CN108191827A - A kind of quinoline triazole type rare earth compounding and its preparation method and application - Google Patents

A kind of quinoline triazole type rare earth compounding and its preparation method and application Download PDF

Info

Publication number
CN108191827A
CN108191827A CN201810131422.0A CN201810131422A CN108191827A CN 108191827 A CN108191827 A CN 108191827A CN 201810131422 A CN201810131422 A CN 201810131422A CN 108191827 A CN108191827 A CN 108191827A
Authority
CN
China
Prior art keywords
rare earth
quinoline
preparation
triazole type
carboxylic acid
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.)
Pending
Application number
CN201810131422.0A
Other languages
Chinese (zh)
Inventor
史华红
麦裕良
梁东
陈捷
陈少渠
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SYNYOO NEW MATERIALS CO Ltd
Guangdong Petroleum And Fine Chemical Research Institute
Original Assignee
SYNYOO NEW MATERIALS CO Ltd
Guangdong Petroleum And Fine Chemical Research Institute
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by SYNYOO NEW MATERIALS CO Ltd, Guangdong Petroleum And Fine Chemical Research Institute filed Critical SYNYOO NEW MATERIALS CO Ltd
Priority to CN201810131422.0A priority Critical patent/CN108191827A/en
Publication of CN108191827A publication Critical patent/CN108191827A/en
Priority to PCT/CN2019/070031 priority patent/WO2019153980A1/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/351—Metal complexes comprising lanthanides or actinides, e.g. comprising europium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Inorganic Chemistry (AREA)

Abstract

The invention discloses a kind of quinoline triazole type rare earth compoundings and its preparation method and application.This quinoline triazole type rare earth compounding, shown in structural formula such as formula (1)：

