CN100427441C - Conjugated ramification material of fluorine containing anthracene and pyrene at 9th position, preparation method and application - Google Patents
Conjugated ramification material of fluorine containing anthracene and pyrene at 9th position, preparation method and application Download PDFInfo
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- CN100427441C CN100427441C CNB2005100244399A CN200510024439A CN100427441C CN 100427441 C CN100427441 C CN 100427441C CN B2005100244399 A CNB2005100244399 A CN B2005100244399A CN 200510024439 A CN200510024439 A CN 200510024439A CN 100427441 C CN100427441 C CN 100427441C
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Abstract
The present invention belongs to the technical field of photoelectric materials, particularly to a conjugated derivative material of fluorene whose 9 position is substituted by anthracene and pyrene and a preparation method thereof. The material is applied to the fields of organic electronics, such as organic / polymer electroluminescent materials, organic integrated circuits, organic solar cells, organic field effect pipes, dye lasers, organic non-linear optical materials, fluorescent probes, etc. The anthracene and the pyrene are introduced to an efficient luminescent conjugated fluorene system by a 9 position disubstitution structure. The material has the advantages that (1) the current carrier transmission performance is enhanced, and the high fluorescent efficiency characteristics of the conjugated fluorene system are simultaneously maintained; (2) the synthesis is conveniently operated and can carry out farther result modification; (3) the 9 position diaryl substitution fluorene structure has the characteristics of high thermal stability and high spectral stability. Electroluminescent devices prepared by the material obtain a satisfactory result in brightness, luminous efficiency, etc.
Description
Technical field
The invention belongs to the photoelectric material sciemtifec and technical sphere, be specially 9 of classes and contain the conjugated ramification material and preparation method thereof of the fluorenes of anthracene, pyrene, and such material is applied to organic electronics such as organic/polymer electroluminescence material, organic integration circuit, organic solar batteries, organic field-effect tube, dye laser, organic non linear optical material and fluorescent probe learns fields.
Technical background
Because the fast development of information technology, people have proposed more and more higher requirement to information display technology.1987, people such as the tang of Kodak adopted the ultrathin membrane technology at first to use oxine aluminium (Alq
3) made double-deck organic electroluminescence device (LED) [Tang, C.W. as luminescent layer; Van Slyke, S.A.Appl.Phys.Lett.1987,51,913.], thus the epoch-making progress of organic electroluminescent begun.Nineteen ninety, Britain's Cavan enlightening is permitted breadboard Friend[Burroughes, J.H.; Bradley, D.D.C.; Brown, A.B.; Marks, R.N.; Mackay, K.; Friend, R.H.; Burn, P, L.; Holmes, A.B.Nature 1990,347,539.] etc. people's reported first the electroluminescent of polystyrene support (PPV), 1991 years Heeger groups [Brown, D.; Heeger, A.J.Appl.Phys.Lett 1991,58,1982] the orange LED that makes with spin-coating film, the research of from then on having opened high molecule electroluminescent material and device (PLED) have been made.Show (CRT), liquid-crystal display (LCD) and plasma display (PDP) with respect to existing negative ray, and technology such as inorganic semiconductor LED demonstration compares, by organic materials as the organic/polymer plane technique of display of luminescent layer have energy consumption little, be easy to realize that large screen display, glow color are adjustable continuously, the visual angle wide, active illuminating, response speed are fast, can realize that rigidity shows and advantages such as flexible demonstration.All these nature's mystery semiconductor materials are incomparable, therefore caused various countries scientist, the huge attention of government and industrial community.Organic/polymer plane technique of display has two big gordian techniquies, and the one, the technology of fabricate devices, the 2nd, the luminescent material and the carrier transmission material of exploitation high comprehensive performance.
Concerning luminescent material, green glow is ripe relatively, and blue light and red light material still have much room for improvement.The conjugate derivative of fluorenes has the characteristics of high fluorescence efficiency, but since its HOMO, the anode of LUMO and LED, and the work function of negative electrode is not complementary, therefore cause the injection of hole and electronics difficult and uneven, and form state of aggregation and/or excimer easily because thermostability is relatively poor.Therefore design, synthesize and develop fluorenes class material and seem particularly important with thermostability and electric charge injection transmission performance.The fluorenes class conjugate derivative of 9 diaryl replacements can improve thermostability effectively.Anthracene and pyrene are big conjugation aromatic groups, have the function of transporting holes, but up to the present, the fluorenes system of introducing these two groups on 9 of fluorenes does not also have paper and patent report.
Simultaneously at OFET, organic solar batteries and organic laser field, the fluorenes class conjugate derivative that 9 diaryl replace also shows high carrier transmission performance and high luminous efficiency.
