CN106467485A - A kind of compound with 9 Fluorenones as core and its application - Google Patents

A kind of compound with 9 Fluorenones as core and its application Download PDF

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CN106467485A
CN106467485A CN201610723665.4A CN201610723665A CN106467485A CN 106467485 A CN106467485 A CN 106467485A CN 201610723665 A CN201610723665 A CN 201610723665A CN 106467485 A CN106467485 A CN 106467485A
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compound
fluorenone
core
formula
expressed
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CN106467485B (en
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唐丹丹
李崇
张兆超
叶中华
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 compound with 9 Fluorenones as core and its application, this compound, with 9 Fluorenones as core, has the characteristics that intermolecular be difficult crystallization, be difficult to assemble, have good filming.The compounds of this invention is applied on Organic Light Emitting Diode as emitting layer material, there are good photoelectric properties, can preferably adapt to and meet the application requirement of panel manufacturing enterprise.

Description

A kind of compound with 9-Fluorenone as core and its application
Technical field
The present invention relates to technical field of semiconductors, especially relate to a kind of compound with 9-Fluorenone as core, Yi Jiqi As application on Organic Light Emitting Diode for the emitting layer material.
Background technology
Organic electroluminescent (OLED:Organic Light Emission Diodes) device technology both can be used to make Make new display product it is also possible to 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 device just as the structure of sandwich, including electrode material film layer, and be clipped in Different electrodes film layer it Between organic functional material, various difference in functionality materials are overlapped mutually according to purposes and collectively constitute OLED luminescent device together. As current device, when the two end electrodes applied 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 compound in luminescent layer further, that is, produce OLED electroluminescent.
Organic Light Emitting Diode (OLEDs) large-area flat-plate show and illumination in terms of application cause industrial quarters and The extensive concern of art circle.However, traditional organic fluorescence materials can only be lighted using 25% singlet exciton being electrically excited formation, device The internal quantum efficiency of part is relatively low (being up to 25%).External quantum efficiency is generally less than 5%, also very big with the efficiency of phosphorescent devices Gap.Although phosphor material enhances intersystem crossing due to the strong SO coupling in heavy atom center, can with effectively utilizes electricity Excite singlet exciton and the Triplet exciton of formation, make the internal quantum efficiency of device reach 100%.But phosphor material exists Expensive, stability of material is poor, limits its application in OLEDs the problems such as device efficiency tumbles serious.Hot activation is prolonged Fluorescence (TADF) material is the third generation luminous organic material of development after organic fluorescence materials and organic phosphorescent material late.Should Class material typically has poor (the △ E of little singletstate-tripletST), triplet excitons can be changed by anti-intersystem crossing Singlet exciton is become to light.This can make full use of the singlet exciton being electrically excited lower formation and triplet excitons, device interior Quantum efficiency can reach 100%.Meanwhile, material structure is controlled, stable in properties, low price without precious metal, in OLEDs The having a extensive future of field.
Although TADF material can realize 100% exciton utilization rate in theory, there are in fact following problem:(1) T1 the and S1 state of design molecule has strong CT feature, and very little S1-T1 state energy gap is although can be realized by TADF process High T1→S1State exciton conversion ratio, but also result in low S1 state radiation transistion speed, consequently it is difficult to have (or realizing) concurrently simultaneously High exciton utilization rate and high fluorescent radiation efficiency；(2) even if having adopted 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 the actual demand that current OLED shows Lighting Industry, the development of current OLED material is also far from enough, falls After the requirement of panel manufacturing enterprise, the organic functional material as material enterprise development higher performance is particularly important.
Content of the invention
For prior art exist the problems referred to above, the applicant provide a kind of with the compound with 9-Fluorenone as core And its application on organic electroluminescence device.The compounds of this invention be based on TADF mechanism with 9-Fluorenone as core, as send out Photosphere materials application has good photoelectric properties, disclosure satisfy that panel in Organic Light Emitting Diode, the device that the present invention makes The requirement of manufacturing enterprise.