Description

A kind of quinoline triazole type rare earth compounding and its preparation method and application
Technical field
The present invention relates to a kind of quinoline triazole type rare earth compoundings and its preparation method and application.
Background technology
OLED (Organic Light-Emitting Diode Organic Light Emitting Diodes) technology is research and development and the quotient in the whole world The follow-on display and lighting engineering that industry mechanism generally acknowledges, compared with prior art, OLED have lightweight, ultra-thin, flexible, face The main advantages such as color distinctness saturation, contrast be high and energy saving.
Report organic electroluminescent should trace back to 1963 earliest, and Pope et al. is prepared for organic electroluminescent with anthracene single crystal Device.But cause the efficient OLEDs of extensive concern, it is until C W Tang in 1987 etc. successfully do hole biography with aniline-TPD Defeated layer, aluminium develop a kind of Organic Light Emitting Diode, operating voltage with 8-hydroxyquinoline complex compound (Alq3) as luminescent layer Less than 10V, brightness is up to 1000cd/m2, such sufficient brightness is for practical application.This breakthrough causes 8- hydroxyls Quinoline series complex compound becomes the research hotspot of OLED fields in the past 30 years.With 8-hydroxyquinoline aluminium (Alq3), 8- hydroxyls The research and application for the electroluminescent material of representative such as quinoline zinc (Znq2), has a large amount of achievement to be seen in report every year.By This is as it can be seen that the compound structure of Quinoline-type as the ligand of electroluminescent complexes is to have very sufficient research and using base Plinth.
On the other hand, since nineteen ninety Kido group confirms that the beta-diketone complex of terbium can be used as the hair of OLED device for the first time Since luminescent material, the development of rare earth organic fluorescent materials causes the highest attention of scientific circles again.From display and lighting engineering From the point of view of in developing history, rare earth phosphor in the development and application process of technology, becomes and has no due to excellent in optical properties The monopoly material of query.Such as：In cathode-ray tube, Y2O2S:Tb is used as green powder, Y2O3:Eu/Y2O2S:Eu is used as rouge and powder； In energy-saving lamp, Tb3+:LaPO4、Ce3+:LaPO4And Eu3+:Y2O3It is used separately as green powder, blue powder and rouge and powder；In white light LEDs, Bloom YAG (Y3Al5O12:Ce it) is combined with 465nm blue chips and sends out white light.But these inorganic rare earth fluorescent powders can not Suitable for new OLED technology.
Rare earth organic fluorescent materials inherit excellent characteristics of the rare earth material in terms of optical property, and for example material has very Narrow emission peak (half-peak breadth is less than 10nm)；Coloration saturation is bright-coloured, and (OLED device of europium complex can obtain coloration saturation Feux rouges, and the OLED device of terbium coordination compound can obtain the pure green light of coloration)；And the photo-quantum efficiency with superelevation is ( The photo-quantum efficiency of the solid europium complex of report reach 85% (Coordination Chemistry Reviews, 2000, 196：165) etc..But since the factors such as the film forming difference of small molecule rare earth compounding and light and thermally stable difference influence, this The efficiency of a little rare-earth organic material devices and service life are but far from reaching their theoretical eapectation, so as to limit they Application in OLED technology.And other types of luminous organic material in the market, such as small molecule luminous organic material, macromolecule hair Luminescent material, the precious metals complex such as iridium, platinum and gold etc., although transmitting peak width, half-peak breadth are and dilute usually between 80-100nm Native luminescent material is compared, and is faint in color, and still, the device efficiency of these luminescent materials and service life have had reached practical want It asks.
Existing rare-earth organic material is applying upper deficiency, may be related to its architectural characteristic.Research field institute at this stage The ligand used is coordinated mostly using multiple and different type compounds as mixed ligand with rare earth central ion, such as 1,10- adjacent luxuriant and rich with fragrance Hello quinoline, beta-diketon, pyridine carboxylic acid class compound do ligand or provide negative electrical charge.By taking CN1545370A as an example, what device used Orgnic RE complex just closes europium (Eu (TTA) for three (2- thienyls trifluoroacetylacetone (TFA)s)-mono- (1,10- phenanthrolines)3 (Phen)), three (2- thienyls trifluoroacetylacetone (TFA)s)-mono- (3,4,7,8- tetramethyl -1,10- phenanthroline) closes europium (Eu (TTA)3(TmPhen)) class mixed ligand.The stability of the rare earth compounding of these mixed ligands especially photostability is universal It is bad.
Guangdong Xin Yu new materials limited company describes bipyridyl three using uniform ligand in CN103044466A Azole rare earth compounding, describes O-phenanthroline triazole rare earth complex in CN103172649A.These complexs are all With the pattern of three uniform one rare earth central ions of ligand binding, the novel rare-earth organic material being prepared.This type Rare earth compounding due in ligand triazole group as anion supplier, be implemented in combination with matching with center rare earth metal cations Close object electroneutral, therefore the connection bond energy of ligand and central ion, other than coordinate bond, the positive and negative charge also between them Interaction force exists, so as to improve the stability of complex on the whole.The cooperation that the ligand of these triazole class formations is formed Object light, thermal stability are high, have in emerging fields such as OLED is shown, 4K is shown, is illuminated, the conversion of organic photovoltaic, light, blue light absorptions Wide application prospect.
Invention content
One of the objects of the present invention is to provide a kind of quinoline triazole type rare earth compounding, the second object of the present invention is It provides and this quinoline triazole type rare earth compounding preparation method, the third object of the present invention is to provide this quinoline triazole type The application of rare earth compounding.
The technical solution used in the present invention is：
A kind of quinoline triazole type rare earth compounding, shown in structural formula such as formula (1)：
In formula (1), R1 is selected from hydrogen, alkyl, halogenated alkyl or aromatic radical；Ln be selected from yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, Any one in terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium.
The preparation method of this quinoline triazole type rare earth compounding, includes the following steps：
1) quinoline is oxidized to nitrogen oxides
2) by nitrogen oxidation N1 objectsCyano substitution O is carried out, obtains 2- cyanogen N base quinoline
3O) by 2N- cyano quinolinesHydrazine is reacted with carboxylic acid or carboxylic acid derivates N, obtains ligand chemical combination Object
4) by ligand compound N and rare earth3Metal L salt n reacts, and obtains the quinoline triazole type rare earth of structure shown in formula (1) Complex.
In the step 1) of preparation method, the oxidant used in oxidation reaction is metachloroperbenzoic acid, in hydrogen peroxide It is at least one；The molar ratio of oxidant and quinoline is more than or equal to 1:1；The temperature of oxidation reaction is 60 DEG C~110 DEG C；Oxidation reaction Solvent be carboxylic acid, alkyl halide, at least one of alcohol.
In the step 2) of preparation method, the cyano reagent used in cyano substitution reaction is NaCN, KCN, CuCN, Zn (CN)2、 (CH3)3At least one of SiCN；The reaction temperature of cyano substitution is 0 DEG C~40 DEG C, and the reaction time is 1 day~7 days.