Summary of the invention
The objective of the invention is to propose a kind of luminescent material and synthetic method thereof that is used for efficient and long life OLED device.By fluorenes 9 of big plane aromatic nucleus anthracene, pyrene are replaced introduce, modify and two angles of electronic structure modulation are considered to synthesize and had high performance organic photoelectrical material from material.Study of the application of such material simultaneously in organic electronic fields such as organic/polymer electroluminescence material, organic integration circuit, organic solar batteries, organic field-effect tube, dye laser, organic non linear optical material and fluorescent probes.
The present invention adopts Suzuki and Yamamoto idol chain reaction to synthesize 9 conjugated ramification materials that contain the fluorenes of anthracene, pyrene of a class, and the molecular structure of compound is as follows:
Compound I
Ar wherein
1, Ar
2In have at least one to be anthracene or pyrenyl group.N is the numeral (being oligomer this moment) in 1～50 or has certain distribution (being superpolymer this moment).If 9 substituents of fluorenes have one to be anthracene or pyrene, then the another one aromatic nucleus can be following any: furyl, thienyl, pyrryl, pyrazolyl, imidazolyl connects triazolyl, 1,2, the 4-triazolyl, 1,2, the 5-triazolyl, 1,3, the 4-triazolyl, 1,2,3, the 4-tetrazyl, 1,2,3,5-tetrazyl isoxazolyl oxazolyl, 1,2,3-oxadiazole base, 1,2,4-oxadiazole base, 1,3,4-oxadiazole base, the furazan base, 1,2,3,5-oxatriazole base, 1,2,3,4-oxatriazole base, 1,3,2-Er oxazolyl, 1,2,3-Er oxazolyl, 1,2,3,4-Er oxadiazole base, 1,2,3,4-Er oxadiazole base, 1,3,2,4-Er oxadiazole base, 1,3,4,5-Er oxadiazole base, 1,2,3,4-trioazole base, isothiazolyl, phenyl, α-pyrans ketone group gamma-pyrone, pyrazinyl, pyridyl, pyridazinyl, the U-triazine base, 1,2, the 4-triazinyl, 1,3, the 5-triazinyl, pyrimidyl, 1,2,4,5-tetrazine base, pentazine base 1,2-Yi oxazinyl, 1,4-Yi oxazinyl, indenyl, benzofuryl (tonka-bean ketone group), the thianaphthenyl indyl, pseudoindoyl, the 3-indyl, iso indazolyl, naphthyl, tonka bean camphor base (1,2-chomene ketone group), chromone base (1,4-chomene ketone group), 2,1-chomene ketone group thiochromone base (1,4-sulphur naphthalenone base), quinolyl (1-quinoline base), isoquinoline 99.9, cinnolines base (1,2-phenodiazine naphthyl), quinazolyl quinoxalinyl, 1,5-pyridopyridine base, 1,6-phenodiazine naphthyl, 1,7-phenodiazine naphthyl, 1,3-phenodiazine naphthyl, 1,4-phenodiazine naphthyl, connect three quinoline bases, 1,2,4-phenodiazine base, 1,6,7-three quinoline bases, 1,2,3,4-petrin base, 1,4,5,7-petrin base, 1,3, the 2-benzoxazinyl, 1,4, the 2-benzoxazinyl, 2,3,1-oxygen quinoline base, 2,4,1-oxygen quinoline base, 1,2-sulphur quinoline base, 1,4-sulphur nitrogen base, the fluorenyl carbazyl, dibenzofuran group, the dibenzothiophen base, the oxa-anthryl, azophenlyene (folder) phenodiazine anthryl; phenoxazine (folder) oxygen acridine base, phenarsazine (folder) arsenic acridine base perylene base, 1,6-dihydro pentalene base, phenanthryl, acenaphthenyl phenanthroline base, connect phenyl, the 12H-phenalene base, benzo [9,10] phenanthryl, phenothiazinyl.Structure is seen appendix.
Among the present invention, Ar
1And Ar
2Both can have or not have the alkyl or the alkoxyl group of replacement, and wherein the carbochain of alkyl or alkoxyl group is that carbonatoms is the saturated alkyl of 1-20.
The synthetic of above-claimed cpd comprises that 9 fluorenes that contain anthracene, pyrene are monomeric synthetic, and adopts Suzuki and Yamamoto linked reaction to prepare described compound.
9 monomeric synthetic routes of fluorenes that contain anthracene, pyrene are as follows:
Wherein, X is in chlorine, bromine, iodine, the hydrogen, and will have one at least among two X is halogen; A and B are boric acid ester or boric acid, and perhaps one of them is boric acid ester or boric acid, and another is halogen or hydrogen atom; Step (i) is oxidized to Fluorenone with fluorenes; Step (ii) comprises the halogenated method of various preparation aromatizes, and the grignard reagent of aryl halide conjugate derivative reacts or replaces halogen atom with butyllithium, with magnesium salts or the lithium salts acidifying that generates; Step (iii) is the Friedel-Craft reaction of pure and mild another Ar2 under acid catalysis; Step (iv) is preparation boric acid or boric acid ester, and method is at first to replace the lithiumation halogen atom by butyllithium, adds boric acid ester then; If generation boric acid is then used methyl-borate, then acid hydrolysis.
