CN114560880A - Organic thermal activation delayed fluorescent material constructed by phenolic oxygen-pyridine chelating boron difluoride receptor and application thereof - Google Patents
Organic thermal activation delayed fluorescent material constructed by phenolic oxygen-pyridine chelating boron difluoride receptor and application thereof Download PDFInfo
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- CN114560880A CN114560880A CN202210204059.7A CN202210204059A CN114560880A CN 114560880 A CN114560880 A CN 114560880A CN 202210204059 A CN202210204059 A CN 202210204059A CN 114560880 A CN114560880 A CN 114560880A
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
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- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
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Abstract
The invention provides an organic thermal activation delayed fluorescence material constructed by a phenol oxygen-pyridine chelating boron difluoride receptor and application thereof, wherein a donor-acceptor framework can realize smaller HOMO and LUMO overlapping and reduce delta ES1‑T1The method is favorable for improving the speed of reverse intersystem crossing and realizing high-efficiency light emission. The heat activation delayed fluorescence material is shown as a general formula (1) or (2):
Description
Technical Field
The invention relates to a thermal activation delayed fluorescence material and application thereof, belongs to the field of organic luminescent materials, and particularly relates to a thermal activation delayed fluorescence organic luminescent material containing a phenol oxygen-pyridine chelating boron difluoride acceptor structural unit, and an organic electroluminescent device containing the thermal activation delayed fluorescence organic luminescent material.
Background
Organic Light-Emitting diodes (OLEDs) have been developed in a rapid manner in recent years, and compared to LCD display technologies, OLEDs have the following advantages: the LED lamp can emit light autonomously without a backlight source, and is energy-saving; can be folded or bent; the response speed is high, and the contrast is high; the working temperature range is wide; low material cost, high luminous efficiency and the like. The OLED has become a new generation of full-color Display and illumination technology, and is widely regarded by academia and industry, and is widely applied in the fields of flat panel Display, solid illumination, military and aerospace, and is expected to replace Liquid Crystal Display (LCD) in the future. In the early development stage of the OLED, the traditional organic small-molecule fluorescent material is mainly adopted, and the material has good device stability. However, it can theoretically utilize only 25% of singlet excitons at most, and the remaining 75% of triplet excitons can be deactivated only by non-radiative transition due to the transition forbidden resistance, limiting their application in OLEDs. The spin orbit coupling effect (SOC) of heavy metal of the second generation phosphorescent material can break the triplet state transition forbidden resistance, can effectively promote electrons to cross from a singlet state to a triplet state, and fully utilizes all singlet state and triplet state excitons generated by electric excitation, so that the maximum theoretical quantum efficiency of the second generation phosphorescent material reaches 100%. The phosphorescent material usually needs to introduce extremely expensive rare heavy metal, the preparation cost is high, and the precious metal reserves are limited, so that the development of second-generation OLED devices is restricted. Then, professor Adachi of Kyushu university in Japan synthesizes a series of Thermally Activated Delayed Fluorescence (TADF) materials for giving acceptor frameworks, and the donor-acceptor molecular design can realize the spatial separation of HOMO and LUMO, achieve smaller HOMO and LUMO overlapping and have smaller singlet state and triplet state energy level difference delta ES1-T1. Reverse intersystem crossing (RISC) from a lowest triplet excited state (T1) to a lowest singlet excited state (S1) can be realized under the excitation of heat in the surrounding environment, so that triplet excitons are effectively utilized to generate delayed fluorescence, and the theoretical internal quantum efficiency can also reach 100%. The TADF material has the greatest advantage that the TADF material adopts pure organic materials, thereby avoiding using materials containing precious materialsThe metal organic complex of metal has great application prospect in the field of OLED, and the OLED based on TADF has made great progress. However, the design of highly efficient TADF materials with long life and high brightness is still challenging, and organoboron compounds, which have unique optical and electronic properties, are widely studied and used as organic optoelectronic materials, are expected to realize highly efficient and stable luminescence, and solve the above problems. Meanwhile, the design and development of novel efficient blue-light thermally-induced delayed fluorescence materials are also important problems in the field of OLED.
Disclosure of Invention
The invention aims to provide a donor-receptor type thermal activation delayed fluorescence material constructed based on a phenoloxy-pyridine chelating boron difluoride receptor structural unit, and the material can be used in the fields of OLED display and illumination.
The compound is characterized in that the chemical formula is shown as a general formula (1) or (2):
wherein,
in the formula (1), Ra1、Rb1Each independently of the others is hydrogen, deuterium, C1-C24Alkyl of (C)1-C24Alkoxy group of (C)3-C24Cycloalkyl of, C1-C24Ether of (C)1-C24Heterocyclic group of (A), C4-C24Aryl of (C)4-C24Aryloxy, halogen, mono-or dialkylamino, mono-or diarylamino, cyano, or a combination thereof;
m1、n1are each Ra1And Rb1The number of (2); wherein m is1Is an integer of 0 to 4, n1Is an integer of 0 to 3;
in the formula (2), Ra2、Rb2Each independently of the other is hydrogen, deuterium, C1-C24Alkyl of (C)1-C24Alkoxy group of (C)3-C24Cycloalkyl of, C1-C24Ether of (C)1-C24A heterocyclic group of,C4-C24Aryl of (C)4-C24Aryloxy, halogen, mono-or dialkylamino, mono-or diarylamino, cyano, or a combination thereof;
m2、n2are each Ra2And Rb2The number of (2); m is2Is an integer of 0 to 4, n2Is an integer of 0 to 3;
donor D1、D2Each independently is one of the following structures:
wherein,
R1、R2、R3、R4、R7、R8、R10、R11、R12、R13、R14and R15Each independently of the others is hydrogen, deuterium, C1-C24Alkyl of (C)1-C24Alkoxy group of (C)3-C24Cycloalkyl of, C1-C24Ether of (C)1-C24Heterocyclic group of (A), C4-C24Aryl of (C)4-C24Aryloxy, halogen, silicon, mono-or dialkylamino, mono-or diarylamino, cyano, or a combination thereof, wherein two adjacent substituents can be fused to form a ring;
o1、p1、q1、r1、s1、t1、u1、v1、w1、x1、y1and z1Are each R1、R2、R3、R4、R7、R8、R10、R11、R12、R13、R14And R15The number of (2);
o1and p1Is an integer of 0 to 5; q. q of1、r1、s1、t1、u1、v1、w1、x1、y1And z1Is an integer of 0 to 4.
Further, the structural formula of the thermally activated delayed fluorescence material may preferably be as shown in (3) and (4):
wherein,
in the formula (3), Ra3、Rb3Each independently of the others is hydrogen, deuterium, C1-C24Alkyl of (C)1-C24Alkoxy group of (C)3-C24Cycloalkyl of, C1-C24Ether of (C)1-C24Heterocyclic group of (A), C4-C24Aryl of (C)4-C24Aryloxy, halogen, mono-or dialkylamino, mono-or diarylamino, cyano, or combinations thereof;
m3、n3are each Ra3And Rb3The number of (2); wherein m is3Is an integer of 0 to 4, n3Is an integer of 0 to 3;
in the formula (4), Ra4、Rb4Each independently of the others is hydrogen, deuterium, C1-C24Alkyl of (C)1-C24Alkoxy group of (C)3-C24Cycloalkyl of, C1-C24Ether of (C)1-C24Heterocyclic group of (2), C4-C24Aryl of (C)4-C24Aryloxy, halogen, mono-or dialkylamino, mono-or diarylamino, cyano, or a combination thereof;
m4、n4are each Ra4And Rb4The number of (2); m is a unit of4Is an integer of 0 to 4, n4Is an integer of 0 to 3;
said donor D3Is one of the following structures:
wherein,
R1'、R2'、R3'、R4'、R7'、R8'、R10'、R11'、R12'、R13'、R14'and R15'Each independently of the other being hydrogen, deuterium, C1-C24Alkyl of (C)1-C24Alkoxy group of (C)3-C24Cycloalkyl of, C1-C24Ether of (C)1-C24Heterocyclic group of (A), C4-C24Aryl of (C)4-C24Aryloxy, halogen, silicon, mono-or dialkylamino, mono-or diarylamino, cyano, or a combination thereof, wherein two adjacent substituents can be fused to form a ring;
o2、p2、q2、r2、s2、t2、u2、v2、w2、x2、y2and z2Are each R1’、R2’、R3’、R4’、R7’、R8’、R10’、R11’、R12’、R13’、R14’And R15’The number of (2);
o2and p2Is an integer of 0 to 5; q. q.s2、r2、s2、t2、u2、v2、w2、x2、y2And z2Is an integer of 0 to 4.
