CN108948041A - A kind of compound and its application based on 5,10- dihydrophenazine - Google Patents

A kind of compound and its application based on 5,10- dihydrophenazine Download PDF

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CN108948041A
CN108948041A CN201810912488.3A CN201810912488A CN108948041A CN 108948041 A CN108948041 A CN 108948041A CN 201810912488 A CN201810912488 A CN 201810912488A CN 108948041 A CN108948041 A CN 108948041A
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substituted
unsubstituted
compound
dihydrophenazine
condensed ring
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谢再锋
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ACC Acoustic Technologies Shenzhen Co Ltd
AAC Technologies Holdings Nanjing Co Ltd
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Abstract

The present invention relates to organic electroluminescence device technical fields, disclose compound of the one kind based on 5,10- dihydrophenazine and its application in the devices.Luminous organic material disclosed in this invention has structure shown in general formula (I) or (II).Such compound is a kind of hot activation delayed fluorescence organic material, is suitable as emitting layer material applied in the technical fields such as OLED, OFT, OPV, QLED.

Description

A kind of compound and its application based on 5,10- dihydrophenazine
Technical field
The present invention relates to organic electroluminescence device technical field, in particular to a kind of change for being based on 5,10- dihydrophenazine Close object and its application in the devices.
Background technique
It reports from Kodak C.W.Tang in 1987 et al. and is prepared by vacuum thermal evaporation method with Alq for the first time3For Since the bi-layer devices structure of luminescent material, electroluminescent organic material is just received much attention.Such as Samsung Galaxy series mobile phone, S6 etc. are OLED mobile phones.2017, Apple Inc. also used OLED display screen configuration in its hand On machine.
Organic electroluminescent can be divided into fluorescence and electrophosphorescence.According to spin quantum statistical theory, singlet state swashs The formation probability ratio of son and triplet exciton is 1:3, i.e., singlet excitons only account for the 25% of " electron-hole pair ".Therefore, come The 25% of total input energy is just only accounted for from the fluorescence of the radiation transistion in singlet excitons, and the electroluminescent of phosphor material is just The energy of whole excitons can be used by heavy metal effect, thus there is bigger superiority.
It is most of in present electrophosphorescence device to use Subjective and Objective structure, i.e., by phosphorescent light-emitting materials with certain Doped in concentrations profiled is buried in oblivion into material of main part to avoid triplet-triplet, to improve phosphorescence luminous efficiency.
From over 2009, by Adachi group (A.Endo, M.Ogasawara, A.Takahashi, D.Yokoyama, Y.Kato, C.Adachi, Adv.Mater.2009,21,4802) the novel heat lag fluorescent material proposed, i.e. TADF (Thermally activated delayed fluorescence) material, because it can utilize triplet excitons under thermal excitation Backlass alter more, to obtain 100% singlet exciton, avoid using expensive heavy metal complex, and device efficiency It can compare favourably with phosphorescent devices.Since then, fluorescent material causes the concern of researcher again.
But it has been found that such material and its OLED device based on TADF effect there is also many deficiencies, such as material The type of material is than relatively limited, and the stability of device is up for improving.For example, in order to reach Δ EST (singlet and triplet Difference) < 0.3eV purpose, just need for HOMO-LUMO track to be kept completely separate on many TADF design of material, so as to cause reduction The light radiation transfer rate of TADF material, reduces material performance.
Summary of the invention
The purpose of the present invention is to provide a kind of compound based on 5,10- dihydrophenazine and its application, this kind is based on 5, The compound of 10- dihydrophenazine is a kind of hot activation delayed fluorescence organic material, luminous efficiency with higher.
In order to solve the above technical problems, embodiments of the present invention provide a kind of chemical combination for being based on 5,10- dihydrophenazine Object, with structure shown in general formula (I) or (II):
Wherein,
N is selected from 0,1 or 2；
R1、R2It is each independently selected from hydrogen atom, D-atom, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted Aryl, substituted or unsubstituted heterocycle, substituted or unsubstituted condensed ring radical；
R3For substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted condensed ring radical；
A is electrophilic organo-functional group.
Optionally, A has structure shown in logical formula (III) or (IV):
Wherein,
X1、X2It is each independently S or O；
R4It does not take selected from hydrogen atom, D-atom, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substitution or The heterocycle in generation, substituted or unsubstituted condensed ring radical, amino.
