CN109796296A - A kind of spiro-compound and its application - Google Patents
A kind of spiro-compound and its application Download PDFInfo
- Publication number
- CN109796296A CN109796296A CN201811611789.9A CN201811611789A CN109796296A CN 109796296 A CN109796296 A CN 109796296A CN 201811611789 A CN201811611789 A CN 201811611789A CN 109796296 A CN109796296 A CN 109796296A
- Authority
- CN
- China
- Prior art keywords
- independently represent
- compound
- aryl
- phenyl
- spiro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
The invention belongs to field of organic electroluminescent materials, a kind of spiro-compound and its application are disclosed.Spiro-compound provided by the present invention has good thermal stability and device stability.Material of main part using provided spiro-compound of the invention as electroluminescent device luminescent layer, or guest materials further is adulterated in the luminescent layer of device, the cut-in voltage of obtained device is significantly reduced, and luminous efficiency is improved, and device stability is also significantly improved.
Description
Technical field
The invention belongs to field of organic electroluminescent materials, in particular to a kind of spiro-compound and its application.
Background technique
Organic electroluminescence device is to realize that power-up shines by introducing one or more layers organic film in cathode and anode
A kind of device technology, can be realized ultra-thin, flexible and transparent performance, FPD and illuminating industry application year by year
It improves.
The organic electroluminescence device structure of industry, in order to realize that different targets, structure and mode are a variety of more
Sample.For the luminescent layer of emission spectrum, a kind of mode is the promotion of progress efficiency and service life in the form of host-guest system.
Material of main part receives energy and passes to object, and guest materials emits corresponding spectrum after receiving energy.Different main bodys and visitor
Shining for different colours may be implemented in body material.For example there are CBP for common material of main part, and for example there are Ir for common guest materials
(ppy) 3 and AlQ3.Since material of main part and guest materials use the form luminescent layer of doping, guest materials is also referred to as adulterated
Material.
When assessing a device performance superiority and inferiority, efficiency and stability are two important parameters.Therefore, good for performance
Good electroluminescent device, the material with good characteristic used by performance depends primarily on, either auxiliary layer material,
Such as electron injection material, electron transport material, hole mobile material, hole-injecting material or emitting layer material, such as object material
Material, material of main part.
By using host-guest system system, luminescent material luminous excitation purity and luminous efficiency can be improved.In host and guest
In body doping system, relative to material of main part, ratio of the guest materials in luminescent layer be usually it is less, energy gap is also small
, however its luminous quantum efficiency is higher.In host-guest system system, exciton ordinary priority is produced in material of main part
It is raw, it is then transferred into guest materials, finally realizes high efficiency light-emitting.
Phosphor material system, although having theoretically 100% quantum efficiency, the service life of blue light material is extremely low
's.Commercial device architecture at present has been all made of blue-fluorescence and green red phosphorescent system.Common blue fluorescent material is
Diversified, for example there are the blue fluorescent material TBADN of the blue fluorescent material DPVBi of monocycle and tricyclic.It is glimmering for blue
Luminescent material achieves considerable progress by industry and academia's long-term endeavour in terms of excitation purity and thermal stability,
However, the easy crystallinity in blue material causes film forming poor, the long-time stability of device are influenced very big.
Summary of the invention
The purpose of the present invention is to provide a kind of spiro-compound and its applications, are a kind of with good by this kind of compound
Thermal stability and film forming stability blue fluorescent material.
The purpose of the present invention is achieved through the following technical solutions:
Embodiments of the present invention provide a kind of spiro-compound, with structure shown in formula (I):
Wherein,
X indicates carbon atom；
Y1Indicate CRxRy；And Rx, Ry each independently represent hydrogen, deuterium, fluorine, chlorine, bromine, iodine, C1-C24 alkyl or C6-C72
Aryl；
R1-R8Each independently represent hydrogen, deuterium, fluorine, chlorine, bromine, iodine, C1-C24 alkyl, C1-C24 alkoxy, C6-C72 virtue
Base or C6-C72 aryloxy group；
Z1、Z2The aromatic rings for including 1 ring or the aromatic rings comprising being condensed by least two ring are each independently represented, and
Z1、Z2At least one of include the aromatic rings that is condensed by least two ring；The Z1、Z2At least one of replaced by anthryl.
Optionally, Z1、Z2Each independently comprising structure shown in one of formula G1-G14:
Wherein,
N1-N8CRo is each independently represented, the Ro indicates hydrogen, deuterium, fluorine, chlorine, bromine, iodine, C1-C24 alkyl, C1-C24 alkane
Oxygroup, C6-C72 aryl or C6-C72 aryloxy group.
Optionally, the anthryl has structure shown in formula (II):
Wherein,
A1Indicate C1-C24 alkyl, C6-C72 aryl or C3-C72 heteroaryl；
A2Indicate hydrogen, deuterium, C1-C12 alkyl, C6-C24 aryl or C3-C24 heteroaryl.The A2The substituent group of expression can be with
It is one, or multiple.
