CN108467367A - A kind of imidazoles blue light material, crystal and the preparation method of two fluorenes containing spiral shell - Google Patents
A kind of imidazoles blue light material, crystal and the preparation method of two fluorenes containing spiral shell Download PDFInfo
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Abstract
The invention belongs to organic electroluminescence device field more particularly to imidazoles blue light material, crystal and the preparation methods of a kind of two fluorenes containing spiral shell.The present invention provides a kind of imidazoles blue light materials of two fluorenes containing spiral shell, are：Phenanthro- imidazole derivative or pyrene and imidazole derivative；The present invention also provides the preparation methods of a kind of above-mentioned phenanthro- imidazole derivative and pyrene and imidazole derivative；The present invention also provides a kind of preparation methods of above-mentioned imidazoles blue light material crystal.Material produced by the present invention, has well-regulated structure after monocrystalline is made, obtained material has stable macroscopic property, low startup voltage, low efficiency roll-off effect and high fluorescence internal quantum efficiency, it is a kind of good blue light material, can be widely applied to the preparation of controllable luminescent device；Solves the technological deficiency for lacking a kind of blue light material possessing stable macroscopic property, low startup voltage, low efficiency roll-off effect and high fluorescence internal quantum efficiency in the prior art.
Description
Technical field
The invention belongs to the imidazoles blue light material of organic electroluminescence device field more particularly to a kind of two fluorenes containing spiral shell,
Crystal and preparation method.
Background technology
Organic electroluminescence device (Organic Light-Emitting Diode, OLED), and luminescent material is luminous
The substance of lighting function, therefore the luminous efficiency of luminescent material, luminescent lifetime and hair are finally undertaken in device (by taking OLED as an example)
The properties such as photochromism will all have a direct impact the performance of OLED.Should have as the luminescent material in OLED following prerequisite
Condition：1) fluorescent molecular with high-fluorescence quantum yield；2) balance between electrons and holes injection is good, and positions hair
Carrier-recombination region in photosphere；3) energy level of light emitting molecule appropriate and the energy level of peripheral tier or electrode match；4) have
The good mouldability of machine material and morphological stability.
By vicennial development, the research of feux rouges and green light material relative maturity, in contrast, blue light material
Luminescent properties and service life all it is inferior very much, this is because blue light material itself has a wider energy gap, it is big that charge injects energy barrier, leads
Cause the problems such as device efficiency is low, startup voltage is high.So far, possess stable macroscopic property, low startup voltage, low efficiency
The device of roll effect and high fluorescence internal quantum efficiency is still very rare, thus develops dark blue luminescent material with particularly significant
Meaning.Dark blue luminescent material can not only reduce the energy loss of full-color display, and can be as the master of object transmitter
Body prepares the optical transmitting set of white light or other colors.
Therefore, a kind of imidazoles blue light material, crystal and the preparation method of two fluorenes containing spiral shell are developed, for solving existing skill
In art, lacks and a kind of possessing stable macroscopic property, low startup voltage, amount in low efficiency roll-off effect and high fluorescence
The technological deficiency of the blue light material of sub- efficiency becomes those skilled in the art's urgent problem to be solved.
Invention content
In view of this, the present invention provides imidazoles blue light material, crystal and the preparation method of a kind of two fluorenes containing spiral shell, it is used for
It solves in the prior art, to lack and a kind of possessing stable macroscopic property, low startup voltage, low efficiency roll-off effect and height
Fluorescence internal quantum efficiency blue light material technological deficiency.
The present invention provides a kind of imidazoles blue light material of two fluorenes containing spiral shell, the imidazoles blue light materials of two fluorenes containing spiral shell
For：Phenanthro- imidazole derivative or pyrene and imidazole derivative；
The phenanthro- imidazole derivative is：
Simultaneously imidazole derivative is the pyrene：
The present invention also provides a kind of preparation methods such as above-mentioned phenanthro- imidazole derivative, the preparation method is that：
Step 1: bromo- 9,9'- spiral shells, two fluorenes of 2-, to formylphenylboronic acid, catalyst and potassium carbonate be added N, N- dimethyl
Formamide and H2In O solution, heating stirring under nitrogen protection purifies to obtain the first product；
Step 2: first product and 9,10- phenanthrenequione, aniline, ammonium acetate are added in glacial acetic acid, are heated under nitrogen protection
Stirring, purifies to obtain phenanthro- imidazole derivative.
Preferably, in step 1, the temperature of the heating stirring is 80~95 DEG C, time of the heating stirring is 10~
The rotating speed of 12h, the heating stirring are 300~500r/min；
In step 2, the temperature of the heating stirring is 115~120 DEG C, and the time of the heating stirring is 2~2.5h,
The rotating speed of the heating stirring is 400~500r/min.
Preferably, in step 1, the catalyst is bis- (diphenylphosphino) the ferrocene palladium chlorides of 1,1-；
In step 1, in terms of parts by volume, n,N-Dimethylformamide and H2The rate of charge of O solution is (2~3):(1~2).
Preferably, in step 1, in terms of molar part, bromo- 9,9'- spiral shells, two fluorenes of 2-, to formylphenylboronic acid, catalyst and
The rate of charge of potassium carbonate is (1~1.5):(1.2~2):(0.05~0.07):(3.5~4)；
In step 2, in terms of molar part, the first product and 9,10- phenanthrenequione, aniline, ammonium acetate rate of charge be (1~
1.1):(1.2~1.5):(4.6~4.8):(4~5).
