CN102229623A - Spirofluorene xanthene phosphine oxide electro-phosphorescent main materials and synthesis and application methods thereof - Google Patents
Spirofluorene xanthene phosphine oxide electro-phosphorescent main materials and synthesis and application methods thereof Download PDFInfo
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Abstract
The invention relates to spirofluorene xanthene phosphine oxide electro-phosphorescent main materials and synthesis and application methods thereof, belongs to the field of photoelectric material science and technology, and in particular relates to four spirofluorene xanthene organic phosphine oxide materials and application of the materials in the field of organic electronics such as organic electroluminescent materials, organic solar cells, organic field-effect tubes, dye laser, organic nonlinear optical materials, fluorescent probes and the like. The series of materials are obtained by introducing diphenyl phosphine oxide groups to the 2nd site, the 2nd and 7th sites, the 2nd' site and the 2nd' and 7th' sites of spirofluorene xanthene respectively. The series of compounds have good charge transfer performance, thermal stability and high triplet energy level (ET=-2.86eV), and can be used as main materials and applied in phosphorescent devices. When the series of compounds are applied in the organic electro-phosphorescent devices, the maximum external quantum efficiency is 10.78 percent and the maximum brightness is 8,582cd/m<2> in the blue phosphorescent device; and in the green phosphorescent device, the maximum external quantum efficiency is 19.1 percent, and the maximum brightness is 16,943cd/m<2>.
Description
Technical field
The invention belongs to field of organic electroluminescent materials.Be specifically related to diphenylphosphine oxygen series compound synthetic of a class spiral shell fluorenes xanthene, and this material is in the application in organic electroluminescent field.
Technical background
Delivered with organic fluorescence materials from Tang research group of Kodak in 1987 and to have made film-type organic electroluminescence device (Organic Light-emitting Diodes, OLED) since, organic flat pannel display becomes the demonstration product of the another generation marketization after liquid-crystal display.The advantage of OLED is to have luminous, wide viewing angle (reaching 170 °), reaction times fast (1 μ s magnitude), luminous efficiency height, operating voltage low (3～10V), thick ℃ of panel thin (less than 2mm).Therefore, develop the novel organic photoelectric information material of market potential and attracted the scientist of the different subjects of many domestic and international universities and the concern and the input of research institution and company with practicality.
According to the difference of luminous principle, organic electroluminescent can be divided into singlet fluorescence and triplet state phosphorescence.For phosphorescent glow, it can make the internal quantum of the fluorescence hotchpotch that generally is usually used in device be promoted to 100% by 25%.But phosphor material all is the title complex that is made of heavy metal atom usually, utilize the coupling of heavy atom intensive spin orbital to cause minimum triplet state to the transition of singlet state, make the exciton energy of singlet excited and triplet excited state can be used in luminous on.But phosphor material makes the phosphorescence quantum yield reduce because concentration quenching and triplet state-triplet state are buried in oblivion effect, therefore doped body material in the phosphorescence guest materials usually in the phosphorescence device.
The material of main part of report all is limited in the compound that comprises carbazole and silicon mostly at present.The shortcoming of these material of main parts is that triplet is low, and thermostability and morphological stability are low.For the material of main part 4,4 '-two (N-carbazole)-2 that generally uses at present, 2 '-biphenyl (CBP) is because the lower (E of triplet energy state
T=2.65eV), the energy passback from the object phosphor material to material of main part easily takes place, thereby reduced device efficiency, so be difficult for the material of main part as the blue phosphorescent material.The researchist has carried out chemically modified to CBP afterwards, makes its triplet bring up to 2.9～3.0eV.Triplet (the E of silicon-containing organic compound
T＞3.5eV), still, the thermostability and the morphological stability of above-mentioned these materials are relatively poor, its T
gTemperature lower (26～101 ℃).Therefore, because the existence of these shortcomings has limited these materials to a certain extent as the application of material of main part in device.And what deserves to be mentioned is that these material of main part great majority of having reported all are hole mobile materials, have material of main part report few relatively many of electronic transmission performance.The electronic transmission performance of material has significance for the performance of device.Phosphorus oxygen compounds has good electron transmission performance and higher triplet, is the material of main part of a class excellence.
As everyone knows, spiral shell fluorenes xanthene has luminous quantum efficiency and charge transport properties preferably, thermostability and morphological stability preferably.The triplet of entire compound will can be improved behind the diphenylphosphine oxygen groups introducing spiral shell fluorenes xanthene.The spiral shell fluorenes xanthene phosphorus oxygen compounds that obtains has higher triplet, charge transport properties preferably, and higher thermostability and morphological stability can be used as material of main part and are applied in the phosphorescence device.And one kettle way prepares very sophisticated reaction in the laboratory that spiral shell fluorenes xanthene is for we, the productive rate height, and method is simple, is synthetic the laying the foundation of spiral shell fluorenes xanthene phosphorus oxygen human subject material.
Summary of the invention
Technical problem: the objective of the invention is to propose spiral shell fluorenes xanthene phosphorus oxygen class electro-phosphorescent main body material and synthetic and methods for using them thereof.