Optionally, spiro-compound provided by embodiments of the present invention, have formula (III-1), (III-2) or
(III-3) structure shown in:
Wherein,
Y1Indicate CRxRy；
Rx, Ry each independently represent C1-C24 alkyl or C6-C72 aryl；
R1-R8Each independently represent hydrogen, deuterium, fluorine, C1-C24 alkyl, C1-C24 alkoxy, C6-C72 aryl or C6-C72
Aryloxy group；
Z11、Z12Each independently represent phenyl ring, naphthalene nucleus, anthracene nucleus or phenanthrene ring；
R11、R22Each independently represent hydrogen, deuterium, C1-C24 alkyl or C6-C72 aryl；R12、R21、R31、R32It is respectively independent
Ground indicates C1-C24 alkyl or C6-C72 aryl；
B1、B2、B3、B4Each independently represent hydrogen, deuterium, C1-C12 alkyl or C6-C24 aryl.The B1、B2、B3、B4Table
The substituent group shown can be one, or multiple.
Still optionally further, in (III-1), (III-2) or (III-3):
Y1Indicate CRxRy；Rx, Ry each independently represent C1-C24 alkyl or C6-C72 aryl；R1-R8Each independently
Indicate hydrogen, deuterium, methyl, ethyl, propyl, butyl, amyl, hexyl, phenyl, tolyl, ethylbenzene, propyl phenyl, butylbenzene base, penta benzene
Base, own phenyl, phenyl, naphthylphenyl, phenanthryl phenyl, naphthalene, naphthalene of flying, ethyl naphthalene, propyl naphthalene, dibutyl naphthalene
Base, amyl naphthalene, hexyl naphthalene, phenyl napthyl or phenyl anthryl；Z11、Z12Each independently represent phenyl ring, naphthalene nucleus, anthracene nucleus or
Phenanthrene ring；R11、R22Expression hydrogen, deuterium or C6-C72 aryl independent, R12、R21、R31、R32Each independently represent C6-C72 virtue
Base；B1、B2、B3、B4Each independently represent hydrogen, deuterium, methyl, ethyl, propyl, butyl, amyl, hexyl, phenyl, tolyl, second
Phenyl, propyl phenyl, butylbenzene base.
The link position of the substituent group is not limited, and is illustrated but is not limitation, as propyl is chosen as n-propyl
Or isopropyl, butyl are chosen as normal-butyl, isobutyl group or tert-butyl, amyl be chosen as n-pentyl, cyclopenta, neopentyl or other
The amyl of form, hexyl are chosen as the hexyl of n-hexyl, cyclohexyl or other forms, and the position of substitution of tolyl can be methyl
Contraposition, ortho position or meta position, the position of substitution of naphthalene can be 1 or 2 of naphthalene.The position of substitution of anthryl is also unrestricted
System, and 9 and 10 of anthracene nucleus are non-hydrogen substituent.
Optionally, Rx, Ry each independently represent C1-C24 alkyl or C6-C24 aryl, and Rx, Ry pass through chemical bond phase
Even.
Still optionally further, Rx, Ry each independently represent methyl, ethyl, propyl, butyl, deuterated methyl, phenyl, first
Phenyl, ethylbenzene, propyl phenyl, butylbenzene base or benzyl.
Further optionally, Rx, Ry are identical substituent group.
Optionally, spiro-compound provided by embodiments of the present invention has selected from one of following structure:
Another object of the present invention is to provide application of the above-mentioned spiro-compound in organic electroluminescence device.
A further object of the present invention is to provide a kind of electroluminescent device, include at least above-mentioned spiro-compound and
Compound shown in formula (V):
Wherein,
Ar1、Ar2、Ar3、Ar4Each independently represent C6-C36 aryl or C3-C36 heteroaryl；
Q1、Q2、Q3Each independently represent hydrogen atom, D-atom, C1-C12 alkyl, C6-C36 aryl or C3-C36 heteroaryl
Base；
The spiro-compound is the material of main part in the luminescent layer of the device, and compound shown in formula (V) is the device
Guest materials in the luminescent layer of part.
Optionally, formula (V) is selected from one of following structure:
In terms of existing technologies, spiro-compound provided by embodiments of the present invention has the following structure spy
Point: (1) 9 of the anthryl in structure and 10 hydrogen are substituted；(2) there is the spirane structure of rigidity；(3) and not pass through oxygen original
Sub- bridging.Above structure feature makes have lower cut-in voltage, higher with device prepared by compound provided by the present invention
External quantum efficiency, longer service life and better thermal stability and film forming stability.Using embodiments of the present invention
Material of main part of the provided spiro-compound as electroluminescent device luminescent layer, or further with embodiments of the present invention
Compound shown in provided formula (V) is the guest materials in the luminescent layer of the device, and the cut-in voltage of obtained device is significant
It reduces, luminous efficiency is improved, and device stability is also significantly improved.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with embodiment to of the invention each
Specific embodiment is explained in detail.However, it will be understood by those skilled in the art that in each embodiment party of the present invention
In formula, many technical details are proposed in order to make reader more fully understand the present invention.But even if without these technical details
And various changes and modifications based on the following respective embodiments, each claim skill claimed of the present invention also may be implemented
Art scheme.
