CN107973808A - A kind of spherical organic photoelectric material and preparation method and application - Google Patents
A kind of spherical organic photoelectric material and preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of spherical organic photoelectric material and preparation method and application, which is non-conjugated spherical, and the right and left is donor monomer, and centre is receptor unit, there is certain torsion angle between the two, has big energy gap, and is easy to have less △ EST, so as to be easily achieved thermal excitation delayed fluorescence（TADF）, can fully be used as blue light thermal excitation delayed fluorescence material, extend the application available for organic luminescent device, particularly blue-light device.The synthetic method of the organic photoelectrical material is fairly simple, and purification is easy to, and yield is also highly desirable.
Description
Technical field
The present invention relates to field of photovoltaic materials, more particularly to a kind of spherical organic photoelectric material and preparation method thereof is with answering
With.
Background technology
Organic luminescent device, particularly Organic Light Emitting Diode (OLED), since it is high with self-luminous, surface light emitting
The advantages of compliance, high-resolution, high-luminous-efficiency, the response time is fast, high brightness etc., becomes and is most hopeful at present
Display of future generation and lighting engineering.It is subject to scientific and technological circle and industrial circle to pay much attention in recent years, is current research and the heat of exploitation
One of point.
OLED performances based on small molecule have significant progress, have reached the commercialized stage.Especially green light and red
The application of light, phosphorescence green light and phosphorescence red light material, its efficiency has accomplished 30% or so, and the service life is also highly desirable, still
In terms of blue light, whether phosphor material or fluorescent material, its efficiency and service life cannot all reach preferable state, especially
In the service life, under high current density and for a long time startup, its efficiency decays quickly.
Professor Adachi of Kyushu University in 2009 proposes the concept of thermal excitation delayed fluorescence (TADF), it can be filled
Divide the single triplet excitons for utilizing and being formed under electric field action, so as to realize very high efficiency.
Therefore, synthesize blue light to dark blue light thermal excitation delayed fluorescence material (TADF), be it is necessary, it is efficient
Blue light material can not only solve blue light material cannot commercialized problem, while also can be to prepare efficient commercialized white light
Material provides possibility.
In thermotropic delayed fluorescence field, it is all small molecule material to study widest material at present, especially linear
Small molecule material, the small molecule material and dendroid type small molecule material of three-dimensional structure etc. all studies the fewer of report, right
In spherical small molecule material, up to the present it was not yet reported that.
The content of the invention
In order to overcome the disadvantages mentioned above of the prior art and deficiency, it is an object of the present invention to provide a kind of spherical organic
Photoelectric material, has big energy gap, and is easy to have less △ EST, so that thermal excitation delayed fluorescence (TADF) is easily achieved,
Blue light thermal excitation delayed fluorescence material can be fully used as, extended available for organic luminescent device, particularly blue-light device
Material options.
The second object of the present invention is the preparation method for providing above-mentioned organic photoelectrical material, and synthesis is fairly simple, purification
It is easy to, and yield is also highly desirable.
The third object of the present invention is the application for providing above-mentioned organic photoelectrical material.
The purpose of the present invention is achieved through the following technical solutions.
A kind of spherical organic photoelectric material, the general formula of the organic photoelectrical material are as follows：
Wherein, R1, R2For the A races of IV A, V A, VI atom；R3, R4It is not present or is VI A races atom；
The Ar1, Ar2Selected from lower structure：
(a)Wherein, R5、R6、R7、R8For hydrogen, halogen, the alkyl of 1-6 carbon, the alcoxyl of 1-6 carbon
Base, amino, hydroxyl, aryl, heteroaryl；
(b)Wherein, R9、R10、R11For hydrogen, halogen, the alkane of 1-6 carbon
Base, the alkoxy of 1-6 carbon, amino, hydroxyl, aryl, heteroaryl；
(c)Wherein, R12、R13For hydrogen, halogen, the alkyl of 1-6 carbon,
The alkoxy of 1-6 carbon, amino, hydroxyl, aryl, heteroaryl；
(d)Wherein, R14For hydrogen, halogen, the alkyl of 1-6 carbon, the alkoxy of 1-6 carbon, amino, hydroxyl
Base, aryl, heteroaryl；
(e)Wherein, R15、R16For hydrogen, halogen
Element, the alkyl of 1-6 carbon, the alkoxy of 1-6 carbon, amino, hydroxyl, aryl, heteroaryl；
(f)Wherein, R17、R18、R19For hydrogen, halogen, the alkyl of 1-6 carbon, the alkoxy of 1-6 carbon,
Amino, hydroxyl, aryl, heteroaryl.
