CN108892674A - A kind of heat lag fluorescent chemicals and its application - Google Patents
A kind of heat lag fluorescent chemicals and its application Download PDFInfo
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- 239000000126 substance Substances 0.000 title abstract description 3
- 239000000463 material Substances 0.000 claims abstract description 30
- 230000003111 delayed effect Effects 0.000 claims description 16
- 239000007850 fluorescent dye Substances 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 229910052805 deuterium Inorganic materials 0.000 claims description 8
- 125000004431 deuterium atom Chemical group 0.000 claims description 8
- 125000000623 heterocyclic group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 abstract description 25
- 230000005855 radiation Effects 0.000 abstract description 6
- 239000011368 organic material Substances 0.000 abstract description 5
- 238000005401 electroluminescence Methods 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 230000006798 recombination Effects 0.000 description 10
- 238000005215 recombination Methods 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 7
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 7
- 230000007704 transition Effects 0.000 description 7
- 238000003775 Density Functional Theory Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000000859 sublimation Methods 0.000 description 5
- 230000008022 sublimation Effects 0.000 description 5
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 5
- 238000002061 vacuum sublimation Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 230000005281 excited state Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 230000005525 hole transport Effects 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 230000005472 transition radiation Effects 0.000 description 3
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- -1 concentration Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 1
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical group C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 description 1
- ZNPHICPFIHYTRP-UHFFFAOYSA-N 2-thiophen-2-yl-1-benzothiophene Chemical group C1=CSC(C=2SC3=CC=CC=C3C=2)=C1 ZNPHICPFIHYTRP-UHFFFAOYSA-N 0.000 description 1
- 108091006149 Electron carriers Proteins 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 239000011903 deuterated solvents Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007723 transport mechanism Effects 0.000 description 1
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- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
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- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
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- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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Abstract
The present invention relates to organic electroluminescence device technical field, a kind of heat lag fluorescent chemicals and its application in the devices are disclosed.Luminous organic material disclosed in this invention has structure shown in general formula (I).Such compound light radiation transfer rate with higher is conducive to the luminous efficiency for improving material, is particularly suitable as emitting layer material applied in the technical fields such as OLED, OFT, OPV, QLED.
Description
Technical Field
The invention relates to the technical field of organic electroluminescent devices, in particular to a thermal delay fluorescent compound and application thereof in a device.
Background
The first report of Kodak C.W.Tang et al in 1987 made Alq by vacuum thermal evaporation3Since the double-layer device structure of the light-emitting material, the organic electroluminescent material has attracted much attention. Such as the samsung Galaxy series cell phone, S6, etc., are all OLED cell phones. In 2017, apple incorporated has also adopted OLED display configurations on their cell phones.
Organic electroluminescence can be classified into fluorescence and phosphorescence electroluminescence. According to the theory of spin quantum statistics, the probability ratio of formation of singlet excitons to triplet excitons is 1:3, i.e. singlet excitons occupy only 25% of the "electron-hole pairs". Thus, the fluorescence from radiative transitions of singlet excitons can account for only 25% of the total input energy, while the electroluminescence of phosphorescent materials can utilize the energy of all excitons through the heavy metal effect, thus providing a great advantage.
Most of the existing phosphorescent electroluminescent devices adopt a host-guest structure, that is, a phosphorescent material is doped into a host material at a certain concentration to avoid triplet-triplet annihilation, so as to improve the phosphorescent efficiency.
Since 2009, a new thermal delayed fluorescent material, i.e., tadf (thermally activated delayed fluorescence) material, proposed by the group of Adachi (a.endo, m.ogawara, a.takahashi, d.yokoyama, y.kato, c.adachi, adv.mater.2009,21,4802) obtained 100% singlet excitons because it can utilize reverse gap crossing of triplet excitons under thermal excitation, avoiding the use of expensive heavy metal complexes, and the device efficiency was comparable to that of phosphorescent devices. Since then, fluorescent materials have attracted renewed attention from researchers.
However, the applicant finds that the TADF effect-based material and the OLED device thereof have many disadvantages, such as the limited variety of materials, and the stability of the device is to be improved. For example, in order to achieve Δ EST (singlet-triplet energy level difference) <0.3eV, many TADF materials need to be designed with complete separation of HOMO-LUMO orbitals, which results in a decrease in the optical radiation transition rate of the TADF material and a decrease in the performance of the material.
Disclosure of Invention
The invention aims to provide a thermal retardation fluorescent compound and application thereof, and the TADF material has high luminous efficiency.