Technical scheme is as follows：
The applicant provides a kind of compound with 9-Fluorenone as core, structure such as formula (1) institute of described compound Show：
In formula (1), R is expressed as-Ar-R1Or-R2；Wherein, Ar is expressed as phenyl, C1-10Straight or branched alkyl replaces Phenyl, xenyl, terphenyl, naphthyl, anthryl, phenanthryl, benzo phenanthryl, furyl, thienyl or pyridine radicals；N=1 or 2；
R1、R2Independently be expressed as structure shown in formula (2)：
In formula (2), R3、R4Independently be expressed as hydrogen atom, formula (3) or structure shown in formula (4), and R3、R4 It is asynchronously hydrogen atom；
Wherein, a is selected fromX1、X2、X3、X4Independently be expressed as oxygen atom, Sulphur atom, selenium atom, C1-10The alkylidene that the alkylidene of straight or branched alkyl replacement, aryl replace, alkyl or aryl replace One of tertiary amine groups；Formula (3), formula (4) pass through CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL‘1-CL’2Key, CL‘2- CL’3Key or CL‘3-CL’4Key is connected with formula (2).
Preferably, described R1、R2It is expressed as：
In any one.
Preferably, the concrete structure formula of described compound is：
In any one.
The applicant additionally provides a kind of method of described compound, and the reaction equation occurring in preparation process is：
When R is expressed as-R2When,
Specifically preparation method is：
Weigh the bromo compound with 9-Fluorenone as core and R2- H, is dissolved with toluene；Add Pd (dppf) Cl2, tertiary fourth Sodium alkoxide；Under an inert atmosphere, by the mixed solution of above-mentioned reactant in reaction temperature 95-100 DEG C, react 10-24 hour, cold But, filtering reacting solution, filtrate revolving, cross silicagel column, obtain target product；
The described bromo compound with 9-Fluorenone as core and R2The mol ratio of-H is 1:1.0-3.0；Pd(dppf)Cl2With The mol ratio of the bromo compound with 9-Fluorenone as core is as 0.006-0.02:1, sodium tert-butoxide and bromine with 9-Fluorenone as core Mol ratio for compound is 2.0-5.0:1；
When R is expressed as-Ar-R1When,
Specifically preparation method is：
Weigh the boronic acid compounds with 9-Fluorenone as core and R1- Ar-Br, is 2 with volume ratio:1 toluene ethanol mixing Solvent dissolves；Add Na2CO3Aqueous solution, Pd (PPh3)4；Under an inert atmosphere, by the mixed solution of above-mentioned reactant in anti- Answer temperature 95-100 DEG C, react 10-24 hour, cooling, filtering reacting solution, filtrate revolving, cross silicagel column, obtain target and produce Thing；
The described boronic acid compounds with 9-Fluorenone as core and R1The mol ratio of-Ar-Br is 1:1.0-3.0；Pd(PPh3)4 With the mol ratio of the boronic acid compounds with 9-Fluorenone as core as 0.006-0.02:1, Na2CO3With the boron with 9-Fluorenone as core The mol ratio of acid compound is 2.0-5.0:1.
The applicant additionally provides a kind of luminescent device comprising described compound, and described compound is as luminescent layer material Material, for making OLED.
Beneficial the having technical effect that of the present invention：
The compounds of this invention, with 9-Fluorenone as parent nucleus, destroys the crystallinity of molecule, it is to avoid intermolecular aggregation, The film property having had；It mostly is rigid radical in molecule, improve the heat stability of material；There is good photoelectric characteristic, properly HOMO and lumo energy, the compounds of this invention HOMO and lumo energy electron cloud efficiently separate, and can achieve less S1-T1 state Energy gap, can effectively improve exciton utilization rate and high fluorescent radiation efficiency, reduce the efficiency roll-off under high current density, reduce device Voltage, improves device efficiency roll-off problem at higher current densities.
