CN101845040A - Organic second-order non-linear optical chromophore with D-Pi-A structure and decorated by tree-like group, synthesizing method and application thereof - Google Patents
Organic second-order non-linear optical chromophore with D-Pi-A structure and decorated by tree-like group, synthesizing method and application thereof Download PDFInfo
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Abstract
The invention relates to an organic second-order non-linear optical chromophore with a D-Pi-A structure and decorated by a tree-like group, and a synthesizing method and applications thereof. The chromophore of the invention introduces a thiophene ring conjugated Pi electronbridge having stronger electrical transmission capacity and containing branched chains and a tricyano pyrroline receptor having strong electron-withdrawing property; the receptor end is introduced into the tree-like decorative group, the one-order hyperpolarizability of chromophore molecules is greatly improved; the solubility and the film forming ability of the chromophore in polymer is improved, the interaction force among the molecules is reduced. The second-order non-linear optical chromophore with the following structure is doped with polymers, such as amorphous polycarbonate or polymethylmethacrylate and the like according to the mass ratio of 1:10; the electro-optical coefficient of the obtained polarized polymeric materials achieves 217pm/V; in addition, the donor and receptor of the chromophore can be introduced into a crosslinkable group, thus improving oriented stability of the chromophore in polymer, and satisfying the requirements of devices.
Description
Technical field
The present invention relates to organic second-order non-linear optical material field, 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, all must use nonlinear optical material in these devices.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 order of magnitude of inorganic crystal material), optical damage threshold height (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 will to seek single order molecule hyperpolarizability (β value) bigger, 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 by 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 height, be easy to the organic second order non-linear optical chromophore with D-π-A structure of 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 further object of the present invention provides a kind of synthetic 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 hydrogen atom 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, protected silane or the hydroxyalkyl 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 synthetic 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, being 20～50 ℃ in temperature stirred 18～50 hours down, reaction product is poured in the frozen water, separatory, extracted with diethyl ether water, merge 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
2A kind of in the hydroxyalkyl of protecting for alkyl or by ethanoyl respectively or 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 phosphorus oxychloride and N, dinethylformamide solvent are 70～110 ℃ in temperature and reacted 2～5 hours down after mixing under 0 ℃, the cooling of reaction back is poured in the aqueous sodium carbonate, uses the extracted with diethyl ether water, separatory merges organic phase, with saturated common salt water washing organic phase, separatory, 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-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 phosphorus oxychloride is 1: 1～1.2;
Wherein, R
1, R
2A kind of in the hydroxyalkyl of protecting for alkyl or by ethanoyl respectively or 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
2A kind of in the hydroxyalkyl of protecting for alkyl or by ethanoyl respectively or 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, being 50～80 ℃ in temperature reacted 1～10 hour down, washing, 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 the ethanoyl protection before the reaction, and concrete scheme is technical scheme as known to those skilled in the art: with 4-(N-R
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, and concrete scheme is technical scheme as known to 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 that will have the dendroid base group modification of 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, the electro-optic coefficient of the polar polymer material that obtains can reach 217pm/V, is 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 as follows:
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:
Synthetic method is:
1) compound 2 is synthetic
Get 4g (0.0064mol) bromo-3; 4-two hexyloxy thenyl triphenylphosphines; 1.9g (0.0064mol) 4-(N of ethanoyl protection; the N-dihydroxy ethyl) aminobenzaldehyde electron donor(ED); 4.6g (0.192mol) sodium hydride (NaH) is mixed in the 100ml anhydrous diethyl ether solvent; after stirring 18 hours under 50 ℃; reaction product is poured in the 200ml frozen water; separatory; the extracted with diethyl ether water; merge organic phase; use 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) phosphorus oxychloride (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; merge organic phase, with saturated common salt water washing organic phase, separatory; use the anhydrous magnesium sulfate drying organic phase, filter, revolve to steam and remove ether; obtain the orange 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 compound 3 product 2.8g of pure ethanoyl protection, 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 of ethanoyl protection; 3.9g (0.0282mol) Anhydrous potassium carbonate; 50ml water and 150ml methanol mixed; reacted 10 hours down at 70 ℃; revolve to steam and remove methyl alcohol; use the saturated aqueous common salt purging compound; use the extracted with diethyl ether water; separatory; merge organic phase, the organic phase anhydrous magnesium sulfate drying filters; revolve to steam and remove ether; 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); 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 of ethanoyl protection; 0.23g (0.0034mol) imidazoles and 0.5g (0.0034mol) TERT-BUTYL DIMETHYL CHLORO SILANE (TBDMSCl) is dissolved in 40ml N; in the N-dimethylformamide (DMF); stirring at room 24 hours; mixture is poured in the 300ml water; with 200ml ethyl acetate extraction water; separatory, the organic phase anhydrous magnesium sulfate drying filters; revolve to steam to remove and desolvate; 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 5: 1); get 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) target 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, the organic phase anhydrous magnesium sulfate drying, (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 as follows:
Wherein, PPh
3Be triphenylphosphine, TCP is three itrile group pyrroline electron acceptor(EA)s, and its structure is
Synthetic method is:
1) compound 2 is synthetic
Get 4g (0.0064mol) bromo-3,4-two hexyloxy thenyl triphenylphosphines, 1.1g (0.0064mol) 4-(N, the N-diethyl) aminobenzaldehyde electron donor(ED), 2.3g (0.096mol) sodium hydride (NaH) is mixed in the 100ml anhydrous diethyl ether solvent, after stirring 50 hours under 20 ℃, reaction product is poured in the 200ml frozen water, separatory, the extracted with diethyl ether water, merge organic phase, use 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
2C0
3In the solution that is made into 100ml water, divide aqueous phase extracted, separatory three times with the 150ml ether, merge organic phase, with saturated common salt water washing organic phase, separatory, use 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 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) target 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, the organic phase anhydrous magnesium sulfate drying, (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 as follows:
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
Synthetic method is:
1) compound 2 is synthetic
Get 4g (0.0068mol) bromo-3; 4-dibutoxy thenyl triphenylphosphine; 1.5g (0.0068mol) 4-(the N-methyl of ethanoyl protection; the N-hydroxyethyl) aminobenzaldehyde electron donor(ED); 4.1g (0.17mol) sodium hydride (NaH) is mixed in the 100ml anhydrous diethyl ether solvent; after stirring 24 hours under 40 ℃; reaction product is poured in the 200ml frozen water; separatory; the extracted with diethyl ether water; merge organic phase; use 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) phosphorus oxychloride (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; merge organic phase, with saturated common salt water washing organic phase, separatory; use the anhydrous magnesium sulfate drying organic phase, filter, revolve to steam and remove ether; obtain the orange 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 compound 3 product 3.1g of ethanoyl protection, productive rate 60%.
3) compound 4 is synthetic
3.1g (0.0066mol) compound 3 of ethanoyl protection; 5.5g (0.0396mol) Anhydrous potassium carbonate; 50ml water and 150ml methanol mixed; reacted 10 hours down at 70 ℃; revolve to steam and remove methyl alcohol; use the saturated aqueous common salt purging compound; use the extracted with diethyl ether water; separatory; merge organic phase, the organic phase anhydrous magnesium sulfate drying filters; revolve to steam and remove ether; 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); 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; 0.16g (0.0023mol) imidazoles and 0.35g (0.0023mol) TERT-BUTYL DIMETHYL CHLORO SILANE (TBDMSCl) is dissolved in 40ml N; in the N-dimethylformamide (DMF); stirring at room 24 hours; mixture is poured in the 300ml water; with 200ml ethyl acetate extraction water; separatory, the organic phase anhydrous magnesium sulfate drying filters; revolve to steam to remove and desolvate; 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 5: 1); get 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; the extracted with diethyl ether water; separatory; merge organic phase; the organic phase anhydrous magnesium sulfate drying, (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; splash into 1 hydrochloric acid with dropper; at room temperature stirred 3 hours; 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) by simple reflex method (Simple Reflection Method, be called the Teng-Man method again, referring to Teng C.C., Man H.T., Simple refection technique for measuring the electro-optic coefficient of poled polymers, Applied Physics Letters, 1990,56 (18), 1734-1736.) measure.Recording the electro-optic coefficient maximum is 217pm/V.
Claims (7)
1. the organic second order non-linear optical chromophore with D-π-A structure of a dendroid base group modification 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 hydrogen atom 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, acyl group, benzyl, anthracene benzyl or the naphthalene benzyl.
2. the organic second order non-linear optical chromophore with D-π-A structure of dendroid base group modification according to claim 1 is characterized in that: the carbon chain lengths in the described alkyl is a carbonatoms 1～20.
3. the synthetic 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 and 2 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
2A kind of in the hydroxyalkyl of protecting for alkyl or by ethanoyl respectively or 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 phosphorus oxychloride and N, dinethylformamide solvent are 70～110 ℃ of reactions down in temperature after mixing under 0 ℃, the cooling of reaction back is poured in the aqueous sodium carbonate, uses the extracted with diethyl ether water, separatory merges organic phase, with saturated common salt water washing organic phase, separatory, dry organic phase is filtered, and revolves to steam to 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 phosphorus oxychloride is 1: 1～1.2;
R
1, R
2A kind of in the hydroxyalkyl of protecting for alkyl or by ethanoyl respectively or 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; 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
2A kind of in the hydroxyalkyl of protecting for alkyl or by ethanoyl respectively or 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, in temperature is 50～80 ℃ of reactions down, 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 the hydroxyalkyl of alkyl, protected silane or the hydroxyalkyl simultaneously; R
3Be alkyl; R
4A kind of in alkyl, acyl group, benzyl, anthracene benzyl or the naphthalene benzyl.
4. method according to claim 3 is characterized in that: the 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.
5. 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 and 2, 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.
6. according to claim
Described purposes 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.
7. according to claim
Described purposes, it 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 o'clock, and the electro-optic coefficient of the polar polymer material that obtains can reach 217pm/V.
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