CN110183476A - Double boron oxa- dibenzo [A, J] anthracene derivants and its application - Google Patents
Double boron oxa- dibenzo [A, J] anthracene derivants and its application Download PDFInfo
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Abstract
The present invention relates to optics and optoelectronic materials technology, disclose a kind of derivative, preparation method and application based on double boron oxa- dibenzanthracenes.This kind of double boron oxa- dibenzo [A, J] anthracene derivants have the characteristics that high quantum efficiency, thermal decomposition temperature and glass transition temperature height, triplet are easily adjusted, thus have huge application prospect in material of main part or field of light emitting materials.
Description
Technical field
It is the present invention relates to optics and optoelectronic materials technology, in particular to a kind of based on double boron oxa- dibenzo [A, J]
The functional material of anthracene derivant can be applicable in optics or electrooptical device.
Background technique
The compound that can absorb and/or emit light is the ideal material of various optics and electroluminescent device,
It can apply in light absorption device such as solar energy Sensitive Apparatus and light-sensitive device, Organic Light Emitting Diode (OLED), light emitting
Device, or can either carry out light absorption again can be by carry out light emitting and as the device of the marker (marker) for biologic applications
Part.Many researchs oneself be dedicated to finding and optimize for organic used in the optics and electroluminescent device and organic metal material
Material.In general, the research in the field aims at many targets, including absorbing improvement and working ability with emission effciency
Improvement.
Although achieving significant progress, such as red green phosphorescent organometallic material in the research of chemistry and electrooptical material
Be commercialized and be applied to OLED, lighting apparatus and advanced display in, but currently available material still there are many
Disadvantage, including not good enough machining property, inefficient transmitting or absorption and not satisfactory stability.
In addition, good blue light emitting material is very rare, a huge challenge is exactly that blue-light device stability is not good enough, together
When material of main part selection the stability and efficiency of device are had an important influence.Relatively red green phosphor material, blue emitting phosphor material
The lowest triplet state energy level of material is higher, it means that material of main part needs higher triplet in blue-light device.Therefore, blue
It is a major issue that the limitation of material of main part in optical device, which develops it,.Can be applicable in blue-light device has high three line
The compound report of the excellent photophysical property such as state energy level is also seldom.
OLED device is by anode and cathode, and one or more layers organic compound layer of setting between the anode and cathode
Composition.Wherein organic compound layer includes luminescent layer, electrons and holes injection, transport layer.Therefore, people to hole,
There is electronics etc. the organic material (they are likely to be semiconductor) of charge transport ability energetically to be studied, to promote this
The development in field.
In addition, polycyclic aromatic hydrocarbon as organic electronic, pigment, sensor and liquid layer display material, in recent years by wide
General concern, and the synthesis example of a small number of boron azepine polycyclic aromatic hydrocarbon compounds is reported, but it is suitable as the main body of electro-optical device
The related boron azepine polycyclic aromatic hydrocarbon compounds material of material or luminescent material then almost without.
Summary of the invention
The purpose of the present invention is to provide a kind of double boron oxa- dibenzo [A, J] anthracene derivants, and its in optics or electric light
Application in device.
The purpose of the present invention is achieved by the following scheme: a kind of double boron oxa- dibenzo [A, J] anthracene derivants, structure are as follows:
Wherein, Ra、Rb、Rc、RdAnd ReIt is each independently hydrogen, deuterium, alkyl, alkoxy, naphthenic base, ether, heterocycle, benzene
Base, aryloxy group, halogen, cyano or combinations thereof；Ar is hexa-atomic aryl, heteroaryl, thick aryl, the thick aryl of azepine；M is the whole of 0-5
Number；N is the integer of 0-4.
Further, double boron oxa- dibenzo [A, J] anthracene derivants are preferred are as follows:
Further, the derivative is electroneutral.
A kind of application of said derivative, is applied in optics or electrooptical device as luminescent material or material of main part.
Further, Optical devices or electrooptical device include solar energy equipment, photosensitive device, Organic Light Emitting Diode light hair
Emitter part and the device that light absorption and transmitting can be compatible with.
