CN1749254A - Double spiro material containing heteroaton and its synthetic method and use - Google Patents
Double spiro material containing heteroaton and its synthetic method and use Download PDFInfo
- Publication number
- CN1749254A CN1749254A CN 200510029333 CN200510029333A CN1749254A CN 1749254 A CN1749254 A CN 1749254A CN 200510029333 CN200510029333 CN 200510029333 CN 200510029333 A CN200510029333 A CN 200510029333A CN 1749254 A CN1749254 A CN 1749254A
- Authority
- CN
- China
- Prior art keywords
- compound
- chain
- organic
- during appearance
- compound iii
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The present invention belongs to the field of photoelectronic material technology, and is especially double spiro material containing hetero atom and its preparation process and application in organic plate display, photovoltaic cell, organic FET, laser and other organic electronics fields. The compounds are conjugate semiconductor material with double spiro structure introduced hetero atom. The double spiro material has the advantages of simple synthesis, capacity of further modification, effective realization of the photoelectronic property of modulation material, high heat stability, high vitrification point, etc. The material of the present invention may be used in producing photoluminescent device with satisfied brightness and light emitting efficiency, and has commercial application latent.
Description
Technical field
The invention belongs to the photoelectric material technical field.Be specifically related to a kind of double spiro material containing heteroaton and preparation method thereof, and relate to of the application of such material in fields such as organic electroluminescent, organic field-effect tube, organic solar batteries, nonlinear optics, bio-sensing and laser.
Technical background
From Tang research group of Kodak [Tang, C.W. in 1987; Van Slyke, S.A.Appl.Phys.Lett.1987,51,913.] and nineteen ninety univ cambridge uk [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.] delivered respectively make film-type organic electroluminescence device (Organic Light-emittingDiodes) and polymer LED (Polymeric Light-emitting Diodes) with organic and polymer fluorescent material since, organic flat pannel display becomes the demonstration product of the another generation marketization after liquid-crystal display.Meanwhile other organic electronics and photoelectronic industry comprise that field such as organic field-effect tube, organic solar batteries, nonlinear optics, bio-sensing and laser and nonlinear optical material are also just moving towards the marketization.Organic and the advantage plastic electronic product is that the material preparation cost is low, technology simple, has the snappiness and the plasticity-of commodity polymer.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.Up to the present, high stability carrier transmission material of development of new and luminescent material become and improve organic electronic, electric light and photoelectric device efficient and life-span key factor.
Up to the present, the bill of material that contains spiral shell two fluorene structured primitives reveals good optical and electrical properties, because such material has high thermostability and high second-order transition temperature simultaneously, therefore becomes a class practical organic optoelectronic material likely.Contain spiral shell two fluorene structured material systems and formed a large amount of articles and patent.Yet, because its full benzene structure has determined such material to have the problem of modulation electric minor structure difficulty.Therefore, how under the situation that guarantees the spiral shell structure, the heteroatoms composition is effectively introduced the key that becomes the adjustable high stable organic electronic material of preparation electronic structure.Up to the present, the double spiro material patent that contains based on full benzene structure is reported that but contains heteroatomic thiophene double spiro material system do not have article and patent report.Can keep the environmental stability of material and, also can effectively realize modulation in double spiro material in conjunction with the heteroatoms structure the material electronics textural property to the chromophoric obstructing capacity while.Therefore, the present invention has developed a series of novel heteroatomic double spiro materials that contain, and having introduced simultaneously to have increases solubleness, intercepts that chromophoric group is assembled or the structural chain that increases stability enlarges such material in organic electronic, photoelectron or photoelectric material use range.
Summary of the invention
The objective of the invention is to propose heteroatoms is introduced the method for double spiro material and derivant material thereof, heteroatomss such as oxygen, sulphur, nitrogen, silicon effectively can be introduced photoelectric material by this synthetic method design, obtain containing the heteroatomic pair of unitary compound-material of volution.In addition, the application of such material in organic electronic fields such as organic electroluminescent, organic field-effect tube and laser proposed.
The class that the present invention obtains contains the heteroatomic pair of unitary compound-material of volution, has following structure:
Compound I
Symbol in the formula and label have following implication:
R
1, R
2, R
3, R
4R
5, R
6, R
7, R
8R
9, R
10, R
11, R
12R
13, R
14, R
15, R
16, R
17, R
18Identical or different during appearance, and be hydrogen; Halogen; Or have straight chain, side chain or the cyclic alkyl chain of 1 to 22 carbon atom or have the structure of hindered amine chain, one or more non-conterminous carbon atom can be by-NR
19-,-O-,-S-,-CO-O-,-O-CO-O-,-CO-NR
19-,-NR
19-CO-NR
19-,-O-CO-S-,-NR
19-CO-O-,-CS-O-,-CS-NR
19-,-O-CS-O-,-NR
19-CS-NR
20-,-O-CS-S-,-NR
19-CS-O-,-CS-S-,-SiR
19R
20-displacement, perhaps one or more hydrogen atom is replaced by fluorine or cyano group; Or having alkenylene chain, alkynyl chain, the aryl chain of 2 to 40 carbon atoms, wherein one or more carbon atoms can be by heteroatoms Si, Se, O, S, N, S (O)
2Replace, the hydrogen on one or more carbon atoms can be replaced by fluorine or cyano group;
R
19, R
20Identical or different during appearance, and for do not express, hydrogen or have straight chain, side chain or the cyclic alkyl chain of 1 to 22 carbon atom or have the structure of hindered amine chain and oxyalkyl chain;
Ar
2, Ar
3, Ar
4, Ar
5, Ar
6, Ar
7Identical or different during appearance, and for having thiazolinyl, alkynyl, the aryl of 2 to 40 carbon atoms, wherein one or more carbon atoms can be by heteroatoms Si, Se, O, S, N, S (O)
2Replace, the hydrogen on one or more carbon atoms can be replaced by fluorine or cyano group; Wherein the aryl structure is specially a kind of in the following structure:
Symbol in the formula and label have following implication:
-
*Be spiral shell intra-annular Ar
2, Ar
3, Ar
4, Ar
5, Ar
6, Ar
7And the possible position that connects between the carbon of spiral shell center;
D
1, D
2, D
3Identical or different during appearance, and be CR
19R
20, NR
19,-O-,-S-,-Se-,-S (O)
2-or-SiR
19R
20-;
E
1, E
2, E
3, E
4, E
5, E
6Identical or different during appearance, and be CR
19, N, SiR
19
EG
1, EG
2, EG
3, EG
4, EG
5, EG
6Identical or different during appearance, and, comprise hydrogen, halogen, cyano group and conjugation group for forming the group of single chemical bond; Conjugation unit structure unit wherein has thiazolinyl, alkynyl, the aryl of 2 to 40 carbon atoms, and wherein one or more carbon atoms can be by heteroatoms Si, Se, O, S, N, S (O)
2Replace, the hydrogen on one or more carbon atoms can be replaced by fluorine or cyano group; Be specially a kind of in the following structure:
Symbol in the formula and label have following implication:
-
*Be EG between the structural unit
1, EG
2, EG
3, EG
4, EG
5, EG
6With Ar
2, Ar
3, Ar
4, Ar
5, Ar
6, Ar
7The band of position that connects; Greater than one-
*Representative can select arbitrarily one of them-
*As the connection between it;
D
1, D
2, D
3Identical or different during appearance, and be CR
19R
20, NR
19,-O-,-S-,-Se-,-S (O)
2-or-SiR
19R
20-;
E
1, E
2, E
3, E
4, E
5, E
6Identical or different during appearance, and be CR
19, N, SiR
19
AC
1, AC
2, AC
3, AC
4Identical or different during appearance, and be phenyl, indenyl, naphthyl, Azulene base, fluorenyl, phenanthryl, anthryl, pyrenyl, naphthalene embedding phenyl, thienyl, pyrryl, furyl, imidazolyl, thiazole, pyridyl, pyrazinyl, indyl, benzofuryl, benzothienyl, benzimidazolyl-, quinolyl, isoquinolyl, quinoxalinyl, carbazyl, phenanthrolene base; Or be alkyl, fluorine replacement, the oxidized derivatives of its structure.