Further, the thermally activated delayed fluorescence material of the present invention is preferably of one of the following structures:
the term "heteroaryl" as used herein includes azetidinyl, dioxanyl, furyl, imidazolyl, isothiazolyl, isoxazolyl, morpholinyl, oxazolyl (1,2, 3-oxadiazolyl, 1,2, 5-oxadiazolyl and 1,3, 4-oxadiazolyl) piperazinyl, piperidinyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridinyl, pyrimidinyl, pyrrolyl, pyrrolidinyl, tetrahydrofuryl, tetrahydropyranyl, 1,2,4, 5-tetrazinyl, 1,2,3, 4-tetrazolyl, 1,2,4, 5-tetrazolyl, 1,2, 3-thiadiazolyl, 1,2, 5-thiadiazolyl, 1,3, 4-thiadiazolyl, thiazolyl, thienyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazolyl, 1,3, 4-triazolyl and the like.
The term "silyl" as used herein, is defined by the formula-SiR1R2R3Is represented by the formula (I) in which R1,R2And R3And may independently be hydrogen or an alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
"R" used in the present inventiona1,”“Ra2,”“Ra3,”“Ran"(wherein n is an integer) may independently have one or more of the groups listed. For example, if R1Being a straight chain alkyl, then one hydrogen atom of the alkyl group may be optionally substituted with hydroxyl, alkoxy, alkyl, halogen, and the like. Depending on the group selected, the first group may be incorporated within the second group, or alternatively, the first group may be pendent (i.e., attached) to the second group.
The compounds of the present invention may contain "optionally substituted" moieties. Generally, the term "substituted" (whether or not the term "optionally" is present above) means that one or more hydrogens of the indicated moiety are replaced with a suitable substituent. Unless otherwise specified, an "optionally substituted" group may have suitable substituents at each substitutable position of the group, and when more than one position may be substituted with more than one substituent selected from a specified group in any given structure, the substituents at each position may be the same or different. The combinations of substituents contemplated by the present invention are preferably those that form stable or chemically feasible compounds. In certain aspects, it is also contemplated that each substituent may be further optionally substituted (i.e., further substituted or unsubstituted), unless clearly indicated to the contrary.
The structure of the compound can be represented by the following formula:
it is understood to be equivalent to the following formula:
where m is typically an integer. Namely, RaIs understood to mean five individual substituents Ra(1),Ra(2),Ra(3),Ra(4),Ra (5). By "individual substituents" is meant each RaThe substituents may be independently defined. For example, if in one instance Ra(1)Is halogen, then in this case Ra(2)Not necessarily halogen.
In the present invention, the thermally activated delayed fluorescence material based on the boron difluoride acceptor building block containing a phenolic oxy-pyridine chelate is electrically neutral.
The thermal activation delayed fluorescence material containing the phenoloxy-pyridine chelated boron difluoride acceptor structural unit provided by the invention can be used for multiple purposes, can be used as a luminescent material of an organic electroluminescent device, can also be used as a main body material or other functional layer materials, and can be applied to full-color displays, illuminating devices and the like.
The invention relates to an optical or electro-optical device comprising one or more of the thermally activated delayed fluorescence materials described above comprising a phenoloxy-pyridine chelating boron difluoride acceptor building block.
Compared with the prior art, the invention has the beneficial effects that:
phenoxy-pyridine chelating difluorideAccording to the TADF material of the boron acceptor structural unit, a boron atom is firstly connected with a phenol group, and an empty p orbit is coordinated with a lone pair of electrons on a pyridine N atom to form a stable four-coordination structure. The tetra-coordinated boron compounds have good chemical and thermal stability, especially for compounds containing B-O and B-F bonds due to their high bond dissociation energy (536 and 613kJ/mol, respectively). The phenol-based chelating boron difluoride is coordinated with pyridine, electrons are delocalized to a whole conjugated system, pi electron accepting capacity of the pyridine is improved, and then an electron donating group with the pi conjugated system is introduced to construct a molecule with a donor-acceptor structure, so that Intramolecular Charge Transfer (ICT) is promoted, and a TADF effect is obtained. In addition, a rigid pi conjugated skeleton of a parallel-ring structure can be formed, energy loss caused by vibration coupling can be effectively inhibited, and luminous quantum efficiency is improved. The introduction of substituent between the electron acceptor and the donor can effectively adjust the dihedral angle between the donor and the acceptor, and break conjugation to realize blue shift of spectrum. And can realize the separation of HOMO and LUMO to different degrees, and can obtain smaller Delta ES1-T1And TADF luminescence is realized. The TADF material of the phenoloxy-pyridine chelated boron difluoride acceptor structural unit has strong luminous efficiency and high carrier mobility, the photoelectric property of the TADF material strongly depends on the property of a ligand, the photophysical property of the TADF material can be effectively regulated and controlled through the design of the ligand, and the TADF material is a promising luminous material.
Drawings
FIG. 1 shows the emission spectra of the luminescent materials p-Cz-BF2, p-tBuCz-BF2, p-PhCz-BF2, p-DMAC-BF2, p-DPA-BF2, p-PTZ-BF2, p-PXZ-BF2, m-Cz-BF2 and m-PhCz-BF2 in toluene solution at room temperature.
FIG. 2 is an emission spectrum diagram of DEPEO films of luminescent materials p-Cz-BF2, p-tBuCz-BF2, p-PhCz-BF2, p-DMAC-BF2, p-DPA-BF2, p-PTZ-BF2, p-PXZ-BF2, m-Cz-BF2 and m-PhCz-BF2 at room temperature.
FIG. 3 is a DEPEO film luminescence decay (normalized luminescence intensity versus time) curve for the luminescent materials p-Cz-BF2, p-tBuCz-BF2, p-PhCz-BF2, p-DMAC-BF2, p-DPA-BF2, p-PTZ-BF2, p-PXZ-BF2, m-Cz-BF2, and m-PhCz-BF 2.
FIG. 4 is the electroluminescence spectrum of the device with the luminescent material p-Cz-BF2 as the luminophor in different proportions of the double-host material and with different doping of the electron transport material.
FIG. 5 is a graph of current density-voltage-luminous intensity of a device using the luminescent material p-Cz-BF2 as a luminophore in different proportions of the dual host material and with different doping of the electron transport material.
FIG. 6 is a plot of external quantum efficiency versus current density for a device with the luminescent material p-Cz-BF2 as a luminophore in different ratios of the dual host material and with different doping of the electron transport material.
FIG. 7 is a device electroluminescence spectrum diagram of a luminescent material m-PhCz-BF2 as a luminescent body under different functional layer thicknesses.
FIG. 8 is a device current density-voltage-luminous intensity curve of a luminescent material m-PhCz-BF2 as a luminescent body under different functional layer thicknesses.
FIG. 9 is the device external quantum efficiency-current density curve of luminescent material m-PhCz-BF2 as a luminescent body under different functional layer thicknesses.
Detailed Description
The following examples, which are merely exemplary of the present disclosure and are not intended to limit the scope thereof, provide those of ordinary skill in the art with a description of how to make and evaluate the compounds described herein and their OLED devices. Although efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), some errors and deviations should be accounted for. Unless otherwise specified, temperature is in units of ° c or at ambient temperature, and pressure is at or near atmospheric pressure.
The methods described in this example for the preparation of the disclosed compounds described herein are one of many and many others are possible and are not intended to limit the scope of the present application. Thus, one skilled in the art to which this disclosure pertains can readily modify the methods described or utilize different methods to prepare one or more of the disclosed compounds. The following methods are exemplary only, and the temperature, catalyst, concentration, reactant composition, and other process conditions may be varied, and one skilled in the art to which this disclosure pertains may readily select appropriate reactants and conditions for the preparation of the desired compound.