Double boron oxa- dibenzo [A, J] anthracene derivants of the invention have the advantages that first, having very high luminous quantity
Sub- efficiency (PLQY), very short lifetime of excited state.Second, thermal decomposition temperature and glass transition temperature are high, can be used as optics or
Main body or luminescent material in electro-optical device.Third, double boron oxa- dibenzo [A, J] anthracene derivant various structures and being easy to repair
Decorations, make it have the triplet (T that can easily be accommodated1), it can be used as the material of main part of various illuminators.It is provided by the present invention
In double boron oxa- dibenzo [A, J] anthracene derivants, some materials have very high triplet (2.81-2.88eV), can use
Make the material of main part of blue light emitters.Therefore, the present invention provides an effective solution for Blue-light emitting host material in short supply at present
Certainly approach can greatly promote the development in Blue-light emitting host material field.
Detailed description of the invention
Fig. 1 is that the dichloromethane solution of compound BO1 is sharp at 77K with its 2- methyltetrahydrofuran solution at room temperature
Hair and emission spectrum spectrogram；
Fig. 2 is that the dichloromethane solution of compound BO2 is sharp at 77K with its 2- methyltetrahydrofuran solution at room temperature
Hair and emission spectrum spectrogram；
Fig. 3 is that the dichloromethane solution of compound BO7 is sharp at 77K with its 2- methyltetrahydrofuran solution at room temperature
Hair and emission spectrum spectrogram；
Fig. 4 is the dichloromethane solution of compound BO31 at room temperature with its 2- methyltetrahydrofuran solution at 77K
Emission spectrum spectrogram；
Fig. 5 is the dichloromethane solution of compound BO34 at room temperature with its 2- methyltetrahydrofuran solution at 77K
Excitation and emission spectra spectrogram.
Specific embodiment
The structure of compound can be indicated by following formula:
It is understood to be equal to following formula:
Wherein n is usually integer.That is, RnIt is understood to mean five individual substituent Rsn(a), Rn(b), Rn(c), Rn(d), Rn (e)." individual substituent group " refers to that each R substituent can be limited independently.For example, if in a situation Rn(a)For halogen,
So in this case Rn(b)It is not necessarily halogen.
R is referred to for several times in disclosed by the invention and description chemical structure and part1, R2, R3, R4, R5, R6Deng.It is saying
R in bright book1, R2, R3, R4, R5, R6Deng any description be respectively suitable for reference R1, R2, R3, R4, R5, R6Deng any structure or
Person part, unless otherwise mentioned.
Preparation and performance evaluation embodiment
Embodiment set forth below is to provide the change for how manufacturing and evaluating the present invention and describe to those of ordinary skill in the art
Entire disclosure and the description of object, composition, product, device and/or method are closed, and embodiment intention is only this public affairs
Open the demonstration of content and unexpectedly delineation limitation range.Although having been made great efforts to ensure about numerical value (for example, amount, temperature etc.)
Accuracy, but be contemplated that some errors and deviation.Unless otherwise stated, otherwise number be parts by weight, temperature be with DEG C
For unit or at ambient temperature, and pressure be under atmospheric pressure or near.
A variety of methods of the narration for the preparation method of disclosed compound described in the invention in embodiment.It provides
These methods are to illustrate a variety of preparation methods, but present disclosure is not intended to be limited to any for the method that the present invention is described
Kind.Therefore, the technical staff that domain is issued belonging to present disclosure can easily modify described method or utilize different sides
Method prepares the one or more of disclosed compound.Following aspect is merely exemplary, and is not intended to limit in the disclosure
The range of appearance.Temperature, catalyst, concentration, reactant composition and other process conditions are changeable, and match for desired
Object is closed, present disclosure those skilled in the art can readily select suitable reactant and condition.
In CDCl on Varian Liquid State NMR instrument3Or DMSO-d6It is recorded in solution with 500MHz1H
NMR spectra is recorded with 125MHz13C NMR spectra, chemical shift is referring to remaining deuterated (protiated) solvent.If
CDCl3As solvent, then recorded using tetramethylsilane (δ=0.00ppm) as internal standard1H NMR spectra；Using CDCl3(δ=
77.00ppm) recorded as internal standard13C NMR spectra.If DMSO-d6As solvent, then using tetramethylsilane (δ=
0.00ppm) recorded as internal standard1H NMR spectra；Using DMSO-d6(δ=39.52ppm) is recorded as internal standard13C NMR figure
Spectrum.It is explained using following abbreviations (or combinations thereof)1The multiplicity of H NMR: s=substance, d=is dual, and t=is triple, q=tetra-
Weight, m=is multiple, br=wide.