Compound of the present invention can be applicable to OLED luminescent device and makes, and can obtain good device performance, When described compound uses as the emitting layer material of OLED luminescent device, the current efficiency of device, power efficiency and outer quantum Efficiency is all greatly improved.Compound of the present invention has good application effect in OLED luminescent device, has good Good industrialization prospect.
Brief description
The device architecture schematic diagram that Fig. 1 applies for the compounds of this invention；
Wherein, 1 is transparent substrate layer, and 2 is ito anode layer, and 3 is hole injection layer, and 4 is hole transmission layer, and 5 is luminous Layer, 6 is electron transfer layer, and 7 is electron injecting layer, and 8 is negative electrode 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 6：
Synthetic route：
The there-necked flask of 250mL, under the atmosphere being passed through nitrogen, adds 0.01mol2, the bromo- 9-Fluorenone of 7- bis-, 0.025mol Intermediate A 1,0.03mol sodium tert-butoxide, 1 × 10-4molPd(dppf)Cl2, 180mL toluene, it is heated to reflux 10 hours, sample point Plate, raw material reaction is complete；Naturally cool to room temperature (20～25 DEG C), filter, collect filtrate carry out vacuum rotary steam (- 0.09MPa, 85 DEG C), carry out column chromatography, obtain target product, HPLC purity 99.2%, yield 68.5%.
Elementary analysiss structure (molecular formula C55H38N2O)：Theoretical value C, 88.92；H,5.16；N,3.77；O,2.15；Test Value：C,88.93；H,5.15；N,3.76；O,2.16.
HPLC-MS：Materials theory molecular weight is 742.90, surveys molecular weight 743.13.
Embodiment 2：The synthesis of compound 12：
Synthetic route：
The there-necked flask of 250mL, under the atmosphere being passed through nitrogen, adds 0.01mol3, the bromo- 9-Fluorenone of 6- bis-, 0.025mol Intermediate A 1,0.03mol sodium tert-butoxide, 1 × 10-4molPd(dppf)Cl2, 180mL toluene, it is heated to reflux 10 hours, sample point Plate, raw material reaction is complete；Naturally cool to room temperature (20～25 DEG C), filter, collect filtrate carry out vacuum rotary steam (- 0.09MPa, 85 DEG C), carry out column chromatography, obtain target product, HPLC purity 98.8%, yield 67.7%.
Elementary analysiss structure (molecular formula C55H38N2O)：Theoretical value C, 88.92；H,5.16；N,3.77；O,2.15；Test Value：C,88.95；H,5.13；N,3.78；O,2.14.
HPLC-MS：Materials theory molecular weight is 742.90, surveys molecular weight 743.18.
Embodiment 3：The synthesis of compound 22：
Synthetic route：
The there-necked flask of 250mL, under the atmosphere being passed through nitrogen, adds 0.01mol2, the bromo- 9-Fluorenone of 7- bis-, 0.025mol Intermediate B 1,0.03mol sodium tert-butoxide, 1 × 10-4molPd(dppf)Cl2, 180mL toluene, it is heated to reflux 10 hours, sample point Plate, raw material reaction is complete；Naturally cool to room temperature (20～25 DEG C), filter, collect filtrate carry out vacuum rotary steam (- 0.09MPa, 85 DEG C), carry out column chromatography, obtain target product, HPLC purity 99.4%, yield 66.9%.
Elementary analysiss structure (molecular formula C49H26N2O3)：Theoretical value C, 85.20；H,3.79；N,4.06；O,6.95；Test Value：C,85.23；H,3.78；N,4.05；O,6.94.
HPLC-MS：Materials theory molecular weight is 690.74, surveys molecular weight 690.96.
