CN106883231A - Yi Zhong perylene diimide base Developments of Third-order Nonlinear Optical Polymers and its preparation and application - Google Patents
Yi Zhong perylene diimide base Developments of Third-order Nonlinear Optical Polymers and its preparation and application Download PDFInfo
- Publication number
- CN106883231A CN106883231A CN201710228268.4A CN201710228268A CN106883231A CN 106883231 A CN106883231 A CN 106883231A CN 201710228268 A CN201710228268 A CN 201710228268A CN 106883231 A CN106883231 A CN 106883231A
- Authority
- CN
- China
- Prior art keywords
- developments
- nonlinear optical
- benzanthrone
- base
- perylene diimide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
- C07D471/06—Peri-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G02—OPTICS
- 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
- G02F1/361—Organic materials
- G02F1/3611—Organic materials containing Nitrogen
- G02F1/3612—Heterocycles having N as heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Optical Modulation, Optical Deflection, Nonlinear Optics, Optical Demodulation, Optical Logic Elements (AREA)
Abstract
The present invention relates to Yi Zhong perylene diimide base Developments of Third-order Nonlinear Optical Polymers, with 3,4,9,10 perylene 4 formyl-2-imides are core group, are substitution base group with hexamethylene and benzanthrone or triphenylamine；The hexamethylene is connected on the imide nitrogen atom of the core group, and the benzanthrone or triphenylamine are connected at the position of the gulf of the core group, are formed a whole.It is prepared as：(1) dissolved in a chain of hexane perylene diimides derivative, benzanthrone derivative or triphenylamine derivative and potassium carbonate on imide nitrogen atom being added into solvent；(2) lead to nitrogen after 1~30 minute, add tetra-triphenylphosphine palladium catalyst, be heated to 80~100 DEG C, 500~1200r/min reacts 3~24 hours；(3) extracted several times with dichloromethane and distilled water, point liquid is dried；(4) crude product that will be obtained is isolated and purified.Perylene diimide base Developments of Third-order Nonlinear Optical Polymers of the present invention has big non-linear absorption coefficient and two photon absorption cross section value；It is applied to third order non-linear optical material aspect.
Description
Technical field
The invention belongs to organic non linear optical material field, especially third order non-linear optical material field, design one
Zhong perylene diimide base Developments of Third-order Nonlinear Optical Polymers and preparation and the application in third-order nonlinear optical field.
Background technology
Perylene diimide is that one kind common are machine chromophore, has strong and wide absorption band , Qie perylenes acyl sub- in visible region
The fluorescence quantum yield of amine is high, and charge mobility is big, and photo and thermal stability and chemical stability are good.Ling Wai , perylene diimides have big
Common phenyl ring planar structure and two imines ring structures, with electron affinity high can and very strong electronic capability, normal quilt
As electron accepting groups.When perylene diimide group is connected with electronic donor group, overall nonlinear characteristic obtains very big
Enhancing.In organic photovoltaic material, Organic Light Emitting Diode, sensor, the field such as molecule machine has extensively perylene diimide group
General application, so and perylene diimide base chromophore in terms of nonlinear optical material, especially third-order nonlinear optical response
Using relatively fewer.Perylene diimide big molar absorption coefficient and electron delocalization, become a potential non-linear forerunner
Material.The design of Xiao seminars has synthesized a series of chromophore of the trapezoid planar shape of Rong He perylene diimides and carbazole group,
With preferable third-order non-linear absorption coefficient.
Organic non linear optical material has big second order, Nonlinear Third-Order Optical Properties, and transparency wide ranges are supper-fast
Response time, light injury threshold high and the advantages of be readily processible to high-quality optical thin film, they are to information technology
There is tremendous influence with industry application.Organic compound is incomparable with many inorganic material as nonlinear optical material
Advantage：Low cost, be readily synthesized, performance can be adjusted by structural modification, light injury threshold is high, nonlinear optical response
It is quick etc..Two-photon absorption is a kind of phenomenon of light-matter interaction under light laser, belongs to third-order nonlinear optical effect
One kind.Material molecule absorbs two photons of identical or different frequency simultaneously, produces a transient state photon density very high.