Compound
In certain specific embodiments of the invention, a kind of spiro-compound is provided, with knot shown in formula (I)
Structure:
Wherein,
X indicates carbon atom；
Y1Indicate CRxRy；And Rx, Ry each independently represent hydrogen, deuterium, fluorine, C1-C24 alkyl or C6-C72 aryl；
R1-R8Each independently represent hydrogen, deuterium, fluorine, chlorine, bromine, iodine, C1-C24 alkyl, C1-C24 alkoxy, C6-C72 virtue
Base or C6-C72 aryloxy group；
Z1、Z2The aromatic rings for including 1 ring or the aromatic rings comprising being condensed by least two ring are each independently represented, and
Z1、Z2At least one of include the aromatic rings that is condensed by least two ring；The Z1、Z2At least one of replaced by anthryl.
In certain specific embodiments of the invention, Z1、Z2Each independently comprising being tied shown in one of formula G1-G14
Structure:
Wherein,
N1-N8CRo is each independently represented, the Ro indicates hydrogen, deuterium, fluorine, chlorine, bromine, iodine, C1-C24 alkyl, C1-C24 alkane
Oxygroup, C6-C72 aryl or C6-C72 aryloxy group.
In certain specific embodiments of the invention, the anthryl has structure shown in formula (II):
Wherein,
A1Indicate C1-C24 alkyl or C6-C72 aryl；A2Indicate hydrogen, deuterium, C1-C12 alkyl or C6-C24 aryl.The A2
The substituent group of expression can be one, or multiple.
Spiro-compound provided in certain specific embodiments of the invention has formula (III-1), (III-2)
Or structure shown in (III-3):
Wherein,
Y1Indicate CRxRy；
Rx, Ry each independently represent C1-C24 alkyl or C6-C72 aryl；
R1-R8Each independently represent hydrogen, deuterium, fluorine, C1-C24 alkyl, C1-C24 alkoxy, C6-C72 aryl or C6-C72
Aryloxy group；
Z11、Z12Each independently represent phenyl ring, naphthalene nucleus, anthracene nucleus or phenanthrene ring；
R11、R22Each independently represent hydrogen, deuterium, C1-C24 alkyl or C6-C72 aryl；R12、R21、R31、R32It is respectively independent
Ground indicates C1-C24 alkyl or C6-C72 aryl；
B1、B2、B3、B4Each independently represent hydrogen, deuterium, C1-C12 alkyl or C6-C24 aryl.The B1、B2、B3、B4Table
The substituent group shown can be one, or multiple.
In certain specific embodiments of the invention, in (III-1), (III-2) or (III-3) structure:
Y1Indicate CRxRy；
Rx, Ry each independently represent C1-C24 alkyl or C6-C72 aryl；
R1-R8Each independently represent hydrogen, deuterium, methyl, ethyl, propyl, butyl, amyl, hexyl, phenyl, tolyl, second
Phenyl, propyl phenyl, butylbenzene base, penta phenyl, own phenyl, phenyl, naphthylphenyl, phenanthryl phenyl, naphthalene, naphthalene of flying, second
Base naphthalene, propyl naphthalene, butyl naphthalene, amyl naphthalene, hexyl naphthalene, phenyl napthyl or phenyl anthryl；
Z11、Z12Each independently represent phenyl ring, naphthalene nucleus, anthracene nucleus or phenanthrene ring；
R11、R22Expression hydrogen, deuterium or C6-C72 aryl independent；R12、R21、R31、R32Each independently represent C6-
C72 aryl；
B1、B2、B3、B4Each independently represent hydrogen, deuterium, methyl, ethyl, propyl, butyl, amyl, hexyl, phenyl, toluene
Base, ethylbenzene, propyl phenyl, butylbenzene base.The link position of the substituent group is not limited, and is illustrated but is not limitation, such as
Propyl be n-propyl or isopropyl, butyl be normal-butyl, isobutyl group or tert-butyl, amyl be n-pentyl, cyclopenta, neopentyl or
The amyl of other forms, hexyl are the hexyl of n-hexyl, cyclohexyl or other forms, and the position of substitution of tolyl can be methyl
Contraposition, ortho position or meta position, the position of substitution of naphthalene can be 1 or 2 of naphthalene.The position of substitution of anthryl is also unrestricted
System, and 9 and 10 of anthracene nucleus are non-hydrogen substituent.