Preferably, the R1, R2For S, N or C.
Preferably, the R3, R4For O.
Preferably, the Ar1, Ar2For
Wherein, R5、R6、R7、R8For hydrogen.
Preferably, the organic photoelectrical material is any one in following：
A kind of method of above-described spherical organic photoelectric material, comprises the following steps：
By Pd2(dba)3, P (t-Bu)3Add in benzene series solvent after stirring 10-20 minutes, add 3,3 '-dibromo M1,3,
3 '-diaminourea M2, sodium tert-butoxide, when reflux 20~22 is small at 90-100 DEG C, obtains spherical organic photoelectric material；
The Pd2(dba)3Mole be 3, the 2~3% of 3 '-dibromo M1；P(t-Bu)3Mole be 3,3 '-dibromo
The 5~6% of M1；The mole of sodium tert-butoxide be 3, more than 2 times of 3 '-dibromo M1 moles；3, the mole of 3 '-diaminourea M2
For 3,0.4~0.6 times of 3 '-dibromo M1.
Preferably, described 3, the preparation method of 3 '-dibromo M1 is as follows：Using M1 as raw material, N-bromosuccinimide is added,
In concentrated sulfuric acid, when stirring 1~2 is small at 100~110 DEG C, 3 are obtained, 3 '-dibromo M1；Wherein, N-bromosuccinimide and M1
Molar ratio be more than 2.
Preferably, described 3, the preparation method of 3 '-diaminourea M2 is as follows：Using M3 as raw material, hydrazine hydrate is added, in ethanol
In, be heated to reflux 10~12 it is small when, obtain 3,3 '-diaminourea M2；Wherein, the mole of the hydrazine hydrate is more than 4 times of M3,
The structural formula of M3 is as follows：
A kind of method of above-described spherical organic photoelectric material, comprises the following steps：
Under an inert atmosphere, by Pd2 (dba)3With P (t-Bu)3It is dissolved in toluene, adds 3,3 '-dibromo diphenyl sulfide,
3,3 '-diaminodiphenyl sulfide and sodium tert-butoxide, after leading to inert gas, react 12-48h at 80-110 DEG C, obtain spherical having
Machine photoelectric material；The Pd2(dba)3Mole be 3, the 3%-6% of 3 '-dibromo diphenyl sulfide；P(t-Bu)3Mole
For 3, the 15%-40% of 3 '-dibromo diphenyl sulfide；Sodium tert-butoxide mole be 3, more than 2 times of 3 '-dibromo diphenyl sulfide；3,
The mole of 3 '-diaminodiphenyl sulfide be 3,0.4~0.6 times of 3 '-dibromo diphenyl sulfide.
Preferably, metachloroperbenzoic acid is added dropwise into the dichloromethane solution of the spherical organic photoelectric material,
Reacted 5-60 minutes at -10--0 DEG C, obtain spherical organic photoelectric material.
The application in organic electronic device of above-described organic photoelectrical material, the organic electronic device are organic
Light emitting electrochemical cell, Organic Light Emitting Diode, organic field effect tube or organic sensor.
