CN110183361A - ' cross ' type thermal activities delayed fluorescence material being constructed and its applying - Google Patents
' cross ' type thermal activities delayed fluorescence material being constructed and its applying Download PDFInfo
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Abstract
The invention discloses a kind of organic thermal activities delayed fluorescence material based on bis- (phenyl sulfonyl) benzene and its applications in solution processing type organic electroluminescence device.Present invention introduces two-dimensional molecular concepts, introduce triphenylamine, 9,9- dimethyl acridinium and phenthazine donor monomer respectively in bis- (phenyl sulfonyl) the benzene units of electron acceptor, have constructed serial ' cross ' type thermal activities delayed fluorescence material.This kind of material is conducive to separate the highest occupied molecular orbital of molecule and the spatial distribution of lowest unoccupied molecular orbital, and the energy gap obtained between lesser list/triplet state is poor；And the space structure of this kind of material is conducive to increase the dissolubility of material.Using such material as luminescent layer dopant, organic electroluminescence device is prepared by solwution method, obtains up to 20.5% maximum external quantum efficiency.
Description
Technical field
The present invention relates to a kind of organic thermal activities delayed fluorescence (TADF) materials for containing bis- (phenyl sulfonyl) benzene, especially relate to
And one kind is respectively with triphenylamine, 9,9- dimethyl acridinium and phenthazine using bis- (phenyl sulfonyl) benzene units as electron acceptor
The thermal activities of electron donor postpone material, and its emitting layer material as solution processing type organic electroluminescent LED is answered
With belonging to electroluminescent organic material technical field.
Background technique
Thermal activities delayed fluorescence (TADF) is E type delayed fluorescence in the last century 60's, since they are not necessarily to
Noble metal (such as Ir, Pt etc.) can utilize all singlet (S1) and triplet excitons (T1) shine, therefore be concerned.So far
Until the present, constructs the most effective strategy of TADF molecule and be made of donor-receiver (D-A) skeleton distorted.This class formation can be with
Lesser singlet and triplet state are obtained by highest occupied molecular orbital (HOMO) and being spatially separating for lowest unoccupied molecular orbital (LUMO)
Between energy gap (ΔE ST), realize TADF performance.But the TADF molecule reported at present is mostly one-dimentional structure；And it is this kind of
TADF molecule, which is all only at greatly in vacuum evaporation type electroluminescent device, shows higher device external quantum efficiency (> 20%).Cause
This, develops novel solution processing type TADF luminescent material with important research significance.
It is well known that two-dimensional material is widely used in semiconductor material due to its unique physics and chemical property
In, especially the space structure of two-dimensional material can effectively adjust the band gap of molecule and the dissolubility of material.Therefore, of the present invention
Two-dimensional concept is introduced into TADF molecule, constructs the TADF molecule that series has ' cross ' type, further studies their point
Minor structure-property relationship.Diphenyl sulphone (DPS) (diphenylsulfone, DPS) group is because it is with preferable electronegativity and tetrahedron
Structure is widely used in the receptor unit of TADF molecule.In order to further adjust molecule performance, researcher is in DPS group
It is re-introduced into another phenylsulfone unit and forms bis- (phenyl sulfonyl) benzene (bis (phenylsulfonyl) of new receptor unit
Benzene, BPSB), and the blue light TADF material based on BPSP receptor unit that maximum external quantum efficiency is 24.6% is obtained,
But they are to prepare electroluminescent device by vacuum-deposited method.Although the TADF material based on BPSB receptor unit exists
It has a good application prospect in OLEDs, but so far, only several pertinent literature reports.Based on the above reasons, of the invention
In conjunction with the architectural characteristic of two-dimensional molecular and the characteristic electron of BPSB, by donor monomer triphenylamine, 9,9- dimethyl acridinium and pheno thiophene
Piperazine is introduced on the center phenyl ring of BPSB unit, construct series ' cross ' type TADF molecule TPA-BPSB, DMAc-BPSB and
PTZ-BPSP；It is further upper in the molecule to introduce methyl group unit, construct TADF molecule MTPA-BPSB, MDMAc-BPSB and MPTZ-
BPSB；Molecular structure-the property relationship for studying them in detail prepares organic electroluminescence device by solution processing, obtains
External quantum efficiency is up to 20.5% electroluminescent device, provides theoretical foundation to construct efficient two dimension TADF material.