In certain specific embodiments of the invention, Rx, Ry each independently represent C1-C24 alkyl or C6-C24 virtue
Base, and Rx, Ry are connected by chemical bond.
In certain specific embodiments of the invention, Rx, Ry each independently represent methyl, ethyl, propyl, butyl,
Deuterated methyl, phenyl, tolyl, ethylbenzene, propyl phenyl, butylbenzene base or benzyl.
In certain specific embodiments of the invention, Rx, Ry are identical substituent group.
Spiro-compound provided in certain specific embodiments of the invention has selected from one of following knot
Structure:
General synthetic routes:
Specific embodiments of the present invention also provide the synthetic route of above-mentioned heteroaromatic compound, use general conjunction in the industry
At method.The patent that can refer to for example there are US20150333277A1, KR1020160050221A, CN106883215A,
It can be with bibliography physical chemistry periodical (J.Phys.Chem.C 2008,112,14603-14606), materials chemistry periodical
The document of (J.Mater.Chem., 2010,20,1560-1566) open report.
Synthesize example:
The preparation method of disclosed compound of present invention provided below.But present disclosure is not intended to be limited to institute herein
The method of narration it is any.Those skilled in the art can easily modify described method or utilize different sides
Method prepares the one or more of disclosed compound.Following aspect is merely exemplary, and is not intended to limit in the disclosure
The range of appearance.Temperature, catalyst, concentration, reactant composition and other process conditions are changeable, and match for desired
Object is closed, present disclosure those skilled in the art can readily select suitable reactant and condition.
Embodiment 1: the synthesis of compound TM1
Step 1
Compound C-1 (3.5g, 12.2mmol) is added in the tetrahydrofuran of 50mL, normal-butyl is added dropwise in the degree of low temperature -78
Lithium (5.8mL, 14.6mmol) keeps the temperature, is slowly added to compound C-2 after reaction system continues stirring 1 hour
The 10mL solution of (10.8mmol) is further continued for stirring 2 hours, is then warmed to room temperature, and continues stirring 12 hours, reaction system second
Acetoacetic ester extraction, Diethyl ether recrystallization obtain intermediate.Obtained intermediate is added in 30mL acetic acid, 80 DEG C is warming up to, adds
Enter 1 drop concentrated hydrochloric acid, back flow reaction 2 hours, after being cooled to room temperature, filtering obtained compound C-3.Yield 59%.
Step 2
Compound C-3 (4.1g, 10mmol) is dissolved into 50mL DMF, then slowly be added dropwise NBS (2.1g,
12mmol), stirring is lower is added dropwise 50mL distilled water, continues stirring 1 hour after being added dropwise to complete, filtering precipitating is tied again using n-hexane
Crystalline substance obtains compound C-4.Yield 44%.
Step 3
By compound C-4 (4.9g, 10mmol) and compound C-5 (3.3g, 11mmol), tetra-triphenylphosphine palladium (0.6g,
0.5mmol), potassium carbonate (2.8g, 60mmol) is added to the in the mixed solvent of 50mL toluene, 50mL dioxane, 10mL water,
It back flow reaction 12 hours, is extracted with ethyl acetate, column chromatographed column and mentions target compound TM1.Yield 45%.
Nuclear magnetic data: (400mHz, CDCl3) 9.02 (d, 1H), 8.48 (dd, 2H), 7.72-7.45 (m, 13H), 7.34-
6.88 (m, 14H), 1.71 (s, 6H).Mass spectrometric data: [M+]=660.
Using differential scanning calorimetry, the glass transition temperature of compound TM1 is 189 degree, 392 degree of fusing point, thermogravimetric analysis
Temperature when mass loss 5% is 346 degree.
Embodiment 2: the synthesis of compound TM2
Step 1
Compound C-3 (4.1g, 10mmol) is dissolved into 50mL DMF, then slowly be added dropwise NBS (4.2g,
24mmol), stirring is lower is added dropwise 50mL distilled water, continues stirring 1 hour after being added dropwise to complete, filtering precipitating is tied again using n-hexane
Crystalline substance obtains compound C-6.Yield 34%.
Step 2
By compound C-6 (5.7g, 10mmol) and compound C-7 (7.7g, 22mmol), tetra-triphenylphosphine palladium (1.2g,
1mmol), potassium carbonate (5.6g, 120mmol) is added to the in the mixed solvent of 100mL toluene, 100mL dioxane, 20mL water,
It back flow reaction 12 hours, is extracted with ethyl acetate, column chromatographed column and mentions target compound TM2.Yield 27%.
Mass spectrometric data: [M+]=1012.
