CN110698505A - Compound, display panel and display device - Google Patents
Compound, display panel and display device Download PDFInfo
- Publication number
- CN110698505A CN110698505A CN201911054295.XA CN201911054295A CN110698505A CN 110698505 A CN110698505 A CN 110698505A CN 201911054295 A CN201911054295 A CN 201911054295A CN 110698505 A CN110698505 A CN 110698505A
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- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 14
- 125000001424 substituent group Chemical group 0.000 claims abstract description 10
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- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 9
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- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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Abstract
The invention belongs to the technical field of OLED (organic light emitting diode) and provides a compound with a structure shown in a chemical formula 1, wherein L1、L2And L3Each independently selected from a single bond, a C6-C30 aromatic or fused aryl, a C4-C30 heteroaryl or fused heteroaryl; r1、R2And R3At least one is an electron donating group and at least one is an electron accepting group; the electron-donating group is mainly selected from carbazole group, acridine group and diarylamine group; the electron-accepting group is selected from nitrogen-containing heterocycles and cyanogen-containing substituents. The borano-indenofluorene structure in the compound of the invention is not only used as an electron acceptor group, but also used as a linking group. In the compound of the present invention, by attaching a group having a large steric hindrance to a boron atom, effective charge transfer in a molecule is enhanced while avoidingThe aggregation of compound molecules is avoided, and pi aggregation or excimer formation caused by direct accumulation of conjugated planes is avoided, so that the luminous efficiency is improved. The invention also provides a display panel and a display device.
Description
Technical Field
The invention relates to the technical field of organic electroluminescent materials, in particular to a boron heterocyclic compound, a display panel comprising the compound and a display device comprising the compound.
Background
With the development of electronic display technology, Organic Light Emitting Devices (OLEDs) are widely used in various display devices, and research and application of light emitting materials of the OLEDs are increasing.
The materials used for the light-emitting layer of an OLED mainly include the following four types according to the light-emitting mechanism:
(1) a fluorescent material; (2) a phosphorescent material; (3) triplet-triplet annihilation (TTA) material 0; (4) thermally Activated Delayed Fluorescence (TADF) material.
For fluorescent materials, the ratio of singlet to triplet excitons in excitons is 1:3 based on spin statistics, so that the maximum internal quantum yield of the fluorescent material does not exceed 25%. According to the lambertian emission mode, the light extraction efficiency is around 20%, so the External Quantum Effect (EQE) of the OLED based on fluorescent materials does not exceed 5%.
For the phosphorescent material, the phosphorescent material can enhance the intersystem crossing inside molecules through the spin coupling effect due to the heavy atom effect, and can directly utilize 75% of triplet excitons, so that the emission with the participation of S1 and T1 together at room temperature is realized, and the theoretical maximum internal quantum yield can reach 100%. According to the lambertian emission pattern, the light extraction efficiency is about 20%, so that the external quantum effect of OLEDs based on phosphorescent materials can reach 20%. However, the phosphorescent material is basically a heavy metal complex such as Ir, Pt, Os, Re, Ru and the like, and the production cost is high, so that the large-scale production is not facilitated. Under high current density, the phosphorescent material has serious efficiency roll-off phenomenon, and the stability of the phosphorescent device is not good.
For triplet-triplet annihilation (TTA) materials, two adjacent triplet excitons recombine to generate a higher energy singlet excited state molecule and a ground state molecule, but two triplet excitons generate a singlet exciton, so the theoretical maximum internal quantum yield can only reach 62.5%. In order to prevent the generation of the large efficiency roll-off phenomenon, the concentration of triplet excitons needs to be regulated during this process.
For a Thermally Activated Delayed Fluorescence (TADF) material, when the difference between the singlet excited state and the triplet excited state is small, reverse intersystem crossing (RISC) occurs inside the molecule, T1 state excitons are up-converted to S1 state by absorbing environmental heat, 75% of triplet excitons and 25% of singlet excitons can be simultaneously utilized, and the theoretical maximum internal quantum yield can reach 100%. The TADF material is mainly an organic compound, does not need rare metal elements and has low production cost. TADF materials can be chemically modified by a variety of methods. However, the TADF materials found so far are relatively few, and therefore, there is a need to develop new TADF materials that can be used in OLEDs.
Disclosure of Invention
In view of the problems occurring in the prior art, it is an object of the present invention to provide a compound having a structure represented by chemical formula 1:
wherein L is1、L2And L3Each independently selected from a single bond, a C6-C30 aromatic or fused aryl, a C4-C30 heteroaryl or fused heteroaryl;
R1、R2and R3At least one is an electron donating group and at least one is an electron accepting group;
wherein the electron donating group is selected from C1-C20 alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted acenaphthylene, substituted or unsubstituted pyrenyl, substituted or unsubstituted perylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted spirobifluorenylSubstituted or unsubstituted benzophenanthryl, substituted or unsubstituted benzanthryl, substituted or unsubstituted fluoranthryl, substituted or unsubstituted picene, substituted or unsubstituted furyl, substituted or unsubstituted benzofuryl, substituted or unsubstituted dibenzofuryl, substituted or unsubstituted thienyl, substituted or unsubstituted benzofurylAny one of a substituted benzothienyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted phenazinyl group, a substituted or unsubstituted phenothiazinyl group, a substituted or unsubstituted thianthrenyl group, a carbazolyl group and a derivative group thereof, an acridinyl group and a derivative group thereof, a diarylamine group and a derivative group thereof;
the electron-accepting group is selected from nitrogen-containing heterocyclic substituent, cyanogen-containing substituent, carbonyl-containing substituent, sulfone substituent and phosphine-oxygen-containing substituent.
In the compounds of the present invention, the borano-indenofluorene structure serves not only as an electron acceptor group, but also as a linking group. The novel boron-containing heterocyclic organic micromolecule luminescent material avoids the aggregation of compounds by accessing a group with large steric hindrance, and avoids the direct accumulation of a conjugate plane to form pi aggregation or excimer, thereby improving the luminous efficiency.
The material designed by the invention has TADF (TADF light emission) characteristics, and can emit light by utilizing triplet excitons which are forbidden by the transition of the traditional fluorescent molecules, so that the efficiency of the device is improved. The fundamental reasons are that: the designed molecules have large rigid distortion, the overlapping between HOMO and LUMO is reduced, the energy level difference between a triplet state and a singlet state can be reduced to be below 0.25eV, and the reverse crossing of triplet state energy to the singlet state is met, so that the luminous efficiency is improved.
In addition, the novel boron heterocyclic TADF luminescent material provided by the invention has bipolar characteristics, and as a luminescent layer, the transport capability of two kinds of flow can be greatly improved, the carrier balance can be improved, the fluorescence quantum efficiency can be improved, and the voltage of a device can be reduced.
Drawings
FIG. 1 is a general chemical formula of a boron heterocompound of the present invention;
FIG. 2 shows the HOMO distribution diagram of boron hybrid compound M1 of the present invention;
FIG. 3 shows the LUMO distribution diagram of boron hybrid compound M1 according to the present invention;
FIG. 4 is a schematic structural diagram of an OLED device provided by the present invention;
fig. 5 is a schematic diagram of a display device according to an embodiment of the present invention.
Detailed Description
The present invention is further illustrated by the following examples and comparative examples, which are intended to be illustrative only and are not to be construed as limiting the invention. The technical scheme of the invention is to be modified or replaced equivalently without departing from the scope of the technical scheme of the invention, and the technical scheme of the invention is covered by the protection scope of the invention.