Summary of the invention
For solution processing type TADF material shortage, the more low technological deficiency of device efficiency, the purpose of the present invention is be
One kind is provided and is distinguished using bis- (phenyl sulfonyl) benzene units as electron acceptor, with triphenylamine, 9,9-dimethylacridan and phenthazine
For ' cross ' type thermal activities delayed fluorescence material of electron donor.
Another object of the present invention is to be to provide thermal activities delayed fluorescence material as solution processing type organic electroluminescence
The application of lumination of light emitting diode layer material obtains the excellent solution processing type organic electroluminescence device of luminescent properties.
In order to achieve the above technical purposes, the present invention provides a kind of thermal activities for being based on bis- (phenyl sulfonyl) benzene units
Delayed fluorescence material, with 6 structure of formula 1- formula:
Formula 1- formula 6 is using bis- (phenyl sulfonyl) benzene units as electron acceptor, respectively with triphenylamine, 9,9-dimethylacridan and pheno thiophene
Piperazine is ' cross ' type thermal activities delayed fluorescence material of electron donor.This class formation has biggish spatial warping structure, has
Conducive to HOMO and the LUMO distribution of separation molecule, lesser Δ is obtainedE ST；The dissolubility of material can also be increased simultaneously, and then obtained
Obtain efficient solution processing type TADF material.
On the other hand, the present invention also provides the applications of ' cross ' type thermal activities delayed fluorescence material, by it
As the emitting layer material of organic electroluminescent LED, it to be used for solution processing type organic electroluminescence device.Device obtains
Maximum external quantum efficiency 20.5%.
Compared with the prior art, technical solution of the present invention bring beneficial effect is:
The present invention introduces two-dimensional concept in TADF molecule for the first time, constructs ' cross ' type thermal activities delayed fluorescence material.It is this kind of
Material have biggish space donor monomer and receptor unit are spatially separated, this be conducive to separate molecule HOMO and
LUMO distribution, obtains lesser ΔE ST；And the space structure of this kind of material is conducive to increase the dissolubility of material, obtains efficient
The solution processing type organic electroluminescence device of rate.
This kind of ' cross ' type thermal activities delayed fluorescence material is used as solution processing type organic electroluminescent two by the present invention
The emitting layer material of pole pipe, device obtain maximum external quantum efficiency 20.5%, this is currently based on bis- (phenyl sulfonyl) benzene lists
Peak efficiency of the TADF material of member in solution processing type organic electroluminescence device.
Detailed description of the invention
[Fig. 1] is compound TPA-BPSB, DMAc-BPSB, MTPA-BPSB and MDMAc- made from the embodiment of the present invention 1
The thermogravimetric curve of BPSB.
[Fig. 2] is compound TPA-BPSP, DMAc-BPSP, MTPA-BPSP and MDMAc- made from the embodiment of the present invention 1
BPSP is in toluene solution (10-5M the ultraviolet-visible absorption spectroscopy in).
[Fig. 3] is compound TPA-BPSP, DMAc-BPSP, MTPA-BPSP and MDMAc- made from the embodiment of the present invention 1
BPSP is in toluene solution (10-5M the fluorescence spectrum in).
[Fig. 4] is compound TPA-BPSP, DMAc-BPSP, MTPA-BPSP and MDMAc- made from the embodiment of the present invention 1
BPSP transient curve in PMMA film.
[Fig. 5] is external quantum efficiency-electric current of compound TPA-BPSP different levels of doping made from the embodiment of the present invention 1
Density curve (illustration: electroluminescent light spectrogram).
[Fig. 6] is luminance-voltage-electric current of compound TPA-BPSP different levels of doping made from the embodiment of the present invention 1
Densogram.
[Fig. 7] is external quantum efficiency-electricity of compound MTPA-BPSP different levels of doping made from the embodiment of the present invention 1
Current density curve (illustration: electroluminescent light spectrogram).
