CN1315764C - Conjugate derivative material of 9-phenyl-9-pyrenyl fluorene substituted pyrene its preparation method and application - Google Patents
Conjugate derivative material of 9-phenyl-9-pyrenyl fluorene substituted pyrene its preparation method and application Download PDFInfo
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Abstract
The present invention belongs to the technical field of photoelectric materials, particularly to a pyrene conjugated derivative material substituted by 9-phenyl-9-pyrenyl fluorene, a preparation method and application thereof. The structure of the 9-phenyl-9-pyrenyl fluorene is introduced to a pyrene efficient light emitting system. The material has the advantages of cheap raw materials and convenient synthetic method, inhibits exciplex and excimer due to chromophore aggregation, and has strong hole injection capability, hole transport capability and electronic transmission capability. Therefore, the device technology can be simplified. Electroluminescent devices prepared by the material obtain a satisfactory result in brightness, luminous efficiency, voltage resistance stability, etc. The material can be widely applied to the fields of organic electronics, such as organic electroluminescent materials, organic integrated circuits, organic solar cells, organic field effect pipes, dye lasers, organic non-linear optical materials, fluorescent probes, etc.
Description
Technical field
The invention belongs to photoelectric material and applied technical field, be specifically related to-class 9-phenyl-conjugated ramification material of the pyrene that 9-pyrenyl fluorenes replaces and preparation method thereof, 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 (OLED[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.; Bum, 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.These all advantages are that inorganic semiconductor material is incomparable, have 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.Pyrene is owing to there being big conjugation aromatic nucleus to have the characteristics of high fluorescence efficiency, but also just because of this big two dimensional structure, cause chromophoric group to be assembled and generation excimer and exciplex easily, make original well blue light material efficient reduce like this, the emission wavelength red shift occurs, broaden.Therefore the present invention suppresses the chromophoric group gathering to obtain high thermal stability by introducing 9-phenyl-9-pyrenyl fluorene group, is used to improve the hole injectability simultaneously.The material of this structure also has the good electron transmittability except having good cavity transmission ability.Up to the present, there is no pertinent literature and patent report at home and abroad.
At OFET, the conjugated ramification material of the pyrene that organic solar batteries and organic laser field 9-phenyl-9-pyrenyl fluorenes replaces also shows high carrier transmission performance and high luminous efficiency simultaneously.
Summary of the invention
The objective of the invention is to propose a kind of luminescent material that is used for high-level efficiency long lifetime OLED device and its production and application.
The present invention is incorporated into 9-phenyl-9-pyrenyl fluorenes in the aromatic structure of this big plane of pyrene ring, considers the synthetic high performance organic photoelectrical material that has from material modification and two angles of electronic structure modulation.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 idol chain reaction to synthesize the conjugated ramification material of the pyrene of a class 9-phenyl-9-pyrenyl fluorenes replacement, and the molecular structure of compound is as follows.
General structure one general structure two
Wherein, A is (9-phenyl-9-pyrenyl) fluorenyl or (spiral shell-9-phenyl-9-pyrenyl) fluorenyl, and wherein fluorenyl is single replacement the (fluorenes 2) or two replacement (fluorenes 2 and 7); B is hydrogen atom or pyrenyl (1 single replacement).Be the typical material of material of the present invention below:
(1) for general structure one
1. get A and be (9-phenyl-9-pyrenyl) fluorenyl (the single replacement), when B was hydrogen, structure was as follows:
Compound I, Mw:642.8
2. getting A is (9-phenyl-9-pyrenyl) fluorenyl (two replacement), and when B was pyrenyl, structure was as follows:
Compound I I, Mw:843.0
3. getting A is spiral shell-(9-phenyl-9-pyrenyl) fluorenyl (the single replacement), and when B was hydrogen, structure was as follows:
Compound III, Mw:640.8
4. getting A is spiral shell-(9-phenyl-9-pyrenyl) fluorenyl (two replacement), and when B was pyrenyl, structure was as follows:
Compound IV, Mw:841.0
(2) for general structure two
1. getting A is spiral shell-(9-phenyl-9-pyrenyl) fluorenyl (the single replacement), and when pyrene was 2,7 two replacements, structure was as follows:
