CN108822088A - A kind of compound and its application based on glyoxaline structure - Google Patents

A kind of compound and its application based on glyoxaline structure Download PDF

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CN108822088A
CN108822088A CN201810912492.XA CN201810912492A CN108822088A CN 108822088 A CN108822088 A CN 108822088A CN 201810912492 A CN201810912492 A CN 201810912492A CN 108822088 A CN108822088 A CN 108822088A
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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 field, a kind of compound based on glyoxaline structure and its application in the devices are disclosed.Compound disclosed in this invention is based on xanthone-imidazole skeleton structure, such compound is the bipolar organic material that a kind of cavity transmission ability is equal to or is equivalent to electron transport ability, it is applied in the devices such as OLED, hole/electronic carrier transmission the balance for being conducive to balance OLED device, to improve luminous efficiency and the service life of the devices such as OLED.

Description

A kind of compound and its application based on glyoxaline structure
Technical field
The present invention relates to organic electroluminescence device technical field, in particular to a kind of compound based on glyoxaline structure 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.
Forrest and Thompson in 1999 et al. is by green light phosphor material Ir (ppy)3Existed with the doped in concentrations profiled of 6wt% 4, in 4 '-N, N '-two carbazole-biphenyl (CBP) material of main part, and introduce hole barrier layer material 2,9- dimethyl -4,7- Diphenyl -1,10- Phen (BCP), the green light OLED maximum external quantum efficiency 8% of acquisition, power efficiency reaches 31lm/ W, substantially exceeds electroluminescent fluorescent luminescent device, causes people to the extensive concern of heavy metal complex luminescent material immediately.
Blue light one kind the most key as RGB is photochromic, limits the development of OLED always, main problem is to select Blue-light emitting host material is very deficient.The energy that blue light emitting material itself shines is just very high, it is desirable that its material of main part has Higher requirement：1) high singlet and triplet, T1>2.6eV；2) matched hole/electron transport ability in luminescent layer； 3) enough chemical stabilities.
A kind of 1,3- bis- Blue-light emitting host material of (9H- carbazyl -9-) phenyl ring (mCP) as classics, often with object material Expect that FIrpic doping uses, preferable luminescent properties can be obtained.However, mCP is as blue light, the master of even deep Nan dian Yao Body material not yet meets commercialized requirement.First problem is that the singlet and triplet of mCP does not meet enough The energy level requirement that dark blue smooth main body requires.Second Problem is that the inclined hole transport performance of mCP is better than its electron-transporting Can, the carrier further resulted in luminescent layer is uneven, and with superfluous holoe carrier non-spoke will occur for extra exciton That penetrates buries in oblivion, and causes device performance reduction and service life reduction.
Summary of the invention
The purpose of the present invention is to provide a kind of compound based on glyoxaline structure and its application, this kind of compound is based on oxygen Miscellaneous anthrone-imidazole skeleton structure, hole transport performance are extremely matched with electronic transmission performance, and can be used as a kind of blue light main body Material is applied in device.
In order to solve the above technical problems, embodiments of the present invention provide a kind of compound based on glyoxaline structure, institute The general formula for stating compound is D-A or D-A-D or A-D-A, wherein
D has selected from one of following structure：
Wherein, R1、R2、R3It is each independently hydrogen atom, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C30 aryl；
Represent C6-C30 aryl；
A has selected from one of following structure：
Wherein, n is integer；
D1、D2It is each independently selected from hydrogen atom, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6- The aryl or D of C30；
X1、X2It is each independently selected from-O- ,-S- ,-C (=O)-,-S (=O)-or-(O=S=O)-.
Optionally, 1 n.
In the case that n is 1, the general formula D-A of the compound based on glyoxaline structure provided by embodiments of the present invention Or D-A-D or A-D-A, have selected from the structure such as one of (1)~(9)：
Wherein,
D1、D2It is each independently selected from hydrogen atom, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6- The aryl or D of C30；
X1、X2It is each independently selected from-O- ,-S- ,-C (=O)-,-S (=O)-or-(O=S=O)-.