Embodiment 3:
Step 1
By compound C-6 (5.7g, 10mmol) and compound C-5 (3.3g, 11mmol), tetra-triphenylphosphine palladium (0.6g,
0.5mmol), potassium carbonate (2.8g, 60mmol) is added to the in the mixed solvent of 50mL toluene, 50mL dioxane, 10mL water,
It back flow reaction 12 hours, is extracted with ethyl acetate, column chromatographed column and mentions compound C-8.Yield 30%.
Step 2
By compound C-8 (7.9g, 10mmol) and compound C-9 (1.3g, 11mmol), tetra-triphenylphosphine palladium (0.6g,
0.5mmol), potassium carbonate (2.8g, 60mmol) is added to the in the mixed solvent of 50mL toluene, 50mL dioxane, 10mL water,
It back flow reaction 12 hours, is extracted with ethyl acetate, column chromatographed column and mentions compound TM3.Yield 37%.
Mass spectrometric data: [M+]=786.
Embodiment 4:
Step 1
Using the similar operating method of 1 step 1 of embodiment, compound C-1 is only replaced with into compound C-10, yield
66%.
Step 2
Compound C-11 (4.1g, 10mmol) is dissolved into 50mL chloroform, be slowly added dropwise bromine (1.6g,
10mmol), it after being stirred at room temperature 2 hours, is extracted with methylene chloride and water, chromatographic column purification obtains 3.5 grams, yield 72%.
Step 3
Using operating method similar with 1 step 3 of embodiment, compound C-4 is only replaced with into compound C-12, chemical combination
Object C-5 replaces with compound C-13, yield 49%.
Mass spectrometric data: [M+]=716.
Organic light emitting diode device
In order to schematically prove good characteristic of the compound provided by the invention as luminescent device material, using this hair
Compound provided by bright embodiment prepares organic light emitting diode device with conventional method in the art:
The glass plate for being coated with tin indium oxide (ITO) transparency conducting layer is ultrasonically treated in commercial detergent, spend from
After sub- water rinses, in acetone: it is ultrasonic in alcohol mixed solvent, it is baked under clean environment and completely removes moisture, use ultraviolet light
Cleaning agent exposes 20 minutes；Cleaned glass substrate is placed in vacuum chamber, 1 × 10-3~10 are evacuated to-5Pa, vapor deposition one
Layer NPPB is as the first hole transmission layer, evaporation rate 0.1-0.2nm/s, evaporation thickness 10-100nm；Continue vapor deposition one
Layer TNB is as the second hole transmission layer, evaporation rate 0.1-0.2nm/s, evaporation thickness 10-100nm；Continue one layer of vapor deposition
Luminescent layer containing blue material of main part and blue guest material, doping concentration 1-20wt%, evaporation rate 0.1-0.2nm/
S, thickness 10-50nm；Continue that one layer of bis- (2- methyl -8-hydroxyquinoline-N1, O8)-(1,1'- biphenyl -4- hydroxyl) aluminium is deposited
(BAlq), evaporation rate 0.1-0.2nm/s, thickness 10-50nm；Continue that one layer of lithium fluoride is deposited, evaporation rate 1-2nm/s is thick
0.1-10nm is spent, continues that one layer of aluminium, evaporation rate 1-2nm/s, thickness 10-200nm is deposited.
Wherein, blue material of main part used is the compound of the present invention or reference compound BH-1, BH-2, BH-3.Institute
The selection for stating blue dopant material is various, compound of the selection of the embodiment of the present invention with logical formula (V), citing such as BD-1.
The structure of related compound is as follows:
The cut-in voltage (Von) of each device, maximum external quantum efficiency (EQE), light emission luminance decay to original intensity 90%
Time device lifetime (T90) detection data it is as shown in table 1 below.
It can be seen that from the data of upper table 1, the device prepared using compound provided by the present invention, relative to using reference
The device of compound BH-3 preparation, since 9 of anthracene structure and 10 hydrogen are substituted, device lifetime is significantly promoted, explanation
The compound of the embodiment of the present invention is with good stability.Opposite reference compound BH-2, compound provided by the present invention
Steric effect with higher, so that device lifetime is also improved.Opposite reference compound BH-1, with provided by the present invention
Compound preparation device, there is promotion in cut-in voltage and service life, and the compound for illustrating that two aromatic rings are connected directly is better than
Pass through oxygen atom bridging reference compound.