General synthetic routes
The versatility synthetic route of compound disclosed in the invention patent is as follows:
Wherein, Ra、Rb、Rc、RdAnd ReIt is each independently hydrogen, deuterium, alkyl, alkoxy, naphthenic base, ether, heterocycle, benzene
Base, aryloxy group, halogen, cyano or combinations thereof；Ar is hexa-atomic aryl, heteroaryl, thick aryl, the thick aryl of azepine；M is the whole of 0-5
Number；N is the integer of 0-4.
Prepare embodiment
Embodiment 1: compound BO1 can be synthesized by following route:
Bromo- 4, the 6- dimethoxy benzene of 1,3- bis- is sequentially added into the there-necked flask of the drying with magnetic rotor
(4.5773g, 15mmol, 97%, 1.0 equivalents), phenyl boric acid (4.1048g, 33mmol, 98%, 2.2 equivalents), palladium acetate
(0.1010g, 0.45mmol, 0.03 equivalent) and ligand S-Phos (0.3770g, 0.9mmol, 98%, 0.06 equivalent).Substitute nitrogen
Three times, then (10.3650g, 75mmol, 5.0 work as gas for addition Isosorbide-5-Nitrae-dioxane (90mL) and potassium carbonate under nitrogen protection
Amount) aqueous solution (30mL).Then there-necked flask is placed in 110 DEG C of oil baths.After stirring 24 hours, thin-layer chromatography monitoring has been reacted
At.It is cooled to room temperature, separates organic phase, water phase is extracted with ethyl acetate (30mL × 2).Merge all organic phases, anhydrous slufuric acid
Sodium dries, filters, and gained crude product is isolated and purified (eluent: petroleum ether/second by Flash silica column chromatography chromatogram by concentration
Acetoacetic ester=50/1) obtain A1, white solid 4.2107g, yield 97%.1H NMR (500MHz, CDCl3) δ 7.55 (d, J=
7.7Hz, 4H), 7.40 (t, J=7.6Hz, 4H), 7.27-7.36 (m, 3H), 6.67 (s, 1H), 3.88 (s, 6H).
A1 (0.8712g, 3mmol, 1.0 equivalent), toluene are sequentially added into the there-necked flask of the drying with magnetic rotor
(20mL) and n-hexane (20mL).Then under nitrogen protection be added dropwise Boron tribromide (0.72mL, d=2.6g/ml, 7.5mmol,
2.5 equivalents).After being stirred at room temperature 13 hours, it is rapidly added alchlor (0.0160g, 0.12mmol, 0.04 equivalent), then will
There-necked flask is placed in 75 DEG C of oil baths.It after stirring 24 hours, is cooled to room temperature, trimethylphenyl magnesium bromide is added dropwise under nitrogen protection
(15mL, 1M diethyl ether solution, 15mmol, 5.0 equivalents).Continue stirring 1 hour, thin-layer chromatography monitoring reaction is completed.Concentration, by institute
It obtains crude product and (eluent: petroleum ether~petroleum ether/methylene chloride=50/1) is isolated and purified by Flash silica column chromatography chromatogram
Obtain BO1, white solid 1.3019g, yield 84%.1H NMR (500MHz, CDCl3) δ 9.25 (s, 1H), 8.53 (d, J=
8.1Hz, 2H), 7.90-7.80 (m, 4H), 7.70 (s, 1H), 7.47 (t, J=7.3Hz, 2H), 6.95 (s, 4H), 2.37 (s,
6H), 2.22 (s, 12H).
Fig. 1 is that the dichloromethane solution of compound BO1 is sharp at 77K with its 2- methyltetrahydrofuran solution at room temperature
Hair and emission spectrum spectrogram.Its Emission Spectrum Peals at room temperature is 354nm, is in UV light region；The highest hair of 77K energy level
Penetrating spectrum peak is 430nm, thus can calculate its triplet and be up to 2.88eV, can be used as Blue-light emitting host material.