Technical scheme: introduced the diphenylphosphine oxygen groups on the different positions that spiral shell fluorenes xanthene phosphorus oxygen class electro-phosphorescent main body material of the present invention is a spiral shell fluorenes xanthene, its constitutional features is as follows:
Wherein, R
1, R
2, R
3And R
4Be diphenylphosphine oxygen groups or H atom.
R
1Be the diphenylphosphine oxygen groups, and R
2, R
3And R
4Be the H atom, its structure is as follows:
R
1And R
2Be the diphenylphosphine oxygen groups, and R
3And R
4Be the H atom, its structure is as follows:
R
3Be the diphenylphosphine oxygen groups, and R
1, R
2And R
4Be the H atom, its structure is as follows:
R
3And R
4Be diphenylphosphine oxygen groups, R
1And R
2Be the H atom, its structure is as follows:
The concrete preparation process of preparation method of spiral shell fluorenes xanthene phosphorus oxygen class electro-phosphorescent main body material of the present invention is as follows:
The concrete preparation process of the preparation method of Compound I is as follows:
A. under 150 ℃, 10 times of normal phenol and 2-bromo-9-Fluorenone 1 reacted 2 hours under methanesulfonic catalysis, with silica gel column chromatography product were separated obtaining product 2 then;
B. be dissolved in the tetrahydrofuran (THF) 2, down carried out the halogen lithium exchange reactions 1 hour, formation lithium salts 3 with n-Butyl Lithium at-78 ℃;
C. under-78 ℃, diphenyl phosphorus chloride is added in the above-mentioned reaction system, low temperature reacted 1 hour down, at room temperature reacted 10 hours.Add the shrend reaction of going out then, and reactant is extracted, concentrate at last and obtain containing in the crude product product 4 with methylene dichloride;
D. the dissolving that spissated product added methylene chloride adds 2 times of normal hydrogen peroxide and carries out oxidation, reacts 10 hours, and product steams instrument and is spin-dried for the back and separates with column chromatography with revolving, product 5.
The concrete preparation process of the preparation method of Compound I I is as follows:
A. under 150 ℃, 10 times of normal phenol and 2,7-two bromo-9-Fluorenones 1 reacted 2 hours under methanesulfonic catalysis, with silica gel column chromatography product were separated obtaining product 2 then;
B. be dissolved in the tetrahydrofuran (THF) 2, down carried out the halogen lithium exchange reactions 1 hour, formation lithium salts 3 with n-Butyl Lithium at-78 ℃;
C. under-78 ℃, diphenyl phosphorus chloride is added in the above-mentioned reaction system, low temperature reacted 1 hour down, at room temperature reacted 10 hours.Add the shrend reaction of going out then, and reactant is extracted, concentrate at last and obtain containing in the crude product product 4 and product 5 with methylene dichloride
D. the dissolving that spissated product added methylene chloride adds 2 times of normal hydrogen peroxide and carries out oxidation, reacts 10 hours, and product steams instrument and is spin-dried for the back and separates with column chromatography with revolving, product 6 and product 7, its mass ratio is 10: 1.
The concrete preparation process of compound III and compound IV is as follows:
A. under 150 ℃, 10 times of normal phenol and 9-Fluorenone 1 reacted 2 hours under methanesulfonic catalysis, with silica gel column chromatography product were separated obtaining product 2 then;
B. be dissolved in the tetrahydrofuran (THF) 2, down carried out the halogen lithium exchange reactions 1 hour, formation lithium salts 3 with n-Butyl Lithium at-78 ℃;
C. under-78 ℃, diphenyl phosphorus chloride is added in the above-mentioned reaction system, low temperature reacted 1 hour down, at room temperature reacted 10 hours.Add the shrend reaction of going out then, and reactant is extracted, concentrate at last and obtain containing in the crude product product 4 and product 5 with methylene dichloride;
D. the dissolving that spissated product added methylene chloride adds 2 times of normal hydrogen peroxide and carries out oxidation, reacts 10 hours, and product steams instrument and is spin-dried for the back and separates with column chromatography with revolving, product 6 and product 7, its mass ratio is 1.5: 1.
This material of main part is used for organic electro-phosphorescent luminescent device, the structure of device is: transparent anode/hole injection layer/hole transmission layer/electronic barrier layer/material of main part and guest materials/hole blocking layer/electron transfer layer/electron injecting layer/negative electrode, luminescent layer is mixed by material of main part and metal ligand phosphor material and forms the material of main part of luminescent layer such as right 1 described compound.
The application method of spiral shell fluorenes xanthene phosphorus oxygen class electro-phosphorescent main body material of the present invention is, the structure of this device is in the organic electroluminescence blue phosphorescent device: transparent anode/hole injection layer/hole transmission layer/electronic barrier layer/material of main part and guest materials/hole blocking layer/electron transfer layer/electron injecting layer/negative electrode, luminescent layer is made up of material of main part and dopant material, the material of main part of luminescent layer such as right 1 described compound, guest materials is a metal complexes blue phosphorescent material.
The structure of this device is in the organic electroluminescence green phosphorescent device: transparent anode/hole injection layer/hole transmission layer/electronic barrier layer/material of main part and guest materials/hole blocking layer/electron transfer layer/electron injecting layer/negative electrode, luminescent layer is mixed by material of main part and metal ligand phosphor material and forms, the material of main part of luminescent layer such as right 1 described compound, guest materials is a metal complexes green phosphorescent material.