Optionally, the substituted alkyl, substituted aryl, substituted heterocycle, the substituent group in substituted condensed ring radical Selected from C1-C10 alkyl, C6-C36 aryl, C5-C36 heterocycle, C5-C36 condensed ring radical.
Optionally, it is based on the compound of 5,10- dihydrophenazine provided by embodiments of the present invention, has selected from as follows One of structure:
Embodiments of the present invention also provide the above-mentioned compound based on 5,10- dihydrophenazine OLED, OFT, OPV, Application in QLED device.
Optionally, the compound for being based on 5,10- dihydrophenazine is the emitting layer material in the OLED device.
In terms of existing technologies, TADF material provided by embodiments of the present invention.Its Δ EST (singlet with Triplet is poor) it is about 9meV, be conducive to raising triplet excitons to the backlass of singlet exciton and alter more probability.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below will to the embodiments of the present invention into The detailed elaboration of row.However, it will be understood by those skilled in the art that in each embodiment of the present invention, in order to make to read Person more fully understands the present invention and proposes many technical details.But even if without these technical details and based on following Each claim technical solution claimed of the present invention also may be implemented in the various changes and modifications of embodiment.
Compound
A specific embodiment of the invention provides a kind of compound for being based on 5,10- dihydrophenazine, with general formula (I) Or structure shown in (II):
Wherein, n is selected from 0,1 or 2；R1、R2It is each independently selected from hydrogen atom, D-atom, halogen, substituted or unsubstituted Alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, substituted or unsubstituted condensed ring radical；R3For replace or Unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted condensed ring radical；A is electrophilic organo-functional group.
In certain specific embodiments of the invention, A has structure shown in logical formula (III) or (IV):
Wherein, X1、X2It is each independently S or O；R4Selected from hydrogen atom, D-atom, substituted or unsubstituted alkyl, substitution Or unsubstituted aryl, substituted or unsubstituted heterocycle, substituted or unsubstituted condensed ring radical, amino.
In certain specific embodiments of the invention, the substituted alkyl, substituted aryl, substituted heterocycle, Substituent group in substituted condensed ring radical is selected from C1-C10 alkyl, C6-C36 aryl, C5-C36 heterocycle, C5-C36 condensed ring radical.
In certain specific embodiments of the invention, the provided compound for being based on 5,10- dihydrophenazine has choosing From one of following structure:
General synthetic routes
Following part discloses the preparation method of compound provided by the present invention.But present disclosure is not intended to be limited to this Method described in text it is any.Those skilled in the art can easily modify described method or using not With method come the one or more of compound provided by preparing.Following aspect is merely exemplary, and is not intended to limit this Scope of the disclosure.Temperature, catalyst, concentration, reactant composition and other process conditions are changeable, and for the phase The complex of prestige, present disclosure those skilled in the art can be readily selected suitable reactant and condition.
In CDCl on Varian Liquid State NMR instrument3Or DMS0-d6It is recorded in solution with 400MHz1H figure Spectrum, is recorded with 100MHz13C NMR spectra, chemical shift is referring to remaining deuterated (protiated) solvent.If CDCl3It is used as Solvent is then recorded using tetramethylsilane (δ=0.00ppm) as internal standard1H NMR spectra；Using DMSO-d6(δ= 77.00ppm) recorded as internal standard13C NMR spectra.If H2O (δ=3.33ppm) is used as solvent, then uses remaining H2O(δ =3.33ppm) it is recorded as internal standard1H NMR spectra；Using DMSO-d6(δ=39.52ppm) is recorded as internal standard13C NMR figure Spectrum.It is explained using following abbreviations (or combinations thereof)1The multiplicity of H NMR: s=substance, d=is dual, and t=is triple, q=tetra- Weight, five weight of P=, m=is multiple, br=wide.
Used reaction raw materials and reagent are both from commercially available or with side reported in the literature in embodiments of the present invention Method synthesis.
The general synthetic routes of the compounds of this invention are as follows:
Wherein,
N is selected from 0,1 or 2；
R1、R2It is each independently selected from hydrogen atom, D-atom, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted Aryl, substituted or unsubstituted heterocycle, substituted or unsubstituted condensed ring radical；
R3For substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted condensed ring radical；
R4It does not take selected from hydrogen atom, D-atom, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substitution or The heterocycle in generation, substituted or unsubstituted condensed ring radical, amino；
X1、X2It is each independently S or O；
Pd2(dba)3It is tris(dibenzylideneacetone) dipalladium, HPtBu3BF4It is a kind of phosphoric acid.
