CN101845040B - Organic second-order nonlinear optical chromophore with D-pi-A structure modified by dendritic group, and synthetic method and application thereof - Google Patents
Organic second-order nonlinear optical chromophore with D-pi-A structure modified by dendritic group, and synthetic method and application thereof Download PDFInfo
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- 238000010189 synthetic method Methods 0.000 title abstract 2
- 230000004048 modification Effects 0.000 claims abstract description 33
- 238000012986 modification Methods 0.000 claims abstract description 33
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000004417 polycarbonate Substances 0.000 claims abstract description 7
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 6
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 64
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 41
- 239000012074 organic phase Substances 0.000 claims description 41
- 229910052760 oxygen Inorganic materials 0.000 claims description 38
- 239000001301 oxygen Substances 0.000 claims description 38
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 37
- 241000555268 Dendroides Species 0.000 claims description 36
- 125000000217 alkyl group Chemical group 0.000 claims description 32
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 30
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 29
- 238000004440 column chromatography Methods 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 26
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 25
- 239000000370 acceptor Substances 0.000 claims description 24
- 229910000077 silane Inorganic materials 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 claims description 18
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 18
- ADJZESSSQAMIMW-UHFFFAOYSA-N 2,3-dihydropyrrole-1,4,5-tricarbonitrile Chemical compound N#CN1CCC(C#N)=C1C#N ADJZESSSQAMIMW-UHFFFAOYSA-N 0.000 claims description 16
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229930192474 thiophene Natural products 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 13
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 12
- FXWFZIRWWNPPOV-UHFFFAOYSA-N 2-aminobenzaldehyde Chemical compound NC1=CC=CC=C1C=O FXWFZIRWWNPPOV-UHFFFAOYSA-N 0.000 claims description 10
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 10
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 7
- 239000012312 sodium hydride Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229910019213 POCl3 Inorganic materials 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 230000026030 halogenation Effects 0.000 claims description 5
- 238000005658 halogenation reaction Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- 229920006112 polar polymer Polymers 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- -1 stirs Substances 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 5
- 230000003993 interaction Effects 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 78
- 239000003921 oil Substances 0.000 description 36
- 230000005526 G1 to G0 transition Effects 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 239000011259 mixed solution Substances 0.000 description 18
- 239000012071 phase Substances 0.000 description 18
- 239000000741 silica gel Substances 0.000 description 18
- 229910002027 silica gel Inorganic materials 0.000 description 18
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 16
- 238000001035 drying Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000000926 separation method Methods 0.000 description 13
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 description 10
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 description 10
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
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- 235000011181 potassium carbonates Nutrition 0.000 description 5
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
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Abstract
The invention relates to a dendritic group modified organic second-order nonlinear optical chromophore with a D-pi-A structure, a synthetic method and application thereof. The chromophore of the invention introduces a thiophene ring conjugated pi electron bridge with a branched chain with strong electron transmission capability and a tricyano pyrroline receptor with strong electron-withdrawing capability, and the receptor end introduces a dendritic modification group, so that the hyperpolarizability of the first-order molecule of the chromophore molecule is greatly improved, the solubility and the film-forming property of the chromophore in a polymer are improved, and the interaction force among molecules is reduced. The organic second-order nonlinear optical chromophore of the invention with the following structure is doped with polymers such as amorphous polycarbonate or polymethyl methacrylate and the like according to the mass ratio of 1: 10, and the electro-optic coefficient of the obtained polarized polymer material can reach 217 pm/V. In addition, the chromophore donor and the acceptor end of the invention can be introduced with crosslinkable groups, thereby improving the orientation stability of the chromophore in the polymer and meeting the requirements of device formation.
Description
Technical field
The present invention relates to the organic second-order non-linear optical field of materials, particularly a kind of organic second order non-linear optical chromophore and preparation method and use thereof with D-π-A structure with dendroid base group modification of high electro-optical activity.
Background technology
Current social, laser and optical-fibre communications are replacing microelectronics and integrated circuit technique and the emerging communication technology that becomes.Two front subjects as laser communications and optical-fibre communications: integrated optics and photoelectronics obtain swift and violent development.Integrated photosystem has comprised important devices such as waveguide, photoswitch, photoconverter, in these devices, all must use nonlinear optical material.The more nonlinear optical material of practical application mainly is an inorganic crystal material at present.The organic second-order non-linear optical material compare with inorganic crystal material have the nonlinear optical coefficients height, response speed fast (subpicosecond even psec), relatively large nonlinear optical response (usually than high 1～2 one magnitude of inorganic crystal material), optical damage threshold high (GW/cm2 magnitude), uptake factor is low, specific inductivity is low, bandwidth is high, can carry out molecular designing as requested, be easy to advantages such as processing and cheapness, thereby have broad application prospects.
Because the response of organic non linear optical material is closely related with the nonlinear optical properties of chromophore molecule wherein; Institute thinks and satisfies requirement of actual application; Need from the chromophore molecule design and chromophoric group second nonlinear performance is effectively changed into material electro-optical properties two aspects to set about: one to seek single order molecule hyperpolarizability (β value) greatly, the chromophore molecule of high comprehensive performance; Two will carry out structural modification to chromophore molecule and polymer body skeleton; Make the interior chromophore densities of material unit volume bigger; Chromophoric group can obtain to be orientated consistence preferably and to have satisfactory stability property through electropolarization, thereby makes chromophoric single order molecule hyperpolarizability (β value) effectively be converted into the electro-optic coefficient (r of macroscopic material
33).
In existing report about the organic second-order non-linear optical material, most of macroscopical electro-optic coefficients are not high.At Chem.Mater.; Vol.18, No.13,2006 and U.S. Pat 7307173B1 in a series of chromophoric grouies that contain the pyrroline electron acceptor(EA) of reporting have higher single order molecule hyperpolarizability; But these chromophoric grouies are bigger owing to intermolecular interaction in polymkeric substance; Cause its polarization efficiency not high, electro-optic coefficient is less, can not well satisfy the requirement of device.