In the organic electroluminescence red phosphorescent device, the structure of this device is: transparent anode/hole injection layer/hole transmission layer/electronic barrier layer/material of main part and guest materials/hole blocking layer/electron transfer layer/electron injecting layer/negative electrode, luminescent layer is mixed by material of main part and metal ligand phosphor material and forms, the material of main part of luminescent layer such as right 1 described compound are the metal complexes red phosphorescence material.
Beneficial effect: on the basis that the synthetic one kettle way that is based upon spiral shell fluorenes xanthene of this series compound prepares, this synthetic method is simple, and raw materials cost is low, is fit to mass production.Expect target product from former, the whole piece synthetic route only was three steps, and therefore the phosphorus oxygen material of main parts for a large amount of synthetic spiral shell fluorenes xanthenes provide sufficient and necessary condition.For this material of suitability for industrialized production is laid a good foundation.On aspect the material property, the phosphorus oxygen material of main part of spiral shell fluorenes xanthene has high triplet energy state and good charge transport ability, has higher thermostability, for the preparation of organic electro phosphorescent device provides condition.
Description of drawings
Fig. 1 is the nuclear-magnetism H of 2-phenyl phosphorus oxygen-spiral shell fluorenes xanthene
1NMR
Fig. 2 is 2, the nuclear-magnetism H of the two phenyl phosphorus oxygen of 7--spiral shell fluorenes xanthene
1NMR
Fig. 3 is the nuclear-magnetism H of 2 '-phenyl phosphorus oxygen-spiral shell fluorenes xanthene
1NMR
Fig. 4 is the nuclear-magnetism H of 2 ', 7 '-two phenyl phosphorus oxygen-spiral shell fluorenes xanthene
1NMR
Fig. 5 is the ultra-violet absorption spectrum and the fluorescence emission spectrum of 2-phenyl phosphorus oxygen-spiral shell fluorenes xanthene
Fig. 6 is 2, the ultra-violet absorption spectrum and the fluorescence emission spectrum of the two phenyl phosphorus oxygen of 7--spiral shell fluorenes xanthene
Fig. 7 is the ultra-violet absorption spectrum and the fluorescence emission spectrum of 2 '-phenyl phosphorus oxygen-spiral shell fluorenes xanthene
Fig. 8 is the ultra-violet absorption spectrum and the fluorescence emission spectrum of 2 ' 7 '-two phenyl phosphorus oxygen-spiral shell fluorenes xanthene
Fig. 9 is spiral shell fluorenes xanthene phosphorus oxygen prepares the phosphorescence device as material of main part device architecture figure
Figure 10 is the green glow phosphorescence device electroluminescent spectrum figure of spiral shell fluorenes xanthene phosphorus oxygen
Figure 11 is the voltage-brightness curve of the green glow phosphorescence device of spiral shell fluorenes xanthene phosphorus oxygen
Figure 12 is the brightness-external quantum efficiency curve of the green glow phosphorescence device of spiral shell fluorenes xanthene phosphorus oxygen
Figure 13 is the blue light phosphorescence device electroluminescent spectrum figure of spiral shell fluorenes xanthene phosphorus oxygen
Figure 14 is the voltage-brightness curve of the blue light phosphorescence device of spiral shell fluorenes xanthene phosphorus oxygen
Figure 15 is the brightness-external quantum efficiency curve of the blue light phosphorescence device of spiral shell fluorenes xanthene phosphorus oxygen
Embodiment:
Spiral shell fluorenes xanthene phosphorus oxygen human subject material of the present invention has following general structure:
R
1, R
2, R
3And R
4Be diphenylphosphine oxygen groups or H atom
Above-claimed cpd of the present invention is following four kinds:
R
1Be diphenylphosphine oxygen groups, R
2, R
3And R
4Be the H atom, its structure is as follows:
R
1And R
2Be diphenylphosphine oxygen groups, R
3And R
4Be the H atom, its structure is as follows:
R
3Be diphenylphosphine oxygen groups, R
1, R
2And R
4Be the H atom, its structure is as follows:
R
3And R
4Be diphenylphosphine oxygen groups, R
1And R
2Be the H atom, its structure is as follows:
(1) 2,7-two bromo-spiral shell fluorenes xanthenes or 2 ' 7 '-two bromo-spiral shell fluorenes xanthenes are monomeric synthetic
The preparation method who utilizes the one kettle way volution is (as document: Org.Lett.2006 (8); 2787-2790); under protection of inert gas; with 10 times of normal phenol (or p bromophenol) with 1 times normal 2; 7-two bromo-9-Fluorenones (or 9-Fluorenone) are under 150 ℃ of conditions; and then add 4 times of normal methanesulfonics and carry out catalysis, reacted 12 hours.Obtain monomeric products through silica gel column chromatography.