[Fig. 8] is luminance-voltage-electric current of compound MTPA-BPSP different levels of doping made from the embodiment of the present invention 1
Densogram.
Specific embodiment
Case study on implementation is intended to that the present invention is further described in detail below, but these specific embodiments are not in any way
It limits the scope of the invention.
Embodiment 1
Reaction condition: a) cuprous iodide, Anhydrous potassium carbonate, dimethyl sulfoxide, 120 DEG C, for 24 hours;B) hydrogen peroxide,
Acetic acid, reflux, 18h;C) stannous chloride, potassium hydroxide, toluene, reflux, for 24 hours;D) n-BuLi, isopropanol
Pinacol borate, tetrahydrofuran, -78oC, 12h;E) tetrakis triphenylphosphine palladium, Anhydrous potassium carbonate, tetrahydrofuran,
80℃, 24h.
The synthetic route of embodiment 1
The synthesis of compound 1:
Diphenyl disulfide (932 mg, 4.27 mmol), the bromo- 2,5- diiodo-benzene of 1,4- bis- are sequentially added into 200 mL single port bottles
(2.00 g, 3.89 mmol), cuprous iodide (222 mg, 1.16 mmol), Anhydrous potassium carbonate (1.34 g, 9.70 mmol)
With 100 mL dimethyl sulfoxides, mixture 120 DEG C of 24 h of stirring under nitrogen protection.It is cooled to room temperature, pours into reaction solution
In ice water；Mixture is extracted with methylene chloride (3 × 30 mL), collected organic layer；Organic layer pass sequentially through washing (250 mL),
Dry, filtering, vacuum distillation remove solvent；Crude product is that eluant, eluent column chromatography for separation obtains white solid 500 with petroleum ether
Mg, yield 43%.1H NMR (400 MHz, CDCl3) δ 7.42 (m, 10H), 7.06 (s, 2H).
The synthesis of compound M1:
Compound 1 (4.50 g, 9.95 mmol) and 150 mL glacial acetic acid are added in 250 mL two-mouth bottles, are heated to 100
DEG C, then 10 mL, 30% hydrogenperoxide steam generator is dropped in reaction system, is stirred 18 hours.It is cooled to room temperature to reaction solution, it will
Reaction solution pours into 500 mL ice water, filters out sediment and obtains 3.55 g of white solid, yield 66% with ethyl alcohol recrystallization.1H
NMR (400 MHz, CDCl3) δ 8.61 (s, 2H), 7.97-7.95 (m, 4H), 7.68 (t, J = 8.0 Hz,
2H), 7.56 (t, J = 8.0 Hz, 4H).
The synthesis of compound 2:
9,9-dimethylacridan (5.0 g, 24.7 mmol), the bromo- 5- iodobenzene of 2- are sequentially added into 250 mL single port bottles
(9.06 g, 32.1 mmol), stannous chloride (489 mg, 4.94 mmol), potassium hydroxide (6.92 g, 124 mmol), 1,
10- phenanthroline (891 mg, 4.94 mmol) and 130 mL toluene, mixture 120 DEG C of 24 h of stirring under nitrogen protection.To
Reaction solution is cooled to room temperature, and methylene chloride (3 × 30 mL) extraction, organic layer passes sequentially through salt water washing (3 × 30 mL), does
Dry, filtering, vacuum distillation remove solvent；Crude product is that eluant, eluent column chromatography for separation obtains 4.78 g of white solid with petroleum ether,
Yield 53%.1H NMR (300 MHz, CDCl3) δ 7.77-7.74 (m, 2H), 7.47-7.44 (m, 2H), 7.25 -
7.21 (m, 2H), 7.0-6.91 (m, 4H), 6.26-6.23 (m, 2H), 1.68 (s, 6H).