Embodiment 2: compound BO2 can be synthesized by following route:
Bromo- 4, the 6- dimethoxy benzene of 1,3- bis- is sequentially added into the there-necked flask of the drying with magnetic rotor
(2.5000g, 8.53mmol, 1.0 equivalent), 4- methylphenylboronic acid (2.4360g, 17.92mmol, 2.1 equivalent), four triphenylphosphines
Palladium (0.9820g, 0.85mmol, 0.1 equivalent) and potassium carbonate (4.7160g, 34.1mmol, 4.0 equivalent).Substitute nitrogen three times,
Isosorbide-5-Nitrae-dioxane (30mL) and water (10mL) are then added under nitrogen protection.Then there-necked flask is placed in 110 DEG C of oil baths.
After stirring 48 hours, thin-layer chromatography monitoring reaction is completed.Be cooled to room temperature, separate organic phase, water phase with ethyl acetate (30mL ×
2) it extracts.Merge all organic phases, anhydrous sodium sulfate dries, filters, and concentration chromatographs gained crude product by Flash silica column
Chromatographic separation and purification (eluent: petrol ether/ethyl acetate=20/1-10/1) obtains A2, white solid 2.6180g, yield 96%.1H
NMR (500MHz, CDCl3): δ 2.40 (s, 6H), 3.89 (s, 6H), 6.67 (s, 1H), 7.23 (d, J=7.9Hz, 4H), 7.31
(s, 1H), 7.44-7.46 (m, 4H).
A2 (1.5920g, 5mmol, 1.0 equivalent), toluene are sequentially added into the there-necked flask of the drying with magnetic rotor
(15mL) and n-hexane (35mL).Boron tribromide (3.3120g, 12.5mmol, 2.5 equivalent) then is added dropwise under nitrogen protection.
After being stirred at room temperature 18 hours, it is rapidly added alchlor (0.0670g, 0.5mmol, 0.1 equivalent), there-necked flask is then placed in 75
In DEG C oil bath.It after stirring 18 hours, is cooled to room temperature, trimethylphenyl magnesium bromide (15mL, 1M tetrahydro is added dropwise under nitrogen protection
Tetrahydrofuran solution, 15mmol, 3.0 equivalents).Continue stirring 18 hours, thin-layer chromatography monitoring reaction is completed.Concentration, gained is slightly produced
Product isolate and purify (eluent: petroleum ether/methylene chloride=50/1) by Flash silica column chromatography chromatogram and obtain BO2, white solid
0.7370g, yield 27%.1H NMR (400MHz, CDCl3): δ 2.24 (s, 12H), 2.40 (s, 6H), 2.45 (s, 6H), 6.98
(s, 4H), 7.64-7.70 (m, 5H), 8.44 (d, J=8.3Hz, 2H), 9.19 (s, 1H).
Fig. 2 is that the dichloromethane solution of compound BO2 is sharp at 77K with its 2- methyltetrahydrofuran solution at room temperature
Hair and emission spectrum spectrogram.Its Emission Spectrum Peals at room temperature is 375nm, is in UV light region；The highest hair of 77K energy level
Penetrating spectrum peak is 435nm, thus can calculate its triplet and be up to 2.85eV, can be used as Blue-light emitting host material.
Embodiment 3: compound BO7 can be synthesized by following route:
Bromo- 4, the 6- dimethoxy benzene of 1,3- bis- is sequentially added into the there-necked flask of the drying with magnetic rotor
(2.5000g, 8.53mmol, 1.0 equivalent), 4 tert-butylbenzeneboronic acids (3.1890g, 17.92mmol, 2.1 equivalent), four triphenyls
Phosphine palladium (0.9820g, 0.85mmol, 0.1 equivalent) and potassium carbonate (4.7160g, 34.1mmol, 4.0 equivalent).Substitute nitrogen three
It is secondary, Isosorbide-5-Nitrae-dioxane (30mL) and water (10mL) are then added under nitrogen protection.Then there-necked flask is placed in 110 DEG C of oil baths
In.After stirring 48 hours, thin-layer chromatography monitoring reaction is completed.It is cooled to room temperature, separates organic phase, water phase ethyl acetate
(30mL × 2) extraction.Merge all organic phases, anhydrous sodium sulfate dries, filters, concentration, and gained crude product is passed through quick silicon
Plastic column chromatography chromatographic separation and purification (eluent: petrol ether/ethyl acetate=20/1-10/1) obtains A3, white solid 3.4040g,
Yield 99%.1H NMR (500MHz, CDCl3): δ 1.39 (s, 18H), 3.91 (s, 6H), 6.67 (s, 1H), 7.38 (s, 1H),
7.44 (d, J=7.0Hz, 4H), 7.52 (d, J=7.1Hz, 4H).