(2) organo phosphorous compounds of spiral shell fluorenes xanthene is synthetic
Under protection of inert gas; 1 times of normal reactant (bromated spiral shell fluorenes xanthene) is dissolved in the tetrahydrofuran solution (THF) and carries out; (78 ℃) slowly drip 1.5 times of normal n-Butyl Lithiums at low temperatures; utilize n-Butyl Lithium and reactant (bromated spiral shell fluorenes xanthene) to carry out the exchange of halogen lithium; make spiral shell fluorenes xanthene form lithium salts; (78 ℃) reaction is 3 hours then at low temperatures; (78 ℃) add the lithium salts reaction of diphenyl phosphorus chloride and spiral shell fluorenes xanthene at last at low temperatures, generate the product of spiral shell fluorenes xanthene phenyl phosphorus.The crude product product can directly carry out next step reaction through dichloromethane extraction and drying.
(3) the phosphorus oxygen material of main part of spiral shell fluorenes xanthene is synthetic
Utilizing the crude product of the organo phosphorous compounds that obtains containing spiral shell fluorenes xanthene in (two) is raw material, under 0 ℃, adds hydrogen peroxide (30%) (5 times of equivalents) and carries out oxidizing reaction, makes 3 valency phosphorus oxidations become 5 valencys, obtains containing the crude product of diphenylphosphine oxygen.Crude product separates the pure product that obtain through silica gel column chromatography.
Application method, this material of main part is used for organic electro-phosphorescent luminescent device, and the structure of device is: transparent anode/hole injection layer/hole transmission layer/electronic barrier layer/material of main part and guest materials/hole blocking layer/electron transfer layer/electron injecting layer/negative electrode.
Wherein organic electroluminescence blue phosphorescent device architecture is: transparent anode/hole injection layer/hole transmission layer/electronic barrier layer/material of main part and guest materials/hole blocking layer/electron transfer layer/electron injecting layer/negative electrode, luminescent layer is mixed by material of main part and metal ligand phosphor material and forms, the material of main part of luminescent layer compound as claimed in claim 1, guest materials are the blue light metal complexes.
Wherein organic electroluminescence green phosphorescent luminescent device structure is: transparent anode/hole injection layer/hole transmission layer/electronic barrier layer/material of main part and guest materials/hole blocking layer/electron transfer layer/electron injecting layer/negative electrode, luminescent layer is mixed by material of main part and metal ligand phosphor material and forms, the material of main part of luminescent layer compound as claimed in claim 1, guest materials are metal complexes green phosphorescent material.
Wherein organic electroluminescence red phosphorescent device architecture is: transparent anode/hole injection layer/hole transmission layer/electronic barrier layer/material of main part and guest materials/hole blocking layer/electron transfer layer/electron injecting layer/negative electrode, luminescent layer is made up of material of main part and dopant material, the material of main part of luminescent layer compound as claimed in claim 1, guest materials are the metal complexes red phosphorescence material.
Relevant characterization: by nucleus magnetic resonance (NMR), gas chromatograph-mass spectrometer (GC-MS), electrospray ionization mass spectrum (MSI) is characterized phosphorus oxygen material of main part structure; By ultra-violet absorption spectrum (UV), fluorescence emission spectrum (PL), electrochemical analyser (CV), thermogravimetric (DTG) and differential thermal (DSC) characterize carry out the optical physics characteristic and the stability etc. of material.
Synthesizing of above-claimed cpd:
Embodiment 1:
(1) 2-bromo-spiral shell fluorenes xanthene is synthetic
With exsiccant 2-bromine Fluorenone (5.0g, 19.3mmol), phenol (18.2g, 192.8mmol) and methanesulfonic (5mL, 77.2mmol) join together in two mouthfuls of round-bottomed flasks that magneton is housed, install spherical condensation tube additional, closed system, lucifuge, substitute nitrogen 3 times, place oil bath pan, be warming up to 150 ℃, reacted 5 hours.When reaction finishes, add entry (200mL) and stir.(7.7g 192.8mmol) regulates pH value to alkalescence, and suction filtration obtains solid crude product to add sodium hydroxide.Crude product is done leacheate drip washing through silica gel column chromatography with sherwood oil, obtains white solid product (4.8g).Productive rate is 60%.
1H?NMR(400MHz，CDCl
3，ppm)δ：7.783-7.763(d，8.0Hz，1H)，7.667-7.646(d，8.4Hz，1H)，7.5-7.475(d，8.0Hz，1H)，7.406-7.366(t，7.6Hz，1H)，7.285-7.265(d，8.0Hz，1H)，7.246-7.19(m，5H)，7.169-7.15(d，7.6Hz，1H)，6.819-6.779(t，2H)，6.408-6.385(d，7.6Hz，2H).
13CNMR(75MHz，CDCl
3)δ：157.175，154.91，151.466，138.928，138.748，131.329，129.173，129.063，128.623，128.276，128.086，126.05，124.181，123.617，122.118，121.578，120.217，117.161，54.458.m.p.：255℃.GC-MS(EI-m/z)：410[M
+].