Embodiment 4：The synthesis of compound 36：
Synthetic route：
The there-necked flask of 250mL, under the atmosphere being passed through nitrogen, adds the bromo- 9-Fluorenone of 0.01mol3-, in the middle of 0.015mol Body C1,0.03mol sodium tert-butoxide, 1 × 10-4molPd(dppf)Cl2, 180mL toluene, it is heated to reflux 10 hours, sample point plate, Raw material reaction is complete；Naturally cool to room temperature (20～25 DEG C), filter, collect filtrate carry out vacuum rotary steam (- 0.09MPa, 85 DEG C), carry out column chromatography, obtain target product, HPLC purity 99.3%, yield 74.2%.
Elementary analysiss structure (molecular formula C40H25NO2)：Theoretical value C, 87.09；H,4.57；N,2.54；O,5.80；Test Value：C,87.08；H,4.56；N,2.55；O,5.81.
HPLC-MS：Materials theory molecular weight is 551.63, surveys molecular weight 551.86.
Embodiment 5：The synthesis of compound 43：
Synthetic route：
The there-necked flask of 250mL, under the atmosphere being passed through nitrogen, adds the bromo- 9-Fluorenone of 0.01mol2-, in the middle of 0.015mol Body D1,0.03mol sodium tert-butoxide, 1 × 10-4molPd(dppf)Cl2, 180mL toluene, it is heated to reflux 10 hours, sample point plate, Raw material reaction is complete；Naturally cool to room temperature (20～25 DEG C), filter, collect filtrate carry out vacuum rotary steam (- 0.09MPa, 85 DEG C), carry out column chromatography, obtain target product, HPLC purity 98.8%, yield 71.9%.
Elementary analysiss structure (molecular formula C49H29N3O)：Theoretical value C, 87.09；H,4.33；N,6.22；O,2.37；Test Value：C,87.07；H,4.32；N,6.23；O,2.38.
HPLC-MS：Materials theory molecular weight is 675.77, surveys molecular weight 675.98.
Embodiment 6：The synthesis of compound 54：
Synthetic route：
The there-necked flask of 250mL, under the atmosphere being passed through nitrogen, adds the bromo- 9-Fluorenone of 0.01mol2-, in the middle of 0.015mol Body E1,0.03mol sodium tert-butoxide, 1 × 10-4molPd(dppf)Cl2, 180mL toluene, it is heated to reflux 8 hours, sample point plate, former Material reaction is completely；Naturally cool to room temperature (20～25 DEG C), filter, collect filtrate and carry out vacuum rotary steam (- 0.09MPa, 85 DEG C), Carry out column chromatography, obtain target product, HPLC purity 99.1%, yield 72.6%.
Elementary analysiss structure (molecular formula C43H31NO)：Theoretical value C, 89.40；H,5.41；N,2.42；O,2.77；Test Value：C,89.41；H,5.40；N,2.43；O,2.76.
HPLC-MS：Materials theory molecular weight is 577.71, surveys molecular weight 577.94.
Embodiment 7：The synthesis of compound 59：
Synthetic route：
With embodiment 5, difference is to replace intermediate D1 using intermediate F1 the preparation method of compound 59.
Elementary analysiss structure (molecular formula C40H25NO2)：Theoretical value C, 87.09；H,4.57；N,2.54；O,5.80；Test Value：C,87.08；H,4.58；N,2.53；O,5.81.
HPLC-MS：Materials theory molecular weight is 551.63, surveys molecular weight 551.91.
Embodiment 8：The synthesis of compound 70：
Synthetic route：
With embodiment 4, difference is to replace intermediate C1 using intermediate G1 the preparation method of compound 70.
Elementary analysiss structure (molecular formula C43H31NO3)：Theoretical value C, 84.71；H,5.12；N,2.30；O,7.87；Test Value：C,84.70；H,5.13；N,2.31；O,7.86.
HPLC-MS：Materials theory molecular weight is 609.71, surveys molecular weight 609.95.
Embodiment 9：The synthesis of compound 82：
Synthetic route：
With embodiment 5, difference is to replace intermediate D1 using intermediate H1 the preparation method of compound 82.