Performed on a Varian Liquid State NMR instrument1H and13c NMR spectrum test. The solvent is CDCl3Or DMSO-d6. If tetramethylsilane is an internal standard in the solvent, reference is made to tetramethylsilane (δ 0.00 ppm); otherwise, if CDCl is used3Is a solvent, and is prepared by mixing the components,1chemical shifts of H NMR spectra were referenced to residual solvent (δ ═ 7.26 ppm); if DMSO-d is used6Is a solvent, and is prepared by mixing the components,1chemical shift of H NMR spectrum is compared with residual solvent H2O (δ — 3.33 ppm). The nuclear magnetic data in the examples are explained using the following abbreviations (or combinations thereof)1Multiplicity of H NMR: s is singleplex, d is doublet, t is triplet, q is quartet, p is quintuple, m is multiplet, br is wide.
Preparation examples
Example 1: the luminescent material p-Cz-BF2 can be synthesized by the following route:
synthesis of intermediate p-Cz-OMe: 1-Br (2.10g,7.95mmol,1.0 equiv.), carbazole (1.60g,9.54mmol,1.2 equiv.), sodium tert-butoxide (1.91g,19.88mmol,2.5 equiv.), Pd were added in this order in a 100mL three-necked flask2(dba)3(220mg,0.24mmol,0.03 eq.) and XPhos (229mg,0.48mmol,0.06 eq.), then the nitrogen was purged three times, toluene (35mL) was added by injection and reacted for 70 hours in a 120 ℃ oil bath. Cooling the reaction to room temperature, adding water for quenching, extracting for three times by ethyl acetate, combining organic phases, drying by anhydrous sodium sulfate, filtering, distilling under reduced pressure to remove the solvent, and separating a crude product by silica gel column chromatography, wherein an eluent: petroleum ether/ethyl acetate 20:1-5:1 gave 2.63g of a yellow-brown solid in 94% yield.1H NMR(500MHz,CDCl3)δ3.90(s,3H),7.23(d,J＝2.0Hz,1H),7.28-7.37(m,4H),7.43-7.46(m,2H),7.53(d,J＝8.5Hz,2H),7.82-7.87(m,1H),7.97(dt,J＝8.0,1.0Hz,1H),8.04(d,J＝8.0Hz,1H),8.16(dt,J＝8.0,1.0Hz,2H),8.80(d,J＝4.5Hz,1H)。
And (3) synthesizing an intermediate p-Cz-OH: to a dry 250mL three-necked flask was added p-Cz-OMe (2.98g,8.51mmol,1.0 eq.), dry dichloromethane (100 mL). Boron tribromide (1.61mL,17.03mmol,2.0 equiv) was then added dropwise at-15 ℃ and the reaction was allowed to warm to room temperature and stirred for 10 hours. Quenching sodium bicarbonate solution, extracting with dichloromethane for three times, combining organic phases, drying with anhydrous sodium sulfate, filtering, distilling under reduced pressure to remove solvent, separating crude product by silica gel column chromatography, eluting with eluent: petroleum ether/dichloromethane ═ 20:1 to 5:1, 1.82g of yellow solid were obtained in 64% yield.1H NMR(500MHz,DMSO-d6)δ7.17(d,J＝2.0Hz,1H),7.20(dd,J＝8.5,2.0Hz,1H),7.30-7.33(m,2H),7.45-7.54(m,5H),8.10(td,J＝8.0,2.0Hz,1H),8.26(d,J＝7.7Hz,2H),8.33(d,J＝8.5Hz,2H),8.70(dd,J＝5.0,1.0Hz,1H),14.58(s,1H)。
Synthesis of luminescent Material p-Cz-BF 2: in a dry 250mL three-necked flask was added p-Cz-OH (1.82g, 5.41mmol,1.0 equiv.), dichloromethane (100mL), then boron trifluoride diethyl ether (6.8mL, 54.1mmol,10 equiv.) was added at-15 deg.C, the mixture was allowed to stir at room temperature for 10 hours, and then N, N-diisopropylethylamine (14.2mL, 81.15mmol,15 equiv.) was added and the reaction was continued for 11 hours. After the reaction is finished, quenching the mixture by using a sodium carbonate solution, extracting the mixture for three times by using dichloromethane, combining organic phases, drying the organic phases by using anhydrous sodium sulfate, filtering the mixture, distilling the mixture under reduced pressure to remove a solvent, and separating a crude product by using a silica gel column chromatography to obtain an eluent: petroleum ether/dichloromethane ═ 5:1 to 1:3, 1.75g of a yellow-green solid was obtained in 84% yield.1H NMR(500MHz,DMSO-d6)δ7.32-7.35(m,2H),7.39(d,J＝2.0Hz,1H),7.43(dd,J＝8.5,2.0Hz,1H),7.47-7.50(m,2H),7.57(d,J＝8.0Hz,2H),7.90-7.93(m,1H),8.27(dt,J＝8.0,1.0Hz,2H),8.52(d,J＝8.5Hz,1H),8.54-8.58(m,1H),8.71(d,J＝8.5Hz,1H),8.83(d,J＝6.0Hz,1H)。
Example 2: the luminescent material p-PhCz-BF2 can be synthesized by the following route:
synthesis of intermediate p-PhCz-OMe: 1-Br (2.0g,7.57mmol,1.0 eq.) and benzene were added sequentially in a 100mL three-necked flaskCarbazole (2.66g,8.33mmol,1.1 equiv.), sodium tert-butoxide (1.82g,18.93mmol,2.5 equiv.), Pd2(dba)3(208mg,0.23mmol,0.03 equiv.) and XPhos (217mg,0.45mmol,0.06 equiv.), then nitrogen was purged three times, toluene (40mL) was added by injection, and the reaction was carried out in an oil bath at 125 ℃ for 72 hours. Cooling the reaction to room temperature, adding water for quenching, extracting for three times by ethyl acetate, combining organic phases, drying by anhydrous sodium sulfate, filtering, distilling under reduced pressure to remove the solvent, and separating a crude product by silica gel column chromatography, wherein the eluent comprises the following components: petroleum ether/dichloromethane ═ 20:1-1:1, 2.76g of a brown solid were obtained in 73% yield.1H NMR(400MHz,CDCl3)δ3.93(s,3H),7.28(d,J＝2.0Hz,1H),7.35–7.41(m,4H),7.50(t,J＝7.6Hz,4H),7.61(d,J＝8.4Hz,2H),7.71–7.77(m,6H),7.89(t,J＝7.6Hz,1H),8.00(d,J＝8.0Hz,1H),8.07(d,J＝8.0Hz,1H),8.42(d,J＝1.6Hz,2H),8.82(d,J＝4.4Hz,1H)。
And (3) synthesizing an intermediate p-PhCz-OH: in a dry 250mL three-necked flask was added p-PhCz-OMe (2.76g,5.49mmol,1.0 equiv.), dry dichloromethane (60 mL). Boron tribromide (1.04mL,10.98mmol,2.0 equiv) was then added dropwise at-15 ℃ and the reaction was allowed to warm to room temperature and stirred for 20 hours. Quenching sodium bicarbonate solution, extracting with dichloromethane for three times, combining organic phases, drying with anhydrous sodium sulfate, filtering, distilling under reduced pressure to remove solvent, separating crude product by silica gel column chromatography, eluting with eluent: petroleum ether/dichloromethane ═ 20:1 to 1:1, 2.14g of yellow solid were obtained in 80% yield.1H NMR(500MHz,DMSO-d6)δ7.24(d,J＝2.0Hz,1H)7.27(dd,J＝8.5,2.0Hz,1H),7.35–7.39(m,2H),7.49–7.53(m,5H),7.63(d,J＝8.5Hz,2H),7.82–7.85(m,6H),8.11(td,J＝8.0,2.0Hz,1H),8.35–8.38(m,2H),8.71(ddd,J＝5.0,2.0,1.0Hz,1H),8.76(d,J＝1.5Hz,2H),14.64(s,1H)。
Synthesis of luminescent Material p-PhCz-BF 2: in a dry 100mL three-necked flask was added p-PhCz-OH (2.0g, 4.09mmol,1.0 equiv.), methylene chloride (50mL), followed by boron trifluoride diethyl ether (5.2mL, 40.93mmol,10 equiv.) at-15 deg.C, and after 20 hours of reaction at room temperature with stirring, N-diisopropylethylamine (10.72mL, 61.35mmol,15 equiv.) was added and the reaction was continued for 24 hours. Quenching with sodium carbonate solution after reaction, extracting with dichloromethane for three times, mixing organic phases, and removingDrying with sodium sulfate, filtering, distilling under reduced pressure to remove solvent, separating crude product with silica gel column chromatography, eluting: petroleum ether/dichloromethane ═ 5:1 to 1:3, 1.94g of a yellow-green solid was obtained in 88% yield.1H NMR(400MHz,Chloroform-d)δ7.35–7.41(m,3H),7.48–7.54(m,5H),7.65–7.75(m,9H),8.09(d,J＝8.4Hz,1H),8.20–8.29(m,2H),8.40(s,2H),8.79(d,J＝6.0Hz,1H).