Prepare superpolymer by Suzuki and Yamamoto polyreaction, its reaction scheme is as follows.Wherein, dba is a dibenzalacetone, and COD is a cyclooctadiene, and bpy is a dipyridyl, and DMF is N, and dinethylformamide, cyclooctadiene are cyclooctadiene.
Wherein the reaction conditions of Suzuki is Ph (PPh
3)
4/ K
2CO
3/ toluene, or Ph (dba)
2/ CsF/Ph
3P/1, the 2-glycol dimethyl ether adds phase-transfer catalyst to improve productive rate in the reaction; The reaction conditions of Yamamoto is Ni (COD)
2/ bpy/1,5-cyclooctadiene/DMF; The reaction later stage adds single bromo functional groups fluorenes and carries out end-blocking.
By Suzuki prepared in reaction repeating unit is the oligomer of 3-50, and its reaction scheme is as follows:
Wherein the reaction conditions of Suzuki is with aforementioned.
The compound-material that the present invention proposes can be used as OLED and PLED device luminescent layer material, organic integration circuit material, organic laser material, the semiconductor material of organic field-effect tube, organic solar battery material, organic non linear optical material etc.Below the preparation method is described further:
The halo fluorenes is monomeric synthetic: with 2,7-dihalo fluorenes or 2-halo fluorenes be the oxidation with pneumatic blending in the presence of phase-transfer catalyst, obtains corresponding Fluorenone through recrystallization in ethanol.Aryl halide generates grignard reagent with reactive magnesium in anhydrous diethyl ether or anhydrous tetrahydro furan then, grignard reagent is splashed into react 1～10h in the Fluorenone again, with its hydrogenolysis (as using saturated ammonium chloride solution), promptly obtains corresponding alcohol by column chromatography after reaction finishes.Pure and mild another one aromatic nucleus is (the most handy organic acid is as the acid of trifluoromethane semi-annular jade pendant or this methane semi-annular jade pendant acid etc.) under the effect of acid, obtains corresponding monomer behind the column chromatography.If another aromatic ring activity is very big, and a plurality of high reactivity sites that are equal to are arranged, then should adopt the excessive way of this active aromatic ring.
Synthesizing of fluorenes boric acid or boric acid ester: under-10～-78 ℃, butyllithium is slowly splashed in the tetrahydrofuran solution that is dissolved with the halo fluorenes, under this temperature, react 2h again, add (1) 2～10 normal methyl-borate reaction 10～48h then, add the hydrochloric acid hydrolysis of 2M, column chromatography or recrystallization promptly obtain the boration product; (2) 2～10 equivalent 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane or bis (piancolato) diboron, column chromatography or recrystallization obtain the acid esterification product then; (3) 2～10 normal methyl-borate reaction 10～48h, the hydrochloric acid hydrolysis that adds 2M, after column chromatography or recrystallization obtain the boration product, add sheet alcohol (pinacol) (perhaps 1, ammediol, ethylene glycol) in toluene or methylene dichloride, reflux, column chromatography or recrystallization obtain corresponding boric acid ester again.
Yamamoto prepared in reaction superpolymer: with biscyclooctadiene base nickel (O), cyclooctadiene is dissolved in N, in the dinethylformamide, then at inert atmosphere (argon gas, nitrogen) 40～60 ℃ of heating 30min under add 2 of 9 anthracenes, pyrene replacement, 7-dibromo fluorenes monomer then, after 3 days, add bromobenzene or 2-bromine fluorenes end-blocking in reaction under 60～100 ℃.Reaction system is dissolved with toluene then with concentrated hydrochloric acid and methyl alcohol again, obtains polymkeric substance with methanol extraction again.
Suzuki idol chain reaction prepares oligomer:
(1) trimerization fluorenes: directly, dissolve with toluene, add Pd (Pph more therein greater than 2 normal 2-bromine fluorenes with the two boric acid esters of 1 normal fluorenes
3)
4(O), salt of wormwood or sodium carbonate solution, (can also add phase-transfer catalyst), and 60-100 ℃ of following backflow 24-72h under anaerobic, column chromatography or recrystallization obtain the trimerization fluorenes.Its reaction formula is as follows:
(2) repeating unit is greater than three oligomer: with 6 poly-and 7 poly-fluorenes is example: with 1 normal fluorenes list boric acid ester and 2 normal 2,7-dibromo fluorenes carries out suzuki idol chain reaction, obtains the dimer of single bromine; With the dimer of 1 normal single bromine and 2 normal 2,7-dibromo fluorenes carries out suzuki idol chain reaction, obtains the tripolymer of single bromine; This single bromine trimerization fluorenes and the two boric acid esters of fluorenes are carried out suzuki idol chain reaction and obtain 7 poly-fluorenes.If with single bromine trimerization fluorenes acid esterification, carry out suzuki idol chain reaction with single bromine bromine trimerization fluorenes again, then can obtain 6 poly-fluorenes.Can obtain any one oligomer that repeating unit is 3-50 with this method.