Organic compound with big two-photon cross-sections value is due in microscopy, Precision Machining, three-dimensional data storage, luminous power limit
The aspects such as system, up-conversion lasing, PDT, photic release are widely used, and grinding for scientist is had become in recent years
Study carefully focus.The good light of perylene diimide class material, thermally and chemically stability, optical absorption characteristics and fluorescence quantum yield high, greatly
Molar absorption coefficient and electron delocalization, become a potential non-linear precursor material.Therefore, Yan Jiu perylene diimides class
Application of the material in terms of third order non-linear optical material, develops the organic non linear optical material of Yi Zhong perylene diimide bases, tool
There is realistic meaning.
The content of the invention
It is existing to solve it is an object of the invention to provide Yi Zhong perylene diimide base organic non linear optical materials and its preparation
Some problems.
In order to realize above-mentioned purpose, adopt the following technical scheme that：
A perylene diimide base Developments of Third-order Nonlinear Optical Polymers, it is characterised in that with 3, the formyl two of 4,9,10- perylene four
Imines is core group, is substitution base group with hexamethylene and benzanthrone or triphenylamine；The hexamethylene is connected to the core
On the imide nitrogen atom of heart group, the benzanthrone or triphenylamine are connected at the position of the gulf of the core group, composition one
Individual entirety.
Perylene diimide group has strong and wide absorption band, big fluorescence quantum yield, big charge mobility, good light
The advantages of heat endurance and chemical stability, conjugated system of height delocalization.Often by as strong electron acceptor, when its with it is suitable
Electron donor unit can further optimize molecule overall performance when connecting, show more preferable third-order nonlinear characteristic.
Dissolubility is very poor in itself for Dan Shi perylene diimides, and general synthetically prepared and application is all required to material dissolubility, therefore, to it
Improve dissolubilities using being required for doing largely modification.Cyclohexane group is introduced at the imide nitrogen atom of perylene diimide groups,
Molecular melting can be improved.
Triphenylamine is typical nonplanar structure molecule, due to its nonplanar nature can prevent it is unnecessary intermolecular
Interact and mutually accumulation.Triphenylamine has good luminescent properties and cavity transmission ability strong as electron donor unit,
Its derivative is commonly used for opto-electronic device and electro-active materials.Benzanthrone and its derivative represent another kind of valuable
Chromophore, due to being often widely used in the fields such as fluorescence probe, chemical colour reaction with good extinction and fluorescence emitting characteristics.One
Aspect, after introducing benzanthrone and triphenylamine substituted radical, can adding molecular reverse and increase steric hindrance so that it is whole to improve molecule
Body dissolubility.Another aspect , perylene diimides are electron accepting groups, and the substitution base of introducing is electronic donor group, intramolecular
Electric sub- Give-by system can be formed, is conducive to Intramolecular electron transfer, be that molecule entirety electrochemistry and two-photon absorption performance are obtained
Preferably lifting.
Further, the hexamethylene has two, is connected on the imide nitrogen atom at the core group two ends.
Further, the benzanthrone group singly-bound is substituted at the position of the gulf of the core group side.
Further, the benzanthrone is fused at the core group gulf position.
Further, the triphenylamine substitution base has two, is respectively coupled at the position of the gulf of the core group 1 and 7.
The preparation method of Shang Shu perylene diimides base Developments of Third-order Nonlinear Optical Polymers, mainly includes the following steps that：
(1) Suzuki coupling reactions are first passed through, by a chain of hexane perylene diimides derivative, benzo on imide nitrogen atom
Anthracyclinone derivatives or triphenylamine derivative and potassium carbonate dissolve in adding solvent；
(2) lead to nitrogen after 1~30 minute, add tetra-triphenylphosphine palladium catalyst, be heated to 80~100 DEG C, 500~
1200r/min, reacts 3~24 hours；
(3) extracted several times with dichloromethane and distilled water, point liquid is dried；
(4) the crude product dichloromethane/n-hexane that will be obtained is eluant, eluent in 200~300 mesh silica gel column separating purifications.
The Suzuki coupling reactions are the Suzuki coupling reactions of aryl halides and aryl boric acid.
