CN106279133A - Organic second order non-linear optical chromophore and synthetic method and application - Google Patents
Organic second order non-linear optical chromophore and synthetic method and application Download PDFInfo
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Abstract
The open a kind of organic second order non-linear optical chromophore of the present invention and synthetic method and application, this organic second order non-linear optical chromophore has formula (CL) or a structure of formula (HCL):
Description
Technical field
The present invention relates to organic second-order non-linear optical Material Field, particularly to one, there is D-π-A knot
The organic second order non-linear optical chromophore of structure and preparation method and use thereof.
Background technology
The progress of science and technology and the fast development of society so that people are to the demand of quantity of information and information
Spread speed proposes the highest requirement.For at present, up to terabite (Tb, i.e. 1012bits)
Information processing, transmit and store, the super-high speed information stream of terabite per second (Tb/s) and high frequency (THz) ring
Should, the current information transmission technology is proposed stern challenge.The development that information age is the swiftest and the most violent,
Make present stage more and more higher to the requirement of communication information material.In optoelectronics industry as photoswitch,
Optical communication, optical information processing, optical computer, laser technology etc. are required for nonlinear optical material as base
Plinth material, therefore, nonlinear optical material causes the extensive concern of people in recent decades, grinds it
Study carefully and also develop with speed with rapid changepl. never-ending changes and improvements.The most practical second-order non-linear optical materials is with inorganic material
Material is main, but inorganic material due to himself intrinsic defect thus limits it and extensively applies.But,
In recent years it has been found that organic non linear optical material has super fast response speed (Asia compared with inorganic material
Psec even psec), low-k, high light injury threshold (GW/cm2Magnitude), processability good,
At relatively large nonlinear optical response (generally high 1-2 the order of magnitude than mineral crystal) and easily processing
The plurality of advantages such as reason, organic photoelectric functional material can realize the design of structure from molecular level in addition.So
And, the requirement of actual application will be reached, these materials not only to have big nonlinear optical response, and
To meet device to its transparency, photo-thermal and the requirement of the aspect such as chemical stability and machinability simultaneously.
Owing to the nonlinear optical properties of wherein chromophore molecule is depended in the nonlinear optical response of organic material,
So design synthesis has big electro-optic coefficient (the i.e. single order molecular hyperpolarizability (β) of micro molecule level concurrently
Electro-optic coefficient (r with macroscopic material33)) and the good transparency, the second nonlinear light of photo and thermal stability
Learn chromophore molecule and be always the most most one of challenge subjects for a long time.
Patent about second-order nonlinear optical chromophore it has been reported many at present, but has very Gao Fei
Linear optics coefficient and few.The patent that report nonlinear optical coefficients are higher has: CN1466583A,
US2002084446A1, US6067186A, WO/2002/008215A etc..But, these chromophories
Bigger due to intermolecular interaction in the polymer, it is easy to assemble, cause its molten at polymer base
Xie Du is relatively low, and polarization efficiency is the highest, and electro-optic coefficient is less than normal, cannot well meet the requirement of device.
Accordingly, it is desirable to provide the organic second-order non-linear optical that a kind of polarization efficiency is high and electro-optic coefficient is big is sent out
Color group.
Summary of the invention
First technical problem that the invention solves the problems that is to provide a kind of polarization efficiency height and electro-optic coefficient is big
Organic second order non-linear optical chromophore.
Second technical problem that the invention solves the problems that is to provide a kind of polarization efficiency height and electro-optic coefficient is big
The preparation method of organic second order non-linear optical chromophore.
The 3rd technical problem that the invention solves the problems that is to provide a kind of polarization efficiency height and electro-optic coefficient is big
The application of organic second order non-linear optical chromophore.
For solving first technical problem, the present invention uses following technical proposals:
A kind of organic second order non-linear optical chromophore, it has such as following formula (CL) or formula (HCL)
Structure:
Wherein:
G is H, phenyl, palkoxy benzene base, thienyl or to dialkylamino phenyl；
R1For alkyl, benzyl or haloalkyl；
R2For methyl or trifluoromethyl；
R3For alkyl, phenyl, substituted-phenyl, substituted thiophene base or hydroxyalkyl.
The present invention is with aniline, julolidine or derivatives thereof as electron donor, to have the fourth of steric group
Thiazolinyl is conjugated electrons bridge, with tricyano-dihydrofuran (TCF) or the substituted tricyano-dihydrofuran of trifluoro
(CF3-TCF) it is the organic second order non-linear optical chromophore with D-π-A structure of electron acceptor.
Wherein aniline, julolidine or derivatives thereof have that dissolubility is good, good stability, have superelevation single order and divide
Sub-hyperpolarizability (β) and polymer-doped after intermolecular force is little, good film-forming property, be prone to polarization,
Macroscopic view electro-optic coefficient height and the characteristic being prone to device.
Preferably, in described palkoxy benzene base, the carbon chain lengths of alkoxyl is 1-10 carbon atom；
Preferably, described is 1-10 carbon atom to the carbon chain lengths of alkylamino in dialkylamino phenyl；
Preferably, the carbon chain lengths of described alkyl is 1-20 carbon atom.
Preferably, described haloalkyl mainly carbon chain lengths is F substituted alkyl or the Cl of 1-20 carbon atom
Substituted alkyl.
Preferably, the carbon chain lengths of described hydroxyalkyl is preferably 1-10 carbon atom.
Preferably, the described substituent group in substituted-phenyl be halogen, carbon chain lengths be 1-20 carbon atom
Alkyl, carbon chain lengths be the alkoxyl of 1-20 carbon atom, carbon chain lengths be the hydroxyalkyl of 1-10 carbon atom.
It is highly preferred that described halogen is F or Cl.