The synthesis of compound M2:
Compound 2 (5.00 g, 13.7 mmol) and 150 mL anhydrous tetrahydro furans, nitrogen are added into 250 mL two-mouth bottles
It is stirred at -78 DEG C under protection 30 minutes, n-BuLi (2.5 M, 7.14 mL, 17.8 mmol) is then added dropwise to reaction
In liquid, after reaction 1 hour, isopropanol pinacol borate (3.83 g, 20.6 mmol) is added dropwise in reaction solution, reaction 2
After hour, it is transferred to ambient temperature overnight.Reaction is terminated, 20 mL water quenching reactions are added.Reaction solution is with methylene chloride (3 × 30 mL)
Extraction, organic layer pass sequentially through washing (250 mL), drying, filtering, vacuum distillation removing solvent；Crude product petroleum ether: two
Chloromethanes (V:V=10:1) it is that eluant, eluent column chromatography for separation obtains 5.72 g of white solid, yield 78%.1H NMR (400
MHz, CDCl3) δ 8.06 (d, J = 8.0 Hz, 2H), 7.45 (dd, J = 1.9 Hz, 7.4 Hz, 2H),
7.35 (d, J = 12 Hz, 2H), 6.93 (m, 4H), 6.25 (dd, J = 1.6 Hz, 7.8 Hz, 2H),
1.69 (s, 6H), 1.40 (s, 12H).
The synthesis of compound 3:
Synthesis step is similar to compound 2, and crude product is that eluant, eluent column chromatography for separation obtains 3.95 g of white solid with petroleum ether,
Yield 25%.1H NMR (400 MHz, CDCl3) δ 7.35 (d, J = 8.0 Hz, 1H), 7.27-7.22 (m, 4H),
7.07-7.00 (m, 6H), 6.95 (d, J = 4.0 Hz, 1H), 6.77 (dd, J = 2.7 Hz, 8.0 Hz,
1H), 2.28 (s, 3H).
The synthesis of compound M3:
Synthesis step is similar to compound M2, crude product petroleum ether: methylene chloride (V:V=10:1) it is that eluant, eluent column chromatographs
Isolated 2.78 g of white solid, yield 62%.1H NMR (400 MHz, CDCl3) δ 7.63 (d, J = 8.0 Hz,
1H), 7.26-7.22 (m, 4H), 7.09 (dd, J = 1.1 Hz, 8.6 Hz, 4H), 7.05-7.01 (m, 2H),
6.84 (dd, J = 2.0 Hz, 4.2 Hz, 2H), 2.42 (s, 3H), 1.32 (s, 12H).
The synthesis of compound 4:
Synthesis step is similar to compound 2, and crude product is that eluant, eluent column chromatography for separation obtains 7.74 g of white solid with petroleum ether,
Yield 80%.1H NMR (400 MHz, CDCl3) δ 7.78 (d, J = 8.0 Hz, 1H), 7.45 (dd, J = 1.6
Hz, 7.6 Hz, 2H), 7.22 (d, J = 4.0 Hz, 1H), 7.05 (dd, J = 2.4 Hz, 8.3 Hz, 1H),
7.00-6.91 (m, 4H), 6.27 (dd, J = 1.1 Hz, 8.0 Hz, 2H), 2.47 (s, 3H), 1.68 (s,
6H).
The synthesis of compound M4:
Synthesis step is similar to compound M2, crude product petroleum ether: methylene chloride (V:V=10:1) it is that eluant, eluent column chromatographs
Isolated 6.27 g of white solid, yield 79%.1H NMR (400 MHz, CDCl3) δ 8.00 (d, J = 8.0 Hz,
1H), 7.44 (dd, J = 1.7 Hz, 7.5 Hz, 2H), 7.14 (d, J = 8.0 Hz, 2H), 6.96-6.88
(m, 4H), 6.27 (dd, J = 1.4 Hz, 7.9 Hz, 2H), 2.60 (s, 3H), 1.68 (s, 6H), 1.40
(s, 12H).