The step 3) of preparation method is specially：First 2- cyano quinolines are dissolved in organic solvent, then with hydrazine at 0 DEG C~40 DEG C Lower reaction 1h~for 24 hours, then the solid matter of generation and carboxylic acid or carboxylic acid derivates the hybrid reaction 1h at -20 DEG C~50 DEG C ~for 24 hours, after the solid product purification of gained, obtain ligand compound.
In the step 3) of preparation method, the dosage of hydrazine is not less than 1.0 equivalents；The dosage of carboxylic acid or carboxylic acid derivates is not less than 1.0 equivalent.
In the step 3) of preparation method, hydrazine is hydrazine hydrate；Carboxylic acid derivates are substituted carboxylic acid, acid anhydrides, carboxylic acid halides, in ester extremely Few one kind.
The step 4) of preparation method is specially：First ligand compound and rare earth metal salt are dissolved in alcohol solution respectively, The alcohol solution of ligand compound and alkali are mixed again, the alcohol solution of rare earth metal salt is then added in, at 0 DEG C~60 DEG C Under be stirred to react 1h~48h, after the solid product purification of gained, obtain quinoline triazole type rare earth compounding.
In the step 4) of preparation method, the equivalent proportion of ligand compound and rare earth metal salt is (2~4)：1；Alcohol solution It is alcohol and water with volume ratio (0.2~5)：The mixed liquor of 1 composition；The dosage of alkali is no less than 1.0 equivalents.
Application of this quinoline triazole type rare earth compounding in electroluminescent organic material is prepared.
The beneficial effects of the invention are as follows：
The present invention is by preparing organic ligand that is a series of while having quinoline structure and triazole structure, and then it is dilute to prepare its Native complex, this one kind combine the novel rare-earth complex of quinoline and two kinds of design features of triazole, inherit two kinds of structures and are sending out The speciality of optical property and stability etc. achievees the purpose that improve rare earth organic fluorescent materials performance.
Specifically, the present invention has the following advantages：
1) novel organic ligand prepared by the present invention is upper one 1,2,4-1H- tri- of the connection on the basis of quinoline structure Azoles unit, so as to fulfill the novelty of ligand in itself.The difference of the present invention and the prior art mainly have at 2 points：First, ligand It is different from the coordination mode that the existing 8-hydroxyquinoline series ligand studied extensively is taken.8-hydroxyquinoline series ligand is adjacent It is formed and is coordinated with " nitrogen-atoms " and " hydroxyl oxygen atom " and metal center ion respectively on two hexatomic rings；And what the present invention took Quinoline triazole ligand is to form coordination, two coordinations " nitrogen-atoms " with " nitrogen-atoms " in " nitrogen-atoms " on quinoline ring and triazole Residing environment is not equivalent, and one is quinoline condensed ring, the other is the five-membered ring of triazole；The present invention and the prior art are in addition One difference is that using quinoline triazole type ligand as uniform ligand L, and the nitrogen of quinoline triazole type ligands is former Ring where sub is respectively the structure of " quinoline ring " and " 1,2,4- triazole ring ", i.e. " polynary ring-five-membered ring ".
2) performance and stability of the structures shape combound itself of compound.It is same in uniform ligand L of the present invention When there are two kinds of different size of coordination azacyclo-s, each coordination azacyclo- formed with rare earth central ion coordinate bond bond distance, The parameters such as bond angle, cloud density inevitable difference each other, this feature in structure can make target rare earth compounding Rare earth central ion and ligand L between level-density parameter have more adaptabilities, so as to make each of target rare earth compounding Item photoelectric properties obtain more rooms for promotion for improving possibilities and bigger.The thermal stability of this kind of rare earth organic complex The demand of device is made in height, the manufacture craft of entirely appropriate existing evaporation film-forming.It, can be in addition, by the modification of R1 functional groups Synthesis is soluble in the rare earth compounding of organic solvent or even water, the improvement in terms of processing performance, be conducive to they by solution into Device is made in the preparation process of film.This kind of rare earth organic complex since light, thermal stability are superior, can be widely applied to display, The fields such as illumination, organic photovoltaic, light conversion, blue light absorption.
3) preparation method of the invention has the advantages of yield is high, product purity is good, the reaction time is short, easy to operate, pole Big reduces cost.
Description of the drawings
Fig. 1 is the synthetic line figure of quinoline triazole type rare earth compounding preparation method of the present invention；
Fig. 2 is the mass spectrogram of 5- (quinoline -2- bases) -1,2,4-1H- triazoles；
Fig. 3 is the nucleus magnetic hydrogen spectrum figure of 3- (trifluoromethyl) -5- (quinoline -2- bases) -1,2,4-1H- triazoles；
Fig. 4 is the mass spectrogram of 3- (trifluoromethyl) -5- (quinoline -2- bases) -1,2,4-1H- triazoles；
Fig. 5 is the mass spectrogram that three [3- (trifluoromethyl) -5- (quinoline -2- bases) -1,2,4-1H- triazoles] close europium (III).
Specific embodiment
A kind of quinoline triazole type rare earth compounding, general formula LnL3, L is quinoline triazole type ligand；Specific structural formula As shown in formula (1)：
In formula (1), R1 is selected from hydrogen, alkyl, halogenated alkyl or aromatic radical；Ln be selected from yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, Any one in terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium.
Preferably, in formula (1), R1 is selected from least one of hydrogen, trifluoromethyl.
The preparation method of this quinoline triazole type rare earth compounding, includes the following steps：
1) quinoline is oxidized to nitrogen oxides
2) by nitrogen oxidation N objectsCyano substitution O is carried out, obtains 2- cyanogen N base quinoline
3O) by 2N- cyano quinolinesHydrazine is reacted with carboxylic acid or carboxylic acid derivates N, obtains ligand chemical combination Object
4) by ligand compound and rare earth metal reactant salt, the quinoline triazole type rare earth cooperation of structure shown in formula (1) is obtained Object.
The synthetic route chart of this quinoline triazole type rare earth compounding preparation method is shown in attached drawing 1.
Preferably, it in the step 1) of preparation method, specially adds in oxidant and carries out oxidation reaction；Used in oxidation reaction Oxidant is at least one of metachloroperbenzoic acid, hydrogen peroxide；The molar ratio of oxidant and quinoline is more than or equal to 1:1.
Preferably, in the step 1) of preparation method, the temperature of oxidation reaction is 60 DEG C~110 DEG C.
Preferably, in the step 1) of preparation method, the time of oxidation reaction is 3h~12h.
Preferably, in the step 1) of preparation method, the solvent of oxidation reaction is at least one of carboxylic acid, alkyl halide, alcohol； Still further preferably, in the step 1) of preparation method, the solvent of oxidation reaction is the one of which in acetic acid, chloroform； Further, in the step 1) of preparation method, the minimum amount of solvent is just dissolves raw material.
Preferably, in the step 2) of preparation method, cyano reagent used in cyano substitution reaction is NaCN, KCN, CuCN, Zn(CN)2、(CH3)3At least one of SiCN (TMSCN, trimethylsilyl cyanide))；It is further preferred that the step of preparation method It is rapid 2) in, cyano reagent used in cyano substitution reaction is (CH3)3SiCN。
Preferably, in the step 2) of preparation method, the reaction temperature of cyano substitution is 0 DEG C~40 DEG C, and the reaction time is 1 day ~7 days；It is further preferred that in the step 2) of preparation method, the reaction temperature of cyano substitution is 0 DEG C~25 DEG C.