The present invention also provides a kind of preparation methods such as above-mentioned pyrene and imidazole derivative, the preparation method is that：
Step 1: sodium metaperiodate, H2O and catalyst are added in the chloroform, acetonitrile and water mixed solution of pyrene, stirring
Obtain the first product；
Step 2: bromo- 9,9'- spiral shells, two fluorenes of 2-, to formylphenylboronic acid, catalyst and potassium carbonate be added N, N- dimethyl
Formamide and H2In O solution, heating stirring under nitrogen protection purifies to obtain the second product；
Step 3: first product, the second product, aniline and ammonium acetate are added in glacial acetic acid, add under nitrogen protection
Thermal agitation purifies to obtain pyrene and imidazole derivative.
Preferably, in step 1, the catalyst is ruthenium trichloride；
In step 2, the catalyst is bis- (diphenylphosphino) the ferrocene palladium chlorides of 1,1-.
Preferably, in step 1, the temperature of the stirring is room temperature, and the time of the stirring is 8~12h, the stirring
Rotating speed be 300~400r/min
In step 2, the temperature of the heating stirring is 80~95 DEG C, 10~12h of time of the heating stirring, described
The rotating speed of heating stirring is 300~500r/min；
In step 3, the temperature of the heating stirring is 115~120 DEG C, and the time of the heating stirring is 2~2.5h,
The rotating speed of the heating stirring is 400~500r/min.
Preferably, in step 1, in terms of molar part, sodium metaperiodate, H2O, the rate of charge of catalyst and pyrene be (20~
21):(0.6~0.7):(5~6)；
In step 2, in terms of molar part, bromo- 9,9'- spiral shells, two fluorenes of 2-, to formylphenylboronic acid, catalyst and potassium carbonate
Rate of charge be (1~1.5):(1.2~2):(0.05~0.07):(3.5~4)；
In step 3, in terms of molar part, the first product, the second product, aniline and ammonium acetate rate of charge be (1~
1.1):(1.2~1.5):(4.6~4.8):(4~5).
Preferably, in step 1, in terms of parts by volume, chloroform, acetonitrile solution rate of charge be (1~1.1):(1~
1.1):(1.3~1.5)；
In step 2, in terms of parts by volume, n,N-Dimethylformamide and H2The rate of charge (2~3) of O solution:(1~2).
The present invention also provides a kind of preparation method of the imidazoles blue light material crystal of above-mentioned two fluorenes containing spiral shell, the preparations
Method is：
Step 1: after the imidazoles blue light material of two fluorenes containing spiral shell is dissolved in dichloromethane, add n-hexane, be layered first
Product；
Step 2: after the first product freezing, the imidazoles blue light material crystal of two fluorenes containing spiral shell is obtained.
Preferably, in step 1, the imidazoles blue light material of two fluorenes containing spiral shell and the rate of charge of dichloromethane are (5~7):
The volume ratio of (1.5~2) g/ml, dichloromethane and n-hexane is (2~3):1.
Preferably, in step 2, the temperature of the freezing is -18~-30 DEG C, and the time of the freezing is 3~4 weeks.
In conclusion the present invention provides a kind of imidazoles blue light material of two fluorenes containing spiral shell, the imidazoles of two fluorenes containing spiral shell
Class blue light material is：Phenanthro- imidazole derivative or pyrene and imidazole derivative；The present invention also provides a kind of above-mentioned phenanthro- miaows
The preparation method of azole derivative and pyrene and imidazole derivative；The present invention also provides a kind of imidazoles of above-mentioned two fluorenes containing spiral shell
The preparation method of class blue light material crystal.The imidazoles blue light material of two fluorenes provided by the invention containing spiral shell has after monocrystalline is made
Well-regulated structure, being measured through experiment can obtain, and obtained material has stable macroscopic property, low startup voltage, low
Efficiency roll-off effect and high fluorescence internal quantum efficiency, be a kind of good blue light material, can be widely applied to controllable hair
The preparation of optical device.Imidazoles blue light material, crystal and the preparation method of a kind of two fluorenes containing spiral shell provided by the invention solve existing
Have in technology, lacks and a kind of possessing stable macroscopic property, low startup voltage, low efficiency roll-off effect and high fluorescence
The technological deficiency of the blue light material of internal quantum efficiency.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram for the phenanthro- imdazole derivatives that the present invention is prepared；
Fig. 2 is the mass spectrogram for the phenanthro- imdazole derivatives that the present invention is prepared
Fig. 3 is the crystal structure figure for the phenanthro- imdazole derivatives that the present invention is prepared；
Fig. 4 is the crystal molecule intermolecular forces structure chart for the phenanthro- imdazole derivatives that the present invention is prepared：
Fig. 5 is the phenanthro- imdazole derivatives layer structure figure that the present invention is prepared；
Fig. 6 is ultraviolet spectrogram of the phenanthro- imdazole derivatives of the invention being prepared in opposed polarity solvent；
Fig. 7 is the phenanthro- imdazole derivatives of the invention being prepared in opposed polarity solvent liquid fluorescence spectra；
Fig. 8 is the phenanthro- imdazole derivatives crystal ultraviolet spectrogram that the present invention is prepared
Fig. 9 is the phenanthro- imdazole derivatives crystallofluorescence spectrogram that the present invention is prepared；