Compared with prior art, the present invention has the following advantages and beneficial effect：
(1) organic photoelectrical material of the invention is non-conjugated spherical that the right and left is donor monomer (D unit), and centre is
Receptor unit (A units), there is certain torsion angle between the two, has big energy gap, and is easy to have less △ EST, so that
Thermal excitation delayed fluorescence (TADF) is easily achieved, can fully be used as blue light thermal excitation delayed fluorescence material, extend and can be used for
The material options of organic luminescent device, particularly blue-light device.
(2) synthetic method of the invention is fairly simple, and purification is easy to, and yield is also highly desirable.Due to spheroidal material and line
Shape material belongs to competitive relation in synthesis, and spheroidal material is to belong to accessory substance, i.e. generation ratio is small, generally all 10%
Hereinafter, and by the present invention synthetic method illustrated, the yield of spheroidal material is attained by more than 10%, therefore the present invention provides
Synthetic method have more practicality.
Brief description of the drawings
Fig. 1 a~Fig. 1 g are the mass spectrogram of 1~7 products therefrom of the embodiment of the present invention.
Fig. 2 is the absorption figure of 1~7 products therefrom of the embodiment of the present invention.
Fig. 3 is the transmitting figure of 1~7 products therefrom of the embodiment of the present invention.
Fig. 4 is that the low temperature PL of 7 products therefrom of the embodiment of the present invention schemes.
Fig. 5 is the electrochemical Characterization figure of 1~7 products therefrom of the embodiment of the present invention.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1：The synthesis of 3S
(1) 3, the synthesis of 3 '-dibromo diphenyl sulfide
Bromo-iodobenzene (50mmol, 14.145g) between being added into two-mouth bottle, thiosemicarbazide (30mmol, 2.734g), acetic acid
Copper (2.5mmol, 499.12mg), potassium carbonate (50mmol, 6.9105g) and DMSO (50ml), reaction solution is under the conditions of 120 DEG C
12h is stirred, after reaction, is cooled to room temperature, the liquid after reaction is poured into 100mL water, is extracted with dichloromethane, water
Wash, take organic layer, concentrate, cross silicagel column, obtain pure products 3,3 '-dibromo diphenyl sulfide, yield 85%,1H NMR
(500MHz,CDCl3) δ 7.47 (t, J=1.8Hz, 2H), 7.39 (ddd, J=7.9,1.9,1.1Hz, 2H), 7.26-7.23 (m,
2H), 7.17 (t, J=7.9Hz, 2H) share four pairs of totals, 8 hydrogen, nuclear-magnetism coincide very from hydrogen nuclear magnetic resonance modal data
It is good, that is, obtain product 3,3 '-dibromo diphenyl sulfide；Shown in synthetic route such as following formula (1)：
(2) 3, the synthesis of 3 '-dinitro diphenyl sulfide
Nitro iodobenzene (50mmol, 12.45g) between being added into two-mouth bottle, thiosemicarbazide (30mmol, 2.734g), vinegar
Sour copper (2.5mmol, 499.12mg), potassium carbonate (50mmol, 6.9105g) and DMSO (50ml), reaction solution is in 120 DEG C of conditions
Lower stirring 12h, after reaction, is cooled to room temperature, and reaction solution is poured into 100mL water, is extracted with dichloromethane, and washing, takes