The synthesis of compound TPA-BPSP:
Sequentially added into 100 mL single port bottles compound M1 (1.25 g, 2.42 mmol), 4- boric acid triphenylamine (2.10 g,
7.26 mmol), tetrakis triphenylphosphine palladium (190 mg, 0.121 mmol), Anhydrous potassium carbonate (1.67 g, 12.1 mmol), 5
ML deionized water and 30 mL tetrahydrofurans, mixture 120 DEG C of 24 h of stirring under nitrogen protection.Room is cooled to reaction solution
Temperature, methylene chloride (3 × 30 mL) extraction, organic layer pass sequentially through washing (50 mL), drying, filtering, be evaporated under reduced pressure removing it is molten
Agent；Crude product petroleum ether: methylene chloride (V:V=1:1) it is that eluant, eluent column chromatography for separation obtains 880 mg of green solid, it produces
Rate 43%.1H NMR (300 MHz, CDCl3) δ 8.30 (s, 2H), 7.50-7.47 (m, 2H), 7.40-7.39 (m,
1H), 7.38-7.30 (m, 15H), 7.19-7.15 (m, 8H), 7.12-7.07 (m, 4H), 6.94 (s, 8H).13C NMR (125 MHz, CDCl3) δ 148.22, 147.50, 143.57, 141.32, 140.00, 133.36,
133.17, 131.15, 129.91, 129.57, 128.69, 128.14, 124.86, 123.58, 122.17.
MALDI-MS (m/z) of C54H40N2O4S2 for [M]+: calcd. 845.04; found, 844.24.
The synthesis of compound MTPA-BPSP:
Synthesis step is similar to compound TPA-BPSB, crude product petroleum ether: methylene chloride (V:V=1:1) it is eluant, eluent column
Chromatography obtains 600 mg of yellow solid, yield 35%.1H NMR (400 MHz, CDCl3) δ 8.29 (s, 2H),
7.51 (t, J = 8.0 Hz, 2H), 7.38-7.32 (m, 16H), 7.19 (d, J = 8.0 Hz, 8H), 7.09
(t, J = 8.0 Hz, 4H), 6.95 (d, J = 8.0 Hz, 1H), 6.8 (dd, J = 2.0 Hz, 8.3 Hz,
1H), 6.82 (d, J = 8.0 Hz, 2H), 6.77 (d, J = 8.0 Hz, 2H), 1.52 (s, 3H), 1.41
(s, 3H). 13C NMR (75 MHz, CDCl3) δ 148.91, 144.16, 144.29, 141.45, 140.31,
140.15, 138.52, 134.05, 133.82, 132.62, 132.15, 129.94, 129.20, 128.92,
125.06, 123.69, 120.75, 20.59. MALDI-MS (m/z) of C56H44N2O4S2 for calcd:
873.09; found: 872.72.
The synthesis of compound DMAc-BPSP:
Sequentially added into 50 mL single port bottles compound M1 (627 mg, 1.22 mmol), compound M2 (1.25 g, 3.04
Mmol), tetrakis triphenylphosphine palladium (84.0 mg, 72.9 μm of ol), Anhydrous potassium carbonate (839 mg, 6.08 mmol), 3 mL are gone
Ionized water and 20 mL tetrahydrofurans, mixture 120 DEG C of 24 h of stirring under nitrogen protection.It is cooled to room temperature to reaction solution, two
Chloromethanes (3 × 30 mL) extraction, organic layer pass sequentially through washing (30 mL), drying, filtering, vacuum distillation removing solvent；Slightly
Product petroleum ether: methylene chloride (V:V=1.5:1) it is that eluant, eluent column chromatography for separation obtains 400 mg of faint yellow solid, yield
36%。1H NMR (400 MHz, CDCl3) δ 8.52 (s, 2H), 7.57-7.49 (m, 10H), 7.42-7.38 (m,
8H), 7.30 (d, J = 8.0 Hz, 4H), 7.15-7.10 (m, 4H), 7.03-7.00 (m, 4H), 6.42-
6.40 (m, 4H), 1.74 (s, 12H). 13C NMR (125 MHz, CDCl3) δ 143.84, 142.11,
141.61, 141.16, 141.06, 136.51, 134.09, 133.71, 133.07, 131.16, 130.70,
129.36, 128.38, 126.74, 125.81, 121.32, 114.46, 36.44, 31.58. MALDI-MS (m/z)
of C60H48N2O4S2 for calcd: 925.16; found: 925.26.