E, f, identical or different when g occurs, and independently be 0,1,2,3,4,5,6,7,8,9 or 10;
Identical or different when W occurs, be selected from and contain substituent atom; And for not expressing or GeR
19R
20, CR
19R
20, NR
19,-O-,-S-,-Se-,-S (O)
2-,-SiR
19R
20
Be not expressed as and do not occur.
In Compound I, Ar
2, Ar
3, Ar
4, Ar
5, Ar
6, Ar
7Identical or different during appearance, and be preferably as follows a kind of in the structure:
In Compound I, EG
1, EG
2, EG
3, EG
4, EG
5, EG
6Identical or different during appearance, and be preferably as follows a kind of in the structure:
In Compound I, work as R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8R
9, R
10, R
11, R
12R
13, R
14, R
15, R
16, R
17, R
18Be selected from hydrogen, compound-material I is following structure:
Compound I I
In Compound I I, work as Ar
2, Ar
3, Ar
4, Ar
5, Ar
6, Ar
7All be phenyl during appearance or all be pyridyl that compound-material II is following structure:
Compound III A compound III B compound III C
Compound III E compound III F compound III G
Compound III H compound III J compound III K
Compound III L compound III M compound III N
In Compound I I, work as Ar
2, Ar
3, Ar
4, Ar
5, Ar
6, Ar
7All be thienyl during appearance, compound-material II is following structure:
Compound III O compound III P
Compound III Q compound III S
In compound-material I, work as R
1～R
16Identical or different during appearance, and when being hindered amine group, have following general formula (VI):
Each symbol implication specific as follows:
-
*Be hindered amine group structural unit and Ar
2, Ar
3, Ar
4, Ar
5, Ar
6, Ar
7The position that can connect;
X, Y are identical or different and are CR
19, or N;
Key between the X-Y is singly-bound or two key;
R
21, R
22, R
23, R
24For identical or different, and be H or straight chain, ring-type or collateralization alkyl and the alkoxyl group with 1 to 22 carbon atom, one or more non-conterminous carbon atom can be replaced by following connection base,
Perhaps one or more hydrogen atom can be replaced by fluorine; Perhaps R
21, R
22, R
23, R
24For identical or different, also for having alkylene, aryl and/or the aryloxy of 2 to 40 carbon atoms, one or more carbon atom can be by O, S or N displacement simultaneously; Perhaps the hydrogen on the carbon atom can be by one or more alkyl group R
19, halogen, cyano group or N (R
20)
2Replace;
R
25For identical or different, and be R
24Described structure or be oxyradical, hydroxyl, inferior oxygen base;
X, Y in its formula of (VI) structure can and R
24, R
25Connect into ring;
Nitrogen-atoms in its formula of (VI) structure can be electrically charged.
In the synthetic method of compound-material I, comprise that the synthetic route and all kinds of linked reaction that contain heteroatoms two spirane structure module prepare the material method.
Preparation contains heteroatomic two spirane structure modules such as oxygen, sulphur, nitrogen, silicon by following synthetic route:
Wherein, symbol in the formula and label have above-mentioned synonymous.
In the synthetic route, 1. step is the cyclization reaction conditions; 2. step is to prepare the tertiary alcohol by Grignard reagent or lithium reagent; 3. step comprises the halogenated method of various preparation aromatizes, as NBS/DMF, and Br
2/ trichloromethane, Br
2/ AC
2O etc.; 4. step is by Friedel-Craft reaction cyclization step, as HCl/ Glacial acetic acid, toluenesulphonic acids, BF
3/ Et
2Conditions such as O/ methylene dichloride.
In two spirane structure module synthetic route, method (1a) (1b), (1c), (1d) is two pure preparation methods of a step; Method (2a) (2b) is the single pure preparation method of multistep.
After having prepared heteroatomic two spirane structure modules such as containing oxygen, sulphur, nitrogen, silicon, can produce different reaction coupling group by electrophilic substitution reaction.
In the synthetic method of preparation compound-material I, also comprise C-C or carbon-heteroatoms linked reaction method, comprise Gilch, Witting, Ullmann, Stille, Suzuki, Yamamoto, Heck or Rieke transition metal palladium catalysis process; Comprise other ligations simultaneously by being undertaken by heterocycle Cheng Huan.
Wherein, the reactant of method (1) Suzuki linked reaction is aryl hypoboric acid and/or aryl dihalide and 2 equivalent aryl list halogenide and/or aryl list boric acid, and perhaps blended aromatic halides/boric acid is realized coupling with palladium catalyst; Catalyst consumption is for O.1 to 20mol%; Suitable solvent is low-pole or aprotic, polar organic solvent or its mixed solvent; Be reflected at 30 to 150 ℃ of temperature; Reaction times is 1 to 7 day;
Method (2) is the Stille linked reaction: reactant is dihalide and/or two stannates and single stannate and/or single halogenide herein, perhaps corresponding single halogenide-single stannate derivatives monomer is under alkaline condition and coupling under the condition that palladium catalyst and solvent exist;
Method (3) is the Yamamoto linked reaction: reactant is a halogenide; Under alkaline condition, under Ni (O) or Ni (II) or compound for catalysis and the solvent condition, react; Reaction conditions is Ni (COD)
2/ bpy/1,5-cyclooctadiene/DMF (COD=1,5-cyclooctadiene).
Oligomer and high polymer material structure have been characterized by ultimate analysis, infrared spectra (FTIR), nucleus magnetic resonance (NMR), chromaticness online (GCMS), ground substance assistant laser parsing time-of-fight mass spectrometry (MALDI-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.