Example 3: the luminescent material p-tBuCz-BF2 can be synthesized by the following route:
and (3) synthesizing an intermediate p-tBuCz-OH: 2-Br (400mg,1.60mmol,1.0 equiv.), 3, 6-di-tert-butylcarbazole (581mg,2.08mmol,1.3 equiv.), sodium tert-butoxide (384mg,4.0mmol,2.5 equiv.), Pd were added in this order in a 50mL three-necked flask2(dba)3(44mg,0.048mmol,0.03 equiv.) and XPhos (92mg,0.19mmol,0.12 equiv.), then nitrogen was purged three times, toluene (18mL) was added by injection, and reacted for 96 hours at 120 ℃ in an oil bath. Cooling the reaction to room temperature, adding water for quenching, extracting for three times by ethyl acetate, combining organic phases, drying by anhydrous sodium sulfate, filtering, distilling under reduced pressure to remove the solvent, and separating a crude product by silica gel column chromatography, wherein an eluent: petroleum ether/dichloromethane-20: 1-3:1 gave 234mg of white solid in 33% yield.1H NMR(500MHz,CDCl3)δ1.47(s,18H),7.14(dd,J＝8.5,2.0Hz,1H),7.27(d,J＝2.0Hz,1H),7.30(ddd,J＝7.5,5.0,1.0Hz,1H),7.48(dd,J＝9.0,2.0Hz,2H),7.53(d,J＝8.5Hz,2H),7.88-7.91(m,1H),7.97-8.00(m,1H),8.14(d,J＝1.0Hz,2H),8.56(ddd,J＝5.0,2.0,1.0Hz,1H),14.76(s,1H)。
Synthesis of luminescent Material p-tBuCz-BF 2: in a dry 50mL three-necked flask was added p-tBuCz-OH (230mg, 0.52mmol,1.0 equiv.), methylene chloride (15mL), then boron trifluoride diethyl etherate (0.2mL, 1.56mmol,3.0 equiv.) was added at-15 deg.C, after moving to room temperature and stirring for reaction for 2 hours, N-diisopropylethylamine (0.37mL, 2.09mmol,4.0 equiv.) was added and the reaction was continued for 12 hours. Quenching with sodium carbonate solution after the reaction is finished, extracting with dichloromethane for three times, combining organic phases, and using anhydrous sulfuric acidSodium drying, filtering, distilling under reduced pressure to remove solvent, separating crude product by silica gel column chromatography, eluting: petroleum ether/dichloromethane ═ 5:1-1:2, 139mg of a yellow-green solid were obtained in 54% yield.1H NMR(500MHz,CDCl3)δ1.47(s,18H),7.33(dd,J＝8.5,2.0Hz,1H),7.46(d,J＝2.0Hz,1H),7.48(dd,J＝8.5,2.0Hz,2H),7.54(d,J＝8.5Hz,2H),7.61-7.64(m,1H),8.02(d,J＝8.5Hz,1H),8.13(d,J＝1.5Hz,2H),8.18(d,J＝8.5Hz,1H),8.22-8.25(m,1H),8.76(d,J＝5.5Hz,1H)。
Example 4: the luminescent material p-PTZ-BF2 can be synthesized by the following route:
synthesis of intermediate p-PTZ-OH: 2-Br (400mg,1.60mmol,1.0 equiv.), phenothiazine (415mg,2.08mmol,1.3 equiv.), sodium tert-butoxide (461mg,4.8mmol,3.0 equiv.) and palladium acetate (11mg,0.048mmol,0.03 equiv.) were added in this order to a 50mL three-necked flask, then nitrogen was purged three times, and tri-tert-butylphosphine (260mg,0.13mmol,0.08 equiv., 10 wt.% toluene) and 1,4 dioxane (15mL) were injected and reacted at 100 ℃ for 50 hours in an oil bath. Cooling the reaction to room temperature, adding water for quenching, extracting for three times by ethyl acetate, combining organic phases, drying by anhydrous sodium sulfate, filtering, distilling under reduced pressure to remove the solvent, and separating a crude product by silica gel column chromatography, wherein an eluent: petroleum ether/ethyl acetate 50:1-10:1 gave 435mg of a tan solid in 74% yield.1H NMR(500MHz,CDCl3)δ6.70(dd,J＝8.0,1.5Hz,2H),6.83(dd,J＝8.5,2.5Hz,1H),6.92(td,J＝7.5,1.5Hz,2H),6.97–7.01(m,3H),7.13(dd,J＝7.5,1.5Hz,2H),7.26–7.29(m,1H),7.84–7.92(m,3H),8.53(ddd,J＝5.0,2.0,1.0Hz,1H),14.63(s,1H)。
Synthesis of luminescent Material p-PTZ-BF 2: in a dry 50mL three-necked flask was added p-PTZ-OH (400mg, 1.09mmol,1.0 equiv.), dichloromethane (10mL), then boron trifluoride ethyl ether (0.4mL, 3.26mmol,3.0 equiv.) was added at-15 deg.C, the mixture was allowed to stir at room temperature for 3 hours, N-diisopropylethylamine (0.76mL, 4.36mmol,4.0 equiv.) was added, and the reaction was continued for 17 hours. After the reaction is finished, quenching the mixture by using a sodium carbonate solution,extracting with dichloromethane for three times, combining organic phases, drying with anhydrous sodium sulfate, filtering, distilling under reduced pressure to remove solvent, separating crude product by silica gel column chromatography, eluting with eluent: petroleum ether/dichloromethane ═ 5:1-1:1, giving 260mg of an orange solid in 57% yield.1H NMR(500MHz,CDCl3)δ6.13(dd,J＝8.0,1.5Hz,2H),6.63(td,J＝7.5,1.5Hz,2H),6.69(td,J＝7.5,1.5Hz,2H),6.72(dd,J＝7.5,1.5Hz,2H),7.06(dd,J＝8.5,2.0Hz,1H),7.23(d,J＝2.0Hz,1H),7.67(ddd,J＝7.5,6.0,1.0Hz,1H),8.06(d,J＝8.5Hz,1H),8.18(d,J＝8.5Hz,1H),8.26(ddd,J＝9.0,7.5,1.5Hz,1H),8.78(d,J＝6.0Hz,1H)。
Example 5: the luminescent material p-PXZ-BF2 can be synthesized by the following route:
synthesis of intermediate p-PXZ-OH: 2-Br (400mg,1.60mmol,1.0 equiv.), phenoxazine (381mg,2.08mmol,1.3 equiv.), sodium tert-butoxide (461mg,4.8mmol,3.0 equiv.) and palladium acetate (11mg,0.048mmol,0.03 equiv.) were added sequentially in a 50mL three-necked flask, then nitrogen was purged three times, tri-tert-butylphosphine (260mg,0.13mmol,0.08 equiv., 10 wt% toluene) and 1,4 dioxane (15mL) were injected and reacted for 50 hours in an oil bath at 100 ℃. Cooling the reaction to room temperature, adding water for quenching, extracting for three times by ethyl acetate, combining organic phases, drying by anhydrous sodium sulfate, filtering, distilling under reduced pressure to remove the solvent, and separating a crude product by silica gel column chromatography, wherein an eluent: petroleum ether/ethyl acetate 50:1-10:1 gave 570mg of a yellow solid in 88% yield.1H NMR(500MHz,CDCl3)δ6.13(dd,J＝8.0,1.5Hz,2H),6.63(ddd,J＝8.0,7.0,1.5Hz,2H),6.69(td,J＝7.5,1.5Hz,2H),6.73(dd,J＝7.5,1.5Hz,2H),7.06(dd,J＝8.5,2.0Hz,1H),7.23(d,J＝2.0Hz,1H),7.67(ddd,J＝7.5,6.0,1.0Hz,1H),8.06(d,J＝8.5Hz,1H),8.18(d,J＝8.5Hz,1H),8.26(ddd,J＝9.0,7.5,1.5Hz,1H),8.78(d,J＝6.0Hz,1H)。