Preferably, the described substituent group in substituted thiophene base be phenyl, halogen, carbon chain lengths be 1-20
The alkyl of carbon atom, carbon chain lengths are the alkoxyl of 1-20 carbon atom or carbon chain lengths is 1-10 carbon atom
Hydroxyalkyl.It is highly preferred that described halogen is F or Cl.
For solving second technical problem, the present invention adopts the following technical scheme that
The preparation method of a kind of organic second order non-linear optical chromophore, it comprises the steps:
(1) by 4-(lignocaine)-2-R1Epoxide benzaldehyde electron donor, G methyl triphenyl phosphine and cyaniding
Sodium is dissolved in anhydrous tetrahydro furan according to mol ratio 1:1:15-20, is stirred at room temperature 12-24 hour, instead
After Ying, product be poured in frozen water, with ether extract, merge organic facies, be dried merge after organic
Mutually and overnight, filter, revolve and ether, pillar layer separation are evaporated off, obtain that there is formula (I) structure after drying
Compound:
Wherein:
G is H, phenyl, palkoxy benzene base, thienyl or to dialkylamino phenyl；
R1For alkyl, benzyl or haloalkyl.
(2) at N2By the POCl of 1.2-1.5 equivalent under protection3It is added drop-wise to the DMF of 2-2.5 equivalent at 0 DEG C
In, ice bath stirs 1-2 hour, then constant voltage be slowly added dropwise that 1 equivalent step (1) obtains there is formula (I)
The DMF solution of the compound of structure.Being slowly increased to room temperature, 60-90 DEG C is reacted 1-3 hour, reacts complete
Terminate reaction with sodium bicarbonate aqueous solution afterwards, then reaction gained mixture is poured in deionized water, use
Ethyl acetate extracts, separatory, merges organic facies, is dried the organic facies overnight after merging, and filters, and revolves
Ethyl acetate, pillar layer separation are evaporated off, obtain the compound with formula II structure after drying:
(3) compound with formula (II) structure step (2) obtained and substituted tricyano dihydro
Furan electron acceptor is dissolved in ethanol according to mol ratio 1:1.2-1.5, is stirred reaction at 50-80 DEG C,
Being cooled to room temperature after completion of the reaction, rotation is evaporated off ethanol, pillar layer separation, obtains having D-π-A structure
Organic second-order non-linear chromophore, formula (CL), its structure is:
Wherein:
R2For methyl or trifluoromethyl；
R3For alkyl, phenyl, substituted-phenyl, substituted thiophene base or hydroxyalkyl.
Wherein said 4-(lignocaine)-2-R1Epoxide benzaldehyde can use those skilled in the art institute public
The technical scheme known is prepared, such as:
By 4-(lignocaine)-2-R1Epoxide benzaldehyde and halo R1It is that 1:1.2 is dissolved according to mol ratio
In DMF (DMF), at noble gas (such as N2) the protection dried and halogen of lower addition
For R1The Anhydrous potassium carbonate that mol ratio is 1:1 after, at 130 DEG C react 24 hours, obtain 4-(two
Ethylamino)-2-R1Epoxide benzaldehyde；Wherein: halogen is chlorine, bromine or iodine.
Preferably, the carbon chain lengths of the alkoxyl in described palkoxy benzene base is 1-10 carbon atom；
Preferably, the described carbon chain lengths to the alkylamino in dialkylamino phenyl is 1-10 carbon atom；
Preferably, the carbon chain lengths of described alkyl is 1-20 carbon atom.
Preferably, described haloalkyl mainly F generation or Cl generation, carbon chain lengths be 1-20 carbon atom.
Preferably, the carbon chain lengths of described hydroxyalkyl is preferably 1-10 carbon atom.
Preferably, the described substituent group in substituted-phenyl be halogen, carbon chain lengths be 1-20 carbon atom
Alkyl, carbon chain lengths are the alkoxyl of 1-20 carbon atom or hydroxyalkyl that carbon chain lengths is 1-10 carbon atom,
It is highly preferred that described halogen is F or Cl.
Preferably, the described substituent group in substituted thiophene base be phenyl, halogen, carbon chain lengths be 1-20
The alkyl of carbon atom, carbon chain lengths be the alkoxyl of 1-20 carbon atom, carbon chain lengths be 1-10 carbon atom
Hydroxyalkyl, it is preferable that described halogen position F or Cl.
For solving second technical problem, the present invention also can use following technical proposals:
The preparation method of a kind of organic second order non-linear optical chromophore, comprises the steps:
(1) by 8-R1 Oxy-1,1,7,7-tetramethyl julolidine-9-formaldehyde electron donor, G methyl triphen
Base phosphine and Cyanogran. are dissolved in anhydrous tetrahydro furan according to mol ratio 1:1:15-20, are stirred at room temperature 12-24
Hour, after completion of the reaction product is poured in frozen water, extract with ether, merge organic facies, be dried and merge
After organic facies overnight, filter, rotation is evaporated off ether, pillar layer separation, obtain after drying having with
The compound of lower structure:
Wherein:
G is H, phenyl, palkoxy benzene base, thienyl or to dialkylamino phenyl；
R1For alkyl, benzyl or haloalkyl.
(2) at N2By the POCl of 1.2-1.5 equivalent under protection3It is added drop-wise to the DMF of 2-2.5 equivalent at 0 DEG C
In, ice bath stirs 1-2 hour, then constant voltage be slowly added dropwise that 1 equivalent step (1) obtains there is formula (III)
The DMF solution of the compound of structure.Being slowly increased to room temperature, 60-90 DEG C is reacted 1-3 hour, reacts complete
Terminate reaction with sodium bicarbonate aqueous solution afterwards, then reaction gained mixture is poured in deionized water, use
Ethyl acetate extracts, separatory, merges organic facies, is dried the organic facies overnight after merging, and filters, and revolves
Ethyl acetate, pillar layer separation are evaporated off, obtain the compound with formula (IV) structure after drying:
(3) compound with formula (IV) structure step (2) obtained and substituted tricyano two
Hydrogen furan electron acceptor is dissolved in ethanol according to mol ratio 1:1.2-1.5, is stirred reaction at 50-80 DEG C,
Being cooled to room temperature after completion of the reaction, rotation is evaporated off ethanol, pillar layer separation, obtains having D-π-A structure
Organic second-order non-linear chromophore, its structure is:
R2For methyl or trifluoromethyl；
R3For alkyl, phenyl, substituted-phenyl, substituted thiophene base or hydroxyalkyl.
