CN106467485B - Compound with 9-fluorenone as core and application thereof - Google Patents

Compound with 9-fluorenone as core and application thereof Download PDF

Info

Publication number
CN106467485B
CN106467485B CN201610723665.4A CN201610723665A CN106467485B CN 106467485 B CN106467485 B CN 106467485B CN 201610723665 A CN201610723665 A CN 201610723665A CN 106467485 B CN106467485 B CN 106467485B
Authority
CN
China
Prior art keywords
compound
fluorenone
core
taking
butoxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610723665.4A
Other languages
Chinese (zh)
Other versions
CN106467485A (en
Inventor
唐丹丹
李崇
张兆超
叶中华
张小庆
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Sunera Technology Co Ltd
Original Assignee
Valiant Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Valiant Co Ltd filed Critical Valiant Co Ltd
Priority to CN201610723665.4A priority Critical patent/CN106467485B/en
Publication of CN106467485A publication Critical patent/CN106467485A/en
Application granted granted Critical
Publication of CN106467485B publication Critical patent/CN106467485B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/94—[b, c]- or [b, d]-condensed containing carbocyclic rings other than six-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
    • C07D487/14—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/12—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains three hetero rings
    • C07D491/14—Ortho-condensed systems
    • C07D491/147—Ortho-condensed systems the condensed system containing one ring with oxygen as ring hetero atom and two rings with nitrogen as ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/12—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains three hetero rings
    • C07D491/14—Ortho-condensed systems
    • C07D491/153—Ortho-condensed systems the condensed system containing two rings with oxygen as ring hetero atom and one ring with nitrogen as ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D498/14—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D517/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms
    • C07D517/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms in which the condensed system contains two hetero rings
    • C07D517/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D517/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms
    • C07D517/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms in which the condensed system contains three hetero rings
    • C07D517/14—Ortho-condensed systems
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole

Abstract

The invention discloses a compound taking 9-fluorenone as a core and application thereof, wherein the compound takes 9-fluorenone as the core and has the characteristics of difficult intermolecular crystallization and aggregation and good film forming property. The compound of the invention is used as a luminescent layer material to be applied to an organic light-emitting diode, has good photoelectric property, and can better adapt to and meet the application requirements of panel manufacturing enterprises.