A3 (2.0130g, 5mmol, 1.0 equivalent), toluene are sequentially added into the there-necked flask of the drying with magnetic rotor
(15mL) and n-hexane (35mL).Boron tribromide (3.3120g, 12.5mmol, 2.5 equivalent) then is added dropwise under nitrogen protection.
After being stirred at room temperature 18 hours, it is rapidly added alchlor (0.0670g, 0.5mmol, 0.1 equivalent), there-necked flask is then placed in 75
In DEG C oil bath.It after stirring 18 hours, is cooled to room temperature, trimethylphenyl magnesium bromide (15mL, 1M tetrahydro is added dropwise under nitrogen protection
Tetrahydrofuran solution, 15mmol, 3.0 equivalents).Continue stirring 18 hours, thin-layer chromatography monitoring reaction is completed.Concentration, gained is slightly produced
Product isolate and purify (eluent: petroleum ether/methylene chloride=50/1) by Flash silica column chromatography chromatogram and obtain BO7, white solid
1.1660g yield 37%.1H NMR (500MHz, CDCl3): δ 1.79 (s, 18H), 2.22 (s, 12H), 2.37 (s, 6H),
6.95 (s, 4H), 7.48 (t, J=7.2Hz, 2H), 7.70 (s, 1H), 7.84 (d, J=7.5Hz, 2H), 8.54 (d, J=
8.2Hz, 2H), 9.26 (s, 1H).
Fig. 3 is that the dichloromethane solution of compound BO7 is sharp at 77K with its 2- methyltetrahydrofuran solution at room temperature
Hair and emission spectrum spectrogram.Its Emission Spectrum Peals at room temperature is 370nm, is in UV light region；The highest hair of 77K energy level
Penetrating spectrum peak is 442nm, thus can calculate its triplet up to 2.81eV, can be used as Blue-light emitting host material.
Embodiment 4: compound BO31 can be synthesized by following route:
Bromo- 4, the 6- dimethoxy benzene of 1,3- bis- is sequentially added into the there-necked flask of the drying with magnetic rotor
(1.8644g, 6.1mmol, 97%, 1.0 equivalents), 3- biphenylboronic acid (2.7157g, 13.4mmol, 98%, 2.2 equivalents), acetic acid
Palladium (0.0411g, 0.18mmol, 0.03 equivalent) and ligand S-Phos (0.1536g, 0.37mmol, 98%, 0.06 equivalent).It takes out
Change nitrogen three times, be then added under nitrogen protection Isosorbide-5-Nitrae-dioxane (36mL) and potassium carbonate (4.2218g, 30.5mmol,
5.0 equivalents) aqueous solution (12mL).Then there-necked flask is placed in 100 DEG C of oil baths.After stirring 24 hours, thin-layer chromatography monitoring
Reaction is completed.It is cooled to room temperature, separates organic phase, water phase is extracted with ethyl acetate (30mL × 2).Merge all organic phases, nothing
Aqueous sodium persulfate dries, filters, and gained crude product is isolated and purified (eluent: petroleum by Flash silica column chromatography chromatogram by concentration
Ether/ethyl acetate=50/1) obtain A4, white solid 4.0225g, yield 90%.1H NMR (500MHz, DMSO-d6) δ 7.75 (s,
2H), 7.69 (d, J=7.5Hz, 4H), 7.57 (d, J=7.4Hz, 2H), 7.55-7.43 (m, 8H), 7.40 (s, 1H), 7.36
(t, J=7.3Hz, 2H), 6.91 (s, 1H), 3.90 (s, 6H).