Further, also including step (5)：The end-product obtained in step (4) is dissolved in dichloromethane solution, is put
Being placed under sunshine carries out illumination, 12~24 hours, isolates and purifies.
Further, bromine atoms are connected with No. 1 position of step (1) Zhong Suo Shu perylene diimide derivatives；The benzanthrone
Derivative is to introduce boric acid pinacol ester in No. 3 positions of benzanthrone.
Nonlinear characteristic refers to two photon absorption cross section value, third-order non-linear absorption coefficient, third-order non-linear refraction coefficient.
Preparing perylene diimide base Developments of Third-order Nonlinear Optical Polymers has big non-linear absorption coefficient and two-photon absorption
Section is worth.
The application of Shang Shu perylene diimides base Developments of Third-order Nonlinear Optical Polymers, is applied to third order non-linear optical material,
Such as microscopy, Precision Machining, three-dimensional data storage, optical power limit, up-conversion lasing, PDT, photic release etc..
Compared with prior art, cyclohexane group and benzanthrone or triphenylamine base are introduced on perylene diimides base of the present invention
Group, substantially increases third-order nonlinear optical activity, with big non-linear absorption coefficient and two photon absorption cross section value, can answer
For third order non-linear optical material, with two-Photon Absorption Properties high.And preparation method of the invention is simple, easily grasp
Make.
Brief description of the drawings
Fig. 1 is 3,4,9,10- perylene 4 formyl-2-imide structure charts；
Fig. 2 is the structure chart of a chain of hexane perylene diimides on imide nitrogen atom；
Fig. 3 is the structure chart of the compound A that embodiment 1 is obtained；
Fig. 4 is the structure chart of the compound B that embodiment 2 is obtained；
Fig. 5 is the structure chart of the compound C that embodiment 3 is obtained；
Fig. 6 is Z- scanning technique schematic diagrams；
Fig. 7 is the ultra-violet absorption spectrum and fluorescence spectra that embodiment 1 and 2 is obtained compound A and B respectively；
Fig. 8 is the ultra-violet absorption spectrum and fluorescence spectra that embodiment 3 is obtained compound C.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, the present invention is made into one below in conjunction with accompanying drawing
Step ground is described in detail.
Embodiment 1
The preparation of Yi Zhong perylene diimide base organic non linear optical materials, mainly includes the following steps that：
Hexamethylene substitution Hou perylene diimide radical derivatives are first prepared, its reaction equation is as follows：
Again with the benzanthrone for taking hexamethylene substitution Hou perylene diimides radical derivatives and No. 3 position introducing boric acid pinacol esters
Derivatives reaction, its reaction equation is as follows：
Mainly include the following steps that：Take hexamethylene and replace Hou perylene diimides radical derivative (500mg, 0.76mmol), No. 3
Position introduces the benzanthrone derivative (315mg, 0.92mmol) and K of boric acid pinacol ester2CO3(133mg), it is mixed with toluene-ethano
Close solution (volume ratio 3:1,80mL) dissolve.After logical nitrogen 30min, 15mg tetra-triphenylphosphine palladium catalyst is added to solvent, plus
To 80 DEG C, 1000r/min reacts 5 hours heat.Room temperature is cooled to after having reacted, after removing excess of solvent with Rotary Evaporators, plus
Enter 100mL dichloromethane solution dissolved solids, distilled with 40mL and washed, point liquid.Residual moisture is removed with anhydrous sodium sulfate, point
Liquid, dries.Crude product dichloromethane-n-hexane (volume ratio 2:5) it is eluant, eluent in 200-300 mesh silica gel column separating purifications,
Kermesinus compound A is obtained as shown in figure 3, with 3,4,9,10- perylene 4 formyl-2-imides are core group, with hexamethylene and benzo
Anthrone is substitution base group；Two hexamethylenes are connected in the acid imide nitrogen original for connecing 3,4,9,10- perylene 4 formyl-2-imides two ends respectively
On son, benzanthrone group singly-bound replaces at the gulf position of 3,4,9,10- perylene 4 formyl-2-imide sides.
The perylene diimide base organic non linear optical material compound A that must be arrived with above-mentioned preparation method, yield is 60%.