An aspect of the present invention provides a boron heterocyclic compound having a structure represented by chemical formula 1:
wherein L is1、L2And L3Each independently selected from a single bond, a C6-C30 aromatic or fused aryl, a C4-C30 heteroaryl or fused heteroaryl;
R1、R2and R3At least one is an electron donating group and at least one is an electron accepting group;
wherein the electron donating group is selected from C1-C20 alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted acenaphthylene, substituted or unsubstituted pyrenyl, substituted or unsubstituted perylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted spirobifluorenyl
Substituted or unsubstituted benzophenanthryl, substituted or unsubstituted benzanthryl, substituted or unsubstituted fluoranthryl, substituted or unsubstituted picene, substituted or unsubstituted furyl, substituted or unsubstituted benzofuryl, substituted or unsubstituted dibenzofuryl, substituted or unsubstituted thienyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted benzophenanthrenyl, substituted or unsubstituted phenanthrenylAny one of substituted or unsubstituted phenoxazinyl, substituted or unsubstituted phenazinyl, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted thianthrenyl, carbazolyl and derivative group thereof, acridinyl and derivative group thereof, diarylamine and derivative group thereof;
the electron-accepting group is selected from nitrogen-containing heterocyclic substituent, cyanogen-containing substituent, carbonyl-containing substituent, sulfone substituent and phosphine-oxygen-containing substituent.
According to one embodiment of the compound of the present invention, the compound has a structure represented by chemical formula 2:
according to one embodiment of the compounds of the invention, L1、L2And L3Each independently selected from phenyl, naphthyl, anthryl, phenanthryl, pyridyl, furyl, pyrimidinyl.
According to one embodiment of the compounds of the invention, L1、L2And L3The same is true.
According to one embodiment of the compounds of the invention, R1、R2And R3Wherein two groups are the same.
At L1、L2And L3In the same way, on the one hand, the synthesis of the compounds is easier; on the other hand, in L1、L2And L3In the same case, the electron cloud of the compound can be better separated.
According to one embodiment of the compounds of the invention, R1、R2And R3Each independently selected from any one of the following groups:
z is selected from a C atom, a N atom, an O atom or an S atom; q is selected from 0, 1 or 2;
U1、U2and U3Each independently selected from a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group;
when Z is an oxygen atom or a sulfur atom, q is 0;
# denotes the ligation site.
Carbazole is diphenylamine molecule with isoelectronic structure, and has strong electron-donating ability and good hole-transporting ability. The carbazole ring has more active sites, and is easy to introduce various functional groups to functionalize the carbazole ring. When the carbazole group is applied to the compound, a high-efficiency luminescent group is easily introduced through modification of a molecular structure, so that a luminescent material with excellent performance is obtained.
According to one embodiment of the compounds of the invention, R1、R2And R3Each independently selected from any one of the following groups:
according to one embodiment of the compounds of the invention, R1、R2And R3Each independently selected from any one of the following groups:
z is selected from a C atom, a N atom, an O atom, an S atom or a Si atom; x is selected from a C atom, a N atom, an O atom or an S atom; m, n, p and q are each independently selected from 0, 1 or 2;
U1、U2、U3、U4each independently selected from hydrogen atom, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C6-C12 aryl;
when X is an oxygen atom or a sulfur atom, q is 0; when Z is an oxygen atom or a sulfur atom, p is 0;
# denotes the ligation site.
The acridine group is a macrocyclic conjugated system with a rigid planar structure, has excellent fluorescence performance and simultaneously contains a larger pi conjugated system structure. The acridine material has high luminous efficiency, reasonable energy level structure and good host-guest energy transfer characteristics, and a device using the material as a luminous layer has good luminous performance.
According to one embodiment of the compounds of the invention, R1、R2And R3Each independently selected from any one of the following groups:
wherein R and R' are independently selected from hydrogen atom, C1-C3 alkyl and phenyl.
According to one embodiment of the compounds of the invention, R1、R2And R3Each independently selected from any one of the following groups:
U1、U2each independently selected from a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group; m and n are independently selected from 0, 1 or 2;
# denotes the ligation site.
The diphenylamine group and the derivative group thereof have the following advantages: (1) moderate electron donor characteristics; (2) good thermal stability and chemical stability, wide raw material source, low cost and easy chemical modification, and can effectively realize the spatial separation of HOMO and LUMO by combining with an electron acceptor.
According to one embodiment of the compounds of the invention, R1、R2And R3Each independently selected from any one of the following groups:
where, # denotes the ligation position.
According to one embodiment of the compound of the present inventionMode (R)1、R2And R3Each independently selected from any one of the following groups:
x is selected from O atom or S atom; m and n are each independently selected from 0, 1 or 2;
U1and U2Each independently selected from a hydrogen atom, a C1-C6 alkyl group, a C3-C6 cycloalkyl group, a C1-C6 alkoxy group;
# denotes the ligation site.
According to one embodiment of the compounds of the invention, R1、R2And R3Each independently selected from any one of the following groups:
# denotes the ligation site.
According to one embodiment of the compound of the present invention, the nitrogen-containing heterocyclic group is selected from any one of the following groups:
wherein, # denotes the attachment position in chemical formula 1;
r is selected from hydrogen atom, C1-C20 alkyl, C1-C20 alkoxy, C4-C8 cycloalkyl, C6-C40 aryl and C4-C40 heteroaryl.
According to one embodiment of the compound of the present invention, the cyano-containing group is selected from any one of the following groups:
wherein, # denotes the attachment position in chemical formula 1.
According to one embodiment of the compound of the present invention, the carbonyl-containing group is selected from any one of the following groups:
wherein, # denotes the linking position in chemical formula 1, and R denotes C1-C20 alkyl, C1-C20 alkoxy, C2-C20 alkenyl, C2-C20 alkynyl, C4-C8 cycloalkyl, C6-C40 aryl, C4-C40 heteroaryl.
According to an embodiment of the compound of the present invention, the sulfone-containing group is selected from any one of the following groups:
according to one embodiment of the compound of the present invention, the phosphino-containing group is selected from any one of the following groups:
the X is selected from O, S, -BR41、-C(R41)2、-Si(R41)2and-NR41Any one of the above;
the R is30、R31、R32、R33、R34、R35、R36、R37、R38、R39、R40、R41Each independently selected from any one of a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C3-C20 heterocyclic group, a substituted or unsubstituted C6-C40 aryl group and a substituted or unsubstituted C2-C40 heteroaryl group;
# denotes the attachment position in chemical formula 1.
According to one embodiment of the compounds of the invention, L1、L2And L3Each independently selected from the group consisting of:
R1、R2and R3One or both of which are each independently selected from one of the following electron donating groups:
wherein, U1、U2And U3Each independently selected from C1-C3 alkyl, C6-C12 aryl; m and n are 0, p is 0, 1 or 2;
z is selected from C atom, N atom, O atom or S atom, when Z is oxygen atom or sulfur atom, p is 0;
# denotes the linkage position in chemical formula 1;
and R is1、R2And R3One or two of which are each independently selected from cyano or s-triazinyl.
According to one embodiment of the compound of the present invention, the compound is selected from any one of the following compounds:
according to one embodiment of the compounds of the present invention, the energy level difference Δ E between the lowest singlet energy level S1 and the lowest triplet energy level T1 of the compoundST＝ES1-ET1≦0.25eV。
The boron heterocyclic compound has TADF (thermo-induced emission) characteristics, and can be used as a host material or a guest material of an OLED light-emitting layer.
Another aspect of the present invention provides methods for preparing exemplary boron heterocyclic compounds M1, M2, M3, and M4, as described in exemplary examples 1 through 4 below.
Example 1
Synthesis of Compound M1
Synthesis of Compound B
In a 250mL three-necked flask, 9.40g (20mmol) of the substrate A and THF (80mL) were added and dissolved, and nitrogen gas was replaced three times. Cooling to-78 deg.C, controlling temperature below-65 deg.C, slowly adding n-BuLi 20mL (50mmol), stirring for 30 min. 4.35g (40mmol) of TMS-Cl is slowly added dropwise, and the temperature is raised to 0 ℃ for reaction for 4 h. After the reaction is finished, ice water is added for quenching. DCM (80 mL. times.2) was added for extraction. The organic phase was collected and rotary evaporated to give an oil which was crystallised from toluene/EtOH to give a solid. In a 200mL closed pot (pressure tube) were added 9.12g (20mmol) of the solid, an anhydrous toluene solution (70mL) and 2.5g (10mmol) of boron tribromide in this order. Stirring at 120 ℃ for 12 h. After the reaction is finished H2O (100mL) quench. The reaction was extracted with DCM (100 mL. times.3), the organic phase was collected, dried, filtered and the solvent removed by rotary evaporation. Make itCrystallization with DCM/EtOH gave solid B.