Optionally, the compound based on glyoxaline structure provided by embodiments of the present invention has selected from one of following Structure：
Embodiments of the present invention also provide it is above-mentioned based on the compound of glyoxaline structure in OLED, OFT, OPV, QLED device In application.
Optionally, the compound based on glyoxaline structure is the emitting layer material in the OLED device.
In terms of existing technologies, compound provided by embodiments of the present invention is based on xanthone-imidazoles bone Frame structure is the bipolar organic material that a kind of cavity transmission ability is equal to or is equivalent to electron transport ability, is applied to In OLED device, be conducive to the hole/electronic carrier transmission balance for balancing OLED device, to improve OLED luminous efficiency And the service life.
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 based on glyoxaline structure, and the general formula of the compound is D-A or D-A-D or A-D-A, wherein
D has selected from one of following structure：
Wherein, R1、R2、R3It is each independently hydrogen atom, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C30 aryl；
Represent C6-C30 aryl；
A has selected from one of following structure：
Wherein, n is integer；
D1、D2It is each independently selected from hydrogen atom, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6- The aryl or D of C30；
X1、X2It is each independently selected from-O- ,-S- ,-C (=O)-,-S (=O)-or-(O=S=O)-.
In certain specific embodiments of the invention, n 1.
The chemical combination based on glyoxaline structure in the case that n is 1, provided in certain specific embodiments of the invention General formula D-the A or D-A-D or A-D-A of object have selected from the structure such as one of (1)~(9)：
Wherein,
D1、D2It is each independently selected from hydrogen atom, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6- The aryl or D of C30；
X1、X2It is each independently selected from-O- ,-S- ,-C (=O)-,-S (=O)-or-(O=S=O)-.
In certain specific embodiments of the invention, the provided compound based on glyoxaline structure has selected from such as One of lower 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 according to document report side in embodiments of the present invention Method synthesis.
The general synthetic routes of the compounds of this invention are as follows：
Wherein,
Synthesis can refer to《Adv.Mater.2016,28,181》.
For example,
In present disclosure, only detailed description carries out synthesis target product and its chemistry by initial feed of D and A The process of characterization.
Synthesize example：
(1) compound L 2
In the there-necked flask equipped with A in N2Protection under be slowly added into Pd (PPh3)4(Chinese name:Four-(triphenylphosphine)-palladiums (0) compound), K2CO3, then, then after being slowly added into a certain amount of D compound acetone mixed solution slowly adds mixture Heat is to being kept for 5 hours after 100~120 DEG C, until after sufficiently chemical reaction occurs for mixture.Then, mixture is cooled to room Wen Hou, with washed with ether, organic phase is rinsed with salt water, is then carried out removing solvent after sufficiently drying with magnesium sulfate again, be obtained Final product, carrying out pillar by chromatographic column, (organic phase early period is toluene/n-hexane=1:1, later period organic phase be toluene/ Hexane solution=2:1) the product L2 of 98% or more purity, is obtained.For the purity for further increasing L2, using vacuum sublimation instrument One or many distillations are carried out, available purity is greater than 99.0% L2 product.
Using CDCL3As solvent, tetramethylsilane (δ=0.00ppm) is noted down as internal standard1H NMR spectra.
1H NMR(400MHZ,DMSO-d6)：
7.02-7.08ppm(2H,P),7.24-7.3ppm(6H,q),7.38-7.44ppm(9H,m),7.66-7.72ppm (3H,q),7.82-7.88ppm(4H,m),8.12ppm(2H,d),8.93ppm(2H,d)。
(2) compound L 3
In the there-necked flask equipped with A in N2Protection under be slowly added into Pd (PPh3)4(Chinese name:Four-(triphenylphosphine)-palladiums (0) compound), K2CO3, then, then after being slowly added into a certain amount of D compound acetone mixed solution slowly adds mixture Heat is to being kept for 5 hours after 100~120 DEG C, until after sufficiently chemical reaction occurs for mixture.Then, mixture is cooled to room Wen Hou, with washed with ether, organic phase is rinsed with salt water, is then carried out removing solvent after sufficiently drying with magnesium sulfate again, be obtained Final product, carrying out pillar by chromatographic column, (organic phase early period is toluene/n-hexane=1:1, later period organic phase be toluene/ Hexane solution=2:1) the product L3 of 98% or more purity is obtained.For the purity for further increasing L3, using vacuum sublimation instrument One or many distillations are carried out, available purity is greater than 99.0% L3 product.