Preferably, the carbon chain lengths of the alkoxyl in described palkoxy benzene base is 1-10 carbon atom；
Preferably, the described carbon chain lengths to the alkylamino in dialkylamino phenyl is 1-10 carbon atom；
Preferably, the carbon chain lengths of described alkyl is 1-20 carbon atom.
Preferably, described haloalkyl mainly carbon chain lengths is F substituted alkyl or the Cl of 1-20 carbon atom
Substituted alkyl.
Preferably, the carbon chain lengths of described hydroxyalkyl is preferably 1-10 carbon atom.
Preferably, the described substituent group in substituted-phenyl be halogen, carbon chain lengths be 1-20 carbon atom
Alkyl, carbon chain lengths are the alkoxyl of 1-20 carbon atom or hydroxyalkyl that carbon chain lengths is 1-10 carbon atom,
It is highly preferred that described halogen is F or Cl.
Preferably, the described substituent group in substituted thiophene base be phenyl, halogen, carbon chain lengths be 1-20
The alkyl of carbon atom, carbon chain lengths are the alkoxyl of 1-20 carbon atom or carbon chain lengths is 1-10 carbon atom
Hydroxyalkyl, it is preferable that described halogen is F or Cl.
Described 8-R1Oxy-1,1,7,7-tetramethyl julolidine-9-formaldehyde refer to document (J.Wu, S.Bo,
J.Liu,T.Zhou,H.Xiao,L.Qiu,Z.Zhen and X.Liu,Chemical Communications,
2012,48,9637-9639.) synthesize.
Electron donor used in the present invention, conjugated pi electron bridge and electron acceptor can after combining
Well improve intramolecular electron transport ability, G base in intermolecular steric hindrance, especially electron bridge can be increased again
The introducing of group, serves good buffer action.Therefore, this class formation can be effectively improved chromophore molecule
Single order molecular hyperpolarizability (β), and can effectively reduce intermolecular interaction.
For solving the 3rd technical problem, the present invention further provides organic second order non-linear optical chromophore
Application.
The present invention is had the organic second non-thread of the D-π-A structure of formula (CL) or formula (HCL) structure
Property optical chromophore be doped in unformed Merlon (APC) polarized polymer thin film of preparation, can
As the materials'use of the many opto-electronic devices of development, to meet device requirement.
The described organic second order non-linear optical chromophore (CL) with D-π-A structure or (HCL)
The mass ratio adulterated with unformed Merlon is 1:1-100.
In one embodiment, described with 4-(lignocaine)-2-R1Epoxide benzaldehyde be electron donor,
With the compound of the polyenoid conjugated structure with steric group G as electron bridge, with tricyano-dihydrofuran
(TCF) it is the organic second order non-linear optical chromophore (CL) with D-π-A structure of electron acceptor
When the mass ratio of the doping in unformed Merlon is 1:5, to the polarized polymer thin film prepared
Testing its electro-optic coefficient after carrying out corona polarizing, the electro-optic coefficient recorded is 45pm/V.
In one embodiment, described with 8-R1Oxy-1,1,7,7-tetramethyl julolidine-9-formaldehyde
For electron donor, with the compound of the polyenoid conjugated structure with steric group G as electron bridge, with three cyanogen
Base dihydrofuran (TCF) is that the organic second-order non-linear optical with D-π-A structure of electron acceptor is sent out
When the color group (HCL) doping mass ratio in unformed Merlon is 2:5, to the polarization prepared
Its electro-optic coefficient tested by thin polymer film after carrying out corona polarizing, the electro-optic coefficient recorded is 337pm/V.
Beneficial effects of the present invention is as follows:
1) organic second order non-linear optical chromophore with D-π-A structure of the present invention and traditional color development
The structure of group is compared, and electron bridge have chosen the polyenoid conjugated structure with steric group G, and this structure has
Bigger is sterically hindered, it is possible to effectively reduce the transmission of intermolecular interaction force, beneficially electronics.
2) tricyano-dihydrofuran (TCF) or trifluoro substituted tricyano-dihydrofuran (CF3-TCF)
There is the biggest electron attraction, can effectively improve chromophoric electro-optical properties as electron acceptor, this
The high performance organic second order non-linear optical chromophore compound with D-π-A structure of invention is fixed with nothing
Type Merlon (APC) etc. polymer-doped (mass ratio is 1:1-100) can prepare polar polymer.
3) the synthesis step letter of the organic second order non-linear optical chromophore with D-π-A structure of the present invention
Single, prepare productivity high, in most of organic solvents (such as acetone, chloroform etc.), there is good dissolving
Property, higher heat stability, can be widely applied to optical information Material Field.
Detailed description of the invention
In order to be illustrated more clearly that the present invention, below in conjunction with preferred embodiment, the present invention is done further
Bright.It will be appreciated by those skilled in the art that following specifically described content is illustrative rather than limiting
Property, should not limit the scope of the invention with this.