Organic layer, concentration, crosses silicagel column, obtains pure products 3,3 '-dinitro diphenyl sulfide, yield 40%,1H NMR(500MHz,
CDCl3) δ 8.22-8.19 (m, 2H), 8.19-8.15 (m, 2H), 7.70-7.66 (m, 2H), 7.58-7.53 (m, 2H) are by nuclear-magnetism
The hydrogen modal data that resonates is understood, shares four pairs of totals, 8 hydrogen, and nuclear-magnetism coincide fine, that is, obtains product 3,3 '-dinitro diphenyl sulfide
Ether；Shown in synthetic route such as following formula (2)：
(3) 3, the synthesis of 3 '-diaminodiphenyl sulfide
Pd/C (0.5g) is added into 3,3 '-dinitro diphenyl sulfide (10mmol, 2.76g), 80wt% hydrazine hydrates are water-soluble
Liquid (30ml), ethanol (250ml), reaction solution stirs 12h under the conditions of 90 DEG C, after reaction, is cooled to room temperature, after suction filtration,
It is extracted with ethyl acetate, washes, take organic layer, be spin-dried for, obtain pure products 3,3 '-diaminodiphenyl sulfide, yield 98%,1H
NMR(500MHz,DMSO-d6) δ 6.98 (t, J=7.8Hz, 2H), 6.55 (t, J=2.0Hz, 2H), 6.46 (dddd, J=7.0,
3.6,1.9,0.9Hz, 4H), 5.17 (s, 4H) are shown 4 hydrogen at 5.17, are ammonia from hydrogen nuclear magnetic resonance modal data
The hydrogen of base, nuclear-magnetism coincide fine, that is, obtain product 3,3 '-diaminodiphenyl sulfide；Shown in synthetic route such as following formula (3)：
(4) synthesis of 3S
Pd2(dba)3(2.74g, 3mmol), P (t-Bu)3(18mL, 18mmol) is added in two-mouth bottle, substitutes gas (inertia
Gas) 3 times, add 100mL toluene, 15min stirred under normal temperature condition, then by 3,3 '-dibromo diphenyl sulfide (20.6g,
60mmol), 3,3 '-diaminodiphenyl sulfide (6.5g, 30mmol), sodium tert-butoxide (17.3g, 180mmol) is added thereto, and is added
400mL toluene, after leading to inert gas 10min, for oil bath heating to 90 DEG C of reaction 24h, reaction was completed, filters, removes salt and other
Insoluble matter obtains filtrate, then carries out pillar layer separation, obtains pure products 3S, yield 10%,1H NMR(500MHz,CDCl3)δ
7.16 (t, J=7.9Hz, 6H), 7.02 (ddd, J=7.7,1.7,1.0Hz, 6H), 6.94 (ddd, J=8.0,2.2,1.0Hz,
6H), 6.59 (t, J=1.9Hz, 6H)；13C NMR(126MHz,CDCl3)δ149.89,136.06,130.22,125.52,
124.63,124.32；MODI-TOF(m/z):calcd for C36H24N2S3 580.78；found,580.0248[M+]；Close
Into route such as following formula (4) Suo Shi：
Embodiment 2：The synthesis of 2S 1SO
Metachloroperbenzoic acid (36mg) is added dropwise into the dichloromethane solution of 3S (100mg), reaction half is small at 0 DEG C
Shi Hou, is poured into water, and dichloromethane extraction, washing, is spin-dried for, and crosses silicagel column, obtains pure products 2S1SO, yield 50%,1H
NMR(500MHz,CD2Cl2) δ 8.30-8.25 (m, 2H), 8.17-8.10 (m, 2H), 7.94 (td, J=7.9,5.1Hz, 6H),
7.78 (dddd, J=7.7,4.8,1.7,1.0Hz, 4H), 7.75-7.70 (m, 4H), 7.35-7.29 (m, 2H), 7.27 (t, J=
1.7Hz,2H),7.01(s,2H)；13C NMR(126MHz,CD2Cl2)δ150.57,145.69,137.47,131.84,
131.83,131.56,127.32,126.26,126.06,121.55；MODI-TOF(m/z):calcd for
C36H24N2OS3596.78；found,619.0018[M+Na+]；Shown in synthetic route such as following formula (5)：
Embodiment 3：The synthesis of 1S 2SO
Metachloroperbenzoic acid (72mg) is added dropwise into the dichloromethane solution of 3S (100mg), reaction half is small at 0 DEG C
Shi Hou, is poured into water, and dichloromethane extraction, washing, is spin-dried for, and crosses silicagel column, obtains pure products 1S 2SO, yield 30%,1H