The synthesis of compound MDMAc-BPSP:
Synthesis step is identical as compound DMAc-BPSB, crude product petroleum ether: methylene chloride (V:V=1.5:1) it is elution
Agent column chromatography for separation obtains 700 mg of white solid, yield 38%.1H NMR (400 MHz, CDCl3) δ 8.48 (s, 2H),
7.57 (t, J = 8.0 Hz, 2H), 7.54 -7.49 (m, 8H), 7.43-7.39 (m, 4H), 7.35 (d, J =
8.0 Hz, 1H), 7.21-7.12 (m, 9H), 7.02 (t, J = 8.0 Hz, 4H), 6.51 (dd, J = 1.8
Hz, 8.2 Hz, 4H), 1.76 (s, 3H), 1.75 (s, 12H), 1.66 (s, 3H). 13C NMR (75 MHz,
CDCl3) δ 144.11, 142.32, 141.29, 141.11, 140.60, 140.07, 139.94, 135.77,
134.40, 133.75, 132.82, 130.58, 129.47, 128.87, 128.35, 126.85, 125.94,
121.24, 114.48, 36.48, 31.91, 20.50. MALDI-MS (m/z) of C62H52N2O4S2 for calcd:
953.22; [M-CH3]+ found, 937.51.
Embodiment 2
Under nitrogen atmosphere, we test the thermostabilization of TPA-BPSB, DMAc-BPSB, MTPA-BPSB and MDMAc-BPSB
Property, thermogravimetric curve is as shown in Figure 1.As seen from the figure, compound TPA-BPSB, DMAc-BPSB, MTPA-BPSB and MDMAc-
When BPSB thermal weight loss 5% decomposition temperature (T d) it is respectively 487 DEG C, 421 DEG C, 424 DEG C and 430 DEG C.This kind of compound all have compared with
Good thermal stability.
Embodiment 3
In order to inquire into the Photophysics of compound, we are by stable state, transient state Fluorescence Spectrometer to its solution and solid film
It is studied.As shown in Fig. 2, all compounds have absorption in the toluene solution of 250-500 nm.Wherein, short wavelength (<
350 nm) absorption belong to the π-π of intramolecular* Transition, and the absorption between 350-450 nm is attributed to Intramolecular electron transfer
Transition (ICT).Compared with acridine substitution, the TPA-BPSP and MTPA-BPSP that diphenylamines replaces have stronger ICT transition
Absorption peak, this is separated derived from DMAc-BPSP and MDMAc-BPSP with more obvious HOMO-LUMO electron cloud.In toluene solution
In, the maximum emission peak of compound TPA-BPSP, DMAc-BPSP, MTPA-BPSP, MDMAc-BPSP are respectively 517 nm, 543
Nm, 527 nm and 544 nm (Fig. 3).This explanation is by changing donor monomer and introducing methyl group unit energy Effective Regulation material
Light emitting region.
In order to verify the TADF property of compound, we test the decaying longevity of PMMA film under argon atmosphere (5% doping)
Life.As shown in figure 4, all compounds are obvious bi-exponential decaying, respectively nanosecond rank transient lifetime in the solution
Postpone the service life with delicate rank.Wherein compound TPA-BPSB, DMAc-BPSB, MTPA-BPSB and MDMAc-BPSB is being adulterated
The delay service life in film is respectively 24.2,12.3,13.5 and 8.6 μ s, it was confirmed that four target molecules are TADF molecule.
Compound TPA-BPSP, DMAc-BPSP, MTPA-BPSP and MDMAc-BPSP are further tested respectively in argon gas
With in air atmosphere Toluene solution fluorescence quantum efficiency (PLQY).Wherein, TPA-BPSP, DMAc- under argon atmosphere
BPSP, MTPA-BPSP and MDMAc-BPSP'sPLQYRespectively 88,11,58 and 1%；And in air,PLQYRapid drawdown to 74,
3,42 and 1%.This is because the triplet excitons of compound are quenched by triplet oxygen in air, make fluorescence quantum efficiency
It drastically reduces, it was confirmed that the luminous ingredient for having triplet excitons of compound.Meanwhile research finds to introduce first in the molecule
Base leads to moleculePLQYIt drastically reduces, this is because the introducing of methyl makes the HOMO of molecule and lumo energy with smaller heavy
It is folded, cause molecule that there is lower oscillator strength, thus obtain lowerPLQY。
It is poor in order to calculate the energy gap between compound singlet and triplet, compound nothing at 77 K is tested respectively
Fluorescence spectrum and phosphorescence spectrum in oxygen toluene solution.By the starting peak position of low temperature fluorescence spectrum and phosphorescence spectrum, utilize
FormulaE = 1240/λ, the Δ of compound TPA-BPSB, DMAc-BPSB, MTPA-BPSB and MDMAc-BPSB is calculatedE ST
The eV of respectively 0.18,0.02,0.07 and 0.01.Obviously, methyl group unit is introduced in the molecule, can effectively reduce the Δ of moleculeE ST,
Increase its reversed intersystem crossing rate.