A4 (1.1063g, 2.5mmol, 1.0 equivalent), first are sequentially added into the there-necked flask of the drying with magnetic rotor
Benzene (20mL) and n-hexane (20mL).Then under nitrogen protection be added dropwise Boron tribromide (0.60mL, d=2.6g/ml,
6.25mmol, 2.5 equivalents).After being stirred at room temperature 25 hours, being rapidly added alchlor, (0.0133g, 0.1mmol, 0.04 work as
Amount), then there-necked flask is placed in 75 DEG C of oil baths.After stirring 17 hours, it is cooled to room temperature, trimethyl is added dropwise under nitrogen protection
Phenyl-magnesium-bromide (15mL, 1M tetrahydrofuran solution, 15mmol, 5.0 equivalents).Continue stirring 1 hour, thin-layer chromatography monitoring reaction
It completes.Concentration, isolates and purifies (eluent: petroleum ether~petroleum ether/bis- by Flash silica column chromatography chromatogram for gained crude product
Chloromethanes=50/1) obtain BO31, white solid 1.3289g, yield 79%.1H NMR (500MHz, CDCl3) δ 9.33 (s, 1H),
8.64 (d, J=0.9Hz, 2H), 7.91 (d, J=7.7Hz, 2H), 7.78 (d, J=7.1Hz, 4H), 7.74 (s, 1H), 7.66
(dd, J=7.7,1.4Hz, 2H), 7.56 (t, J=7.6Hz, 4H), 7.47 (t, J=7.4Hz, 2H), 6.97 (s, 4H), 2.38
(s, 6H), 2.26 (s, 12H).
Fig. 4 is the dichloromethane solution of compound BO31 at room temperature with its 2- methyltetrahydrofuran solution at 77K
Emission spectrum spectrogram.Its Emission Spectrum Peals at room temperature is 363nm, is in UV light region；The highest transmitting light of 77K energy level
Spectrum peak is 485nm, thus can calculate its triplet and be up to 2.56eV, can be used as green light material of main part.
Embodiment 5: compound BO34 can be synthesized by following route:
Bromo- 4, the 6- dimethoxy benzene of 1,3- bis- is sequentially added into the there-necked flask of the drying with magnetic rotor
(3.0515g, 10mmol, 97%, 1.0 equivalents), 4- biphenylboronic acid (4.4449g, 22mmol, 98%, 2.2 equivalents), palladium acetate
(0.0674g, 0.3mmol, 0.03 equivalent) and ligand S-Phos (0.2513g, 0.6mmol, 98%, 0.06 equivalent).Substitute nitrogen
Three times, Isosorbide-5-Nitrae-dioxane (60mL) and potassium carbonate (6.9100g, 50mmol, 5.0 equivalent) is then added in gas under nitrogen protection
Aqueous solution (20mL).Then there-necked flask is placed in 110 DEG C of oil baths.After stirring 24 hours, thin-layer chromatography monitoring reaction is completed.
It is cooled to room temperature, separates organic phase, water phase is extracted with ethyl acetate (30mL × 2).Merge all organic phases, anhydrous sodium sulfate is dry
It is dry, it filters, gained crude product is isolated and purified (eluent: petroleum ether/acetic acid second by Flash silica column chromatography chromatogram by concentration
Ester=50/1) obtain A5, white solid 4.4216g, yield 99%.1H NMR (500MHz, CDCl3) δ 7.67-7.61 (m, 12H),
7.47-7.41 (m, 5H), 7.34 (t, J=7.4Hz, 2H), 6.69 (s, 1H), 3.91 (s, 6H).
A5 (1.3275g, 3mmol, 1.0 equivalent) and toluene are sequentially added into the there-necked flask of the drying with magnetic rotor
(50mL).Boron tribromide (0.72mL, d=2.6g/ml, 7.5mmol, 2.5 equivalent) then is added dropwise under nitrogen protection.Room temperature is stirred
After mixing 22 hours, it is rapidly added alchlor (0.0160g, 0.12mmol, 0.04 equivalent), there-necked flask is then placed in 75 DEG C of oil
In bath.It after stirring 27 hours, is cooled to room temperature, trimethylphenyl magnesium bromide (12mL, 1M tetrahydrofuran is added dropwise under nitrogen protection
Solution, 12mmol, 4.0 equivalents).Continue stirring 1 hour, thin-layer chromatography monitoring reaction is completed.Concentration, gained crude product is passed through
Flash silica column chromatography chromatogram isolates and purifies (eluent: petroleum ether~petroleum ether/methylene chloride=50/1) and obtains BO34, and white is solid
Body 1.6806g, yield 84%.1HNMR (500MHz, CDCl3) δ 9.29 (s, 1H), 8.62 (d, J=8.5Hz, 2H), 8.11 (dd,
J=8.4,2.1Hz, 2H), 8.04 (d, J=2.0Hz, 2H), 7.72 (s, 1H), 7.62 (d, J=7.1Hz, 4H), 7.45 (t, J
=7.6Hz, 4H), 7.36 (t, J=7.4Hz, 2H), 6.95 (s, 4H), 2.37 (s, 6H), 2.26 (s, 12H).