Synthesis of luminescent material p-PXZ-BF 2: in a dry 50mL three-necked flask was added p-PXZ-OH (570mg, 1.62mmol,1.0 equiv.), dichloromethane (12mL), followed by boron trifluoride diethyl ether (0.6mL,4.85mmol,3.0 equivalents), stirred at room temperature for 2 hours, then added N, N-diisopropylethylamine (0.1.1mL, 6.48mmol,4.0 equivalents), and allowed to react for 17 hours. After the reaction is finished, quenching the mixture by using a sodium carbonate solution, extracting the mixture for three times by using dichloromethane, combining organic phases, drying the organic phases by using anhydrous sodium sulfate, filtering the mixture, distilling the mixture under reduced pressure to remove a solvent, and separating a crude product by using a silica gel column chromatography to obtain an eluent: petroleum ether/dichloromethane ═ 5:1-1:1, yielding 222mg of an orange solid in 39% yield.1H NMR(500MHz,CDCl3)δ6.71(dd,J＝9.0,2.5Hz,1H),6.84(d,J＝2.5Hz,1H),7.18(td,J＝7.5,1.5Hz,2H),7.30(td,J＝7.5,1.5Hz,2H),7.36(dd,J＝8.0,1.5Hz,2H),7.40–7.43(m,3H),7.64(d,J＝9.0Hz,1H),7.91(d,J＝8.5Hz,1H),8.05(ddd,J＝8.5,7.5,1.5Hz,1H),8.57(d,J＝6.0Hz,1H)。
Example 6: the luminescent material p-DMAC-BF2 can be synthesized by the following route:
synthesis of intermediate p-DMAC-OMe: 1-Br (1.0g,3.79mmol,1.0 equiv.), acridine (951mg,4.54mmol,1.2 equiv.), sodium tert-butoxide (728mg,7.58mmol,2.0 equiv.), Pd were added in this order to a 50mL three-necked flask2(dba)3(104mg,0.11mmol,0.03 equiv.) and S-Phos (93mg,0.23mmol,0.06 equiv.), then nitrogen was purged three times, toluene (15mL) was added by injection, and reacted at 110 ℃ for 67 hours in an oil bath. Cooling the reaction to room temperature, adding water for quenching, extracting for three times by ethyl acetate, combining organic phases, drying by anhydrous sodium sulfate, filtering, distilling under reduced pressure to remove the solvent, and separating a crude product by silica gel column chromatography, wherein an eluent: petroleum ether/ethyl acetate 50:1 to 10:1 gave 1.35g of a tan solid in 91% yield.1H NMR(500MHz,CDCl3)δ1.72(s,6H),3.83(s,3H),6.42(dd,J＝8.0,1.5Hz,2H),6.93–6.96(m,3H),7.00(ddd,J＝8.5,7.0,1.5Hz,2H),7.08(dd,J＝8.0,1.5Hz,1H),7.26–7.29(m,1H),7.47(dd,J＝7.5,1.5Hz,2H),7.78(td,J＝7.5,2.0Hz,1H),7.92(dt,J＝8.0,1.0Hz,1H),8.02(d,J＝8.0Hz,1H),8.76(ddd,J＝5.0,2.0,1.0Hz,1H)。
And (3) synthesizing an intermediate p-DMAC-OH: in a dry 50mL volume of trisA neck vial was charged with p-DMAC-OMe (1.18g,3.0mmol,1.0 equiv.), dry dichloromethane (20 mL). Boron tribromide (0.85mL,9.0mmol,3.0 equiv) was then added dropwise at-15 ℃ and the reaction was allowed to warm to room temperature and stirred for 19 hours. Quenching sodium bicarbonate solution, extracting with dichloromethane for three times, combining organic phases, drying with anhydrous sodium sulfate, filtering, distilling under reduced pressure to remove solvent, separating crude product by silica gel column chromatography, eluting with eluent: petroleum ether/ethyl acetate-20: 1-1:1 gave 760mg of a yellow solid in 67% yield.1H NMR(500MHz,CDCl3)δ1.69(s,6H),6.48(dd,J＝8.0,1.5Hz,2H),6.88(dd,J＝8.5,2.0Hz,1H),6.93(td,J＝7.5,1.5Hz,2H),6.97–7.01(m,2H),7.05(d,J＝2.0Hz,1H),7.32(ddd,J＝7.5,5.0,1.0Hz,1H),7.46(dd,J＝7.5,1.5Hz,2H),7.91(td,J＝8.0,2.0Hz,1H),7.98–8.01(m,1H),8.04(d,J＝8.5Hz,1H),8.58(ddd,J＝5.0,2.0,1.0Hz,1H),14.67(s,1H)。
Synthesis of luminescent Material p-DMAC-BF 2: in a dry 50mL three-necked flask was added p-DMAC-OH (620mg, 1.64mmol,1.0 equiv.), dichloromethane (10mL), then boron trifluoride ethyl ether (2.07mL, 10.4mmol,10 equiv.) was added at-15 deg.C, the mixture was allowed to stir at room temperature for 3 hours, N-diisopropylethylamine (4.3mL, 24.6mmol,15 equiv.) was added, and the reaction was continued for 42 hours. After the reaction is finished, quenching the mixture by using a sodium carbonate solution, extracting the mixture for three times by using dichloromethane, combining organic phases, drying the organic phases by using anhydrous sodium sulfate, filtering the mixture, distilling the mixture under reduced pressure to remove a solvent, and separating a crude product by using a silica gel column chromatography to obtain an eluent: petroleum ether/dichloromethane ═ 5:1-1:1, 570mg of a yellow solid were obtained in 82% yield.1H NMR(400MHz,CDCl3)δ1.67(s,6H),6.55(d,J＝7.6Hz,2H),6.96–7.05(m,5H),7.24(s,1H),7.47(d,J＝7.2Hz,2H),7.64(t,J＝6.4Hz,1H),8.05(d,J＝8.4Hz,1H),8.18(d,J＝8.4Hz,1H),8.24(t,J＝8.0Hz,1H),8.76(d,J＝6.0Hz,1H)。
Example 7: the luminescent material p-DPA-BF2 can be synthesized by the following route:
and (3) synthesizing an intermediate p-DPA-OMe: 1-Br (788mg,2.98mmol,1.0 m) was added to a 50mL three-necked flask in that orderAmount), diphenylamine (606mg,3.58mmol,1.2 equiv.), sodium tert-butoxide (573mg,5.96mmol,2.0 equiv.), Pd2(dba)3(82mg,0.09mmol,0.03 eq.) and S-Phos (73mg,0.18mmol,0.06 eq.), then the nitrogen was purged three times, toluene (12mL) was added by injection and allowed to react for 96 hours in a 110 ℃ oil bath. Cooling the reaction to room temperature, adding water for quenching, extracting for three times by ethyl acetate, combining organic phases, drying by anhydrous sodium sulfate, filtering, distilling under reduced pressure to remove the solvent, and separating a crude product by silica gel column chromatography, wherein an eluent: petroleum ether/ethyl acetate 50:1-10:1 gave 975mg of a tan solid in 93% yield.1H NMR(400MHz,CDCl3)δ3.70(s,3H),6.68(s,1H),6.74(d,J＝8.8Hz,1H),7.07(t,J＝7.2Hz,2H),7.16(d,J＝8.0Hz,4H),7.21(d,J＝6.4Hz,1H),7.26–7.31(m,4H),7.69(d,J＝8.4Hz,1H),7.76(t,J＝8.0Hz,1H),7.86(d,J＝8.0Hz,1H),8.72(d,J＝4.8Hz,1H)。
And (3) synthesizing an intermediate p-DPA-OH: in a dry 50mL three-necked flask was added p-DPA-OMe (925mg,2.62mmol,1.0 equiv.), dry dichloromethane (30 mL). Boron tribromide (0.74mL,7.87mmol,3.0 equiv) was then added dropwise at-15 ℃ and the reaction was allowed to warm to room temperature and stirred for 26 hours. Quenching sodium bicarbonate solution, extracting with dichloromethane for three times, combining organic phases, drying with anhydrous sodium sulfate, filtering, distilling under reduced pressure to remove solvent, separating crude product by silica gel column chromatography, eluting with eluent: petroleum ether/ethyl acetate 20:1-1:1 gave 297mg of white solid in 33% yield.1H NMR(400MHz,CDCl3)δ6.57(dd,J＝8.4,2.4Hz,1H),6.69(s,1H),7.09(t,J＝7.2Hz,2H),7.15–7.22(m,5H),7.27–7.31(m,4H),7.60(d,J＝8.4Hz,1H),7.79–7.86(m,2H),8.46(d,J＝4.8Hz,1H),14.40(s,1H)。