Wherein contain the thermogravimetric analysis and the differential thermal analysis test of thiophene double spiro material, shown good thermostability, the thermostability that contains the two volution primitive structures of thiophene is greater than spiral shell two fluorene materials.The electrochemical properties that contains the cyclic voltammetry sign of the two volution primitives of thiophene shows that oxidation potential reduces greatly, effectively the injectability in the hole of improving; The blue light material that contains the two volutions of thiophene has kept high luminous efficiency.Therefore, such device of being made up of such material can the effective simplification device architecture, perhaps removes hole mobile material, perhaps removes electron transport material and can show as stable electrical electroluminescence device efficiently equally.The part material character is seen accompanying drawing.
Such compound-material also can be applied to the organic electronic fields such as organic semiconductor layer, solar-energy photo-voltaic cell, organic laser material and organic non linear optical material in the field effect transistor.Compound-material I is suitable for and makes plastic electronic material, photoelectron material; The device in plastic electronic field or element comprise polymkeric substance and organic light emitting diode device, organic solar batteries, organic laser diode component, organic field-effect tube, OTFT, organic integration circuit, bio-sensing device, nonlinear optical element etc.; Use transport material, interface injecting material, conductive material, photoelectric material, electro-conductive material, superconducting material, the off-color material that comprises as luminescent material, electronics and hole as organic electronic material.
One or more contain hindered amine group compound-material I and add use on a small quantity as the direct use of active material or as auxiliary agent; As promoter material mainly is the stabiliser materials and the optical brightener of heat, light, oxygen, wherein stabiliser materials can add in above-mentioned all kinds of organic electronics and the photoelectron material and general and engineering polymers material in; Add using amount ranges 0.01%～80% as auxiliary agent, is benchmark with the quality of active material.
In addition, on this basis, the various light emission behaviors that preliminary device is estimated the heteroatoms double spiro material have been designed.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 Subjective and Objective transmission ofenergy behavior and light amplification behavior design and study.Transparent anode is produced on on glass or the plastic, and vacuum evaporation hole mobile material on conductive layer then, the compound among evaporation or spin coating the present invention be as luminescent layer or doped body material, evaporation one deck electron transfer layer again, last evaporation negative electrode.Compound-material I is as OLED and PLED device material, wherein the structure of electroluminescent device is transparent anode/hole injection layer/hole transmission layer/electronic barrier layer/luminescent layer hole blocking layer/electron transfer layer/electron injecting layer/negative electrode, wherein except that anode and negative electrode, other each layer whiles or do not exist simultaneously are perhaps as the device of the material of main part of the material of main part of white light and phosphorescence.The device property test shows that heteroatoms double spiro material major advantage of the present invention is:
1. effectively modulate the electronic structure of spiro material by heteroatomic introducings such as sulphur, effectively improve the transmission and the injectability of current carrier, can prepare good individual layer or double-deck OLED and PLED device.
2. the high glass transition temperature and the high thermal stability that have kept spiral shell to keep are fluoridized two volutions and are had good evaporation performance.
3. effectively modulate fluorescence emission spectrum and triplet, thereby formed good material of main part.
4. the heteroatoms double spiro material has good electron transmission and hole barrier ability, is suitable for as transport material and OTFT material.
5. have tangible light amplification phenomenon, be suitable for as the organic laser material.
Description of drawings
Fig. 1. two volutions [9H-fluorenes-9,5 ' (7 ' H)-two indenes [2,1-b:1 ', 2 '-d] thiophene-7 ', 9 " and [9H] fluorenes] hot analysis and characterization.
Fig. 2 .2,7,2 ", 7 " four (9,9 '-spiral shell two fluorenes-2-yl)-two volutions [9H-fluorenes-9,5 ' (7 ' H)-two indenes [2,1-b:1 ', 2 '-d] thiophene-7 ', 9 " and [9H] fluorenes] the electrochemical analysis sign.
Fig. 3 .2,7,2 ", 7 " four (9,9 '-spiral shell two fluorenes-2-yl)-two volutions [9H-fluorenes-9,5 ' (7 ' H)-two indenes [2,1-b:1 ', 2 '-d] thiophene-7 ', 9 " and [9H] fluorenes] electroluminescent spectrum.
Embodiment
In order to understand the content of patent of the present invention better, further specify technical scheme of the present invention below by concrete example and legend, specifically comprise the preparation of synthetic, property testing and device.But these embodiments do not limit the present invention.
Embodiment 1, the two spirocyclic compound materials of thiophene:
Two spiral shells [9H-fluorenes-9,1 ' (3 ' H)-two indenes [2,1-b:1 ', 2 '-d] thiophene-3 ', 9 " and [9H] fluorenes]
Dispiro[9H-fluorene-9，1′(3′H)-diindeno[2，1-b：1′，2′-d]thiophene-3′，9″-[9H]fluorene]
3, the 4-diphenyl thiophene
3，4-diphenylthiophene
Under nitrogen atmosphere, get magnesium Mg bits (1equiv.) and a little I
2Mix, under 35 ℃ of degree, bromobenzene is slowly splashed into reaction flask, reaction backflow 20min; Cooling is reacted and is used transfer pipeline slowly to transfer to the Grignard reagent that forms and contains catalyst n i (dppp) Cl
2With 3, in the reaction flask of 4-dibromo thiophene, add and refluxed 24 hours, the frozen water dilution, extracted with diethyl ether, drying is revolved steaming, and sherwood oil silicagel column purifying obtains clear crystal (productive rate is 78.8%).
mp?115-116℃(lit.112-113℃)；
Ultimate analysis: C
16H
12S, observed value: C, 81.31; H, 5.12; S, 13.57; GC-MS (EI-m/z): 236.33 (M
+).
1H?NMR(400MHz，DMSO，ppm)：δ7.609(s，2H)，7.29-7.233(m，6H)，7.141-7.118(dd，J＝8.0Hz，4H).
13C?NMR(CDCl
3，ppm)：δ141.966，136.748，129.23，128.354，127.09，124.245.
2,5-two bromo-3,4-diphenyl thiophene
2，5-dibromo-3，4-diphenylthiophene
Under the condition of 0 ℃ and lucifuge, will be dissolved in DMF (abs., NBS 40mL) (10.4g, 58.4mmol) slowly be added drop-wise to be dissolved in DMF (abs., 40mL) 3,4-diphenyl thiophene (28.3mmol) after dropwising, is got back to room temperature, and reaction is spent the night.The frozen water dilution, extracted with diethyl ether, drying is revolved steaming, and ethyl alcohol recrystallization obtains clear crystal (productive rate is 91%).
mp?149℃；
FT-IR(KBr)：v＝3065w，3024w，1509m，1482m，1442m，1029m，997s，775s，764s，698s，608s?cm
-1；
1H?NMR(400MHz，DMSO，ppm)：δ7.276-7.247(m，6H)，7.072-7.049(m，4H).