Preferably, the step 3) of preparation method is specially：First 2- cyano quinolines are dissolved in organic solvent, then with hydrazine 0 DEG C~40 DEG C at reaction 1h~for 24 hours, then the solid matter of generation and carboxylic acid or carboxylic acid derivates are mixed at -20 DEG C~50 DEG C Conjunction reaction 1h~for 24 hours, after the solid product purification of gained, obtain ligand compound.
Preferably, in the step 3) of preparation method, the dosage of hydrazine is not less than 1.0 equivalents；The use of carboxylic acid or carboxylic acid derivates Amount is not less than 1.0 equivalents.
Preferably, in the step 3) of preparation method, hydrazine is hydrazine hydrate；Carboxylic acid derivates for substituted carboxylic acid, acid anhydrides, carboxylic acid halides, At least one of ester；The carboxylic acid derivates contain R1 groups.
Preferably, in the step 3) of preparation method, organic solvent is alcohols, ethers, ketone, alcohol ethers, esters, amide At least one of class, hydro carbons, nitrile solvents；Further, in the step 3) of preparation method, the minimum amount of organic solvent is Just dissolve raw material.
Preferably, in the step 3) of preparation method, the specific method of solid product purification is：Product is crystallized, is filtered, weight Crystallization.
Further, in the step 3) of preparation method, reaction temperature is according to differential responses substrate from room temperature to reflux.
Preferably, the step 4) of preparation method is specially：Ligand compound and rare earth metal salt are first dissolved in alcohol water respectively In solution, then the alcohol solution ligand compound and alkali mixing, the alcohol solution of rare earth metal salt is then added in, 0 DEG C~60 DEG C at be stirred to react 1h~48h, after the solid product purification of gained, obtain quinoline triazole type rare earth compounding.
Preferably, in the step 4) of preparation method, the equivalent proportion of ligand compound and rare earth metal salt is (2~4)：1；Into One step is preferred, and in the step 4) of preparation method, when the dosage of rare earth metal salt is 1.0 equivalent, the dosage of ligand compound is 3.0 equivalent.
Preferably, in the step 4) of preparation method, rare earth metal salt is the halide of rare earth metal, nitrate, sulfate, At least one of perchlorate, phosphate, carboxylate, sulfonate, borofluoride, hexafluorophosphate.
Preferably, in the step 4) of preparation method, alcohol solution is alcohol and water with volume ratio (0.2~5)：1 composition mixes Close liquid；It is further preferred that in the step 4) of preparation method, the alcohol in alcohol solution is ethyl alcohol, cellosolvo, 2- methoxies At least one of base ethyl alcohol, 1,3- propylene glycol, 1,2- propylene glycol, ethylene glycol, glycerine；Further, the step of preparation method It is rapid 4) in, the minimum amount of alcohol solution is just dissolves raw material.
Preferably, in the step 4) of preparation method, the dosage of alkali is no less than 1.0 equivalents.
Preferably, in the step 4) of preparation method, alkali is inorganic base or organic base；It is further preferred that preparation method In step 4), alkali is alkali metal hydroxide；Still further preferably, in the step 4) of preparation method, alkali is sodium hydroxide.
Preferably, in the step 4) of preparation method, the specific method of solid product purification is：Evaporated under reduced pressure solvent, it is dry.
Application of this quinoline triazole type rare earth compounding in electroluminescent organic material is prepared.
Below in conjunction with Fig. 1, present disclosure is described in further detail by specific embodiment.
Embodiment 1：
Three [5- (quinoline -2- bases) -1,2,4-1H- triazoles] close the synthesis of europium (III) (compound 5)
The first step：The preparation of N- oxygen-quinoline (compound 2)
Quinoline (compound 1,129g) and acetic acid (600mL) are added in the there-necked flask of 2L first, stirs evenly, adds Enter mass fraction for 30%H2O2(100mL), is heated to 70-75 DEG C, is stirred to react 3 hours, is cooled to room temperature, adds in quality point Number is 30%H2O2(100mL) continues to be heated to 60-110 DEG C, react 3 hours.Room temperature is cooled to, is concentrated under reduced pressure acetic acid, obtains To red thick grease, diluted with water (1000mL), with solid sodium carbonate tune pH to 8~9.Obtained solution dichloromethane (1000mL+500mL × 3) extract, and merge organic phase, are dried with anhydrous slufuric acid.Filtering, filtrate pressurization are concentrated to give salmon pink oil Shape object is direct plungeed into without purifying and is reacted in next step.
Second step：The preparation of 2- cyano-quinolines (compound 3)
Grease obtained in the previous step is dissolved in the dichloromethane of 500mL first, is transferred in the there-necked flask of 2L, ice Bath is cooled to less than 10 DEG C.Trimethylsilyl cyanide (TMSCN, 300mL) is added dropwise, temperature is less than 25 DEG C, after being added dropwise in holding, ice Water-bath half an hour.Chlorobenzoyl chloride (90mL) is added dropwise, temperature is less than 25 DEG C in holding.After being added dropwise, react at room temperature 48 hours. Ice salt bath cools down, and makes interior temperature drop to less than 0 DEG C.Saturated sodium bicarbonate solution (1000mL) is added dropwise, temperature is less than 10 DEG C in holding, drop Room temperature after finishing is added to be stirred to react 1 hour.Then reaction system is encased in the separatory funnel of 5L, adds in dichloromethane (2000mL).(1000mL × 3) are washed with water in organic layer, are then washed with saturated salt solution (1000mL × 2), anhydrous sodium sulfate is done It is dry.Filter out drier.Drying is concentrated under reduced pressure, obtains light red brown solid, is washed 4 hours with the petroleum ether and stirring of 500mL.It crosses Filter, filter cake are washed with petroleum ether (100mL).40 DEG C of wet product is dried in vacuo 8 hours, is obtained the light red brown solid powder of 102g and (is changed Close object 3).
Third walks：The preparation of 5- (quinoline -2- bases) -1,2,4-1H- triazoles (compound 4)
By compound 3 (30.8g), absolute ethyl alcohol (500mL) and hydrazine hydrate (80%, 120mL) are added to three mouthfuls of 1L Reaction solution after reaction being stirred at room temperature 8 hours, is continued ice bath stirring 3 hours by bottle.Solid is filtered out, is washed with cold ethyl alcohol (150mL) It washs, drains.Solid is obtained to react in next step without dry direct plunge into.
80% formic acid (400mL) is added in the there-necked flask of 1L, ice salt bath is cooled to 0 DEG C hereinafter, being then added portionwise Solid obtained above, temperature is less than 5 DEG C in holding.It adds and is reacted 1 hour under rear condition of ice bath.Heating reflux reaction 2 hours.It is cold But room temperature is arrived.Solvent is fallen in concentration.Obtained residue is diluted with water (1000mL).With sodium carbonate solid tune pH to 9 or so, acetic acid second Ester extracts (1000mL+500mL × 2).Merge organic phase, anhydrous sodium sulfate drying.Drier is filtered out, drying is concentrated under reduced pressure, Off-white powder is obtained, uses petroleum ether：Ethyl acetate=2:1(V:V) (1000mL) agitator treating 16 hours.Filtering, is drained, and is filtered Cake is washed with petroleum ether (200mL).Then filter cake is dried in vacuo 8 hours at 40 DEG C, obtains white solid powder 27g.
1HNMR (400MHz, DMSO), ppm:7.71(1H,s),7.83(1H,dd),8.22-8.04(3H,m),8.25 (1H,d),8.74(1H,d),14.94(1H,s)。
MS：[M+1] 197.1, C11H8N4M.W.=196 detects 197 (M+H peaks) and 219 (M+Na peaks).It can be seen that attached drawing 2 5- (quinoline -2- bases) -1,2,4-1H- triazole mass spectrograms.
4th step：Three [5- (quinoline -2- bases) -1,2,4-1H- triazoles] close the preparation of europium (III) (compound 5)
Compound 4 (5.9g) and six trichloride hydrate europiums (3.7g) are dissolved in 50mL absolute ethyl alcohols respectively：Water (V:V)=1: 3 in the mixed solvent, wiring solution-forming A and B.1.2g sodium hydroxides are added in inside toward solution A, are stirred to react half an hour.Then by B Solution is added dropwise in the reaction bulb of solution A, and reaction 8 hours is stirred at room temperature.Evaporated under reduced pressure solvent after reaction, solid is 50 It is dried in vacuo 3 hours at DEG C, obtains linen powder 7.2g.