Embodiment 2
The preparation of Yi Zhong perylene diimide base organic non linear optical materials, its reaction equation is as follows：
Mainly include the following steps that：Take compound A (92mg, 0.12mmol) to be dissolved in 100ml dichloromethane, be transferred to
In quartz beaker, illumination under outdoor solar light is positioned over.Illumination reaction progress is observed with thin-layered chromatography, due to compound B dissolvings
Property it is poor, compound B after illumination closed loop forms floccule, suspends or be sunken to beaker bottom.By micro porous filtration, washing is collected
Compound B after closed loop.Compound B is obtained after 24 hours as shown in figure 4, with 3,4,9,10- perylene 4 formyl-2-imides are core
Group, is substitution base group with hexamethylene and benzanthrone；Two hexamethylenes are connected to the Asia of four formyl of 3,4,9,10- perylenes two
On the imide nitrogen atom at amine two ends, benzanthrone is fused at the position of the gulf of 3,4,9,10- perylene 4 formyl-2-imides.
The perylene diimide base organic non linear optical material compound B that must be arrived with above-mentioned preparation method, yield is 73%.
Embodiment 3
The preparation of Yi Zhong perylene diimide base organic non linear optical materials, reaction equation is as follows：
Mainly include the following steps that：Qu perylene diimides derivative (0.356g, 0.5mmol) and triphenylamine derivative
(0.445g, 1.2mmol) is dissolved in 40ml tetrahydrofurans.The solution of potassium carbonate of 20ml 2M is added, is added after nitrogen treatment 30min
Enter tetra-triphenylphosphine palladium catalyst 15mg, be heated to 80 DEG C, 1000r/min reacts 24 hours.Dichloromethane and water are used after cooling
Extract several times, organic phase removes excessive moisture with anhydrous sodium sulfate, point liquid is dried.Crude product 200-300 mesh silicagel columns,
Dichloromethane-n-hexane (volume ratio 1:3) mixed solvent eluant, eluent, isolates and purifies, and obtains compound C as shown in figure 5, with 3, and 4,
9,10- perylene 4 formyl-2-imides are core group, are substitution base group with hexamethylene and triphenylamine；Two hexamethylenes are connected respectively
3, on the imide nitrogen atom at 4,9,10- perylene 4 formyl-2-imide two ends, triphenylamine substitution base has two, is respectively coupled in institute
State at the position of the gulf of core group 1 and 7.
The perylene diimide base organic non linear optical material compound C that must be arrived with above-mentioned preparation method, yield is 37%.
Embodiment 4
From gulf bit substituent, group is benzanthrone and triphenylamine, and different substituents group (triphenylamine and benzene have been inquired into respectively
And anthrone two types group), different substitution mode (before gulf position and ring A and and ring after B) to overall third-order nonlinear characteristic
Influence.
By embodiment 1, that 2,3 Bei perylene diimides base organic non linear optical material compound A, B, C processed are applied to three ranks is non-
Linear optical material, is measured with Z- scanning techniques thirdly rank non-linear absorption coefficient, third-order non-linear refractive index and two-photon are inhaled
Receive section value.
Z- scanning technique principles are as shown in Figure 6：Concretely comprise the following steps：The laser sent from laser is decayed by attenuator A,
Lens L focuses on light beam, a beam splitter is put before lens laser is divided into two beams, and a branch of detector D1 that is directly entered is for measuring
Through the transmitted light after aperture, another beam into another detector D2 after the aperture of a center and optical axis coincidence by being used for
Measure the situation of change of input light.Test sample compound A is fixed on into one has on the movable stand of scale, and sample position is by marking
Chi reads.Focus is taken for the origin of coordinates, sample is moved forward and backward in focus along Z axis, with sample near focal point along light propagation side
To the movement of (Z-direction), due to the nonlinear interaction of medium, the diverging or convergence of light beam will be caused, then normalized transmittance T
(D1/D2) will have has one-to-one relation with sample position, it is possible thereby to obtain nonlinear refractive index.Normalized light beam
Transmitance is represented by：
Wherein, Z represents the distance of sample and focusing center, Z0Represent Ruili diffraction length, l0It is peak power density,It is effective length, L is sample length, and β is non-linear absorption coefficient.Two-photon absorption coefficient passes through
The transmitance data that formula (1) fitting experiment is measured draw, then by formula δ=h ω β/(2 π N0) calculate two-photon suction
Section value is received, wherein, h ω/(2 π) is excitation photon energy, N0It is molecule amount per cubic centimeter.Two photon absorption cross section value
Generally represented with GM, 1GM=1 × 10-50cm4s/photon。
The compound A-C of table 1 scans the nonlinear refraction index n measured at 800 (A, B) and 1000 (C) nm by Z-2,
Two-photon absorption factor beta and two-photon absorption interface value.