13C?NMR(CDCl
3，ppm)：δ142.07，134.165，129.986，127.899，127.636，109.354；
EI-MS，m/z(％)：396(54)，394(100)[M
+]，392(51)，315(12)[M-Br]，314(14)，313(12)[M-Br]，312(12)，235(11)，234(60)[M-2Br]，232(10)，189(34)，117(28)，116(17)，95(12)；
C
16H
10Br
2S(394.1)：calc.C?48.76，H?2.56，S?8.14；found?C?48.71，H?2.57，S?8.17％。
Two volutions [9H-fluorenes-9,5 ' (7 ' H)-two indenes [2,1-b:1 ', 2 '-d] thiophene-7 ', 9 " and [9H] fluorenes]
Dispiro[fluorene-9，5′(7′H)-diindeno[2，1-b：1′，2′-d]thiophene-7′，9″-fluorene]
Get 2,5-two bromo-3,4-diphenyl thiophene (2.1mmol) and magnesium Mg0.1004g (4.2mmol) reaction generates Grignard reagent, and is dissolved in Fluorenone in the 16mL tetrahydrofuran (THF) (4.2mmol) 60 ℃ of reactions 24 hours, generate a large amount of white precipitates, add saturated colour NHCl at last
4Ge Shi salt is converted into alcohol.After reaction finishes, extracted with diethyl ether, drying is revolved steaming, sherwood oil: methylene dichloride mixed solvent (3: 2) silicagel column purifying obtains the slightly yellowish white solid tertiary alcohol (productive rate is 36%).Above-mentioned fluorenol is dissolved in the Glacial acetic acid, under 110 ℃ condition, drips several concentrated hydrochloric acid reactions and generated white precipitate in 10 minutes, add the more precipitations of water generates, filter, obtain white powder solid (productive rate is 91%) with tetrahydrofuran (THF) and sherwood oil recrystallization.
MALDI-TOF-MS:560 (M
+); Ultimate analysis: C42H24S, observed value: C, 90.27; H, 4.34; S, 5.76.
1H?NMR(400MHz，CDCl
3，ppm)：δ8.077-8.058(d，J＝7.6Hz，2H)，7.764-7.744(d，J＝8.0Hz，4H)，7.468-7.43(t，J＝7.2Hz，2H)，7.35-7.312(t，J＝7.6Hz，4H)，7.15-7.112(t，J＝7.2Hz，4H)，7.082-7.045(t，J＝7.6Hz，2H)，6.926-6.907(d，J＝7.2Hz，4H)，6.704-6.686(d，J＝8.0Hz，2H).
13C?NMR(CDCl
3，ppm)：154.906，152.819，147.49，141.621，139.638，139.011，128.27，128.168，127.874，125.863，124.094，123.946，120.894，120.311，64.938.
Embodiment 2, the two spirocyclic compound modules of tetrabromothiophene:
2,2 ", 7,7 "-tetrabromo-two volution [9H-fluorenes-9,5 ' (7 ' H)-two indenes [2,1-b:1 ', 2 '-d] thiophene-7 ', 9 "-[9H] fluorenes]
2，2”，7，7”-tetrabromo-dispiro[fluorene-9，5’(7’H)-diindeno[2，1-b：1’，2’-d]thiophene-7’，9”-fluorene]
Get 2,5-two bromo-3,4-diphenyl thiophene (2.1mmol) generates Grignard reagent with magnesium Mg0.1004g (4.2mmol) reaction, with be dissolved in the 16mL tetrahydrofuran (THF) 2,7-dibromo fluorenone (4.2mmol) generates a large amount of white precipitates 60 ℃ of reactions 24 hours, adds saturated colour NHCl at last
4Ge Shi salt is converted into alcohol.After reaction finishes, extracted with diethyl ether, drying is revolved steaming, sherwood oil: methylene dichloride mixed solvent (4: 1) silicagel column purifying obtains the slightly yellowish white solid tertiary alcohol (productive rate is 34%).Above-mentioned fluorenol is dissolved in the Glacial acetic acid, under 110 ℃ condition, drips several concentrated hydrochloric acid reactions and generated white precipitate in 10 minutes, add the more precipitations of water generates, filter, obtain white powder solid (productive rate is 88.1%) with tetrahydrofuran (THF) and sherwood oil recrystallization.
MALDI-TOF-MS:871.8 (M
+); Ultimate analysis: C
42H
20Br
4O
2S, observed value: C, 57.79; H, 2.30; S, 3.74.
Embodiment 3, the two spirocyclic compound modules of dibromo thiophene:
2,2 " two bromo-, two volutions [9H-fluorenes-9,5 ' (7 ' H)-two indenes [and 2,1-b:1 ', 2 '-d] thiophene-7 ', 9 " [9H] fluorenes]
2，2″-dibromo-dispiro[fluorene-9，5′(7′H)-diindeno[2，1-b：1′，2′-d]thiophene-7′，9″-fluorene]
Get 2,5-two bromo-3,4-diphenyl thiophene (2.1mmol) and magnesium Mg0.1004g (4.2mmol) reaction generates Grignard reagent, and is dissolved in the 16mL tetrahydrofuran (THF) 2-bromine Fluorenone (4.2mmol) 60 ℃ of reactions 24 hours, generate a large amount of white precipitates, add saturated colour NHCl at last
4Ge Shi salt is converted into alcohol.After reaction finishes, extracted with diethyl ether, drying is revolved steaming, and dichloromethane solvent silicagel column purifying obtains the slightly yellowish white solid tertiary alcohol (productive rate is 35.6%).Above-mentioned fluorenol is dissolved in the Glacial acetic acid, under 110 ℃ condition, drips several concentrated hydrochloric acid reactions and generated white precipitate in 10 minutes, add the more precipitations of water generates, filter, obtain white powder solid (productive rate is 79.9%) with tetrahydrofuran (THF) and sherwood oil recrystallization.
MALDI-TOF-MS:748.2 (M
+); Ultimate analysis: C
42H
22Br
2O
2S, observed value: C, 67.99; H, 2.42; O, 4.43; S, 4.55.
3 ', 9 '-two bromo-, two volutions [9H-fluorenes-9,5 ' (7 ' H)-two indenes [2,1-b:1 ', 2 '-d] thiophene-7 ', 9 "-[9H] fluorenes]
3’，9’-dibromo-dispiro[fluorene-9，5’(7’H)-diindeno[2，1-b：1’，2’-d]thiophene-7’，9”-fluorene]
Under the condition of 0 ℃ and lucifuge, to be dissolved in DMF (abs., (10.4g 58.4mmol) slowly is added drop-wise to and is dissolved in DMF (abs. NBS 40mL), two volutions [9H-fluorenes-9 40mL), 5 ' (7 ' H)-two indenes [2,1-b:1 ', 2 '-d] thiophene-7 ', 9 " [9H] fluorenes] (28.3mmol); after dropwising, get back to room temperature, and reaction is spent the night.The frozen water dilution, extracted with diethyl ether, drying is revolved steaming, and ethyl alcohol recrystallization obtains clear crystal (productive rate is 91%).
MALDI-TOF-MS:715.98 (M
+); Ultimate analysis: C
42H
22Br
2O
2S, observed value: C, 69.34; H, 3.29; S, 4.98.