Description

Compound with 9-fluorenone as core and application thereof
Technical Field
The invention relates to the technical field of semiconductors, in particular to a compound taking 9-fluorenone as a core and application of the compound as a light-emitting layer material in an organic light-emitting diode.
Background
The Organic Light Emission Diodes (OLED) device technology can be used for manufacturing novel display products and novel lighting products, is expected to replace the existing liquid crystal display and fluorescent lamp lighting, and has wide application prospect.
The OLED light-emitting device is of a sandwich structure and comprises electrode material film layers and organic functional materials clamped between different electrode film layers, and the various different functional materials are mutually overlapped together according to the application to form the OLED light-emitting device. When voltage is applied to two end electrodes of the OLED light-emitting device as a current device, positive and negative charges in the organic layer functional material film layer are acted through an electric field, and the positive and negative charges are further compounded in the light-emitting layer, namely OLED electroluminescence is generated.
However, conventional organic fluorescent materials can only emit light using 25% singlet excitons formed by electrical excitation, the internal quantum efficiency of the device is low (up to 25%), the external quantum efficiency is generally lower than 5%, and there is a great difference from the efficiency of phosphorescent devices, although the phosphorescent materials can effectively emit light using singlet excitons and triplet excitons formed by electrical excitation due to strong spin-orbit coupling of heavy atom centers, the application of the phosphorescent materials in OLEDs is limited by problems such as high price, poor material stability, and serious roll-off of device efficiencyST) The triplet excitons may be converted to singlet excitons by intersystem crossing to emit light. This can make full use of singlet excitons and triplet excitons formed under electrical excitation, and the internal quantum efficiency of the device can reach 100%. Meanwhile, the material has controllable structure, stable property and low price, does not need precious metal, and is applied to the field of OLEDsThe scene is wide.
Although the TADF material can theoretically achieve 100% exciton utilization, in practice there is the problem that (1) the T1 and S1 states of the design molecule have strong CT characteristics, very small energy gaps of S1-T1 states, although high T can be achieved by the TADF process1→S1State exciton conversion but at the same time results in a low S1 state radiative transition rate, and therefore it is difficult to achieve both (or both) high exciton utilization and high fluorescence radiation efficiency; (2) even though doped devices have been employed to mitigate the T exciton concentration quenching effect, most devices of TADF materials suffer from severe roll-off in efficiency at high current densities.
In terms of the actual demand of the current OLED display illumination industry, the development of the current OLED material is far from enough, and lags behind the requirements of panel manufacturing enterprises, and the development of organic functional materials with higher performance is very important as a material enterprise.
Disclosure of Invention
In view of the above problems in the prior art, the present applicant provides a compound with 9-fluorenone as a core and an application thereof in an organic electroluminescent device. The compound takes 9-fluorenone as a core based on a TADF mechanism, is used as a luminescent layer material to be applied to an organic light-emitting diode, and the device manufactured by the method has good photoelectric property and can meet the requirements of panel manufacturing enterprises.
The technical scheme of the invention is as follows:
the applicant provides a compound taking 9-fluorenone as a core, and the structure of the compound is shown as a general formula (1):
Figure BDA0001089912210000021
in the general formula (1), R represents-Ar-R1or-R2(ii) a Wherein Ar represents phenyl or C1-10Straight or branched chain alkyl substituted phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, benzophenanthryl, furyl, thienyl or pyridyl; n is 1 or 2;
R1、R2each independently is represented by the general formula (2)The structure is as follows:
Figure BDA0001089912210000022
in the general formula (2), R3、R4Each independently represents a hydrogen atom, a structure represented by the general formula (3) or the general formula (4), and R3、R4Not being hydrogen atoms at the same time;
Figure BDA0001089912210000023
wherein a is selected from
Figure BDA0001089912210000031
X1、X2、X3、X4Each independently represents an oxygen atom, a sulfur atom, a selenium atom, C1-10One of linear or branched alkyl substituted alkylene, aryl substituted alkylene, alkyl or aryl substituted tertiary amine; general formula (3) and general formula (4) through CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL‘1-CL’2Key, CL‘2-CL’3Bond or CL‘3-CL’4The bond is linked to formula (2).
Preferably, said R is1、R2Expressed as:
Figure BDA0001089912210000032
Figure BDA0001089912210000041
Figure BDA0001089912210000051
Figure BDA0001089912210000061
Figure BDA0001089912210000071
Figure BDA0001089912210000081
Figure BDA0001089912210000091
Figure BDA0001089912210000101
Figure BDA0001089912210000111
Figure BDA0001089912210000121
Figure BDA0001089912210000131
Figure BDA0001089912210000132
any one of them.
Preferably, the specific structural formula of the compound is:
Figure BDA0001089912210000133
Figure BDA0001089912210000141
Figure BDA0001089912210000151
Figure BDA0001089912210000161
Figure BDA0001089912210000171
Figure BDA0001089912210000181
Figure BDA0001089912210000191
Figure BDA0001089912210000201
Figure BDA0001089912210000211
Figure BDA0001089912210000212
any one of the above.
The applicant also provides a process for the preparation of said compounds, the reaction equation occurring during the preparation being:
when R represents-R2When the temperature of the water is higher than the set temperature,
Figure BDA0001089912210000221
the preparation method comprises the following steps:
weighing bromo compound with 9-fluorenone as core and R2-H, dissolved with toluene; further adding Pd (dppf) Cl2Sodium tert-butoxide; reacting the mixed solution of the reactants at the reaction temperature of 95-100 ℃ for 10-24 hours under the inert atmosphere, cooling, filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain a target product;
the bromo compound taking 9-fluorenone as core and R2-the molar ratio of-H is 1: 1.0-3.0; pd (dppf) Cl2With 9-fluorenoneThe mol ratio of the brominated compound as the core is 0.006-0.02:1, and the mol ratio of the sodium tert-butoxide to the brominated compound with 9-fluorenone as the core is 2.0-5.0: 1;
when R represents-Ar-R1When the temperature of the water is higher than the set temperature,
Figure BDA0001089912210000222
the preparation method comprises the following steps:
weighing boric acid compound with 9-fluorenone as core and R1-Ar-Br, dissolved in a toluene ethanol mixed solvent with a volume ratio of 2: 1; then adding Na2CO3Aqueous solution, Pd (PPh)3)4(ii) a Reacting the mixed solution of the reactants at the reaction temperature of 95-100 ℃ for 10-24 hours under the inert atmosphere, cooling, filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain a target product;
the boric acid compound taking 9-fluorenone as core and R1The molar ratio of-Ar to Br is 1: 1.0-3.0; pd (PPh)3)4The molar ratio of the compound to the boric acid compound taking 9-fluorenone as the core is 0.006-0.02:1, and Na2CO3The molar ratio of the compound to the boric acid compound taking 9-fluorenone as the core is 2.0-5.0: 1.
The applicant also provides a light-emitting device comprising the compound as a light-emitting layer material for making an OLED device.
The beneficial technical effects of the invention are as follows:
the compound takes 9-fluorenone as a mother nucleus, so that the crystallinity of molecules is damaged, the intermolecular aggregation is avoided, and the compound has good film-forming property; most of molecules are rigid groups, so that the thermal stability of the material is improved; the compound has good photoelectric characteristics and proper HOMO and LUMO energy levels, electron clouds of the HOMO and LUMO energy levels are effectively separated, a smaller S1-T1 state energy gap can be realized, the exciton utilization rate and the high fluorescence radiation efficiency can be effectively improved, the efficiency roll-off under high current density is reduced, the voltage of a device is reduced, and the problem of the efficiency roll-off of the device under high current density is solved.
The compound can be applied to the manufacture of OLED light-emitting devices and can obtain good device performance, and when the compound is used as a light-emitting layer material of the OLED light-emitting devices, the current efficiency, the power efficiency and the external quantum efficiency of the devices are greatly improved. The compound has good application effect in OLED luminescent devices and good industrialization prospect.
Drawings
FIG. 1 is a schematic diagram of a device structure employing the compounds of the present invention;
wherein, 1 is a transparent substrate layer, 2 is an ITO anode layer, 3 is a hole injection layer, 4 is a hole transport layer, 5 is a luminescent layer, 6 is an electron transport layer, 7 is an electron injection layer, and 8 is a cathode reflection electrode layer.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
Example 1: synthesis of Compound 6:
the synthetic route is as follows:
Figure BDA0001089912210000231
a250 mL three-necked flask was charged with 2, 7-dibromo-9-fluorenone (0.01 mol), intermediate A1 (0.025 mol), sodium tert-butoxide (0.03 mol), and 1X 10 under a nitrogen atmosphere-4molPd(dppf)Cl2180mL of toluene, heating and refluxing for 10 hours, sampling a sample, and completely reacting the raw materials; naturally cooling to room temperature (20-25 ℃), filtering, collecting filtrate, performing reduced pressure rotary evaporation (-0.09MPa, 85 ℃), and performing column chromatography to obtain a target product, wherein the HPLC purity is 99.2%, and the yield is 68.5%.
Elemental analysis Structure (molecular formula C)55H38N2O): theoretical value C, 88.92; h, 5.16; n, 3.77; o, 2.15; test values are: c, 88.93; h, 5.15; n, 3.76; o, 2.16.
HPLC-MS: the theoretical molecular weight of the material is 742.90, and the measured molecular weight is 743.13.
Example 2: synthesis of compound 12:
the synthetic route is as follows:
Figure BDA0001089912210000241
a250 mL three-necked flask was charged with 3, 6-dibromo-9-fluorenone (0.01 mol), intermediate A1 (0.025 mol), sodium tert-butoxide (0.03 mol), and 1X 10 under a nitrogen atmosphere-4molPd(dppf)Cl2180mL of toluene, heating and refluxing for 10 hours, sampling a sample, and completely reacting the raw materials; naturally cooling to room temperature (20-25 ℃), filtering, collecting filtrate, performing reduced pressure rotary evaporation (-0.09MPa, 85 ℃), and performing column chromatography to obtain a target product, wherein the HPLC purity is 98.8%, and the yield is 67.7%.
Elemental analysis Structure (molecular formula C)55H38N2O): theoretical value C, 88.92; h, 5.16; n, 3.77; o, 2.15; test values are: c, 88.95; h, 5.13; n, 3.78; o, 2.14.
HPLC-MS: the theoretical molecular weight of the material is 742.90, and the measured molecular weight is 743.18.
Example 3: synthesis of compound 22:
the synthetic route is as follows:
Figure BDA0001089912210000242
a250 mL three-necked flask was charged with 2, 7-dibromo-9-fluorenone (0.01 mol), intermediate B1 (0.025 mol), sodium tert-butoxide (0.03 mol), and 1X 10 under a nitrogen atmosphere-4molPd(dppf)Cl2180mL of toluene, heating and refluxing for 10 hours, sampling a sample, and completely reacting the raw materials; naturally cooling to room temperature (20-25 ℃), filtering, collecting filtrate, performing reduced pressure rotary evaporation (-0.09MPa, 85 ℃), and performing column chromatography to obtain a target product, wherein the HPLC purity is 99.4%, and the yield is 66.9%.