Using CDCL3As solvent, tetramethylsilane (δ=0.00ppm) is noted down as internal standard1H NMR spectra.
1H NMR(400MHZ,DMSO-d6)：
7.02-7.08ppm(4H,P),7.24-7.3ppm(9H,q),7.41ppm(2H,t),7.66-7.72ppm(6H, q),7.82-7.88ppm(4H,m),8.12ppm(2H,d),8.93ppm(2H,d)。
(3) compound L 41
In the there-necked flask equipped with A in N2Protection under be slowly added into Pd (PPh3)4(Chinese name:Four-(triphenylphosphine)-palladiums (0) compound), K2CO3, then, then after being slowly added into a certain amount of D compound acetone mixed solution slowly adds mixture Heat is to being kept for 5 hours after 100~120 DEG C, until after sufficiently chemical reaction occurs for mixture.Then, mixture is cooled to room Wen Hou, with washed with ether, organic phase is rinsed with salt water, is then carried out removing solvent after sufficiently drying with magnesium sulfate again, be obtained Final product, carrying out pillar by chromatographic column, (organic phase early period is toluene/n-hexane=1:1, later period organic phase be toluene/ Hexane solution=2:1) the product L41 of 98% or more purity is obtained.For the purity for further increasing L41, using vacuum sublimation Instrument carries out one or many distillations, and available purity is greater than 99.0% L41 product.Using CDCL3As solvent, tetramethyl Silane (δ=0.00ppm) is noted down as internal standard1H NMR spectra.
1H NMR(400MHZ,DMSO-d6)：
7.3ppm(5H,S),7.55ppm(4H,m),7.66ppm(3H,s),7.77-7.88ppm(12H,m),8.02ppm (2H,s),8.12ppm(2H,d),8.93ppm(2H,d)。
(4) compound L 44
In the there-necked flask equipped with A in N2Protection under be slowly added into Pd (PPh3)4(Chinese name:Four-(triphenylphosphine)-palladiums (0) compound), K2CO3, then, then after being slowly added into a certain amount of D compound acetone mixed solution slowly adds mixture Heat is to being kept for 5 hours after 100~120 DEG C, until after sufficiently chemical reaction occurs for mixture.Then, mixture is cooled to room Wen Hou, with washed with ether, organic phase is rinsed with salt water, is then carried out removing solvent after sufficiently drying with magnesium sulfate again, be obtained Final product, carrying out pillar by chromatographic column, (organic phase early period is toluene/n-hexane=1:1, later period organic phase be toluene/ Hexane solution=2:1) the product L44 of 98% or more purity is obtained.For the purity for further increasing L44, using vacuum sublimation Instrument carries out one or many distillations, and available purity is greater than 99.0% L44 product.
Using CDCL3As solvent, tetramethylsilane (δ=0.00ppm) is noted down as internal standard1H NMR spectra.
1H NMR(400MHZ,DMSO-d6)：
7.3ppm(5H,S),7.4ppm(1H,t),7.54-7.62ppm(6H,p),7.82-7.88ppm(5H,m), 8.00ppm(1H,d),8.12ppm(2H,d),8.22ppm(1H,s),8.93ppm(2H,d)。
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 be expressed as：
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 be expressed as：
λhole=IP (v)-HEP
λelecton=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-L9HOMO energy level, the lumo energy that prepare in the specific embodiment of the invention are calculated in method as above, The Cloud Distribution and Δ EST and T1 energy level of HOMO and LUMO：
1 optical physics information data of table
According to above-mentioned calculated result, compound provided by embodiments of the present invention has suitable Δ EST, high T1 Energy level, these properties are conducive to these compounds and obtain 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.It is illustrated below for part of compounds.