Embodiment 4
All compounds all show mechanical color-changing light-emitting property in the case where applying external condition (such as grind and fumigate).TPA-
Peak occurs for the primary sample maximum of BPSB, DMAc-BPSB, MTPA-BPSB and MDMAc-BPSB respectively in 484,521,506 and
At 510 nm.After being ground in mortar with pestle, apparent red shift occurs for emission spectrum, and emission peak is respectively 530 (TPA-
), BPSB 546 (DMAc-BPSB), 535 (MTPA-BPSB) and 560 nm (MDMAc-BPSB).Then pass through methylene chloride
After steam steaming 15 minutes, what the luminescent color of DMAc-BPSB and MDMAc-BPSB can be reversible becomes 527 nm and 508 nm again,
This is consistent with the emission spectrum under reset condition.Although compound TPA-BPSB and MTPA-BPSB is at methylene chloride steam
Spectrum shows blue shift after reason, but compared with reset condition, there is the red-shifted emission of about 18 nm.In addition, for all compounds,
Color change between gas phase and ground sample is reversible.
Embodiment 5
The HOMO and lumo energy of four pure films of compound are tested by cyclic voltammetry, all compounds are in 0 V -2.0
Only show irreversible oxidation potential in the range of V, respectively 1.04 V (TPA-BPSB), 1.03 V (DMAc-BPSP),
1.06 V (MTPA-BPSP), 1.0 V (MDMAc-BPSP).Pass through formulaE HOMO = -(Eox onset- EFc/Fc+
Onset) -4.8 eV, which are calculated, knows that the HOMO of molecule TPA-BPSB, DMAc-BPSB, MTPA-BPSB and MDMAc-BPSB can fractions
It Wei not -5.44, -5.37, -5.41 and -5.33 eV.Compared with the compound that diphenylamines replaces, the compound that acridine replaces is presented
Higher HOMO energy level, this is mainly due to acridines to have stronger electron donation.Likewise, the introducing of methyl group also may be used
High molecular HOMO energy level is slightly lifted, this may be because the electron donation of methyl causes.Further using optical band gap and
HOMO energy level, the lumo energy that four compounds are calculated is respectively -2.71, -2.43, -2.55 and -2.21 eV.
Embodiment 6
In view of its higher fluorescence quantum efficiency and good dissolubility energy, thus we have chosen compound TPA-BPSP and
MTPA-BPSP prepares device as light-emitting dopant, by solution processing method, probes into the relationship of molecular structure and device performance.
Optimal device architecture be ITO/PEDOT:PSS (40 nm)/CzAcSF:emitter (x wt%, 50 nm)/DEPEO (9
Nm)/Tmpypb (40 nm)/CsF (1.2 nm)/Al (120 nm), wherein ito glass makees anode, and PEDOT:PSS makees hole
Implanted layer, CzAcSF make material of main part, and DPEPO and TmPyPB are respectively hole blocking layer and electron transfer layer.
It is found that doping concentration is improved by 4 % to 10%, the electroluminescent spectrum of compound TPA-BPSP occurs light Fig. 5 illustration
Micro- red shift, this may be because of the increase with doping concentration, and intermolecular interaction enhancing causes spectrum that red shift occurs.Device
Part doping concentration be 4%, 7% and 10% when CIE coordinate be respectively (0.28,0.47), (0.30,0.49) and (0.31,
0.51).When compound TPA-BPSP doping concentration is 4%, the device of preparation has optimal performance, and wherein maximum brightness is
877.8 cd m-2, maximum current efficiencyCE=20.8 cd A-1And maximum external quantum efficiencyEQE=7.27% (Fig. 5 and Fig. 6).