MALDI-TOF:401.81
1H NMR(500MHz,CDCl3):δ7.84(s,2H),7.79(d,J＝40.0Hz,2H),7.45(s,2H).
13C NMR(125MHz,CDCl3):δ142.41(s),138.98(s),131.38(s),128.89(s),126.84(s),124.35(s).
Synthesis of Compound D
In a 250mL three-necked flask, 8.01g (20mmol) of the compound B, 7.18g (25mmol) of the compound C, 150mL of toluene freed of water and oxygen, 9.21g (40mmol) of cerium carbonate, 0.23g (0.2mmol) of tetrakis (triphenylphosphine) palladium and 40.5mg (0.2mmol) of tri-tert-butylphosphine were successively added, followed by reaction at 120 ℃ for 24 hours under a nitrogen atmosphere. Cooling to room temperature, pouring the reaction liquid into 200mL of ice water, extracting with dichloromethane three times, combining organic phases, spinning into silica gel, and separating and purifying by column chromatography (dichloromethane: n-hexane, v: v ═ 1:1) to obtain the compound D.
MALDI-TOF:562.99
1H NMR(500MHz,CDCl3):δ8.55(s,1H),8.27(s,1H),8.19(s,1H),8.13(s,1H),7.92(d,J＝5.0Hz,4H),7.87(s,1H),7.83(s,1H),7.75(s,1H),7.52(s,1H),7.45(s,1H),7.40(s,1H),7.16(dd,J＝27.5,17.5Hz,4H).
13C NMR(125MHz,CDCl3):δ142.91(s),142.41(s),140.19(s),138.98(s),138.51(s),135.38(s),134.16(s),131.38(s),130.43(d,J＝13.8Hz),128.89(s),128.25(s),127.72(s),126.84(s),125.67(s),124.35(s),122.72(s),121.15(d,J＝3.4Hz),118.04(s),114.95(s).
Synthesis of Compound F
In a 250mL three-necked flask, 11.26g (20mmol) of the compound D, 4.31g (25mmol) of the compound E, 150mL of toluene freed of water and oxygen, 9.21g (40mmol) of cerium carbonate, 0.23g (0.2mmol) of tetrakis (triphenylphosphine) palladium and 40.5mg (0.2mmol) of tri-tert-butylphosphine were successively added, followed by reaction at 120 ℃ for 24 hours under a nitrogen atmosphere. Cooling to room temperature, pouring the reaction liquid into 200mL of ice water, extracting with dichloromethane three times, combining organic phases, spinning into silica gel, and separating and purifying by column chromatography (dichloromethane: n-hexane, v: v ═ 1:1) to obtain the compound F.
MALDI-TOF:609.10.
1H NMR(500MHz,CDCl3):δ8.55(s,1H),8.33–8.24(m,4H),8.19(s,1H),8.13(s,2H),8.07(s,1H),7.91(d,J＝5.0Hz,4H),7.87(s,2H),7.52(s,1H),7.40(s,1H),7.16(dd,J＝27.5,17.5Hz,4H).
13C NMR(125MHz,CDCl3):δ142.89(d,J＝5.3Hz),142.41(s),140.98(s),140.19(s),138.47(d,J＝10.7Hz),136.19(s),135.38(s),134.16(s),132.71(s),130.63–130.27(m),128.25(s),127.83–127.61(m),125.67(s),122.78(d,J＝14.9Hz),121.15(d,J＝3.4Hz),118.64(s),118.04(s),114.95(s),104.23(s).
Synthesis of Compound H
Compound F12.21g (20mmol) was charged into a reaction flask, dissolved in diethyl ether (50mL), and replaced with nitrogen three times. Cooling to-78 deg.C, controlling temperature below-65 deg.C, slowly adding n-BuLi 8.04mL (2.5M, 20mmol), stirring for 30 min. Then, 9.54G (20mmol) of the monomer G was dissolved in 60mL of toluene, and the solution was slowly added dropwise to the reaction mixture, and the mixture was allowed to naturally warm to room temperature after completion of the dropwise addition and reacted for 6 hours. After the reaction was completed, 100mL of ice water was added to quench the reaction. Then, DCM (80 mL. times.2) was added and the mixture was extracted once with saturated brine. The organic phase was collected and rotary evaporated to give a pale yellow oil. The product was purified by column chromatography (mobile phase n-hexane: dichloromethane ═ 3:1) to give compound M1.
MALDI-TOF:926.22.
1H NMR(500MHz,CDCl3):δ8.55(s,2H),8.37(d,J＝7.7Hz,2H),8.33(s,2H),8.19(s,2H),8.13(s,2H),8.07(s,2H),7.91(d,J＝5.0Hz,8H),7.87(s,1H),7.83(s,1H),7.71(s,2H),7.52(s,2H),7.42(d,J＝25.0Hz,2H),7.16(dd,J＝27.5,17.5Hz,8H).
13C NMR(125MHz,CDCl3):δ158.86(s),143.97(s),142.87(s),141.93(d,J＝3.3Hz),140.19(s),139.36(d,J＝14.9Hz),138.68(s),136.19(s),135.38(s),134.16(s),133.66(s),132.71(s),130.52–130.27(m),127.66(d,J＝14.6Hz),127.13(d,J＝16.3Hz),126.86(s),125.67(s),123.68(s),123.37(s),121.15(d,J＝3.4Hz),118.64(s),118.04(s),117.08(s),114.95(s),104.23(s).
Synthesis of Compound M1
In a 250mL three-necked flask were added, in order, compound H18.55g (20mmol), 150mL of THF which had been deoxygenated by removal of water, 17.74g (40mmol) of PivOCs (cerium pivalate), 44.9mg (0.2mmol) of palladium acetate, and PCy356.09mg (0.2mmol) then under N2The reaction was carried out at 120 ℃ for 24 hours under an atmosphere. After cooling to room temperature, the reaction mixture was poured into 200mL of ice water, extracted three times with dichloromethane, the organic phases were combined, spun into silica gel, and subjected to column chromatography (dichloromethane: n-hexane, v: v ═ 1:1) for separation and purification to give compound M1.
MALDI-TOF:846.30.
1H NMR(500MHz,CDCl3):δ8.55(s,2H),8.38–8.30(m,6H),8.19(s,2H),8.13(s,2H),8.07(s,2H),7.92(d,J＝5.0Hz,8H),7.87(s,1H),7.52(s,2H),7.40(s,2H),7.16(dd,J＝27.5,17.5Hz,8H).
13C NMR(125MHz,CDCl3):δ143.09(s),142.73(s),142.26(s),141.96(s),140.19(s),139.58(s),136.74(s),135.38(s),134.16(s),132.27(s),131.41(s),130.38(s),129.54(s),128.07(s),127.72(s),125.67(s),123.74(s),123.57(s),121.15(d,J＝3.4Hz),118.64(s),118.04(s),114.95(s),104.38(s).