1 device performance data of table
| Embodiment | Main body | Object | Cut-in voltage (V) | Quantum efficiency (EQE) | T90(h) |
| Device embodiments 1 | TM1 | BD-1 | 3.8 | 8.1 | 145 |
| Device embodiments 2 | TM2 | BD-1 | 3.9 | 7.9 | 165 |
| Device embodiments 3 | TM3 | BD-1 | 4.0 | 7.9 | 139 |
| Device embodiments 4 | TM4 | BD-1 | 3.9 | 7.8 | 142 |
| Comparative example 1 | BH-1 | BD-1 | 4.1 | 7.5 | 125 |
| Comparative example 2 | BH-2 | BD-1 | 4.4 | 5.6 | 95 |
| Comparative example 3 | BH-3 | BD-1 | 4.2 | 7.3 | 26 |
| Comparative example 4 | TM1 | BD-C1 | 4.0 | 5.2 | 29 |
Compound provided by the present invention has the following structure feature simultaneously: (1) 9 and 10 hydrogen of the anthryl in structure
It is substituted, (2) have the spirane structure of rigidity；(3) do not pass through oxygen atom bridging.In general, those skilled in the art are easy
It will think equivalent by the compound of oxygen atom bridging and the compound being connected directly, and applicants have unexpectedly found that, relativization
Object BH-1 is closed, with device prepared by compound TM3 provided by the invention, external quantum efficiency improves 5%, and device lifetime mentions
Rise 11%；With device prepared by compound TM2 provided by the invention, life-span upgrading 32%；With provided by the present invention
The device of compound TM1 preparation, external quantum efficiency rise 8%, and cut-in voltage has dropped 7%, and device lifetime improves 16%.
Obviously, the device prepared using compound provided by the present invention, the improvement of performance is significantly, to illustrate provided by the present invention
Compound be creative.Moreover, the glass transition temperature of control compounds BH-1 is 173 degree, the glass of compound TM1
Changing temperature is 189 degree, illustrates that the glass transition temperature of compound TM1 is higher than BH-1, the compounds of this invention has good thermostabilization
Property.
In addition, additionally using in device architecture provided by embodiments of the present invention with structure shown in logical formula (V)
Compound is as guest materials, and according to embodiment, it can be seen that, BD-1 is a particular compound of logical formula (V), relative to
Compound of the embodiment of the present invention has the similitude in structure, so that stable blend is advantageously formed in device vapor deposition,
Relative to comparative device, the device prepared using compound provided by the present invention, cut-in voltage is lower, external quantum efficiency compared with
Height, time device lifetime are longer.According to the experimental data in table 1 it is recognised that using BD-1 compound device, performance is remote
More than the device performance using BD-C1.Versus compound BH-1, compound TM3 external quantum efficiency improve 5%, device lifetime
Improve 11%, compound TM2 device lifetime promotes 32%, and the external quantum efficiency of compound TM1 rises 8%, under cut-in voltage
7% is dropped, device lifetime improves 16%, is significantly using the device improvements that the compounds of this invention obtains.Therefore, using this
The device performance of invention compound and BD-1 compound be it is outstanding, may infer that its energy transmission be it is very efficient, can be with
See, luminous efficiency of the invention, has been more than the theoretical limitation of 5% external quantum efficiency of conventional fluorescent material, this is mainly device
Triplet is produced in part and buries in oblivion phenomenon, so its luminous efficiency is improved, it is ratio that the triplet of comparative device 2, which buries in oblivion phenomenon,
Weaker, so external quantum efficiency is also relatively low.
In conclusion using there is the compound (compound of the structure as shown in BD-1) of structure shown in formula (V) as visitor
As material of main part, the improvement of the various aspects of performance of obtained device is significant for body material, compound provided by the present invention
's.
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 (11)
1. a kind of spiro-compound has structure shown in formula (I):
Wherein,
X indicates carbon atom；
Y1Indicate CRxRy；And Rx, Ry each independently represent hydrogen, deuterium, fluorine, C1-C24 alkyl or C6-C72 aryl；
R1-R8Each independently represent hydrogen, deuterium, fluorine, chlorine, bromine, iodine, C1-C24 alkyl, C1-C24 alkoxy, C1-C24 alkylthio group,
C6-C72 aryl or C6-C72 aryloxy group；
Z1、Z2Each independently represent the aromatic rings for including 1 ring or the aromatic rings comprising being condensed by least two ring, and Z1、Z2
At least one of include the aromatic rings that is condensed by least two ring；The Z1、Z2At least one of replaced by anthryl.
2. spiro-compound according to claim 1, which is characterized in that the Z1、Z2It each independently include formula G1-G14
One of shown in structure:
Wherein,
N1-N8CRo is each independently represented, the Ro indicates hydrogen, deuterium, fluorine, chlorine, bromine, iodine, C1-C24 alkyl, C1-C24 alcoxyl
Base, C6-C72 aryl or C6-C72 aryloxy group.
3. spiro-compound according to claim 1, which is characterized in that the anthryl has structure shown in formula (II):
Wherein,
A1Indicate C1-C24 alkyl or C6-C72 aryl；
A2Indicate hydrogen, deuterium, C1-C12 alkyl or C6-C24 aryl.