Elementary analysiss structure (molecular formula C41H23NO3)：Theoretical value C, 85.25；H,4.01；N,2.42；O,8.31；Test Value：C,85.24；H,4.03；N,2.40；O,8.33.
HPLC-MS：Materials theory molecular weight is 577.63, surveys molecular weight 577.88.
Embodiment 10：The synthesis of compound 85：
Synthetic route：
The there-necked flask of 250mL, under the atmosphere being passed through nitrogen, addition 0.01mol 9-Fluorenone -2,7- hypoboric acid, 0.025mol intermediate compound I 1, dissolves (180ml toluene, 90ml ethanol) with mixed solvent, is subsequently adding 0.03mol Na2CO3Water-soluble Liquid (2M), logical nitrogen gas stirring 1 hour, it is subsequently adding 0.0002mol Pd (PPh3)4, it is heated to reflux 20 hours, sample point plate, instead Should be completely.Natural cooling, filters, filtrate revolving, crosses silicagel column, obtains target product, HPLC purity 98.6%, yield 64.2%.
Elementary analysiss structure (molecular formula C57H34N2O)：Theoretical value C, 89.74；H,4.49；N,3.67；O,2.10；Test Value：C,89.75；H,4.48；N,3.65；O,2.12.
HPLC-MS：Materials theory molecular weight is 762.89, surveys molecular weight 763.12.
Embodiment 11：The synthesis of compound 87：
Synthetic route：
With embodiment 10, difference is to replace intermediate compound I 1 using intermediate J1 the preparation method of compound 87.
Elementary analysiss structure (molecular formula C61H34N2O3)：Theoretical value C, 86.92；H,4.07；N,3.32；O,5.69；Test Value：C,86.93；H,4.06；N,3.33；O,5.68.
HPLC-MS：Materials theory molecular weight is 842.93, surveys molecular weight 843.17.
Embodiment 12：The synthesis of compound 98：
Synthetic route：
The there-necked flask of 250mL, under the atmosphere being passed through nitrogen, addition 0.01mol 9-Fluorenone -3,6- hypoboric acid, 0.025mol intermediate K1, dissolves (180ml toluene, 90ml ethanol) with mixed solvent, is subsequently adding 0.03mol Na2CO3Water-soluble Liquid (2M), logical nitrogen gas stirring 1 hour, it is subsequently adding 0.0002mol Pd (PPh3)4, it is heated to reflux 20 hours, sample point plate, instead Should be completely.Natural cooling, filters, filtrate revolving, crosses silicagel column, obtains target product, HPLC purity 98.8%, yield 63.5%.
Elementary analysiss structure (molecular formula C67H46N2O)：Theoretical value C, 89.90；H,5.18；N,3.13；O,1.79；Test Value：C,89.93；H,5.17；N,3.12；O,1.78.
HPLC-MS：Materials theory molecular weight is 895.09, surveys molecular weight 895.32.
Embodiment 13：The synthesis of compound 112：
Synthetic route：
The there-necked flask of 250mL, under the atmosphere being passed through nitrogen, adds 0.01mol9- Fluorenone -2- boric acid, in 0.015mol Mesosome L1, dissolves (180ml toluene, 90ml ethanol) with mixed solvent, is subsequently adding 0.03mol Na2CO3Aqueous solution (2M), leads to Nitrogen gas stirring 1 hour, is subsequently adding 0.0001mol Pd (PPh3)4, it is heated to reflux 15 hours, sample point plate, reaction is completely.From So cool down, filter, filtrate revolving, cross silicagel column, obtain target product, HPLC purity 98.5%, yield 72.4%.
Elementary analysiss structure (molecular formula C46H29NO2)：Theoretical value C, 88.01；H,4.66；N,2.23；O,5.10；Test Value：C,88.02；H,4.65；N,2.22；O,5.11.
HPLC-MS：Materials theory molecular weight is 627.73, surveys molecular weight 627.97.