Intermediate oligomer and high polymer material structure have been characterized by nucleus magnetic resonance (NMR), chromaticness online (GC-MS), laser parsing time-of-fight mass spectrometry (LDI-TOF-MS), gel chromatography (GPC), by the thermostability that thermogravimetric analysis and differential thermal analysis have been tested material, characterized their electrochemical properties by cyclic voltammetry.
On this basis, primary design device to estimate the various light emission behaviors that 9 anthracenes, pyrene substituted fluorene are gripped derivant material altogether.Device during at the luminescent properties of the injection of current carrier and transmission performance, material and as white light and phosphorescent light body material the behavior of Subjective and Objective transmission ofenergy design and research and light amplification behavior.Transparent anode is produced on on glass or the plastic, the vacuum evaporation hole is injected and transport material on conductive layer then, compound among evaporation or spin coating the present invention is as luminescent layer or doped body material, evaporation one deck electron transfer layer and electron injecting layer again, last evaporation negative electrode.Experimental result shows: 9 anthracenes, pyrene substituted fluorenes are gripped current carrier injection and transport material, luminescent material and white light and the phosphorescent light body material that derivant material can be used as high comprehensive performance altogether.In addition, such compound-material can be applied to organic electronics such as organic integration circuit, organic solar batteries, organic field-effect tube, dye laser, organic non linear optical material and fluorescent probe and learn the field.
Major advantage of the present invention is:
1. synthetic 9 anthracenes, the monomeric route of pyrene substituted fluorene are simple, but but easily by introducing alkoxyl group or alkyl with the polymkeric substance of realizing spin coating or the oligomer of spin coating.
2. by introducing anthracene, this big aromatic nucleus of pyrene, improve the injection and the transmittability in hole effectively, improved device efficiency, and may be used for current carrier injection or transport layer material.
3. kept 9, the high glass transition temperature and the high thermal stability of 9-diaryl substituted fluorene.
4. effectively modulate fluorescence emission spectrum and triplet, thereby formed good material of main part.
5. have high carrier transport ability, be suitable for as transport material and OTFT material.
6. have tangible light amplification phenomenon, be suitable for as the organic laser material
Description of drawings
Fig. 1. trimerization (9-phenyl-9-pyrenyl fluorenes) (ter (9-phenyl-9-pyrenylfluorene) (TPPF) absorption and photoluminescence spectrum, and solid luminescence spectrum.Considerable change does not take place in spectrum after 100 ℃ and 230 ℃ of annealing.
Fig. 2. trimerization (9-anthryl-9-phenyl fluorenes) absorption and photoluminescence spectra (TAPF), and solid luminescence spectrum.150 ℃ annealing 24 hours after spectrum considerable change does not take place.
Embodiment
In order to understand the content of patent of the present invention better, further specify technical scheme of the present invention below by specific embodiment.Specifically comprise the preparation of synthetic, property testing and device.But these embodiments do not limit the present invention.
Embodiment 1: (TPPF) synthetic of trimerization (9-phenyl-9-pyrenyl fluorenes) ter (9-phenyl-9-pyrenylfluorene)
(1) 2,7-dibromo fluorenone and 2-bromine Fluorenone.
With 10.1g 2,7-dibromo fluorenes is dissolved in the 150mL pyridine solution, add 1mLbenzyltrimethylammonium hydroxide in methnol (40%) (perhaps tetrabutylammonium hydroxidein methanol) in this solution, blowing air stirs 24h then.Remove pyridine by underpressure distillation, obtain the reddish-brown solid.This solid obtains the 9.8g yellow solid, productive rate 93% through recrystallization (perhaps using ethyl acetate/petroleum ether=10: 1 column chromatographies) in ethanol.
1HNMR(400MHz，CDCl3)δ(ppm)：7.77(d，J＝1.6Hz，2H)；7.63(dd，J＝8.0，1.6Hz，2H)，7.39(d，J＝8.0Hz，2H).
Adopting 2-bromine fluorenes is raw material, can obtain the 2-bromine Fluorenone of 93% productive rate with similar method.