Compound V, Mw:1079.3
2. get A and be (9-phenyl-9-pyrenyl) fluorenyl (the single replacement), when pyrene was 2,7 two replacements, structure was as follows:
Compound VI, Mw:1083.3
3. get A and be spiral shell-(9-phenyl-9-pyrenyl) fluorenyl (the single replacement), when pyrene was 1,6 pair of replacement and 3,6 disubstituted mixtures, structure was as follows:
Compound VI I, Mw:1066.3
4. get A and be (9-phenyl-9-pyrenyl) fluorenyl (single replace), when pyrene was 1,6 pair of replacement and 3,6 disubstituted mixtures, structure was as follows:
* be another the position of substitution
Compound VIII, Mw:1070.3
The preparation method of above-claimed cpd adopts suzuki idol chain reaction:
M+N——→Target
Wherein M and N are two reacting precursors, and Target represents resulting target product.Suzuki idol chain reaction condition is: with two reacting precursor M, N, K
2CO
3(perhaps NaCO
3), the Ph (PPh of toluene and catalytic amount
3)
4Mix, reheat to temperature is 60～100 ℃, and the reaction times is 10～36 hours, reacts to be the anaerobic reaction, and lucifuge adds phase-transfer catalyst productive rate is improved in the reaction.Reaction finishes the back and adds the water separatory, and extraction is purified with the method for recrystallization or column chromatography at last again.
For different compounds, difference is that precursor M and N's is synthetic different, specific as follows:
(1) preparation of Compound I and Compound I I:
It respectively becomes route as follows:
Wherein, step (i) bromobenzene generates grignard reagent (phenyl-magnesium-bromide), same then Fluorenone (2-bromine Fluorenone or 2 with magnesium under the anhydrous and oxygen-free condition, the 7-dibromo fluorenone) reaction generates corresponding form magnesium salts, time is 4～6 hours, with the magnesium salts acidifying that generates, obtains compound 11 at last; Step (ii) prepares precursor M, fluorenol under acid catalysis and the Friedel-Craft of excessive pyrene reaction, be specially the dissolved fluorenol is splashed in the solution of excessive pyrene (〉=2 equivalent), add acid (for avoiding by product, preferably≤1 equivalent), be warming up to 40～80 ℃, reaction times is 10～30 minutes, promptly get two precursor M after separating purification, when X got H, precursor M was 12a; When X got Br, precursor M was 12b; Step (iii) prepares precursor N, i.e. the pyrene boric acid ester.With a normal NBS reagent bromination pyrene (the direct bromination of bromine also can, but will note controlling rate of addition, otherwise generate many brominations pyrene); By butyllithium displacement lithiumation halogen atom, be reflected under-78 degree and carry out; Add methyl-borate or boric acid isopropyl ester reaction 15～30 hours, use acid hydrolysis again, then generate corresponding pyrene boric acid, promptly get precursor N with the pure esterification of sheet then; Perhaps behind butyllithium displacement lithiumation halogen atom, directly add corresponding boric acid ester and also can obtain precursor N, be designated as compound 13; The method that step (iv) adopts is the reaction of Suzuki, the amount ratio of two precursor substances of preparation Compound I is compound 12a: compound 13=1: 0.8～1.2 (compound 12a or 13 consumption increases can be so that productive rate improve, but wastage of material some), the reactant ratio of preparation Compound I I is compound 12b: compound 13=1: 2～2.2 (compound 13 consumption increases can be so that productive rate improves, but wastage of material some).
(2) preparation of compound III and compound IV:
The synthetic route of precursor M is as follows:
Wherein, step: (i) pyrene boric acid ester (being compound 13) is with excessive 1, and 2-dibromobenzene (＞1 equivalent) is by suzuki reacting generating compound 22; Step (ii) uses lithiation reagent (the most frequently used is butyllithium) lithiated compound 22 to react 40～120 minutes down at-78 ℃, generates corresponding lithium salts 23; Step (iii) lithium salts 23 same Fluorenones (2-bromine Fluorenone or 2,7-dibromo fluorenone) was reacted 50～90 minutes, and acidifying then generates corresponding fluorenol 24; Step (iv) issues intercrescence ring reaction (being actually the Friedel-Craft reaction) in acid catalysis at last and generates precursor M, be that (simple operation is that fluorenol 24 is dissolved in the Glacial acetic acid to compound 25, be heated to 90～110 ℃ then, splash into hydrochloric acid, restir obtained the cyclization product in 1～5 hour).Wherein, when X got H, precursor M was 25a; When X got Br, precursor M was 25b, and precursor N still is a compound 13;
Adopt the Suzuki reaction when synthesizing target product, when synthetic compound III, the amount of substance ratio is compound 25a: compound 13=1: 0.8～1.2: during synthetic compound IV, the amount of substance ratio is compound 25b: compound 13=1: 2.0～2.2.