Elemental analysis Structure (molecular formula C)49H26N2O3): theoretical value C, 85.20; h, 3.79; n, 4.06; o, 6.95; test values are: c, 85.23; h, 3.78; n, 4.05; and O, 6.94.
HPLC-MS: the theoretical molecular weight of the material is 690.74, and the measured molecular weight is 690.96.
Example 4: synthesis of compound 36:
the synthetic route is as follows:
Figure BDA0001089912210000251
in a 250mL three-necked flask, 0.01mol of 3-bromo-9-fluorenone, 0.015mol of intermediate C1, 0.03mol of sodium tert-butoxide, and 1X 10-4molPd(dppf)Cl2180mL of toluene, heating and refluxing for 10 hours, sampling a sample, and completely reacting the raw materials; naturally cooling to room temperature (20-25 ℃), filtering, collecting filtrate, performing reduced pressure rotary evaporation (-0.09MPa, 85 ℃), and performing column chromatography to obtain a target product, wherein the HPLC purity is 99.3%, and the yield is 74.2%.
Elemental analysis Structure (molecular formula C)40H25NO2): theoretical value C, 87.09; h, 4.57; n, 2.54; o, 5.80; test values are: c, 87.08; h, 4.56; n, 2.55; and O, 5.81.
HPLC-MS: the theoretical molecular weight of the material is 551.63, and the measured molecular weight is 551.86.
Example 5: synthesis of compound 43:
the synthetic route is as follows:
Figure BDA0001089912210000252
in a 250mL three-necked flask, 0.01mol of 2-bromo-9-fluorenone, 0.015mol of intermediate D1, 0.03mol of sodium tert-butoxide, and 1X 10 mol of sodium tert-butoxide are added under an atmosphere of introducing nitrogen gas-4molPd(dppf)Cl2180mL of toluene, heating and refluxing for 10 hours, sampling a sample, and completely reacting the raw materials; naturally cooling to room temperature (20-25 ℃), filtering, collecting filtrate, performing reduced pressure rotary evaporation (-0.09MPa, 85 ℃), and performing column chromatography to obtain a target product, wherein the HPLC purity is 98.8%, and the yield is 71.9%.
Elemental analysis Structure (molecular formula C)49H29N3O): theoretical value C, 87.09; h, 4.33; n, 6.22; o, 2.37; test values are: c, 87.07; h, 4.32; n, 6.23; o, 2.38.
HPLC-MS: the theoretical molecular weight of the material is 675.77, and the measured molecular weight is 675.98.
Example 6: synthesis of compound 54:
the synthetic route is as follows:
Figure BDA0001089912210000261
in a 250mL three-necked flask, 0.01mol of 2-bromo-9-fluorenone, 0.015mol of intermediate E1, 0.03mol of sodium tert-butoxide and 1X 10 mol of sodium tert-butoxide are added under an atmosphere of introducing nitrogen-4molPd(dppf)Cl2180mL of toluene, heating and refluxing for 8 hours, sampling a sample, and completely reacting the raw materials; naturally cooling to room temperature (20-25 ℃), filtering, collecting filtrate, performing reduced pressure rotary evaporation (-0.09MPa, 85 ℃), and performing column chromatography to obtain a target product, wherein the HPLC purity is 99.1%, and the yield is 72.6%.
Elemental analysis Structure (molecular formula C)43H31NO): theoretical value C, 89.40; h, 5.41; n, 2.42; o, 2.77; test values are: c, 89.41; h, 5.40; n, 2.43; o, 2.76.
HPLC-MS: the theoretical molecular weight of the material is 577.71, and the measured molecular weight is 577.94.
Example 7: synthesis of compound 59:
the synthetic route is as follows:
Figure BDA0001089912210000262
compound 59 was prepared as in example 5, except intermediate F1 was used instead of intermediate D1.
Elemental analysis Structure (molecular formula C)40H25NO2): theoretical value C, 87.09; h, 4.57; n, 2.54; o, 5.80; test values are: c, 87.08; h, 4.58; n, 2.53; and O, 5.81.
HPLC-MS: the theoretical molecular weight of the material is 551.63, and the measured molecular weight is 551.91.
Example 8: synthesis of compound 70:
the synthetic route is as follows:
Figure BDA0001089912210000263
compound 70 was prepared as in example 4, except intermediate G1 was used instead of intermediate C1.
Elemental analysis Structure (molecular formula C)43H31NO3): theoretical value C, 84.71; h, 5.12; n, 2.30; o, 7.87; test values are: c, 84.70; h, 5.13; n, 2.31; and O, 7.86.
HPLC-MS: the theoretical molecular weight of the material is 609.71, and the measured molecular weight is 609.95.
Example 9: synthesis of compound 82:
the synthetic route is as follows:
Figure BDA0001089912210000271
compound 82 was prepared as in example 5, except intermediate H1 was used instead of intermediate D1.
Elemental analysis Structure (molecular formula C)41H23NO3): theoretical value C, 85.25; h, 4.01; n, 2.42; o, 8.31; test values are: c, 85.24; h, 4.03; n, 2.40; o, 8.33.
HPLC-MS: the theoretical molecular weight of the material is 577.63, and the measured molecular weight is 577.88.
Example 10: synthesis of compound 85:
the synthetic route is as follows:
Figure BDA0001089912210000272
a250 mL three-necked flask was charged with 0.01mol of 9-fluorenone-2, 7-diboronic acid and 0.025mol of intermediate I1 in a nitrogen-purged atmosphere, dissolved in a mixed solvent (180mL of toluene and 90mL of ethanol), and then charged with 0.03mol of Na2CO3The aqueous solution (2M) was stirred under nitrogen for 1 hour, then 0.0002mol Pd (PPh) was added3)4The reaction was heated to reflux for 20 hours, and the sample was taken from the plate and the reaction was complete. Naturally cooling, filtering, rotatably evaporating filtrate, and passing through a silica gel column to obtain a target product with the HPLC purity of 98.6 percent and the yield of 64.2 percent.
Elemental analysis Structure (molecular formula C)57H34N2O): theoretical value C, 89.74; h, 4.49; n, 3.67; o, 2.10; test values are: c, 89.75; h, 4.48; n, 3.65; o, 2.12.
HPLC-MS: the theoretical molecular weight of the material is 762.89, and the measured molecular weight is 763.12.
Example 11: synthesis of compound 87:
the synthetic route is as follows:
Figure BDA0001089912210000281
compound 87 was prepared as in example 10, except intermediate J1 was used instead of intermediate I1.
Elemental analysis Structure (molecular formula C)61H34N2O3): theoretical value C, 86.92; h, 4.07; n, 3.32; o, 5.69; test values are: c, 86.93; h, 4.06; n, 3.33; and O, 5.68.