1HNMR(400MHz，CDCl3)δ(ppm)：7.77(d，J＝1.6Hz，1H)；7.66(dt，J＝7.2Hz，1.2Hz，1H)；7.61(dd，J＝8.4Hz，1.6Hz，1H)；7.51(d，J＝1.2Hz，1H)；7.49-7.51(m，1H)；7.40(d，J＝7.2Hz，1H)；7.30-7.35(m，1H).
(2) 2,7-two bromo-9-phenyl fluorenes-9-alcohol (2,7-Dibromo-9-phenylfluoren-9-ol)
With magnesium chips (0.58g, 24mmol), a spot of iodine and bromine are stupid, and ((4.48g 29mmol) makes the phenyl-magnesium-bromide grignard reagent at anhydrous diethyl ether (perhaps anhydrous tetrahydro furan) in (30mL), and this reagent is with the dilution of 20mL anhydrous diethyl ether, be dissolved with 2 then, ((4.09g, anhydrous tetrahydro furan 12.1mmol) splash in the grignard reagent 7-dibromo fluorenone, stir 4h, the cooling back adds saturated ammonium chloride solution hydrogenolysis 2h.Reaction mixture washes with water with dichloromethane extraction twice, uses anhydrous magnesium sulfate drying again.Obtain faint yellow solid (4.58g, 91%) with ethyl acetate/petroleum ether=10: 1 as eluent column chromatography on silica gel.
1HNMR(400MHz，CDCl3)δ(ppm)：7.51(d，J＝1.2Hz，4H)；7.44(t，J＝1.2Hz，2H)；7.27-7.36(m，5H)；2.45(s，1H).
(3) 2-bromo-9-phenyl fluorenes-9-alcohol (2-Bromo-9-phenyl-fluoren-9-ol)
2-bromine Fluorenone (3.77g, 14.6mmol) adopt and (2) similar methods can obtain yellow solid (4.65g, 13.8mmol), productive rate 94%.
1HNMR(400MHz，CDCl3)δ(ppm)：7.65(d，J＝8.0Hz，1H)；7.44-7.55(m，3H)；7.32-7.4(m，3H)；7.23-7.31(m，5H)；2.45(s，1H)；MS(m/z，EI，70eV)：Calcd.forC
19H
13 79BrO?336.01，found?336；Calcd.for?C
19H
13 81BrO?338.01，found?338.
(4) 2,7-two bromo-9-phenyl-9-pyrenyl fluorenes (2,7-Dibromo-9-phenyl-9-pyrenylfluorene) with pyrene (5g, 24.7mmol) and the acid of trifluoromethane semi-annular jade pendant (0.72g 4.8mmol) is dissolved in 100mL 1,1,2, in the 2-tetrachloroethane, will be dissolved in 1,1 then, 2, in the 2-tetrachloroethane 2,7-two bromo-9-phenyl fluorenes-9-alcohol splashing in the system dropwise, system are warming up to 60 ℃ and stir 30min.Add excessive saturated sodium bicarbonate solution to finish reaction, separatory obtains organic phase, and this organic phase is washed twice with saturated sodium bicarbonate again.The water that merges dichloromethane extraction three times merge organic phase, and it is used anhydrous magnesium sulfate drying.Obtain white solid (2.3g, 79%) with sherwood oil/methylene dichloride=5: 1 as the eluent silica gel column chromatography.
1HNMR(400MHz，CDCl3)δ(ppm)：7.58-8.24(m，11H)；7.67(d，J＝8.0Hz，2H)；7.52(dd，J＝8.0Hz，2.0Hz)；7.23-7.32(broad，3H)，7.12-7.23(broad，2H).LDI-TOF-MS(m/z)：Calcd.for?C
35H
20 79Br
79Br?598.0，found?598.1；Calcd.forC
35H
20 79Br
81Br?600.0，found?600.0；Calcd.for?C
35H
20 81Br
81Br?602.0，found?602.3
(5) 2-bromo-9-phenyl-9-pyrenyl fluorenes (2-Bromo-9-phenyl-9-pyrenylfluorene)
(2.0g 6mmol) adopts 2-bromo-9-phenyl fluorenes-9-alcohol and (4) similar methods can obtain white solid (2.5g, 80%).
1HNMR(400MHz，CDCl3)δ(ppm)：7.90-8.20(m，8H)；7.78-7.86(broad，2H)；7.64-7.76(m，3H)；7.56-7.64(broad，1H)；7.52(d，J＝8.0Hz，1H)；7.39(t，8.0Hz，1H)；7.16-7.26(broad，5H).LDI-TOF-MS(m/z)：Calcd.for?C
35H
21 79Br?520.1，found?520.8；Calcd.for?C
35H
21 81Br?522.1，found?522.2.