Synthesize example:
(1) compound L 1
Under the protection of argon inert gas, K and M is added in flask, is then sufficiently returned by dry toluene solution Stream reaction 30 minutes~60 minutes, is slowly added into Pd2(dba)3/HPtBu3BF4As catalyst, sufficiently react 30~60 minutes, NaO is slowly added under the protection of Ar gastIt is heated to 100~120 DEG C after Bu solution, and is stirred to react 24 hours.It is taken out after reaction Filter, toluene are washed, and ethyl alcohol is washed, and then use pillar to purify, organic solvent CH2Cl2/ n-hexane obtains purity 99% after purification Above powder.For the purity for further increasing L1, one or many distillations, available purity are carried out using vacuum sublimation instrument L1 product greater than 99.5%.
Using CDCL3As solvent, tetramethylsilane (δ=0.00ppm) is noted down as internal standard1H NMR spectra.
1H NMR (400MHZ, DMSO-d6):
6.21ppm(4H,p),6.37ppm(4H,P),6.53ppm(2H,d),7.06ppm(2H,s),7.31-7.33ppm (4H,q),7.53ppm(2H,d),7.78ppm(2H,m),7.86ppm(2H,m)。
(2) compound L 4
Under the protection of argon inert gas, in flask plus M and K, the toluene solution for then passing through drying sufficiently flow back Reaction 30 minutes~60 minutes, is slowly added into Pd2(dba)3/HPtBu3BF4As catalyst sufficiently reaction 30~60 minutes again, most Afterwards, NaO is slowly added under the protection of Ar gastAfter Bu solution, it is heated to 100~120 DEG C and is stirred to react 24 hours.After reaction It filters, toluene is washed, and ethyl alcohol is washed, and then uses pillar to purify, organic solvent CH2Cl2/ n-hexane obtains purity after purification 99% or more powder.For the purity for further increasing L4, one or many distillations are carried out using vacuum sublimation instrument, it is available Purity is greater than 99.5% L4 product.
Using CDCL3As solvent, tetramethylsilane (δ=0.00ppm) is noted down as internal standard1H NMR spectra.
1H NMR (400MHZ, DMSO-d6):
6.21ppm(4H,p),6.37ppm(4H,p),6.62ppm(2H,s),7.13-7.24ppm(6H,m),7.42ppm (2H,d),7.49ppm(2H,d)。
(3) compound L 21
Under the protection of argon inert gas, M and K is added in flask, is then sufficiently returned by dry toluene solution Stream reaction 30 minutes~60 minutes, is slowly added into Pd2(dba)3/HPtBu3BF4As catalyst, sufficiently react 30~60 minutes, NaO is slowly added under the protection of Ar gastAfter Bu solution, it is heated to 100-120 DEG C, and is stirred to react 24 hours.It is taken out after reaction Filter, toluene are washed, and ethyl alcohol is washed, and then use pillar to purify, organic solvent CH2Cl2/ n-hexane obtains purity 99% after purification Above powder.For the purity for further increasing L21, one or many distillations are carried out using vacuum sublimation instrument, it is available pure Degree is greater than 99.5% L21 product.
Using CDCL3As solvent, tetramethylsilane (δ=0.00ppm) is noted down as internal standard1H NMR spectra.
1H NMR (400MHZ, DMSO-d6):
6.21ppm(4H,p),6.31-6.37ppm(6H,p),6.46ppm(2H,d),6.53ppm(1H,d),6.62ppm (1H,t),7.01-7.06ppm(3H,q),7.31-7.33ppm(2H,p),7.53ppm(1H,d),7.78ppm(1H,m), 7.86ppm(1H,m)。
Optical physics information:
When studying the electronic structure of fluorescent small molecule compound, influences each other and be very important between electronics, density is general Letter theory (DFT) has been widely used for studying pi-conjugated system, and the result of the compound using the DFT method research disclosure It is more more accurate than other methods.To the excellent of the geometry under the ground state of compound molecule, cation state and negative particle state Change, using the method for DFT//B3LYP/6-31G (d), DFT//B3LYP/6- is used to the geometry of the excitation state of compound What the method for 31G (d) obtained.On the basis of ground state and excitation state geometry, using time-depentent DFT (TDDFT) Method calculates the Absorption and emission spectra of these compounds.By above-mentioned calculation method, studied compound can be obtained Various properties, including ionization energy IP, electron affinity EA, Reorganization Energy λ, highest occupied molecular orbital HOMO are minimum to occupy track LUMO, energy gap Eg.