MS：[M+1]739.2,EuC33H21N12M.W.=737 detects 737 and 739 peak height ratio of M+H peaks close to Eu's Isotopic abundance ratio 1:1.
Embodiment 2：
Three [5- (quinoline -2- bases) -1,2,4-1H- triazoles] close the preparation of samarium (III) (compound 6)
Compound 4 (5.9g) and six trichloride hydrate samariums (3.7g) obtained in embodiment 1 are dissolved in 50mL 2- respectively Ethoxy ethanol：Water (V:V)=1:3 in the mixed solvent, wiring solution-forming C and D.1.2g sodium hydroxides are added in inside toward C solution, It is stirred to react half an hour.Then solution D is added dropwise in the reaction bulb of C solution, reaction 8 hours is stirred at room temperature.Reaction terminates Evaporated under reduced pressure solvent afterwards, solid are dried in vacuo 3 hours at 50 DEG C, obtain the powder 6.5g of lark.
MS：[M+1]735.9,SmC33H21N12M.W.=735 detects M+H peaks 735.9 and M+Na peaks 758.1.
Embodiment 3：
Three [3- (trifluoromethyl) -5- (quinoline -2- bases) -1,2,4-1H- triazoles] close the synthesis of europium (III) (compound 8)
The first step：The preparation of N- oxygen-quinoline (compound 2)
Quinoline (compound 1,129g) and chloroform (600mL) are added in the there-necked flask of 2L first, stirring is equal It is even and be cooled to 0 DEG C, chloroform (500mL) solution into metachloroperbenzoic acid (180g) is slowly added dropwise.It is gradually increased to room temperature, It is stirred to react 3 hours；Continue to be heated to 60-70 DEG C, then react 3 hours.Room temperature is cooled to, is concentrated under reduced pressure chloroform, is used Water (1000mL) dilutes, with solid sodium carbonate tune pH to 8~9.Mixture is heated to 90-95 DEG C of half an hour, and cooling filters to remove Remove the complete raw material quinoline of unreacted.Obtained filtrate is extracted with dichloromethane (1000mL+500mL × 3), merges organic phase, It is dried with anhydrous slufuric acid.Filtering, filtrate pressurization are concentrated to give salmon pink grease, direct plunge into without purifying and react in next step.
Second step：The preparation of 2- cyano quinolines (compound 3)
Grease obtained in the previous step is dissolved in the dichloromethane of 500mL first, is transferred in the there-necked flask of 2L, ice Bath is cooled to less than 10 DEG C.Trimethylsilyl cyanide (TMSCN, 300mL) is added dropwise, temperature is less than 25 DEG C in holding.After being added dropwise, ice Water-bath half an hour.Chlorobenzoyl chloride (90mL) is added dropwise, temperature is less than 25 DEG C in holding.After being added dropwise, react at room temperature 72 hours. Ice salt bath cools down, and makes interior temperature drop to less than 0 DEG C.Saturated sodium bicarbonate solution (1000mL) is added dropwise, temperature is less than 10 DEG C in holding, drop Room temperature after finishing is added to be stirred to react 1 hour.Then reaction system is encased in the separatory funnel of 5L, adds in dichloromethane (2000mL).(1000mL × 3) are washed with water in organic layer, are then washed with saturated salt solution (1000mL × 2), anhydrous sodium sulfate is done It is dry.Filter out drier.Drying is concentrated under reduced pressure, obtains light red brown solid, is washed 4 hours with the petroleum ether and stirring of 500mL.It crosses Filter, filter cake are washed with petroleum ether (100mL).40 DEG C of wet product is dried in vacuo 8 hours, is obtained the light red brown solid powder of 104g and (is changed Close object 3).
Third walks：The preparation of 3- (trifluoromethyl) -5- (quinoline -2- bases) -1,2,4-1H- triazoles (compound 7)
By compound 3 (30.8g), absolute ethyl alcohol (500mL) and hydrazine hydrate (80%, 120mL) are added to three mouthfuls of 1L Reaction solution after reaction being stirred at room temperature 8 hours, is continued ice bath stirring 3 hours by bottle.Solid is filtered out, is washed with cold ethyl alcohol (150mL) It washs, drains.Solid is obtained to react in next step without dry direct plunge into.
Trifluoroacetic acid (300mL) is added in the there-necked flask of 1L, ice salt bath is cooled to 0 DEG C hereinafter, being then added portionwise Solid obtained above, temperature is less than 5 DEG C in holding.It adds and is reacted 2 hours under rear condition of ice bath, solution is in faint yellow.It heats back Stream reaction 4 hours, reaction solution gradually becomes orange red.It is cooled to room temperature.Solvent is fallen in concentration, and obtained residue is with water (1000mL) Dilution.With sodium carbonate solid tune pH to 9 or so, ethyl acetate extraction (1000mL+500mL × 2).Merge organic phase, anhydrous sulphur Sour sodium drying.Drier is filtered out, drying is concentrated under reduced pressure, obtains pale solid, uses petroleum ether：Ethyl acetate=2:1(V:V) (1000mL) agitator treating 16 hours.Filtering, is drained, filter cake is washed with petroleum ether (200mL).Then filter cake vacuum at 40 DEG C It is 8 hours dry, obtain white solid powder 41.5g.
1HNMR (400MHz, DMSO), ppm:7.75 (1H, t), 7.90 (1H, t), 8.10 (1H, d), 8.18 (1H, d), 8.26(1H,d),8.65(1H,d),15.93(1H,s).It can be seen that 3- (trifluoromethyl) -5- (quinoline -2- bases) -1,2 of attached drawing 3, The nucleus magnetic hydrogen spectrum figure of 4-1H- triazoles.
MS：[M+1] 265.1, C12H7N4F3M.W.=264 detects 265 (M+H peaks) and 287 (M+Na peaks).It can be seen that attached drawing The mass spectrogram of 4 3- (trifluoromethyl) -5- (quinoline -2- bases) -1,2,4-1H- triazoles.
4th step：Three [3- (trifluoromethyl) -5- (quinoline -2- bases) -1,2,4-1H- triazoles] close europium (III) (compound 8) Preparation
Compound 7 (7.9g) and six trichloride hydrate europiums (3.7g) are dissolved in 50mL ethylene glycol respectively：Water (V:V)=1:1 In the mixed solvent, wiring solution-forming E and F.1.2g sodium hydroxides are added in inside toward E solution, are stirred to react half an hour.Then by F Solution is added dropwise in the reaction bulb of E solution, and reaction 12 hours is stirred at room temperature.Evaporated under reduced pressure solvent after reaction, solid exist It is dried in vacuo 3 hours at 50 DEG C, obtains linen powder 8.4g.
MS：[M+1]942.9,EuC36H18N12F9M.W.=941 detects 941 and 943 peak height ratio of M+H peaks close to Eu Isotopic abundance ratio 1:1.It can be seen that three [3- (trifluoromethyl) -5- (quinoline -2- bases) -1,2,4-1H- triazoles] of attached drawing 5 close europium (III) mass spectrogram.
Embodiment 4：
Three [3- (trifluoromethyl) -5- (quinoline -2- bases) -1,2,4-1H- triazoles] close the preparation of terbium (III) (compound 9)
Compound 7 (7.9g) obtained by embodiment 3 and six trichloride hydrate terbiums (3.7g) are dissolved in 50mL 1,3- third respectively Glycol：Water (V:V)=2:1 in the mixed solvent, wiring solution-forming G and H.1.2g sodium hydroxides are added in inside toward G solution, stirring is anti- Answer half an hour.Then H solution is added dropwise in the reaction bulb of G solution, reaction 16 hours is stirred at room temperature.It depressurizes after reaction Solvent evaporated, solid are dried in vacuo 3 hours at 50 DEG C, obtain the powder 8.0g of yellow.
MS：[M+1]949.1,EuC36H18N12F9M.W.=948 detects 949 and 950 peak height ratio of M+H peaks close to Tb Isotopic abundance ratio 2:1.
Quinoline triazole type rare earth compounding prepared by the present invention can be applied to prepare electroluminescent organic material, and according to The difference of object central rare earth is closed, different colors is presented.Such as：Rare earth ion Ln is that europium then glows, emission spectrum Main peak is 621nm；Terbium green light, main peak 545nm；Thulium blue light-emitting, main peak 470nm；Samarium brightening pink light, main peak 640nm；Dysprosium is sent out Yellow light, main peak 570nm；Neodymium, erbium, ytterbium hair infrared light, main peak is respectively 1065nm, 1509nm and 978nm.By quinoline three of the present invention The electroluminescent organic material that azole rare earth compounding is prepared can be applied to the multiple fields such as OLED, have wide application Prospect.

