B I is (1.0~3.0):1；
    Under the atmosphere of nitrogen, intermediate C, double (pinacol conjunctions) two boron, Pd (dppf) Cl are weighed2, potassium acetate be dissolved in toluene, Reacted 12~24 hours at 100~120 DEG C, sample point plate, reaction is complete, natural cooling, filtering, filtrate revolving, is slightly produced Product, cross neutral silica gel post and obtain intermediate B II；The mol ratio of intermediate C and double (pinacol conjunction) two boron is 2:(1~1.5), in Mesosome C and Pd (dppf) Cl2Mol ratio be 1:The mol ratio of (0.01~0.05), intermediate C and potassium acetate is 1:(2~ 2.5)。
  7. 7. the organic compound containing spiral shell dibenzocycloheptene fluorenes as described in any one of Claims 1 to 4 is organic for preparing Electroluminescent device.
  8. 8. a kind of organic electroluminescence device, it is characterised in that the organic electroluminescence device includes at least one layer of functional layer Contain the organic compound containing spiral shell dibenzocycloheptene fluorenes described in any one of Claims 1 to 4.
  9. 9. a kind of organic electroluminescence device, including hole transmission layer or electronic barrier layer, it is characterised in that the hole transport Layer or electronic blocking layer material are the organic compound containing spiral shell dibenzocycloheptene fluorenes described in any one of Claims 1 to 4.
  10. 10. a kind of organic electroluminescence device, including luminescent layer, it is characterised in that the luminescent layer contains Claims 1 to 4 The organic compound containing spiral shell dibenzocycloheptene fluorenes described in any one.
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CN110218156A (en) * 2018-03-02 2019-09-10 北京鼎材科技有限公司 A kind of preparation and its device application of hole mobile material
CN110343049B (en) * 2018-04-04 2022-09-09 江苏三月科技股份有限公司 Organic compound with spiro dibenzosuberene fluorene as skeleton and application thereof
CN110343048A (en) * 2018-04-04 2019-10-18 江苏三月光电科技有限公司 A kind of organic compound and its application fluorene structured containing spiral shell dibenzocycloheptene
CN110343049A (en) * 2018-04-04 2019-10-18 江苏三月光电科技有限公司 It is a kind of using spiral shell dibenzocycloheptene fluorenes as the organic compound of skeleton and its application
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CN110526825A (en) * 2018-05-25 2019-12-03 江苏三月光电科技有限公司 It is a kind of using it is different bend and tertiary aromatic amine structure as the compound of core and its application
CN110655498A (en) * 2018-06-29 2020-01-07 江苏三月光电科技有限公司 Compound with dibenzosuberene as central skeleton and application thereof
CN110655438A (en) * 2018-06-29 2020-01-07 江苏三月光电科技有限公司 Cycloheptene-based compound and application thereof in organic electroluminescent device
CN109265399B (en) * 2018-08-09 2022-05-13 石家庄诚志永华显示材料有限公司 Compound and organic electroluminescent device
CN109265399A (en) * 2018-08-09 2019-01-25 石家庄诚志永华显示材料有限公司 Compound and organic electroluminescent device
CN110003024B (en) * 2019-04-17 2022-03-01 中节能万润股份有限公司 Organic hole transport material containing spirodi (dibenzosuberene) and preparation method and application thereof
CN110003024A (en) * 2019-04-17 2019-07-12 中节能万润股份有限公司 One kind containing the organic hole transport material and the preparation method and application thereof of spiral shell two (dibenzocycloheptene)
CN112079784A (en) * 2020-09-18 2020-12-15 吉林奥来德光电材料股份有限公司 Organic electroluminescent compound containing adamantane and heterocyclic structure and preparation method and application thereof
CN112079784B (en) * 2020-09-18 2022-05-20 吉林奥来德光电材料股份有限公司 Organic electroluminescent compound containing adamantane and heterocyclic structure and preparation method and application thereof

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