Embodiment 1
Synthesizing the organic second order non-linear optical chromophore of D-π-A structure as follows, it has formula
(CL) structure:
Synthetic route is as follows:
Synthetic method is:
1) synthesis of the compound 1 shown in formula
3.86g (0.02mol) 4-(lignocaine)-2-hydroxy benzenes first is added in 100mL glass there-necked flask
Aldehyde, 3.60g (0.03mol) 1-chlorohexane and 60mL heavily steam DMF, add the most dry
Dry Anhydrous potassium carbonate 4.14g (0.03mol), the lower backflow of nitrogen protection 12 hours, thin layer chromatography (TLC)
Observing response progress, after raw material point almost disappears, cold filtration removes potassium carbonate, pours 250mL into saturated
In saline solution, ethyl acetate extracts, and anhydrous magnesium sulfate is dried overnight filtration, and rotation is evaporated off ethyl acetate,
Residue pillar layer separation (with the silica gel of 200-300 mesh for fixing phase, mixed with petroleum ether and acetone
Closing liquid is flowing phase, wherein: petroleum ether is 15:1 with the volume ratio of acetone), obtain orange oily after drying
Liquid compound 1, productivity 91%.
MS (MALDI-TOF), m/z:277.205 (M+)；1H NMR(400MHz,CDCl3)δ:10.18
(s, 1H), 7.70 (d, J=9.0Hz, 1H), 6.25 (d, J=9.0Hz, 1H), 6.01 (s, 1H), 4.02 (t, J=
6.3Hz, 2H), 3.41 (q, J=7.1Hz, 4H), 1.87 1.75 (m, 2H), 1.55 1.43 (m, 2H),
1.35 (dt, J=7.3,4.8Hz, 4H), 1.21 (t, J=7.1Hz, 6H), 0.90 (t, J=7.0Hz, 3H).
2) synthesis of the compound 2 shown in formula
10.30g triphenyl phosphorus hydrogen bromide (0.03mol), thenyl alcohol 3.80 is added in 250mL flask
The chloroform that g (0.033mol), 200mL magnesium sulfate are dried, is heated to reflux 3-4 hour, is spin-dried for.
Adding a small amount of chloroform to dissolve, pour in a large amount of absolute ether, sucking filtration obtains white solid, productivity 95%.
3) synthesis of the compound 3 shown in formula
Under nitrogen protection, 100mL flask adds 1.39g (0.005mol) compound 1 and 3.47
G (0.006mol) compound 2 (phosphonium salt) 1:1.2 in molar ratio is dissolved in and heavily steams in oxolane, adds
Enter 1.20g (10 times of equivalents) NaH, stirring at normal temperature 48 hours, be poured slowly into 200mL after completion of the reaction
Frozen water in, with ether extract, merge organic facies, anhydrous MgSO4It is dried the organic facies after merging mistake
At night, filter, revolve and ether is evaporated off, pillar layer separation (petroleum ether/acetone volume ratio=20:1), after drying
Obtain obtaining orange/red oil compound 3, productivity 84%.
MS(MALDI-TOF),m/z:357.863(M+)；1H NMR(400MHz,CDCl3)δ:7.26
(d, J=8.7Hz, 1H), 7.15 (d, J=11.7Hz), 7.07 (d, J=11.7Hz, 1H), 7.00 (d, J=4.6
Hz, 1H), 6.87 (m, 2H), 6.20 (d, J=10.3Hz, 1H), 6.09 (s, 1H), 3.92 (t, J=6.4Hz,
2H), 3.28 (q, J=7.0Hz, 4H), 1.83 1.72 (m, 2H), 1.46 (m, 2H), 1.30 (m, 4H), 1.10
(t, J=7.0Hz, 6H), 0.85 (t, J=6.7Hz, 3H).
4) synthesis of the compound 4 shown in formula
Adding 10mL DMF in the 100mL there-necked flask sealed, at 0 DEG C, ice bath stirring, is slowly added dropwise
POCl30.64g (0.0042mol), ice bath stirs 1-2 hour, then constant voltage is slowly added dropwise containing 0.72g
(0.002mol) DMF solution (30mL) of compound 4.Being slowly increased to room temperature, 90 DEG C of reactions 3 are little
Shi Hou, pours cancellation in the sodium bicarbonate aqueous solution of 200mL mass fraction 10%, acetic acid into by reaction solution
Ethyl ester extracts three times, and anhydrous magnesium sulfate is dried overnight, pillar layer separation (petroleum ether/acetone volume ratio=
10:1), Orange red solid compound 4, productivity 73% are obtained after drying.
MS(MALDI-TOF),m/z:385.802(M+)；1H NMR(400MHz,CDCl3)δ:9.87
(s, 0.11H), 9.52 (s, 0.89H), 8.17 (s, 0.11H), 7.79 (s, 0.89H), 7.31 (d, J=6.2Hz,
1H), 7.00 (dd, J=5.1,3.5Hz, 1H), 6.98 (m, 1H) 6.95 (dd, J=8.6,5.1Hz, 1H),
5.98 (d, J=2.0Hz, 1H), 5.95 (m, 1H), 3.95 (t, J=6.4Hz, 2H), 3.27 (q, J=7.1Hz,
4H), 1.83 1.73 (m, 2H), 1.50 1.40 (m, 4H), 1.35 1.25 (m, 2H), 1.14 (t, J=7.1Hz,
0.66H), 1.09 (t, J=7.1Hz, 5.34H), 0.84 (t, J=7.4Hz, 3H).
5) synthesis of 3-hydroxy-3-methyl-2-butanone (compound 5 shown in formula)
19mL concentrated sulphuric acid (98wt%) is slowly mixed together with 100mL water, is subsequently adding 13.00g yellow
Color mercury oxide, dropping 84.00g (1.0mol) 2-methyl-3-fourth in the solution (about 70 DEG C) of this heat
Alkynes-2-alcohol, about dropping 1.5 hours；Mixed liquor stirs reaction 30 minutes under about 70 DEG C, is cooled to room
Temperature, sucking filtration, filtrate extracts with ether, and organic facies is respectively with water, sodium bicarbonate solution washing, anhydrous sulfur
Acid magnesium is dried the organic facies after merging；Filtering, filtrate, after concentrated by rotary evaporation, is distilled, is collected 140 DEG C of fractions,
The dried light yellow liquid obtaining 45.60g is compound 6, productivity: 32.2%.