Embodiment 14：The synthesis of compound 157：
Synthetic route：
With embodiment 13, difference is to replace intermediate L1 using intermediate M1 the preparation method of compound 157.
Elementary analysiss structure (molecular formula C55H47NO)：Theoretical value C, 89.51；H,6.42；N,1.90；O,2.17；Test Value：C,89.52；H,6.42；N,1.91；O,2.15.
HPLC-MS：Materials theory molecular weight is 737.97, surveys molecular weight 738.13.
Embodiment 15：The synthesis of compound 164：
Synthetic route：
With embodiment 13, difference is to replace intermediate L1 using intermediate N1 the preparation method of compound 164.
Elementary analysiss structure (molecular formula C49H35NO2)：Theoretical value C, 87.86；H,5.27；N,2.09；O,4.78；Test Value：C,87.88；H,5.28；N,2.07；O,4.77.
HPLC-MS：Materials theory molecular weight is 669.81, surveys molecular weight 670.03.
Embodiment 16：The synthesis of compound 170：
Synthetic route：
The there-necked flask of 250mL, under the atmosphere being passed through nitrogen, adds 0.01mol9- Fluorenone -3- boric acid, in 0.015mol Mesosome O1, dissolves (180ml toluene, 90ml ethanol) with mixed solvent, is subsequently adding 0.03mol Na2CO3Aqueous solution (2M), leads to Nitrogen gas stirring 1 hour, is subsequently adding 0.0001mol Pd (PPh3)4, it is heated to reflux 15 hours, sample point plate, reaction is completely.From So cool down, filter, filtrate revolving, cross silicagel column, obtain target product, HPLC purity 98.6%, yield 72.7%.
Elementary analysiss structure (molecular formula C58H39N3O2)：Theoretical value C, 86.01；H,4.85；N,5.19；O,3.95；Test Value：C,86.03；H,4.85；N,5.18；O,3.94.
HPLC-MS：Materials theory molecular weight is 809.95, surveys molecular weight 810.18.
The compounds of this invention can use as emitting layer material, to the compounds of this invention 43, compound 77, compound 167th, current material CBP carries out the test of hot property, luminescent spectrum and cyclic voltammetric stability, and test result is as shown in table 1.
Table 1
Compound Td(℃) λPL(nm) Cyclic voltammetric stability
Compound 43 417 621 Excellent
Compound 77 403 614 Excellent
Compound 167 423 619 Excellent
Material C BP 353 369 Difference
Note：Thermal weight loss temperature Td is in nitrogen atmosphere weightless 1% temperature, in the TGA-50H heat of Japanese Shimadzu Corporation It is measured on weight analysis instrument, nitrogen flow is 20mL/min；λPLIt is sample solution fluorescence emission wavelengths, open up Pu Kang using Japan SR-3 spectroradiometer measures；Cyclic voltammetric stability is to be entered by the redox characteristic that cyclic voltammetry observes material Row identification；Test condition：It is 2 that test sample is dissolved in volume ratio:1 dichloromethane and acetonitrile mixed solvent, concentration 1mg/mL, electricity Solution 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.
From upper table data, the compounds of this invention has a preferable oxidation-reduction stability, higher heat stability, closes Suitable luminescent spectrum is so that application the compounds of this invention gets a promotion as the OLED efficiency of emitting layer material and life-span.
17-22 and comparative example 1 describe the OLED material conduct in the devices that the present invention synthesizes in detail by the following examples The application effect of luminescent layer material of main part.18-22 of the present invention, the processing technology of comparative example 1 device compared with embodiment 17 Identical, and employed identical baseplate material and electrode material, the thickness of electrode material is also consistent, and institute is different Be that material of main part to the luminescent layer 5 in device converts.The structure composition of each embodiment obtained device is as shown in table 2. The test result of obtained device is shown in Table 3.