HPLC-MS: the theoretical molecular weight of the material is 842.93, and the measured molecular weight is 843.17.
Example 12: synthesis of compound 98:
the synthetic route is as follows:
Figure BDA0001089912210000282
a250 mL three-necked flask was charged with 0.01mol of 9-fluorenone-3, 6-diboronic acid and 0.025mol of intermediate K1 in a nitrogen-purged atmosphere, dissolved in a mixed solvent (180mL of toluene and 90mL of ethanol), and then charged with 0.03mol of Na2CO3The aqueous solution (2M) was stirred under nitrogen for 1 hour, then 0.0002mol Pd (PPh) was added3)4The reaction was heated to reflux for 20 hours, and the sample was taken from the plate and the reaction was complete. Naturally cooling, filtering, rotatably evaporating filtrate, and passing through a silica gel column to obtain a target product with the HPLC purity of 98.8 percent and the yield of 63.5 percent.
Elemental analysis Structure (molecular formula C)67H46N2O): theoretical value C, 89.90; h, 5.18; n, 3.13; o, 1.79; test values are: c, 89.93; h, 5.17; n, 3.12; o, 1.78.
HPLC-MS: the theoretical molecular weight of the material is 895.09, and the measured molecular weight is 895.32.
Example 13: synthesis of compound 112:
the synthetic route is as follows:
Figure BDA0001089912210000283
a250 mL three-necked flask was charged with 9-fluorenone-2-boronic acid (0.01 mol) and intermediate L1 (0.015 mol) in a nitrogen-purged atmosphere, dissolved in a mixed solvent (180mL of toluene and 90mL of ethanol), and then charged with Na (0.03 mol)2CO3The aqueous solution (2M) was stirred under nitrogen for 1 hour, then 0.0001mol of Pd (PPh) was added3)4And heating and refluxing for 15 hours, sampling a sample point plate, and completely reacting. Naturally cooling, filtering, rotatably evaporating filtrate, and passing through a silica gel column to obtain a target product with the HPLC purity of 98.5 percent and the yield of 72.4 percent.
Elemental analysis Structure (molecular formula C)46H29NO2): theoretical value C, 88.01; h, 4.66; n, 2.23; o, 5.10; test values are: c, 88.02; h, 4.65; n, 2.22; and O, 5.11.
HPLC-MS: the theoretical molecular weight of the material is 627.73, and the measured molecular weight is 627.97.
Example 14: synthesis of compound 157:
the synthetic route is as follows:
Figure BDA0001089912210000291
compound 157 was prepared as in example 13, except intermediate M1 was used in place of intermediate L1.
Elemental analysis Structure (molecular formula C)55H47NO): theoretical value C, 89.51; h, 6.42; n, 1.90; o, 2.17; test values are: c, 89.52; h, 6.42; n, 1.91; o, 2.15.
HPLC-MS: the theoretical molecular weight of the material is 737.97, and the measured molecular weight is 738.13.
Example 15: synthesis of compound 164:
the synthetic route is as follows:
Figure BDA0001089912210000292
compound 164 was prepared as in example 13, except intermediate N1 was used instead of intermediate L1.
Elemental analysis Structure (molecular formula C)49H35NO2): theoretical value C, 87.86; h, 5.27; n, 2.09; o, 4.78; test values are: c, 87.88; h, 5.28; n, 2.07; o, 4.77.
HPLC-MS: the theoretical molecular weight of the material is 669.81, and the measured molecular weight is 670.03.
Example 16: synthesis of compound 170:
the synthetic route is as follows:
Figure BDA0001089912210000301
a250 mL three-necked flask was charged with 9-fluorenone-3-boronic acid (0.01 mol) and intermediate O1 (0.015 mol) in a nitrogen-purged atmosphere, dissolved in a mixed solvent (180mL of toluene and 90mL of ethanol), and then charged with Na (0.03 mol)2CO3The aqueous solution (2M) was stirred under nitrogen for 1 hour, then 0.0001mol of Pd (PPh) was added3)4And heating and refluxing for 15 hours, sampling a sample point plate, and completely reacting. Naturally cooling, filtering, rotatably evaporating filtrate, and passing through a silica gel column to obtain a target product with the HPLC purity of 98.6 percent and the yield of 72.7 percent.
Elemental analysis Structure (molecular formula C)58H39N3O2): theoretical value C, 86.01; h, 4.85; n, 5.19; o, 3.95; test values are: c, 86.03; h, 4.85; n, 5.18; and O, 3.94.
HPLC-MS: the theoretical molecular weight of the material is 809.95, and the measured molecular weight is 810.18.
The compound of the present invention can be used as a light emitting layer material, and the compound 43, the compound 77, the compound 167 and the conventional material CBP of the present invention are tested for thermal performance, light emission spectrum and cyclic voltammetry stability, and the test results are shown in table 1.
TABLE 1
Compound (I) Td(℃) λPL(nm) Cyclic voltammetric stability
Compound 43 417 621 Superior food
Compound 77 403 614 Superior food
Compound 167 423 619 Superior food
Material CBP 353 369 Difference (D)
Note: the thermogravimetric temperature Td is a temperature at which 1% of the weight loss is observed in a nitrogen atmosphere, and is measured on a TGA-50H thermogravimetric analyzer of Shimadzu corporation, Japan, and the nitrogen flow rate is 20 mL/min; lambda [ alpha ]PLThe fluorescence emission wavelength of the sample solution is measured by using a Japanese topotecan SR-3 spectroradiometer; cyclic voltammetry stability is observed by cyclic voltammetryIdentifying the redox property of the sample; and (3) testing conditions are as follows: the test sample was dissolved in a mixed solvent of dichloromethane and acetonitrile at a volume ratio of 2:1 at a concentration of 1mg/mL, and the electrolyte was 0.1M of an organic solution of tetrabutylammonium tetrafluoroborate or hexafluorophosphate. The reference electrode is an Ag/Ag + electrode, the counter electrode is a titanium plate, the working electrode is an ITO electrode, and the cycle time is 20 times.
As can be seen from the data in the table above, the compound of the present invention has good oxidation-reduction stability, high thermal stability and appropriate light emission spectrum, such that the efficiency and lifetime of the OLED device using the compound of the present invention as the light emitting layer material are improved.