6) 2,2-dicyano methene base-3-cyano group-4,5,5-trimethyl-2,5-dihydrofuran (TCF) receptor (formula
Shown in compound 6) synthesis
1.50g (0.065mol) metallic sodium is dissolved in the dehydrated alcohol of 190mL, adds 6.7mL
(0.064mol) step 6) compound 6 and 8.50g (0.13mol) Cyanoacetyl-Cyacetazid that obtains；Room temperature is stirred
Mixing 20 hours, rotation is evaporated off ethanol, and residue adds water about 50mL, adjusts pH value to be 4-5 with 6M hydrochloric acid,
Separate out a large amount of sepia grease；After fully washing with water, then with ethyl alcohol recrystallization twice, dried
The pale yellow solid of 4.50g is compound 7, productivity: 35%.
7) synthesis of the compound CL1 shown in formula
Compound 4 (0.39g, 0.001mol) and compound 6 1:1.1 in molar ratio are dissolved in 60mL
In methanol, in solution, drip several triethylamines, back flow reaction 5 hours, be cooled to room temperature, concentrate out
Remove solvent, pillar layer separation (petrol ether/ethyl acetate volume ratio=5:1), obtain green solid after drying
Powder compounds CL1, productivity 44%.
MS(MALDI-TOF),m/z:566.213(M+)；1H NMR(400MHz,CDCl3)δ:7.94
(d, J=15.1Hz, 1H), 7.76 (s, 1H), 7.49 (d, J=5.0Hz, 1H), 7.18 (dd, J=5.0,3.5
Hz, 1H), 6.92 (d, J=3.0Hz, 1H), 6.58 (d, J=9.8Hz, 1H), 6.00 (d, J=7.2Hz, 2H),
5.89 (d, J=15.1Hz, 1H), 4.03 (t, J=6.6Hz, 2H), 3.38 (q, J=7.0Hz, 4H), 1.62 (s,
6H), 1.54 1.49 (m, 2H), 1.44 1.36 (m, 4H), 1.30 (m, 2H), 1.18 (t, J=7.0Hz, 6H).
The organic second order non-linear optical chromophore molecule with D-π-A structure obtained has good heat
Stability；Acetone, chloroform or the non-polar solven such as ethanol polar solvent and ether all have good
Dissolubility.
Embodiment 2
Synthesize the organic second order non-linear optical chromophore with D-π-A structure as follows, formula
(HCL1):
Synthetic route is as follows:
Synthetic method is:
1) synthesis of the compound 1 shown in formula
2.73g (0.01mol) 8-hydroxyl-1,1,7,7-tetramethyl is added long in 100mL glass there-necked flask
Luo Niding-9-formaldehyde, 2.33g (0.015mol) 1,6-dichloro hexane and 40mL heavily steam N, N-dimethyl
Methanamide, adds the Anhydrous potassium carbonate 2.07g (0.015mol) being dried, the lower backflow 12 of nitrogen protection
Hour, thin layer chromatography (TLC) observing response progress, after raw material point almost disappears, cold filtration removes
Potassium carbonate, pours in 250mL saturated aqueous common salt, and ethyl acetate extracts, and anhydrous magnesium sulfate was dried overnight
Filter, rotation is evaporated off ethyl acetate, and residue pillar layer separation (is fixing with the silica gel of 200-300 mesh
Phase, with the mixed liquor of petroleum ether and acetone for flowing phase, wherein: petroleum ether is 20:1 with the volume ratio of acetone,
Obtaining yellow solid after drying is compound 1, productivity 83%.
MS(MALDI-TOF),m/z:391.953(M+)；1H NMR(400MHz,CDCl3)δ:9.92(s,
1H), 7.57 (s, 1H), 3.96 (t, J=6.6Hz, 2H), 3.66 (t, J=5.5Hz, 2H), 3.29 (t, J=5.9
Hz, 2H), 3.26 3.18 (m, 2H), 2.02 (s, 1H), 1.89 (dt, J=13.5,6.6Hz, 2H), 1.70 (d,
J=6.2Hz, 4H), 1.61 (d, J=6.6Hz, 2H), 1.42 (s, 7H), 1.26 (s, 6H).
2) synthesis of the compound 2 shown in formula is same as in Example 1.
3) synthesis of the compound 3 shown in formula
In 100mL flask, add 3.92g (0.01mol) compound 1 and 4.84g (0.011mol) change
Compound 2 (phosphonium salt) 1:1.1 in molar ratio is dissolved in and heavily steams in oxolane, adds 2.40g and (works as 10 times
Amount) NaH, stirring at normal temperature 24 hours, it is poured slowly into after completion of the reaction in the frozen water of 200mL, uses second
Ether extracts, and merges organic facies, and anhydrous MgSO4 is dried the organic facies after merging overnight, filters, rotation steaming
Remove ether, pillar layer separation (petroleum ether/acetone volume ratio=30:1), obtain light yellow solid after drying
Body compound 3, productivity 61%.
MS(MALDI-TOF),m/z:472.374(M+).1H NMR(400MHz,CDCl3)δ:7.10
(s, 0.6H), 7.03 (dd, J=9.5,5.4Hz, 1.2H), 7.00 6.96 (m, 1H), 6.92 (dd, J=9.6,
6.4Hz, 1.4H), 6.87 6.79 (m, 0.6H), 6.57 (d, J=11.9Hz, 0.6H), 6.47 (d, J=11.9
Hz, 0.6H), 4.68 (s, 1H), 3.86 3.78 (m, 2H), 3.56 (q, J=6.9Hz, 2H), 3.04 (ddd, J
=18.2,11.6,5.8Hz, 4H), 1.75 1.61 (m, 6H), 1.50 (ddd, J=21.0,14.0,7.1Hz,
4H), 1.37 (d, J=4.2Hz, 6H), 1.35 1.27 (m, 2H), 1.25 (s, 3H), 1.12 (s, 3H).