The third order non-linear optical property of compound A, B, C for measuring as shown in table 1, is modified by Z scanning discoveries
Later compound A-C nonlinear refraction indexes are all higher than zero, have preferable two-photon absorption coefficient and absorption cross-section value, especially
It is the two-photon absorption coefficient of compound B up to 22.15 × 10-12cm W-1, two photon absorption cross section value reach 1072.83GM.Tool
There is preferable two-photon absorption effect, be suitably applied third order non-linear optical material.
Embodiment 1,2,3 Bei perylene diimides base organic non linear optical material compound A, B, C processed are carried out into UV absorption
Spectrum and fluorescence spectrum are tested, using rhodamine 6G (Φ FL=0.76) in H2O as fluorescence standard substance.Test collection of illustrative plates such as Fig. 7,
Shown in Fig. 8, test data is as shown in table 2, it can be deduced that the excitation wavelength of compound A-C is respectively 526,527 and 637nm.By
After benzanthrone or triphenylamine substituted radical being introduced at the position of one side , perylene core gulfs, expansible molecule π systems.On the other hand,
The introducing of benzanthrone or triphenylamine substituted radical can Yan perylene core plane and twist, so as to increase steric hindrance, make pi-electron
It is linked to be short chain, extends pi-electron system.Therefore, compared to the CH-PDI not replaced by anthrone, the chemical combination after substitution modification is carried out
Thing A-C line spectrums advantageously reduce the generation of energy gap and Intramolecular electron transfer to low energy Tape movement.Change after being replaced
Compound A-C fluorescence capabilities substantially reduce (fluorescence quantum yield reduction), illustrate that the main characteristics of luminescences of compound A-C of new synthesis subtract
Weak, extinction characteristic increases, and is conducive to the increase of the two-Photon Absorption Properties in Third-order nonlinearity.
The ultra-violet absorption spectrum and fluorescence data of compound A, B and C that table 2 is measured in CH2Cl2.
Embodiment 1,2,3 Bei perylene diimides base organic non linear optical material compound A, B, C processed are circulated volt-ampere
Method is tested, and the redox potential of compound A-C is measured by cyclic voltammetry, is then calculated accordingly by formula [b]
LUMO, HOMO and energy gap.From result of study it can be seen that the lumo energy of the compound A-C after being modified is relative to non-gulf position
Substituted CH-PDI is substantially reduced, and energy gap also decreases, and is more beneficial for energy level transition and electric charge transfer.Compound B is due to simultaneously
Molecule coplanarity increases after ring, and the pi-conjugated of compound is expanded, and is more beneficial for molecule pi-pi accumulation, causes molecule more steady
Determine and energy gap is bigger.Shown in test result chart 3.
The related data that the compound A-C of table 3 is measured by cyclic voltammetry
[a] irreversible potential [b] ELUMO=-(4.4eV+Ered (1)), EHOMO=-(4.4eV+Eox (1)), △ E=ELUMO-
EHOMO
By above-mentioned analysis contrast can learn acene anthrone singly-bound (and before ring) Qu Dai perylene diimides gulf position formed change
Compound A has best third-order non-linear property, and far above other two kinds of structures.Illustrating the molecule of Compound A structure most has
Beneficial to being applied to third order non-linear optical material.
Explained above is only present pre-ferred embodiments, it is impossible to the interest field of the present invention is limited with this.Therefore
The equivalent variations made according to the claims in the present invention, still belong to the scope that the present invention is covered.