The effect of the synthesized OLED material of the present invention as a host material for the light emitting layer in a device is detailed by examples 17-22 and comparative example 1. The manufacturing processes of 18-22 of the present invention and comparative example 1 are completely the same as those of example 17, and the same substrate material and electrode material are used, and the film thickness of the electrode material is also kept the same, except that the host material of the light-emitting layer 5 in the device is changed. The structural composition of the resulting devices of each example is shown in table 2. The test results of the resulting devices are shown in table 3.
Example 17
ITO anode layer 2/hole injection layer 3 (molybdenum trioxide, MoO)3Thickness 10 nm)/hole transport layer 4(TAPC, thickness 140 nm)/light-emitting layer 5 (Compound 6 and Ir (pq)2acac as 100: 5, 30nm in thickness)/electron transport layer 6(TPBI, 40nm in thickness)/electron injection layer 7(LiF, 1nm in thickness)/Al. The molecular structure of the relevant materials is shown below:
Figure BDA0001089912210000311
the preparation process comprises the following steps:
the transparent substrate layer 1 is a transparent substrate such as a transparent PI film, glass, or the like.
The ITO anode layer 2 (having a film thickness of 150nm) was washed by alkali washing, pure water washing, drying, and then ultraviolet-ozone washing to remove organic residues on the surface of the transparent ITO.
On the washed ITO anode layer 2, molybdenum trioxide MoO having a film thickness of 10nm was deposited by a vacuum deposition apparatus3The hole injection layer 3 is used. Subsequently, TAPC was evaporated to a thickness of 140nm as the hole transport layer 4.
After the evaporation of the hole transport material is finished, the light-emitting layer 5 of the OLED light-emitting device is manufactured, and the structure of the light-emitting layer 5 comprises a material compound 6 used by the OLED light-emitting layer 5 as a main material, Ir (pq)2acac is used as a doping material, the doping proportion of the doping material is 5 percent by weight, and the thickness of the luminescent layer is 30 nm.
After the light-emitting layer 5, the electron transport layer material is continuously vacuum evaporated to be TPBI. The vacuum evaporation film thickness of the material was 40nm, and this layer was an electron transport layer 6.
On the electron transport layer 6, a lithium fluoride (LiF) layer having a film thickness of 1nm was formed by a vacuum deposition apparatus, and this layer was an electron injection layer 7.
On the electron injection layer 7, an aluminum (Al) layer having a film thickness of 80nm was formed by a vacuum deposition apparatus, and this layer was used as the cathode reflection electrode layer 8.
After the OLED light emitting device was completed as described above, the anode and cathode were connected by a known driving circuit, and the current efficiency of the device and the lifetime of the device were measured. The test results of the fabricated OLED light emitting device are shown in table 3.
TABLE 2
Figure BDA0001089912210000321
TABLE 3
Device code Current efficiency LT95 Life
Example 17 1.1 3.1
Example 18 1.3 3.6
Example 19 1.4 2.5
Example 20 1.2 2.9
Example 21 1.3 4.2
Example 22 1.4 3.3
Comparative example 1 1.0 1.0
The device test performance is referred to comparative example 1, and each performance index of the device of comparative example 1 is set to 1.0. The current efficiency of comparative example 1 was 14.8cd/A (@10 mA/cm)2) (ii) a CIE color coordinates (0.66, 0.33); the LT95 lifetime decay was 11Hr at 3000 luminance.
The life test system is an OLED device life tester which is researched by the owner of the invention together with Shanghai university.
The results in table 3 show that the compound of the present invention can be used as a host material of a light emitting layer for fabrication of an OLED light emitting device, and compared with comparative example 1, the compound has greatly improved efficiency and lifetime, and particularly the driving lifetime of the device is greatly improved.
The effect of the synthesized compound of the present invention as a doping material for a light emitting layer in a device is illustrated by examples 23 to 29 and comparative example 2. In comparison with the embodiment 17, the manufacturing processes of the devices 23 to 29 and the comparative example 2 of the present invention are completely the same, and the same substrate material and electrode material are used, and the film thicknesses of the electrode materials are also kept consistent, except that the hole transport layer material and the doping material of the light emitting layer 5 in the device are different, and the doping concentration is 3%. The structural composition of each device is shown in table 4. The test results of the resulting devices are shown in table 5.
TABLE 4
Figure BDA0001089912210000331
TABLE 5
Figure BDA0001089912210000332
Figure BDA0001089912210000341
Note: the device test performance was defined as comparative example 2, and each performance index of the device of comparative example 2 was 1.0. The current efficiency of comparative example 2 was 2.3 cd/A; CIE color coordinates (0.64, 0.37); the driving voltage was 5.2v (@10 mA/cm)2)。
The results in table 5 show that the compound of the present invention can be applied as a doping material of a light emitting layer and manufactured into an OLED light emitting device, and compared with comparative example 2, the efficiency and the starting voltage are greatly improved compared with the known OLED material, and especially the efficiency roll-off of the device at high current density is improved.
From the data application, the material with the TADF characteristic has good application effect in OLED light-emitting devices and good industrialization prospect.
Although the present invention has been disclosed by way of examples and preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. On the contrary, it is intended to cover various modifications and similar arrangements as would be apparent to those skilled in the art. The scope of the following claims is, therefore, to be accorded the broadest interpretation so as to encompass all such modifications and similar arrangements.