4) synthesis of the compound 4 shown in formula
Adding 10mL DMF in the 100mL there-necked flask sealed, at 0 DEG C, ice bath stirring, is slowly added dropwise
POCl30.8mL (about 0.008mol), ice bath stirs 1-2 hour, then constant voltage is slowly added dropwise containing 1.89g
(0.004mol) DMF solution (30mL) of compound 3.Being slowly increased to room temperature, 90 DEG C of reactions 3 are little
Shi Hou, pours in 200mL sodium bicarbonate aqueous solution by reaction solution, and ethyl acetate extracts three times, anhydrous
Magnesium sulfate is dried overnight, pillar layer separation (petroleum ether/acetone volume ratio=15:1), obtains orange after drying
Color solid chemical compound 4, productivity 62%.
MS(MALDI-TOF),m/z:500.649(M+).1H NMR(400MHz,CDCl3)δ:9.61
(s, 1H), 7.57 (s, 1H), 7.41 7.35 (m, 1H), 7.09 (d, J=3.1Hz, 2H), 7.00 (s, 1H),
3.94 (t, J=6.5Hz, 2H), 3.57 (t, J=6.6Hz, 2H), 3.17 (dt, J=11.5,5.9Hz, 4H),
1.96–1.87(m,2H),1.88–1.80(m,2H),1.74–1.70(m,2H),1.63–1.54(m,7H),
1.42(s,6H),0.92(s,6H).
5) synthesis of 3-hydroxy-3-methyl-2-butanone (compound 5 shown in formula) is same as in Example 1.
6) 2,2-dicyano methene base-3-cyano group-4,5,5-trimethyl-2,5-dihydrofuran (TCF) receptor (formula
Shown in compound 6) synthesis same as in Example 1.
7) synthesis of the compound HCL1 shown in formula
Compound 4 (0.80g, 0.0016mol) and compound 6 1:1.1 in molar ratio are dissolved in ethanol
In solution, in microwave, back flow reaction 2 hours, are cooled to room temperature, concentrate away solvent, pillar layer separation
(petrol ether/ethyl acetate volume ratio=3:1), obtains green solid powder compounds HCL1 after drying, produces
Rate 25%.
MS(MALDI-TOF),m/z:679.746(M+).1H NMR(400MHz,CDCl3)δ:8.06
(d, J=15.2Hz, 1H), 7.50 (d, J=5.1Hz, 1H), 7.44 (s, 1H), 7.20 (dd, J=5.1,3.5
Hz, 1H), 6.96 (d, J=2.6Hz, 1H), 6.71 (s, 1H), 5.92 (d, J=15.1Hz, 1H), 3.91 (t, J
=6.5Hz, 2H), 3.58 (t, J=6.6Hz, 2H), 3.25 (dd, J=13.4,8.5Hz, 4H), 1.98 1.89
(m, 2H), 1.89 1.80 (m, 2H), 1.76 (d, J=5.6Hz, 2H), 1.69 1.63 (m, 2H), 1.59 (s,
12H), 1.42 (d, J=8.4Hz, 6H), 1.28 1.19 (m, 4H).
The organic second order non-linear optical chromophore molecule with D-π-A structure obtained has good heat
Stability；In acetone, chloroform or ethanol polar solvent and the non-polar solven such as ether, epoxy six alkane
All there is good dissolubility.
Embodiment 3
Synthesize the organic second order non-linear optical chromophore with D-π-A structure as follows, formula
(HCL2):
Synthetic route is as follows:
Synthetic method is:
1) synthesis of the compound 1 shown in formula is same as in Example 2.
2) synthesis of the compound 2 shown in formula
10.30g triphenyl phosphorus hydrogen bromide (0.03mol), 4-(dimethylamino) is added in 250mL flask
The chloroform that benzylalcohol 4.98g (0.033mol), 200mL magnesium sulfate are dried, is heated to reflux 3-4 hour,
It is spin-dried for.Adding a small amount of chloroform to dissolve, pour in a large amount of absolute ether, sucking filtration obtains white solid, productivity
95%.
3) synthesis of the compound 3 shown in formula
In 100mL flask, add 3.92g (0.01mol) compound 1 and 5.24g (0.011mol) change
The ratio of compound 2 (phosphonium salt) 1:1.1 in molar ratio is dissolved in heavily steams in oxolane, adds 2.40g (10
Times equivalent) NaH, stirring at normal temperature 24 hours, it is poured slowly into after completion of the reaction in the frozen water of 200mL,
Extracting with ether, merge organic facies, anhydrous MgSO4 is dried the organic facies after merging overnight, filtration,
Rotation is evaporated off ether, pillar layer separation (petroleum ether/acetone volume ratio=30:1), obtains pale yellow after drying
Color solid chemical compound 3, productivity 73%.
4) synthesis of the compound 4 shown in formula
Adding 10mL DMF in the 100mL there-necked flask sealed, at 0 DEG C, ice bath stirring, is slowly added dropwise
POCl30.95mL (about 0.01mol), ice bath stirs 1-2 hour, then constant voltage is slowly added dropwise containing 2.55g
(0.005mol) DMF solution (30mL) of compound 3.Being slowly increased to room temperature, 60 DEG C of reactions 2 are little
Shi Hou, pours in 200mL sodium bicarbonate aqueous solution by reaction solution, and ethyl acetate extracts three times, anhydrous
Magnesium sulfate is dried overnight, pillar layer separation (petroleum ether/acetone volume ratio=15:1), obtains yellow after drying
Solid chemical compound 4, productivity 68%.