Figure 10 is the phenanthro- imdazole derivatives fluorescent liquid life diagram that the present invention is prepared；
Figure 11 is the phenanthro- imdazole derivatives crystallofluorescence life diagram that the present invention is prepared：
Figure 12 is fluorescent quantum of the phenanthro- imdazole derivatives of the invention being prepared in dichloromethane and dimethyl sulfoxide (DMSO)
Rate comparison diagram
Figure 13 is the thermogravimetric analysis figure (TGA) for the phenanthro- imdazole derivatives that the present invention is prepared
Figure 14 is the hydrogen nuclear magnetic resonance spectrogram for the pyrene benzimidazole derivative that the present invention is prepared；
Figure 15 is the mass spectrogram for the pyrene benzimidazole derivative that the present invention is prepared
Figure 16 is the crystal structure figure for the pyrene benzimidazole derivative that the present invention is prepared；
Figure 17 is the crystal molecule intermolecular forces structure chart for the pyrene benzimidazole derivative that the present invention is prepared：
Figure 18 is the pyrene benzimidazole derivative layer structure figure that the present invention is prepared；
Figure 19 is ultraviolet spectrogram of the pyrene benzimidazole derivative of the invention being prepared in opposed polarity solvent；
Figure 20 is the pyrene benzimidazole derivative of the invention being prepared in opposed polarity solvent liquid fluorescence spectra；
Figure 21 is the pyrene benzimidazole derivative crystal ultraviolet spectrogram that the present invention is prepared
Figure 22 is the pyrene benzimidazole derivative crystallofluorescence spectrogram that the present invention is prepared；
Figure 23 is the pyrene benzimidazole derivative fluorescent liquid life diagram that the present invention is prepared；
Figure 24 is the pyrene benzimidazole derivative crystallofluorescence life diagram that the present invention is prepared：
Figure 25 is fluorescent quantum of the pyrene benzimidazole derivative of the invention being prepared in dichloromethane and dimethyl sulfoxide (DMSO)
Rate compares；
Figure 26 is the thermogravimetric analysis figure (TGA) for the pyrene benzimidazole derivative that the present invention is prepared.
Specific implementation mode
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
The every other embodiment that technical staff is obtained without making creative work belongs to the model that the present invention protects
It encloses.
In order to which the present invention is described in more detail, with reference to embodiment to provided by the invention, it is specifically described.
Embodiment 1
Bromo- 9,9'- spiral shells, two fluorenes of 1.26mmol 2-, 1.51mmol are to formylphenylboronic acid, 0.06mmol 1, the bis- (hexichol of 1-
Base phosphino-) 20mLN, dinethylformamide and 10mLH is added in ferrocene palladium chloride and 4.41mmol potassium carbonate2O solution
In, under nitrogen protection, 12h is stirred with the rotating speed of 80 DEG C of heating, 400r/min, purifies to obtain the first product.Wherein, it is purified after reaction
Method be：Reaction system is cooled to room temperature, desolventizing after being extracted with dichloromethane, and column chromatography after-purification is completed.
The first products of 1.68mmol and 2.01mmol9,10- phenanthrenequione, 7.73mmol aniline, 5.88mmol ammonium acetates are added
In 15mL glacial acetic acids, with 120 DEG C heating, 400r/min rotating speed stir 2h, purify phenanthro- imidazole derivative, yield are
51%.Wherein, the method purified after reaction is：Reaction system filters after being cooled to room temperature, and is 1 with volume ratio:1 glacial acetic acid-
Water mixed solution flushes three times, and column chromatography purification after drying, purification is completed.
Embodiment 2
Bromo- 9,9'- spiral shells, two fluorenes of 1.26mmol 2-, 1.89mmol are to formylphenylboronic acid, 0.07mmol 1, the bis- (hexichol of 1-
Base phosphino-) 25mLN, dinethylformamide and 10mLH is added in ferrocene palladium chloride and 4.66mmol potassium carbonate2O solution
In, under nitrogen protection, 11h is stirred with the rotating speed of 90 DEG C of heating, 400r/min, purifies to obtain the first product.Wherein, it is purified after reaction
Method be：Reaction system is cooled to room temperature, desolventizing after being extracted with dichloromethane, and column chromatography after-purification is completed.
The first products of 1.68mmol and 2.35mmol9,10- phenanthrenequione, 7.89mmol aniline, 6.21mmol ammonium acetates are added
In 12mL glacial acetic acids, with 123 DEG C heating, 400r/min rotating speed stir 2.2h, purify phenanthro- imidazole derivative, yield are
48%.Wherein, the method purified after reaction is：Reaction system filters after being cooled to room temperature, and is 1 with volume ratio:1 glacial acetic acid-
Water mixed solution flushes three times, and column chromatography purification after drying, purification is completed.
Embodiment 3
Bromo- 9,9'- spiral shells, two fluorenes of 1.26mmol 2-, 2.35mmol are to formylphenylboronic acid, 0.09mmol 1, the bis- (hexichol of 1-
Base phosphino-) 15mLN, dinethylformamide and 20mLH is added in ferrocene palladium chloride and 5.04mmol potassium carbonate2O solution
In, under nitrogen protection, 10h is stirred with the rotating speed of 95 DEG C of heating, 300r/min, purifies to obtain the first product.Wherein, it is purified after reaction
Method be：Reaction system is cooled to room temperature, desolventizing after being extracted with dichloromethane, and column chromatography after-purification is completed.
The first products of 1.68mmol and 2.52mmol9,10- phenanthrenequione, 8.06mmol aniline, 6.72mmol ammonium acetates are added
In 8mL glacial acetic acids, with 125 DEG C heating, 300r/min rotating speed stir 2.5h, purify phenanthro- imidazole derivative, yield are
45%.Wherein, the method purified after reaction is：Reaction system filters after being cooled to room temperature, and is 1 with volume ratio:1 glacial acetic acid-
Water mixed solution flushes three times, and column chromatography purification after drying, purification is completed.
Embodiment 4
The present embodiment is the specific embodiment for verifying phenanthro- imidazole derivative chemical constitution made from Examples 1 to 3.
Measure the hydrogen nuclear magnetic resonance spectrogram and mass spectrogram of gained phenanthro- imidazole derivative.
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of phenanthro- imidazole derivative, can be obtained from Fig. 1, and characteristic waves (ppm) are δ
9.97 (s, 1H), 8.74 (dd, J=45.8,8.3Hz, 2H), 7.96-7.85 (m, 3H), 7.82 (s, 1H), 7.60 (dd, J=
25.9,7.8Hz, 5H), 7.52 (s, 2H), 7.45-7.33 (m, 3H), 7.17-7.03 (m, 3H), 6.92 (s, 1H), 6.74 (dd,
J=21.4,7.6Hz, 2H), 1.55 (s, 5H), 1.25 (s, 2H), 0.90-0.77 (m, 3H).
Fig. 2 be phenanthro- imidazole derivative mass spectrogram, as can be drawn from Figure 2, phenanthro- imidazole derivative it is opposite
Molecular mass is 685.8, consistent with the relative molecular mass of the structural formula of phenanthro- imidazole derivative.
The hydrogen spectrogram of phenanthro- imidazole derivative made from Examples 1 to 3 is consistent with mass spectrogram, and details are not described herein.
Embodiment 5
The present embodiment is the specific embodiment for preparing phenanthro- imidazole derivative crystal.
5-10 milligrams of phenanthro- imdazole derivatives are dissolved in 1.5ml dichloromethane, it is and then that the n-hexane of 3ml is slow
Ground is added in dichloromethane, and dichloromethane and n-hexane is made to be layered, and it is -20 DEG C~-30 DEG C refrigerators that solution, which is then put into temperature,
In allow it slowly to volatilize, pay attention to that solution can not be stirred in the process occur after 3~4 week, in solution blocky solid
Body obtains phenanthro- imdazole derivatives crystal.
The structure of crystal, can see from the visual field in Electronic Speculum obtained by electron microscope observation, obtained monocrystalline tool
Well-regulated structure.
Herein further referring to Fig. 3~Fig. 5.It is 123K that Fig. 3 and Fig. 4, which is in temperature, in BrukerSmart1000CCD
On diffractometer, the crystal structure figure that data convert is integrated is carried out with SAINT programs.
Can be obtained from figure, the crystal obtained by the present embodiment belong to anorthic system ( α=77.628 (4) °, β=86.612 (4) °, γ=68.539 (6) °,Z=2, T=150 (2) K, μ (CuK α)=1.808mm-1, Dcalc=1.314g/cm3,
11971reflectionsmeasured (6.722 °≤2 Θ≤131.998 °), 6591unique (Rint=0.1042,
Rsigma=0.1178) finalR1was0.1254 (I>2 σ (I)) andwR2was0.2946, space group is P-1 (no.2).
It is centered around in compound around N1 atomsAnd the N-C around N2 atoms
ForAnd interaction (1.345 (7) -1.661 (7) between C atoms.It is worth noting that,
In molecular cluster bc planes, being connected on C19 atoms on N1 phenyl ring, there is a large amount of C π phases with adjacent phenanthrene ring
Interreaction forceAnd the presence of the C2 on phenanthrene ring and the phenyl ring for adjoining two fluorene group of bridging imidazoles and spiral shell
The interaction of C π(Fig. 4).In phenanthro- imdazole derivatives packing of molecules, intermolecular accumulation is tighter
Close (Fig. 5).
Embodiment 6
It is herein ultraviolet-visible absorbance of the phenanthro- imdazole derivatives in opposed polarity solvent further referring to Fig. 6, Fig. 6
Figure.It can be seen from the figure that in methylene chloride, absorption peak be broadly divided into positioned at 340nm maximum absorption band and be located at
Weaker absorption band in 260nm wave-length coverages；Wherein, the relatively strong absorption band in wave-length coverage is primarily due to compound
π-π the transition of middle fluorenes ring；Relatively weak absorbing in wave-length coverage is mainly since the π-π transition of compound itself generates.
Herein further referring to Fig. 7, Fig. 7 is phenanthro- imdazole derivatives in the solvent of several opposed polarities, is measured
Solvent effect in terms of fluorescence (PL).Such as toluene inside low polar solvent, its fluorescence spectrum are shown by locally swashing
Send out vibrational structure good caused by state.With the increase of solvent polarity, fluorescence spectrum constantly broadens and gradually becomes no knot
Structure.Improve the red shift 13nm (toluene (427nm of Toluene to dimethyl sulfoxide (DMSO) (DMSO) that polar solvent produces in total
440nm)
Fig. 8-9 is the UV absorption and fluorescence spectrum that respectively phenanthro- imdazole derivatives measure on crystal, to its property
Matter is further explored.8 it can be seen that its a length of 368nm of maximum absorption wave from figure, it is most as can see from Figure 9
Big launch wavelength 430nm, is in the region of dark blue light.
It it is herein fluorescence longevity of the phenanthro- imdazole derivatives in dichloromethane solution further referring to Figure 10, Figure 10
Life, test data is fitted, by calculate phenanthro- imidazole derivative solution fluorescence lifetime be 1.21ns.
Herein further referring to Figure 11, Figure 11 is the fluorescence lifetime of phenanthro- imdazole derivatives crystal as a result, to test
Data are fitted, by calculate phenanthro- imdazole derivatives crystal fluorescence lifetime be 0.87ns.
Herein further referring to Figure 12, Tu12Zhong, phenanthro- imdazole derivatives are in dichloromethane and dimethyl sulphoxide solution
In fluorescence quantum yield be respectively 90.98% and 99.9%, there is higher fluorescence quantum yield, it is controllable luminous preparing
The application aspects such as material or photo-electroluminescence device have Potential feasibility..
It is herein the result that phenanthro- imdazole derivatives crystal carries out thermogravimetric analysis further referring to Figure 13, Figure 13.It measures
Condition is：Heating rate is 10 DEG C/min, and measuring temperature is ranging between 30~800 DEG C, it can be seen from the figure that phenanthro- imidazoles
The heat decomposition temperature (Td) of up to 412 DEG C of crystal performance illustrates that it can stablize relatively at a higher temperature, is vacuum evaporation work
Skill making devices provides necessary condition.
Embodiment 7
5.00mmol pyrenes are dissolved in 21.5mL chloroforms, 21.5mL acetonitriles and 28.5mL water mixed solutions, 20.00mmol
Sodium metaperiodate, 0.61mmol ruthenium trichlorides are added in aforementioned mixture, and 10h, purification are stirred with the rotating speed of 350r/min under room temperature
Obtain the first product；Wherein, the method for purification is desolventizing after chloroform extraction, column chromatography purifying.
Bromo- 9,9'- spiral shells, two fluorenes of 1.26mmol 2-, 1.51mmol are to formylphenylboronic acid, 0.06mmol 1, the bis- (hexichol of 1-
Base phosphino-) 20mLN, dinethylformamide and 10mLH is added in ferrocene palladium chloride and 4.41mmol potassium carbonate2O solution
In, under nitrogen protection, 12h is stirred with the rotating speed of 80 DEG C of heating, 400r/min, purifies to obtain the first product.Wherein, it is purified after reaction
Method be：Reaction system is cooled to room temperature, desolventizing after being extracted with dichloromethane, and column chromatography after-purification is completed.
The first products of 0.52mmol, the second products of 0.62mmol, 2.37mmol aniline and 2.07mmol ammonium acetates are added
In 8mL glacial acetic acids, under nitrogen protection, with the rotating speed of 350r/min, 120 DEG C of heating stirring 2h, pyrene and imidazoles derivative are purified to obtain
Object, yield 52%.Wherein, the method for purification is：It is filtered after being cooled to room temperature, is 1 with volume ratio:1 glacial acetic acid-water mixing
After solution flushes three times, column chromatography purifying.
Embodiment 8
5.50mmol pyrenes are dissolved in 21.5mL chloroforms, 23.6mL acetonitriles and 32.2mL water mixed solutions, 20.00mmol
Sodium metaperiodate, 0.65mmol ruthenium trichlorides are added in aforementioned mixture, stir 8h with the rotating speed of 350r/min under room temperature, purify
First product；Wherein, the method for purification is desolventizing after chloroform extraction, column chromatography purifying.
Bromo- 9,9'- spiral shells, two fluorenes of 1.26mmol 2-, 1.89mmol are to formylphenylboronic acid, 0.07mmol 1, the bis- (hexichol of 1-
Base phosphino-) 25mLN, dinethylformamide and 10mLH is added in ferrocene palladium chloride and 4.66mmol potassium carbonate2O solution
In, under nitrogen protection, 11h is stirred with the rotating speed of 90 DEG C of heating, 400r/min, purifies to obtain the first product.Wherein, it is purified after reaction
Method be：Reaction system is cooled to room temperature, desolventizing after being extracted with dichloromethane, and column chromatography after-purification is completed.
The first products of 1.20mmol, the second products of 1.56mmol, 5.64mmol aniline and 4.44mmol ammonium acetates are added
In 12mL glacial acetic acids, under nitrogen protection, with the rotating speed of 400r/min, 123 DEG C of heating stirring 2.3h, purify pyrene and imidazoles are spread out
Biology, yield 45%.Wherein, the method for purification is：It is filtered after being cooled to room temperature, is 1 with volume ratio:1 glacial acetic acid-water is mixed
After conjunction solution flushes three times, column chromatography purifying.
Embodiment 9
6.00mmol pyrenes are dissolved in 21.5mL chloroforms, 22.6mL acetonitriles and 30.1mL water mixed solutions, 20.00mmol
Sodium metaperiodate, 0.70mmol ruthenium trichlorides are added in aforementioned mixture, and 12h, purification are stirred with the rotating speed of 350r/min under room temperature
Obtain the first product；Wherein, the method for purification is desolventizing after chloroform extraction, column chromatography purifying.
Bromo- 9,9'- spiral shells, two fluorenes of 1.26mmol 2-, 2.35mmol are to formylphenylboronic acid, 0.09mmol 1, the bis- (hexichol of 1-
Base phosphino-) 15mLN, dinethylformamide and 20mLH is added in ferrocene palladium chloride and 5.04mmol potassium carbonate2O solution
In, under nitrogen protection, 10h is stirred with the rotating speed of 95 DEG C of heating, 300r/min, purifies to obtain the first product.Wherein, it is purified after reaction
Method be：Reaction system is cooled to room temperature, desolventizing after being extracted with dichloromethane, and column chromatography after-purification is completed.
The first products of 1.96mmol, the second products of 2.94mmol, 5.76mmol aniline and 4.80mmol ammonium acetates are added
In 15mL glacial acetic acids, under nitrogen protection, with the rotating speed of 500r/min, 125 DEG C of heating stirring 2.5h, purify pyrene and imidazoles are spread out
Biology, yield 42%.Wherein, the method for purification is：It is filtered after being cooled to room temperature, is 1 with volume ratio:1 glacial acetic acid-water is mixed
After conjunction solution flushes three times, column chromatography purifying.
Embodiment 10
The present embodiment is to verify pyrene made from embodiment 7~9 and the specific embodiment of imidazole derivative chemical constitution.
Measure the hydrogen nuclear magnetic resonance spectrogram and mass spectrogram of gained pyrene and imidazole derivative.
Figure 14 is the hydrogen nuclear magnetic resonance spectrogram of pyrene and imidazole derivative, can be obtained from Figure 14, and characteristic waves (ppm) are δ
9.62 (s, 1H), 8.24 (d, J=7.6Hz, 1H), 8.18 (t, J=7.5Hz, 1H), 8.11 (t, J=7.1Hz, 1H), 8.04
(d, J=8.8Hz, 1H), 7.92-7.85 (m, 2H), 7.65 (ddd, J=34.2,33.0,23.6Hz, 4H), 7.51-7.29 (m,
4H), 7.13 (t, J=7.4Hz, 1H), 6.94 (s, 1H), 6.75 (dd, J=22.0,7.5Hz, 1H), 1.87-1.84 (m, 1H),
1.75 (s, 1H), 1.67 (s, 11H), 1.25 (s, 1H).
Figure 15 is the mass spectrogram of pyrene and imidazole derivative, can be obtained from Figure 15, the phase of pyrene and imidazole derivative
It is 709.3 to molecular mass, it is consistent with pyrene and the relative molecular mass of structural formula of imidazole derivative.
The hydrogen spectrogram of phenanthro- imidazole derivative made from embodiment 7~9 is consistent with mass spectrogram, and details are not described herein.
Embodiment 11
The present embodiment is the specific embodiment for preparing pyrene and imidazole derivative crystal.
5-10 milligrams of pyrene benzimidazole derivative solid is dissolved in 1.5ml dichloromethane, and then by the n-hexane of 3ml
It is slowly added into dichloromethane, so that dichloromethane and n-hexane is layered, then solution is put into -20 DEG C~-30 DEG C refrigerators
It allows it slowly to volatilize, pays attention to that during this solution can not be stirred, occur blocks of solid in solution after 3-4 week, obtain
Pyrene benzimidazole derivative crystal.
The structure of crystal, can see from the visual field in Electronic Speculum obtained by electron microscope observation, obtained monocrystalline tool
Well-regulated structure.
Herein further referring to Figure 16~Figure 18.It is 30.15K that Figure 16~Figure 18, which is in temperature, in BrukerSmart
On 1000CCD diffractometers, the crystal structure figure that data convert is integrated is carried out with SAINT programs.
It can be obtained from figure, the crystal obtained by the present embodiment belongs to anorthic system α=82.604 (4) °, β=75.416 (4) °, γ=69.652 (4) °,Z=4, T=150.00 (10) K, μ (CuK α)=1.788mm-1, Dcalc=1.324g/cm3,
21875reflectionsmeasured (6.688 °≤2 Θ≤132.016 °), 13697unique (Rint=
0.0446Rsigma=0.0595) finalR1was0.0708 (I>2 σ (I)) andwR2was0.2023 space groups are P-1.Chemical combination
The N-C being centered around in object around N1 atoms isAnd the N-C around N2 atoms isAnd the interaction between C atomsIt is noticeable
Be, in molecular cluster ab planes, be connected on C16 atoms of pyrene ring and two fluorenes ring of spiral shell there is a large amount of C π interactions
C37 in two fluorenes ring of power (3.889A) and spiral shell in the two fluorenes fluorenes ring of spiral shell adjoined phenyl ring there are the phase interactions of C π
With(Figure 17).In phenanthro- imdazole derivatives packing of molecules, there are one the ducts 1D (Figure 18) for prolonging c-axis direction
Embodiment 12
It is herein ultraviolet-visible suction of the pyrene benzimidazole derivative in opposed polarity solvent further referring to Figure 19, Figure 19
Receive figure.It can be seen from the figure that absorption peak is broadly divided into positioned at the maximum absorption band of 341nm and positioned at 385nm wave-length coverages
Interior weaker absorption band.The relatively strong absorption band being wherein located in 300-340nm wave-length coverages is primarily due in compound
Fluorenes ring π-π transition；Relatively weak absorbing in 360-390 wave-length coverages is mainly since the π-π transition of compound itself generates
's.
Herein further referring to Figure 20, Figure 20 is pyrene benzimidazole derivative in the solvent of several opposed polarities, is measured
Solvent effect in terms of fluorescence (PL).It compares, pyrene benzimidazole derivative such as n-hexane and first inside low polar solvent
Benzene, its fluorescence spectrum show good vibrational structure caused by local excitation state.And phenanthro- imdazole derivatives only just oneself
The vibrational structure shown in alkane.Moreover, with the increase of solvent polarity, fluorescence spectrum constantly broadens and gradually becomes
Without structure.Improve polar solvent produce in total 35nm red shift (420nm's of n-hexane to dimethyl sulfoxide (DMSO) (DMSO)
455nm), bigger red shift is shown compared to phenanthro- imdazole derivatives.In addition, from low polar n-hexane to highly polar DMSO
Solvent, compared to the half peak breadth (fwhm) that phenanthro- imdazole derivatives show bigger.The experimental results showed that pyrene benzimidazole derivative
There is stronger solvent effect than phenanthro- imdazole derivatives, this demonstrate pyrene benzimidazole derivatives to turn with more obvious charge
The characteristics of moving excitation state.
Figure 21 and Figure 22 is pyrene benzimidazole derivative the crystal UV absorption and fluorescence spectra that measure, to its property into
Row is further explored.21 it can be seen that its a length of 380nm of maximum absorption wave, can see emission peak from Figure 22 from figure
To there is very strong luminescence generated by light at 463nm, there is electric charge transfer with receptor in mainly molecule donor in aggregation, thus occurs
Bigger red shift.
It is herein fluorescence lifetime of the pyrene benzimidazole derivative in dichloromethane solution further referring to Figure 23, Figure 23,
Test data is fitted, by calculate pyrene benzimidazole derivative crystal fluorescence lifetime be 1.70ns.
Herein further referring to Figure 24, Figure 24 is the fluorescence lifetime of pyrene benzimidazole derivative crystal, to test data
Be fitted, by calculate pyrene benzimidazole derivative crystal fluorescence lifetime be 2.75ns.
Herein further referring to Figure 25, Tu25Zhong, pyrene benzimidazole derivative is in dichloromethane and dimethyl sulphoxide solution
In fluorescence quantum yield be respectively 91.35% and 92.25%, there is higher fluorescence quantum yield, preparing controllable hair
The application aspects such as luminescent material or photo-electroluminescence device have Potential feasibility..
It is herein the result that pyrene benzimidazole derivative crystal carries out thermogravimetric analysis further referring to Figure 26, Figure 26.It measures
Condition is：Heating rate is 10 DEG C/min, and measuring temperature is ranging between 30~800 DEG C, it can be seen from the figure that performance is up to
DEG C heat decomposition temperature 395 DEG C (Td), illustrate its can at a higher temperature relatively stablize, be vacuum evaporation process making devices
Provide necessary condition.
It can be obtained from above-mentioned technical proposal, technical solution provided in an embodiment of the present invention, the obtained phenanthrene containing fluorenes
And imidazoles and pyrene benzimidazole derivative crystal have high fluorescence quantum yield simultaneously, have both preferable thermal stability, shine by force
Degree etc..It is extensive to prepare raw material sources, it is cheap, and synthesis condition is mild, and it is easy to operate, it is suitable for preparing regulatable hair
Optical device.
In conclusion the present invention provides a kind of imidazoles blue light material of two fluorenes containing spiral shell, the imidazoles of two fluorenes containing spiral shell
Class blue light material is：Phenanthro- imidazole derivative or pyrene and imidazole derivative；The present invention also provides a kind of above-mentioned phenanthro- miaows
The preparation method of azole derivative and pyrene and imidazole derivative；The present invention also provides a kind of imidazoles of above-mentioned two fluorenes containing spiral shell
The preparation method of class blue light material crystal.The imidazoles blue light material of two fluorenes provided by the invention containing spiral shell has after monocrystalline is made
Well-regulated structure, being measured through experiment can obtain, and obtained material has stable macroscopic property, low startup voltage, low
Efficiency roll-off effect and high fluorescence internal quantum efficiency, be a kind of good blue light material, can be widely applied to controllable hair
The preparation of optical device.Imidazoles blue light material, crystal and the preparation method of a kind of two fluorenes containing spiral shell provided by the invention solve existing
Have in technology, lacks and a kind of possessing stable macroscopic property, low startup voltage, low efficiency roll-off effect and high fluorescence
The technological deficiency of the blue light material of internal quantum efficiency.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (13)
1. a kind of imidazoles blue light material of two fluorenes containing spiral shell, which is characterized in that the imidazoles blue light material of two fluorenes containing spiral shell
Structural formula is：Phenanthro- imidazole derivative or pyrene and imidazole derivative；
The phenanthro- imidazole derivative is：
Simultaneously imidazole derivative is the pyrene：
2. a kind of preparation method of phenanthro- imidazole derivative as described in claim 1, which is characterized in that the preparation method
For：
Step 1: bromo- 9,9'- spiral shells, two fluorenes of 2-, to formylphenylboronic acid, catalyst and potassium carbonate be added N, N- dimethyl formyls
Amine and H2In O solution, heating stirring under nitrogen protection purifies to obtain the first product；
Step 2: first product and 9,10- phenanthrenequione, aniline, ammonium acetate are added in glacial acetic acid, heat and stir under nitrogen protection
It mixes, purifies to obtain phenanthro- imidazole derivative.