Claims (4)

1. A compound with 9-fluorenone as a core is characterized in that the structure of the compound is shown as a general formula (1):
Figure FDA0002192528490000011
in the general formula (1), R represents-Ar-R1or-R2(ii) a Wherein Ar represents phenyl; n is 1 or 2;
R1、R2each independently represents:
Figure FDA0002192528490000012
Figure FDA0002192528490000021
Figure FDA0002192528490000031
Figure FDA0002192528490000041
Figure FDA0002192528490000042
any one of them.
2. The compound of claim 1, wherein the compound has the specific formula:
Figure FDA0002192528490000043
Figure FDA0002192528490000051
Figure FDA0002192528490000061
Figure FDA0002192528490000071
Figure FDA0002192528490000081
Figure FDA0002192528490000091
Figure FDA0002192528490000101
Figure FDA0002192528490000102
any one of the above.
3. A process for the preparation of a compound according to any one of claims 1 to 2, characterized in that the reaction equation occurring during the preparation is:
when R represents-R2When the temperature of the water is higher than the set temperature,
Figure FDA0002192528490000103
the preparation method comprises the following steps:
weighing 9-fluorenone as coreBromo compound of core and R2-H, dissolved with toluene; further adding Pd (dppf) Cl2Sodium tert-butoxide; reacting the mixed solution of the reactants at the reaction temperature of 95-100 ℃ for 10-24 hours under the inert atmosphere, cooling, filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain a target product;
the bromo compound taking 9-fluorenone as core and R2-the molar ratio of-H is 1: 1.0-3.0; pd (dppf) Cl2The mol ratio of the sodium tert-butoxide to the bromo-compound taking 9-fluorenone as the core is 0.006-0.02:1, and the mol ratio of the sodium tert-butoxide to the bromo-compound taking 9-fluorenone as the core is 2.0-5.0: 1;
when R represents-Ar-R1When the temperature of the water is higher than the set temperature,
Figure FDA0002192528490000111
the preparation method comprises the following steps:
weighing boric acid compound with 9-fluorenone as core and R1-Ar-Br, dissolved in a toluene ethanol mixed solvent with a volume ratio of 2: 1; then adding Na2CO3Aqueous solution, Pd (PPh)3)4(ii) a Reacting the mixed solution of the reactants at the reaction temperature of 95-100 ℃ for 10-24 hours under the inert atmosphere, cooling, filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain a target product;
the boric acid compound taking 9-fluorenone as core and R1The molar ratio of-Ar to Br is 1: 1.0-3.0; pd (PPh)3)4The molar ratio of the compound to the boric acid compound taking 9-fluorenone as the core is 0.006-0.02:1, and Na2CO3The molar ratio of the compound to the boric acid compound taking 9-fluorenone as the core is 2.0-5.0: 1.
4. A light-emitting device comprising a compound according to any of claims 1-2 as a light-emitting layer material for use in the fabrication of an OLED device.
CN201610723665.4A 2016-08-24 2016-08-24 Compound with 9-fluorenone as core and application thereof Active CN106467485B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610723665.4A CN106467485B (en) 2016-08-24 2016-08-24 Compound with 9-fluorenone as core and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610723665.4A CN106467485B (en) 2016-08-24 2016-08-24 Compound with 9-fluorenone as core and application thereof