Claims (10)

1. a kind of quinoline triazole type rare earth compounding, shown in structural formula such as formula (1)：
In formula (1), R1 is selected from hydrogen, alkyl, halogenated alkyl or aromatic radical；Ln be selected from yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, Any one in dysprosium, holmium, erbium, thulium, ytterbium, lutetium.
2. a kind of preparation method of quinoline triazole type rare earth compounding described in claim 1, it is characterised in that：Including following step Suddenly：
1) quinoline is oxidized to nitrogen oxides
2) by nitrogen oxidation N objectsCyano substitution is carried out, obtains 2- cyano quinolines
3) by 2- cyano quinolinesHydrazine is reacted with carboxylic acid or carboxylic acid derivates, obtains ligand compound
4) by ligand compound and rare earth metal reactant salt, the quinoline triazole type rare earth compounding of structure shown in formula (1) is obtained.
3. a kind of preparation method of quinoline triazole type rare earth compounding according to claim 2, it is characterised in that：Step 1) In, the oxidant used in oxidation reaction is at least one of metachloroperbenzoic acid, hydrogen peroxide；Oxidant and quinoline rub You are than being more than or equal to 1:1；The temperature of oxidation reaction is 60 DEG C~110 DEG C；The solvent of oxidation reaction is carboxylic acid, in alkyl halide, alcohol At least one.
4. a kind of preparation method of quinoline triazole type rare earth compounding according to claim 2, it is characterised in that：Step 2) In, the cyano reagent used in cyano substitution reaction is NaCN, KCN, CuCN, Zn (CN)2、(CH3)3At least one of SiCN；Cyanogen The reaction temperature of base substitution is 0 DEG C~40 DEG C, and the reaction time is 1 day~7 days.
5. a kind of preparation method of quinoline triazole type rare earth compounding according to claim 2, it is characterised in that：Step 3) Specially：First 2- cyano quinolines are dissolved in organic solvent, then react at 0 DEG C~40 DEG C with hydrazine 1h~for 24 hours, then generation Solid matter and carboxylic acid or carboxylic acid derivates hybrid reaction 1h~for 24 hours at -20 DEG C~50 DEG C, the solid product purification of gained Afterwards, ligand compound is obtained.
6. a kind of preparation method of quinoline triazole type rare earth compounding according to claim 5, it is characterised in that：Step 3) In, the dosage of hydrazine is not less than 1.0 equivalents；The dosage of carboxylic acid or carboxylic acid derivates is not less than 1.0 equivalents.
7. a kind of preparation method of quinoline triazole type rare earth compounding according to claim 6, it is characterised in that：Step 3) In, hydrazine is hydrazine hydrate；Carboxylic acid derivates are at least one of substituted carboxylic acid, acid anhydrides, carboxylic acid halides, ester.
8. a kind of preparation method of quinoline triazole type rare earth compounding according to claim 2, it is characterised in that：Step 4) Specially：First ligand compound and rare earth metal salt are dissolved in alcohol solution respectively, then the alcohol solution ligand compound It is mixed with alkali, then adds in the alcohol solution of rare earth metal salt, 1h~48h is stirred to react at 0 DEG C~60 DEG C, gained After solid product purification, quinoline triazole type rare earth compounding is obtained.
9. a kind of preparation method of quinoline triazole type rare earth compounding according to claim 8, it is characterised in that：Step 4) In, the equivalent proportion of ligand compound and rare earth metal salt is (2~4)：1；Alcohol solution is alcohol and water with volume ratio (0.2~5)： The mixed liquor of 1 composition；The dosage of alkali is no less than 1.0 equivalents.
10. a kind of application of the quinoline triazole type rare earth compounding described in claim 1 in electroluminescent organic material is prepared.
CN201810131422.0A 2018-02-09 2018-02-09 A kind of quinoline triazole type rare earth compounding and its preparation method and application Pending CN108191827A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201810131422.0A CN108191827A (en) 2018-02-09 2018-02-09 A kind of quinoline triazole type rare earth compounding and its preparation method and application
PCT/CN2019/070031 WO2019153980A1 (en) 2018-02-09 2019-01-02 Quinoline triazole rare earth complex, preparation method thereof, and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810131422.0A CN108191827A (en) 2018-02-09 2018-02-09 A kind of quinoline triazole type rare earth compounding and its preparation method and application