Two (4,4,5,5-tetramethyl--1,3,2-dioxo boric acid ester-2-the yl)-9 phenyl-9-pyrenyl fluorenes of (6) 2,7-(2, and 7-Bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9-phenyl-9-pyrenylfluorene)
2, (1.3g 2.2mmol) is dissolved in the tetrahydrofuran (THF) (20mL) 7-two bromo-9-phenyl-9-pyrenyl fluorenes, is cooled to-78 ℃, and (8.5mL 13.6mmol) dropwise splashes into system with syringe with n-Butyl Lithium (cyclohexane solution of 1.6M).System adds 2-sec.-propyls-4,4,5 after the reaction 2 down at-78 ℃, 5-tetramethyl--1,3,2-dioxo borine boric acid ester (2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (9.12g, 49mmol), react 2h again, allow system slowly rise to room temperature then and react 24h again at-78 ℃.Add the saturated sodium bicarbonate solution separatory, with methylene dichloride extracting twice again.With and organic phase with anhydrous magnesium sulfate drying after, revolve to steam and remove solvent, obtain white solid (0.8g, 52.3%) with sherwood oil/methylene dichloride=2: 1 as the eluent silica gel column chromatography.
1HNMR(400MHz，CDCl3)δ(ppm)：8.13(d，J＝7.6Hz，1H)；7.84-8.10(m，12H)；7.66-7.84(broad，2H)；7.27-7.38(broad，2H)；7.18-7.26(broad，3H)；1.30(s，24H).
(7) trimerization (9-phenyl-9-pyrenyl fluorenes) ter (9-phenyl-9-pyrenylfluorene) 2-bromo-9-phenyl-9-pyrenyl fluorenes (1.82g, 3.5mmol), 2,7-two (4,4,5,5-tetramethyl--1,3,2-dioxo boric acid ester-2-yl)-9 phenyl-9-pyrenyl fluorenes (0.81,1.2mmol), four (triphenyl phosphorus) are changed palladium (0.05mmol) and the 2M solution of potassium carbonate is blended in the flask that contains toluene 150mL.Reaction system is heated to 90 ℃ of reaction 72h.Add saturated sodium bicarbonate solution and finish reaction, with dichloromethane extraction twice, the organic phase anhydrous magnesium sulfate drying of merging revolves to steam and removes solvent, obtain white solid (1.03g, 64.8%) with sherwood oil/methylene dichloride=2: 1 as the eluent silica gel column chromatography.
1HNMR (400MHz, CDCl3) δ (ppm): 7.98-8.18 (m, 12H); 7.83-7.96 (m, 7H); (7.68-7.83 m, 10); 7.42-7.68 (m, 14H); 7.32-7.38 (t, J=8.0Hz, 4H); 7.22 (d, J=7.6Hz, 4H); 7.15-7.20 (broad, 5H), 7.05-7.14 (m, 4H); 6.97-7.05 (broad, 2H) .LDI-TOF-MS (m/z): Calcd.forC
105H
621322.5 found 1322.1. structural formula is as follows:
Embodiment 2: to 9 ultra-violet absorption spectrums that contain the tripolymer TPPF (implementing the product among the embodiment 1) of anthracene, pyrene fluorenes, and photoluminescence spectra, spectrum thermostability and quantum yield are measured:
TPPF is dissolved in the methylene dichloride dilute solution of saturated nitrogen, adopts Tianjin, island UV-3150 ultraviolet-visual spectrometer and RF-530XPC fluorescence spectrophotometer to carry out absorption spectrum and emission spectrometry.Photoluminescence spectra is that the maximum absorption wavelength (351nm) in uv-absorbing is measured down.The photoluminescence spectra of solid film is that the quartz plate by vacuum evaporation carries out, and thickness is 300nm.The fluorescence quantum efficiency of solution be by in pimelinketone 10
-69 of M, 10-dibenzanthracene solution (quantum yield is 1.0) is measured as standard.
TPPF solution is 351nm at the maximum absorption band greater than 300nm, and photoluminescence spectra has two characteristic absorbance, promptly 399 and 419nm.
The maximum emission wavelength of solid film is 436nm.Under nitrogen atmosphere, spectrum does not change behind annealing 24h under 100 ℃ with solid film, and at 230 ℃ of 3h that anneal down, considerable change does not take place spectrum yet, illustrates owing to thermal stability is good to cause spectrum stability fine again.Specifically see accompanying drawing 1.
Embodiment 3: trimerization (9-anthryl-9 phenyl fluorenes) synthetic and spectrometry (TAPF).
Adopt and the similar method of TAPF, just pyrene is changed to anthracene can obtain TAPF with similar productive rate.
Adopt the method for similar TAPF can measure uv-absorbing and photoluminescence spectra.Photoluminescence spectra is that the maximum absorption wavelength (355nm) in uv-absorbing is measured down.