Publications (2)

Publication Number Publication Date
CN106467485A CN106467485A (en) 2017-03-01
CN106467485B true CN106467485B (en) 2020-04-03

Family

ID=58230579

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610723665.4A Active CN106467485B (en) 2016-08-24 2016-08-24 Compound with 9-fluorenone as core and application thereof

Country Status (1)

Country Link
CN (1) CN106467485B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190118821A (en) 2018-04-11 2019-10-21 삼성전자주식회사 Condensed cyclic compound and organic light-emitting device including the same
CN109574823A (en) * 2018-12-03 2019-04-05 武汉尚赛光电科技有限公司 A kind of fluorenone derivatives and its preparation and application
CN111377937B (en) * 2018-12-29 2022-09-27 江苏三月科技股份有限公司 Organic compound with carbazole derivative as core and application thereof in organic electroluminescent device
CN113683498B (en) * 2021-09-07 2023-04-18 郑州大学 Green light material based on 9-fluorenone structural framework and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201509882A (en) * 2013-04-10 2015-03-16 Univ Kyushu Nat Univ Corp Light-emitting material, oragnic electroluminescence device and compound
CN105503766A (en) * 2015-12-18 2016-04-20 昆山国显光电有限公司 Thermal activation delayed fluorescent material and organic electroluminescent device

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2439030B (en) * 2005-04-18 2011-03-02 Konica Minolta Holdings Inc Organic electroluminescent device, display and illuminating device
US9090819B2 (en) * 2009-06-24 2015-07-28 Konica Minolta, Inc. Organic electroluminescent element, display device, illuminating device and condensed polycyclic heterocyclic compound

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201509882A (en) * 2013-04-10 2015-03-16 Univ Kyushu Nat Univ Corp Light-emitting material, oragnic electroluminescence device and compound
CN105503766A (en) * 2015-12-18 2016-04-20 昆山国显光电有限公司 Thermal activation delayed fluorescent material and organic electroluminescent device

Also Published As

Publication number Publication date
CN106467485A (en) 2017-03-01

Similar Documents

Publication Publication Date Title
CN108586507B (en) Long-life boron-containing organic electroluminescent compound and application thereof
CN106397423B (en) Organic compound with aza-benzene as core and application thereof in OLED
CN107602601B (en) Boron-containing multi-heterocyclic organic compound and application thereof in organic electroluminescent device
CN107586261B (en) Organic compound containing spiro dibenzosuberene fluorene and application thereof
CN106467484B (en) Compound with 9-fluorenone as core and application thereof in OLED device
CN107056748B (en) Compound with triazine and ketone as cores and application thereof in organic electroluminescent device
CN106467529B (en) It is a kind of using 9-Fluorenone as the electroluminescent organic material of core and its application
CN106279203A (en) Compound containing ketone and nitrogen heterocycle and application thereof in organic electroluminescent device
CN109354588B (en) Organic electroluminescent compound with nitrogen-containing five-membered heterocyclic ring as core and application thereof
CN106467485B (en) Compound with 9-fluorenone as core and application thereof
CN107880030B (en) Triazine-based compound and organic electroluminescent device
CN106220645A (en) Compound based on monosubstituted-9-fluorenone and application thereof
CN109575039B (en) Azabenzene organic compound and application thereof
CN106543071B (en) Compound with dibenzoheptenone as core and application of compound in OLED
WO2019062686A1 (en) Compound with cyanobenzene as core, and application of compound in oled devices
CN110835351A (en) Organic compound with pyrromethene boron complex as core and preparation and application thereof
CN107880028B (en) Compound with aza-benzene as core and organic electroluminescent device
CN107021925B (en) Compound with aza-dibenzosuberone as core and application thereof in OLED
CN109912564B (en) Compound with cyano-group aza-benzene as core and application of compound in OLED device
CN107652225B (en) Compound with cyanobenzene as core and application of compound in OLED device
WO2019085759A1 (en) Compound provided with an aza-spirofluorene and aryl ketone core, preparation method thereof, and application of same in oleds
CN107056770A (en) A kind of compound as core using nitrogenous five-ring heterocycles and its application on organic electroluminescence device
CN106699731B (en) A kind of maleic acid hydrazide analog derivative and its preparation method and application
CN112479904B (en) Organic compound with indeno-anthracene derivative as core and application thereof
CN106467532B (en) It is a kind of using nitrogenous five-ring heterocycles as the compound of core and its application in OLED device

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right

Effective date of registration: 20200213

Address after: 264006 No. 11 Wuzhishan Road, Yantai economic and Technological Development Zone, Shandong

Applicant after: VALIANT Co.,Ltd.

Address before: 214112 No. 210, Xinzhou Road, New District, Jiangsu, Wuxi

Applicant before: JIANGSU SUNERA TECHNOLOGY Co.,Ltd.

TA01 Transfer of patent application right
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20211207

Address after: 214112 No.210 Xinzhou Road, Wuxi City, Jiangsu Province

Patentee after: Jiangsu March Technology Co., Ltd

Address before: 264006 No. 11 Wuzhishan Road, Yantai economic and Technological Development Zone, Shandong

Patentee before: VALIANT Co.,Ltd.

TR01 Transfer of patent right