NMR(500MHz,CD2Cl2) δ 8.29 (dd, J=54.8,16.2Hz, 4H), 8.14 (dt, J=14.3,7.0Hz, 6H), 7.96
(dt, J=8.0,7.5Hz, 6H), 7.89 (dd, J=8.1,1.0Hz, 2H), 7.53 (s, 2H), 7.31-7.02 (m, 4H)；13C
NMR(126MHz,CD2Cl2)δ151.75,150.94,150.90,149.92,139.48,131.97,131.90,131.60,
131.57,129.70,129.55,129.41,128.40,128.28,119.71；MODI-TOF(m/z):calcd
forC36H24N2O2S3 612.78；found,634.9948[M+Na+]；Shown in synthetic route such as following formula (6)：
Embodiment 4：The synthesis of 3SO
Metachloroperbenzoic acid (108mg) is added dropwise into the dichloromethane solution of 3S (100mg), reacts half at 0 DEG C
After hour, it is poured into water, dichloromethane extraction, washing, is spin-dried for, and crosses silicagel column, obtains pure products 3SO, yield 80%,1H
NMR(500MHz,DMSO-d6)δ7.62–7.52(m,6H),7.51–7.40(m,6H),7.39–7.27(m,6H),6.80–6.69
(m,3H),6.52–6.40(m,3H)；13CNMR(126MHz,DMSO-d6)δ151.17,151.10,150.03,149.98,
149.86,149.76,149.67,149.13,148.85,148.74,131.73,131.59,131.45,131.39,131.30,
129.35,129.20,129.00,121.25,121.04,119.38,119.25,119.03,117.48,117.41,117.31,
117.04,116.95,116.81；MODI-TOF(m/z):calcd for C36H24N2O3S3 628.78；found,
650.9911[M+Na+]；Shown in synthetic route such as following formula (7)：
Embodiment 5：The synthesis of 2SO 1SO2
Metachloroperbenzoic acid (144mg) is added dropwise into the dichloromethane solution of 3S (100mg), reacts half at 0 DEG C
After hour, it is poured into water, dichloromethane extraction, washing, is spin-dried for, and crosses silicagel column, obtains pure products 2SO 1SO2, yield is
70%,1H NMR(500MHz,DMSO-d6)δ7.67–7.28(m,18H),6.81–6.63(m,6H)；13C NMR(126MHz,
DMSO-d6)δ151.29,150.97,150.00,149.77,149.73,149.41,143.37,132.05,131.88,
131.53,131.40,129.57,129.17,128.99,123.63,123.50,121.43,121.04,120.43,117.64,
117.21,116.40；MODI-TOF(m/z):calcd for C36H24N2O4S3 644.78；found,666.9832[M+Na+]；Shown in synthetic route such as following formula (8)：
Embodiment 6：The synthesis of 1SO 2SO2
Metachloroperbenzoic acid (180mg) is added dropwise into the dichloromethane solution of 3S (100mg), reacts half at 0 DEG C
After hour, it is poured into water, dichloromethane extraction, washing, is spin-dried for, and crosses silicagel column, obtains pure products 1SO 2SO2, yield is
60%,1H NMR(500MHz,DMSO-d6)δ7.77–7.48(m,16H),7.43–7.36(m,2H),6.85(s,1H),6.70–
6.59(m,5H)；13C NMR(126MHz,DMSO-d6)δ151.23,150.91,150.73,150.69,150.62,150.05,
149.81,149.62,143.64,143.41,132.47,132.43,132.29,132.24,132.14,131.90,131.77,
131.62,129.39,128.86,123.91,123.79,123.70,123.57,123.38,123.22,122.82,122.73,
121.72,120.15,117.64,116.30；MODI-TOF(m/z):calcd for C36H24N2O5S3 660.78；
found,682.9808[M+Na+]；Shown in synthetic route such as following formula (9)：
Embodiment 7：The synthesis of 3SO2
Metachloroperbenzoic acid (216mg) is added dropwise into the dichloromethane solution of 3S (100mg), reacts half at 0 DEG C
After hour, it is poured into water, dichloromethane extraction, washing, is spin-dried for, and crosses silicagel column, obtains pure products 3SO2, yield 90%,1H
NMR(500MHz,CDCl3)δ7.80–7.67(m,6H),7.56–7.47(m,6H),7.46–7.37(m,6H),6.82–6.74
(m,6H)；13C NMR(126MHz,CDCl3)δ150.15,144.08,131.51,131.13,123.86,123.39；MODI-
TOF(m/z):calcd for C36H24N2O6S3 676.78；found,698.9717[M+Na+]；Synthetic route such as following formula