(3) compound V and compound VI is synthetic:
The synthetic route of precursor N is as follows:
Wherein, intermediate 31 synthetic has two kinds of ways, and first kind is to be generated under aluminum chloride-catalyzed by biphenyl and ethylene dichloride, 20～50 minutes reaction times, 40～70 ℃ of temperature of reaction (Friedel-Craft reaction); Second kind is the catalytic hydrogenation of pyrene (Pd/C is a catalyzer), room temperature reaction, and the time is 20～30 minutes.Bromination obtains intermediate 32 then, and catalyzer adopts anhydrous FeCl
3, equivalent is 1～10% of a reactant, 1～4 hour reaction times; (the 1mmol bromine is dissolved in dithiocarbonic anhydride 20～60mL) cancellation hydrogen bromides and obtains 2,7-dibromo pyrene 33 to use bromine water again; Dibromo pyrene 33 is by butyllithium displacement lithiumation halogen atom (carrying out under-78 ℃), add at least 2 times of normal methyl-borates or boric acid isopropyl ester, reacted 15～30 hours, use acid hydrolysis again, then generate the two boric acid of corresponding pyrene, promptly get the two boric acid esters 34 of pyrene with the pure esterification of sheet then; Perhaps behind butyllithium displacement lithiumation halogen atom, directly add corresponding boric acid ester and also can obtain the two boric acid esters 34 of pyrene, the two boric acid esters 23 of pyrene are precursor N.
When precursor M is compound 25a, be compound 34 in the amount of substance ratio: compound 25a=1: 2.0～2.2, the Suzuki reaction conditions obtains compound V; When precursor M is compound 12a, be compound 34 in the amount of substance ratio: compound 12a=1: 2.0～2.2 o'clock, the Suzuki reaction conditions obtained compound VI.
(4) compound VI I, VIII's is synthetic:
The synthetic route of precursor N is as follows:
Wherein, accurate two normal NBS reagent or bromine water splash in the pyrene solution, the dropping time was greater than 2 (as 2-5) hours, at room temperature continue after dripping off to stir 2～6 hours, underpressure distillation removes and to desolvate (go back original reagent and remove unnecessary bromine as also need to add Sulfothiorine etc. with the direct bromination of bromine), recrystallization obtains 1 again, 6-dibromo pyrene and 1, the mixture of 8-dibromo pyrene (the two ratio is for being approximately 1: 1) 41; Compound 41 is by butyllithium displacement lithiumation halogen atom (carrying out under-78 ℃), add at least 2 times of normal methyl-borates or boric acid isopropyl ester reaction 15～30 hours, use acid hydrolysis again, then generate the two boric acid of corresponding pyrene, promptly get compound 42 with the pure esterification of sheet then; Perhaps behind butyllithium displacement lithiumation halogen atom, the boric acid ester that directly adds correspondence also can obtain compound is not had 42.Compound 42 is precursor N.
When precursor M is compound 25a, be compound 42 in the amount of substance ratio: compound 25a=1: 2.0～2.2 o'clock, the Suzuki reaction conditions obtained compound VI I; When precursor M is compound 12a, be compound 42 in the amount of substance ratio: compound 12a=1: 2.0～2.2 o'clock, the Suzuki reaction conditions obtained compound VIII.
Characterized the structure of material by nucleus magnetic resonance (NMR), chromaticness online (GC-MS), laser parsing time-of-fight mass spectrometry (LDI-TOF-MS), gel chromatography (GPC), tested the thermostability of material by thermogravimetric analysis and differential thermal analysis, measure its spectral quality by ultraviolet and fluorometric analysis, characterized their electrochemical properties by cyclic voltammetry.