Publications (1)

Publication Number Publication Date
CN108191827A true CN108191827A (en) 2018-06-22

Family

ID=62593452

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810131422.0A Pending CN108191827A (en) 2018-02-09 2018-02-09 A kind of quinoline triazole type rare earth compounding and its preparation method and application

Country Status (2)

Country Link
CN (1) CN108191827A (en)
WO (1) WO2019153980A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109652063A (en) * 2018-12-29 2019-04-19 宁波大榭开发区综研化学有限公司 A kind of blue light transforming agent, anti-blue light adhesive and anti-blue light adhesive tape and preparation method thereof
WO2019153980A1 (en) * 2018-02-09 2019-08-15 广东省石油与精细化工研究院 Quinoline triazole rare earth complex, preparation method thereof, and application thereof
CN110256342A (en) * 2019-07-16 2019-09-20 河南省科学院化学研究所有限公司 A kind of synthetic method of 2- cyano-quinoline derivatives
CN111662644A (en) * 2020-05-06 2020-09-15 佛山华铕光电材料股份有限公司 Photovoltaic packaging adhesive film and preparation method and application thereof
CN112592529A (en) * 2020-11-19 2021-04-02 广东省科学院化工研究所 Light conversion film and preparation method and application thereof
CN113801651A (en) * 2021-09-24 2021-12-17 广东省科学院化工研究所 Composite luminescent material and preparation method and application thereof

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115141381A (en) * 2022-08-16 2022-10-04 河西学院 Rare earth metal praseodymium (III) complex and preparation method thereof
CN115746028B (en) * 2022-10-14 2024-10-01 华南师范大学 Fluorescent rare earth complex and preparation method and application thereof
CN116814245B (en) * 2023-07-07 2023-12-19 山东首明科技有限公司 Composite material for manufacturing luminous plate and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005255890A (en) * 2004-03-12 2005-09-22 Toyo Ink Mfg Co Ltd Material for organic electroluminescent element and organic electroluminescent element using the same
CN101058620A (en) * 2007-04-30 2007-10-24 中国科学院广州化学研究所 Linear polymer containing cavity transmission unit of 8-hydroxyquinoline metal complex and preparation method
US20080286604A1 (en) * 2007-05-18 2008-11-20 Semiconductor Energy Laboratory Co., Ltd. Organometallic Complex, Composition and Light Emitting Element Including the Organometallic Complex
CN102741265A (en) * 2009-10-28 2012-10-17 巴斯夫欧洲公司 Heteroleptic carbene complexes and use thereof in organic electronics
CN103172649A (en) * 2012-10-26 2013-06-26 广东鑫钰新材料股份有限公司 O-phenanthroline triazole rare earth complex and preparation method thereof
CN103265567A (en) * 2012-11-28 2013-08-28 广东鑫钰新材料股份有限公司 Nitrogen-containing bidentate heterocycle-substituted 1,2,3-triazole rare earth complex and synthetic method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106928282A (en) * 2015-12-31 2017-07-07 季昀 Platinum misfit thing and use its Organic Light Emitting Diode
CN108191827A (en) * 2018-02-09 2018-06-22 广东省石油与精细化工研究院 A kind of quinoline triazole type rare earth compounding and its preparation method and application