To solve the above technical problems, embodiments of the present invention provide a thermally delayed fluorescent compound having a structure represented by general formula (i) or (II):
wherein,
X1、X2each independently is O or S;
R1、R2each independently is a hydrogen atom, a deuterium atom, a halogen, substituted or unsubstitutedSubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocyclic group, substituted or unsubstituted condensed ring group;
d is an electron-donating organofunctional group.
Alternatively, D has a structure represented by formula (III):
wherein,
X3is an N atom;
X4selected from O or S;
R3、R4each independently selected from a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted fused ring group, an amino group;
n is selected from 0, 1 or 2.
Alternatively, the thermally delayed fluorescent compound provided by the embodiments of the present invention has a structure selected from one of the following:
embodiments of the present invention also provide applications of the above thermal retardation fluorescent compound in OLED, OFT, OPV, QLED devices.
Optionally, the thermally delayed fluorescent compound is a light emitting layer material in the OLED device.
Embodiments of the present invention provide TADF materials that are comparable to the prior art. The delta EST (singlet state and triplet state energy level difference) is about 9meV, which is beneficial to improving the reverse gap crossing probability of triplet state excitons to singlet state excitons; in addition, while the lower delta EST (singlet state and triplet state energy level difference) is kept, the TADF material provided by the embodiment of the invention also has higher S1- > S0 electron transition matrix intensity, f @ S1- > S0>0.3, so that the material has higher light radiation transition rate, and the light emission efficiency of the material is favorably improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail below. However, it will be appreciated by those of ordinary skill in the art that numerous technical details are set forth in order to provide a better understanding of the present invention in its various embodiments. However, the technical solutions claimed in the claims of the present invention can be implemented without these technical details and with various changes and modifications based on the following embodiments.
Compound (I)
Embodiments of the present invention provide a thermally retarded fluorescent compound having a structure represented by general formula (i) or (II):
wherein, X1、X2Each independently is O or S; r1、R2Each independently is a hydrogen atom, a deuterium atom, a halogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted condensed ring group; d is an electron-donating organofunctional group.
In some embodiments of the invention, D has a structure represented by formula (III):
wherein, X3Is an N atom; x4Selected from O or S; r3、R4Each independently selected from a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted fused ring group, an amino group; n is selected from 0, 1 or 2.
In some embodiments of the invention, a thermally delayed fluorescent compound is provided having a structure selected from one of:
general synthetic route
The following sections disclose methods for preparing the compounds provided by the present invention. The present disclosure is not intended to be limited to any one of the methods recited herein. One skilled in the art can readily modify the methods described or utilize different methods to prepare one or more of the provided compounds. The following aspects are merely exemplary and are not intended to limit the scope of the present disclosure. The temperature, catalyst, concentration, reactant composition, and other process conditions may vary, and one skilled in the art to which this disclosure pertains may readily select appropriate reactants and conditions for the desired complex.
CDCl on a Varian Liquid State NMR instrument3Or DMS0-d6Recording at 400MHz in solution1H spectrum, recorded at 100MHz13C NMR spectrum, chemical shift referenced to residual deuterated solvent. If CDCl3As a solvent, tetramethylsilane (δ ═ 0.00ppm) was used as an internal standard for recording1H NMR spectrum; using DMSO-d6(δ 77.00ppm) is reported as an internal standard13C NMR spectrum. If H is present2When O (delta. 3.33ppm) is used as solvent, residual H is used2O (δ ═ 3.33ppm) was recorded as an internal standard1H NMR spectrum; using DMSO-d6(delta. 39.52ppm) is recorded as internal standard13C NMR spectrum. The following abbreviations (or combinations thereof) are used for explanation1Multiplicity of H NMR: s is singleplex, d is doublet, t is triplet, q is quartet, P is quintuple, m is multiplet, br is wide.
The starting materials and reagents for the reaction used in the embodiments of the present invention are commercially available or synthesized by literature methods.
The general synthetic route for the compounds of the invention is as follows:
wherein,
Pd2(dba)3is tris (dibenzylideneacetone) dipalladium, HPtBu3BF4Is aSeeding with phosphoric acid;
X1、X2each independently is O or S;
R1、R2each independently is a hydrogen atom, a deuterium atom, a halogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted condensed ring group;
X3is a N atom, X4Selected from O or S;
R3、R4each independently selected from a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted fused ring group, an amino group;
n is selected from 0, 1 or 2.