On this basis, the various light emission behaviors of device have been designed with the conjugated ramification material of evaluation 9-phenyl-pyrene that 9-pyrenyl fluorenes replaces.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, and the vacuum evaporation hole is injected and transport material on conductive layer then, and the compound among evaporation the present invention is as luminescent layer or doped body material, evaporation one deck electron transfer layer again, last evaporation negative electrode.Experimental result shows: the conjugated ramification material of the pyrene that 9-phenyl-9-pyrenyl fluorenes replaces can be used as current carrier injection and transport material, luminescent material and white light and the phosphorescent light body material of high comprehensive performance.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:
1, synthesis technique is simple, and the raw material cheapness is therefore with low cost.
2, because the existence of this big conjugation aromatic nucleus of pyrene has improved the injection and the transmittability in hole effectively, also improve device efficiency simultaneously, and may be used for current carrier injection or transport layer material.
3, pass through to introduce 9-phenyl-9-pyrenyl fluorenes unit, thereby improved the thermostability of this big aromatic nucleus of pyrene, also avoided their easy crystallization, generate the shortcoming of excimer and exciplex easily.Thereby make the high stability of 9 diaryl substituted fluorenes and the efficientibility of the big aromatic nucleus of pyrene be able to combination.
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. 1,2P9PPF absorption and photoluminescence spectrum, and solid luminescence spectrum.
The absorption of Fig. 2, DPPPF and photoluminescence spectra, and solid luminescence spectrum.
Fig. 3, device ITO/TCTA (8nm)/2P9PPF (30nm) or DPPPF (30nm)/BCP (40nm)/Mg:Ag (d1, performance d2).Wherein, current efficiency-current density c a) voltage-brightness curve b)) power efficiency-current density.
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 embodiment do not limit the present invention.
Synthesizing of embodiment 1:2-pyrenyl-9-phenyl-9-pyrenyl fluorenes (2P9PPF) (Compound I).
(1) Synthetic 2-bromo-9-phenyl fluorenes-9-alcohol (2-Bromo-9-phenyl-fluoren-9-ol)
With magnesium chips (0.58g, 24mmol), the stupid ((4.48g of a spot of iodine and bromine, 29mmol) make the phenyl-magnesium-bromide grignard reagent at anhydrous diethyl ether (perhaps anhydrous tetrahydro furan) in (30mL), this reagent will be dissolved with 2-bromine Fluorenone (3.77g then with the dilution of 20mL anhydrous diethyl ether, 14.6mmol) anhydrous tetrahydro furan, splash in the grignard reagent, 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 (4.65g, 13.8mmol), productive rate 94%) with ethyl acetate/petroleum ether=10: 1 as eluent column chromatography on silica gel.
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，70?eV)：Calcd.for?C
19H
13 79BrO?336.01，found?336；Calcd.for?C
19H
13 81BrO?338.01，found?338.
(2) Synthetic 2-bromo-9-phenyl-9-pyrenyl fluorenes (2-bromo-9-pheny1-9-pyrenylfluorene)
With pyrene (6g, 30mmol) and trifluoromethane semi-annular jade pendant acid (6.0mmol) be dissolved in the 200mL chloroform, (system is warming up to 60 ℃ and stirred 20 minutes for 2.0g, 6mmol) splashing in the system dropwise will to be dissolved in 2-bromo-9-phenyl fluorenes-9-alcohol in the chloroform then.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)：7.90-8.20(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.forC
35H
21 81Br?522.1，found?522.2.
(3) synthetic 1-(4,4,5,5-tetramethyl--1,3,2-dioxo boric acid ester-2-yl) pyrene (1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyrene)
(3.6g, DMF 20mmol) (150mL) solution dropwise splash into pyrene, and (8.1g is in DMF solution 40mmol) (250mL) with NBS, drip off back restir 2 hours, reaction system is used dichloromethane extraction after using the salt acid treatment, and water again with dichloromethane extraction several times.Except that desolvating, remove the initial point pigment with sherwood oil as the eluent column chromatography with underpressure distillation then.The crude product that obtains is dried through vacuum drying oven.This product is being dissolved among the anhydrous THF, is being cooled to-78 ℃, (25mL 40mmol) dropwise splashes into system with syringe with n-Butyl Lithium (cyclohexane solution of 1.6M).System-78 ℃ down reaction three methyl-borates after 2 hours (20g 190mmol), reacted 2 hours at-78 ℃ again, allowed system slowly rise to room temperature then reacted 36 hours again, added hydrochloric acid (300mL) hydrolysis 8 hours of 2M.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, 30 ℃ of vacuum-dryings.This product is dissolved in the methylene dichloride, and (23g 200mmol) refluxed 4 hours to add sheet alcohol.Revolve to steam to remove and desolvate, obtain product (3.6g, 55%) as the eluent column chromatography with petrol ether/ethyl acetate=(10: 1).