(10) shown in：
Embodiment 8：The synthesis of 3SO2
By Pd2(dba)3(2.74g, 3mmol), P (t-Bu)3(18mL, 18mmol) is added in two-mouth bottle, and it is (lazy to substitute gas
Property gas) 3 times, add 100mL toluene, 15min stirred under normal temperature condition, then by 3,3 '-dibromo diphenyl sulphone (DPS) (20.6g,
60mmol), 3,3 '-diaminodiphenylsulfone (6.5g, 30mmol), sodium tert-butoxide (17.3g, 180mmol) is added thereto, and is added
400mL toluene, after leading to inert gas 10min, for oil bath heating to 90 DEG C of reaction 24h, reaction was completed, filters, removes salt and other
Insoluble matter obtains filtrate, then carries out pillar layer separation, obtains pure products 3SO2.
The test result of the organic photoelectrical material of embodiment 1~7 is as follows：
Fig. 1 a~Fig. 1 g are the mass spectrogram of final products obtained by 1-7 of the embodiment of the present invention, can from Fig. 1 a~Fig. 1 g
Go out, each mass spectrogram coincide fine with corresponding compound, that is, has obtained target compound；Fig. 2 and Fig. 3 is real for the present invention
The absorption of final product and a transmitting figure obtained by 1-7 are applied, is final product prepared by each embodiment in dichloromethane solution state
Under, its absorption is tested by UV-Vis absorption spectrometers and tests what its transmitting was got by Fluorescence Spectrometer；Fig. 4 is this hair
The low temperature PL figures of bright 7 gained final product of embodiment, are by Fluorescence Spectrometer, it are tested two under cryogenic conditions (77K)
What the transmitting under the weak solution state of chloromethanes was got, as can be seen from the figure embodiment 7 prepare final product phosphorescence peak,
And then its triplet can be tried to achieve；Fig. 5 is the electrochemical Characterization figure of various embodiments of the present invention, is used by electrochemical workstation
Cyclic voltammetry measures Current Voltage figure of the final product of each embodiment preparation under filminess, can be in the hope of each embodiment
The HOMO energy levels of the final product of preparation.
In order to better illustrate organic photoelectrical material, and the organic photoelectric material can be successfully synthesized with the method for the present invention
Material has lag characteristic and optical property, therefore has carried out performance test to the embodiment 1-7 final products prepared, predominantly detects
Its nuclear-magnetism, mass spectrum, △ EST, HOMO, LUMO, hot property and optical property etc., testing result is as shown in table 1.Wherein nuclear-magnetism
It is to be measured by nuclear magnetic resonance chemical analyser；Mass spectrum is measured by Maldi TOF mass spectrographs；△ESTIt is by measuring low temperature
After PL, S1 and T1 are obtained, then subtracts each other to obtain；HOMO, LUMO are to survey electrochemistry by cyclic voltammetry to obtain, with ferrocene
As calibration, saturated calomel electrode is as reference electrode, and platinum electrode is as working electrode；Heat decomposition temperature (Td) is to pass through measurement
Sample weight variation with temperature in an inert atmosphere, heat decomposition temperature is used as using 5% weightless corresponding temperature.