Summary of the invention
The object of the present invention is to provide a kind of single order molecule hyperpolarizability (β value), solvability with superelevation good, with polymer-doped after good film-forming property, be easy to polarize, macroscopical electro-optic coefficient is high, the organic second order non-linear optical chromophore with D-π-A structure that is easy to the dendroid base group modification of device; Wherein, D is an electron donor(ED), and π is the conjugated pi electron bridge, and A is an electron acceptor(EA).
A purpose more of the present invention provides a kind of compound method of the organic second order non-linear optical chromophore with D-π-A structure of dendroid base group modification.
An also purpose of the present invention provides a kind of purposes of the organic second order non-linear optical chromophore with D-π-A structure of dendroid base group modification.
The organic second order non-linear optical chromophore with D-π-A structure of dendroid base group modification of the present invention has following structure:
D in described D-π-A structure is 4-(N-R
1, N-R
2) the amino-benzene electron-like is to body, π is 3,4-two R
3Oxygen base thiophene-based conjugated electrons bridge, A are tricyano pyrroline (TCP) electron-like acceptors, and the Wasserstoffatoms on the acceptor nitrogen-atoms is by dendritic 3,5-two R
4Oxy-benzyl replaces.
Wherein, R
1, R
2Respectively or be a kind of in hydroxyalkyl or the hydroxyalkyl of alkyl, protected silane simultaneously; R
3Be alkyl; R
4A kind of in alkyl, acyl group, benzyl, anthracene benzyl or the naphthalene benzyl etc.
Carbon chain lengths in the described alkyl is a carbonatoms 1～20.
Have the phenyl amines electron donor(ED), the chromophoric group of thiophene-based conjugated electrons bridge and tricyano pyrroline (TCP) electron-like acceptor has very high single order molecule hyperpolarizability.The steric group that contains on the conjugated electrons bridge and on electron acceptor(EA), introduce the dendroid modification group; Can increase the distance between chromophore molecule; Reduce the interaction force between chromophore molecule; Reduce chromophore molecule accumulative probability, thereby improve the electro-optic coefficient that polarization efficiency improves material monolithic; In addition, if adopt flexible chain, can improve chromophoric group in solvent solvability and with the consistency of polymkeric substance, help preparation of devices.
The compound method of the organic second order non-linear optical chromophore with D-π-A structure of dendroid base group modification of the present invention may further comprise the steps:
1) with bromo-3,4-two R
3Oxygen base thenyl triphenylphosphine and 4-(N-R
1, N-R
2) amino benzaldehyde electron donor(ED) and sodium hydride be mixed in the anhydrous diethyl ether solvent, is 20～50 ℃ in temperature and stirred 18～50 hours down that reaction product is poured in the frozen water; Separatory, the extracted with diethyl ether water merges organic phase; Use the anhydrous magnesium sulfate drying organic phase, filter, revolve to steam and remove ether; Column chromatography is separated, and obtains 4-(N-R
1, N-R
2) amino-benzene ethene-3,4-two R
3Oxygen base thiophene, wherein, bromo-3,4-two R
3Oxygen base thenyl triphenylphosphine: 4-(N-R
1, N-R
2) the amino benzaldehyde electron donor(ED): the mol ratio of sodium hydride is 1: 1: 15～30;
Wherein, R
1, R
2Respectively or be a kind of in alkyl or the hydroxyalkyl protected by ethanoyl simultaneously, R
3Be alkyl;
2) 4-(N-R that step 1) is obtained
1, N-R
2) amino-benzene ethene-3,4-two R
3Oxygen base thiophene and POCl3 and N, dinethylformamide solvent are 70～110 ℃ in temperature and reacted 2～5 hours down, cooling after the reaction after mixing under 0 ℃; Pour in the aqueous sodium carbonate, use the extracted with diethyl ether water, separatory merges organic phase; With saturated common salt water washing organic phase, separatory is used the anhydrous magnesium sulfate drying organic phase, filters; Revolve to steam and remove ether, column chromatography is separated, and obtains 4-(N-R
1, N-R
2) amino-benzene ethene-3,4-two R
3Oxygen base thiophenecarboxaldehyde, wherein, 4-(N-R
1, N-R
2) amino-benzene ethene-3,4-two R
3Oxygen base thiophene: the mol ratio of POCl3 is 1: 1～1.2;
Wherein, R
1, R
2Respectively or be a kind of in alkyl or the hydroxyalkyl protected by ethanoyl simultaneously; R
3Be alkyl;
3) with step 2) 4-(N-R that obtains
1, N-R
2) amino-benzene ethene-3,4-two R
3Oxygen base thiophenecarboxaldehyde and three itrile group pyrroline electron acceptor(EA)s are dissolved in the ethanol, are 40～70 ℃ in temperature and react 30～60 minutes down, revolve to steam and remove ethanol, and column chromatography is separated, and obtains the chromophoric group of D-π-A structure, and product can further be purified; Wherein, 4-(N-R
1, N-R
2) amino-benzene ethene-3,4-two R
3Oxygen base thiophenecarboxaldehyde: the mol ratio of three itrile group pyrroline electron acceptor(EA)s is 1: 3～6;
4-(N-R
1, N-R
2) amino-benzene ethene-3,4-two R
3R in the oxygen base thiophenecarboxaldehyde
1, R
2Respectively or be a kind of in alkyl or the hydroxyalkyl protected by ethanoyl simultaneously; R
3Be alkyl;
Wherein: the D in D-π-A structure is 4-(N-R
1, N-R
2) the amino-benzene electron-like is to body, π is 3,4-two R
3Oxygen base thiophene-based conjugated electrons bridge, A are tricyano pyrroline electron-like acceptors;
4-(N-R
1, N-R