TPPF solution is 355nm at the maximum absorption band greater than 300nm, and photoluminescence spectra has two characteristic absorbance, promptly 397 and 417nm.
The maximum emission wavelength of solid film is 442nm.Under nitrogen atmosphere, at 150 ℃ of 24h that anneal down, considerable change does not take place in spectrum, illustrates owing to thermal stability is good to cause spectrum stability fine with solid film.See accompanying drawing 2.
The structural formula of TAPF is as follows:
Appendix: in the Compound I, Ar in anthracene and pyrene and the general formula
1, Ar
2Structural formula:
The anthryl pyrenyl
Furyl thienyl pyrryl pyrazolyl imidazolyl
Connect triazolyl 1,2,4-triazolyl oso-triazole base 1,3,4-triazolyl
Pyrrotriazole base 1,2,3,5-tetrazolium isoxazole base oxazolyl 1,2,3-oxadiazole base
1,2,4-oxadiazole base 1,3,4-oxadiazole base furazan base 1,2,3,5-oxatriazole base 1,2,3,4-oxatriazole base
1,3,2-Er oxazolyl 1,2,3-Er oxazolyl 1,2,3,4-Er oxadiazole base 1,2,3,4-Er oxadiazole base 1,3,2,4-Er oxadiazole base
1,, 3,4,5-two oxadiazole bases 1,2,3,4-trioazole base isothiazolyl phenyl α-pyrans ketone group
Gamma-pyrone pyrazinyl pyridyl pyridazinyl U-triazine base
1,2,4-triazinyl 1,3,5-triazines yl pyrimidines base 1,2,4,5-tetrazine base pentazine base
1, the different oxazinyl 1 of 2-, the different oxazinyl indenyl of 4-benzofuryl (tonka-bean ketone group) thianaphthenyl
Indyl pseudoindoyl 3-indyl iso indazolyl
Naphthyl tonka bean camphor base (1,2-chomene ketone group) chromone base (1,4-chomene ketone group) 2,1-chomene ketone group
Thiochromone base (1,4-sulphur naphthalenone base) quinolyl (1-quinoline base) isoquinoline 99.9 cinnolines base (1,2-phenodiazine naphthyl)
Quinazolyl quinoxalinyl 1,5-pyridopyridine base 1,6-phenodiazine naphthyl 1,7-phenodiazine naphthyl
1,3-phenodiazine naphthyl 1,4-phenodiazine naphthyl connects three quinoline bases 1,2,4-phenodiazine base 1,6,7-three quinoline bases
1,2,3,4-petrin base 1,4,5,7-petrin base 1,3,2-benzoxazinyl 1,4,2-benzoxazinyl 2,3,1-oxygen quinoline base
2,4,1-oxygen quinoline base 1,2-sulphur quinoline base 1,4-sulphur nitrogen base fluorenyl
Carbazyl dibenzofuran group dibenzothiophen base xanthene base
Azophenlyene (folder) phenodiazine anthryl phenoxazine (folder) oxygen acridine base phenarsazine (folder) arsenic acridine base
Perylene base 1,6-dihydro pentalene Ji Feiji acenaphthenyl
The phenanthroline base connects phenyl 12H-phenalene base benzo [9,10] phenanthrene
Phenothiazinyl
Claims (7)
1, the conjugated ramification material of the fluorenes of a kind of 9 anthracenes, pyrene replacement is characterized in that having following structure:
Compound I
Ar wherein
2Be anthracene or pyrenyl group, Ar
1A kind of for following radicals: anthryl, pyrenyl, furyl, thienyl, pyrryl, phenyl, pyrimidyl, indenyl, quinolyl, isoquinoline 99.9, quinoxalinyl, pyridyl, fluorenyl, carbazyl, dibenzofuran group, dibenzothiophen base, oxa-anthryl, perylene base, phenanthryl, phenanthroline base, connect phenyl, phenothiazinyl, n be in 3～50 concrete numeral or for having the indefinite numeral of certain distribution.
2, according to the said conjugated ramification material of claim 1, it is characterized in that Ar
1And Ar
2Both can have or not have the alkyl or the alkoxyl group of replacement, and wherein the carbochain of alkyl or alkoxyl group is that carbonatoms is the saturated alkyl of 1-20.
3, a kind of preparation method as the said conjugated ramification material of claim 1 is characterized in that earlier synthetic 9 fluorenes monomers that contain anthracene, pyrene, adopts Suzuki and Yamamoto linked reaction to prepare described conjugate derivative then.