Example 2
Synthesis of Compound M2
Synthesis of Compound B
In a 250mL three-necked flask, 9.40g (20mmol) of the substrate A and THF (80mL) were added and dissolved, and nitrogen gas was replaced three times. Cooling to-78 deg.C, controlling temperature below-65 deg.C, slowly adding n-BuLi 20mL (50mmol), stirring for 30 min. 4.35g (40mmol) of TMS-Cl is slowly added dropwise, and the temperature is raised to 0 ℃ for reaction for 4 h. After the reaction is finished, ice water is added for quenching. DCM (80 mL. times.2) was added for extraction. The organic phase was collected and rotary evaporated to give an oil which was crystallised from toluene/EtOH to give a solid. In a 200 mL-stoppered jar were added 9.12g (20mmol) of the solid, an anhydrous toluene solution (70mL) and 2.5g (10mmol) of boron tribromide in that order. Stirring at 120 ℃ for 12 h. After the reaction is finished H2O (100mL) quench. The reaction was extracted with DCM (100 mL. times.3), the organic phase was collected, dried, filtered and the solvent removed by rotary evaporation. Crystallization using DCM/EtOH gave solid B.
MALDI-TOF:401.81
1H NMR(500MHz,CDCl3):δ7.84(s,2H),7.79(d,J＝40.0Hz,2H),7.45(s,2H).
13C NMR(125MHz,CDCl3):δ142.41(s),138.98(s),131.38(s),128.89(s),126.84(s),124.35(s).
Synthesis of Compound D
In a 250mL three-necked flask, 8.01g (20mmol) of the compound B, 7.18g (25mmol) of the compound C, 150mL of toluene freed of water and oxygen, 9.21g (40mmol) of cerium carbonate, 0.23g (0.2mmol) of tetrakis (triphenylphosphine) palladium and 40.5mg (0.2mmol) of tri-tert-butylphosphine were successively added, followed by reaction at 120 ℃ for 24 hours under a nitrogen atmosphere. Cooling to room temperature, pouring the reaction liquid into 200mL of ice water, extracting with dichloromethane three times, combining organic phases, spinning into silica gel, and separating and purifying by column chromatography (dichloromethane: n-hexane, v: v ═ 1:1) to obtain the compound D.
MALDI-TOF:562.99
1H NMR(500MHz,CDCl3):δ8.55(s,1H),8.27(s,1H),8.19(s,1H),8.13(s,1H),7.92(d,J＝5.0Hz,4H),7.87(s,1H),7.83(s,1H),7.75(s,1H),7.52(s,1H),7.45(s,1H),7.40(s,1H),7.16(dd,J＝27.5,17.5Hz,4H).
13C NMR(125MHz,CDCl3):δ142.91(s),142.41(s),140.19(s),138.98(s),138.51(s),135.38(s),134.16(s),131.38(s),130.43(d,J＝13.8Hz),128.89(s),128.25(s),127.72(s),126.84(s),125.67(s),124.35(s),122.72(s),121.15(d,J＝3.4Hz),118.04(s),114.95(s).
Synthesis of Compound F
Into a 250mL three-necked flask were successively added compound D11.26g (20mmol), compound E3.12g (25mmol), 150mL of toluene with water and oxygen removed, 9.21g (40mmol) of cerium carbonate, 0.23g (0.2mmol) of tetrakis (triphenylphosphine) palladium and 40.5mg (0.2mmol) of tri-t-butylphosphine, followed by reaction at 120 ℃ for 24 hours under a nitrogen atmosphere. Cooling to room temperature, pouring the reaction liquid into 200mL of ice water, extracting with dichloromethane three times, combining organic phases, spinning into silica gel, and separating and purifying by column chromatography (dichloromethane: n-hexane, v: v ═ 1:1) to obtain the compound F.
MALDI-TOF:562.10.
1H NMR(500MHz,CDCl3):δ8.70(s,1H),8.55(s,1H),8.40(s,1H),8.19(s,1H),8.16–7.88(m,9H),7.87(s,1H),7.52(s,1H),7.40(s,1H),7.16(dd,J＝22.0,14.0Hz,4H).
13C NMR(125MHz,CDCl3):δ170.97(s),167.31(s),143.31(s),142.91(s),142.41(s),140.19(s),138.51(s),135.36(d,J＝3.5Hz),134.16(s),133.59(s),130.43(d,J＝11.1Hz),128.25(s),127.72(s),126.21(s),125.62(d,J＝8.9Hz),122.72(s),121.15(d,J＝2.7Hz),118.04(s),114.95(s).
Synthesis of Compound H
Compound F12.21g (20mmol) was charged into a reaction flask, dissolved in diethyl ether (50mL), and replaced with nitrogen three times. Cooling to-78 deg.C, controlling temperature below-65 deg.C, slowly adding n-BuLi 8.04mL (2.5M, 20mmol), stirring for 30 min. Then, 7.24G (20mmol) of the monomer G was dissolved in 60mL of toluene, and the solution was slowly added dropwise to the reaction mixture, and the mixture was allowed to naturally warm to room temperature after completion of the dropwise addition and reacted for 6 hours. After the reaction was completed, 100mL of ice water was added to quench the reaction. Then, DCM (80 mL. times.2) was added and the mixture was extracted once with saturated brine. The organic phase was collected and rotary evaporated to give a pale yellow oil. The product was purified by column chromatography (mobile phase n-hexane: dichloromethane ═ 3:1) to give compound H.
MALDI-TOF:766.15.
1H NMR(500MHz,CDCl3):δ8.81(s,1H),8.53(d,J＝17.7Hz,2H),8.29(s,2H),8.19(s,1H),8.16–7.76(m,6H),8.04–7.76(m,3H),7.98–7.74(m,3H),7.71(s,1H),7.52(s,1H),7.42(d,J＝20.0Hz,2H),7.16(dd,J＝22.0,14.0Hz,4H).
13C NMR(125MHz,CDCl3):δ170.97(s),167.31(s),158.86(s),144.02(d,J＝10.5Hz),142.87(s),140.70(s),140.19(s),139.30(s),138.29(s),136.19(s),135.38(s),134.42–134.05(m),132.71(s),131.98(s),130.40(d,J＝3.4Hz),128.44(s),127.66(d,J＝11.7Hz),127.15(s),126.88(s),125.67(s),123.74(s),123.37(s),121.15(d,J＝2.7Hz),118.64(s),118.04(s),117.08(s),114.95(s),104.23(s).
Synthesis of Compound M2
In a 250mL three-necked flask were added, in order, compound H15.31g (20mmol), 150mL of THF which had been deoxygenated by removal of water, 17.74g (40mmol) of PivOCs, 44.9mg (0.2mmol) of palladium acetate, and PCy356.09mg (0.2mmol) then under N2The reaction was carried out at 120 ℃ for 24 hours under an atmosphere. After cooling to room temperature, the reaction mixture was poured into 200mL of ice water, extracted three times with dichloromethane, the organic phases were combined, spun into silica gel, and subjected to column chromatography (dichloromethane: n-hexane, v: v ═ 1:1) for separation and purification to give compound M2.
MALDI-TOF:684.22.
1H NMR(500MHz,CDCl3):δ8.80(s,1H),8.72(s,1H),8.55(s,1H),8.46(s,1H),8.34(d,J＝14.6Hz,3H),8.19(s,1H),8.16–7.78(m,3H),8.04–7.78(m,4H),7.98–7.69(m,4H),7.52(s,1H),7.40(s,1H),7.16(dd,J＝22.0,14.0Hz,4H).
13C NMR(125MHz,CDCl3):δ170.00(s),167.16(s),150.20(s),143.09(s),142.87(s),141.12(s),140.19(s),139.84–139.48(m),136.19(s),135.38(s),134.16(s),132.71(s),131.41(s),130.32(d,J＝11.4Hz),129.65–129.44(m),128.07(s),127.64(d,J＝17.2Hz),125.67(s),123.80(s),123.57(s),121.15(d,J＝2.7Hz),118.64(s),118.04(s),114.95(s),104.23(s).