Embodiment 17
Ito anode layer 2/ hole injection layer 3 (molybdenum trioxide MoO3, thickness 10nm) and/hole transmission layer 4 (TAPC, thickness 140nm)/luminescent layer 5 (compound 6 and Ir (pq)2Acac is according to 100：5 weight is than blending, thickness 30nm)/electron transfer layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/Al.The molecular structure of associated materials is as follows：
Concrete preparation process is as follows：
Transparent substrate layer 1 is transparent base, such as transparent PI film, glass etc..
Ito anode layer 2 (thickness is 150nm) is washed, carries out neutralizing treatment, pure water, drying successively, then enter Row ultraviolet-ozone washs to remove the organic residue on transparent ITO surface.
On the ito anode layer 2 having carried out after above-mentioned washing, using vacuum deposition apparatus, being deposited with thickness is 10nm's Molybdenum trioxide MoO3Use as hole injection layer 3.And then the TAPC of evaporation 140nm thickness is as hole transmission layer 4.
After above-mentioned hole mobile material evaporation terminates, make the luminescent layer 5 of OLED luminescent device, its structure includes OLED and sends out The used material compound 6 of photosphere 5 is as material of main part, Ir (pq)2Acac as dopant material, dopant material doping ratio is 5% weight ratio, luminescent layer thickness is 30nm.
After above-mentioned luminescent layer 5, continuation vacuum evaporation electron transport layer materials are TPBI.The vacuum evaporation coating of this material Thick is 40nm, and this layer is electron transfer layer 6.
On electron transfer layer 6, by vacuum deposition apparatus, make lithium fluoride (LiF) layer that thickness is 1nm, this layer is Electron injecting layer 7.
On electron injecting layer 7, by vacuum deposition apparatus, make aluminum (Al) layer that thickness is 80nm, this layer is negative electrode Reflection electrode layer 8 uses.
After OLED luminescent device accomplished as described above, with known drive circuit, anode and negative electrode are coupled together, survey The current efficiency of metering device and the life-span of device.The test result of made OLED luminescent device is shown in Table 3.
Table 2
Table 3
Device code name Current efficiency The LT95 life-span
Embodiment 17 1.1 3.1
Embodiment 18 1.3 3.6
Embodiment 19 1.4 2.5
Embodiment 20 1.2 2.9
Embodiment 21 1.3 4.2
Embodiment 22 1.4 3.3
Comparative example 1 1.0 1.0
Explanation:Using comparative example 1 as reference, comparative example 1 device property indices are set to 1.0 to device detection performance.Than It is 14.8cd/A (@10mA/cm compared with the current efficiency of example 12)；CIE chromaticity coordinates is (0.66,0.33)；The LT95 longevity under 3000 brightness Life decays to 11Hr.
Life-span test system is the OLED life-span tester of owner of the present invention and Shanghai University's joint research.
The result of table 3 can be seen that compound of the present invention can be applied and OLED luminous organ as luminescent layer material of main part Part makes, and compared with comparative example 1, either efficiency or life-span all obtain larger change, particularly the driving longevity of device Life obtains larger lifting.
23-29 and comparative example 2 illustrate the compound of present invention synthesis in the devices as luminescent layer by the following examples The application effect of dopant material.23-29 of the present invention, comparative example 2 described device compared with embodiment 17 processing technology complete Exactly the same, and employed identical baseplate material and electrode material, the thickness of electrode material is also consistent, different Be hole transport layer material in device and luminescent layer 5 dopant material different, doping content is 3%.The structure group of each device Become as shown in table 4.The test result of obtained device is shown in Table 5.
Table 4
Table 5
Note：Using comparative example 2 as reference, comparative example 2 device property indices are set to 1.0 to device detection performance.Relatively The current efficiency of example 2 is 2.3cd/A；CIE chromaticity coordinates is (0.64,0.37)；Driving voltage is 5.2v (@10mA/cm2).