Synthesis example:
(1) compound L1
Adding A and B into a flask under the protection of argon inert gas, then fully refluxing and reacting for 30-60 minutes through a dry toluene solution, and slowly adding Pd2(dba)3/HPtBu3BF4Fully reacting for 30-60 min as catalyst, and slowly adding NaO under the protection of Ar gastAnd heating the Bu solution to 100-120 ℃, and stirring for reacting for 24 hours. After reaction, the mixture is filtered, washed by toluene and ethanol, and then purified by using a column, wherein the organic solvent is CH2Cl2N-hexane, and purifying to obtain powder with purity of more than 99%. In order to further improve the purity of the L1, the L1 product with the purity of more than 99.5 percent can be obtained by one or more times of sublimation by a vacuum sublimation apparatus.
Using CDCL3As solvent tetramethylsilane (δ ═ 0.00ppm) was recorded as internal standard1H NMR spectrum.
1H NMR(400MHZ,DMSO-d6)：
6.42ppm(4H,d)6.52-6.58ppm(8H,p),6.67-6.73ppm(8H,p),7.23ppm(4H,d),7.55ppm(2H,d),7.84ppm(2H,d),8.08ppm(2H,s)。
(2) Compound L3
Adding A and B into a flask under the protection of argon inert gas, then fully refluxing and reacting for 30-60 minutes through a dry toluene solution, and slowly adding Pd2(dba)3/HPtBu3BF4Fully reacting for 30-60 minutes as a catalyst, and finally slowly adding NaO under the protection of Ar gastAnd heating the Bu solution to 100-120 ℃, and stirring for reacting for 24 hours. After reaction, the mixture is filtered, washed by toluene and ethanol, and then purified by using a column, wherein the organic solvent is CH2Cl2N-hexane, and purifying to obtain powder with purity of more than 99%. In order to further improve the purity of the L3, the L3 product with the purity of more than 99.5 percent can be obtained by one or more times of sublimation by a vacuum sublimation apparatus.
Using CDCL3As solvent tetramethylsilane (δ ═ 0.00ppm) was recorded as internal standard1H NMR spectrum.
1H NMR(400MHZ,DMSO-d6)：
6.42ppm(4H,d),6.53-6.58ppm(6H,q),6.67-6.73ppm(8H,p),7.06ppm(2H,s),7.53ppm(2H,d)。
(3) Compound L8
Adding into a flask under the protection of argon inert gasAdding A and B, then fully refluxing and reacting for 30-60 minutes by a dry toluene solution, and slowly adding Pd2(dba)3/HPtBu3BF4Fully reacting for 30-60 minutes as a catalyst, and finally slowly adding NaO under the protection of Ar gastAnd heating the Bu solution to 100-120 ℃, and stirring for reacting for 24 hours. After reaction, the mixture is filtered, washed by toluene and ethanol, and then purified by using a column, wherein the organic solvent is CH2Cl2N-hexane, and purifying to obtain powder with purity of more than 99%. In order to further improve the purity of the L8, the L8 product with the purity of more than 99.5 percent can be obtained by one or more times of sublimation by a vacuum sublimation apparatus. In order to further improve the purity of the L8, the L8 product with the purity of more than 99.5 percent can be obtained by one or more times of sublimation by a vacuum sublimation apparatus.
Using CDCL3As solvent tetramethylsilane (δ ═ 0.00ppm) was recorded as internal standard1H NMR spectrum.
1H NMR(400MHZ,DMSO-d6)：
6.33ppm(2H,d),6.62-6.75ppm(10H,m),6.91-6.99ppm(8H,p),7.24ppm(2H,d)。
Adding A and B into a flask under the protection of argon inert gas, then fully refluxing and reacting for 30-60 minutes through a dry toluene solution, and slowly adding Pd2(dba)3/HPtBu3BF4Fully reacting for 30-60 min as catalyst, and slowly adding NaO under the protection of Ar gastAnd heating the Bu solution to 100-120 ℃, and stirring for reacting for 24 hours. After reaction, the mixture is filtered, washed by toluene and ethanol, and then purified by using a column, wherein the organic solvent is CH2Cl2N-hexane, and purifying to obtain powder with purity of more than 99%. In order to further improve the purity of L37, sublimation is carried out once or more times by using a vacuum sublimation apparatus to obtain the purityGreater than 99.5% of L37 product.
Using CDCL3As solvent tetramethylsilane (δ ═ 0.00ppm) was recorded as internal standard1H NMR spectrum.