1HNMR(400MHz，CDCl3)δ(ppm)：9.10(d，J＝9.2Hz，1H)；8.56(d，J＝7.6Hz，1H)；8.25-7.98(m，7H)；1.51(s，12H).LDI-TOF-MS(m/z)：Calcd.for?C
22H
21 10BO
2?328.2，found?328.1；Calcd.forC
22H
21 11BO
2?329.2，found?329.1.
(4) Synthetic 2-pyrenyl-9-phenyl-9-pyrenyl fluorenes (2-pyrenyl-9-phenyl-9-pyrenylfluroene) (2P9PPF)
2-bromo-9-phenyl-9-pyrenyl fluorenes (0.78g, 1.5mmol), 1-(4,4,5,5-tetramethyl--1,3,2-dioxo boric acid ester-2-yl) (0.5g, 1.5mmol), four (triphenyl phosphorus) are changed palladium (0.05mmol) to pyrene and the 2M solution of potassium carbonate is blended in the flask that contains toluene 150mL.Reaction system is heated to 90 ℃ of reactions 48 hours.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 (0.75g, 78%) with sherwood oil/methylene dichloride=4: 1 as the eluent silica gel column chromatography.
1HNMR(400MHz，CDCl3)δ(ppm)：8.15(t，J＝9.2Hz，4H)；8.08-7.90(m，15H)；7.90-7.80(d，J＝8.0Hz，2H)；7.76-7.66(t，J＝9.2Hz，3H)；7.46(t，J＝7.6Hz)；7.40-7.30(m，3H)；7.30-7.18(m，2H).
13CNMR(400MHz，CDCl3)δ(ppm)：152.35，147.18，140.81，140.05，139.22，137.77，131.63，131.23，131.05，130.73，130.58，130.39，129.82，129.13，128.55，128.26，128.11，127.79，127.68，127.58，126.90，126.82，126.40，126.17，125.37，125.24，125.18，124.94，124.83，120.82，120.71，67.18.LDI-TOF-MS(m/z)：Calcd.for?C
51H
30?642.2，found?642.4.Anal.Calcd.C，95.30；H，4.70.found?C，95.25，H，4.62.
The chemical structural formula of 2P9PPF is as follows:
Compound I
Embodiment 2: to 9 ultra-violet absorption spectrums that contain the tripolymer 2P9PPF (product among the embodiment 1) of anthracene, pyrene fluorenes, and photoluminescence spectra, spectrum thermostability and quantum yield are measured:
2P9PPF is dissolved in the methylene dichloride dilute solution, 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 passing through of solid film forms drips of solution after solvent evaporates on the transparent glass sheet.The fluorescence quantum efficiency of solution be by in hexanaphthene 10
-69 of M, 10-dibenzanthracene solution (quantum yield is 0.9) is measured as standard.
2P9PPF solution is 351nm at the maximum absorption band greater than 300nm, and the photoluminescence spectra emission maximum is 408nm.
The maximum emission wavelength of solid film is 462nm.Under nitrogen atmosphere, spectrum does not have considerable change behind annealing 24h under 150 ℃ with solid film, and this explanation causes spectrum stability fine owing to thermal stability is good.Specifically see accompanying drawing 1.
Embodiment 3:2, the synthetic and spectrometry of 7-two pyrenyls-9-phenyl-9-pyrenyl fluorenes (DPPPF) (Compound I I).