The result of table 5 can be seen that compound of the present invention can be applied and OLED luminous organ as luminescent layer dopant material Part makes, and compared with comparative example 2, either efficiency still starts voltage all ratio known OLED material larger changes of acquisition, Efficiency roll-off particularly under device high current density obtains to be improved.
From the point of view of data above application, of the present invention have TADF elastomeric material and have in OLED luminescent device well Application effect, there is good industrialization prospect.
Although the present invention has been disclosed by embodiment and preferred implementation it should be appreciated that the invention is not restricted to institute's public affairs 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 The scope of attached claim should arrangement to cover all such modifications and be similar to consistent with explanation the widest.

Claims (5)

1. a kind of compound with 9-Fluorenone as core is it is characterised in that the structure such as formula (1) of described compound is shown：
In formula (1), R is expressed as-Ar-R1Or-R2；Wherein, Ar is expressed as phenyl, C1-10The benzene that straight or branched alkyl replaces Base, xenyl, terphenyl, naphthyl, anthryl, phenanthryl, benzo phenanthryl, furyl, thienyl or pyridine radicals；N=1 or 2；
R1、R2Independently be expressed as structure shown in formula (2)：
In formula (2), R3、R4Independently be expressed as hydrogen atom, formula (3) or structure shown in formula (4), and R3、R4Different When be hydrogen atom；
Wherein, a is selected fromX1、X2、X3、X4Independently to be expressed as oxygen atom, sulfur former Son, selenium atom, C1-10The uncle that the alkylidene of straight or branched alkyl replacement, the alkylidene of aryl replacement, alkyl or aryl replace One of amido；Formula (3), formula (4) pass through CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL‘1-CL’2Key, CL‘2-CL’3Key Or CL‘3-CL’4Key is connected with formula (2).
2. organic compound according to claim 1 is it is characterised in that described R1、R2It is expressed as：
In any one.
3. compound according to claim 1 is it is characterised in that the concrete structure formula of described compound is：
In any one.
4. a kind of method preparing compound described in any one of claims 1 to 3 is it is characterised in that occur in preparation process is anti- The equation is answered to be：
When R is expressed as-R2When,
Specifically preparation method is：
Weigh the bromo compound with 9-Fluorenone as core and R2- H, is dissolved with toluene；Add Pd (dppf) Cl2, the tert-butyl alcohol Sodium；Under an inert atmosphere, by the mixed solution of above-mentioned reactant in reaction temperature 95-100 DEG C, react 10-24 hour, cool down, Filtering reacting solution, filtrate revolving, cross silicagel column, obtain target product；
The described bromo compound with 9-Fluorenone as core and R2The mol ratio of-H is 1:1.0-3.0；Pd(dppf)Cl2With with 9- Fluorenone is the mol ratio of the bromo compound of core is 0.006-0.02:1, sodium tert-butoxide with bromo with 9-Fluorenone as core The mol ratio of compound is 2.0-5.0:1；
When R is expressed as-Ar-R1When,
Specifically preparation method is：
Weigh the boronic acid compounds with 9-Fluorenone as core and R1- Ar-Br, is 2 with volume ratio:1 toluene alcohol mixed solvent is molten Solution；Add Na2CO3Aqueous solution, Pd (PPh3)4；Under an inert atmosphere, by the mixed solution of above-mentioned reactant in reaction temperature 95-100 DEG C, react 10-24 hour, cooling, filtering reacting solution, filtrate revolving, cross silicagel column, obtain target product；
The described boronic acid compounds with 9-Fluorenone as core and R1The mol ratio of-Ar-Br is 1:1.0-3.0；Pd(PPh3)4With with 9-Fluorenone is the mol ratio of the boronic acid compounds of core is 0.006-0.02:1, Na2CO3With the boration with 9-Fluorenone as core The mol ratio of compound is 2.0-5.0:1.
5. a kind of luminescent device comprising compound described in any one of claim 1-3 is it is characterised in that described compound conduct Emitting layer material, for making OLED.
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