1H NMR(400MHZ,DMSO-d6)：
2.35ppm(6H,s),6.53-6.56ppm(3H,t),6.71ppm(2H,s),6.79ppm(2H,d),7.06ppm(1H,s),7.31-7.33ppm(2H,m),7.53ppm(1H,d),7.78ppm(1H,m),7.86ppm(1H,m)。
Photophysical information:
in the study of the electronic structure of fluorescent small molecule compounds, the interaction between electrons is very important, the Density Functional Theory (DFT) has been widely used to study the pi-conjugated system, and the DFT method is more accurate to study the compound of the present disclosure than other methods. The geometric structure of the compound molecule in the ground state, the cation state and the anion state is optimized by adopting the method of DFT// B3LYP/6-31G (d), and the geometric structure of the excited state of the compound is obtained by adopting the method of DFT// B3LYP/6-31G (d). The absorption and emission spectra of these compounds were calculated using the time-density functional theory (TDDFT) method on the basis of the ground state and excited state geometries. By the above calculation methods, various properties of the compound under study can be obtained, including ionization energy IP, electron affinity EA, recombination energy λ, highest occupied orbital HOMO, lowest occupied orbital LUMO, energy gap Eg.
It is very important for organic light emitting devices that holes and electrons can be injected and transported in an efficient balance. The ionization energy and electron affinity of a molecule are used to evaluate the injection capability of holes and electrons, respectively. The following table lists the calculated vertical and adiabatic ionization energies, vertical and adiabatic electron affinities, hole extraction energy and electron extraction energy of the compounds. Vertical ionization energy ip (v) refers to the energy difference of the cation and the molecule in neutral molecular geometry; adiabatic ionization energy ip (a) refers to the difference in energy in neutral and cationic geometries; the hole extraction energy HEP refers to the energy difference between a molecule and a cation in the cation geometry; the vertical electron affinity ea (v) refers to the difference in energy in neutral and anionic geometries; electron extraction energy, EEP, refers to the difference in energy between a molecule and an anion in anion geometry. Generally, for small molecule organic materials, the smaller the ionization energy, the easier the injection of holes; the greater the electron affinity, the easier the electron injection.
From a microscopic perspective, the transport mechanism of charges in organic thin films can be described as a process of self-transport. Wherein an electron or hole is transferred from one charged electron molecule to an adjacent neutral molecule. According to Marcus theory, the mobility of the charge can be expressed as:
wherein T represents temperature; v represents a pre-exponential factor and is a coupling matrix element between two types of particles; λ is the recombination energy; kb is boltzmann's constant. It is clear that λ and V are the decisions KetImportant factors of the value. Generally, the range of charge transfer in the amorphous state is limited, and the variation in V value is small. Therefore, the mobility is determined mainly by λ in the index. The smaller the λ, the faster the transmission rate. For convenience of study, the influence of external environment is ignored, and the main discussion is the internal recombination energy.
According to computational derivation, the recombination energy can be finally expressed as:
λhole＝IP(v)-HEP
λelectron＝EEP-EA(v)
in general, in organic materials, the energy of S1 excited state and T1 excited state is different due to different degrees of spontaneous rotation, and the energy of ES1 is 0.5-1.0ev greater than that of ET1, so that the luminous efficiency of pure organic fluorescent materials is low. The thermal delayed fluorescence TADF material separates the HOMO-LUMO orbital and reduces the electron exchange energy of the HOMO-LUMO orbital and the TAEST-0 can be realized theoretically due to unique molecular design. To effectively evaluate the effect of thermally delayed fluorescence of the materials of the present invention, a Δ EST evaluation was performed. By using a TDDFT method, the difference value delta EST between the lowest singlet excitation energy Es and the lowest triplet excitation energy ET of the compound provided by the invention is obtained. f @ S1-S0, defined as the transition lattice intensity of the exciton at S1- > S0, meaning that the larger f @ S1-S0, the larger the transition radiation rate Kr of the exciton at S1- > S0; conversely, a smaller f @ S1-S0 means a smaller transition radiation rate Kr of the exciton at S1- > S0. If the transition radiation rate Kr of the exciton at S1- > S0 is larger, the transition non-radiation rate Knr of the exciton at S1- > S0 is reduced, which is advantageous for improving the luminous efficiency of the material, meaning that the exciton is either used for light radiation or is annihilated by non-radiation (e.g., thermally inactivated). Therefore, f @ S1-S0 constants were also evaluated.
The HOMO energy level, LUMO energy level, electron cloud distribution of HOMO and LUMO, f @ S1-S0 constant, and Δ EST and T1 energy levels of the compounds L1-L9 prepared in the embodiment of the present invention were calculated as above:
TABLE 1 photophysical information data
According to the above calculation results, the embodiment of the present invention provides a compound in which the C — N bond between the thienylbenzothiophene functional group and the phenoxazine derivative functional group forms a specific 90-degree space angle, thereby allowing the thienylthiophene functional group-phenoxazine compound to have a lower Δ ESTA suitable T1 energy level, and ensuring proper orbital overlap between HOMO-LUMOs to achieve higher radiative transition rate constants, which are advantageous for achieving higher optoelectronic properties of such compounds.