Example 3
Synthesis of Compound M3
Synthesis of Compound B
In a 250mL three-necked flask, 9.40g (20mmol) of the substrate A and THF (80mL) were added and dissolved, and nitrogen gas was replaced three times. Cooling to-78 deg.C, controlling temperature below-65 deg.C, slowly adding n-BuLi 20mL (50mmol), stirring for 30 min. 4.35g (40mmol) of TMS-Cl is slowly added dropwise, and the temperature is raised to 0 ℃ for reaction for 4 h. After the reaction is finished, ice water is added for quenching. DCM (80 mL. times.2) was added for extraction. The organic phase was collected and rotary evaporated to give an oil which was crystallised from toluene/EtOH to give a solid. In a 200 mL-stoppered jar were added 9.12g (20mmol) of the solid, an anhydrous toluene solution (70mL) and 2.5g (10mmol) of boron tribromide in that order. Stirring at 120 ℃ for 12 h. After the reaction is finished H2O (100mL) quench. The reaction was extracted with DCM (100 mL. times.3), the organic phase was collected, dried, filtered and the solvent removed by rotary evaporation. Crystallization using DCM/EtOH gave solid B.
MALDI-TOF:401.81
1H NMR(500MHz,CDCl3):δ7.84(s,2H),7.79(d,J＝40.0Hz,2H),7.45(s,2H).
13C NMR(125MHz,CDCl3):δ142.41(s),138.98(s),131.38(s),128.89(s),126.84(s),124.35(s).
Synthesis of Compound D
In a 250mL three-necked flask, 8.01g (20mmol) of the compound B, 8.83g (25mmol) of the compound C, 150mL of toluene freed of water and oxygen, 9.21g (40mmol) of cerium carbonate, 0.23g (0.2mmol) of tetrakis (triphenylphosphine) palladium and 40.5mg (0.2mmol) of tri-tert-butylphosphine were successively added, followed by reaction at 120 ℃ for 24 hours under a nitrogen atmosphere. Cooling to room temperature, pouring the reaction liquid into 200mL of ice water, extracting with dichloromethane three times, combining organic phases, spinning into silica gel, and separating and purifying by column chromatography (dichloromethane: n-hexane, v: v ═ 1:1) to obtain the compound D.
MALDI-TOF:629.15
1H NMR(500MHz,CDCl3):δ8.61(s,1H),8.47(s,1H),8.25(s,1H),8.14(d,J＝12.0Hz,2H),7.97–7.66(m,4H),7.50(d,J＝44.0Hz,3H),7.14(s,2H),7.08–6.86(m,6H).
13C NMR(125MHz,CDCl3):δ146.32(s),143.38(s),142.61(s),142.41(s),141.51(s),138.98(s),137.23(s),135.10(s),132.83(s),131.38(s),131.05(s),128.89(s),128.03(s),126.97(dd,J＝23.3,6.5Hz),126.29(s),124.99(s),124.72(s),124.35(s),123.97(d,J＝11.1Hz),123.45(s),119.67(s),117.60(s),116.20(s).
Synthesis of Compound F
A250 mL three-necked flask was charged with 12.58g (20mmol) of the compound D, 7.18g (25mmol) of the compound E, 150mL of toluene freed of water and oxygen, 9.21g (40mmol) of cerium carbonate, 0.23g (0.2mmol) of tetrakis (triphenylphosphine) palladium and 40.5mg (0.2mmol) of tri-tert-butylphosphine in this order, and then reacted at 120 ℃ for 24 hours under a nitrogen atmosphere. Cooling to room temperature, pouring the reaction liquid into 200mL of ice water, extracting with dichloromethane three times, combining organic phases, spinning into silica gel, and separating and purifying by column chromatography (dichloromethane: n-hexane, v: v ═ 1:1) to obtain the compound F.
MALDI-TOF:792.18.
1H NMR(500MHz,CDCl3):δ8.61(s,1H),8.51(d,J＝32.0Hz,1H),8.36(d,J＝1.3Hz,1H),8.25–8.05(m,3H),7.87(dd,J＝38.0,22.0Hz,5H),7.65–7.33(m,3H),7.29–7.08(m,4H),7.08–6.85(m,4H).
13C NMR(125MHz,CDCl3):δ146.32(s),143.38(s),142.91(s),142.61(s),142.41(s),141.51(s),140.19(s),138.51(s),137.23(s),135.38(s),135.10(s),134.16(s),132.83(s),131.05(s),130.43(d,J＝11.1Hz),128.25(s),128.03(s),127.72(s),127.25–126.77(m),126.29(s),125.67(s),124.99(s),124.72(s),123.97(d,J＝11.1Hz),123.45(s),122.72(s),121.15(d,J＝2.7Hz),119.67(s),118.04(s),117.60(s),116.20(s),114.95(s).
Synthesis of Compound H
Compound F15.83g (20mmol) was charged into a reaction flask, dissolved by adding diethyl ether (50mL), and replaced with nitrogen three times. Cooling to-78 deg.C, controlling temperature below-65 deg.C, slowly adding n-BuLi 8.04mL (2.5M, 20mmol), stirring for 30 min. Then, 7.24G (20mmol) of the monomer G was dissolved in 60mL of toluene, and the solution was slowly added dropwise to the reaction mixture, and the mixture was allowed to naturally warm to room temperature after completion of the dropwise addition and reacted for 6 hours. After the reaction was completed, 100mL of ice water was added to quench the reaction. Then, DCM (80 mL. times.2) was added and the mixture was extracted once with saturated brine. The organic phase was collected and rotary evaporated to give a pale yellow oil. The product was purified by column chromatography (mobile phase n-hexane: dichloromethane ═ 3:1) to give compound H.
MALDI-TOF:992.23.
1H NMR(500MHz,CDCl3):δ8.67–8.34(m,3H),8.28(s,2H),8.23–8.01(m,5H),7.90(t,J＝10.0Hz,6H),7.74(d,J＝24.0Hz,3H),7.48(dd,J＝46.0,18.0Hz,5H),7.27–7.05(m,6H),7.06–6.87(m,6H),6.57(s,1H),6.32(s,1H).
13C NMR(125MHz,CDCl3):δ158.86(s),146.32(s),145.58(s),143.97(s),142.87(s),142.61(s),141.51(s),140.70(s),140.19(s),139.30(s),138.31(d,J＝5.3Hz),136.19(s),135.38(s),135.10(s),134.22(d,J＝12.8Hz),132.77(d,J＝11.1Hz),130.78(s),130.40(d,J＝3.4Hz),128.02(d,J＝2.1Hz),127.66(d,J＝11.7Hz),127.42–126.68(m),125.67(s),124.99(s),124.72(s),123.97(d,J＝11.1Hz),123.41(d,J＝7.3Hz),121.15(d,J＝2.7Hz),119.67(s),118.64(s),118.04(s),117.60(s),117.08(s),116.20(s),114.95(s),104.23(s).
Synthesis of Compound M3
A250 mL three-necked flask was charged with, in order, compound H19.88g (20mmol), 150mL of THF which had been deoxygenated by removal of water, 17.74g (40mmol) of PivOCs, 44.9mg (0.2mmol) of palladium acetate, and PCy356.09mg (0.2mmol) then under N2The reaction was carried out at 120 ℃ for 24 hours under an atmosphere. After cooling to room temperature, the reaction mixture was poured into 200mL of ice water, extracted three times with dichloromethane, the organic phases were combined, spun into silica gel, and subjected to column chromatography (dichloromethane: n-hexane, v: v ═ 1:1) for separation and purification to give compound M3.
MALDI-TOF:912.31.
1H NMR(500MHz,CDCl3):δ8.71–8.40(m,3H),8.29(s,2H),8.26–8.01(m,5H),7.90(t,J＝10.0Hz,6H),7.77(s,1H),7.64–7.32(m,5H),7.28–7.06(m,6H),7.06–6.85(m,6H),6.58(s,1H),6.50(s,1H),6.38(s,1H).