For organic luminescent device, injects to hole and electronics energy active balance and transmission is very important.Molecule Ionization energy and electron affinity be injectability for assessing hole and electronics respectively.Following table, which lists, to be calculated Vertical and Adiabatic ionization potential, Vertical electron affinity and the Adiabatic electron affinity of compound, hole extract energy and electronics extracts Energy.Vertical detachment energy IP (v) refers to the energy difference of cation and molecule under neutral molecule geometric configuration；Adiabatic ionization potential IP (A) refer to the energy difference under neutral and cationic geometric configuration；It extracts energy HEP and refers to molecule under cationic geometric configuration in hole With the energy difference of cation；Vertical electron affinity EA (v) refers to the energy difference under neutral and anion geometric configuration；Electronics Extract the energy difference that energy EEP refers to molecule and anion under anion geometric configuration.Generally, for the organic material of small molecule Material, ionization energy is smaller, and the injection in hole is easier；And electron affinity is bigger, the injection of electronics is easier.
In terms of microcosmic angle, the transporting mechanism of charge be can be described as from the process transmitted in organic film.Wherein, one Electronics or hole are transferred on adjacent neutral molecule from a having electronic molecule.According to Marcus theory, the mobility of charge It can indicate are as follows:
Wherein, T represents temperature；V represents pre-exponential factor, is the Coupling matrix element between two kinds of particles；λ is Reorganization Energy；Kb It is Boltzmann constant.Obviously, λ and V is to determine KetAn important factor for value.Generally, under amorphous state charge transfer range It is limited, V value varies less.So the speed of mobility is mainly determined by the λ on index.λ is smaller, transmission rate It is faster.In order to study conveniently, ignore the influence of external environment, what is mainly discussed is reorganization energy.
It is derived according to calculating, reorganization energy may finally indicate are as follows:
λhole=IP (v)-HEP
λelectron=EEP-EA (v)
In general organic material, cause S1 excitation state different with T1 excited energy due to different from curl, and ES1 energy Amount is 0.5-1.0ev bigger than ET1 energy, causes pure organic fluorescence materials luminous efficiency low.Heat lag fluorescence TADF material, by It is designed in unique molecular, HOMO-LUMO track is separated, reduced the two electron exchange energy, Δ EST theoretically may be implemented ∽0.In order to effectively assess the heat lag fluorescent effect of material in the present invention, Δ EST assessment is carried out.Using TDDFT method, obtain The minimum singlet state excitation of compound provided by the present invention can Es and minimum triplet excitation energy ET difference DELTA EST.
The compound L 1-L4HOMO energy level, the lumo energy that prepare in the specific embodiment of the invention are calculated in method as above, Cloud Distribution, f@S1-S0 constant and Δ EST and the T1 energy level of HOMO and LUMO:
1 optical physics information data of table
According to above-mentioned calculated result, 5,10- dihydro-azophenlyene compound is based on provided by embodiments of the present invention In, thienyl benzothiophene functional group and 5, the C-N key between 10- dihydro-phenazene derivative functional group forms specific 90 degree Space angle so that such compound has lower Δ EST, suitable T1 energy level, and guarantees to fit between HOMO-LUMO When Orbital Overlap to obtain higher radiation transistion rate constant, these photoelectric properties are conducive to embodiment of the present invention and are mentioned The compound of confession obtains higher photoelectric properties.
The present invention makes provided compound reach higher hole transport performance or electricity with very simple MOLECULE DESIGN The characteristic of sub- transmission performance.The technical program bring technological merit is described in detail below for compound L 1-L4.
Table 2.IPV, IPA, EAV, EAA, HEP, EEP, λ h, λ e computational chart
The hole recombination calculated from upper table can judge with electron recombination energy data, for L1 molecule: [electron recombination energy λ e- hole recombination energy λ h]=0.10eV, therefore, L1 molecule is that the hot activation of an ideal inclined electronic transmission performance is prolonged Slow fluorescence organic material.