A further advantage of the compounds disclosed in embodiments of the present invention is that they have a very high f @ S1-S0A constant. For example, f @ S in the molecule L11-S00.3529, f @ S in L4 molecule1-S00.5381. It is expected that the thermally activated delayed fluorescence compound disclosed in the embodiments of the present invention has very good luminous efficiency.
Still another advantage of the present invention is that it provides a compound that achieves superior hole or electron transport properties with a very simple molecular design. The technical advantages of the present solution are explained in detail below for the compounds L1-L9.
TABLE 2 IPV, IPA, EAV, EAA, HEP, EEP, λ h, λ e calculation Table
As judged from the hole recombination energy and electron recombination energy in the above table, for the L1 molecule: [ electron recombination energy λ e-hole recombination energy λ h ] ═ 0.26eV, and therefore, the molecule L1 is a thermally activated delayed fluorescence organic material having a highly desirable hole-bias transport property.
For the L6 molecule: [ electron recombination energy λ e — hole recombination energy λ h ] ═ 0.05eV, and therefore, the L6 molecule is a thermally activated delayed fluorescence organic material with slightly stronger electron transport ability than hole transport ability. Such a molecular structure is advantageous in balancing the hole/electron carrier transport balance of the OLED device, thereby improving the OLED light emission efficiency and lifetime.
Device with a metal layer
The specific embodiments of the present invention also provide the use of the thermally retarded fluorescent compounds of the above examples in devices.
In some embodiments of the invention, the device may be an OLED, OFT, OPV, QLED device.
Embodiments of the present invention also provide an organic light emitting diode device comprising the thermally retarded fluorescent compound of the above examples.
In some embodiments, the thermal delayed fluorescence compound is a material of a light emitting layer in the organic light emitting diode device.
In some embodiments of the present invention, there is provided an organic light emitting diode device comprising: the fluorescent material comprises a first electrode, a hole transport layer formed on the first electrode, a light-emitting layer formed on the hole transport layer, an electron transport layer formed on the light-emitting layer, and a second electrode covering the electron transport layer, wherein the light-emitting layer is a thermal retardation fluorescent compound in the invention.
Organic light emitting diode device example
(1) As guest materials
And constructing a multilayer device structure of ITO/HIL/HTL/light-emitting layer/ETL/EIL/cathode. To facilitate the understanding of the technical advantages and device principles of the present invention, the present invention is described in terms of the simplest device structure.
ITO/HIL(10nm)/HTL(30nm)/HTL(30nm)/HOST：L1,6wt％,30nm/ETL(30nm)/LiF(1nm)/Al。
TABLE 3 partial comparison of device Performance
Efficiency roll off, defined herein as 0.1mA/cm2Efficiency to 100mA/cm2Rate of change of performance.
As can be seen from the data in table 3, the OLED devices using the compound provided by the present invention all have relatively small performance roll-off, and the maximum EQE is greater than 5%, because L4 is a TADF material with hole transport capability comparable to electron transport capability.
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples for carrying out the invention, and that various changes in form and details may be made therein without departing from the spirit and scope of the invention in practice.
Claims (5)
1. A thermally retarded fluorescent compound having the structure of formula (i) or (II):
wherein,
X1、X2each independently is O or S;
R1、R2each independently is a hydrogen atom, a deuterium atom, a halogen, a substituted or unsubstituted alkaneA substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted fused ring group;
d is an electron-donating organofunctional group.
2. The thermally delayed fluorescent compound of claim 1, wherein D has a structure represented by general formula (III):
wherein,
X3is an N atom;
X4selected from O or S;
R3、R4each independently selected from a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted fused ring group, an amino group;
n is selected from 0, 1 or 2.
3. The thermally delayed fluorescent compound of claim 2, having a structure selected from one of:
4. use of the thermally delayed fluorescent compound of any of claims 1 to 4 in OLED, OFT, OPV, QLED devices.
5. The use according to claim 4, wherein the thermally delayed fluorescent compound is a light emitting layer material in the OLED device.
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| CN107325084A (en) * | 2017-07-14 | 2017-11-07 | 瑞声科技（南京）有限公司 | A kind of spiro fluorene oxa anthracene compound and its luminescent device |
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