13C NMR(125MHz,CDCl3):δ146.32(s),144.90(s),144.29(s),142.87(s),142.61(s),141.98(s),141.51(s),141.12(s),140.16(s),139.74(s),138.87(s),136.19(s),135.38(s),135.10(s),133.65(s),132.77(d,J＝11.1Hz),131.41(s),131.17(s),130.52(s),129.54(s),127.98(d,J＝9.1Hz),127.64(d,J＝17.2Hz),126.95(d,J＝16.7Hz),126.36(s),125.67(s),124.99(s),124.72(s),124.41(s),124.13–123.69(m),123.45(s),121.15(d,J＝2.7Hz),119.67(s),118.64(s),117.97(s),117.60(s),116.20(s),114.95(s),104.23(s).
Example 4
Synthesis of Compound M4
Synthesis of Compound B
In a 250mL three-necked flask, 9.40g (20mmol) of the substrate A and THF (80mL) were added and dissolved, and nitrogen gas was replaced three times. Cooling to-78 deg.C, controlling temperature below-65 deg.C, slowly adding n-BuLi 20mL (50mmol), stirring for 30 min. 4.35g (40mmol) of TMS-Cl is slowly added dropwise, and the temperature is raised to 0 ℃ for reaction for 4 h. After the reaction is finished, ice water is added for quenching. DCM (80 mL. times.2) was added for extraction. The organic phase was collected and rotary evaporated to give an oil which was crystallised from toluene/EtOH to give a solid. In a 200 mL-stoppered jar were added 9.12g (20mmol) of the solid, an anhydrous toluene solution (70mL) and 2.5g (10mmol) of boron tribromide in that order. Stirring at 120 ℃ for 12 h. After the reaction is finished H2O (100mL) quench. The reaction was extracted with DCM (100 mL. times.3), the organic phase was collected, dried, filtered and the solvent removed by rotary evaporation. Crystallization using DCM/EtOH gave solid B.
MALDI-TOF:401.81
1H NMR(500MHz,CDCl3):δ7.84(s,2H),7.79(d,J＝40.0Hz,2H),7.45(s,2H).
13C NMR(125MHz,CDCl3):δ142.41(s),138.98(s),131.38(s),128.89(s),126.84(s),124.35(s).
Synthesis of Compound D
In a 250mL three-necked flask, 8.01g (20mmol) of the compound B, 8.83g (25mmol) of the compound C, 150mL of toluene freed of water and oxygen, 9.21g (40mmol) of cerium carbonate, 0.23g (0.2mmol) of tetrakis (triphenylphosphine) palladium and 40.5mg (0.2mmol) of tri-tert-butylphosphine were successively added, followed by reaction at 120 ℃ for 24 hours under a nitrogen atmosphere. Cooling to room temperature, pouring the reaction liquid into 200mL of ice water, extracting with dichloromethane three times, combining organic phases, spinning into silica gel, and separating and purifying by column chromatography (dichloromethane: n-hexane, v: v ═ 1:1) to obtain the compound D.
MALDI-TOF:629.15
1H NMR(500MHz,CDCl3):δ8.61(s,1H),8.47(s,1H),8.25(s,1H),8.14(d,J＝12.0Hz,2H),7.95–7.70(m,4H),7.50(d,J＝44.0Hz,3H),7.14(s,2H),7.08–6.82(m,6H).
13C NMR(125MHz,CDCl3):δ146.32(s),143.38(s),142.61(s),142.41(s),141.51(s),138.98(s),137.23(s),135.10(s),132.83(s),131.38(s),131.05(s),128.89(s),128.03(s),126.97(dd,J＝23.3,6.5Hz),126.29(s),124.99(s),124.72(s),124.35(s),123.97(d,J＝11.1Hz),123.45(s),119.67(s),117.60(s),116.20(s).
Synthesis of Compound F
A250 mL three-necked flask was charged with 12.58g (20mmol) of the compound D, 3.12g (25mmol) of the compound E, 150mL of toluene freed of water and oxygen, 9.21g (40mmol) of cerium carbonate, 0.23g (0.2mmol) of tetrakis (triphenylphosphine) palladium, and 40.5mg (0.2mmol) of tri-t-butylphosphine in this order, and then reacted at 120 ℃ for 24 hours under a nitrogen atmosphere. Cooling to room temperature, pouring the reaction liquid into 200mL of ice water, extracting with dichloromethane three times, combining organic phases, spinning into silica gel, and separating and purifying by column chromatography (dichloromethane: n-hexane, v: v ═ 1:1) to obtain the compound F.
MALDI-TOF:628.11.
1H NMR(500MHz,CDCl3):δ8.69(s,1H),8.61(s,1H),8.47(s,1H),8.40(s,1H),8.14(d,J＝12.0Hz,3H),7.88(d,J＝12.0Hz,4H),7.77(s,1H),7.56(s,1H),7.45(s,1H),7.14(s,2H),7.10–6.85(m,6H).
13C NMR(125MHz,CDCl3):δ170.97(s),167.31(s),146.32(s),143.34(d,J＝7.1Hz),142.61(s),142.41(s),141.51(s),137.23(s),135.35(s),135.10(s),133.59(s),132.83(s),131.05(s),128.03(s),127.25–126.77(m),126.25(d,J＝7.7Hz),125.58(s),124.99(s),124.72(s),123.97(d,J＝11.1Hz),123.45(s),119.67(s),117.60(s),116.20(s).
Synthesis of Compound H
Compound F12.59g (20mmol) was charged into a reaction flask, dissolved by adding diethyl ether (50mL), and replaced with nitrogen three times. Cooling to-78 deg.C, controlling temperature below-65 deg.C, slowly adding n-BuLi 8.04mL (2.5M, 20mmol), stirring for 30 min. Then, 9.34G (20mmol) of the monomer G was dissolved in 60mL of toluene, and the solution was slowly added dropwise to the reaction mixture, and the mixture was allowed to naturally warm to room temperature after completion of the dropwise addition and reacted for 6 hours. After the reaction was completed, 100mL of ice water was added to quench the reaction. Then, DCM (80 mL. times.2) was added and the mixture was extracted once with saturated brine. The organic phase was collected and rotary evaporated to give a pale yellow oil. The product was purified by column chromatography (mobile phase n-hexane: dichloromethane ═ 3:1) to give compound H.
MALDI-TOF:935.21.
1H NMR(500MHz,CDCl3):δ8.61(s,2H),8.51(d,J＝32.0Hz,2H),8.24–8.03(m,6H),7.90(s,4H),7.87–7.76(m,4H),7.71(d,J＝1.7Hz,2H),7.54(d,J＝16.0Hz,2H),7.41(t,J＝13.0Hz,4H),7.28–7.09(m,4H),7.09–6.84(m,5H).
13C NMR(125MHz,CDCl3):δ170.97(s),167.31(s),158.86(s),150.60(s),146.38(d,J＝10.7Hz),145.58(s),144.08(s),142.61(s),141.51(s),138.33(d,J＝2.7Hz),137.90(s),135.10(s),134.31(s),132.84(d,J＝3.5Hz),131.98(s),131.63(s),130.78(s),129.66(s),128.44(s),128.02(d,J＝2.1Hz),127.61(s),127.10(dd,J＝28.2,16.5Hz),126.20(s),124.99(s),124.72(s),123.94(dd,J＝22.1,11.0Hz),123.45(s),121.23(s),119.67(s),117.61(d,J＝1.6Hz),117.08(s),116.20(s),109.09(s),86.05(s).
Synthesis of Compound M4
In a 250mL three-necked flask were added, in order, compound H18.73g (20mmol), 150mL of THF which had been deoxygenated by removal of water, 17.74g (40mmol) of PivOCs, 44.9mg (0.2mmol) of palladium acetate, and PCy356.09mg (0.2mmol) then under N2The reaction was carried out at 120 ℃ for 24 hours under an atmosphere. After cooling to room temperature, the reaction mixture was poured into 200mL of ice water, extracted three times with dichloromethane, the organic phases were combined, spun into silica gel, and subjected to column chromatography (dichloromethane: n-hexane, v: v ═ 1:1) for separation and purification to give compound M4.