For L2 molecule: [electron recombination energy λ e- hole recombination energy λ h]=0.10eV, therefore, L2 molecule is a hole Transmittability is slightly better than the hot activation delayed fluorescence organic material of electron transport ability.
Device
A specific embodiment of the invention also provides existing in above-described embodiment based on 5,10- dihydro-azophenlyene compound Application in device.
In certain specific embodiments of the invention, the device can be OLED, OFT, OPV, QLED device.
A specific embodiment of the invention also provides a kind of organic light emitting diode device, the organic light emitting diode device Comprising in above-described embodiment based on 5,10- dihydro-azophenlyene compound.
In some specific embodiments provided by the present invention, 5,10- bis- is based on provided by embodiments of the present invention Hydrogen-azophenlyene compound is the emitting layer material in the organic light emitting diode device.
In some embodiments of the invention, provided organic light emitting diode device includes: first electrode, The hole transmission layer that is formed in first electrode, the luminescent layer formed on the hole transport layer, the electronics formed on the light-emitting layer pass Defeated layer, and the second electrode of covering on the electron transport layer, and luminescent layer is in the present invention based on 5,10- dihydro-azophenlyene Compound.
Organic light emitting diode device example
(1) it is used as guest materials
Construct ITO/HIL/HTL/ luminescent layer/ETL/EIL/ cathode multilayer device structure.In order to facilitate technical staff, reason Solve technical advantage and device principle of the invention, the present invention is illustrated with simplest device architecture.
ITO/HIL (10nm)/HTL (30nm)/HTL (30nm)/HOST:L1,4wt%, 30nm/ETL (30nm)/LiF (1nm)/Al。
The partial properties of 3. device of table compare
* efficiency roll-off this is defined herein as 0.1mA/cm2When efficiency to 100mA/cm2When performance change rate.
As shown in Table 3, it is roll-offed using the OLED device performance of compound provided by the present invention all smaller, and maximum EQE > 5%.
It will be understood by those skilled in the art that the respective embodiments described above are to realize specific embodiments of the present invention, And in practical applications, can to it, various changes can be made in the form and details, without departing from the spirit and scope of the present invention.

Claims (6)

1. the compound that one kind is based on 5,10- dihydrophenazine, which is characterized in that have structure shown in general formula (I) or (II):
Wherein,
N is selected from 0,1 or 2；
R1、R2It is each independently selected from hydrogen atom, D-atom, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted virtue Base, substituted or unsubstituted heterocycle, substituted or unsubstituted condensed ring radical；
R3For substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted condensed ring radical；
A is electrophilic organo-functional group.
2. the compound according to claim 1 for being based on 5,10- dihydrophenazine, which is characterized in that A has logical formula (III) Or structure shown in (IV):
Wherein,
X1、X2It is each independently S or O；
R4Selected from hydrogen atom, D-atom, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted miscellaneous Ring group, substituted or unsubstituted condensed ring radical, amino.
3. the compound according to claim 2 for being based on 5,10- dihydrophenazine, which is characterized in that the substituted alkyl, Substituted aryl, substituted heterocycle, the substituent group in substituted condensed ring radical are selected from C1-C10 alkyl, C6-C36 aryl, C5- C36 heterocycle, C5-C36 condensed ring radical.
4. the compound according to claim 3 for being based on 5,10- dihydrophenazine, which is characterized in that have selected from it is following it One structure:
5. the compound described in any one of Claims 1-4 based on 5,10- dihydrophenazine is in OLED, OFT, OPV, QLED Application in device.
6. application according to claim 5, which is characterized in that the compound for being based on 5,10- dihydrophenazine is described Emitting layer material in OLED device.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110299460A (en) * 2019-06-24 2019-10-01 武汉华星光电半导体显示技术有限公司 A kind of hole mobile material, preparation method and electroluminescent device
US11355713B2 (en) 2019-06-24 2022-06-07 Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. Hole transport material, manufacturing method thereof, and electroluminescent device thereof
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CN111875551A (en) * 2019-09-02 2020-11-03 广东聚华印刷显示技术有限公司 Organic compound, electronic device and corresponding preparation method
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