2) the amino-benzene electron-like gives the R in the body
1, R
2Respectively or be the hydroxyalkyl of alkyl or protected silane simultaneously;
3,4-two R
3R in the oxygen base thiophene-based conjugated electrons bridge
3Be alkyl;
Described 4-(N-R
1, N-R
2) the amino-benzene electron-like gives the R in the body
1, R
2Be to work as 4-(N-R respectively or be the hydroxyalkyl of protected silane simultaneously,
1, N-R
2) amino-benzene ethene-3,4-two R
3R in the oxygen base thiophenecarboxaldehyde
1, R
2During the hydroxyalkyl protected for ethanoyl respectively or simultaneously, 4-(N-R
1, N-R
2) amino-benzene ethene-3,4-two R
3Need the ethanoyl protection is removed before oxygen base thiophenecarboxaldehyde and the reaction of three itrile group pyrroline electron acceptor(EA)s are carried out, recycle silicon alkane is protected hydroxyalkyl, obtains having the 4-(N-R of protected silane
1, N-R
2) amino-benzene ethene-3,4-two R
3Oxygen base thiophenecarboxaldehyde;
The chromophoric group and the dendroid 3 of the D-π-A structure that 4) step 3) is synthesized, 5-two R
4Oxygen base halogenation benzyl and salt of wormwood were dissolved in the acetonitrile in 1: 1: 1 in molar ratio, were 50～80 ℃ in temperature and reacted 1～10 hour washing down; The extracted with diethyl ether water, separatory merges organic phase; The anhydrous magnesium sulfate drying organic phase; Column chromatography is separated, and generates the organic second order non-linear optical chromophore with D-π-A structure of dendroid base group modification, and structure is:
Wherein, R
1, R
2Respectively or be a kind of in the hydroxyalkyl of alkyl, hydroxyalkyl or protected silane simultaneously; R
3Be alkyl; R
4A kind of in alkyl, acyl group, benzyl, anthracene benzyl or the naphthalene benzyl etc.
Carbon chain lengths in the described alkyl is a carbonatoms 1～20.
Reactant 4-(N-R described in the step 1)
1, N-R
2) the amino benzaldehyde electron donor(ED), R wherein
1And/or R
2During for hydroxyalkyl, hydroxyalkyl needs with ethanoyl protection, concrete scheme such as technical scheme known in those skilled in the art: with 4-(N-R before the reaction
1, N-R
2) amino benzaldehyde electron donor(ED) and diacetyl oxide be dissolved in the pyridine, at N
2Protection is reflux (being generally about 2 hours) down, can obtain having the 4-(N-R of the hydroxyalkyl of ethanoyl protection
1, N-R
2) the amino benzaldehyde electron donor(ED), wherein, R
1, R
2The total mole number of middle hydroxyl: the mole number of diacetyl oxide is 1: 1.
The described ethanoyl protection of step 3) removes concrete scheme such as technical scheme known in those skilled in the art: the 4-(N-R that will have the ethanoyl protection
1, N-R
2) amino-benzene ethene-3,4-two R
3Oxygen base thiophenecarboxaldehyde and wet chemical and methanol mixed, 70 ℃ of reactions (being generally about 10 hours) down, thus the ethanoyl blocking group is removed, wherein, have the 4-(N-R of ethanoyl protection
1, N-R
2) amino-benzene ethene-3,4-two R
3Oxygen base thiophenecarboxaldehyde: the mol ratio of salt of wormwood is 1: 6.
The described protected silane hydroxyalkyl of step 3) is with 4-(N-R
1, N-R
2) amino-benzene ethene-3,4-two R
3Oxygen base thiophenecarboxaldehyde and TERT-BUTYL DIMETHYL CHLORO SILANE and imidazoles are dissolved in N, in the N-dimethylformamide (DMF), stir (being generally about 24 hours), obtain having the 4-(N-R of protected silane
1, N-R
2) amino-benzene ethene-3,4-two R
3Oxygen base thiophenecarboxaldehyde, wherein, R
1, R
2The total mole number of middle hydroxyl: the mole number of TERT-BUTYL DIMETHYL CHLORO SILANE: the mole number of imidazoles is 1: 1: 1.
R in the organic second order non-linear optical chromophore with D-π-A structure of the dendroid base group modification that step 4) obtains
1, R
2Respectively or when being the hydroxyalkyl of protected silane simultaneously, obtain R after removing the protected silane group
1, R
2Be the organic second order non-linear optical chromophore with D-π-A structure of the dendroid base group modification of hydroxyalkyl respectively or simultaneously.
The described protected silane group that removes is that the organic second order non-linear optical chromophore with D-π-A structure with the dendroid base group modification that has protected silane is dissolved in the acetone; Splash into the hydrochloric acid of catalytic amount, at room temperature stirring (being generally about 3 hours) can remove blocking group.
Described step 1), step 2), the column chromatography of step 3) and step 4) separates: stationary phase is 200～300 purpose silica gel, and moving phase is the mixed solution of sherwood oil and acetone, sherwood oil: the volume ratio of acetone is 3: 1.
The organic second order non-linear optical chromophore with D-π-A structure of dendroid base group modification of the present invention can prepare polar polymer with polymer-doped (mass ratio are 1: 1～100) such as unformed polycarbonate or polymethylmethacrylates; The prepared polar polymer film forming that can stretch, and use as the material in integrated optics or the photoelectronics.
The invention has the advantages that:
1) organic second order non-linear optical chromophore with D-π-A structure of dendroid base group modification of the present invention is owing to introduced stronger thiphene ring conjugated pi electron bridge of electron transport ability and the tricyano pyrroline receptor with strong electron-withdrawing power, and the single order molecule hyperpolarizability of chromophore molecule improves greatly.
2) organic second order non-linear optical chromophore with D-π-A structure of dendroid base group modification of the present invention; Its thiophene electronic bridge 3; The side chain that the ehter bond that has on 4 connects and the introducing of acceptor end dendroid modification group have improved solvability and the film-forming properties of chromophoric group in polymkeric substance; Reduced intermolecular interaction force; Improved the polarization efficiency of molecule; The organic second order non-linear optical chromophore with D-π-A structure of dendroid base group modification of the present invention and unformed polycarbonate or the adulterated mass ratio of polymethylmethacrylate are 1: 10 o'clock, and the electro-optic coefficient of the polar polymer material that obtains can reach 217pm/V, are higher than traditional D-π-A structure chromophoric group of having reported far away.
3) organic second order non-linear optical chromophore with D-π-A structure of dendroid base group modification of the present invention; All can introduce crosslinkable type group to body and acceptor end; Thereby can improve the orientation stability of chromophoric group in polymkeric substance greatly; Thereby improve the work-ing life of material, satisfy the requirement of device.
Embodiment
Embodiment 1
The chromophoric group with D-π-A structure of dendroid base group modification synthetic as follows
Synthetic route is following:
Wherein, Me is a methyl, PPh
3Be triphenylphosphine, TBDMSCl is a TERT-BUTYL DIMETHYL CHLORO SILANE, and TCP is three itrile group pyrroline electron acceptor(EA)s, and its structure is:
Compound method is:
1) compound 2 is synthetic
Get 4g (0.0064mol) bromo-3,4-(N, N-dihydroxy ethyl) aminobenzaldehyde electron donor(ED), 4.6g (0.192mol) sodium hydride (NaH) of 4-two hexyloxy thenyl triphenylphosphines, the protection of 1.9g (0.0064mol) ethanoyl are mixed in the 100ml anhydrous diethyl ether solvent; Stirring is after 18 hours down at 50 ℃, and reaction product is poured in the 200ml frozen water, separatory; The extracted with diethyl ether water merges organic phase, uses the anhydrous magnesium sulfate drying organic phase; Filter, revolve to steam and remove ether, obtain the red-brown dope; Column chromatography is separated compound 2 products that obtain pure ethanoyl protection, and (stationary phase is 200～300 purpose silica gel; Moving phase is the mixed solution of sherwood oil and acetone, sherwood oil: the volume ratio of acetone is 3: 1) 3.1g, productive rate 86%.
MS，m/z：573(M
+)；
1H?NMR(400MHz；CDCl
3)，δ：7.35(d，2H)，7.06(d，1H)，6.76(d，1H)，6.73(d，2H)，5.95(s，1H)，4.25(t，4H)，4.05(t，2H)，3.94(t，2H)，3.64(t，4H)，2.06(s，6H)，1.76(m，4H)，1.48(m，4H)，1.34(m，8H)，0.91(m，6H)。
2) compound 3 is synthetic
0.8ml (0.0087mol) POCl3 (POCl
3), the compound 2 and the 15mlN of 5g (0.0087mol) ethanoyl protection, dinethylformamide (DMF) 0 ℃ mix down after, heat up, 70 ℃ of reactions 5 hours down, 2gNa is poured in the cooling of reaction back into
2CO
3In the solution that is made into 80ml water, with extracted with diethyl ether water three times, separatory merges organic phase; With saturated common salt water washing organic phase, separatory is used the anhydrous magnesium sulfate drying organic phase, filters; Revolve to steam and remove ether, obtain the orange dope, (stationary phase is 200～300 purpose silica gel, and moving phase is the mixed solution of sherwood oil and acetone in the column chromatography separation; Sherwood oil: the volume ratio of acetone is 3: 1), obtain the compound 3 product 2.8g that pure ethanoyl is protected, productive rate 54%.MS，m/z：601(M
+)；
1H?NMR(400MHz，CDCl
3)，δ：9.91(s，1H)，7.39(d，2H)，7.24(d，1H)，7.02(d，1H)，6.79(d，2H)，4.28(t，4H)，3.98(m，4H)，3.65(t，4H)，2.08(s，6H)，1.75(m，4H)，1.46(m，4H)，1.37(m，8H)，0.90(m，6H)。
3) compound 4 is synthetic
2.8g (0.0047mol) compound 3,3.9g (0.0282mol) Anhydrous potassium carbonate, 50ml water and the 150ml methanol mixed of ethanoyl protection were reacted 10 hours down at 70 ℃, revolved to steam to remove methyl alcohol; Use the saturated aqueous common salt purging compound, use the extracted with diethyl ether water, separatory; Merge organic phase, organic phase is used anhydrous magnesium sulfate drying, filters; Revolve to steam and remove ether, (stationary phase is 200～300 purpose silica gel, and moving phase is the mixed solution of sherwood oil and acetone in the column chromatography separation; Sherwood oil: the volume ratio of acetone is 1: 1), get the compound 4 solid 2g that orange removes the ethanoyl protection, productive rate 85%.
4) compound 5 is synthetic
0.9g (0.0017mol) remove the compound 4 that ethanoyl is protected, 0.23g (0.0034mol) imidazoles and 0.5g (0.0034mol) TERT-BUTYL DIMETHYL CHLORO SILANE (TBDMSCl) are dissolved in 40ml N, in the N-dimethylformamide (DMF); Stirring at room 24 hours is poured mixture in the 300ml water into, with 200ml ethyl acetate extraction water; Separatory, organic phase is used anhydrous magnesium sulfate drying, filters; Revolve to steam to remove and desolvate, (stationary phase is 200～300 purpose silica gel, and moving phase is the mixed solution of sherwood oil and acetone in the column chromatography separation; Sherwood oil: the volume ratio of acetone is 5: 1), the compound 5 solid 1g of protected silane, productive rate 80%.
5) D-π-A chromophoric group 6 is synthetic
0.5g (0.00066mol) compound 5 of protected silane is dissolved in the ethanol with 0.73g (0.00396mol) three itrile group pyrroline (TCP) electron acceptor(EA)s; Reacted 30 minutes down at 70 ℃, revolve to steam and remove ethanol, (stationary phase is 200～300 purpose silica gel in the column chromatography separation; Moving phase is the mixed solution of sherwood oil and acetone; Sherwood oil: the volume ratio of acetone is 3: 1), get blackish green compound 6 solid 0.125g, productive rate 21%.UV-Vis(CH
3COCH
3)：λ
max＝796.5；MS(MALDI-TOF)，m/z：911(M
+)；
1H?NMR(400MHz，CDCl
3)，δ：8.39(s，1H)，7.39(d，2H)，7.08(m，4H)，6.73(d，2H)，4.35(t，2H)，4.02(t，2H)，3.79(t，4H)，3.59(t，4H)，1.79(m，4H)，1.49(m，4H)，1.35(m，8H)，0.92(t，6H)，0.85(s，18H)，0.15(s，12H)。
6) title product 7 is synthetic
With chromophoric group 6, Anhydrous potassium carbonate 7.6mg (0.055mmol) and the dendroid 3 of 50mg (0.055mmol), 5-two octane-iso oxygen base halogenation benzyl 23mg (0.055mmol) are dissolved in the acetonitrile, react 1 hour down at 80 ℃.Washing, extracted with diethyl ether water, separatory; Merge organic phase, organic phase is used anhydrous magnesium sulfate drying, and (stationary phase is 200～300 purpose silica gel in the column chromatography separation; Moving phase is the mixed solution of sherwood oil and acetone, sherwood oil: the volume ratio of acetone is 3: 1) obtain pure product 39mg, productive rate 57%.UV-Vis(CH
3COCH
3)：λ
max＝826.5；MS(MALDI-TOF)，m/z：1260(M
+)；
1H?NMR(400MHz，CDCl
3)，δ：7.26(d，2H)，6.52(m，6H)，6.39(s，3H)，4.41(m，6H)，3.82(m，12H)，1.71(m，6H)，1.45(m，8H)，1.32(m，20H)，0.91(m，36H)，0.15(s，12H)。
Embodiment 2
The chromophoric group with D-π-A structure of dendroid base group modification synthetic as follows
Synthetic route is following:
Wherein, PPh
3Be triphenylphosphine, TCP is three itrile group pyrroline electron acceptor(EA)s, and its structure does
Compound method is:
1) compound 2 is synthetic
Get 4g (0.0064mol) bromo-3,4-two hexyloxy thenyl triphenylphosphines, 1.1g (0.0064mol) 4-(N, N-diethylammonium) aminobenzaldehyde electron donor(ED), 2.3g (0.096mol) sodium hydride (NaH) are mixed in the 100ml anhydrous diethyl ether solvent; Stirring is after 50 hours down at 20 ℃, and reaction product is poured in the 200ml frozen water, separatory; The extracted with diethyl ether water merges organic phase, uses the anhydrous magnesium sulfate drying organic phase; Filter, revolve to steam and remove ether, obtain red dope; Column chromatography is separated (stationary phase is 200～300 purpose silica gel, and moving phase is the mixed solution of sherwood oil and acetone, sherwood oil: the volume ratio of acetone is 3: 1); Obtain the pure compound of 2.4g 2, productive rate 82%.
2) compound 3 is synthetic
1.1ml (0.012mol) POCl
3, 4.6g (0.01mol) compound 2 and 20ml N, dinethylformamide (DMF) 0 ℃ mix down after, heat up, 110 ℃ of reactions 2 hours down, 2.5gNa is poured in the cooling of reaction back into
2CO
3In the solution that is made into 100ml water, divide aqueous phase extracted three times with the 150ml ether, separatory merges organic phase; With saturated common salt water washing organic phase, separatory is used the anhydrous magnesium sulfate drying organic phase, filters; Revolve to steam and remove ether, obtain red dope, (stationary phase is 200～300 purpose silica gel, and moving phase is the mixed solution of sherwood oil and acetone in the column chromatography separation; Sherwood oil: the volume ratio of acetone is 3: 1), obtain the pure compound of 3.4g 3, productive rate 70%.
3) D-π-A chromophoric group 4 is synthetic
1.1g (0.0023mol) compound 3 is dissolved in the ethanol with 1.27g (0.0069mol) three itrile group pyrroline (TCP) electron acceptor(EA)s; Reacted 60 minutes down at 40 ℃, revolve to steam and remove ethanol, (stationary phase is 200～300 purpose silica gel in the column chromatography separation; Moving phase is the mixed solution of sherwood oil and acetone; Sherwood oil: the volume ratio of acetone is 3: 1), get greenization compound 4 solid 0.6g, productive rate 40%.
4) title product 5 is synthetic
With chromophoric group 4, the dendroid 3 of 55mg (0.084mmol), 5-benzyloxy halogenation benzyl 32mg (0.084mmol) and Anhydrous potassium carbonate 11.6mg (0.084mmol) are dissolved in the acetonitrile, react 10 hours down at 50 ℃.Washing, the extracted with diethyl ether water, separatory merges organic phase; Organic phase is used anhydrous magnesium sulfate drying, and (stationary phase is 200～300 purpose silica gel, and moving phase is the mixed solution of sherwood oil and acetone in the column chromatography separation; Sherwood oil: the volume ratio of acetone is 3: 1), obtain pure product 52mg, productive rate 65%.m/z：953(M
+)；
1H?NMR(400MHz，CDCl
3)，δ：7.32(m，12H)，6.61(m，6H)，6.24(s，3H)5.39(s，4.31(s，2H)，3.69(m，84H)，H)，1.71(m，4H)，1.32(m，12H)，0.98(m，12H)。
Embodiment 3
The chromophoric group with D-π-A structure of dendroid base group modification synthetic as follows
Synthetic route is following:
Wherein, Me is a methyl, PPh
3Be triphenylphosphine, TBDMSCl is a TERT-BUTYL DIMETHYL CHLORO SILANE, and TCP is three itrile group pyrroline electron acceptor(EA)s, and its structure does
Compound method is:
1) compound 2 is synthetic
Get 4g (0.0068mol) bromo-3,4-(N-methyl, N-hydroxyethyl) aminobenzaldehyde electron donor(ED), 4.1g (0.17mol) sodium hydride (NaH) of 4-dibutoxy thenyl triphenylphosphine, the protection of 1.5g (0.0068mol) ethanoyl are mixed in the 100ml anhydrous diethyl ether solvent; Stirring is after 24 hours down at 40 ℃, and reaction product is poured in the 200ml frozen water, separatory; The extracted with diethyl ether water merges organic phase, uses the anhydrous magnesium sulfate drying organic phase; Filter, revolve to steam and remove ether, obtain the red-brown dope; Column chromatography is separated compound 2 products that obtain pure ethanoyl protection, and (stationary phase is 200～300 purpose silica gel; Moving phase is the mixed solution of sherwood oil and acetone, sherwood oil: the volume ratio of acetone is 3: 1) 2.6g, productive rate 85%.
2) compound 3 is synthetic
1ml (0.011mol) POCl3 (POCl
3), the compound 2 and the 15mlN of 4.9g (0.011mol) ethanoyl protection, dinethylformamide (DMF) 0 ℃ mix down after, heat up, 70 ℃ of reactions 5 hours down, 2gNa is poured in the cooling of reaction back into
2CO
3In the solution that is made into 80ml water, with extracted with diethyl ether water three times, separatory merges organic phase; With saturated common salt water washing organic phase, separatory is used the anhydrous magnesium sulfate drying organic phase, filters; Revolve to steam and remove ether, obtain the orange dope, (stationary phase is 200～300 purpose silica gel, and moving phase is the mixed solution of sherwood oil and acetone in the column chromatography separation; Sherwood oil: the volume ratio of acetone is 3: 1), obtain the compound 3 product 3.1g that ethanoyl is protected, productive rate 60%.
3) compound 4 is synthetic
3.1g (0.0066mol) compound 3,5.5g (0.0396mol) Anhydrous potassium carbonate, 50ml water and the 150ml methanol mixed of ethanoyl protection were reacted 10 hours down at 70 ℃, revolved to steam to remove methyl alcohol; Use the saturated aqueous common salt purging compound, use the extracted with diethyl ether water, separatory; Merge organic phase, organic phase is used anhydrous magnesium sulfate drying, filters; Revolve to steam and remove ether, (stationary phase is 200～300 purpose silica gel, and moving phase is the mixed solution of sherwood oil and acetone in the column chromatography separation; Sherwood oil: the volume ratio of acetone is 1: 1), get the compound 4 solid 2g that orange removes the ethanoyl protection, productive rate 83%.
4) compound 5 is synthetic
1g (0.0023mol) removes the compound 4 of ethanoyl protection, and 0.16g (0.0023mol) imidazoles and 0.35g (0.0023mol) TERT-BUTYL DIMETHYL CHLORO SILANE (TBDMSCl) are dissolved in 40ml N, in the N-dimethylformamide (DMF); Stirring at room 24 hours is poured mixture in the 300ml water into, with 200ml ethyl acetate extraction water; Separatory, organic phase is used anhydrous magnesium sulfate drying, filters; Revolve to steam to remove and desolvate, (stationary phase is 200～300 purpose silica gel, and moving phase is the mixed solution of sherwood oil and acetone in the column chromatography separation; Sherwood oil: the volume ratio of acetone is 5: 1), the compound 5 solid 1g of protected silane, productive rate 82%.
5) D-π-A chromophoric group 6 is synthetic
0.5g (0.0009mol) compound 5 of protected silane is dissolved in the ethanol with 0.83g (0.0045mol) three itrile group pyrroline (TCP) electron acceptor(EA)s; Reacted 45 minutes down at 60 ℃, revolve to steam and remove ethanol, (stationary phase is 200～300 purpose silica gel in the column chromatography separation; Moving phase is the mixed solution of sherwood oil and acetone; Sherwood oil: the volume ratio of acetone is 3: 1), the compound 6 green solid 0.16g of protected silane, productive rate 25%.
6) compound 7 is synthetic
With chromophoric group 6, Anhydrous potassium carbonate 9.7mg (0.07mmol) and the dendroid 3 of 50mg (0.07mmol), 5-dibenzoyl oxygen base halogenation benzyl 29mg (0.07mmol) is dissolved in the acetonitrile, reacts 3 hours down at 70 ℃.Washing, extracted with diethyl ether water, separatory; Merge organic phase; Organic phase is used anhydrous magnesium sulfate drying, and (stationary phase is 200～300 purpose silica gel, and moving phase is the mixed solution of sherwood oil and acetone in the column chromatography separation; Sherwood oil: the volume ratio of acetone is 3: 1) obtain the compound 7 solid 36mg of protected silane, productive rate 49%.m/z：1041(M
+)。
7) target compound 8 is synthetic
The compound 7 of 36mg protected silane is dissolved in the 10ml acetone, splashes into 1 hydrochloric acid, at room temperature stirred 3 hours with dropper; Revolve to steam and remove acetone; Column chromatography is separated (stationary phase is 200～300 purpose silica gel, and moving phase is the mixed solution of sherwood oil and acetone, sherwood oil: the volume ratio of acetone is 1: 1); Obtain removing the target compound 8 solid 28mg of protected silane, productive rate 88%.
m/z：927(M
+)；δ：8.23(d，4H)，7.48(m，6H)，7.19(d，2H)，6.72(m，6H)，6.33(s，3H)，4.24(s，2H)，3.72(m，8H)，2.98(s，3H)，1.98(s，1H)，1.69(m，4H)，1.30(m，4H)，0.96(m，6H)。
Embodiment 4
Film preparation
0.1 gram polycarbonate (APC) is joined in the middle of the 1.00ml methylene bromide; Stir dissolved fully to APC in 3～5 hours after; Add 1 synthetic chromophoric group of 0.010 gram embodiment, obtain the mixing solutions of chromophoric group and APC, on the ito glass substrate, film with spin-coating method.The control rotating speed is 500～1000 rev/mins, the film that obtains in 60 ℃ vacuum drying oven dry 24 hours.Film thickness is between 1.8～3.5 μ m.
Embodiment 5
The polarization of embodiment 4 prepared films and electro-optic coefficient are measured
Film adopts the corona method polarization, and the polarization temperature is between 90～100 ℃, and the polarization time is 10～30 minutes, and polarizing voltage is controlled at about 9000～10000V, and the distance between polarizing electrode and the polymeric film is 1 centimetre; Electro-optic coefficient (r
33) (Simple Reflection Method is called the Teng-Man method again, referring to Teng C.C. through the simple reflex method; Man H.T.; Simple refection technique formeasuring the electro-optic coefficient of poled polymers, Applied Physics Letters, 1990; 56 (18), 1734-1736.) measure.Recording the electro-optic coefficient mxm. is 217pm/V.
Claims (5)
1. the organic second order non-linear optical chromophore with D-π-A structure of a dendroid base group modification, it is characterized in that: the organic second order non-linear optical chromophore with D-π-A structure of this dendroid base group modification has following structure:
D in described D-π-A structure is 4-(N-R
1, N-R
2) the amino-benzene electron-like is to body, π is 3,4-two R
3Oxygen base thiophene-based conjugated electrons bridge, A are tricyano pyrroline electron-like acceptors, and the Wasserstoffatoms on the acceptor nitrogen-atoms is by dendritic 3,5-two R
4Oxy-benzyl replaces;
Wherein, R
1, R
2Respectively or be a kind of in the hydroxyalkyl of alkyl, hydroxyalkyl or protected silane simultaneously; R
3Be alkyl; R
4A kind of in alkyl, benzyl, anthracene benzyl or the naphthalene benzyl;
Carbon chain lengths in the described alkyl is a carbonatoms 1～20.
2. the compound method of the organic second order non-linear optical chromophore with D-π-A structure of a dendroid base group modification according to claim 1 is characterized in that this method may further comprise the steps:
1) with bromo-3,4-two R
3Oxygen base thenyl triphenylphosphine and 4-(N-R
1, N-R
2) amino benzaldehyde electron donor(ED) and sodium hydride be mixed in the anhydrous diethyl ether solvent, stirs, reaction product is poured in the frozen water, separatory, and the extracted with diethyl ether water merges organic phase, and dry organic phase is filtered, and revolves to steam to remove ether, and column chromatography is separated, and obtains 4-(N-R
1, N-R
2) amino-benzene ethene-3,4-two R
3Oxygen base thiophene, wherein, bromo-3,4-two R
3Oxygen base thenyl triphenylphosphine: 4-(N-R
1, N-R
2) the amino benzaldehyde electron donor(ED): the mol ratio of sodium hydride is 1: 1: 15～30;
R
1, R
2Respectively or be a kind of in alkyl or the hydroxyalkyl protected by ethanoyl simultaneously, R
3Be alkyl;
2) 4-(N-R that step 1) is obtained
1, N-R
2) amino-benzene ethene-3,4-two R
3Oxygen base thiophene and POCl3 and N, dinethylformamide solvent are 70～110 ℃ of reactions down in temperature after mixing under 0 ℃, cooling after the reaction; Pour in the aqueous sodium carbonate, use the extracted with diethyl ether water, separatory merges organic phase; With saturated common salt water washing organic phase, separatory, dry organic phase is filtered; Revolve to steam and remove ether, column chromatography is separated, and obtains 4-(N-R
1, N-R
2) amino-benzene ethene-3,4-two R
3Oxygen base thiophenecarboxaldehyde, wherein, 4-(N-R
1, N-R
2) amino-benzene ethene-3,4-two R
3Oxygen base thiophene: the mol ratio of POCl3 is 1: 1～1.2;
R
1, R
2Respectively or be a kind of in alkyl or the hydroxyalkyl protected by ethanoyl simultaneously; R
3Be alkyl;
3) with step 2) 4-(N-R that obtains
1, N-R
2) amino-benzene ethene-3,4-two R
3Oxygen base thiophenecarboxaldehyde and tricyano pyrroline electron acceptor(EA) are dissolved in the ethanol, are 40～70 ℃ in temperature and react 30～60 minutes down, revolve to steam and remove ethanol, and column chromatography is separated, and obtains the chromophoric group of D-π-A structure; Wherein, 4-(N-R
1, N-R
2) amino-benzene ethene-3,4-two R
3Oxygen base thiophenecarboxaldehyde: the mol ratio of tricyano pyrroline electron acceptor(EA) is 1: 3～6;
4-(N-R
1, N-R
2) amino-benzene ethene-3,4-two R
3R in the oxygen base thiophenecarboxaldehyde
1, R
2Respectively or be a kind of in alkyl or the hydroxyalkyl protected by ethanoyl simultaneously; R
3Be alkyl;
Wherein: the D in D-π-A structure is 4-(N-R
1, N-R
2) the amino-benzene electron-like is to body, π is 3,4-two R
3Oxygen base thiophene-based conjugated electrons bridge, A are tricyano pyrroline electron-like acceptors;
4-(N-R
1, N-R
2) the amino-benzene electron-like gives the R in the body
1, R
2Respectively or be the hydroxyalkyl of alkyl or protected silane simultaneously;
3,4-two R
3R in the oxygen base thiophene-based conjugated electrons bridge
3Be alkyl;
Described 4-(N-R
1, N-R