MS(MALDI-TOF),m/z:537.194(M+).1H NMR(400MHz,CDCl3)δ:9.65
(s, 1H), 7.43 (s, 1H), 7.14 (d, J=8.3Hz, 2H), 6.85 (s, 1H), 6.79 (d, J=7.2Hz,
2H), 3.96 (t, J=6.6Hz, 2H), 3.57 (t, J=6.6Hz, 2H), 3.19 3.07 (m, 4H), 2.93 (s,
6H),1.95–1.89(m,2H),1.84(m,2H),1.74–1.68(m,2H),1.62–1.53(m,6H),
1.41(s,6H),0.83(s,6H)。
5) synthesis of 3-hydroxy-3-methyl-2-butanone (compound 5 shown in formula) is same as in Example 1.
6) 2,2-dicyano methene base-3-cyano group-4,5,5-trimethyl-2,5-dihydrofuran (TCF) receptor (formula
Shown in compound 6) synthesis same as in Example 1.
7) synthesis of the compound HCL2 shown in formula
Compound 4 (1.07g, 0.002mol) and compound 6 1:1.1 in molar ratio are dissolved in ethanol molten
In liquid, in microwave, back flow reaction 4 hours, are cooled to room temperature, concentrate away solvent, pillar layer separation (stone
Oil ether/ethyl acetate volume ratio=3:1), obtain dark green solid powder compounds HCL2, productivity after drying
34%.
MS(MALDI-TOF),m/z:718.382(M+).1H NMR(400MHz,CDCl3)δ:8.06
(d, J=15.0Hz, 1H), 7.36 (s, 1H), 7.04 (d, J=8.3Hz, 2H), 6.86 (s, 2H), 6.58 (s,
1H), 5.88 (d, J=15.0Hz, 1H), 3.92 (t, J=6.5Hz, 2H), 3.59 (t, J=6.6Hz, 2H),
3.21 (dd, J=13.5,7.5Hz, 4H), 3.01 (s, 6H), 1.93 1.85 (m, 2H), 1.85 1.83 (s,
2H),1.71–1.67(m,2H),1.62–1.55(m,12H),1.39(s,6H),0.80(s,6H).
The organic second order non-linear optical chromophore molecule with D-π-A structure obtained has good heat
Stability；In acetone, chloroform or ethanol polar solvent and the non-polar solven such as ether, epoxy six alkane
All there is good dissolubility.
Embodiment 4
0.1 gram of unformed Merlon (APC) is joined in the middle of 1.00mL methylene bromide, stirs 3-5
After hour being completely dissolved to APC, add the organic second-order non-linear light synthesized by 0.020 gram of embodiment 1
Learn chromophore compound (formula be CL1), obtain organic second order non-linear optical chromophore compound with
The mixed solution of APC, (controls the mixed solution obtained with spin-coating method film on ito glass substrate
Rotating speed is 800-1200 rev/min), then it is dried 24 hours in the vacuum drying oven of 60 DEG C.Gained
The thickness of thin polymer film is between 2-4 μm.
Embodiment 5
0.1 gram of unformed Merlon (APC) is joined in the middle of 1.00mL methylene bromide, stirs 3-5
After hour being completely dissolved to APC, add the organic second-order non-linear light synthesized by 0.040 gram of embodiment 2
Learn chromophore compound (formula be HCL1), obtain organic second order non-linear optical chromophore compound with
The mixed solution of APC, uses spin-coating method film on ito glass substrate, and controlling rotating speed is that 800-1200 turns
/ minute, then it is dried 24 hours in the vacuum drying oven of 60 DEG C.The thickness of resulting polymers thin film exists
Between 2-4 μm.
Embodiment 6
The polarization of thin polymer film prepared by embodiment 4 and 5 and electro-optic coefficient measure
1) carrying out corona polarizing to being prepared thin polymer film by embodiment 4, poling temperature is 130-140 DEG C
Between, the polarization time is 10-20 minute, and polarizing voltage controls at about 10000-12000V, needle point with
Distance between thin polymer film is 1 centimetre；Electro-optic coefficient (r33) (is seen by simple reflex method
C.C.Teng, H.T.Man, App.Phys.lett., 56 (1990), 1734) it is measured, the maximum electricity recorded
Backscatter extinction logarithmic ratio is 45pm/V.
2) carrying out corona polarizing to being prepared thin polymer film by embodiment 5, poling temperature is 120-130 DEG C
Between, the polarization time is 10-20 minute, and polarizing voltage controls at about 10000-12000V, needle point with
Distance between thin polymer film is 1 centimetre；Electro-optic coefficient (r33) (seen by simple reflex method
C.C.Teng, H.T.Man, App.Phys.lett., 56 (1990), 1734) it is measured, the maximum electricity recorded
Backscatter extinction logarithmic ratio is 337pm/V.
Obviously, the above embodiment of the present invention is only for clearly demonstrating example of the present invention, and
It is not the restriction to embodiments of the present invention, for those of ordinary skill in the field,
Can also make other changes in different forms on the basis of described above, here cannot be to all
Embodiment give exhaustive, every belong to the obvious change that technical scheme extended out
Change or change the row still in protection scope of the present invention.
Claims (10)
1. an organic second order non-linear optical chromophore, it is characterised in that there is formula (CL) or the structure of formula (HCL):
Wherein:
G is H, phenyl, palkoxy benzene base, thienyl or to dialkylamino phenyl；
R1For alkyl, benzyl, haloalkyl；
R2For methyl or trifluoromethyl；
R3For alkyl, phenyl, substituted-phenyl, substituted thiophene base or hydroxyalkyl.
Optical chromophore the most according to claim 1, it is characterised in that in described palkoxy benzene base, the carbon chain lengths of alkoxyl is 1-10 carbon atom.
Optical chromophore the most according to claim 1, it is characterised in that described is 1-10 carbon atom to the carbon chain lengths of alkylamino in dialkylamino phenyl.
Optical chromophore the most according to claim 1, it is characterised in that the carbon chain lengths of described alkyl is 1-20 carbon atom.