Table 1
The wherein △ E of 7 gained final product of embodimentSTLess than 0.30eV, the final production of the gained of embodiment 7 is fully shown
The lag characteristic of thing.
The S1 and T1 of embodiment 7 are that 7 products therefrom of embodiment is made into the weak solution of dichloromethane in table 1, then are passed through
Low temperature time resolved spectroscopy and emission spectrum measure to obtain, in addition the fluorescent emission peak-to-peak value under room temperature all 420nm it
Before, compared to the emission peak (474nm) of traditional day blue light TADF materials DMAC-DPS, it is glimmering that this fully compensate for thermotropic delay
Vacancy of light (TADF) material in terms of dark blue light to purplish blue light.
As shown in Table 1, the Td of embodiment 1-7 products therefroms has respectively reached more than 338 DEG C, illustrates embodiment 1-7 institutes
Obtaining product all has preferable heat endurance.
As shown in Table 1, the emission peak of embodiment 1-7 products therefroms is all in visible region, and produced obtained by embodiment 1-7
The singlet energy level (S1) of thing all in more than 3.18eV, postpones so embodiment 1-7 products therefroms perfect can be used as hot activation
Fluorescent material and its material of main part, are highly suitable in a kind of organic electronic device, especially Organic Light Emitting Diode
(OLED) material of main part of the emitting layer material in device and luminescent layer；It can be certainly also used to other illumination fields.
In thermotropic delayed fluorescence field, it is all small molecule material to study widest material at present, especially linear
Small molecule material, the small molecule material and dendroid type small molecule material of three-dimensional structure etc. all studies the fewer of report, right
In spherical small molecule material, up to the present it was not yet reported that, therefore material structure of the present invention is novel, additionally, due to spherical
Material belongs to competitive relation with linear material in synthesis, and spheroidal material is to belong to accessory substance, i.e. generation ratio is small, generally
All below 10%, and the synthetic method illustrated by the present invention, the yield of ring-shaped material are attained by more than 10%, therefore this
The synthetic method that invention provides has more practicality.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention and from the embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
- A kind of 1. spherical organic photoelectric material, it is characterised in that, the general formula of the organic photoelectrical material is as follows：Wherein, R1, R2For the A races of IV A, V A, VI atom；R3, R4It is not present or is VI A races atom；The Ar1, Ar2Selected from lower structure：(a)Wherein, R5、R6、R7、R8For hydrogen, halogen, the alkyl of 1-6 carbon, the alkoxy of 1-6 carbon, ammonia Base, hydroxyl, aryl, heteroaryl；(b)Wherein, R9、R10、R11For hydrogen, halogen, the alkyl of 1-6 carbon, 1-6 The alkoxy of a carbon, amino, hydroxyl, aryl, heteroaryl；(c)Wherein, R12、R13It is a for hydrogen, halogen, the alkyl of 1-6 carbon, 1-6 The alkoxy of carbon, amino, hydroxyl, aryl, heteroaryl；(d)Wherein, R14For hydrogen, halogen, the alkyl of 1-6 carbon, the alkoxy of 1-6 carbon, amino, hydroxyl, virtue Base, heteroaryl；(e)Wherein, R15、R16For hydrogen, halogen, 1-6 The alkyl of a carbon, the alkoxy of 1-6 carbon, amino, hydroxyl, aryl, heteroaryl；(f)Wherein, R17、R18、R19For hydrogen, halogen, the alkyl of 1-6 carbon, the alkoxy of 1-6 carbon, amino, Hydroxyl, aryl, heteroaryl.
- A kind of 2. spherical organic photoelectric material according to claim 1, it is characterised in that, the R1, R2For S, N or C.
- A kind of 3. spherical organic photoelectric material according to claim 1, it is characterised in that, the R3, R4For O.