MALDI-TOF:855.28.
1H NMR(500MHz,CDCl3):δ8.61(s,2H),8.51(d,J＝32.0Hz,2H),8.22–8.08(m,6H),7.99–7.83(m,6H),7.73(d,J＝30.4Hz,2H),7.54(d,J＝16.0Hz,2H),7.40(dd,J＝18.0,10.2Hz,4H),7.27–7.09(m,4H),7.09–6.88(m,6H).
13C NMR(125MHz,CDCl3):δ170.00(s),167.16(s),150.60(s),150.20(s),146.38(d,J＝10.7Hz),144.90(s),144.29(s),142.61(s),141.51(s),139.69(s),138.87(s),137.90(s),136.30(s),135.10(s),132.83(s),131.41(s),131.14(d,J＝5.9Hz),130.26(s),127.98(d,J＝9.1Hz),127.09(dd,J＝26.5,14.8Hz),126.28(d,J＝15.4Hz),124.99(s),124.72(s),123.94(dd,J＝21.7,10.6Hz),123.45(s),121.23(s),119.67(s),117.61(d,J＝1.6Hz),116.20(s),109.09(s),86.05(s).
Example 5
The electroluminescent properties of exemplary boron heterocyclic compounds M1, M2, M3, and M4 described herein were simulated using Gaussian software.
FIGS. 2 and 3 show the HOMO and LUMO energy level diagrams of an exemplary boron heterocyclic compound M1 of the present invention, respectively, it is evident from FIGS. 2 and 3 that the arrangement of the HOMO and LUMO of compound molecule M1 on the donor and acceptor units, respectively, results in a complete separation of the HOMO and LUMO, which helps to reduce the energy difference between the systems △ ESTThereby improving the capability of crossing between the inversed systems.
The HOMO, LUMO and other parameters of the boron heterocyclic compounds M1, M2, M3 and M4 were tested, and the results obtained are shown in table 1.
TABLE 1 parameters of four representative boron heterocyclic compounds
As can be seen from Table 1, the boron heterocyclic compounds of the present invention have very little △ ESTThe energy level difference between the singlet and triplet states is small (△ E)ST) The efficient photophysical process of reverse intersystem crossing between the singlet state and the triplet state can utilize the jump of the traditional fluorescent moleculesThe triplet excitons which are forbidden to be transferred emit light, thereby improving the efficiency of the device.
Another aspect of the present invention provides a display panel comprising an organic light emitting device comprising an anode, a cathode, and a light emitting layer between the anode and the cathode, wherein a light emitting material of the light emitting layer comprises one or more of the boron heterocyclic compounds described in the present invention.
According to one embodiment of the display panel of the present invention, the light emitting material of the light emitting layer includes a host material and a guest material, wherein the host material is one or more of the compounds of the present invention.
According to one embodiment of the display panel of the present invention, the organic light emitting device further includes one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, or an electron injection layer. The better light emitting performance of the device requires reasonable matching of the light emitting function layers. Thus, different organic light emitting functional layers may be selected according to different display requirements and selected compounds.
In one embodiment of the display panel according to the present invention, the structure of an Organic Light Emitting Device (OLED) is as shown in fig. 4. Wherein 1 is a substrate (substrate) made of glass or other suitable materials (such as plastics); 2 is a transparent anode such as ITO or IGZO; 3 is an organic film layer (including a luminescent layer); and 4, metal cathodes which jointly form a complete OLED device.
In the display panel provided by the present invention, the anode material of the organic light emitting device may be selected from metals such as copper, gold, silver, iron, chromium, nickel, manganese, palladium, platinum, and the like, and alloys thereof. The anode material may also be selected from metal oxides such as indium oxide, zinc oxide, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), and the like; the anode material may also be selected from conductive polymers such as polyaniline, polypyrrole, poly (3-methylthiophene), and the like. In addition, the anode material may be selected from materials that facilitate hole injection in addition to the listed anode materials and combinations thereof, including known materials suitable for use as anodes.
In the invention providedIn the display panel, a cathode material of the organic light emitting device may be selected from metals such as aluminum, magnesium, silver, indium, tin, titanium, etc., and alloys thereof. The cathode material may also be selected from multi-layered metallic materials such as LiF/Al, LiO2/Al、BaF2Al, etc. In addition to the cathode materials listed above, the cathode materials can also be materials that facilitate electron injection and combinations thereof, including materials known to be suitable as cathodes.
In the display panel of the present invention, the organic light emitting device may be fabricated by: an anode is formed on a transparent or opaque smooth substrate, an organic thin layer is formed on the anode, and a cathode is formed on the organic thin layer. The organic thin layer can be formed by a known film formation method such as evaporation, sputtering, spin coating, dipping, ion plating, or the like.
Examples 6 and 7 below provide illustrative examples for illustrating the practical use of the boron heterocyclic compounds of the present invention in organic inventive display panels.
Example 6
The manufacturing steps of the organic light-emitting device are as follows:
the anode substrate having an ITO thin film with a film thickness of 100nm was ultrasonically cleaned with distilled water, acetone, isopropyl alcohol and placed in an oven to be dried, the surface was treated by UV for 30 minutes, and then moved to a vacuum evaporation chamber. Under vacuum degree of 2X 10-6The evaporation of the films was started under Pa, PSS of 5nm thickness was evaporated to form a hole injection layer, PEDOT of 40nm thickness was evaporated, and TAPC of 20nm thickness was evaporated to form a Hole Transport Layer (HTL). On the hole transport layer, the compound M1 of the present invention was used as a dopant of the light-emitting layer, and 3,3 '-bis (N-carbazolyl) -1,1' -biphenyl (mCBP) was used as a host of the light-emitting layer, and the dopant and the host were simultaneously deposited to form a light-emitting layer having a thickness of 35 nm. Then, TmPyPb was deposited on the light-emitting layer to form an Electron Transport Layer (ETL) of 50 nm. LiF with the thickness of 2.5nm and Al with the thickness of 100nm are sequentially evaporated on the electron transport layer to be used as an Electron Injection Layer (EIL) and a cathode, so that the organic light-emitting device is manufactured.
Example 7
Taking the boron heterocyclic compound M1 of the present invention as an example, the following light-emitting device D1 was designed using it as a fluorescent dopant. The structure of the light emitting device D1 is as follows:
ITO(100nm)/PEDOT:PSS(40nm)/TAPC(20nm)/mCBP:M1(35nm,8％)/TmPyPb(50nm)/LiF(2.5nm)/Al(100nm)。
light-emitting devices D2, D3, and D4 were designed by replacing the fluorescent dopant boron heterocyclic compound M1 in the above light-emitting device with the boron heterocyclic compounds M2, M3, and M4 of the present invention on the basis of the structure of the above light-emitting device.
TABLE 2 measurement results of luminescent properties of devices
Vturn-on: starting voltage; eL(10mA/cm 2 ): the current density is 10mA/cm2Current efficiency of time; h isp(max): maximum power efficiency; EQE(max)：EQE(max): external Quantum Efficiency (External Quantum Efficiency); CIE (x, y): color coordinates
As can be seen from Table 2, the OLED devices using the boron heterocyclic compounds M1, M2, M3 and M4 of the present invention have high External Quantum Efficiency (EQE), and the maximum of them can reach 19.4%. Compared with the comparative example, the structure of the boron heterocyclic compound of the present invention has TADF characteristics, and when it is used in an organic light emitting device, it can emit light using triplet excitons which are conventionally fluorescent molecular transition forbidden, thereby improving device efficiency. Meanwhile, the boron heterocyclic compound disclosed by the invention has a bipolar characteristic, and can be used as a material of a light-emitting layer to greatly improve the transmission capability of two carriers, improve the carrier balance and improve the external quantum efficiency of fluorescence.