The synthetic method of similar 2P9PPF can Synthetic 2,7-two pyrenyls-9-phenyl-9-pyrenyl fluorenes (DPPPF), just fluorenes will be with 2,7-dibromo fluorenes, during the idol chain reaction, 1-(4,4,5,5-tetramethyl--1,3,2-dioxo boric acid ester 2-yl) amount of pyrene should be greater than 2, two times of 7-two bromo-9-phenyl-9-pyrenyl fluorenes.
The NMR of DPPPF, MS and ultimate analysis data are as follows.
1H-NMR(400MHz，CDCl3)δ(ppm)：8.24-8.12(m，8H)；8.10-7.92(m，19H)；7.77(dd，J＝8.4Hz，1.6Hz，2H)；7.64(d，8.4Hz，2H)；7.46(s，2H)；7.34-7.28(s，3H)；7.27-7.22(m，2H).
13C-NMR(400MHz，CDCl3)δ(ppm)：152.80，140.92，139.04，137.75，131.63，131.06，130.76，130.62，129.27，128.56，128.48，127.85，127.60，126.98，126.57，126.18，125.37，125.28，125.04，124.98，124.88.LDl-TOF-MS(m/z)：Calcd.for?C
67H
38?842.3，found?842.2.Anal.Calcd.C，95.46；H，4.54；found?C，95.36；H，4.58.
Adopt the method for similar 2P9PPF can measure uv-absorbing and photoluminescence spectra.Photoluminescence spectra is that the maximum absorption wavelength (352nm) in uv-absorbing is measured down.
TPPF solution is 352nm at the maximum absorption band greater than 300nm, and the photoluminescence spectra emission maximum is 424nm.
The maximum emission wavelength of solid film is 450nm.Solid film under nitrogen atmosphere, was annealed 24 hours down at 150 ℃, and considerable change does not take place in spectrum, illustrates owing to thermal stability is good to cause spectrum stability fine.Specifically see accompanying drawing 2.
The structure of DPPPF is as follows:
Compound I I
The electroluminescent device preparation of embodiment 4:2P9PPF and DPPPF
Device architecture is ITO/TCTA (8nm)/2P9PPF or DPPPF (30nm)/BCP (40nm)/Mg:Ag.Concrete preparation method is 10
-4Under the pressure of pa, successively with 4,4 '; 4 "-three (N-carbazyl) triphenylamine (4,4', 4 "-tri (N-carbazolyl) triphenylamine) (TCTA); 2P9PPF or DPPPF, 2,9-dimethyl-4; 7-phenylbenzene-1; (2,9-dimethyl-4,7-diphenyl-1; 10-phenanthroline) (BCP) steam and go up the Mg:Ag alloy electrode 10-phenanthroline then.The device trigger voltage is respectively 4 and 3.5 V, high-high brightness～17000cd/m
2With～19000cd/m
2, maximum current efficient is greater than 2.0 and 2.5cd/A, and maximum power efficiency is greater than 0.6 and 0.9lm/w.Specifically see accompanying drawing 4.
Embodiment 5: Synthetic 2,7-two (9 '-phenyl-9 '-pyrenyl fluorenes-2-yl) pyrene (2,7-di (9 '-phenyl-9'-pyrenylfluoren-2-yl) pyrene) (compound VI).
(1) Synthetic 2,7-dibromo pyrene.2,7-two bromo-4,5,7, (4.41g, dithiocarbonic anhydride 12.1mmol) (300mL) solution dropwise splash into bromine, and (the dropping time, fire was in 3 hours for 4.26g, dithiocarbonic anhydride 26.6mmol) (300mL) solution for 9-tetrahydrochysene pyrene.Reaction system restir 1 hour.Distillation is removed solvent and is obtained product 4.3g, productive rate 99%.LDI-TOF-MASS：358。
(2) the two boric acid esters of synthetic pyrene, synthetic method is with pyrene list boric acid ester (seeing embodiment 1)
(3) even chain reaction prepares product: adopt 2-bromo-9-phenyl-9-pyrenyl fluorenes and the two boric acid esters of pyrene can obtain product by the Suzuki reaction.LDI-TOF-MASS：1083。
Compound VI
Compound III, IV, V, VII, the synthetic method of VIII all is similar to Compound I, II.Its spectrum property, all with compound I, II is similar for spectrum stability and electroluminescent properties.