Synthesis of luminescent material p-DPA-BF 2: in a dry 50mL three-necked flask, p-DPA-OH (250mg, 0.74mmol,1.0 equiv.) and methylene chloride (10mL) were added followed by boron trifluoride diethyl ether (0.93mL, 7.39mmol,10 equiv.) at-15 deg.C, the mixture was allowed to warm to room temperature and stirred for reaction for 1.5 hours, then N, N-diisopropylethylamine (1.94mL, 11.1mmol,15 equiv.) was added and the reaction was continued for 26 hours. Quenching with sodium carbonate solution after reaction, extracting with dichloromethane for three times, mixing organic phases, drying with anhydrous sodium sulfate, filtering, distilling under reduced pressure to remove solvent, and purifying with silica gelColumn chromatography, eluent: petroleum ether/dichloromethane ═ 5:1-1:1, giving 245mg of yellow solid in 86% yield.1H NMR(400MHz,CDCl3)δ6.62–6.66(m,2H),7.14–7.20(m,6H),7.31–7.35(m,4H),7.39(t,J＝6.8Hz,1H),7.59(d,J＝8.8Hz,1H),7.91(d,J＝8.8Hz,1H),8.04(t,J＝8.0Hz,1H),8.56(d,J＝6.0Hz,1H)。
Example 8: the luminescent material m-Cz-BF2 can be synthesized by the following route:
synthesis of intermediate 1-Cl: 2-bromopyridine (13.53g,85.84mmol,2.0 equiv.), 5-chloro-2-methoxyphenylboronic acid (8.0g,42.92mmol,1.0 equiv.), cesium carbonate (34.96g,107.3mmol,2.5 equiv.), and tetratriphenylphosphine palladium (992mg,0.86mmol,0.02 equiv) were added sequentially to a 250mL three-necked flask, followed by purging nitrogen three times, and ethanol (120mL) and water (50mL) were injected and reacted at 80 ℃ for 96 hours in an oil bath. Cooling the reaction to room temperature, adding water for quenching, extracting for three times by ethyl acetate, combining organic phases, drying by anhydrous sodium sulfate, filtering, distilling under reduced pressure to remove the solvent, and separating a crude product by silica gel column chromatography, wherein the eluent comprises the following components: petroleum ether/ethyl acetate 50:1 to 10:1 gave 7.07g of a colorless liquid in a yield of 75%.1H NMR(500MHz,CDCl3)δ3.86(s,3H),6.94(d,J＝8.5Hz,1H),7.27–7.29(m,1H),7.33(dd,J＝8.5,2.5Hz,1H),7.75–7.78(m,2H),7.83(dt,J＝7.5,1.0Hz,1H),8.73(d,J＝4.5Hz,1H)。
Synthesis of intermediate m-Cz-OMe: 1-Cl (2.0g,9.10mmol,1.0 equiv.), carbazole (1.83g,10.93mmol,1.2 equiv.), sodium tert-butoxide (2.19g,22.75mmol,2.5 equiv.), Pd were added in this order in a 100mL three-necked flask2(dba)3(250mg,0.27mmol,0.03 equiv.) and XPhos (260mg,0.55mmol,0.06 equiv.), then the nitrogen was purged three times and o-xylene (30mL) was injected and reacted for 50 hours in an oil bath at 140 ℃. Cooling the reaction to room temperature, adding water for quenching, extracting for three times by ethyl acetate, combining organic phases, drying by anhydrous sodium sulfate, filtering, distilling under reduced pressure to remove the solvent, and separating a crude product by silica gel column chromatography, wherein the eluent comprises the following components: petroleum ether/dichloromethane ═ 30:11:1, 2.93g of a brown solid was obtained in 92% yield.1H NMR(500MHz,CDCl3)δ4.01(s,3H),7.23–7.26(m,1H),7.26–7.34(m,3H),7.38–7.42(m,4H),7.57(dd,J＝9.0,2.5Hz,1H),7.84(t,J＝7.5Hz,1H),7.93(d,J＝8.0Hz,1H),7.96(d,J＝2.5Hz,1H),8.14(dt,J＝7.5,1.0Hz,2H),8.73(d,J＝2.0Hz,1H)。
And (3) synthesizing an intermediate m-Cz-OH: to a dry 500mL three-necked flask were added m-Cz-OMe (2.94g,8.39mmol,1.0 equiv.), dry dichloromethane (150 mL). Boron tribromide (1.59mL,16.78mmol,2.0 equiv) was then added dropwise at-15 ℃ and the reaction was allowed to warm to room temperature and stirred for 18 hours. Quenching sodium bicarbonate solution, extracting with dichloromethane for three times, combining organic phases, drying with anhydrous sodium sulfate, filtering, distilling under reduced pressure to remove solvent, separating crude product by silica gel column chromatography, eluting with eluent: petroleum ether/ethyl acetate 20:1-10:1 gave 2.25g of a yellow solid in 80% yield.1H NMR(500MHz,CDCl3)δ7.27–7.37(m,5H),7.40–7.44(m,3H),7.47(dd,J＝8.5,2.5Hz,1H),7.83–7.86(m,2H),7.94(d,J＝2.5Hz,1H),8.17(d,J＝7.5Hz,2H),8.61(d,J＝5.0Hz,1H),14.39(s,1H)。
Synthesis of luminescent material m-Cz-BF 2: in a dry 250mL three-necked flask, m-Cz-OH (2.25g, 6.69mmol,1.0 equiv.) and methylene chloride (100mL) were added followed by boron trifluoride diethyl ether (2.53mL, 20.07mmol,3.0 equiv.) at-15 deg.C, the mixture was allowed to warm to room temperature and stirred for reaction for 9 hours, then N, N-diisopropylethylamine (4.67mL, 26.76mmol,4.0 equiv.) was added and the reaction was continued for 28 hours. After the reaction is finished, quenching the mixture by using a sodium carbonate solution, extracting the mixture for three times by using dichloromethane, combining organic phases, drying the organic phases by using anhydrous sodium sulfate, filtering the mixture, distilling the mixture under reduced pressure to remove a solvent, and separating a crude product by using a silica gel column chromatography to obtain an eluent: petroleum ether/dichloromethane ═ 5:1-1:1, giving 970mg of a yellow solid in 38% yield.1H NMR(500MHz,CDCl3)δ7.30–7.35(m,4H),7.41–7.45(m,3H),7.66–7.69(m,2H),8.02(d,J＝2.5Hz,1H),8.07(d,J＝8.5Hz,1H),8.17(dt,J＝7.5,1.0Hz,2H),8.21(ddd,J＝9.0,7.5,1.5Hz,1H),8.81(dd,J＝6.0,1.5Hz,1H)。
Example 9: the luminescent material m-PhCz-BF2 can be synthesized by the following route:
synthesis of intermediate m-PhCz-OMe: 1-Cl (2.0g,9.10mmol,1.0 equiv.), phenylcarbazole (3.49g,10.93mmol,1.2 equiv.), sodium tert-butoxide (2.19g,22.75mmol,2.5 equiv.), Pd were added in this order to a 100mL three-necked flask2(dba)3(250mg,0.27mmol,0.03 equiv.) and XPhos (260mg,0.55mmol,0.06 equiv.), then the nitrogen was purged three times and o-xylene (30mL) was injected and reacted for 48 hours in an oil bath at 140 ℃. Cooling the reaction to room temperature, adding water for quenching, extracting for three times by ethyl acetate, combining organic phases, drying by anhydrous sodium sulfate, filtering, distilling under reduced pressure to remove the solvent, and separating a crude product by silica gel column chromatography, wherein an eluent: petroleum ether/dichloromethane ═ 5:1-1:100, 2.98g of a brown solid were obtained in 65% yield.1H NMR(500MHz,CDCl3)δ4.03(s,3H),7.27(d,J＝9.0Hz,1H),7.33–7.37(m,3H),7.47–7.51(m,6H),7.64(dd,J＝8.5,3.0Hz,1H),7.68(dd,J＝8.5,2.0Hz,2H),7.72–7.75(m,4H),7.89–7.90(m,1H),7.96(d,J＝8.0Hz,1H),8.01(d,J＝2.5Hz,1H),8.40(d,J＝2.0Hz,2H),8.78(d,J＝2.0Hz,1H)。