Still another aspect of the present invention also provides a display device including the organic light emitting display panel as described above.
In the present invention, the organic light emitting device may be an OLED, which may be used in an organic light emitting display device, wherein the organic light emitting display device may be a display screen of a mobile phone, a display screen of a computer, a display screen of a television, a display screen of a smart watch, a display panel of a smart car, a display screen of a VR or AR helmet, a display screen of various smart devices, and the like. Fig. 5 is a schematic diagram of a display device according to an embodiment of the present invention. In fig. 5, 10 denotes a display panel of a cellular phone, and 20 denotes a display device.
Although the present application has been described with reference to preferred embodiments, it is not intended to limit the scope of the claims, and many possible variations and modifications may be made by one skilled in the art without departing from the spirit of the application.
Claims (25)
1. A compound having a structure represented by chemical formula 1:
wherein L is1、L2And L3Each independently selected from a single bond, a C6-C30 aromatic or fused aryl, a C4-C30 heteroaryl or fused heteroaryl;
R1、R2and R3At least one is an electron donating group and at least one is an electron accepting group;
wherein the electron donating group is selected from C1-C20 alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted acenaphthylene, substituted or unsubstituted pyrenylSubstituted or unsubstituted perylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted spirobifluorenylAny one of a group, a substituted or unsubstituted benzophenanthryl group, a substituted or unsubstituted benzanthracene group, a substituted or unsubstituted fluoranthene group, a substituted or unsubstituted picene group, a substituted or unsubstituted furyl group, a substituted or unsubstituted benzofuryl group, a substituted or unsubstituted dibenzofuryl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted benzothienyl group, a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted phenazinyl group, a substituted or unsubstituted phenothiazinyl group, a substituted or unsubstituted thianthrenyl group, a carbazolyl group and a derivative group thereof, an acridinyl group and a derivative group thereof, a diarylamine group and a derivative group thereof;
the electron-accepting group is selected from nitrogen-containing heterocyclic substituent, cyanogen-containing substituent, carbonyl-containing substituent, sulfone substituent and phosphine-oxygen-containing substituent.
2. The compound of claim 1, wherein the compound has the structure of formula 2:
3. the compound of claim 1, wherein L is1、L2And L3Each independently selected from phenyl, naphthyl, anthryl, phenanthryl, pyridyl, furyl, pyrimidinyl.
4. The compound of claim 1, wherein L is1、L2And L3The same is true.
5. The compound of claim 1The compound is characterized in that R1、R2And R3Wherein two groups are the same.
6. A compound according to any one of claims 1 to 5, wherein R is1、R2And R3Each independently selected from any one of the following groups:
z is selected from a C atom, a N atom, an O atom or an S atom; q is selected from 0, 1 or 2;
U1、U2and U3Each independently selected from a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group;
when Z is an oxygen atom or a sulfur atom, q is 0;
# denotes the ligation site.
7. A compound of claim 6, wherein R is1、R2And R3Each independently selected from any one of the following groups:
8. a compound according to any one of claims 1 to 5, wherein R is1、R2And R3Each independently selected from any one of the following groups:
z is selected from a C atom, a N atom, an O atom, an S atom or a Si atom; x is selected from a C atom, a N atom, an O atom or an S atom; m, n, p and q are each independently selected from 0, 1 or 2;
U1、U2、U3、U4each independently selected from hydrogen atom, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C6-C12 aryl;
when X is an oxygen atom or a sulfur atom, q is 0; when Z is an oxygen atom or a sulfur atom, p is 0;
# denotes the ligation site.
9. A compound of claim 8, wherein R is1、R2And R3Each independently selected from any one of the following groups:
wherein R and R' are independently selected from hydrogen atom, C1-C3 alkyl and phenyl.
10. A compound according to any one of claims 1 to 5, wherein R is1、R2And R3Each independently selected from any one of the following groups:
U1、U2each independently selected from a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group; m and n are independently selected from 0, 1 or 2;
# denotes the ligation site.
11. The compound of claim 10, wherein R is1、R2And R3Each independently selected from any one of the following groups:
where, # denotes the ligation position.
12. According to the rightA compound according to any one of claims 1 to 5, wherein R is1、R2And R3Each independently selected from any one of the following groups:
x is selected from O atom or S atom; m and n are each independently selected from 0, 1 or 2;
U1and U2Each independently selected from a hydrogen atom, a C1-C6 alkyl group, a C3-C6 cycloalkyl group, a C1-C6 alkoxy group;
# denotes the ligation site.
13. The compound of claim 12, wherein R is1、R2And R3Each independently selected from any one of the following groups:
# denotes the ligation site.
14. A compound according to any one of claims 1 to 5, wherein the nitrogen-containing heterocyclic group is selected from any one of the following groups:
wherein, # denotes the attachment position in chemical formula 1;
r is selected from hydrogen atom, C1-C20 alkyl, C1-C20 alkoxy, C4-C8 cycloalkyl, C6-C40 aryl and C4-C40 heteroaryl.
15. The compound of any one of claims 1 to 5, wherein the cyano-containing group is selected from any one of the following groups:
wherein, # denotes the attachment position in chemical formula 1.
16. The compound of any one of claims 1 to 5, wherein the carbonyl-containing group is selected from any one of the following groups:
wherein, # denotes the linking position in chemical formula 1, and R denotes C1-C20 alkyl, C1-C20 alkoxy, C2-C20 alkenyl, C2-C20 alkynyl, C4-C8 cycloalkyl, C6-C40 aryl, C4-C40 heteroaryl.
17. The compound of any one of claims 1 to 5, wherein the sulfone-containing group is selected from any one of the following groups:
18. a compound according to any one of claims 1 to 5, wherein the phosphino-containing group is selected from any one of the following groups:
the X is selected from O, S, -BR41、-C(R41)2、-Si(R41)2and-NR41Any one of the above;
the R is30、R31、R32、R33、R34、R35、R36、R37、R38、R39、R40、R41Each independently selected from hydrogen atom, substitutedOr any one of unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C3-C20 heterocyclic group, substituted or unsubstituted C6-C40 aryl and substituted or unsubstituted C2-C40 heteroaryl;
# denotes the attachment position in chemical formula 1.
19. The compound of claim 1, wherein L is1、L2And L3Each independently selected from the group consisting of:
R1、R2and R3One or both of which are each independently selected from one of the following electron donating groups:
wherein, U1、U2And U3Each independently selected from C1-C3 alkyl, C6-C12 aryl; m and n are 0, p is 0, 1 or 2;
z is selected from C atom, N atom, O atom or S atom, when Z is oxygen atom or sulfur atom, p is 0;
# denotes the linkage position in chemical formula 1;
and R is1、R2And R3One or two of which are each independently selected from cyano or s-triazinyl.
20. The compound of claim 1, wherein the compound is selected from any one of the following compounds:
21. the compound of any one of claims 1 to 20, wherein the energy level difference Δ Ε between the lowest singlet energy level S1 and the lowest triplet energy level T1 is the compoundST＝ES1-ET1≦0.25eV。
22. A display panel comprising an organic light emitting device comprising an anode, a cathode, a light emitting layer between the anode and the cathode, wherein the light emitting material of the light emitting layer comprises one or more of the compounds of any one of claims 1 to 21.
23. The display panel according to claim 22, wherein a host material or a guest material of the light-emitting layer is one or more compounds according to any one of claims 1 to 21.
24. The display panel according to claim 22 or 23, wherein the display panel further comprises one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, or an electron injection layer.
25. A display device comprising the display panel of any one of claims 22 to 24.
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| CN110003254A (en) * | 2018-01-05 | 2019-07-12 | 北京夏禾科技有限公司 | The heterocyclic compound of boracic and nitrogen |
| CN108409762A (en) * | 2018-02-07 | 2018-08-17 | 瑞声科技（南京）有限公司 | A kind of luminous organic material and its application by energy resonance formation |
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