Table 2.IPV, IPA, EAV, EAA, HEP, EEP, λ h, λ e computational chart
The hole recombination that is calculated from upper table can and electron recombination can judge, for L2 molecule：[electron recombination energy λ e- Hole recombination energy λ h]=0.014eV, therefore, L2 molecule is that an ideal cavity transmission ability is equal to electron-transport The bipolar organic material of ability is advantageous in that the hole/electronic carrier transmission balance for being conducive to balance OLED device, To improve OLED luminous efficiency and service life.
For L3 molecule：[electron recombination energy λ e- hole recombination energy λ h]=0.024eV, therefore, L3 molecule is a hole Transmittability is equivalent to the bipolar organic material of electron transport ability.It is advantageous in that, is conducive to the sky for balancing OLED device Cave/electronic carrier transmission balance, to improve OLED luminous efficiency and service life.
For L4 molecule：[electron recombination energy λ e- hole recombination energy λ h]=0.01eV, therefore, L4 molecule be one very Ideal cavity transmission ability is equal to the bipolar organic material of electron transport ability.It is advantageous in that, is conducive to balance Hole/electronic carrier transmission of OLED device balances, to improve OLED luminous efficiency and service life.
For L6 molecule：[electron recombination energy λ e- hole recombination energy λ h]=0.01eV, therefore, L6 molecule be one very Ideal cavity transmission ability is equal to the bipolar organic material of electron transport ability.It is advantageous in that, is conducive to balance Hole/electronic carrier transmission of OLED device balances, to improve OLED luminous efficiency and service life.
For L8 molecule：[electron recombination energy λ e- hole recombination energy λ h]=0.023eV, therefore, L8 molecule is a hole The bipolar organic material that transmittability and electron transport ability match.It is advantageous in that, is conducive to balance OLED device Hole/electronic carrier transmission balance, to improve OLED luminous efficiency and service life.
Device
A specific embodiment of the invention also provides the compound based on glyoxaline structure in above-described embodiment in the devices Application.
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 Include the compound based on glyoxaline structure in above-described embodiment.
In some specific embodiments provided by the present invention, glyoxaline structure is based on provided by embodiments of the present invention Compound be the organic light emitting diode device in emitting layer material.
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 the chemical combination based on glyoxaline structure in the present invention Object.
Organic light emitting diode device example
(1) it is used as material of main part
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)/L：Ir (ppy) 3,10wt%, 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> 10%, this is because there is compound disclosed in this technology preferable hole-electron to transmit balance, be conducive to improve OLED device The efficiency roll-off of part at higher current densities.
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. a kind of compound based on glyoxaline structure, which is characterized in that the general formula of the compound is D-A or D-A-D or A-D- A, wherein D has selected from one of following structure：
In D structure, R1、R2、R3It is each independently hydrogen atom, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C30 aryl；
Represent C6-C30 aryl；
A has selected from one of following structure：
In A structure, n is integer；
D1、D2It is each independently selected from hydrogen atom, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C30 Aryl or D；
X1、X2It is each independently selected from-O- ,-S- ,-C (=O)-,-S (=O)-or-(O=S=O)-.
2. the compound according to claim 1 based on glyoxaline structure, which is characterized in that n 1.
3. the compound according to claim 2 based on glyoxaline structure, which is characterized in that the general formula D-A of the compound Or D-A-D or A-D-A, have selected from the structure such as one of (1)~(9)：
Wherein,
D1、D2It is each independently selected from hydrogen atom, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C30 Aryl or D；
X1、X2It is each independently selected from-O- ,-S- ,-C (=O)-,-S (=O)-or-(O=S=O)-.
4. the compound according to claim 3 based on glyoxaline structure, which is characterized in that have selected from one of following knot Structure：
5. it is described in any one of Claims 1-4 based on the compound of glyoxaline structure in OLED, OFT, OPV, QLED device Application.
6. application according to claim 5, which is characterized in that the compound based on glyoxaline structure is the OLED device Emitting layer material in part.
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Application publication date: 20181116