And (3) synthesizing an intermediate m-PhCz-OH: in a dry 500mL three-necked flask were added m-PhCz-OMe (2.98g,5.93mmol,1.0 equiv.), dry dichloromethane (150 mL). Boron tribromide (1.12mL,11.86mmol,2.0 equiv) was then added dropwise at-15 ℃ and the reaction was allowed to warm to room temperature and stirred for 18 hours. Quenching with sodium bicarbonate solution, extracting with dichloromethane for three times, combining organic phases, drying with anhydrous sodium sulfate, filtering, distilling under reduced pressure to remove the solvent, separating the crude product by silica gel column chromatography, eluting with an eluent: petroleum ether/dichloromethane ═ 20:1-1:1, 2.48g of a yellow solid were obtained in 86% yield.1H NMR(500MHz,DMSO-d6)δ7.25(d,J＝8.7Hz,1H),7.34–7.38(m,2H),7.43(d,J＝8.5Hz,2H),7.49–7.53(m,5H),7.58(dd,J＝8.5,2.5Hz,1H),7.79(dd,J＝8.5,2.0Hz,2H),7.81–7.84(m,4H),8.02(td,J＝8.5,2.0Hz,1H),8.34–8.36(m,2H),8.70–8.72(m,1H),8.74(d,J＝2.0Hz,2H),14.49(s,1H)。
Synthesis of luminescent material m-PhCz-BF 2: in a dry 250mL three-necked flask, m-PhCz-OH (2.28g, 4.67mmol,1.0 equiv.), dichloromethyl was addedAlkane (50mL), then boron trifluoride diethyl etherate (5.89mL, 46.67mmol,10 equiv.) was added at-15 deg.C, the mixture was allowed to warm to room temperature and stirred for reaction for 9 hours, then N, N-diisopropylethylamine (12.26mL, 70.05mmol,15 equiv.) was added and the reaction was continued for 28 hours. After the reaction is finished, quenching the mixture by using a sodium carbonate solution, extracting the mixture for three times by using dichloromethane, combining organic phases, drying the organic phases by using anhydrous sodium sulfate, filtering the mixture, distilling the mixture under reduced pressure to remove a solvent, and separating a crude product by using a silica gel column chromatography to obtain an eluent: petroleum ether/dichloromethane ═ 20:1 to 1:1, 1.70g of yellow solid were obtained in 68% yield.1H NMR(500MHz,CDCl3)δ7.35–7.39(m,2H),7.42(dd,J＝8.5,1.0Hz,2H),7.47–7.51(m,5H),7.68–7.71(m,3H),7.73–7.75(m,5H),8.07(d,J＝2.5Hz,1H),8.11(d,J＝8.5Hz,1H),8.23(ddd,J＝9.0,7.5,1.5Hz,1H),8.43(dd,J＝1.8,0.5Hz,2H),8.83(d,J＝6.0Hz,1H)。
Performance evaluation examples
The complexes prepared in the above examples of the invention were subjected to photophysical, electrochemical and thermogravimetric analyses as follows:
and (3) photophysical analysis: the phosphorescence emission spectrum, the fluorescence emission spectrum, the triplet state lifetime and the excited state lifetime are tested and finished on a HORIBA FL3-11 spectrometer. And (3) testing conditions are as follows: in the low and room temperature emission spectra, all samples were toluene (chromatographic grade) dilute solutions (10)-5-10-6M); the luminescence quantum efficiency (PLQY) and luminescence decay curves were measured for a 10 wt% doped DEPEO film sample of the luminescent material.
FIG. 1 shows the emission spectra of the luminescent materials p-Cz-BF2, p-tBuCz-BF2, p-PhCz-BF2, p-DMAC-BF2, p-DPA-BF2, p-PTZ-BF2, p-PXZ-BF2, m-Cz-BF2 and m-PhCz-BF2 in toluene solution at room temperature.
FIG. 2 is an emission spectrum diagram of DEPEO films of luminescent materials p-Cz-BF2, p-tBuCz-BF2, p-PhCz-BF2, p-DMAC-BF2, p-DPA-BF2, p-PTZ-BF2, p-PXZ-BF2, m-Cz-BF2 and m-PhCz-BF2 at room temperature.
FIG. 3 is a DEPEO film luminescence decay (normalized luminescence intensity versus time) curve for the luminescent materials p-Cz-BF2, p-tBuCz-BF2, p-PhCz-BF2, p-DMAC-BF2, p-DPA-BF2, p-PTZ-BF2, p-PXZ-BF2, m-Cz-BF2, and m-PhCz-BF 2.
TABLE 1 photophysical Properties of the luminescent materials
| Luminescent material | Peak/nm | PLQY/％ |
| p-Cz-BF2 | 438 | 99 |
| p-tBuCz-BF2 | 459 | 99 |
| p-PhCz-BF2 | 455 | 99 |
| p-DPA-BF2 | 474 | 93 |
| p-PXZ-BF2 | 565 | 24 |
| p-PTZ-BF2 | 457、583 | 36 |
| p-DMAC-BF2 | 528 | 78 |
| m-Cz-BF2 | 487 | 99 |
| m-PhCz-BF2 | 491 | 99 |
Note: peak refers to the strongest emission Peak of the emission spectrum of the luminescent material in toluene solution at room temperature. PLQY refers to the absolute luminescence quantum efficiency of 10 wt% doped DEPEO thin film samples of the luminescent material.
As can be seen from figures 1,2 and table 1: firstly, the luminescent color of the material is easy to adjust: under the condition of keeping the structure of the acceptor unchanged, the structure of the donor is simply adjusted, namely the luminescent color of the material can cover the whole visible light region from blue light to orange light; secondly, the material quantum efficiency is high: the material has very high luminescent quantum efficiency (PLQY), especially the blue material can reach 99%. Thirdly, thermally induced delayed fluorescent material: as can be seen from the DEPEO film luminescence decay (normalized luminescence intensity-time) curve of the material shown in FIG. 3, most of the luminescence decay is in a double-exponential decay mode, and is a typical thermal induced delayed fluorescent material, and the triplet excitons can be fully utilized through reverse intersystem crossing theoretically, so that the quantum efficiency of 100% is achieved. The properties are beneficial to the application of the doped luminescent material in OLED devices, and an effective way is provided for solving the problem of the existing short blue light luminescent material, so that the development of the field is greatly promoted.
Device examples
All materials are subjected to a high vacuum (10) prior to use-5-10-6Torr) for sublimation purification by gradient heating. Indium Tin Oxide (ITO) substrates used by the devices were sequentially sonicated in deionized water, acetone, and isopropanol. The device passes through the vacuum degree of less than 10-7And vacuum thermal evaporation is carried out under the pressure of Torr. Anode electrodeIs of thickness of
Indium Tin Oxide (ITO), the cathode is made of a material having a thickness of
Li of (2)2CO3And
al of (1). After all devices are prepared, the glass cover and the epoxy resin are packaged in a nitrogen glove box, and a moisture absorbent is added into the package.