Embodiment 5, thiophene bis oxide spirocyclic compound material:
Two volutions [9H-fluorenes-9,5 ' (7 ' H)-two indenes [2,1-b:1 ', 2 '-d] thiophene-S, S-two sulfones-7 ', 9 " and [9H] fluorenes]
dispiro[fluorene-9，5′(7′H)-diindeno[2，1-b：1′，2′-d]thiophene-S，S-dioxide-7′，9″-fluorene]
The 3-chlorine peroxybenzoic acid (0.67g that crosses through super-dry, 3.86mmol) be dissolved in methylene dichloride (15mL) solution, and slowly be added drop-wise to two spiral shells [the 9H-fluorenes-9 that is dissolved in methylene dichloride (15mL), 1 ' (3 ' H)-two indenes [2,1-b:1 ', 2 '-d] thiophene-3 ', 9 " [9H] fluorenes] (0.90mmol) in; Reactant mixing is at room temperature stirred and is spent the night, and reaction finishes, and uses 10%KOH successively
Aq, 10%NaHCO
3aqAnd the salt water washing, extraction, and dry, vacuum rotary steam, sherwood oil silicagel column purifying obtains yellow solid (productive rate is 47%).
MALDI-TOF-MS:592.1 (M
+); Ultimate analysis: C
42H
24O
2S, observed value: C, 85.12; H, 4.32; O, 5.32; S, 5.32.
Embodiment 6, the two spirocyclic compound materials of thiophene:
2,2 ", 7,7 "-four ([1,1 '-biphenyl]-4-yls)-two volutions [9H-fluorenes-9,5 ' (7 ' H)-two indenes [2,1-b:1 ', 2 '-d] thiophene-7 ', 9 "-[9H] fluorenes]
2，2”，7，7”-tetrakis([1，1’-biphenyl]-4-yl)--dispiro[fluorene-9，5’(7’H)-diindeno[2，1-b：1’，2’-d]thiophene-7’，9”-fluorene]
Get 2,7,2 "; 7 "-tetrabromo-two volution [9H-fluorenes-9, and 5 ' (7 ' H)-two indenes [2,1-b:1 ', 2 '-d] thiophene-7 ', 9 "-[9H] fluorenes] (1equiv., 1.36mmol) and 2-([1; 1 '-biphenyl]-4-yl)-4,4,5; 5-tetramethyl--[1,3,2] dioxo bora pentamethylene (4.0equiv.; 5.42mmol) mixed dissolution adds catalyst P d (PPh in the mixed solvent of 20ml toluene and tetrahydrofuran (THF)
3)
4156.6mg (5mol%) the logical nitrogen of lucifuge adds K again
2CO
32.71ml (2mol/L, 2equiv.), reaction is 48 hours under 90 ℃ condition, adds entry after the reaction, uses CHCl
3Extraction, drying is revolved steaming, sherwood oil silicagel column purifying obtains solid 2,2 ", 7,7 "-four ([1,1 '-biphenyl]-4-yls)-two volutions [9H-fluorenes-9,5 ' (7 ' H)-two indenes [2,1-b:1 ', 2 '-d] thiophene-7 ', 9 "-[9H] fluorenes] (productive rate is 95%).
MALDI-TOF-MS:1168.41 (M
+); Ultimate analysis: C
90H
56S, observed value: C, 92.43; H, 4.43; S, 2.79.
Embodiment 7, the two spirocyclic compound materials of thiophene:
2,7,2 ", 7 "-four (9,9 '-spiral shell, two fluorenes-2-yl)-two volutions [9H-fluorenes-9,5 ' (7 ' H)-two indenes [2,1-b:1 ', 2 '-d] thiophene-7 ', 9 "-[9H] fluorenes]
2，7，2”，7”-tetrakis(9，9’-spirobifluorene-2-yl)-dispiro[fluorene-9，5’(7’H)-diindeno[2，1-b：1’，2’-d]thiophene-7’，9”-fluorene]
Get 2,7,2 "; 7 "-tetrabromo-two volution [9H-fluorenes-9, and 5 ' (7 ' H)-two indenes [2,1-b:1 ', 2 '-d] thiophene-7 ', 9 "-[9H] fluorenes] (1equiv., 2.71mmol) and 2-(9; 9 '-spiral shell two fluorenes-2-yl)--4,4,5; 5-tetramethyl--[1,3,2] dioxo bora pentamethylene (2.0equiv.; 5.42mmol) mixed dissolution adds catalyst P d (PPh in the mixed solvent of 20ml toluene and tetrahydrofuran (THF)
3)
4156.6mg (5mol%) the logical nitrogen of lucifuge adds K again
2CO
32.71ml (2mol/L, 2equiv.), reaction is 48 hours under 90 ℃ condition, adds entry after the reaction, uses CHCl
3Extraction, drying is revolved steaming, sherwood oil silicagel column purifying obtains solid 2,7,2 ", 7 " four (9,9 '-spiral shell two fluorenes-2-yl)-two volutions [9H-fluorenes-9,5 ' (7 ' H)-two indenes [2,1-b:1 ', 2 '-d] thiophene-7 ', 9 " and [9H] fluorenes] (productive rate is 89%).
MALDI-TOF-MS:1816.6 (M
+); Ultimate analysis: Cl
42H
80S, observed value: C, 93.80; H, 4.43; S, 1.76.
Embodiment 8, the two spirocyclic compound materials of thiophene:
2,2 " two (10-benzene anthracenes-9-yl)-two volutions [9H-fluorenes-9,5 ' (7 ' H)-two indenes [and 2,1-b:1 ', 2 '-d] thiophene-7 ', 9 " [9H] fluorenes]
2，2″-bis(10-phenylanthracene-9-yl)-dispiro[fluorene-9，5′(7′H)-Diindeno[2，1-b：1′，2′-d]thiophene-7′，9″-fluorene]
Get 2,2 " two bromo-, two volutions [9H-fluorenes-9; 5 ' (7 ' H)-two indenes [and 2; 1-b:1 '; 2 '-d] thiophene-7 ', 9 " [9H] fluorenes] (1equiv., 1.36mmol) and 10-benzene anthracene-9-boric acid (2.0equiv., 2.71mmol) mixed dissolution in the mixed solvent of 20mL toluene and tetrahydrofuran (THF), add catalyst P d (PPh
3)
4156.6mg (5mol%) the logical nitrogen of lucifuge adds K again
2CO
32.71mL (2mol/L 2equiv.) reacted 48 hours under 90 ℃ condition, added entry after the reaction, used CHCl
3Extraction, drying is revolved steaming, sherwood oil silicagel column purifying obtains white solid 2,2 " two (10-benzene anthracenes-9-yl)-two volutions [9H-fluorenes-9,5 ' (7 ' H)-two indenes [2,1-b:1 ', 2 '-d] thiophene-7 ', 9 " and [9H] fluorenes] (productive rate is 83%).
MALDI-TOF-MS:1064.35 (M
+); Ultimate analysis: C
82H
48S, observed value: C, 92.45; H, 4.54; S, 3.0.
