CN107936013A - A kind of D π A π D type quinazolinone third order non-linear optical materials and its preparation method and application - Google Patents
A kind of D π A π D type quinazolinone third order non-linear optical materials and its preparation method and application Download PDFInfo
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- CN107936013A CN107936013A CN201711112410.5A CN201711112410A CN107936013A CN 107936013 A CN107936013 A CN 107936013A CN 201711112410 A CN201711112410 A CN 201711112410A CN 107936013 A CN107936013 A CN 107936013A
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- RPJFJMZAEUXPMT-UHFFFAOYSA-N C[BrH]c(cc1)cnc1Br Chemical compound C[BrH]c(cc1)cnc1Br RPJFJMZAEUXPMT-UHFFFAOYSA-N 0.000 description 1
- MBVCESWADCIXJN-UHFFFAOYSA-N O=C(c1cc(Br)ccc1N1)C1=O Chemical compound O=C(c1cc(Br)ccc1N1)C1=O MBVCESWADCIXJN-UHFFFAOYSA-N 0.000 description 1
- GQPYRDPFUVXPNP-UHFFFAOYSA-N OC(c1c2)N(C=C(C=C3)Br)C3=Nc1ccc2Br Chemical compound OC(c1c2)N(C=C(C=C3)Br)C3=Nc1ccc2Br GQPYRDPFUVXPNP-UHFFFAOYSA-N 0.000 description 1
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- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
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Abstract
The object of the present invention is to provide the synthetic method of D π A π D type quinazolinone third order non-linear optical materials, this kind of compound is the good organic fluorescence materials of excellent in optical properties, stability.The present invention introduces triple carbon-carbon bonds using quinazolinone as precursor structure, in female ring and extends whole big pi-conjugated system, has obtained a kind of optical material for having preferable third-order non-linear response.The technical solution adopted by the present invention is：The present invention provides D π A π D type quinazolinone third order non-linear optical materials shown in a kind of formula (I)：In formula (I)：R is the alkoxy of hydrogen, halogen, the alkyl of C1 C4 or C1 C4.
Description
(1) technical field
The invention belongs to new material technology field, and in particular to a kind of D- π-A- π-D type quinazolinone third-order non-linear light
Learn material and its preparation method and application.
(2) background technology
21 century is an information age to run at high speed, as a large amount of processing people of information are to devices such as display imagings
The performance requirement of part is higher and higher, and developing rapidly for photoelectronics is greatly facilitated.Therefore, have specific information processing function and
The nonlinear optical material of super fast response becomes the main body of Future Information Materials.Different from inorganic nonlinear optics function material
Material, organic non-linear luminous energy material have can MOLECULE DESIGN and cutting, response is high, switching speed is fast, light injury threshold is high, machine
The advantages that tool intensity is excellent, dielectric constant is low, processing performance is good.The application of organic non linear optical material is concentrated mainly on two sides
Face：First, carrying out the conversion of frequency of light wave, i.e., widened by modes such as frequency multiplication and frequency, difference frequency or mixing, optical parameter vibrations sharp
The scope of optical wavelength, opens up new laser light source.Two in fields such as image procossing, all-optical switch, optical storage and memory systems
There is larger application potential.Therefore, design and synthesize has with the new of excellent optical performance, heat endurance and processing performance
Machine third order non-linear optical material is current very active research field.
The polarization of Developments of Third-order Nonlinear Optical Polymers comes from the delocalization of pi-electron on main chain, and electric charge is be easily moved, medium grain
The time that muon polarization is produced needed for electric dipole is shorter, shows strong photoelectricity Coincidence.The pi-conjugated polymer in part has
Good electrochemical properties, spectrochemical property and good mechanical performance and processing performance, pass through rationally repairing for molecular structure
Decorations, to make molecule displays go out big delocalization degree, larger absorbing wavelength, less band gap, big molecular dipole moment, obtains
The third order non-linear optical material of higher three ranks hyperpolarizability χ (3) value.11H pyridos [2,1-b] quinoline azoles -11- ketone, structural formulaAbbreviation quinazolinone, due to, there are stronger π-π interactions, easily being formed between its planar rigidity molecule of the skeleton
Molecular columns, form layer by continuous intramolecular hydrogen bond between molecular columns, stereochemical structure are reconstructed by layer.In addition, quinazoline
Ketone makes it be widely used in chemical sensitisation, especially molecule assembling, organic photoelectric field because of larger pi-conjugated system.
There is be closely connected between organic pigment electronic structure of molecule and geometric configuration.It is generally acknowledged that third-order non-linear light
It is related with the big pi-conjugated structure of delocalization in molecule to learn performance, the big π structures that Quinazol derivative is highly conjugated by its female ring,
And its multiple avtive spots that can be modified, there is very big application potential as third order non-linear optical material.With reference to three ranks
The design principle of nonlinear optical material, is subject to quinazolinone is modified to obtain special with high response and stronger photoelectric coupling
The quinazolinone third order non-linear optical material of sign.
(3) content of the invention
The object of the present invention is to provide a kind of D- π-A- π-D type quinazolinone third order non-linear optical materials and its preparation side
Method and application, the present invention are devised using quinazolinone as mother according to the molecular characterization of Developments of Third-order Nonlinear Optical Polymers
Ring and electron acceptor, triple carbon-carbon bonds are introduced in female ring and extend whole big pi-conjugated system, have obtained a series of excellent in optical properties
Organic fluorescence materials.
The technical solution adopted by the present invention is：
The present invention provides D-pi-A-π-D type quinazolinone third order non-linear optical materials, it is characterised in that described
Shown in D- π-A- π-D type quinazolinone third order non-linear optical materials structural formula such as formula (I),
In formula (I)：R is hydrogen, halogen, the alkyl of C1-C4, the alkoxy of C1-C4.
Second object of the present invention is to provide a kind of above-mentioned D- π-A- π-D type quinazolinone third-order nonlinear opticals of synthesis
The method of material (compound shown in formula I), the synthetic method include the following steps：
(1) Ullmann reacts
Under the conditions of alkali A and copper catalyst A, the 5-bromoisatin and 2,5- dibromo pyridine shown in formula (II) in solvent orange 2 A,
Ullmann reactions are carried out at 90~150 DEG C, obtain two bromo compounds shown in formula (III)；
(2) Sonogashira coupling reactions
Under nitrogen protection, two bromo compounds shown in formula (III) are added in solvent B, in alkali B, palladium catalyst A and copper
Under the action of catalyst B, Sonogashira coupling reactions are carried out at 60~100 DEG C with phenylacetylene or substituted phenylacetylene, are obtained
To the Quinazol derivative shown in formula (I)；
In formula (I)：R is hydrogen, halogen, the alkyl of C1-C4, the alkoxy of C1-C4
Preferably, solvent orange 2 A described in step (1) is n,N-Dimethylformamide, n,N-dimethylacetamide, dimethyl
Sulfoxide, toluene or Isosorbide-5-Nitrae-dioxane, alkali A are sodium acid carbonate, potassium hydroxide, sodium carbonate, potassium carbonate or cesium carbonate, copper catalyst
A is stannous chloride, cuprous bromide, cuprous iodide, cupric oxide or copper acetate monohydrate, the 5- bromine indigo shown in the formula (II)
The molar ratio of red, 2,5- dibromo pyridines, alkali A and copper catalyst A is 1：1~2：2~4：0.1~0.6, the organic solvent A
Volumetric usage 10~30mL/g is calculated as with the quality of the quinazolinone shown in formula (II).
Preferably, step (2) the solvent B is tetrahydrofuran, n,N-Dimethylformamide, N, N- dimethylacetamides
Amine, dimethyl sulfoxide (DMSO), toluene or 1,4- dioxane；The palladium catalyst A is double (triphenylphosphine) palladium chloride (PPh3)2PdCl2Or tetrakis triphenylphosphine palladium Pd (PPh3)4；Copper catalyst B is stannous chloride, cuprous bromide or cuprous iodide；Alkali B is organic
Amine, is preferably triethylamine, ethylenediamine or diisopropylamine；Two bromo compounds, phenylacetylene or substitution shown in the formula (III)
Phenylacetylene, the molar ratio of palladium catalyst A and copper catalyst B be 1：2~6：0.05~0.3：0.1~0.6；Described is organic molten
The volumetric usage of agent B is calculated as 20~50mL/g with the quality of two bromo compounds shown in formula (III)；The volume of the alkali B
The volumetric usage of dosage and organic solvent B ratio is 2：1.
Third object of the present invention provides the D- π-A- π-D type quinazolinone third order non-linear optical materials in fluorescence
Application in material.
Beneficial effects of the present invention：
The present invention introduces the pi-conjugated system that the phenylacetylene base with substituent expands molecule on quinazolinone, reduces molecule
Band gap so that ultraviolet spectra occur red shift.
D- π-A- π-D type quinazolinones the third order non-linear optical materials of the synthesis of the present invention have preferable heat endurance
(TD (5%)>250 DEG C), chemical property shows that its HOMO/LUMO energy level difference reduces, and is conducive to the transfer of intramolecular charge.Should
Series compound has excellent third order non-linear optical property, has in the application of device for non-linear optical latent well
Power.
(4) illustrate
Fig. 1 is the quinazolinone female ring and D- π-A- π-D types Quinazol derivatives (I) prepared in embodiment 1-6 two
Ultraviolet visible absorption spectra figure in chloromethanes.
Fig. 2 is the quinazolinone female ring and D- π-A- π-D types Quinazol derivatives (I) prepared in embodiment 1-6 two
Fluorescence spectra in chloromethanes.
Fig. 3 is the quinazolinone female ring and D- π-A- π-D types Quinazol derivatives (I) prepared in embodiment 1-6 two
Normalization perforate Z scanning curves in chloromethanes.
Fig. 4 is the quinazolinone female ring and D- π-A- π-D types Quinazol derivatives (I) prepared in embodiment 1-6 two
Normalization closed pore Z scanning curves in chloromethanes.
(5) embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This：
Embodiment 1
(1) Ullmann reacts
By 5-bromoisatin (1.13g, 5mmol), 2,5- dibromo pyridines (1.18mg, 5mmol), sodium acid carbonate (0.84g,
10mmol), and Cu (OAc)2·H2O (0.10mg, 0.5mmol) is dissolved in 20mL DMF, after stirring 24h at 90 DEG C, is stopped
Reaction, reaction solution is poured into 150mL saturated salt solutions, treats that solid separates out completely, is filtered, and filter cake purifies (V through silica gel column chromatography
(petroleum ether)/V (dichloromethane)=2/1) to obtain yellow solid be that compound III is 1.17g, yield 67% is (with compound
The gauge of material).
(2) Sonogashira coupling reactions
Under nitrogen protection, by two bromo compound III (0.12g, 0.35mmol), cuprous iodide (0.0065g,
0.035mmol) it is added in three-neck flask with tetrakis triphenylphosphine palladium (0.021g, 0.0175mmol), adds under a nitrogen atmosphere
Enter the anhydrous triethylamines of 20mL and the DMF of 10mL.Reactant first at 80 DEG C stirs 1h, add dropwise phenylacetylene (0.071g,
0.7mmol) into reaction system, reaction solution is warming up to 90 DEG C, and TCL detections, stirring stops after reacting 20h.After cooling, will be anti-
Answer liquid to be poured into 30mL saturated salt solutions, treat that solid separates out completely, filter, filter cake purifies (V (oil through silica gel column chromatography
Ether)/V (dichloromethane)=1/1) to obtain yellow Quinazol derivative I-1 be 0.11g, yield 82% is (with the material of compound
Gauge).
Embodiment 2
(1) Ullmann reacts
By 5-bromoisatin (1.13g, 5mmol), 2,5- dibromo pyridines (1.42mg, 6mmol), potassium carbonate (1.38g,
10mmol), it is dissolved in CuI (0.19mg, 1mmol) in 15mL DMSO, after stirring 24h at 100 DEG C, stops reaction, will be anti-
Answer liquid to be poured into 150mL saturated salt solutions, treat that solid separates out completely, filter, filter cake purify through silica gel column chromatography (V (petroleum ether)/
V (dichloromethane)=2/1) to obtain yellow solid be that compound III is 0.91g, yield 52% is (with the amount of the material of compound
Meter).
(2) Sonogashira coupling reactions
Under nitrogen protection, by two bromo compound III (0.12g, 0.35mmol), stannous chloride (0.003g,
0.04mmol) it is added to double (triphenylphosphine) palladium chlorides (0.01g, 0.02mmol) in three-neck flask, under a nitrogen atmosphere
Add the anhydrous diisopropylamines of 20mL and the 1,4- dioxane of 10mL.Reactant first stirs 1h at 80 DEG C, adds dropwise
To Methoxy-phenylacetylene (0.28g, 2.10mmol) into reaction system, reaction solution is warming up to 90 DEG C, and TCL detections, stirring is reacted
Stop after 20h.After cooling, reaction solution is poured into 30mL saturated salt solutions, treats that solid separates out completely, filtered, filter cake warp
It is 0.13g that silica gel column chromatography purification (V (petroleum ether)/V (dichloromethane)=1/1), which obtains yellow Quinazol derivative I-2, is received
Rate 79% (with the gauge of the material of compound).
Embodiment 3
(1) Ullmann reacts
By 5-bromoisatin (1.13g, 5mmol), 2,5- dibromo pyridines (1.66mg, 7mmol), sodium carbonate (1.59g,
15mmol), it is dissolved in 20mL Isosorbide-5-Nitraes-dioxane with CuBr (0.14mg, 1mmol), after stirring 24h at 90 DEG C, stops
Reaction, reaction solution is poured into 150mL saturated salt solutions, treats that solid separates out completely, is filtered, and filter cake purifies (V through silica gel column chromatography
(petroleum ether)/V (dichloromethane)=2/1) to obtain yellow solid be that compound III is 0.97g, yield 55% is (with compound
The gauge of material).
(2) Sonogashira coupling reactions
Under nitrogen protection, by two bromo compound III (0.12g, 0.35mmol), cuprous bromide (0.03g,
0.21mmol) it is added in three-neck flask with tetrakis triphenylphosphine palladium (0.12g, 0.11mmol), adds under a nitrogen atmosphere
The DMSO of the anhydrous ethylenediamines of 20mL and 10mL.Reactant first stirs 1h at 80 DEG C, adds dropwise to chlorobenzene acetylene
(0.10g, 0.7mmol) into reaction system, reaction solution is warming up to 90 DEG C, and TCL detections, stirring stops after reacting 20h.It is to be cooled
Afterwards, reaction solution is poured into 30mL saturated salt solutions, treats that solid separates out completely, filtered, filter cake purifies (V through silica gel column chromatography
(petroleum ether)/V (dichloromethane)=1/1) to obtain yellow Quinazol derivative I-3 be 0.11g, yield 69% is (with compound
Material gauge).
Embodiment 4
(1) Ullmann reacts
By 5-bromoisatin (1.13g, 5mmol), 2,5- dibromo pyridines (1.18mg, 5mmol), cesium carbonate (3.26g,
10mmol), and Cu (OAc)2·H2O (0.20mg, 1mmol) is dissolved in 30mL toluene, after stirring 24h at 100 DEG C, is stopped
Reaction, reaction solution is poured into 150mL saturated salt solutions, treats that solid separates out completely, is filtered, and filter cake purifies (V through silica gel column chromatography
(petroleum ether)/V (dichloromethane)=2/1) to obtain yellow solid be that compound III is 1.23g, yield 70% is (with compound
The gauge of material).
(2) Sonogashira coupling reactions
Under nitrogen protection, by two bromo compound III (0.12g, 0.35mmol), stannous chloride (0.02g,
0.21mmol) it is added to double (triphenylphosphine) palladium chlorides (0.07g, 0.11mmol) in three-neck flask, under a nitrogen atmosphere
Add the anhydrous diisopropylamines of 20mL and the THF of 10mL.Reactant first stirs 1h at 80 DEG C, adds dropwise to methylbenzene second
Alkynes (0.24g, 2.10mmol) is into reaction system, and reaction solution is warming up to 90 DEG C, and TCL detections, stirring stops after reacting 20h.Treat
After cooling, reaction solution is poured into 30mL saturated salt solutions, treats that solid separates out completely, is filtered, filter cake is carried through silica gel column chromatography
It is 0.12g that pure (V (petroleum ether)/V (dichloromethane)=1/1), which obtains yellow Quinazol derivative I-4, and yield 80% is (to change
The gauge of the material of compound).
Embodiment 5
(1) Ullmann reacts
By 5-bromoisatin (1.56g, 5mmol), 2,5- dibromo pyridines (1.42mg, 6mmol), potassium hydroxide (0.56g,
10mmol), it is dissolved in CuCl (0.10mg, 1mmol) in 30mL DMF, after stirring 24h at 150 DEG C, stops reaction, will be anti-
Answer liquid to be poured into 150mL saturated salt solutions, treat that solid separates out completely, filter, filter cake purify through silica gel column chromatography (V (petroleum ether)/
V (dichloromethane)=2/1) to obtain yellow solid be that compound III is 0.83g, yield 47% is (with the amount of the material of compound
Meter).
(2) Sonogashira coupling reactions
Under nitrogen protection, by two bromo compound III (0.12g, 0.35mmol), cuprous iodide (0.03g,
0.18mmol) it is added to double (triphenylphosphine) palladium chlorides (0.02g, 0.04mmol) in three-neck flask, under a nitrogen atmosphere
Add the anhydrous triethylamines of 20mL and the DMA of 10mL.Reactant first stirs 1h at 80 DEG C, adds dropwise to propyl group phenylacetylene
(0.25g, 1.75mmol) into reaction system, reaction solution is warming up to 90 DEG C, and TCL detections, stirring stops after reacting 20h.Treat cold
But after, reaction solution is poured into 30mL saturated salt solutions, treats that solid separates out completely, is filtered, filter cake is purified through silica gel column chromatography
It is 0.12g that (V (petroleum ether)/V (dichloromethane)=1/1), which obtains yellow Quinazol derivative I-5, and yield 74% is (with chemical combination
The gauge of the material of thing).
Embodiment 6
(1) Ullmann reacts
By 5-bromoisatin (1.13g, 5mmol), 2,5- dibromo pyridines (2.37mg, 10mmol), sodium carbonate (2.12g,
20mmol), it is dissolved in CuO (0.24mg, 3mmol) in 15mL DMSO, after stirring 24h at 100 DEG C, stops reaction, will be anti-
Answer liquid to be poured into 150mL saturated salt solutions, treat that solid separates out completely, filter, filter cake purify through silica gel column chromatography (V (petroleum ether)/
V (dichloromethane)=2/1) to obtain yellow solid be that compound III is 0.9g, yield 51% is (with the amount of the material of compound
Meter).
(2) Sonogashira coupling reactions
Under nitrogen protection, by two bromo compound III (0.12g, 0.35mmol), cuprous iodide (0.01g,
0.07mmol) it is added in three-neck flask with tetrakis triphenylphosphine palladium (0.04g, 0.04mmol), adds under a nitrogen atmosphere
The toluene of the anhydrous triethylamines of 20mL and 10mL.Reactant first stirs 1h at 80 DEG C, adds dropwise to butyl phenylacetylene
(0.17g, 1.05mmol) into reaction system, reaction solution is warming up to 90 DEG C, and TCL detections, stirring stops after reacting 20h.Treat cold
But after, reaction solution is poured into 30mL saturated salt solutions, treats that solid separates out completely, is filtered, filter cake is purified through silica gel column chromatography
It is 0.13g that (V (petroleum ether)/V (dichloromethane)=1/1), which obtains yellow Quinazol derivative I-6, and yield 73% is (with chemical combination
The gauge of the material of thing).
Embodiment 7
Ultraviolet, the photoluminescent property of quinazolinone female ring and compound (I)
Wherein quinazolinone female ring structure is as follows：
D- π-A- π-D types Quinazol derivatives (I) and quinazolinone female ring are prepared in embodiment 1-6 in methylene chloride
Ultraviolet visible absorption spectra figure see attached drawing 1, fluorescence spectra in methylene chloride is shown in attached drawing 2：Compound is made into concentration is
1×10-5The solution of M, solvent are dichloromethane, and the instrument used is Shimadzu UV-1800 spectrophotometers.Fluorescence closes spectrum
See Fig. 2：Compound is made into concentration as 1 × 10-6The solution of M, solvent are dichloromethane, and the instrument used is Shimadzu RF-
6000PC spectrometers.(I) test performance is as shown in table 1：
Table 1：The optical property of D- π-A- π-D types Quinazol derivatives (I)
(Fig. 1) observes two prominent Absorption Characteristics in the spectrum of I-1~I-6.Relatively low wavelengthBar
Band is associated by the π-π * transition with benzene unit in molecule.Upper wavelengthBand may be with quinazolinone in molecule
π-π * the transition of unit is related.In contrast, compound I-2 shows slight red shift, and this phenomenon has two reasons.One side
Face, when the intensity increase of electron donor, red shift can occur for the absorption band of molecule, and the methoxyl group of I-2 is stronger donor residues
Group.On the other hand, it is pi-conjugated to form effective p- for the lone pair electrons of oxygen atom and the pi-electron of double bond.The absorption maximum of female ring is
354nm.Obviously, the λ abs of I-1~I-6 become red shift significantly compared with female ring, and which reflects extend pi-conjugated effect, i.e. benzene
The integration of ethyl-acetylene key causes.Ultraviolet-visible absorption spectroscopy shows, the functional group on quinazolinone can influence molecule ground state and
Excitation state, can carry out the photophysical property of modulating compound in the specific functional group of multiple avtive spots introducing.
Fluorescence emission spectrum (Fig. 2) has consistent variation tendency with ultra-violet absorption spectrum, and compound I-2 is shown slightly
Red shift, this is because to form effective p- pi-conjugated for the lone pair electrons of oxygen atom and the pi-electron of double bond.The fluorescent emission of female ring
Wavelength is about 440nm, shows strong blue-fluorescence.Obviously, the λ em of disubstituted quinazoline ketone derivatives I-1~I-6 are shown
Go out significant red shift, because pi-conjugated extend the integration for causing phenylacetylene base key.
Embodiment 8
The third-order non-linear of quinazolinone female ring and compound (I) detects
Wherein quinazolinone female ring structure is as follows：
D- π-A- π-D types the Quinazol derivatives (I) and quinazolinone female ring prepared in embodiment 1-6 is in dichloromethane
In normalization perforate Z scanning curves see attached drawing 3, normalization closed pore Z scanning curves in methylene chloride are shown in attached drawing 4：We
Test third-order non-linear is carried out using Z scanning techniques.Sample is made into concentration as 1 × 10-5The dichloromethane solution of M, is placed in thickness
Spend in the sample cell for 2mm, it is 0.1uJ, wavelength 532nm, pulse width 120fs to test pulsed laser energy used,
The hot spot waist radius of focal position is 30um.Before test sample, the non-of methylene chloride is under equal conditions tested
Linear optics effect, it is found that non-linear absorption is not present in it, therefore, can ignore the nonlinear optical effect of solvent to test
Influence.
Fig. 3 show the normalized signal that Quinazol derivative measures under the conditions of perforate, non-thread for describing three ranks
Property optical absorption process, wherein black small circle is the obtained data of experiment, and red solid line obtains curve for fitting.Allization
What compound was shown is all that at focal position, sample is respectively provided with most on the symmetrical anti-saturated absorption curve of focus (Z=0)
Low intensity in transmission.
In the presence of non-linear absorption, a perforate and closed pore curve have been done respectively, has been removed using the data measured under closed pore
To obtain single nonlinear refraction property after perforate data normalization.By this data processing, D- π-A- π-D types have been obtained
The nonlinear refraction property of Quinazol derivative, as shown in Figure 4.Figure 4, it is seen that after there is first paddy in all figures
The shape at peak, shows nonlinear refractive index n2>0, it is Self-focusing, the difference (Δ Tp-v) and three between wave crest and trough
Rank nonlinear refractive index n2 (m2/W) is related.
Third order non-linear optical material performance is by third order nonlinear susceptibility χ(3)Value assessment.Third-order non-linear polarization system
Number χ(3)Value is bigger, and the third-order non-linear performance of material is better.
According to equation calculation NLO parameters, and it is summarised in table 2.
Wherein n0It is the linear refractive index of methylene chloride, ω is the angular frequency of light field, and N is molecule per cubic centimeter
Number density, F is local field correction factor, equal to (n0 2+2)/3。
Table 2：The third-order non-linear parameter of D- π-A- π-D types Quinazol derivatives (I)
In table 2, χ(3)It is a macroscopical polarity effect parameter, with measured material for the third-order nonlinear susceptibility of material
Concentration it is related, embody molecule and intermolecular interactively；γ is the molecule second hyperpolarizabilitieof of material, is one microcosmic
Polarity effect parameter, it is unrelated with the concentration of measured material, do not embody molecule and intermolecular interactively, can more explain molecule
The nonlinear effect of microstructure aspect.Both characterize the important of material molecule micro molecule third order non-linear optical property
Index.
Data in Fig. 3 and table 2 clearly illustrate, the third-order nonlinear susceptibility χ of compound I-1~I-6(3)It is female ring
1.2~3.0 times, molecule second hyperpolarizabilitieof γ is 2.8~7.0 times of female ring.This is because by extending pi-conjugated system, it is right
The significant raising of Intramolecular electron transfer efficiency of whole quinazolinone structure.Meanwhile the because molecule both sides phenyl ring of compound I-2
The oxygen atom of upper methoxyl group can be pi-conjugated with phenyl ring and the whole big pi-conjugated effective p- of System forming, can with inhaling electrical quinoline
Oxazoline ketone female ring forms an electronics and inhales the system that supplies, therefore is responded than the third-order non-linear that other several compounds have higher.
In conclusion the Quinazol derivative that the present invention designs and synthesizes is a kind of very promising third order non-linear optical material.
The preferred embodiments of the invention are only listed above, and protection scope of the present invention is not restricted to this, this area
Any change that technical staff is made within the scope of the invention as claimed is each fallen within the scope of the present invention.
Claims (6)
- A kind of 1. D- π-A- π-D type quinazolinone third order non-linear optical materials, it is characterised in that the D- π-A- π-D types Shown in quinazolinone third order non-linear optical material structural formula such as formula (I),In formula (I)：R is the alkoxy of hydrogen, halogen, the alkyl of C1-C4 or C1-C4.
- 2. a kind of D- π-A- π-D type quinazolinone third order non-linear optical materials according to claim 1, its feature exist In the D- π-A- π-D type quinazolinone third order non-linear optical material structural formulas are preferably as follows：
- 3. a kind of method of the D- π-A- π-D type quinazolinone third order non-linear optical materials prepared described in claim 1, it is special Sign is that the preparation method includes the following steps：(1) Ullmann reactsUnder the conditions of alkali A and copper catalyst A, the 5-bromoisatin and 2,5- dibromo pyridine shown in formula (II) in solvent orange 2 A, 90~ Ullmann reactions are carried out at 150 DEG C, obtain two bromo compounds shown in formula (III)；(2) Sonogashira coupling reactionsUnder nitrogen protection, two bromo compounds shown in formula (III) are added in solvent B, in alkali B, palladium catalyst A and copper catalysis Under the action of agent B, Sonogashira coupling reactions are carried out at 60~100 DEG C with phenylacetylene or substituted phenylacetylene, obtain formula (IV) Quinazol derivative shown in；
- 4. D- π-A- π-D type quinazolinone optical material preparation methods as claimed in claim 3, it is characterised in that step (1) Described in solvent orange 2 A be n,N-Dimethylformamide, n,N-dimethylacetamide, dimethyl sulfoxide (DMSO), toluene or Isosorbide-5-Nitrae-dioxane, Alkali A is sodium acid carbonate, potassium hydroxide, sodium carbonate, potassium carbonate or cesium carbonate, and copper catalyst A is stannous chloride, cuprous bromide, iodine Change cuprous, cupric oxide or copper acetate monohydrate, the 5-bromoisatin, 2,5- dibromo pyridines, alkali A and copper shown in the formula (II) are urged The molar ratio of agent A is 1：1~2：2~4：0.1~0.6, the 5- of the volumetric usage of the organic solvent A shown in formula (II) The quality of bromo-isatin is calculated as 10~30mL/g.
- 5. D- π-A- π-D type quinazolinone optical material preparation methods as claimed in claim 3, it is characterised in that step (2) The solvent B is tetrahydrofuran, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO), toluene or 1,4- bis- Six ring of oxygen；The palladium catalyst A is double (triphenylphosphine) palladium chloride (PPh3)2PdCl2Or tetrakis triphenylphosphine palladium Pd (PPh3)4；Copper catalyst C is stannous chloride, cuprous bromide or cuprous iodide；Alkali B organic amines, are preferably triethylamine, ethylenediamine Or diisopropylamine；Two bromo compounds, phenylacetylene or substituted phenylacetylene, palladium catalyst A and copper shown in the formula (III) are urged The molar ratio of agent B is 1：2~6：0.05~0.3：0.1~0.6；The volumetric usage of the organic solvent C is with formula (III) institute The quality of two bromo compounds shown is calculated as 20~50mL/g；The volumetric usage of alkali B and the volumetric usage of organic solvent B Than for 2：1.
- 6. D- π-A- π-D type quinazolinone third order non-linear optical materials are in device for non-linear optical described in a kind of claim 1 Application.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108558872A (en) * | 2018-05-17 | 2018-09-21 | 浙江工业大学 | A kind of 8- substituted-phenyls-quinazolinones and its preparation method and application |
| CN108623584A (en) * | 2018-05-08 | 2018-10-09 | 浙江工业大学 | Bis- (aryl ethane base) quinazolinones of 2,8- and its preparation method and application |
| CN108727371A (en) * | 2018-05-21 | 2018-11-02 | 浙江工业大学 | Bis- (substituted-phenyl) quinazolinones of 2,8- and its preparation method and application |
| CN116003329A (en) * | 2023-01-10 | 2023-04-25 | 浙江工业大学 | T-type benzimidazole third-order nonlinear optical material, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104447580A (en) * | 2014-12-23 | 2015-03-25 | 湖南大学 | Method for synthesizing quinazolone compounds |
| CN108623584A (en) * | 2018-05-08 | 2018-10-09 | 浙江工业大学 | Bis- (aryl ethane base) quinazolinones of 2,8- and its preparation method and application |
-
2017
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104447580A (en) * | 2014-12-23 | 2015-03-25 | 湖南大学 | Method for synthesizing quinazolone compounds |
| CN108623584A (en) * | 2018-05-08 | 2018-10-09 | 浙江工业大学 | Bis- (aryl ethane base) quinazolinones of 2,8- and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 贾建洪等: "喹唑啉酮类化合物的合成及光电性能", 《精细化工》 * |
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| CN108623584A (en) * | 2018-05-08 | 2018-10-09 | 浙江工业大学 | Bis- (aryl ethane base) quinazolinones of 2,8- and its preparation method and application |
| CN108623584B (en) * | 2018-05-08 | 2020-07-21 | 浙江工业大学 | 2, 8-bis (aryl ethynyl) quinazolinone compound and preparation method and application thereof |
| CN108558872A (en) * | 2018-05-17 | 2018-09-21 | 浙江工业大学 | A kind of 8- substituted-phenyls-quinazolinones and its preparation method and application |
| CN108727371A (en) * | 2018-05-21 | 2018-11-02 | 浙江工业大学 | Bis- (substituted-phenyl) quinazolinones of 2,8- and its preparation method and application |
| CN108727371B (en) * | 2018-05-21 | 2020-04-17 | 浙江工业大学 | 2, 8-bis (substituted phenyl) quinazolinone compound and preparation method and application thereof |
| CN116003329A (en) * | 2023-01-10 | 2023-04-25 | 浙江工业大学 | T-type benzimidazole third-order nonlinear optical material, and preparation method and application thereof |
| CN116003329B (en) * | 2023-01-10 | 2024-09-24 | 浙江工业大学 | T-type benzimidazole third-order nonlinear optical material, and preparation method and application thereof |
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