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005255890A (en) * 2004-03-12 2005-09-22 Toyo Ink Mfg Co Ltd Material for organic electroluminescent element and organic electroluminescent element using the same
CN101058620A (en) * 2007-04-30 2007-10-24 中国科学院广州化学研究所 Linear polymer containing cavity transmission unit of 8-hydroxyquinoline metal complex and preparation method
US20080286604A1 (en) * 2007-05-18 2008-11-20 Semiconductor Energy Laboratory Co., Ltd. Organometallic Complex, Composition and Light Emitting Element Including the Organometallic Complex
CN102741265A (en) * 2009-10-28 2012-10-17 巴斯夫欧洲公司 Heteroleptic carbene complexes and use thereof in organic electronics
CN103172649A (en) * 2012-10-26 2013-06-26 广东鑫钰新材料股份有限公司 O-phenanthroline triazole rare earth complex and preparation method thereof
CN103265567A (en) * 2012-11-28 2013-08-28 广东鑫钰新材料股份有限公司 Nitrogen-containing bidentate heterocycle-substituted 1,2,3-triazole rare earth complex and synthetic method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
宋雪琴等: "《配位化学》", 30 April 2013 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019153980A1 (en) * 2018-02-09 2019-08-15 广东省石油与精细化工研究院 Quinoline triazole rare earth complex, preparation method thereof, and application thereof
CN109652063A (en) * 2018-12-29 2019-04-19 宁波大榭开发区综研化学有限公司 A kind of blue light transforming agent, anti-blue light adhesive and anti-blue light adhesive tape and preparation method thereof
CN109652063B (en) * 2018-12-29 2022-03-01 宁波大榭开发区综研化学有限公司 Blue light conversion agent, blue light-proof adhesive tape and preparation method thereof
CN110256342A (en) * 2019-07-16 2019-09-20 河南省科学院化学研究所有限公司 A kind of synthetic method of 2- cyano-quinoline derivatives
CN110256342B (en) * 2019-07-16 2022-06-07 河南省科学院化学研究所有限公司 Synthetic method of 2-cyano quinoline derivative
CN111662644A (en) * 2020-05-06 2020-09-15 佛山华铕光电材料股份有限公司 Photovoltaic packaging adhesive film and preparation method and application thereof
CN112592529A (en) * 2020-11-19 2021-04-02 广东省科学院化工研究所 Light conversion film and preparation method and application thereof
CN113801651A (en) * 2021-09-24 2021-12-17 广东省科学院化工研究所 Composite luminescent material and preparation method and application thereof
CN113801651B (en) * 2021-09-24 2023-10-13 广东省科学院化工研究所 Composite luminescent material and preparation method and application thereof

Also Published As

Publication number Publication date
WO2019153980A1 (en) 2019-08-15

Similar Documents

Publication Publication Date Title
CN108191827A (en) A kind of quinoline triazole type rare earth compounding and its preparation method and application
CN103044466B (en) Dipyridyl triazole rare-earth complex and preparation method thereof
CN103172649B (en) O-phenanthroline triazole rare earth complex and preparation method thereof
CN101333438B (en) Material with bipolar carrier transmission performance and uses thereof
CN103665048B (en) One metal complexes and the application in organic electroluminescence device
CN103265567B (en) The 1,2,3-triazoles class rare earth compounding of nitrogenous bidentate heterocyclic substituted and synthetic method thereof
CN104130771A (en) Triple-core rare earth europium complex luminescent material, preparation method and application thereof
CN106753359A (en) A kind of blue light excites Mn4+The oxyfluoride red fluorescence powder and preparation method of doping
CN105524114A (en) Series of deep blue metal iridium phosphorescence OLED materials
CN103570627B (en) A kind of indenofluorene analog derivative and application containing pyrimidine or pyrazine or triazine group
CN103588795A (en) Ionic cuprous luminous complexes and use thereof
CN101274916B (en) Multifunctional bipolar carrier transmission material and application thereof
Guo et al. Photofunctional Eu 3+/Tb 3+ hybrids through sulfoxide linkages: coordination bonds construction, characterization and luminescence
CN103242354B (en) Four azole rare earth compoundings of nitrogenous bidentate heterocyclic substituted and preparation method thereof
CN107502343A (en) A kind of electroluminescent organic material and application
CN106432353A (en) Ruthenium complex with characteristic of strengthening aggregation state induced phosphorescence as well as preparation method and application of ruthenium complex
CN105440084B (en) Three metallic core platinum complex phosphor materials and its synthetic method based on triphenylamine
CN103242369A (en) Aromatic five-membered heterocyclo-substituted quinoline iridium (III) complex as well as preparation method and application thereof
CN108892691A (en) One kind containing iridium metal complexes and its organic luminescent device
CN105481905A (en) Asymmetric organic metal iridium complex phosphorescent material and preparation method thereof
CN113105509B (en) Complex phosphorescent material based on electron-deficient functional group
CN112812049B (en) Dimethylcholines rare earth complex and preparation method and application thereof
CN103804424A (en) Blue organic electroluminescent phosphorescent material-iridium metal complex, preparation method thereof and organic electroluminescence device
CN107311999A (en) A kind of organometallic complex, preparation method and its organic luminescent device
CN103254244A (en) Aryl five-membered heterocyclic substituted quinoline platinum (II) complex, preparation method thereof and application

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
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20180622