(2) 2-diphenylphosphine-spiral shell fluorenes xanthene is synthetic
(2.0g 4.86mmol) joins in dry two mouthfuls of round-bottomed flasks crossing, and closed system immediately adds purified tetrahydrofuran (THF) (50mL) sample dissolution after substituting nitrogen 3 times again to get dried 2-bromo-spiral shell fluorenes xanthene.System is placed (dry ice acetone under the cold condition,-78 ℃), lowered the temperature 10 minutes, slowly drip n-Butyl Lithium hexane solution (4.6mL then, 7.3mmol, 1.6M), after dropwising, low temperature reacted 30 minutes down, having lithium salts forms, at low temperatures (78 ℃) (0.9mL 7.3mmol) splashes in the system, and reaction is spent the night with diphenyl phosphorus chloride.Aftertreatment adds entry (50mL) cancellation, ethyl acetate extraction (30mL * 3), and anhydrous sodium sulfate drying, suction filtration, filtrate is revolved inspissation and is contracted.Obtain the faint yellow solid crude product, stand-by.
(3) 2-diphenylphosphine oxygen-spiral shell fluorenes xanthene (SFX2PO) is synthetic
The crude product of 2-diphenylphosphine-spiral shell fluorenes xanthene is placed in the round-bottomed flask, and with methylene dichloride (50mL) dissolving, (0 ℃) slowly drips hydrogen peroxide (1.7mL 14.6mmol), reacted 10 hours under the ice bath.Aftertreatment is spin-dried for product, and put into vacuum drying oven and descended dry 2 hours at 60 ℃, then through the silica gel column chromatography sherwood oil: ethyl acetate=do leacheate drip washing at 1: 1, obtain white solid product (1.26g), productive rate is 50%.
1HNMR(400MHz，DMSO，ppm)δ：8.139(t，1H，2.16，7.76)，8.06(d，1H，7.6)，7.573-7.387(m，13H)，7.316(t，1H，7.5)，7.251(t，4H，8.0)，7.120(d，1H，7.598)，6.834(m，2H)，6.282(d，2H，7.568)，m.p.：258℃.GC-MS(EI-m/z)：532[M
+].
Synthesizing of (4) 2,7-two bromo-spiral shell fluorenes xanthenes
With exsiccant 2, and the 7-dibromo fluorenone (6g, 17.8mmol), phenol (16.7g, 177.5mmol), and methanesulfonic (4.6mL, 71.0mmol) join in two mouthfuls of round-bottomed flasks that magneton is housed, install spherical condensation tube additional, closed system, lucifuge, substitute nitrogen 3 times, place oil bath pan, be warming up to 150 ℃, reacted 5 hours.When reaction finishes, add entry (200mL) and stir.Add sodium hydroxide and regulate pH value to alkalescence, suction filtration obtains solid crude product.Crude product is done leacheate drip washing through silica gel column chromatography with sherwood oil, obtains white solid product (4.8g).Productive rate is 50%.
1H?NMR(400MHz，CDCl
3，ppm)δ：7.642-7.621(d，8.0Hz，2H)，7.514-7.49(d，8.0Hz，2H)，7.272-7.239(m，6H)，6.849-6.808(m，2H)，6.4-6.379(d，7.6Hz，2H)，m.p.：266℃.GC-MS(EI-m/z)：488[M
+].
Synthesizing of the two diphenylphosphines of (5) 2,7--spiral shell fluorenes xanthene
Get driedly 2, (3.0g 6.1mmol), joins in dry two mouthfuls of round-bottomed flasks crossing 7-two bromo-spiral shell fluorenes xanthenes, and closed system is substituted nitrogen 3 times immediately, adds purified tetrahydrofuran (THF) (70mL) sample dissolution.System is placed (dry ice acetone under the cold condition,-78 ℃), lowered the temperature 10 minutes, slowly drip n-Butyl Lithium hexane solution (5.7mL then, 9.2mmol, 1.6M), after dropwising, low temperature reacted 2 hours down, having lithium salts forms, at low temperatures (78 ℃) (1.1mL 9.2mmol) splashes in the system, and reaction is spent the night with diphenyl phosphorus chloride.Aftertreatment adds entry (70mL) quencher, ethyl acetate extraction (30mL * 3), and anhydrous sodium sulfate drying, suction filtration, filtrate is revolved inspissation and is contracted.Obtain the faint yellow solid crude product, stand-by.
(6) 2,7 pairs-diphenylphosphine oxygen-spiral shell fluorenes xanthene (SFX27PO) synthetic
With 2, the crude product of the two diphenylphosphines of 7--spiral shell fluorenes xanthene is placed in the round-bottomed flask, and with methylene dichloride (70mL) dissolving, (0 ℃) slowly drips hydrogen peroxide (2.1mL 18.3mmol), reacted 10 hours under the ice bath.Aftertreatment is spin-dried for product, puts into 60 ℃ of following dryings of vacuum drying oven 2 hours, then through the silica gel column chromatography sherwood oil: ethyl acetate: ethanol=do leacheate drip washing at 2: 2: 1, obtain white solid product (2.02g), productive rate is 47%.Need to prove in the column chromatography for separation process, contain a spot of 2-diphenylphosphine oxygen-spiral shell fluorenes xanthene in the gained by product,
1HNMR (400MHz, DMSO, ppm) δ: 8.225 (dd, 2H, 2.389Hz, 7.916Hz), 7.551-7.639 (m, 6H), 7.408-7.512 (m, 18H), and 7.248-7.269 (m, 4H), 6.847-6.887 (m, 2H), 6.314 (d, 2H, 7.58Hz) m.p.: greater than 300 ℃ of .ESI-MS:732[M
+]. need to prove: in the sepn process of 2,7 pairs-diphenylphosphine oxygen-spiral shell fluorenes xanthene, contain a spot of 2-diphenylphosphine oxygen-spiral shell fluorenes xanthene in the gained by product.