Embodiment 09, the photoluminescence spectra of double spiro material containing heteroaton and quantum yield are measured:
Product is made into the trichloromethane dilute solution of 1 μ M accurately, and removes oxygen by argon cleaning.Adopt Tianjin, island UV-3150 ultraviolet-visual spectrometer and RF-530XPC fluorescence spectrophotometer to carry out absorption spectrum and emission spectrometry.Photoluminescence spectra is to measure under the maximum absorption wavelength of uv-absorbing.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 is that 10-dibenzanthracene solution is measured as standard by 1 μ M 9 in pimelinketone.
2,7,2 "; 7 "-four (9,9 '-spiral shell two fluorenes-2-yl)-two volutions [9H-fluorenes-9,5 ' (7 ' H)-two indenes [2,1-b:1 ', 2 '-d] thiophene-7 ', 9 " and [9H] fluorenes] solution of material and the emmission spectrum of solid film be respectively 399 (422nm is the side peak) and 428nm.The solution quantum yield is greater than 75%.
Embodiment 10, to the hot assay determination of double spiro material containing heteroaton:
Thermogravimetric analysis (TGA)) carry out on the DTG-60H of Tianjin, island company (Shimadzu) thermogravimetric analyzer, the heating sweep velocity is that 10 ℃/min and nitrogen flow rate are 20cm
3/ min.Differential scanning calorimetry (DSC) carries out on the DSC-60A of Tianjin, island company (Shimadzu) tester, sample at first is heated to the state of low ten degree of decomposed sample temperature with the speed of 10 ℃/min, then, the beginning temperature is got back in cooling under the liquid nitrogen condition, and the same second time is with the speed heat temperature raising scanning of 10 ℃/min.
Two volutions [9H-fluorenes-9,5 ' (7 ' H)-two indenes [and 2,1-b:1 ', 2 '-d] thiophene-7 ', 9 " [9H] fluorenes] heat decomposition temperature be 350 ℃, see accompanying drawing 1.
Embodiment 11, to the electrochemical gaging of double spiro material containing heteroaton:
Electrochemistry cyclic voltammetric (CV) experiment is finished on an Eco Chemie B.V.AUTOLAB potentiostat voltammetric analyzer, adopts three-electrode system, comprises platinum carbon working electrode, Ag/Ag
+For reference electrode, platinum filament are counter electrode.Oxidising process adopts methylene dichloride as solvent, and reduction process adopts tetrahydrofuran (THF) as solvent, hexafluoro phosphorus TBuA (Bu
4N
+PF
6 -) as supporting electrolyte, concentration is 0.1M.All electrochemistry experiments all are to carry out under the normal temperature condition nitrogen atmosphere, voltage sweep speed 0.1V/s.Use ferrocene (FOC) as benchmark, can calculate the HOMO and the lumo energy of material by the beginning voltage of measuring oxidation and reduction process.
2,7,2 ", 7 " four (9,9 '-spiral shell two fluorenes-2-yl)-two volution [9H-fluorenes-9,5 ' (7 ' H)-two indenes [2,1-b:1 ', 2 '-d] thiophene-7 ', 9 " [9H] fluorenes] oxidation to begin current potential be 0.81V; this result begins to see accompanying drawing 2 about the low 0.5V of current potential than the oxidation of trimerization spiral shell two fluorene materials (1.22).
Embodiment 12, to the preparation of the electroluminescent device of double spiro material containing heteroaton:
One prepares as the luminescent layer single layer device with the thiophene spirane structure material: ITO/ thiophene spirane structure material/LiF (5 )/Al, and, wherein ITO is the transparency electrode of square resistance 10-20 Ω; 2,7,2 ", 7 " four (9,9 '-spiral shell two fluorenes-2-yl)-two volutions [9H-fluorenes-9,5 ' (7 ' H)-two indenes [2,1-b:1 ', 2 '-d] thiophene-7 ', 9 " [9H] fluorenes] material is as luminescent layer employing vacuum thermal evaporation technology, and evaporation rate 1-2 /s, film thickness are 10～200nm; Evaporation LiF buffer layer again; At last, AM aluminum metallization negative electrode.
2,7,2 ", 7 " four (9,9 '-spiral shell two fluorenes-2-yl)-two volutions [9H-fluorenes-9,5 ' (7 ' H)-two indenes [2,1-b:1 ', 2 '-d] thiophene-7 ', 9 " and [9H] fluorenes], it is 431nm (acromion 404nm) that electricity causes the spectrum emission maximum, sees accompanying drawing 3.
Claims (10)
1, a class contains the two unitary compound-materials of volution of heteroatoms, it is characterized in that having following structure:
Compound I
Symbol in the formula and label have following implication:
R
1, R
2, R
3, R
4R
5, R
6, R
7, R
8R
9, R
10, R
11, R
12R
13, R
14, R
15, R
16, R
17, R
18Identical or different during appearance, and be hydrogen; Halogen; Or have straight chain, side chain or the cyclic alkyl chain of 1 to 22 carbon atom or have the structure of hindered amine chain, one or more non-conterminous carbon atom can be by-NR
19-,-O-,-S-,-CO-O-,-O-CO-O-,-CO-NR
19-,-NR
19-CO-NR
19-,-O-CO-S-,-NR
19-CO-O-,-CS-O-,-CS-NR
19-,-O-CS-O-,-NR
19-CS-NR
20-,-O-CS-S-,-NR
19-CS-O-,-CS-S-,-SiR
19R
20-displacement, perhaps one or more hydrogen atom is replaced by fluorine or cyano group; Or having alkenylene chain, alkynyl chain, the aryl chain of 2 to 40 carbon atoms, wherein one or more carbon atoms can be by heteroatoms Si, Se, O, S, N, S (O)
2Replace, the hydrogen on one or more carbon atoms can be replaced by fluorine or cyano group;
R
19, R
20Identical or different during appearance, and for do not express, hydrogen or have straight chain, side chain or the cyclic alkyl chain of 1 to 22 carbon atom or have the structure of hindered amine chain and oxyalkyl chain;
Ar
2, Ar
3, Ar
4, Ar
5, Ar
6, Ar
7Identical or different during appearance, and for having thiazolinyl, alkynyl, the aryl of 2 to 40 carbon atoms, wherein one or more carbon atoms can be by heteroatoms Si, Se, O, S, N, S (O)
2Replace, the hydrogen on one or more carbon atoms can be replaced by fluorine or cyano group; Wherein the aryl structure is specially a kind of in the following structure:
Symbol in the formula and label have following implication:
-
*Be spiral shell intra-annular Ar
2, Ar
3, Ar
4, Ar
5, Ar
6, Ar
7And the possible position that connects between the carbon of spiral shell center;
D
1, D
2, D
3Identical or different during appearance, and be CR
19R
20, NR
19,-O-,-S-,-Se-,-S (O)
2-or-SiR
19R
20-;
E
1, E
2, E
3, E
4, E
5, E
6Identical or different during appearance, and be CR
19, N, SiR
19
EG
1, EG
2, EG
3, EG
4, EG
5, EG
6Identical or different during appearance, and, comprise hydrogen, halogen, cyano group and conjugation group for forming the group of single chemical bond; Conjugation unit structure unit wherein has thiazolinyl, alkynyl, the aryl of 2 to 40 carbon atoms, and wherein one or more carbon atoms can be by heteroatoms Si, Se, O, S, N, S (O)
2Replace, the hydrogen on one or more carbon atoms can be replaced by fluorine or cyano group; Be specially a kind of in the following structure:
Symbol in the formula and label have following implication:
-
*Be EG between the structural unit
1, EG
2, EG
3, EG
4, EG
5, EG
6With Ar
2, Ar
3, Ar
4, Ar
5, Ar
6, Ar
7The band of position that connects; Greater than one-
*Representative can select arbitrarily one of them-
*As the connection between it;
D
1, D
2, D
3Identical or different during appearance, and be CR
19R
20, NR
19,-O-,-S-,-Se-,-S (O)
2-or-SiR
19R
20-;
E
1, E
2, E
3, E
4, E
5, E
6Identical or different during appearance, and be CR
19, N, SiR
19
AC
1, AC
2, AC
3, AC
4Identical or different during appearance, and be phenyl, indenyl, naphthyl, Azulene base, fluorenyl, phenanthryl, anthryl, pyrenyl, naphthalene embedding phenyl, thienyl, pyrryl, furyl, imidazolyl, thiazole, pyridyl, pyrazinyl, indyl, benzofuryl, benzothienyl, benzimidazolyl-, quinolyl, isoquinolyl, quinoxalinyl, carbazyl, phenanthrolene base; Or be alkyl, fluorine replacement, the oxidized derivatives of its structure.