4. spiro-compound according to claim 1, which is characterized in that have formula (III-1), (III-2) or (III-3)
Shown in structure:
Wherein,
Y1Indicate CRxRy；
Rx, Ry each independently represent C1-C24 alkyl or C6-C72 aryl；
R1-R8Each independently represent hydrogen, deuterium, fluorine, C1-C24 alkyl, C1-C24 alkoxy, C6-C72 aryl or C6-C72 virtue oxygen
Base；
Z11、Z12Each independently represent phenyl ring, naphthalene nucleus, anthracene nucleus or phenanthrene ring；
R11、R22Each independently represent hydrogen, deuterium, C1-C24 alkyl or C6-C72 aryl；R12、R21、R31、R32Table each independently
Show C1-C24 alkyl or C6-C72 aryl；
B1、B2、B3、B4Each independently represent hydrogen, deuterium, C1-C12 alkyl or C6-C24 aryl.
5. spiro-compound according to claim 4, which is characterized in that (III-1), (III-2) or (III-3)
In:
Y1Indicate CRxRy；
Rx, Ry each independently represent C1-C24 alkyl or C6-C72 aryl；
R1-R8Each independently represent hydrogen, deuterium, methyl, ethyl, propyl, butyl, amyl, hexyl, phenyl, tolyl, ethylbenzene,
Propyl phenyl, butylbenzene base, penta phenyl, own phenyl, phenyl, naphthylphenyl, phenanthryl phenyl, naphthalene, naphthalene of flying, ethylnaphthalene
Base, propyl naphthalene, butyl naphthalene, amyl naphthalene, hexyl naphthalene, phenyl napthyl or phenyl anthryl；
Z11、Z12Each independently represent phenyl ring, naphthalene nucleus, anthracene nucleus or phenanthrene ring；
R11、R22Expression hydrogen, deuterium or C6-C72 aryl independent；R12、R21、R31、R32Each independently represent C6-C72 virtue
Base；
B1、B2、B3、B4Each independently represent hydrogen, deuterium, methyl, ethyl, propyl, butyl, amyl, hexyl, phenyl, tolyl, second
Phenyl, propyl phenyl or butylbenzene base.
6. spiro-compound according to claim 5, which is characterized in that Rx, Ry each independently represent C1-C24 alkyl
Or C6-C24 aryl, and Rx, Ry are connected by chemical bond.
7. spiro-compound according to claim 5, which is characterized in that Rx, Ry each independently represent methyl, ethyl,
Propyl, butyl, deuterated methyl, phenyl, tolyl, ethylbenzene, propyl phenyl, butylbenzene base or benzyl.
8. spiro-compound according to claim 6, which is characterized in that Rx, Ry are identical substituent group.
9. spiro-compound according to claim 1, which is characterized in that have selected from one of following structure:
10. spiro-compound according to claim 1 to 9, which is characterized in that the spiro-compound application
In organic electroluminescence device.
11. a kind of electroluminescent device, which is characterized in that including at least spiro compounds described in any one of claims 1 to 9
Compound shown in object and formula (V):
Wherein,
Ar1、Ar2、Ar3、Ar4Each independently represent C6-C36 aryl or C3-C36 heteroaryl；
Q1、Q2、Q3Each independently represent hydrogen atom, D-atom, C1-C12 alkyl, C6-C36 aryl or C3-C36 heteroaryl；
The spiro-compound is the material of main part in the luminescent layer of the device, and compound shown in formula (V) is the device
Guest materials in luminescent layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811611789.9A CN109796296A (en) | 2018-12-27 | 2018-12-27 | A kind of spiro-compound and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811611789.9A CN109796296A (en) | 2018-12-27 | 2018-12-27 | A kind of spiro-compound and its application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109796296A true CN109796296A (en) | 2019-05-24 |
Family
ID=66557857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811611789.9A Withdrawn CN109796296A (en) | 2018-12-27 | 2018-12-27 | A kind of spiro-compound and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109796296A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110835328A (en) * | 2019-11-18 | 2020-02-25 | 苏州久显新材料有限公司 | Spirobenzofluorenone derivatives and electronic devices |
| CN111454161A (en) * | 2020-03-23 | 2020-07-28 | 陕西莱特光电材料股份有限公司 | Spiro compound, application thereof, organic electroluminescent device using spiro compound and electronic device using spiro compound |
| CN112358471A (en) * | 2020-10-26 | 2021-02-12 | 吉林奥来德光电材料股份有限公司 | Heteroatom-containing spiro organic electroluminescent compound and preparation method and application thereof |
| CN112993199A (en) * | 2021-02-25 | 2021-06-18 | 上海蓝骋光电科技有限公司 | Ternary composition, organic light-emitting element containing ternary composition and application of ternary composition |
| WO2022191299A1 (en) * | 2021-03-10 | 2022-09-15 | 出光興産株式会社 | Organic electroluminescent element and electronic device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105408303A (en) * | 2012-10-10 | 2016-03-16 | 大州电子材料株式会社 | Spiro-type organic material, and organic electroluminescent device using same |
| KR20170116885A (en) * | 2016-04-12 | 2017-10-20 | 주식회사 엘지화학 | Anthracene based compound and organic light emitting device comprising the same |