Synthesizing of (7) 2 ', 7 '-two bromo-spiral shell fluorenes xanthenes
With exsiccant 9-Fluorenone (5g, 27.8mmol), p bromophenol (24.7g, 138.7mmol), (7.21mL 110.9mmol) joins in two mouthfuls of round-bottomed flasks that magneton is housed, and installs spherical condensation tube additional to reach methanesulfonic, closed system, lucifuge is substituted nitrogen 3 times, places oil bath pan, be warming up to 150 ℃, reacted 5 hours.When reaction finishes, add entry (200mL) and stir.Add sodium hydroxide and regulate pH value to alkalescence, suction filtration obtains solid crude product.Crude product is done leacheate drip washing through silica gel column chromatography with sherwood oil, and obtaining white solid product (3.4g) productive rate is 30%.
1HNMR(400MHz，DMSO，ppm)δ：8.02(d，2H，7.618Hz)，7.434-7.491(m，4H)，7.321-7.281(t，4H，8.77Hz)，7.148(d，2H，7.56Hz)，6.265(d，2H，2.39Hz).m.p.：260，GC-MS(EI-m/z)：488[M
+].
Synthesizing of (8) 2 '-diphenylphosphines-spiral shell fluorenes xanthene and 2 ', 7 '-two diphenylphosphines-spiral shell fluorenes xanthene
(2.0g 4.1mmol), joins in dry two mouthfuls of round-bottomed flasks crossing, and closed system is substituted nitrogen 3 times immediately, adds purified tetrahydrofuran (THF) (70mL) sample dissolution to get dried 2 ', 7 '-two bromo-spiral shell fluorenes xanthenes.System is placed (dry ice acetone under the cold condition,-78 ℃), lowered the temperature 10 minutes, slowly drip n-Butyl Lithium hexane solution (3.8mL then, 6.1mmol, 1.6M), after dropwising, low temperature reacted 2 hours down, having lithium salts forms, at low temperatures (78 ℃) (0.7mL 6.1mmol) splashes in the system, and reaction is spent the night with diphenyl phosphorus chloride.Aftertreatment adds entry (70mL) quencher, ethyl acetate extraction (30mL * 3), and anhydrous sodium sulfate drying, suction filtration, filtrate is revolved inspissation and is contracted.Obtain the faint yellow solid crude product, stand-by.
(9) 2 '-diphenylphosphines oxygen-spiral shell fluorenes xanthene (SFX2 ' PO) and 2 ', 7 '-two diphenylphosphine oxygen-spiral shell fluorenes xanthene (SFX2 ' 7 ' PO) synthetic
The crude product that last step reaction is obtained is placed in the round-bottomed flask, and with methylene dichloride (70mL) dissolving, (0 ℃) slowly drips hydrogen peroxide (1.6mL 14.4mmol), reacted 10 hours under the ice bath.Aftertreatment is spin-dried for product, put into 60 ℃ of following dryings of vacuum drying oven 2 hours, then through the silica gel column chromatography sherwood oil: acetate second=do leacheate drip washing at 1: 1 obtains white solid product 2 '-diphenylphosphine oxygen-spiral shell fluorenes xanthene (0.7g), productive rate is (64%)
1HNMR (400MHz, DMSO, ppm) δ: 7.919 (d, 2H, 7.593), 7.519 (m, 2H, 1.32,7.40), 7.438 (m, 1H, 2.6,8.4), 7.41-7.36 (m, 6.5H), 7.34-7.28 (m, 6.8H), 7.23 (m, 2.3H, 1.08,7.67), 7.09 (d, 2H, 7.58), 6.89-6.85 (m, 1H), 6.608 (m, 1H, 1.9,10.25), (6.277 m, 1H, 1.43,7.83), m.p.:230 ℃ of .GC-MS (m/z): 532[M
+]., increase leacheate polarity, use sherwood oil: ethyl acetate: ethanol=do leacheate drip washing at 1: 2, obtain white solid product 2 ', 7 '-two diphenylphosphine oxygen-spiral shell fluorenes xanthene (0.4g), productive rate is 27%.1HNMR(400MHz，DMSO，ppm)δ：7.864(d，2H，7.6)，7.54-7.47(m，6H)，7.413-7.351(m，12H，7.324-7.277(m，8.5H)，7.229(m，2H，0.64，7.68)，7.13(d，2H，7.55)，6.613(m，2H，1.81，10.28)，m.p.：299℃.ESI-MS(m/z)：732[M+].
Example two: the ultra-violet absorption spectrum of (product among the embodiment 1), photoluminescence spectra, spectrum thermostability and quantum yield are measured
(1) SFX2PO 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 (312nm) 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 maximum absorption band of SFX2PO solution is 312nm, and the emission peak of fluorescence spectrum is 319nm and 332nm.The maximum emission wavelength of solid film is 369nm.Specifically see accompanying drawing 5.