The device structures of luminescent materials p-Cz-BF2 and m-PhCz-BF2 as luminophors under different host materials and transport materials are as follows:
ITO/HATCN(10nm)/TAPC(60nm)/mCBP:PPT:p-Cz-BF2(1:1,5％,30nm)/PPT(2nm)/Bepp2:Li2CO3(5％,35nm)/Li2CO3(1nm)/Al, device 1;
ITO/HATCN(10nm)/TAPC(60nm)/mCBP:PPT:p-Cz-BF2(1:2,5％,30nm)/PPT(2nm)/Bepp2:Li2CO3(5％,35nm)/Li2CO3(1nm)/Al, device 2;
ITO/HATCN(10nm)/TAPC(60nm)/mCBP:PPT:p-Cz-BF2(1:1,5％,30nm)/PPT(2nm)/PPT:Li2CO3(5％,35nm)/Li2CO3(1nm)/Al, device 3;
ITO/HATCN(10nm)/TAPC(60nm)/mCBP:PPT:p-Cz-BF2(1:2,5％,30nm)/PPT(2nm)/PPT:Li2CO3(5％,35nm)/Li2CO3(1nm)/Al, device 4;
ITO/HATCN(10nm)/NPB(40nm)/mCBP(10nm)/PPT:m-PhCz-BF2(10％,30nm)/PPT(5nm)/Bepp2:Li2CO3(5％,30nm)/Li2CO3(1nm)/Al, device 5;
ITO/HATCN(10nm)/NPB(50nm)/PPT:m-PhCz-BF2(10％,30nm)/PPT(5nm)/Bepp2:Li2CO3(5％,30nm)/Li2CO3(1nm)/Al, device 6;
ITO/HATCN(10nm)/NPB(40nm)/PPT:m-PhCz-BF2(10％,30nm)/PPT(5nm)/Bepp2:Li2CO3(5％,30nm)/Li2CO3(1nm)/Al, device 7;
ITO/HATCN(15nm)/NPB(50nm)/PPT:m-PhCz-BF2(10％,30nm)/PPT(5nm)/Bepp2:Li2CO3(5％,30nm)/Li2CO3(1nm)/Al, device 8;
the molecular structure of the materials used in the above devices is as follows:
FIG. 4 is the electroluminescence spectrum of the device with the luminescent material p-Cz-BF2 as the luminophor in different proportions of the double-host material and with different doping of the electron transport material.
FIG. 5 is a graph of current density-voltage-luminous intensity of a device using the luminescent material p-Cz-BF2 as a luminophore in different proportions of the dual host material and with different doping of the electron transport material.
FIG. 6 is a plot of external quantum efficiency versus current density for a device with the luminescent material p-Cz-BF2 as a luminophore in different ratios of the dual host material and with different doping of the electron transport material.
FIG. 7 is a device electroluminescence spectrum diagram of a luminescent material m-PhCz-BF2 as a luminescent body under different functional layer thicknesses.
FIG. 8 is a device current density-voltage-luminous intensity curve of a luminescent material m-PhCz-BF2 as a luminescent body under different functional layer thicknesses.
FIG. 9 is the device external quantum efficiency-current density curve of luminescent material m-PhCz-BF2 as a luminescent body under different functional layer thicknesses.
As can be seen from the attached figures 8 and 9, the luminescent material m-PhCz-BF2 has good device performance under different devices, and the maximum external quantum efficiencies of the devices 5, 6, 7 and 8 are respectively as high as 23.9%, 25.6%, 22.4% and 10.2%; the maximum luminous brightness of the devices 5, 6, 7 and 8 is as high as 17493, 12633, 14029 and 13250cd/m respectively2. The device data fully indicate that the organic luminescent material containing the phenol oxygen-pyridine chelating boron difluoride acceptor is feasible as a luminescent materialThe excellent performance of the material can be used as a thermal-induced delayed fluorescent material, and the material has a huge application prospect in the field of OLED and promotes the further development of the field.
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples for carrying out the invention, and that various changes in form and details may be made therein without departing from the spirit and scope of the invention in practice. For example, many of the materials and structures described herein may be substituted with other materials and structures without departing from the spirit of the invention.
Claims (4)
1. An organic thermal activation delayed fluorescence material constructed by a phenol oxygen-pyridine chelating boron difluoride receptor is characterized by having a chemical formula shown as a general formula (1) or (2):
wherein,
in the formula (1), Ra1、Rb1Each independently of the others is hydrogen, deuterium, C1-C24Alkyl of (C)1-C24Alkoxy group of (C)3-C24Cycloalkyl of, C1-C24Ether of (C)1-C24Heterocyclic group of (A), C4-C24Aryl of (C)4-C24Aryloxy, halogen, mono-or dialkylamino, mono-or diarylamino, cyano, or a combination thereof;
m1、n1are each Ra1And Rb1The number of (2); wherein m is1Is an integer of 0 to 4, n1Is an integer of 0 to 3;
in the formula (2), Ra2、Rb2Each independently of the other is hydrogen, deuterium, C1-C24Alkyl of (C)1-C24Alkoxy group of (C)3-C24Cycloalkyl of, C1-C24Ether of (C)1-C24Heterocyclic group of (A), C4-C24Aryl of, C4-C24Aryloxy, halogen, mono-or dialkylamino, mono-or diarylamino, cyano, or a combination thereof;
m2、n2are each Ra2And Rb2The number of (2); m is2Is an integer of 0 to 4, n2Is an integer of 0 to 3;
donor D1、D2Each independently is one of the following structures:
wherein,
R1、R2、R3、R4、R7、R8、R10、R11、R12、R13、R14and R15Each independently of the others is hydrogen, deuterium, C1-C24Alkyl of (C)1-C24Alkoxy group of (1), C3-C24Cycloalkyl of, C1-C24Ether of (C)1-C24Heterocyclic group of (A), C4-C24Aryl of (C)4-C24Aryloxy, halogen, silicon, mono-or dialkylamino, mono-or diarylamino, cyano, or a combination thereof, wherein two adjacent substituents can be fused to form a ring;
o1、p1、q1、r1、s1、t1、u1、v1、w1、x1、y1and z1Are each R1、R2、R3、R4、R7、R8、R10、R11、R12、R13、R14And R15The number of (2);
o1and p1Is an integer of 0 to 5; q. q.s1、r1、s1、t1、u1、v1、w1、x1、y1And z1Is an integer of 0 to 4.
2. A thermally activated delayed fluorescence material as claimed in claim 1, wherein: the heat activation delayed fluorescence material is a compound shown as a formula (3) or (4):
wherein,
in the formula (3), Ra3、Rb3Each independently of the others is hydrogen, deuterium, C1-C24Alkyl of (C)1-C24Alkoxy group of (C)3-C24Cycloalkyl of (C)1-C24Ether of (C)1-C24Heterocyclic group of (2), C4-C24Aryl of (C)4-C24Aryloxy, halogen, mono-or dialkylamino, mono-or diarylamino, cyano, or a combination thereof;
m3、n3are each Ra3And Rb3The number of (2); wherein m is3Is an integer of 0 to 4, n3Is an integer of 0 to 3;
in the formula (4), Ra4、Rb4Each independently of the other is hydrogen, deuterium, C1-C24Alkyl of (C)1-C24Alkoxy group of (C)3-C24Cycloalkyl of, C1-C24Ether of (C)1-C24Heterocyclic group of (A), C4-C24Aryl of (C)4-C24Aryloxy, halogen, mono-or dialkylamino, mono-or diarylamino, cyano, or a combination thereof;
m4、n4are each Ra4And Rb4The number of (2); m is a unit of4Is an integer of 0 to 4, n4Is an integer of 0 to 3;
said donor D3Is one of the following structures:
wherein,
R1'、R2'、R3'、R4'、R7'、R8'、R10'、R11'、R12'、R13'、R14'and R15'Each independently of the other being hydrogen, deuterium, C1-C24Alkyl of (C)1-C24Alkoxy group of (1), C3-C24Cycloalkyl of, C1-C24Ether of (C)1-C24Heterocyclic group of (A), C4-C24Aryl of (C)4-C24Aryloxy, halogen, silicon, mono-or dialkylamino, mono-or diarylamino, cyano, or a combination thereof, wherein two adjacent substituents can be fused to form a ring;
o2、p2、q2、r2、s2、t2、u2、v2、w2、x2、y2and z2Are each R1’、R2’、R3’、R4’、R7’、R8’、R10’、R11’、R12’、R13’、R14’And R15’The number of (2);
o2and p2Is an integer of 0 to 5; q. q.s2、r2、s2、t2、u2、v2、w2、x2、y2And z2Is an integer of 0 to 4.
3. A thermally activated delayed fluorescence material as claimed in claim 1 or claim 2, wherein: the heat activation delayed fluorescence material is one of the following materials:
4. an organic electroluminescent device, wherein at least one of the luminescent material, the host material and the other functional layer material in the organic electroluminescent device comprises the thermally activated delayed fluorescence material according to any one of claims 1 to 3.
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