As doping concentration is improved from 4% to 10%, device efficiency is gradually reduced, this is by strong interaction intermolecular under high-dopant concentration
Caused by caused quenching.
By Fig. 6 illustration it is found that compound MTPA-BPSP is with the increase of doping concentration, electroluminescent emission peak is red by 520 nm
Move to 528 nm.Based on the device of MTPA-BPSP doping concentration be 4%, 7% and 10% when CIE coordinate be respectively (0.28,
0.48), (0.29,0.50) and (0.28,0.51).When the doping concentration of compound TPA-BPSP is 7%, device shows
Optimal performance, wherein maximum brightness, maximum current efficiency and maximum external quantum efficiency are respectively 1239 cd m-2, 53.28 cd
A-1With 20.5% (Fig. 7 and Fig. 8).As far as we know, this is to report the highest unit containing BPSP based on solwution method preparation at present
TADF material electroluminescent device.
Claims (4)
1. having constructed 6 kinds of organic thermal activities delayed fluorescence materials for being based on bis- (phenyl sulfonyl) benzene, it is characterised in that: have formula
6 structure of 1- formula:
。
2. thermal activities delayed fluorescence material formula 1- formula 6 according to claim 1, it is characterised in that: with bis- (phenylSulphons
Base) benzene be electron acceptor, with triphenylamine, 9,9- dimethyl acridinium and phenthazine be electron donor；Electron donor unit and electronics
Receptor unit is spatially separated, and forms ' cross ' type.
3. according to claim 1 with thermal activities delayed fluorescence material formula 1- formula 6 as claimed in claim 2, it is characterised in that: material
Luminescent color significant change occurs with the change (friction and solvent stifling) of environmental stimuli condition.
4. the application of ' cross ' type thermal activities delayed fluorescence material of any of claims 1 or 2, it is characterised in that: as hair
Photosphere dopant material is used for solution processing type organic electroluminescence device, and maximum external quantum efficiency is up to 20.5%.
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| CN111620817A (en) * | 2020-06-04 | 2020-09-04 | 常州大学 | Novel blue thermal activity delayed fluorescent material and application thereof |
| CN113683555A (en) * | 2021-08-06 | 2021-11-23 | 常州大学 | Biphenyl derivative receptor unit-based D2A-type violet organic luminescent material and application thereof |
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| WO2015121241A1 (en) * | 2014-02-14 | 2015-08-20 | Yersin, Hartmut | Organic tadf molecules having steric hindrance at the donor and at the acceptor for optoelectronic devices |
| CN106328816A (en) * | 2015-06-16 | 2017-01-11 | 昆山国显光电有限公司 | Organic light emitting device and manufacturing method thereof |
| CN107056627A (en) * | 2017-04-14 | 2017-08-18 | 南京邮电大学 | A kind of organic semiconductor laser material and preparation method and application |
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| WO2015121241A1 (en) * | 2014-02-14 | 2015-08-20 | Yersin, Hartmut | Organic tadf molecules having steric hindrance at the donor and at the acceptor for optoelectronic devices |
| CN106328816A (en) * | 2015-06-16 | 2017-01-11 | 昆山国显光电有限公司 | Organic light emitting device and manufacturing method thereof |
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| CN111620817A (en) * | 2020-06-04 | 2020-09-04 | 常州大学 | Novel blue thermal activity delayed fluorescent material and application thereof |
| CN111620817B (en) * | 2020-06-04 | 2022-09-27 | 常州大学 | Novel blue thermal activity delayed fluorescent material and application thereof |
| CN113683555A (en) * | 2021-08-06 | 2021-11-23 | 常州大学 | Biphenyl derivative receptor unit-based D2A-type violet organic luminescent material and application thereof |
| CN113683555B (en) * | 2021-08-06 | 2024-01-23 | 常州大学 | D based on biphenyl derivative receptor unit 2 A-type purple light organic luminescent material and application thereof |
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