4,, it is characterized in that 9 monomeric synthetic routes of fluorenes that contain anthracene, pyrene are as follows according to the said preparation method of claim 3:
Wherein, X is in chlorine, bromine, iodine, the hydrogen, and will have one at least among two X is halogen; A and B are boric acid ester or boric acid, and perhaps one of them is boric acid ester or boric acid, and another is halogen or hydrogen atom; Step (i) is oxidized to Fluorenone with fluorenes; Step (ii) comprises the halogenated method of various preparation aromatizes, and the grignard reagent of aryl halide conjugate derivative reacts or replaces halogen atom with butyllithium, with magnesium salts or the lithium salts acidifying that generates; Step (iii) is pure and mild another Ar under acid catalysis
2Friedel-Craft reaction; Step (iv) is preparation boric acid or boric acid ester, and method is at first to replace the lithiumation halogen atom by butyllithium, adds boric acid ester then; If generation boric acid is then used methyl-borate, then acid hydrolysis.
5, preparation method according to claim 3 is characterized in that preparing superpolymer by Suzuki and Yamamoto polyreaction, and its reaction scheme is as follows:
Wherein the reaction conditions of Suzuki is Ph (PPh
3)
4/ K
2CO
3/ toluene, or Ph (dba)
2/ CsF/Ph
3P/1, the 2-glycol dimethyl ether adds phase-transfer catalyst to improve productive rate in the reaction; The reaction conditions of Yamamoto is Ni (COD)
2/ bpy/1,5-cyclooctadiene/DMF; The reaction later stage adds single bromo functional groups fluorenes and carries out end-blocking; Here, dba is a dibenzalacetone, and COD is a cyclooctadiene, and bpy is a dipyridyl, and DMF is N, and dinethylformamide, cyclooctadiene are cyclooctadiene.
6, preparation method according to claim 3 is characterized in that by Suzuki prepared in reaction repeating unit be the oligomer of 3-50, and its reaction scheme is as follows:
Wherein the reaction conditions of Suzuki is with aforementioned.
7, preparing OLED and PLED device luminescent layer material as the said conjugated ramification material of one of claim 1～2, the organic integration circuit, the organic laser material, the semiconductor material of organic field-effect tube, the application in organic solar battery material or the organic non linear optical material.
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| GB2471062B (en) * | 2009-04-16 | 2012-10-31 | Cambridge Display Tech Ltd | Organic light-emitting materials and devices |
| CN101974145A (en) * | 2010-10-12 | 2011-02-16 | 南京邮电大学 | Conjugated polymer material of fluorene and perylene and preparation method thereof |
| CN102093158A (en) * | 2010-12-01 | 2011-06-15 | 上海大学 | Fluorene-anthracene compound for preparing luminescent materials and synthesis method thereof |
| CN102167913B (en) * | 2011-02-25 | 2013-09-25 | 中国科学院上海有机化学研究所 | Organic dye containing polycarbazole and preparation method and application thereof |
| CN102167656A (en) * | 2011-03-17 | 2011-08-31 | 上海大学 | 9-(1-fluoro-9H-fluoren-9-yl)anthracene and preparation method thereof |
| CN102898270B (en) * | 2011-07-25 | 2015-08-19 | 海洋王照明科技股份有限公司 | A kind of anthracene derivative organic semiconductor material and its preparation method and application |
| WO2016031406A1 (en) * | 2014-08-27 | 2016-03-03 | 富士フイルム株式会社 | Compound, composition, film and optical device |
| CN106700038B (en) * | 2016-12-21 | 2019-01-29 | 北京化工大学 | It is a kind of to use fluorescence probe detection gas signaling molecule H2The method of S |
| CN107254032A (en) * | 2017-05-09 | 2017-10-17 | 华南理工大学 | A kind of conjugated polymer based on anthra indenofluorene unit and preparation method and application |
| CN108912311A (en) * | 2018-04-27 | 2018-11-30 | 华南理工大学 | A kind of polyfluorene and the preparation method and application thereof of the side group containing anthryl group |
| CN110964210B (en) * | 2019-12-26 | 2021-02-09 | 吉林大学 | Porous organic material and preparation method and application thereof |
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| JPH06234668A (en) * | 1993-02-10 | 1994-08-23 | Nippon Steel Corp | Production of 9,9-dialkylfulorene |
| CN1501899A (en) * | 2001-04-09 | 2004-06-02 | �Ѻ߷�����ʽ���� | Curable polyvinylbenzyl compound and process for producing the same |
| JP2004154409A (en) * | 2002-11-07 | 2004-06-03 | Fuji Photo Film Co Ltd | Picture imaging unit for breast |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06234668A (en) * | 1993-02-10 | 1994-08-23 | Nippon Steel Corp | Production of 9,9-dialkylfulorene |
| CN1501899A (en) * | 2001-04-09 | 2004-06-02 | �Ѻ߷�����ʽ���� | Curable polyvinylbenzyl compound and process for producing the same |
| JP2004154409A (en) * | 2002-11-07 | 2004-06-03 | Fuji Photo Film Co Ltd | Picture imaging unit for breast |
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