Claims (4)
1, the conjugated ramification material of the pyrene of 9-phenyl-9-pyrenyl fluorenes replacement is characterized in that having a kind of of following general structure:
General structure one general structure two
Wherein, A is (9-phenyl-9-pyrenyl) fluorenyl or (spiral shell-9-phenyl-9-pyrenyl) fluorenyl, and wherein fluorenyl is 2 mono-substituted fluorenyls or 2 and 7 disubstituted fluorenyls; B is hydrogen atom or 1 mono-substituted pyrenyl.
2,, it is characterized in that having any in the following structure according to the said conjugated ramification material of claim 1:
(1) for general structure one
1. getting A is mono-substituted (9-phenyl-9-pyrenyl) fluorenyl, and when B was hydrogen, structure was as follows:
Compound I, Mw:642.8
2. getting A is disubstituted (9-phenyl-9-pyrenyl) fluorenyl, and when B was pyrenyl, structure was as follows:
Compound I I, Mw:843.0
3. getting A is mono-substituted spiral shell-(9-phenyl-9-pyrenyl) fluorenyl, and when B was hydrogen, structure was as follows:
Compound III, Mw:640.8
4. getting A is disubstituted spiral shell-(9-phenyl-9-pyrenyl) fluorenyl, and when B was pyrenyl, structure was as follows:
Compound IV, Mw:841.0
(2) for general structure two
1. getting A is mono-substituted spiral shell-(9-phenyl-9-pyrenyl) fluorenyl, and when pyrene was 2,7 two replacements, structure was as follows:
Compound V, Mw:1079.3
2. getting A is mono-substituted (9-phenyl-9-pyrenyl) fluorenyl, and when pyrene was 2,7 two replacements, structure was as follows:
Compound VI, Mw:1083.3
3. getting A is mono-substituted spiral shell-(9-phenyl-9-pyrenyl) fluorenyl, and when pyrene was 1,6 pair of replacement and 3,6 disubstituted mixtures, structure was as follows:
* be another the position of substitution
Compound VI I, Mw:1066.3
4. getting A is mono-substituted (9-phenyl-9-pyrenyl) fluorenyl, and when pyrene was 1,6 pair of replacement and 3,6 disubstituted mixtures, structure was as follows:
* be another the position of substitution
Compound VIII, Mw:1070.3
3, a kind of preparation method as claim 1 or 2 said conjugated ramification materials is characterized in that adopting suzuki idol chain reaction:
M+N→Target
Wherein M and N are two reacting precursors, and Target represents resulting target product, and Suzuki idol chain reaction condition is Ph (PPh
3)
4/ K
2CO
3Perhaps NaCO
3/ toluene, temperature of reaction are 60～100 ℃, and the reaction times is 10～36 hours, react to be anaerobic reaction, lucifuge; Wherein:
(1) preparation of Compound I and Compound I I:
Its preparation route is as follows:
Wherein, step (i) bromobenzene generates grignard reagent with magnesium under the anhydrous and oxygen-free condition, generates corresponding form magnesium salts with the Fluorenone reaction then, and the time is 4～6 hours, with the magnesium salts acidifying that generates, obtains compound 11 at last; Step (ii) prepares precursor M, fluorenol under acid catalysis and the Friedel-Craft of excessive pyrene reaction, be specially the dissolved fluorenol is splashed in the solution of excessive pyrene, add acid, be warming up to 40～80 ℃, the reaction times is 10～30 minutes, and separation promptly gets two precursor M after purifying, when X got H, precursor M was 12a; When X got Br, precursor M was 12b; Step (iii) prepares precursor N, and promptly the pyrene boric acid ester with a normal NBS reagent bromination pyrene, by butyllithium displacement lithiumation halogen atom, is reflected under-78 degree and carries out; Add methyl-borate or boric acid isopropyl ester reaction 15～30 hours, use acid hydrolysis again, then generate corresponding pyrene boric acid, promptly get precursor N with the pure esterification of sheet then; Perhaps behind butyllithium displacement lithiumation halogen atom, directly add corresponding boric acid ester and also can obtain precursor N, be designated as compound 13; Step (iv) adopts the reaction of Suzuki, and the amount ratio of two precursor substances of preparation Compound I is compound 12a: compound 13=1: 0.8～1.2, and the reactant ratio of preparation Compound I I is compound 12b: compound 13=1: 2～2.2;
(1) preparation of compound III and compound IV:
The synthetic route of precursor M is as follows:
Wherein, step (i) pyrene boric acid ester is with excessive 1, and the 2-dibromobenzene is by suzuki reacting generating compound 22; Step was (ii) reacted 40～120 minutes down at-78 ℃ with lithiation reagent lithiated compound 22, generated corresponding lithium salts 23; (iii) lithium salts 23 was with Fluorenone reaction 50～90 minutes for step, and acidifying then generates corresponding fluorenol 24; Step (iv) issues the reaction of intercrescence ring in acid catalysis at last and generates precursor M, and promptly compound 25; Wherein, when X got H, precursor M was 25a; When X got Br, precursor M was 25b, and precursor N still is a compound 13;
Adopt the Suzuki reaction, when synthetic compound III, the amount of substance ratio is compound 25a: compound 13=1: 0.8～1.2; During synthetic compound IV, the amount of substance ratio is compound 25b: compound 13=1: 2.0～2.2;
(3) compound V and compound VI is synthetic:
The synthetic route of precursor N is as follows:
Wherein, intermediate 31 synthetic has two kinds of ways, and first kind is to be generated under aluminum chloride-catalyzed by biphenyl and ethylene dichloride, 20～50 minutes reaction times, 40～70 ℃ of temperature of reaction; Second kind is the catalytic hydrogenation of pyrene, room temperature reaction, and the time is 20～30 minutes, and bromination obtains intermediate 32 then, and catalyzer adopts anhydrous FeCl
3, equivalent is 1～10% of a reactant, 1～4 hour reaction times; Obtain 2 with bromine water cancellation hydrogen bromide again, 7-dibromo pyrene 33; Dibromo pyrene 33 adds at least 2 times of normal methyl-borates or boric acid isopropyl ester by butyllithium displacement lithiumation halogen atom, reacts 15～30 hours, uses acid hydrolysis again, then generates the two boric acid of corresponding pyrene, promptly gets the two boric acid esters 34 of pyrene with the pure esterification of sheet then; Perhaps behind butyllithium displacement lithiumation halogen atom, directly add corresponding boric acid ester and also can obtain the two boric acid esters 34 of pyrene;
When precursor M is compound 25a, be compound 34 in the amount of substance ratio: compound 25a=1: 2.0～2.2, the Suzuki reaction conditions obtains compound V; When precursor M is compound 12a, be compound 34 in the amount of substance ratio: compound 12a=1: 2.0～2.2 o'clock, the Suzuki reaction conditions obtained compound VI;
(4) compound VI I, VIII's is synthetic:
The synthetic route of precursor N is as follows:
Wherein, accurate two normal NBS reagent or bromine water splash in the pyrene solution, and the dropping time at room temperature continued after dripping off to stir 2～6 hours greater than 2 hours, and underpressure distillation removes and desolvates, and recrystallization obtains 1 again, 6-dibromo pyrene and 1, the mixture 41 of 8-dibromo pyrene; Compound 41 adds at least 2 times of normal methyl-borates or boric acid isopropyl ester reaction 15～30 hours by butyllithium displacement lithiumation halogen atom, uses acid hydrolysis again, then generates the two boric acid of corresponding pyrene, promptly gets compound 42 with the pure esterification of sheet then; Perhaps behind butyllithium displacement lithiumation halogen atom, the boric acid ester that directly adds correspondence also can obtain compound is not had 42;
When precursor M is compound 25a, be compound 42 in the amount of substance ratio: compound 25a=1: 2.0～2.2 o'clock, the Suzuki reaction conditions obtained compound VI I; When precursor M is compound 12a, be compound 42 in the amount of substance ratio: compound 12a=1: 2.0～2.2 o'clock, the Suzuki reaction conditions obtained compound VIII.
4, the application of conjugate derivative according to claim 1 and 2 is characterized in that material of main part, electronics or hole carrier transport material, organic integration circuit material, the organic laser material of material of main part, phosphorescence as organic electroluminescence device luminescent layer material, white light, semiconductor material, organic solar battery material and the organic non linear optical material of organic field-effect tube.
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