(2) SFX27PO 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 (305nm) 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 maximum absorption band of SFX27PO solution is 305nm, and the emission peak of fluorescence spectrum is 364nm and 381nm.The maximum emission wavelength of solid film is 374nm.Specifically see accompanying drawing 6.
(3) SFX2 ' PO 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 (304nm) 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 maximum absorption band of SFX27PO solution is 304nm, and the emission peak of fluorescence spectrum is 310nm and 321nm.The maximum emission wavelength of solid film is 328nm.Specifically see accompanying drawing 7.
(4) SFX2 ' 7 ' PO 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 (304nm) 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 maximum absorption band of SFX27PO solution is 304nm, and the emission peak of fluorescence spectrum is 310nm and 321nm.The maximum emission wavelength of solid film is 325nm.Specifically see accompanying drawing 8.
Example three: SFX2PO, SFX27PO, the electro phosphorescent device preparation of SFX2 ' PO and SFX2 ' 7 ' PO
As scheme shown in the X, comprise the structure of phosphorescence device of the phosphorus oxygen material of main part of spiral shell fluorenes xanthene.Can comprise glass and conductive glass (ITO) substrate layer 1, hole injection layer 2 (molybdenum oxide MoO3), hole transmission layer 3 (m-MTDATA :), luminescent layer 4 (material of main part and object luminescent layer), electron transfer layer 5 (BPhen), electron injecting layer (KBH4), cathode layer (aluminium Al)
The structure of green phosphorescent device 1: ITO/MoOx (2nm)/m-MTDATA:MoOx (15wt.%, 30nm)/and m-MTDATA (10nm)/Ir (ppz) 3 (10nm)/SFX-2-dpop:Ir (ppy) 2 (acac) (6wt.%, 20nm)/BPhen (30nm)/KBH4 (1nm)
The structure of green phosphorescent device 2: ITO/MoOx (2nm)/m-MTDATA:MoOx (15wt.%, 30nm)/m-MTDATA (10nm)/Ir (ppz) 3 (10nm)/SFX-2,7-Didpop:Ir (ppy) 2 (acac) (6wt.%, 20nm)/BPhen (30nm)/KBH4 (1nm)
The structure of green phosphorescent device 3: ITO/MoOx (2nm)/m-MTDATA:MoOx (15wt.%, 30nm)/and m-MTDATA (10nm)/Ir (ppz) 3 (10nm)/SFX-2 '-dpop:Ir (ppy) 2 (acac) (6wt.%, 20nm)/BPhen (30nm)/KBH4 (1nm)
The structure of green phosphorescent device 4: ITO/MoOx (2nm)/m-MTDATA:MoOx (15wt.%, 30nm)/m-MTDATA (10nm)/Ir (ppz) 3 (10nm)/SFX-2 ', 7 '-Didpop:Ir (ppy) 2 (acac) (6wt.%, 20nm)/BPhen (30nm)/KBH4 (1nm)
The structure of blue phosphorescent device 1: ITO/MoOx (2nm)/m-MTDATA:MoOx (15wt.%, 30nm)/m-MTDATA (10nm)/Ir (ppz) 3 (10nm)/SFX-2-dpop:FIrpic (10wt.%, 20nm)/BPhen (20nm)/KBH4 (1nm)
The structure of blue phosphorescent device 2: ITO/MoOx (2nm)/m-MTDATA:MoOx (15wt.%, 30nm)/m-MTDATA (10nm)/Ir (ppz) 3 (10nm)/SFX-2,7-Didpop:FIrpic (10wt.%, 20
nm)/BPhen(20nm)/KBH4(1nm)
The structure of blue phosphorescent device 3: ITO/MoOx (2nm)/m-MTDATA:MoOx (15wt.%, 30nm)/m-MTDATA (10nm)/Ir (ppz) 3 (10nm)/SFX-2 '-dpop:FIrpic (10wt.%, 20nm)/BPhen (20nm)/KBH4 (1nm)
The structure of blue phosphorescent device 4: ITO/MoOx (2nm)/m-MTDATA:MoOx (15wt.%, 30nm)/m-MTDATA (10nm)/Ir (ppz) 3 (10nm)/SFX-2 ', 7 '-Didpop:FIrpic (10wt.%, 20nm)/BPhen (20nm)/KBH4 (1nm)
Claims (10)
1. spiral shell fluorenes xanthene phosphorus oxygen class electro-phosphorescent main body material is characterized in that such material is to have introduced the diphenylphosphine oxygen groups on the different positions of spiral shell fluorenes xanthene, and its constitutional features is as follows:
Wherein, R
1, R
2, R
3And R
4Be diphenylphosphine oxygen groups or H atom.