Fig. 5 is the dichloromethane solution of compound BO34 at room temperature with its 2- methyltetrahydrofuran solution at 77K
Excitation and emission spectra spectrogram.Its Emission Spectrum Peals at room temperature is 373nm, is in UV light region；77K energy level is highest
Emission Spectrum Peals are 482nm, thus can calculate its triplet and be up to 2.57eV, can be used as green light material of main part.
Performance evaluation embodiment
Light object is carried out to double boron oxa- dibenzo [A, J] anthracene derivants prepared in the above embodiment of the present invention below
Reason, electrochemistry and thermogravimetric analysis:
Optical physics analysis: phosphorescence emission spectra, fluorescence emission spectrum, triplet lifetime, lifetime of excited state are in HORIBA
It tests and completes on FL3-11 spectrometer.Test condition: in Room temperature emission spectra, all samples are that methylene chloride (chromatographic grade) is dilute
Solution (10-5-10-6M), and sample is completed to prepare in glove box, and logical nitrogen 5 minutes；Triplet lifetime detects in sample
It is measured at the highest peak of product emission spectrum.
Electrochemical analysis: it is tested on CH670E type electrochemical workstation using cyclic voltammetry.With the four of 0.1M positive fourths
Base ammonium hexafluorophosphate (nBu4NPF6) n,N-dimethylacetamide (DMF) solution be electrolyte solution；Metal foil electrodes are positive
Pole；Graphite is cathode；Metallic silver is as reference electrode；Ferrocene is reference internal standard, and its redox potential is set to zero.
Thermogravimetric analysis: thermal gravimetric analysis curve is completed in TGA2 (SF) thermogravimetric analysis.Thermogravimetric analysis test condition are as follows: survey
Trying temperature is 50-700 DEG C；Heating rate is 20K/min；Crucible material is aluminum oxide；And it completes to survey under nitrogen atmosphere
Examination；Sample quality is generally 2-5mg.
Double boron oxa- dibenzo [A, J] anthracene derivants of above-described embodiment 1-5 preparation and the structure of reference material are as follows.
The photophysical property and thermogravimetric analysis data of 1. pairs of boron oxa- dibenzo [A, J] anthracene derivant materials of table
Note: Peak refers to the most strong emission peak of double boron oxa- dibenzo [A, J] anthracene derivant material Room temperature emission spectras.
PLQY refers to absolute luminescence quantum efficiency.The Room temperature emission spectra of double boron oxa- dibenzo [A, J] anthracene derivant materials is in dichloro
It is measured in dichloromethane, the measurement in 2- methyltetrahydrofuran (2-Me-THF) of 77K emission spectrum.Triplet (T1) by it
Phosphorescence spectrum under 77K is calculated.Thermal decomposition temperature (Td) obtained by thermogravimetric analysis (TGA) curve.Glass transition temperature
(Tg) and fusing point (m.p.) obtained by differential scanning calorimetry (DSC) curve.
Double boron oxa- dibenzo [A, J] anthracene derivant materials at room temperature the excitation in dichloromethane solution and transmitting light
Excitation and emission spectra under spectrum, 77K in 2- methyltetrahydrofuran (2-Me-THF) refers to attached drawing 1-5.
Thin-film device photophysical property data of the 2. pairs of boron oxa- pyrene derivatives of table as blue light and deep Blue-light emitting host material
Wherein, the structure of blue light material PtON1 is as follows:
It was found from attached drawing 1-5 and table 1: first, double boron oxa- dibenzo [A, J] anthracene derivant materials provided by the present invention
Material has very high luminous quantum efficiency (PLQY), is approximately 2-4 times of reference material up to 51.4-95.5%；And it all shows
Very short lifetime of excited state 1.21-2.06ns, nanosecond (ns, 10-9Second) order of magnitude.Second, thermal decomposition temperature and vitrifying
Transition temperature is high, such as BO34 thermal decomposition temperature is higher by nearly 100 more than reference material and spends, and glass transition temperature is the close of reference material
2 times.Third, double boron oxa- dibenzo [A, J] anthracene derivant various structures and being easy to modify, three lines that can easily be accommodated are made it have
State energy level (T1), it can be used as the material of main part of various illuminators.As shown in table 1, the triplet of BO31 and BO34 between
Between 2.56-2.57eV, it can be used as the material of main part of feux rouges and green emission body；And BO1, BO2 and BO7 have very high three line
State energy level (2.81-2.88eV), can be used as the material of main part of blue light emitters；So that derivative of the invention can be used as luminous material
Material or material of main part are applied in optics or electro-optical device, including photosensitive device, Organic Light Emitting Diode, light emitting devices and energy
The device of enough compatible light absorption and transmitting.As shown in table 2, using BO1 and BO2 as the absolute quantum of the thin-film device of material of main part
Efficiency is above 80%, and the high efficiency energy for illustrating to have occurred main body to guest materials under excitation state shifts, at the same show BO1 and
BO2 is feasible as Blue-light emitting host material.An effective solution way is provided for Blue-light emitting host material in short supply at present
Diameter, to push the development in this field significantly.
It will be understood by those skilled in the art that the respective embodiments described above are to realize specific embodiments of the present invention,
And in practical applications, can to it, various changes can be made in the form and details, without departing from the spirit and scope of the present invention.
For example, many materials and structure described herein can use other materials and knot without departing substantially from spirit of the invention
Structure replaces.
Claims (5)
1. a kind of double boron oxa- dibenzo [A, J] anthracene derivants, which is characterized in that the structure of the derivative are as follows:
Wherein, Ra、Rb、Rc、RdAnd ReIt is each independently hydrogen, deuterium, alkyl, alkoxy, naphthenic base, ether, heterocycle, phenyl, virtue
Oxygroup, halogen, cyano or combinations thereof；Ar is hexa-atomic aryl, heteroaryl, thick aryl, the thick aryl of azepine；M is the integer of 0-5；N is
The integer of 0-4.
2. double boron oxa- dibenzo [A, J] anthracene derivants according to claim 1, which is characterized in that the derivative is excellent
It is selected as:
3. double boron oxa- dibenzo [A, J] anthracene derivants according to claim 1, which is characterized in that the derivative is
Electroneutral.
4. a kind of application of derivative described in claim 1, which is characterized in that the derivative is as luminescent material or main body
Material is applied in optics or electrooptical device.
5. a kind of application according to claim 4, which is characterized in that the optics or electrooptical device include photosensitive device,
Organic Light Emitting Diode, light emitting devices and the device that light absorption and transmitting can be compatible with.
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| CN112225752A (en) * | 2020-11-11 | 2021-01-15 | 浙江虹舞科技有限公司 | Centrosymmetric type double-boron oxapolycyclic aromatic compound luminescent material and application thereof |
| CN112442057A (en) * | 2020-11-19 | 2021-03-05 | 浙江工业大学 | Deep blue light luminescent material containing plane-symmetric type bisboroxapolycyclic aromatic compound |
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| KR20090008736A (en) * | 2007-07-18 | 2009-01-22 | 제일모직주식회사 | Aza-/oxa-boraphenanthrene derivatives for organic electroluminescent device thereby |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112225752A (en) * | 2020-11-11 | 2021-01-15 | 浙江虹舞科技有限公司 | Centrosymmetric type double-boron oxapolycyclic aromatic compound luminescent material and application thereof |
| CN112225752B (en) * | 2020-11-11 | 2023-01-06 | 浙江虹舞科技有限公司 | Centrosymmetric type double-boron oxapolycyclic aromatic compound luminescent material and application thereof |
| CN112442057A (en) * | 2020-11-19 | 2021-03-05 | 浙江工业大学 | Deep blue light luminescent material containing plane-symmetric type bisboroxapolycyclic aromatic compound |
| CN112442057B (en) * | 2020-11-19 | 2022-07-08 | 浙江工业大学 | Deep blue light luminescent material containing plane-symmetric type bisboroxapolycyclic aromatic compound |
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