| WO2018216887A1 (en) * | 2017-05-22 | 2018-11-29 | 주식회사 엘지화학 | Novel compound and organic light-emitting device using same |
-
2018
- 2018-12-27 CN CN201811611789.9A patent/CN109796296A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105408303A (en) * | 2012-10-10 | 2016-03-16 | 大州电子材料株式会社 | Spiro-type organic material, and organic electroluminescent device using same |
| KR20170116885A (en) * | 2016-04-12 | 2017-10-20 | 주식회사 엘지화학 | Anthracene based compound and organic light emitting device comprising the same |
| WO2018216887A1 (en) * | 2017-05-22 | 2018-11-29 | 주식회사 엘지화학 | Novel compound and organic light-emitting device using same |
Non-Patent Citations (1)
| Title |
|---|
| YOUNG-MIN JEON，ET AL.: "Deep-blue OLEDs using novel efficient spiro-type dopant materials", 《ORGANIC ELECTRONICS》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110835328A (en) * | 2019-11-18 | 2020-02-25 | 苏州久显新材料有限公司 | Spirobenzofluorenone derivatives and electronic devices |
| CN111454161A (en) * | 2020-03-23 | 2020-07-28 | 陕西莱特光电材料股份有限公司 | Spiro compound, application thereof, organic electroluminescent device using spiro compound and electronic device using spiro compound |
| CN112358471A (en) * | 2020-10-26 | 2021-02-12 | 吉林奥来德光电材料股份有限公司 | Heteroatom-containing spiro organic electroluminescent compound and preparation method and application thereof |
| CN112993199A (en) * | 2021-02-25 | 2021-06-18 | 上海蓝骋光电科技有限公司 | Ternary composition, organic light-emitting element containing ternary composition and application of ternary composition |
| CN112993199B (en) * | 2021-02-25 | 2023-03-07 | 上海弗屈尔光电科技有限公司 | Ternary composition, organic light-emitting element containing ternary composition and application of ternary composition |
| WO2022191299A1 (en) * | 2021-03-10 | 2022-09-15 | 出光興産株式会社 | Organic electroluminescent element and electronic device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109796296A (en) | A kind of spiro-compound and its application | |
| CN108689972A (en) | One kind containing the aromatic amine compound and its organic electroluminescence device of 9,9 '-spiral shell, two fluorenes and dibenzofurans | |
| JP2014116639A (en) | Organic electroluminescent compound and light-emitting diode using the same | |
| KR20150111106A (en) | An organoelectro luminescent compounds and organoelectro luminescent device using the same | |
| JP7458483B2 (en) | Metal complexes and their uses | |
| KR20090093688A (en) | Novel organic electroluminescent compounds and organic electroluminescent device using the same | |
| KR20140070450A (en) | An electroluminescent compound and an electroluminescent device comprising the same | |
| JP5591464B2 (en) | Novel red electroluminescent compound and organic electroluminescent device using the same | |
| CN110563746B (en) | Novel SO2 spiro-structure-containing compound and application thereof in OLED (organic light emitting diode) device | |
| WO2020124771A1 (en) | Thermally activated delayed fluorescent compound, preparation method therefor and organic electroluminescent diode device thereof | |
| CN109503427B (en) | D-A type organic blue fluorescent material and preparation method and application thereof | |
| CN109970642A (en) | Bipolarity thermal activation delayed fluorescence material and preparation method thereof and organic electroluminescent diode apparatus | |
| CN110330472A (en) | A kind of blue light material and its preparation method and application | |
| CN107056807B (en) | It is a kind of using equal benzene as the compound of core and its application in organic electroluminescence device | |
| CN108997201A (en) | A kind of miscellaneous anthracene compound of spiro fluorene and its organic electroluminescence device | |
| CN105924383B (en) | Electroluminescent organic material and preparation method thereof and organic electroluminescence device | |
| JP7402979B2 (en) | Platinum metal complexes and their applications in organic electroluminescent devices | |
| CN108165264A (en) | A kind of organic luminescent compounds and its preparation method and application | |
| CN116854677A (en) | Capping layer material, preparation method thereof, organic electroluminescent device and display device | |
| WO2016138710A1 (en) | Metal complex and manufacturing method and usage, display device thereof | |
| JP2022506647A (en) | Use for organic electroluminescent materials and their photoelectric elements | |
| CN109369598A (en) | A kind of luminous organic material and preparation method and the organic luminescent device containing the material | |
| CN105777809B (en) | Electroluminescent organic material and organic electroluminescence device | |
| CN104230930B (en) | A kind of OLED material and application thereof | |
| CN109776490B (en) | Non-aromatic amine micromolecule photoelectric material and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20190524 |
|
| WW01 | Invention patent application withdrawn after publication |