2. spiral shell fluorenes xanthene phosphorus oxygen class electro-phosphorescent main body material according to claim 1 is characterized in that R
1Be the diphenylphosphine oxygen groups, and R
2, R
3And R
4Be the H atom, its structure is as follows:
3. spiral shell fluorenes xanthene phosphorus oxygen class electro-phosphorescent main body material according to claim 1 is characterized in that R
1And R
2Be the diphenylphosphine oxygen groups, and R
3And R
4Be the H atom, its structure is as follows:
4. spiral shell fluorenes xanthene phosphorus oxygen class electro-phosphorescent main body material according to claim 1 is characterized in that R
3Be the diphenylphosphine oxygen groups, and R
1, R
2And R
4Be the H atom, its structure is as follows:
5. spiral shell fluorenes xanthene phosphorus oxygen class electro-phosphorescent main body material according to claim 1 is characterized in that R
3And R
4Be diphenylphosphine oxygen groups, R
1And R
2Be the H atom, its structure is as follows:
6. the preparation method of a spiral shell fluorenes xanthene phosphorus oxygen class electro-phosphorescent main body material as claimed in claim 2 is characterized in that the preparation method of Compound I, and concrete preparation process is as follows:
A. under 150 ℃, 10 times of normal phenol and 2-bromo-9-Fluorenone 1 reacted 2 hours under methanesulfonic catalysis, with silica gel column chromatography product were separated obtaining product 2 then;
B. be dissolved in the tetrahydrofuran (THF) 2, down carried out the halogen lithium exchange reactions 1 hour, formation lithium salts 3 with n-Butyl Lithium at-78 ℃;
C. under-78 ℃, diphenyl phosphorus chloride is added in the above-mentioned reaction system, low temperature reacted 1 hour down, at room temperature reacted 10 hours.Add the shrend reaction of going out then, and reactant is extracted, concentrate at last and obtain containing in the crude product product 4 with methylene dichloride;
D. the dissolving that spissated product added methylene chloride adds 2 times of normal hydrogen peroxide and carries out oxidation, reacts 10 hours, and product steams instrument and is spin-dried for the back and separates with column chromatography with revolving, product 5.
7. one kind as spiral shell fluorenes xanthene phosphorus oxygen class electro-phosphorescent main body material as described in the claim 3, it is characterized in that the concrete preparation process of preparation method of Compound I I is as follows:
A. under 150 ℃, 10 times of normal phenol and 2,7-two bromo-9-Fluorenones 1 reacted 2 hours under methanesulfonic catalysis, with silica gel column chromatography product were separated obtaining product 2 then;
B. be dissolved in the tetrahydrofuran (THF) 2, down carried out the halogen lithium exchange reactions 1 hour, formation lithium salts 3 with n-Butyl Lithium at-78 ℃;
C. under-78 ℃, diphenyl phosphorus chloride is added in the above-mentioned reaction system, low temperature reacted 1 hour down, at room temperature reacted 10 hours.Add the shrend reaction of going out then, and reactant is extracted, concentrate at last and obtain containing in the crude product product 4 and product 5 with methylene dichloride
D. the dissolving that spissated product added methylene chloride adds 2 times of normal hydrogen peroxide and carries out oxidation, reacts 10 hours, and product steams instrument and is spin-dried for the back and separates with column chromatography with revolving, product 6 and product 7, its mass ratio is 10: 1.
8. preparation method as spiral shell fluorenes xanthene phosphorus oxygen class electro-phosphorescent main body material as described in claim 3 or 4 is characterized in that the concrete preparation process of compound III and compound IV is as follows:
A. under 150 ℃, 10 times of normal phenol and 9-Fluorenone 1 reacted 2 hours under methanesulfonic catalysis, with silica gel column chromatography product were separated obtaining product 2 then;
B. be dissolved in the tetrahydrofuran (THF) 2, down carried out the halogen lithium exchange reactions 1 hour, formation lithium salts 3 with n-Butyl Lithium at-78 ℃;
C. under-78 ℃, diphenyl phosphorus chloride is added in the above-mentioned reaction system, low temperature reacted 1 hour down, at room temperature reacted 10 hours.Add the shrend reaction of going out then, and reactant is extracted, concentrate at last and obtain containing in the crude product product 4 and product 5 with methylene dichloride;
D. the dissolving that spissated product added methylene chloride adds 2 times of normal hydrogen peroxide and carries out oxidation, reacts 10 hours, and product steams instrument and is spin-dried for the back and separates with column chromatography with revolving, product 6 and product 7, its mass ratio is 1.5: 1.
9. the application method of a spiral shell fluorenes xanthene phosphorus oxygen class electro-phosphorescent main body material as claimed in claim 1, it is characterized in that this material of main part is used for organic electro-phosphorescent luminescent device, the structure of device is: transparent anode/hole injection layer/hole transmission layer/electronic barrier layer/material of main part and guest materials/hole blocking layer/electron transfer layer/electron injecting layer/negative electrode, luminescent layer is mixed by material of main part and metal ligand phosphor material and forms the material of main part of luminescent layer such as compound.
10. the application method of a spiral shell fluorenes xanthene phosphorus oxygen class electro-phosphorescent main body material as claimed in claim 7, it is characterized in that can be used as material of main part and metal complexes blueness or redness or green phosphorescent material and mix the back as the luminescent layer of organic electro phosphorescent device, the structure of device is: transparent anode/hole injection layer/hole transmission layer/electronic barrier layer/luminescent layer (material of main part and metal complexes blueness or redness or green phosphorescent material)/hole blocking layer/electron transfer layer/electron injecting layer/negative electrode.
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