Optical chromophore the most according to claim 1, it is characterised in that described haloalkyl be carbon chain lengths be F substituted alkyl or the Cl substituted alkyl of 1-20 carbon atom.
Optical chromophore the most according to claim 1, it is characterised in that the carbon chain lengths of described hydroxyalkyl is 1-10 carbon atom.
Optical chromophore the most according to claim 1, it is characterized in that, the described substituent group in substituted-phenyl be halogen, carbon chain lengths be the alkyl of 1-20 carbon atom, carbon chain lengths be the alkoxyl of 1-20 carbon atom or hydroxyalkyl that carbon chain lengths is 1-10 carbon atom, preferably, described halogen is F or Cl.
Optical chromophore the most according to claim 1, it is characterized in that, the described substituent group in substituted thiophene base be phenyl, halogen, carbon chain lengths be the alkyl of 1-20 carbon atom, carbon chain lengths be the alkoxyl of 1-20 carbon atom or hydroxyalkyl that carbon chain lengths is 1-10 carbon atom, preferably, described halogen is F or Cl.
9. the preparation method of the optical chromophore described in any one of claim 1-8, it is characterised in that comprise the steps:
(1) by 4-(lignocaine)-2-R1Epoxide benzaldehyde electron donor, G methyl triphenyl phosphine and Cyanogran. are dissolved in anhydrous tetrahydro furan according to mol ratio 1:1:15-20, it is stirred at room temperature 12-24 hour, after completion of the reaction product is poured in frozen water, extract with ether, merge organic facies, be dried the organic facies overnight after merging, filter, rotation is evaporated off ether, pillar layer separation, obtains the compound with formula (I) structure after drying:
Wherein:
G is H, phenyl, palkoxy benzene base, thienyl or to dialkylamino phenyl；
R1For alkyl, benzyl or haloalkyl.
(2) at N2By the POCl of 1.2-1.5 equivalent under protection3Being added drop-wise at 0 DEG C in the DMF of 2-2.5 equivalent, ice bath stirs 1-2 hour, then constant voltage is slowly added dropwise the DMF solution of the compound with formula (I) structure that 1 equivalent step (1) obtains.It is slowly increased to room temperature, 60-90 DEG C is reacted 1-3 hour, terminates reaction with sodium bicarbonate aqueous solution after completion of the reaction, then pour in deionized water by reaction gained mixture, it is extracted with ethyl acetate, separatory, merges organic facies, is dried the organic facies overnight after merging, filter, rotation is evaporated off ethyl acetate, pillar layer separation, obtains the compound with formula II structure after drying:
(3) compound with formula (II) structure and substituted tricyano-dihydrofuran electron acceptor step (2) obtained is dissolved in ethanol according to mol ratio 1:1.2-1.5, reaction it is stirred at 50-80 DEG C, it is cooled to room temperature after completion of the reaction, rotation is evaporated off ethanol, pillar layer separation, obtain the organic second-order non-linear chromophore with D-π-A structure, i.e. there is the organic second order non-linear optical chromophore of formula (CL) structure.
10. the preparation method of the optical chromophore described in any one of claim 1-8, it is characterised in that comprise the steps: that (1) is by 8-R1Oxy-1,1,7,7-tetramethyl julolidine-9-formaldehyde electron donor, G methyl triphenyl phosphine and Cyanogran. are dissolved in anhydrous tetrahydro furan according to mol ratio 1:1:15-20, it is stirred at room temperature 12-24 hour, after completion of the reaction product is poured in frozen water, extract with ether, merge organic facies, it is dried the organic facies overnight after merging, filters, revolve and ether is evaporated off, pillar layer separation, is had the compound of (III) structure after drying:
Wherein:
G is H, phenyl, palkoxy benzene base, thienyl or to dialkylamino phenyl；
R1For alkyl, benzyl or haloalkyl.
(2) at N2By the POCl of 1.2-1.5 equivalent under protection3Being added drop-wise at 0 DEG C in the DMF of 2-2.5 equivalent, ice bath stirs 1-2 hour, then constant voltage is slowly added dropwise the DMF solution of the compound with formula (III) structure that 1 equivalent step (1) obtains.It is slowly increased to room temperature, 60-90 DEG C is reacted 1-3 hour, terminates reaction with sodium bicarbonate aqueous solution after completion of the reaction, then pour in deionized water by reaction gained mixture, it is extracted with ethyl acetate, separatory, merges organic facies, is dried the organic facies overnight after merging, filter, rotation is evaporated off ethyl acetate, pillar layer separation, obtains the compound with formula (IV) structure after drying:
(3) compound with formula (IV) structure and substituted tricyano-dihydrofuran electron acceptor step (2) obtained is dissolved in ethanol according to mol ratio 1:1.2-1.5, reaction it is stirred at 50-80 DEG C, it is cooled to room temperature after completion of the reaction, rotation is evaporated off ethanol, pillar layer separation, obtain the organic second-order non-linear chromophore with D-π-A structure, i.e. there is the organic second order non-linear optical chromophore of formula (HCL) structure.
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| CN115960093A (en) * | 2021-10-09 | 2023-04-14 | 香港城市大学深圳研究院 | Optical chromophore compound, composite material containing optical chromophore compound, thin film and photoelectric integrated device |
| WO2023231528A1 (en) * | 2022-05-30 | 2023-12-07 | 华为技术有限公司 | Chromophore compound, preparation method therefor, and use of chromophore compound |
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| CN115960093A (en) * | 2021-10-09 | 2023-04-14 | 香港城市大学深圳研究院 | Optical chromophore compound, composite material containing optical chromophore compound, thin film and photoelectric integrated device |
| WO2023231528A1 (en) * | 2022-05-30 | 2023-12-07 | 华为技术有限公司 | Chromophore compound, preparation method therefor, and use of chromophore compound |
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