3. preparation method according to claim 2, which is characterized in that in step 1, the temperature of the heating stirring is 80
~95 DEG C, the time of the heating stirring is 10~12h, and the rotating speed of the heating stirring is 300~500r/min；
In step 2, the temperature of the heating stirring is 115~120 DEG C, and the time of the heating stirring is 2~2.5h, described
The rotating speed of heating stirring is 400~500r/min.
4. preparation method according to claim 2, which is characterized in that in step 1, the catalyst is the bis- (hexichol of 1,1-
Base phosphino-) ferrocene palladium chloride；
In step 1, in terms of parts by volume, n,N-Dimethylformamide and H2The rate of charge of O solution is (2~3):(1~2).
5. preparation method according to claim 2, which is characterized in that in step 1, in terms of molar part, bromo- 9, the 9'- spiral shells of 2-
Two fluorenes, the rate of charge (1~1.5) to formylphenylboronic acid, catalyst and potassium carbonate:(1.2~2):(0.05~0.07):
(3.5~4)；
In step 2, in terms of molar part, the first product and 9,10- phenanthrenequione, aniline, ammonium acetate rate of charge be (1~1.1):
(1.2~1.5):(4.6~4.8):(4~5).
6. the preparation method of a kind of pyrene as described in claim 1 and imidazole derivative, which is characterized in that the preparation method
For：
Step 1: sodium metaperiodate, H2O and catalyst are added in the chloroform, acetonitrile and water mixed solution of pyrene, stir
One product；
Step 2: bromo- 9,9'- spiral shells, two fluorenes of 2-, to formylphenylboronic acid, catalyst and potassium carbonate be added N, N- dimethyl formyls
Amine and H2In O solution, heating stirring under nitrogen protection purifies to obtain the second product；
Step 3: first product, the second product, aniline and ammonium acetate are added in glacial acetic acid, heat and stir under nitrogen protection
It mixes, purifies to obtain pyrene and imidazole derivative.
7. preparation method according to claim 6, which is characterized in that in step 1, the catalyst is ruthenium trichloride；
In step 2, the catalyst is bis- (diphenylphosphino) the ferrocene palladium chlorides of 1,1-.
8. preparation method according to claim 6, which is characterized in that in step 1, the temperature of the stirring is room temperature, institute
The time for stating stirring is 8~12h, and the rotating speed of the stirring is 300~400r/min
In step 2, the temperature of the heating stirring is 80~95 DEG C, and the time of the heating stirring is 10~12h, described to add
The rotating speed of thermal agitation is 300~500r/min；
In step 3, the temperature of the heating stirring is 115~120 DEG C, and the time of the heating stirring is 2~2.5h, described
The rotating speed of heating stirring is 400~500r/min.
9. preparation method according to claim 6, which is characterized in that in step 1, in terms of molar part, sodium metaperiodate is urged
The rate of charge of agent and pyrene is (20~21):(0.6~0.7):(5~6)；
In step 2, in terms of molar part, bromo- 9,9'- spiral shells, two fluorenes of 2-, the throwing to formylphenylboronic acid, catalyst and potassium carbonate
Material is than being (1~1.5):(1.2~2):(0.05~0.07):(3.5~4)；
In step 3, in terms of molar part, the first product, the second product, aniline and ammonium acetate rate of charge be (1~1.1):
(1.2~1.5):(4.6~4.8):(4~5).
10. preparation method according to claim 6, which is characterized in that in step 1, in terms of parts by volume, chloroform, second
The rate of charge of nitrile and aqueous solution is (1~1.1):(1~1.1):(1.3~1.5)；
In step 2, in terms of parts by volume, n,N-Dimethylformamide and H2The rate of charge (2~3) of O solution:(1~2).
11. a kind of preparation method of the imidazoles blue light material crystal of two fluorenes containing spiral shell as described in claim 1, which is characterized in that
The preparation method is that：
Step 1: after the imidazoles blue light material of two fluorenes containing spiral shell is dissolved in dichloromethane, n-hexane is added, is layered to obtain the first production
Object；
Step 2: after the first product freezing, the imidazoles blue light material crystal of two fluorenes containing spiral shell is obtained.
12. preparation method according to claim 11, which is characterized in that in step 1, the imidazoles blue light of two fluorenes containing spiral shell
The rate of charge of material and dichloromethane is (5~7):The volume ratio of (1.5~2) g/ml, dichloromethane and n-hexane is (2~3):
1。
13. preparation method according to claim 11, which is characterized in that in step 2, the temperature of the freezing is -18
~-30 DEG C, the time of the freezing is 3~4 weeks.
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| CN113651757A (en) * | 2021-09-16 | 2021-11-16 | 河北工业大学 | Hole transport material containing spiro [ fluorene-heterocycle ] structure and preparation method and application thereof |
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