E, f, identical or different when g occurs, and independently be 0,1,2,3,4,5,6,7,8,9 or 10;
Identical or different when W occurs, be selected from and contain substituent atom; And for not expressing or GeR
19R
20, CR
19R
20, NR
19,-O-,-S-,-Se-,-S (O)
2-,-SiR
19R
20
Be not expressed as and do not occur.
2, compound-material according to claim 1 is characterized in that working as Ar
2, Ar
3, Ar
4, Ar
5, Ar
6, Ar
7Identical or different during appearance, a kind of in the following structure:
3, compound-material according to claim 1 is characterized in that EG
1, EG
2, EG
3, EG
4, EG
5, EG
6Identical or different during appearance, and be preferably as follows a kind of in the structure:
4, compound-material according to claim 1 is characterized in that working as R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8R
9, R
10, R
11, R
12R
13, R
14, R
15, R
16, R
17, R
18Be selected from hydrogen, work as Ar
2, Ar
3, Ar
4, Ar
5, Ar
6, Ar
7All be phenyl during appearance or all be pyridyl, a kind of in the following structure:
Compound III A compound III B compound III C
Compound III E compound III F compound III G
Compound III H compound III J compound III K
Compound III L compound III M compound III N
5, compound-material according to claim 1 is characterized in that working as R
1～R
18Identical or different during appearance, and when being the hindered amine group chain, have following general structure (VI):
Each symbol implication specific as follows:
-
*Be hindered amine group structural unit and Ar
2, Ar
3, Ar
4, Ar
5, Ar
6, Ar
7The position that can connect;
X, Y are identical or different and are CR
19, or N;
Key between the X-Y is singly-bound or two key;
R
21, R
22, R
23, R
24For identical or different, and be H or straight chain, ring-type or collateralization alkyl and the alkoxyl group with 1 to 22 carbon atom, one or more non-conterminous carbon atom can be replaced by following connection base:
One or more hydrogen atom can be replaced by fluorine; Perhaps R
21, R
22, R
23, R
24For identical or different, also for having alkylene, aryl and/or the aryloxy of 2 to 40 carbon atoms, one or more carbon atom can be by O, S or N displacement simultaneously; Perhaps the hydrogen on the carbon atom can be by one or more alkyl group R
19, halogen, cyano group or N (R
20)
2Replace;
R
25For identical or different, and be R
24Described structure or be oxyradical, hydroxyl, inferior oxygen base;
X, Y and R in its formula of (VI) structure
24, R
25Connect into ring;
Nitrogen-atoms in its formula of (VI) structure is electrically charged.
6, a kind of synthetic method as the described compound-material of one of claim 1～5, it is characterized in that comprising the synthetic and all kinds of linked reactions that contain heteroatoms two spirane structure module, it is as follows wherein to contain heteroatomic two spirane structure module synthetic routes such as oxygen, sulphur, nitrogen, silicon:
Symbol in the formula and label have above-mentioned synonymous;
In the synthetic route, 1. step is the cyclization reaction; 2. step is to prepare the tertiary alcohol by Grignard reagent or lithium reagent; 3. step comprises the halogenated method of various preparation aromatizes; 4. step is by Friedel-Craft reaction cyclization step.
7, a kind of synthetic method of compound-material as claimed in claim 6, it is characterized in that further comprising Gilch, Witting, Ullmann, Stille, Suzuki, Yamamoto, Heck or Rieke transition metal palladium catalysis process with C-C or carbon-heteroatoms linked reaction; Comprise other ligations simultaneously by being undertaken by heterocycle Cheng Huan.
8, the synthetic method of compound-material according to claim 7 is characterized in that:
The reactant of method (1) Suzuki linked reaction is aryl hypoboric acid and/or aryl dihalide and 2 equivalent aryl list halogenide and/or aryl list boric acid, and perhaps blended aromatic halides/boric acid is realized coupling with palladium catalyst; Catalyst consumption is 0.1 to 20mol%; Solvent is low-pole or aprotic, polar organic solvent or its mixed solvent; Be reflected at 30 to 150 ℃ of temperature; Reaction times is 1 to 7 day;
Method (2) is the Stille linked reaction: reactant is dihalide and/or two stannates and single stannate and/or single halogenide herein, perhaps corresponding single halogenide-single stannate derivatives monomer, linked reaction under alkaline condition and under the condition of palladium catalyst and solvent existence;
Method (3) is the Yamamoto linked reaction: reactant is a halogenide; Under alkaline condition, under Ni (0) or Ni (II) or compound for catalysis and the solvent condition, react; Reaction conditions is Ni (COD)
2/ bpy/1,5-cyclooctadiene/DMF, COD is 1 here, the 5-cyclooctadiene.