- A kind of 4. spherical organic photoelectric material according to claim 1, it is characterised in that, the Ar1, Ar2ForWherein, R5、R6、R7、R8For hydrogen.
- A kind of 5. spherical organic photoelectric material according to claim 1, it is characterised in that, the organic photoelectrical material be with Any one in lower：
- 6. prepare a kind of method of spherical organic photoelectric material of claim 1-5 any one of them, it is characterised in that, including with Lower step：By Pd2(dba)3, P (t-Bu)3Add in benzene series solvent after stirring 10-20 minutes, add 3,3 '-dibromo M1,3,3 '- Diaminourea M2, sodium tert-butoxide, when reflux 20~22 is small at 90-100 DEG C, obtains spherical organic photoelectric material；The Pd2(dba)3Mole be 3, the 2~3% of 3 '-dibromo M1；P(t-Bu)3Mole be 3,3 '-dibromo M1's 5~6%；The mole of sodium tert-butoxide be 3, more than 2 times of 3 '-dibromo M1 moles；The mole of 3,3 '-diaminourea M2 are 3, 0.4~0.6 times of 3 '-dibromo M1.
- A kind of 7. preparation method of spherical organic photoelectric material according to claim 6, it is characterised in that described 3,3 '- The preparation method of dibromo M1 is as follows：Using M1 as raw material, N-bromosuccinimide is added, in concentrated sulfuric acid, at 100~110 DEG C When stirring 1~2 is small, 3 are obtained, 3 '-dibromo M1；Wherein, the molar ratio of N-bromosuccinimide and M1 are more than 2；Described 3,3 '- The preparation method of diaminourea M2 is as follows：Using M3 as raw material, add hydrazine hydrate, in ethanol, be heated to reflux 10~12 it is small when, obtain To 3,3 '-diaminourea M2；Wherein, the mole of the hydrazine hydrate is more than 4 times of M3, and the structural formula of M3 is as follows：
- 8. prepare a kind of method of spherical organic photoelectric material of claim 1-5 any one of them, it is characterised in that, including with Lower step：Under an inert atmosphere, by Pd2(dba)3With P (t-Bu)3It is dissolved in toluene, adds 3,3 '-dibromo diphenyl sulfide, 3,3 '- Diaminodiphenyl sulfide and sodium tert-butoxide, after leading to inert gas, react 12-48h at 80-110 DEG C, obtain spherical organic photoelectricity Material；The Pd2(dba)3Mole be 3, the 3%-6% of 3 '-dibromo diphenyl sulfide；P(t-Bu)3Mole for 3,3 '- The 15%-40% of dibromo diphenyl sulfide；Sodium tert-butoxide mole be 3, more than 2 times of 3 '-dibromo diphenyl sulfide；3,3 '-diamino The mole of base diphenyl sulfide be 3,0.4~0.6 times of 3 '-dibromo diphenyl sulfide.
- A kind of 9. preparation method of spherical organic photoelectric material according to claim 8, it is characterised in that, to described spherical Metachloroperbenzoic acid is added dropwise in the dichloromethane solution of organic photoelectrical material, reacts 5-60 minutes, obtains at -10-0 DEG C To spherical organic photoelectric material.
- 10. the application in organic electronic device of claim 1-4 any one of them organic photoelectrical materials, its feature exist In the organic electronic device is organic light emission battery, Organic Light Emitting Diode, organic field effect tube or organic sensing Device.
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| CN114026711A (en) * | 2019-04-03 | 2022-02-08 | 图尔库大学 | White organic light emitting device and method for producing the same |
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| YANG, HE等: "A Phosphanthrene Oxide Host with Close Sphere Packing for Ultralow-Voltage-Driven Efficient Blue Thermally Activated Delayed Fluorescence Diodes", 《ADVANCED MATERIALS (WEINHEIM, GERMANY)》 * |
| 郭文生等: "球形主体分子的包结性能及其在制备有机非线性光学材料中的应用", 《化学学报》 * |
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