Claims (9)
1. a perylene diimide base Developments of Third-order Nonlinear Optical Polymers, it is characterised in that with 3,4,9,10- perylene, four formyl two is sub-
Amine is core group, is substitution base group with hexamethylene and benzanthrone or triphenylamine；The hexamethylene is connected to the core
On the imide nitrogen atom of group, the benzanthrone or triphenylamine are connected at the position of the gulf of the core group, constitute one
It is overall.
2. according to claim 1 Suo Shu perylene diimide base Developments of Third-order Nonlinear Optical Polymers, it is characterised in that the hexamethylene
There are two, be connected on the imide nitrogen atom at the core group two ends.
3. according to claim 2 Suo Shu perylene diimide base Developments of Third-order Nonlinear Optical Polymers, it is characterised in that the benzanthracene
Ketone groups singly-bound is substituted at the position of the gulf of the core group side.
4. according to claim 2 Suo Shu perylene diimide base Developments of Third-order Nonlinear Optical Polymers, it is characterised in that the benzanthracene
Ketone is fused at the core group gulf position.
5. according to claim 2 Suo Shu perylene diimide base Developments of Third-order Nonlinear Optical Polymers, it is characterised in that the triphenylamine
Substitution base has two, is respectively coupled at the position of the gulf of the core group 1 and 7.
6. according to the preparation method of claim 1-5 any one Suo Shu perylene diimide base Developments of Third-order Nonlinear Optical Polymers, its
It is characterised by, mainly includes the following steps that：
(1) Suzuki coupling reactions are first passed through, by a chain of hexane perylene diimides derivative, benzanthrone on imide nitrogen atom
Derivative or triphenylamine derivative and potassium carbonate dissolve in adding solvent；
(2) lead to nitrogen after 1~30 minute, add tetra-triphenylphosphine palladium catalyst, be heated to 80~100 DEG C, 500~1200r/
Min, reacts 3~24 hours；
(3) extracted several times with dichloromethane and distilled water, point liquid is dried；
(4) the crude product dichloromethane/n-hexane that will be obtained is eluant, eluent in 200~300 mesh silica gel column separating purifications.
7. preparation method according to claim 6, it is characterised in that also including step (5)：The end that will be obtained in step (4)
Product is dissolved in dichloromethane solution, and being positioned under sunshine carries out illumination, 12~24 hours, isolates and purifies.
8. preparation method according to claim 6, it is characterised in that No. 1 position of step (1) Zhong Suo Shu perylene diimide derivatives
On be connected with bromine atoms；The benzanthrone derivative is to introduce boric acid pinacol ester in No. 3 positions of benzanthrone.
9. according to the application of claim 1-5 any one Suo Shu perylene diimide base Developments of Third-order Nonlinear Optical Polymers, its feature
It is to be applied to third order non-linear optical material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710228268.4A CN106883231A (en) | 2017-04-10 | 2017-04-10 | Yi Zhong perylene diimide base Developments of Third-order Nonlinear Optical Polymers and its preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710228268.4A CN106883231A (en) | 2017-04-10 | 2017-04-10 | Yi Zhong perylene diimide base Developments of Third-order Nonlinear Optical Polymers and its preparation and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106883231A true CN106883231A (en) | 2017-06-23 |
Family
ID=59183260
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710228268.4A Pending CN106883231A (en) | 2017-04-10 | 2017-04-10 | Yi Zhong perylene diimide base Developments of Third-order Nonlinear Optical Polymers and its preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106883231A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113307809A (en) * | 2020-02-26 | 2021-08-27 | 北京化工大学 | Graphene imide and unilateral perylene imide based on cyclooctatetraene and synthesis and application thereof |
| CN113321653A (en) * | 2021-05-25 | 2021-08-31 | 汕头大学 | Perylene diimide fluorescent dye of ortho-substituted benzanthrone and preparation and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104152137A (en) * | 2014-05-06 | 2014-11-19 | 上海大学 | Fluorine-perylene bisimide molecule internal-energy transferring fluorescence split compound and preparation method thereof |
-
2017
- 2017-04-10 CN CN201710228268.4A patent/CN106883231A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104152137A (en) * | 2014-05-06 | 2014-11-19 | 上海大学 | Fluorine-perylene bisimide molecule internal-energy transferring fluorescence split compound and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| LIU CAO ET AL.: "Perylenediimide-Benzanthrone Dyad: Organic Chromophores with Enhanced Third-Order Nonlinear-Optical Activities", 《EUROPEAN JOURNAL OF ORGANIC CHEMISTRY》 * |
| 施敏敏等: "桥位芳香性给电子基团取代的苝二酰亚胺的合成及其光伏性能", 《功能材料》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113307809A (en) * | 2020-02-26 | 2021-08-27 | 北京化工大学 | Graphene imide and unilateral perylene imide based on cyclooctatetraene and synthesis and application thereof |
| CN113307809B (en) * | 2020-02-26 | 2022-10-28 | 北京化工大学 | Graphene imide and unilateral perylene imide based on cyclooctatetraene and synthesis and application thereof |
| CN113321653A (en) * | 2021-05-25 | 2021-08-31 | 汕头大学 | Perylene diimide fluorescent dye of ortho-substituted benzanthrone and preparation and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sayresmith et al. | Photostable voltage-sensitive dyes based on simple, solvatofluorochromic, asymmetric thiazolothiazoles | |
| Ren et al. | Synthesis, structures and two-photon pumped up-conversion lasing properties of two new organic salts | |
| Karothu et al. | Multifunctional deformable organic semiconductor single crystals | |
| Huo et al. | Novel nonlinear optical push–pull fluorene dyes chromophore as promising materials for telecommunications | |
| Liu et al. | The design of nonlinear optical chromophores exhibiting large electro-optic activity and high thermal stability: the role of donor groups | |
| Tian et al. | Investigations and facile synthesis of a series of novel multi-functional two-photon absorption materials | |
| Ju et al. | Solvent dependent linear and nonlinear optical properties of triphenylamine unit incorporated difluoroboron β-diketonate complexes | |
| CN106883231A (en) | Yi Zhong perylene diimide base Developments of Third-order Nonlinear Optical Polymers and its preparation and application | |
| Cheng et al. | Microscopic visualization and mechanism investigation of the crystal jumping behavior of a cyclic chalcone derivative | |
| Tu et al. | Advances in pure organic mechanoluminescence materials | |
| WO2012018342A1 (en) | Photorefractive composition responsive to multiple laser wavelengths across the visible light spectrum | |
| Liu et al. | Synthesis of julolidine-containing nonlinear optical chromophores: Achieving excellent electro-optic activity by optimizing the bridges and acceptors | |
| Xu et al. | Design and synthesis of novel H-Shaped chromophore for enhanced nonlinear optical properties | |
| Zhang et al. | Systematic study of the structure-property relationship of a series of near-infrared absorbing push-pull heptamethine chromophores for electro-optics | |
| Sharma et al. | Synthesis and photovoltaic application of NIR-emitting perylene-monoimide dyes with large Stokes-shift | |
| EP2547732A2 (en) | Higher order structured dyes with enhanced optical features | |
| CN103130846A (en) | Photochromic bi-thiophene six-sugar water-solubility symmetrical octafluorocyclopentene compound and preparation method and application | |
| Zhai et al. | Functionalized twistacenes for solid state nonlinear optical materials | |
| Tian et al. | Two novel two-photon polymerization initiators with extensive application prospects | |
| Liu et al. | Design and synthesis of various double donors for nonlinear optical chromophores with enhanced electro-optic activity | |
| Zhang et al. | Optimizing the molecular structure of 1, 1, 7, 7-tetramethyl julolidine fused furan based chromophores by introducing a heterocycle ring to achieve high electro-optic activity | |
| Zhang et al. | Synthesis and photophysical properties of three ladder-type chromophores with large and rigid conjugation structures | |
| CN116854652A (en) | Self-crosslinking organic electro-optical molecular glass material and preparation method and application thereof | |
| Maleki et al. | Third-order nonlinear optical properties of unsymmetrical tetrazole-based dyes and study the effect of electrostriction on reverse saturation absorption | |
| CN109776471B (en) | Coumarin type organic third-order nonlinear optical material and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170623 |