9, according to the purposes of the described compound-material of one of claim 1～5, it is characterized in that: be suitable for and make plastic electronic material, photoelectron material; The device in plastic electronic field or element comprise polymkeric substance and organic light emitting diode device, organic solar batteries, organic laser diode component, organic field-effect tube, OTFT, organic integration circuit, bio-sensing device, nonlinear optical element etc.; Use transport material, interface injecting material, conductive material, photoelectric material, electro-conductive material, superconducting material, the off-color material that comprises as luminescent material, electronics and hole as organic electronic material;
10,, it is characterized in that one or more using method that contain the hindered amine group compound-material comprise as active material directly to use or add use on a small quantity as auxiliary agent according to the purposes of the described compound-material of one of claim 1～5; As promoter material mainly is the stabiliser materials and the optical brightener of heat, light, oxygen, wherein stabiliser materials can add in above-mentioned all kinds of organic electronics and the photoelectron material and general and engineering polymers material in; Add using amount ranges 0.01%～80% as auxiliary agent, is benchmark with the quality of active material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510029333 CN1749254A (en) | 2005-09-01 | 2005-09-01 | Double spiro material containing heteroaton and its synthetic method and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510029333 CN1749254A (en) | 2005-09-01 | 2005-09-01 | Double spiro material containing heteroaton and its synthetic method and use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1749254A true CN1749254A (en) | 2006-03-22 |
Family
ID=36604929
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510029333 Pending CN1749254A (en) | 2005-09-01 | 2005-09-01 | Double spiro material containing heteroaton and its synthetic method and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1749254A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101884122B (en) * | 2007-10-24 | 2012-06-06 | 巴斯夫欧洲公司 | Use of diphenylamino-bis(phenoxy)- and bis(diphenylamino)-phenoxytriazine compounds |
| CN101492443B (en) * | 2009-02-23 | 2012-06-27 | 南京邮电大学 | Complex whorl aryl fluorene material, preparation and application method thereof |
| CN105675677A (en) * | 2016-01-26 | 2016-06-15 | 南京工业大学 | Spiro material based cholesterol biosensor preparation method |
| CN105884795A (en) * | 2016-04-27 | 2016-08-24 | 扬州鑫晶光伏科技有限公司 | Organic photovoltaic material containing thiophene ring and preparation method thereof |
| CN105924446A (en) * | 2016-04-27 | 2016-09-07 | 扬州鑫晶光伏科技有限公司 | Organic photovoltaic material and preparation method thereof |
| CN106187861A (en) * | 2016-07-18 | 2016-12-07 | 华中科技大学 | A kind of spiral shell two fluorenes diindyl derivant, its preparation method and application |
| CN109053740A (en) * | 2018-09-20 | 2018-12-21 | 南京邮电大学 | A kind of H-type acceptor material and preparation method thereof |
| CN109761878A (en) * | 2019-01-04 | 2019-05-17 | 南京邮电大学 | A kind of cyanalation photoelectricity transmission profile material of H-Shape and its preparation method and application |
-
2005
- 2005-09-01 CN CN 200510029333 patent/CN1749254A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101884122B (en) * | 2007-10-24 | 2012-06-06 | 巴斯夫欧洲公司 | Use of diphenylamino-bis(phenoxy)- and bis(diphenylamino)-phenoxytriazine compounds |
| CN101492443B (en) * | 2009-02-23 | 2012-06-27 | 南京邮电大学 | Complex whorl aryl fluorene material, preparation and application method thereof |
| CN105675677A (en) * | 2016-01-26 | 2016-06-15 | 南京工业大学 | Spiro material based cholesterol biosensor preparation method |
| CN105675677B (en) * | 2016-01-26 | 2018-03-20 | 南京工业大学 | A kind of preparation method of the Cholesterol Biosensor based on spiro material |
| CN105884795A (en) * | 2016-04-27 | 2016-08-24 | 扬州鑫晶光伏科技有限公司 | Organic photovoltaic material containing thiophene ring and preparation method thereof |
| CN105924446A (en) * | 2016-04-27 | 2016-09-07 | 扬州鑫晶光伏科技有限公司 | Organic photovoltaic material and preparation method thereof |
| CN106187861A (en) * | 2016-07-18 | 2016-12-07 | 华中科技大学 | A kind of spiral shell two fluorenes diindyl derivant, its preparation method and application |
| CN106187861B (en) * | 2016-07-18 | 2018-08-21 | 华中科技大学 | A kind of two fluorenes diindyl derivative of spiral shell, preparation method and application |
| CN109053740A (en) * | 2018-09-20 | 2018-12-21 | 南京邮电大学 | A kind of H-type acceptor material and preparation method thereof |
| CN109761878A (en) * | 2019-01-04 | 2019-05-17 | 南京邮电大学 | A kind of cyanalation photoelectricity transmission profile material of H-Shape and its preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Low turn-on voltage, high-power-efficiency, solution-processed deep-blue organic light-emitting diodes based on starburst oligofluorenes with diphenylamine end-capper to enhance the HOMO level | |
| Tu et al. | Highly Efficient Pure‐White‐Light‐Emitting Diodes from a Single Polymer: Polyfluorene with Naphthalimide Moieties | |
| CN1206254C (en) | Fluorene copolymers and devices made therefrom | |
| CN106467549B (en) | A kind of compound containing benzimidazole and its application on organic electroluminescence device | |
| Adhikari et al. | Synthesis and photophysical properties of carbazole-based blue light-emitting dendrimers | |
| Wang et al. | C-9 Fluorenyl substituted anthracenes: A promising new family of blue luminescent materials | |
| CN1749254A (en) | Double spiro material containing heteroaton and its synthetic method and use | |
| CN1769269A (en) | End-blocked triarylamine and carbazoles material, handling method and uses | |
| CN1487937A (en) | Monomer for use in preparation of a polymer to be used in optical devices | |
| Zhao et al. | Stable and efficient deep-blue terfluorenes functionalized with carbazole dendrons for solution-processed organic light-emitting diodes | |
| Zhou et al. | Efficient solution-processed red organic light-emitting diode based on an electron-donating building block of pyrrolo [3, 2-b] pyrrole | |
| CN106467548A (en) | A kind of compound containing benzimidazole and its application | |
| CN106220645B (en) | Compound based on monosubstituted-9-fluorenone and application thereof | |
| CN1686976A (en) | Conjugated ramification material of fluorine containing anthracene and pyrene at 9th position, preparation method and application | |
| Gu et al. | Aggregation-induced emission polymers for high performance PLEDs with low efficiency roll-off | |
| CN101492442A (en) | Complex diaryl fluorene material, preparation and application method thereof | |
| CN106467552A (en) | A kind of compound containing benzimidazole and its application in OLED | |
| Zhang et al. | Achieving High‐Performance Solution‐Processed Deep‐Red/Near‐Infrared Organic Light‐Emitting Diodes with a Phenanthroline‐Based and Wedge‐Shaped Fluorophore | |
| CN107586299A (en) | A kind of organic compound and its application using pyridine as core | |
| Li et al. | Sky-blue fluorescent small-molecules with high quantum efficiency: synthesis, structures, AIE properties, and applications in solution-processed non-doped OLEDs | |
| Adhikari et al. | Ethynylphenyl-linked carbazoles as a single-emitting component for white organic light-emitting diodes | |
| CN1757645A (en) | Material contg. thiophene spirane structure, its synthesis and application | |
| Xie et al. | Tetraphenylcyclopentadiene-based hyperbranched polymers: convenient syntheses from one pot “A4+ B2” polymerization and high external quantum yields up to 9.74% in OLED devices | |
| CN101492443A (en) | Complex whorl aryl fluorene material, preparation and application method thereof | |
| Loythaworn et al. | An efficient solution-processable non-doped hybridized local and charge-transfer (HLCT) emitter for a simplified organic light-emitting diode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |