CN104498025B - Many phenyl benzene constructs cyano-containing light emitting molecule and its production and use - Google Patents
Many phenyl benzene constructs cyano-containing light emitting molecule and its production and use Download PDFInfo
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Abstract
The invention discloses a kind of many phenyl benzene and construct cyano-containing light emitting molecule, its general structure is:Wherein, R=H or-C ≡ N, Ar1ForOr
Description
Technical field
The present invention relates to many phenyl benzene and construct cyano-containing light emitting molecule and preparation method thereof and as blue light organic emissive two
The purposes of pole tube light-emitting layer material.
Background technology
Last century the eighties Kodak the organic light-emitting diodes of doctor Deng Qingyun et al. invention sandwich construction first
Since pipe, the research work of high efficiency organic electroluminescence material just enters brand-new epoch.In order to realize full-color display and
Solid-state illumination, ruddiness, green glow and blue light material efficient, that stable, excitation is high are indispensable.Through the development of more than 20 years,
Ruddiness and green light material can meet business-like demand, but the blue light material of excellent performance is the most rare, because blue light emitting
The bigger energy gap that material is had is disadvantageous for carrier to injection and the transmission of luminescent layer.Therefore, how height is obtained
Performance, the blue light material of high color purity become the emphasis of current electroluminescent organic material research.Although more existing blue light materials
Material appears in the newspapers, but the dark blue luminescent material of efficient stable, especially chromaticity coordinates are near the mark, saturated blue light material is the most rare.
Luminescent material is presented in thin-film state in electroluminescent device, and most of fluorescent material is because of intramolecular
π-π interacts and there is " aggregation inducing fluorescent quenching " (ACQ) and the problem of spectral red shift.Although scientists have employed
Various methods reduce or prevent the gathering of fluorescence molecule, such as the side utilizing host-guest system system to be blended with transparent polymer
Formula disperses light emitting molecule, or modifies the spacer group etc. of various large volume in light emitting molecule structure, but these methods are led to
Often can bring the element manufacturing of high cost and complicated building-up process, the spacer group of large volume often reduces device simultaneously
Energy.
Calendar year 2001, this loyalty academician seminar of Tang finds and reports a class first and has aggregation-induced emission (AIE) character
Compound, the luminescence when solution state of this compounds is the most weak or the most luminous, and has high fluorescence quantum yield when solid-state.
The luminescent behavior of this " unusual " causes great interest and the extensive concern of people.M ü llen etc. hexaphenyl benzene synthesis and
Research has outstanding contributions.It was noticed that hexaphenyl benzene unit has aggregation inducing Fluorescence Increasing (AEE) character, and
Hexaphenyl benzene itself is transmitted in blue light range, and the distortion between its phenyl ring makes it have big steric effect and can effectively prevent point
Interaction between son.This series of properties is all extremely advantageous condition in constructing dark blue luminescent material.But at present, with phenyl
The report that benzene structure builds light emitting molecule is little, and its chromaticity coordinates (CIE) deviation dark blue light of standard is more.Traditional passes through
Diels-Alder is synthesized hexaphenyl benzene method and significantly limit the development as luminescence unit of the hexaphenyl benzene, new energy
The method enough making its functionalization more enrich is to be developed.
Summary of the invention
It is an object of the invention to by the new method building many phenyl benzene, it is provided that class many phenyl benzene constructs cyano-containing
Light emitting molecule and preparation method thereof and the purposes as blue light organic emissive LED lighting layer, this compounds has good
Heat endurance and higher luminous efficiency.
The technical scheme realizing the object of the invention is specific as follows:
A kind of many phenyl benzene constructs cyano-containing light emitting molecule, has a structure shown in logical formula (I):
Wherein:
R=H or-C ≡ N；
During R=H, Ar1ForOr
During R=-C ≡ N, Ar1ForOr
Present invention also offers above-mentioned many phenyl benzene and construct the preparation method of cyano-containing light emitting molecule, comprise the following steps:
(1), under protective gas atmosphere, adding mol ratio in Schlenk pipe is the 3 of 1:6:30,4,5-tri-bromo nitrobenzenes, right
Tert-butylbenzeneboronic acid, potassium carbonate, and the Pd (PPh of catalytic amount3)4, it is subsequently adding appropriate toluene, second alcohol and water, wherein, water
Consumption is potassium carbonate molal quantity 1/2, in 90 DEG C react 12 hours.After completion of the reaction, product is cooled to room temperature, uses toluene
Extraction, collects organic phase, uses anhydrous Na2SO4It is dried, obtains thick product.With petroleum ether and dichloromethane (v/v, 2/1) for drip washing
Agent, uses silica gel chromatograph column chromatography by product, isolated and purified, vacuum drying, obtains compound 1；Described compound 1 structural formula is
(2) compound 1 is added in glacial acetic acid, be heated to reflux to solid being completely dissolved, obtain solution A；Solution A is lowered the temperature
To 90-100 DEG C, adding the water that volume is glacial acetic acid 2%, be then slowly added into reduced iron powder, solution A immediately becomes black, black
Look continues backflow 30 minutes after taking off；Stop heating, after solution A is down to room temperature, be poured in a large amount of water, have solid to analyse
Go out, filter out solid and be dried；Dried solid is dissolved in chloroform or dichloromethane, slow dropping liquid the most wherein under ice bath
Bromine, recession in 20 minutes removes ice bath, adds reducing agent cancellation reaction, and dichloromethane extracts, with petroleum ether and dichloromethane (v/v, 2/
1) it is eluent, product is used silica gel chromatograph column chromatography, isolated and purified, vacuum drying, obtain compound 2；Described compound 2
Structural formula isWherein, the mol ratio of compound 1, reduced iron powder and bromine is 1:5:2；
(3) compound 2, cuprous cyanide and solvent dimethyl sulfoxide are added in Schlenk pipe, under protective gas atmosphere, 50 DEG C
After stirring half an hour, in above-mentioned reactant liquor, it is slowly added to nitrite tert-butyl, continues stirring 2 hours.After reaction terminates, to instead
Answer the aqueous hydrochloric acid solution adding 1M concentration in liquid, extract with dichloromethane, collect organic phase and be dried with anhydrous sodium sulfate.With stone
Oil ether and dichloromethane (v/v, 1/1) are eluent, and product is used silica gel chromatograph column chromatography, isolated and purified, vacuum drying, simultaneously
Obtain compound 3 and 4；The structural formula of described compound 3 isThe structural formula of compound 4 isWherein, the mol ratio of compound 2, cuprous cyanide and nitrite tert-butyl is 1:1.3:3；
(4), under protective gas atmosphere, Schlenk pipe adds compound 3 or compound 4,4-boric acid triphenylamine, potassium carbonate
Pd (PPh with catalytic amount3)4, it is subsequently adding toluene, ethanol and deoxidized water, within 24 hours, makes it the most anti-in 90-100 DEG C of stirring
Should.After completion of the reaction, product is cooled to room temperature, extracts with toluene, collect organic phase, use anhydrous Na2SO4It is dried, is slightly produced
Product.With petroleum ether and dichloromethane (v/v, 2/1) for eluent, product being used silica gel chromatograph column chromatography, isolated and purified, vacuum is done
Dry, obtain compound 5 or compound 7；Described compound 5 structural formula isThe structure of compound 7
Formula isOr by compound 3 or 4, compound 4-(9-carbazyl) phenyl boric acid, potassium carbonate and catalysis
Pd (the PPh of amount3)4, it is subsequently adding toluene, ethanol and deoxidized water, within 24 hours, makes it fully react in 90-100 DEG C of stirring.Reaction
After, product is cooled to room temperature, extracts with toluene, collect organic phase, use anhydrous Na2SO4It is dried, obtains thick product.To produce
Product silica gel chromatograph column chromatography for separation is purified, and obtains compound 6 or compound 8；The structural formula of described compound 6 isThe structural formula of compound 8 isOr by compound 4, compound
3-boric acid triphenylamine or 3-(9-carbazyl) phenyl boric acid or N-phenyl carbazole-3-boric acid, the Pd (PPh of potassium carbonate and catalytic amount3)4,
It is subsequently adding toluene, ethanol and deoxidized water, within 24 hours, makes it fully react in 90-100 DEG C of stirring.After completion of the reaction, by product
It is cooled to room temperature, extracts with toluene, collect organic phase, use anhydrous Na2SO4It is dried, obtains thick product.By product silica gel chromatograph
Column chromatographic isolation and purification, obtains compound 9 or 10 or 11；The structural formula of described compound 9 isCompound
The structural formula of 10 isThe structural formula of compound 11 is
In described step (1), toluene, the volume ratio of second alcohol and water are 4:1:2, or the volume ratio of oxolane and water is 2:
1。
Reducing agent described in step (2) is sodium sulfite or sodium thiosulfate.
Protective gas described in step (1), step (3) and step (4) is nitrogen.
Many phenyl benzene of the present invention is constructed cyano-containing light emitting molecule and is used as blue light organic emissive LED lighting layer material
Material.
The present invention is from 3, and 4,5-tri-bromo nitrobenzenes set out, and introduces three tert-butyl benzene unit, profit by Suzuki reaction
Replacing with being reduced by nitro and changing into halogen atom, triphenylamine or carbazole etc. are introduced many phenyl benzene list by recycling Suzuki reaction
Unit, finally gives target compound by amino functional further.
The present invention has the following advantages and beneficial effect:
(1) present invention passes through a kind of new precursor, utilizes progressively Suzuki reaction to build many phenyl benzene unit.
(2) by the precise controlling of structure, by this kind of for many phenyl benzene, there is dividing of aggregation inducing Fluorescence Increasing (AEE) characteristic
Son is used for constructing light emitting molecule, effectively overcomes the device effect that aggregation inducing fluorescent quenching (ACQ) characteristic of light emitting molecule causes
Rate reduces and red shift of the emission spectra problem.
(3) compound of the present invention can be used as organic light-emitting diode layer material, and organic light emitting diode device
Demonstrating deep blue emission, chromaticity coordinates is positioned at (0.15,0.08), and current efficiency is 2.0cd/A.By doping, electric current further
Efficiency is up to 4.5cd/A, external quantum efficiency 3.98%.
Detailed description of the invention
In order to be more fully understood that present disclosure, below in conjunction with specific embodiment, present disclosure is made furtherly
Bright, but the protection content of the present invention is not limited to following example.
Raw material used in the embodiment of the present invention can be buied by market, or available methods known in the art synthesize
Arrive.
The synthesis of embodiment 1 compound 5-11
The synthetic route of the present invention is as follows:
(1) under nitrogen atmosphere, in Schlenk pipe add compound 3,4,5-tri-bromo nitrobenzene (0.9g, 2.5mmol),
To tert-butylbenzeneboronic acid (2.67g, 15mmol), potassium carbonate (10.35g, 75mmol) and the Pd (PPh of catalytic amount3)4, it is subsequently adding
Toluene or oxolane (75mL), deoxidized water (37.5mL) and ethanol (20mL), make it fully react in 12 hours in 90 DEG C of reactions.
After completion of the reaction, reactant liquor is cooled to room temperature, extracts with toluene, collect organic phase, then use anhydrous Na2SO4It is dried, obtains
Thick product.It is with petroleum ether and dichloromethane (v/v, 2/1) for eluent, by thick product silica gel chromatograph column chromatography, isolated and purified,
Vacuum drying, obtains white solid (1.13g, productivity 87%), and uses1H NMR、13C NMR, MS and EA carry out structural characterization to it,
Confirm that this white solid is compound 1.1H NMR(300MHz,CDCl3) δ (ppm): 8.27 (s, 2H), 7.20 (d, J=8.1Hz,
4H), 7.01 (m, 6H), 6.70 (d, J=8.1Hz, 2H), 1.26 (s, 18H), 1.19 (s, 9H).13C NMR(100MHz,
CDCl3)δ(ppm):150.2,150.0,146.9,146.3,143.7,137.3,135.2,130.9,129.6,124.9,
124.4,123.9,34.6,31.5.MS(EI),m/z:519.61([M+],calcd for C36H41NO2,519.31)
.Anal.Calcd for C36H41NO2:C,83.20；H,7.95；N,2.70.Found:C,83.46；H,8.10；N,2.74.
The structural formula of compound 1 is
(2) 250mL round-bottomed flask adds compound 1 (519mg, 1mmol) and 150mL glacial acetic acid, reflux and fill for 15 minutes
Divide and be down to 100 DEG C after dissolving, after adding 3mL water, be slowly added to reproducibility iron powder (280mg, 5mmol).After reacting 30 minutes, will
Reactant liquor is poured in a large amount of water, and precipitation solid is collected by filtration, and is dried and is directly used in next step.
Dried solid is dissolved under 10mL chloroform and the mixed solvent of 30mL acetic acid, ice bath and is slowly added to bromine
(320mg, 2mmol), recession in 20 minutes is removed ice bath, is added sodium sulfite aqueous solution and (can be selected for other reducing agent, if sulphur is for sulphur
Acid sodium) cancellation reaction.Dichloromethane extracts, with petroleum ether and dichloromethane (v/v, 2/1) for eluent, by thick product silica gel
Column chromatography, isolated and purified, vacuum drying, obtain white solid (511mg, productivity 79%), and use1H NMR、13C NMR、MS
With EA, structure is characterized, it was demonstrated that this white solid is compound 2.1H NMR(300MHz,CDCl3)δ(ppm):7.13(d,J
=8.1Hz, 4H), 6.93 (d, J=8.7Hz, 4H), 6.74 (d, J=8.1Hz, 2H), 6.48 (d, J=8.4Hz, 2H), 1.20
(s,18H),1.04(s,9H).13C NMR(100MHz,CDCl3)δ(ppm):149.4,147.8,142.2,141.4,138.2,
137.0,133.8,131.0,129.9,124.2,123.2,110.0,34.5,34.1,31.5,31.3.MS(EI),m/z:
647.52([M+],calcd for C36H41Br2N,645.16).Anal.Calcd for C36H41Br2N:C,66.78；H,
6.38；N,2.16.Found:C,66.58；H,6.41；N,2.33.
The structural formula of compound 2 is
(3) compound 2 (647mg, 1mmol), cuprous cyanide (117mg, 1.3mmol) and 40mL solvent dimethyl sulfoxide are added
Enter in Schlenk pipe, under protective gas atmosphere, after 50 DEG C are stirred half an hour, in above-mentioned reactant liquor, be slowly added to the tertiary fourth of nitrous acid
Ester (0.357mL, 3mmol), continues stirring 2 hours.Reaction is cooled to room temperature after terminating, and adds the hydrochloric acid of 1M concentration in reactant liquor
The aqueous solution, extracts with dichloromethane, collects organic phase and is dried with anhydrous sodium sulfate.With petroleum ether and dichloromethane (v/v, 1/
1) being eluent, product is used silica gel chromatograph column chromatography, isolated and purified, vacuum drying, obtain white solid (453mg produces simultaneously
Rate 72%) and faint yellow solid (137mg, productivity 21%), and use1H NMR、13C NMR, MS and EA carry out structural table to the two
Levying, it was demonstrated that this white solid is compound 3, faint yellow solid is compound 4.
Compound 3:1H NMR(300MHz,CDCl3) δ (ppm): 8.01 (s, 1H), 7.13 (d, J=8.4Hz, 4H), 6.91
(d, J=8.4Hz, 4H), 6.78 (d, J=8.4Hz, 2H), 6.50 (d, J=8.4Hz, 2H), 1.20 (s, 18H), 1.05 (s,
9H).13C NMR(100MHz,CDCl3)δ(ppm):149.7,148.6,145.2,141.9,137.1,136.5,134.7,
130.3,130.0,124.3,123.5,123.4,34.6,34.3,31.4,31.3.MS(EI),m/z:632.50([M+],
calcd for C36H40Br2,630.15).Anal.Calcd for C36H40Br2:C,68.36；H,6.37.Found:C,
68.48；H,6.14.
The structural formula of compound 3 is
Compound 4:1H NMR(300MHz,CDCl3) δ (ppm): 7.16 (d, J=8.4Hz, 4H), 6.89 (d, J=
8.7Hz, 4H), 6.81 (d, J=8.7Hz, 2H), 6.48 (d, J=8.4Hz, 2H), 1.20 (s, 18H), 1.05 (s, 9H).13C
NMR(100MHz,CDCl3)δ(ppm):150.5,149.4,148.9,143.6,136.3,135.5,129.8,129.6,
127.3,124.6,123.6,118.7,117.5,34.6,34.3,31.4,31.2.MS(EI),m/z:657.51([M+],
calcd for C36H37Br2N,655.14).Anal.Calcd for C36H37Br2N:C,67.19；H,5.80；N,
2.18.Found:C,67.45；H,6.09；N,2.21.
The structural formula of compound 4 is
(4), under protective gas atmosphere, Schlenk pipe adds compound 3 (211mg, 0.33mmol), 4-boric acid triphenylamine
(381mg, 1.32mmol), potassium carbonate (920mg, 6.6mmol) and the Pd (PPh of catalytic amount3)4, it is subsequently adding toluene (8mL), second
Alcohol (1.5mL) and deoxidized water (3.3mL), make it fully react in 24 hours in 90-100 DEG C of stirring.After completion of the reaction, product is cold
But to room temperature, extract with toluene, collect organic phase, use anhydrous Na2SO4It is dried, obtains thick product.With petroleum ether and dichloromethane
(v/v, 1/1) is eluent, and product is used silica gel chromatograph column chromatography, isolated and purified, vacuum drying, obtain white solid (234mg,
Productivity 74%), and use1H NMR、13Structure is characterized by C NMR, MS and EA, it was demonstrated that this white solid is compound 5.1H
NMR(300MHz,CDCl3)δ(ppm):7.57(s,1H),7.19(m,8H),7.04(m,20H),6.86(m,6H),6.75(d,J
=8.7Hz, 4H), 6.66 (d, J=8.4Hz, 2H), 1.19 (s, 18H), 1.11 (s, 9H).13C NMR(100MHz,CDCl3)δ
(ppm):148.1,147.8,145.6,142.0,140.2,139.3,137.5,137.2,136.4,131.2,131.1,
130.8,130.2,129.1,124.0,123.4,123.1,123.0,122.5,34.2,34.1,31.3,31.2.MS(EI),m/
z:960.90([M+],calcd for C72H68N2,960.54).Anal.Calcd for C72H68N2:C,89.96；H,7.13；
N,2.91.Found:C,89.74；H,7.35；N,2.73.
The structural formula of compound 5 is
(5) synthesis step of compound 6-11 is identical with compound 5, and its structure is all passed through1H NMR、13C NMR, MS and EA
Sign, specific as follows:
Compound 6: white powder, productivity is 83%.1H NMR(300MHz,CDCl3) δ (ppm): 8.15 (d, J=
7.8Hz, 4H), 7.82 (s, 1H), 7.38 (m, 20H), 7.05 (d, J=8.1Hz, 4H), 6.92 (d, J=8.1Hz, 2H), 6.85
(d, J=7.8Hz, 4H), 6.76 (d, J=8.1Hz, 2H), 1.24 (s, 18H), 1.15 (s, 9H).13C NMR(100MHz,
CDCl3)δ(ppm):148.5,148.1,142.4,141.1,140.8,140.1,140.0,137.1,136.8,135.5,
131.4,131.3,131.1,130.2,126.0,125.8,123.8,123.3,120.3,119.8,109.7,106.1,34.3,
34.1,31.3,31.2.MS(EI),m/z:956.81([M+],calcd for C72H64N2,956.51).Anal.Calcd for
C72H64N2:C,90.34；H,6.74；N,2.93.Found:C,90.43；H,6.89；N,3.17.
The structural formula of compound 6 is
Compound 7: white powder, productivity is 85%.1H NMR(300MHz,CDCl3)δ(ppm):7.20(m,8H),7.02
(m, 24H), 6.84 (d, J=7.8Hz, 2H), 6.69 (d, J=8.1Hz, 4H), 6.62 (d, J=8.7Hz, 2H), 1.18 (s,
18H),1.08(s,9H).13C NMR(100MHz,CDCl3)δ(ppm):148.6,148.4,147.6,146.7,146.0,
144.4,141.4,136.3,135.9,132.4,131.1,130.7,130.3,129.1,124.3,123.5,123.3,
122.7,122.6,118.1,112.6,34.2,34.1,31.2,31.1.MS(EI),m/z:985.79([M+],calcd for
C73H67N3,985.53).Anal.Calcd for C73H67N3:C,88.89；H,6.85；N,4.26.Found:C,88.65；H,
7.03；N,4.11.
The structural formula of compound 7 is
Compound 8: white powder, productivity is 79%.1H NMR(300MHz,CDCl3) δ (ppm): 8.14 (d, J=
7.5Hz, 4H), 7.51 (d, J=8.1Hz, 4H), 7.44 (d, J=8.4Hz, 4H), 7.38 (d, J=7.2Hz, 4H), 7.30 (m,
8H), 7.03 (d, J=8.1Hz, 4H), 6.92 (d, J=7.8Hz, 2H), 6.79 (d, J=8.1Hz, 4H), 6.73 (d, J=
7.8Hz,2H),1.22(s,18H),1.12(s,9H).13C NMR(100MHz,CDCl3)δ(ppm):149.2,146.8,
144.0,142.3,140.9,137.7,136.9,135.7,132.1,131.0,130.9,130.6,126.6,126.1,
124.1,123.8,123.5,120.4,120.1,112.4,109.9,34.5,34.4,31.4,31.3.MS(EI),m/z:
981.98([M+],calcd for C73H63N3,981.50).Anal.Calcd for C73H63N3:C,89.26；H,6.46；N,
4.28.Found:C,88.91；H,6.58；N,4.23.
The structural formula of compound 8 is
Compound 9: white powder, productivity 71%.1H NMR(300MHz,CDCl3)δ(ppm):7.18(m,8H),6.97
(m,20H),6.76(m,6H),6.48(m,6H),1.17(s,18H),1.06(s,9H).13C NMR(100MHz,CDCl3)δ
(ppm):148.8,148.6,147.7,147.2,144.3,141.4,139.7,136.3,135.7,131.0,130.6,
130.5,129.3,128.9,124.9,124.6,124.4,123.9,123.8,123.4,122.9,122.8,117.8,
113.0,34.4,34.3,31.4,31.3.MS(EI),m/z:985.83([M+],calcd for C73H67N3,985.53)
.Anal.Calcd for C73H67N3:C,88.89；H,6.85；N,4.26.Found:C,88.70；H,6.58；N,4.37.
The structural formula of compound 9 is
Compound 10: white powder, productivity is 74%.1H NMR(300MHz,CDCl3) δ (ppm): 8.09 (d, J=
8.1Hz, 4H), 7.58 (m, 4H), 7.45 (m, 4H), 7.29 (m, 8H), 7.03 (m, 6H), 6.83 (m, 4H), 6.71 (d, J=
7.8Hz, 2H), 6.67 (d, J=7.8Hz, 2H), 6.54 (d, J=8.1Hz, 2H), 1.14 (s, 18H), 1.09 (s, 9H).13C
NMR(100MHz,CDCl3)δ(ppm):149.5,149.1,147.3,143.8,142.2,141.0,140.7,137.5,
136.2,135.6,131.2,131.0,130.6,129.8,129.6,129.3,128.9,126.7,126.3,124.4,
123.8,123.6,120.4,120.2,117.9,113.4,110.2,34.6,34.5,31.6,31.5.MS(EI),m/z:
981.92([M+],calcd for C73H63N3,981.50).Anal.Calcd for C73H63N3:C,89.26；H,6.46；N,
4.28.Found:C,89.01；H,6.55；N,4.33.
The structural formula of compound 10 is
Compound 11: pale yellow powder, productivity is 72%.1H NMR(300MHz,CDCl3)δ(ppm):8.13(s,2H),
8.07 (d, J=7.5Hz, 2H), 7.54 (m, 8H), 7.38 (m, 6H), 7.25 (m, 6H), 6.82 (m, 6H), 6.80 (m, 4H),
6.64(m,2H),1.08(s,9H),1.04(s,18H).13C NMR(100MHz,CDCl3)δ(ppm):148.4,148.2,
146.4,145.1,141.6,141.0,137.6,136.7,136.1,131.0,130.8,130.7,130.6,130.4,
130.2,129.9,129.7,128.4,127.4,127.3,126.9,125.8,123.9,123.6,123.5,123.3,
122.9,122.4,120.4,119.9,118.6,114.2,109.7,109.0,34.1,31.1,30.9.MS(EI),m/z:
981.86([M+],calcd for C73H63N3,981.50).Anal.Calcd for C73H63N3:C,89.26；H,6.46；N,
4.28.Found:C,88.83；H,6.59；N,4.15.
The structural formula of compound 11 is
After the embodiment of the present invention collects organic phase, use anhydrous Na2SO4It is dried, it would however also be possible to employ other drier, as long as
The moisture in organic phase can be removed and do not react with organic phase.
The compound 5-11 of the present invention is used as the emitting layer material of blue light organic emissive diode.Divide with the luminescence of the present invention
The device current efficiency that sub-5-11 records as emitting layer material is up to 4.5cd/A, the chromaticity coordinates of its correspondence be (0.16,
0.11).Undoped device current efficiency 2.0cd/A, the chromaticity coordinates of its correspondence is (0.15,0.08).
Claims (6)
1. more than phenyl benzene constructs cyano-containing light emitting molecule, it is characterised in that have a structure shown in logical formula (I):
Wherein:
R=-C ≡ N, Ar1For
2. the method that many phenyl benzene that one kind is prepared described in claim 1 constructs cyano-containing light emitting molecule, it is characterised in that include
Following steps:
(1) under protective gas atmosphere, in Schlenk pipe add mol ratio be the 3 of 1:6:30,4,5-tri-bromo nitrobenzenes, to tertiary fourth
Base phenyl boric acid, potassium carbonate, and the Pd (PPh of catalytic amount3)4, it is subsequently adding toluene, second alcohol and water or oxolane and water, in
80-100 DEG C of reaction, to fully, obtains compound 1；Wherein, water is 1L/2mol with the amount ratio of potassium carbonate, the structure of compound 1
Formula is
(2) compound 1 is added in glacial acetic acid, be heated to reflux to solid being completely dissolved, obtain solution A；Solution A is cooled to
90-100 DEG C, adding the water that volume is glacial acetic acid 2%, be then slowly added into reduced iron powder, solution A immediately becomes black, black
Backflow 30 minutes is continued after taking off；Stop heating, after solution A is down to room temperature, be poured in a large amount of water, have solid to separate out,
Filter out solid and be dried；Dried solid is dissolved in chloroform or dichloromethane, under ice bath, slowly drips bromine wherein,
Ice bath is removed in recession in 20 minutes, adds reducing agent cancellation reaction, i.e. obtains compound 2；Wherein, compound 1, reduced iron powder and bromine
Mol ratio be 1:5:2, the structural formula of described compound 2 is
(3) under protective gas atmosphere, compound 2, cuprous cyanide and dimethyl sulfoxide being added in Schlenk pipe, 50 DEG C are stirred 30 points
Zhong Hou, is slowly added to nitrite tert-butyl, continues stirring reaction 2 hours, i.e. obtains compound 4；Wherein, compound 2, cyaniding Asia
The mol ratio of copper and nitrite tert-butyl is 1:1.3:3；The structural formula of described compound 4 is
(4), under protective gas atmosphere, Schlenk pipe adds compound 4, boric acid compound, potassium carbonate and the Pd of catalytic amount
(PPh3)4, wherein, compound 4, boric acid compound, the mol ratio of potassium carbonate are 1:4:20；It is subsequently adding toluene, ethanol and goes
Oxygen water, in 90-100 DEG C of stirring to fully reaction；I.e. obtain the compound of structure shown in logical formula (I)；Described boric acid class chemical combination
Thing is 4-boric acid triphenylamine, 4-(9-carbazyl) phenyl boric acid, 3-boric acid triphenylamine, 3-(9-carbazyl) phenyl boric acid, N-phenyl click
One in azoles-3-boric acid.
Many phenyl benzene the most according to claim 2 constructs the preparation method of cyano-containing light emitting molecule, it is characterised in that: described
In step (1), toluene, the volume ratio of second alcohol and water are 4:1:2, or the volume ratio of oxolane and water is 2:1.
Many phenyl benzene the most according to claim 2 constructs the preparation method of cyano-containing light emitting molecule, it is characterised in that: step
(2) reducing agent described in is sodium sulfite or sodium thiosulfate.
Many phenyl benzene the most according to claim 2 constructs the preparation method of cyano-containing light emitting molecule, it is characterised in that: step
(1), the protective gas described in step (3) and step (4) is nitrogen.
6. the many phenyl benzene described in claim 1 constructs cyano-containing light emitting molecule as blue light organic emissive LED lighting layer material
The application of material.
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