2) the amino-benzene electron-like gives the R in the body
1, R
2Be to work as 4-(N-R respectively or be the hydroxyalkyl of protected silane simultaneously,
1, N-R
2) amino-benzene ethene-3,4-two R
3R in the oxygen base thiophenecarboxaldehyde
1, R
2During the hydroxyalkyl protected for ethanoyl respectively or simultaneously, 4-(N-R
1, N-R
2) amino-benzene ethene-3,4-two R
3Need the ethanoyl protection is removed before oxygen base thiophenecarboxaldehyde and the reaction of tricyano pyrroline electron acceptor(EA) are carried out, recycle silicon alkane is protected hydroxyalkyl, obtains having the 4-(N-R of protected silane
1, N-R
2) amino-benzene ethene-3,4-two R
3Oxygen base thiophenecarboxaldehyde;
The chromophoric group and the dendroid 3 of the D-π-A structure that 4) step 3) is synthesized, 5-two R
4Oxygen base halogenation benzyl and salt of wormwood were dissolved in the acetonitrile in 1: 1: 1 in molar ratio, were 50～80 ℃ of reactions down in temperature, washing; The extracted with diethyl ether water, separatory merges organic phase; Dry organic phase; Column chromatography is separated, and generates the organic second order non-linear optical chromophore with D-π-A structure of dendroid base group modification, and structure is:
Wherein, R
1, R
2Respectively or be a kind of in hydroxyalkyl or the hydroxyalkyl of alkyl, protected silane simultaneously;
R
3Be alkyl; R
4A kind of in alkyl, benzyl, anthracene benzyl or the naphthalene benzyl;
R in the organic second order non-linear optical chromophore with D-π-A structure of the dendroid base group modification that step 4) obtains
1, R
2Respectively or when being the hydroxyalkyl of protected silane simultaneously, obtain R after removing the protected silane group
1, R
2Be the organic second order non-linear optical chromophore with D-π-A structure of the dendroid base group modification of hydroxyalkyl respectively or simultaneously;
Carbon chain lengths in the alkyl described in the above-mentioned steps is a carbonatoms 1～20.
3. the purposes of the organic second order non-linear optical chromophore with D-π-A structure of a dendroid base group modification according to claim 1; It is characterized in that: the organic second order non-linear optical chromophore with D-π-A structure of described dendroid base group modification mixes with unformed polycarbonate or polymethylmethacrylate and prepares polar polymer, and uses as the material in integrated optics or the photoelectronics.
4. purposes according to claim 4 is characterized in that: the organic second order non-linear optical chromophore with D-π-A structure of described dendroid base group modification is 1: 1～100 with unformed polycarbonate or the adulterated mass ratio of polymethylmethacrylate.
5. purposes according to claim 5 is characterized in that: the organic second order non-linear optical chromophore with D-π-A structure of described dendroid base group modification and unformed polycarbonate or the adulterated mass ratio of polymethylmethacrylate are 1: 10.
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| CN103373990B (en) * | 2012-04-19 | 2016-03-09 | 中国科学院理化技术研究所 | Chromophore molecule containing triptycene rigid three-dimensional structure and synthetic method and application thereof |
| CN103969879B (en) * | 2013-01-25 | 2016-12-28 | 北京京东方光电科技有限公司 | Display base plate and display device |
| CN104558004B (en) * | 2013-10-11 | 2017-12-15 | 中国科学院理化技术研究所 | Organic second-order nonlinear optical chromophore with D-pi-A structure and synthesis method and application thereof |
| CN109293643A (en) * | 2017-07-24 | 2019-02-01 | 中国科学院理化技术研究所 | Flexible spacer group modified organic second-order nonlinear optical chromophore, and preparation method and application thereof |
| CN108977889B (en) * | 2018-07-16 | 2020-11-20 | 北京科技大学 | Organic salt optical crystal containing benzindole group, preparation method and application thereof |
| CN111040186B (en) * | 2019-12-27 | 2020-11-17 | 华中科技大学 | AB2Second-order nonlinear optical hyperbranched polymer, and preparation and application thereof |
| CN114591276A (en) * | 2022-04-01 | 2022-06-07 | 广州大学 | Dendritic self-assembly optical nonlinear chromophore and synthetic method and application thereof |
| CN114656432B (en) * | 2022-04-01 | 2023-05-26 | 广州大学 | Self-assembled organic optical nonlinear chromophore, and synthesis method and application thereof |
| CN117186080A (en) * | 2022-05-30 | 2023-12-08 | 华为技术有限公司 | Chromophore compound, preparation method thereof and application of chromophore compound |
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| US6067186A (en) * | 1998-07-27 | 2000-05-23 | Pacific Wave Industries, Inc. | Class of high hyperpolarizability organic chromophores and process for synthesizing the same |
| CN1466583A (en) * | 2000-08-17 | 2004-01-07 | �¬ | Design and synthesis of advanced NLO materials for electro-optic applications |
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| US6067186A (en) * | 1998-07-27 | 2000-05-23 | Pacific Wave Industries, Inc. | Class of high hyperpolarizability organic chromophores and process for synthesizing the same |
| CN1466583A (en) * | 2000-08-17 | 2004-01-07 | �¬ | Design and synthesis of advanced NLO materials for electro-optic applications |
| US7307173B1 (en) * | 2004-02-19 | 2007-12-11 | University Of Washington | Pyrroline chromophores |
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