CN102250153B - Symmetric Schiff base ferrocene derivatives as well as preparation method and application thereof - Google Patents
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- -1 Schiff base ferrocene derivatives Chemical class 0.000 title claims abstract description 61
- 239000002262 Schiff base Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000002879 Lewis base Substances 0.000 claims abstract description 15
- 239000000010 aprotic solvent Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 150000007527 lewis bases Chemical class 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000006482 condensation reaction Methods 0.000 claims abstract description 5
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 38
- 150000004753 Schiff bases Chemical class 0.000 claims description 33
- 230000003287 optical effect Effects 0.000 claims description 21
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012043 crude product Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003921 oil Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- 150000004705 aldimines Chemical class 0.000 claims description 4
- 239000003480 eluent Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 abstract 1
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 30
- 230000009021 linear effect Effects 0.000 description 23
- 238000012360 testing method Methods 0.000 description 21
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 14
- 239000007787 solid Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 239000004576 sand Substances 0.000 description 6
- 230000021615 conjugation Effects 0.000 description 4
- 230000007850 degeneration Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000009795 derivation Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 230000009022 nonlinear effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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Abstract
The invention discloses symmetric Schiff base ferrocene derivatives shown in a formula (I) as well as preparation method and application thereof. The preparation method comprises the following steps: dissolving a diamine compounds shown in a formula (II) and a substituted benzaldehyde compound shown in a formula (III) in an aprotic solvent at the temperature of between 40 and 150 DEG C, performing aldehyde amine condensation reaction for 5 to 15 hours in the presence of a Lewis base catalyst; and post-treating the reaction liquid to prepare the symmetric Schiff base ferrocene derivatives shown in the formula (1). The method has the advantages of few reaction steps, easily available raw materials, simple synthesis process, mild reaction condition and the like, simultaneously can be used for enlarging the application of the symmetric Schiff base ferrocene derivatives in third-order nonlinear optics, and has great implementation value and excellent social and economic benefit.
Description
(1) technical field
The present invention relates to a kind of symmetric form Schiff bases ferrocene deriv and preparation method thereof, with the application in third order non-linear optical material.
(2) background technology
Along with the develop rapidly of optical communication and psec and femtosecond etc. are ultrafast, the appearance of superpower laser, more and more active to the study on the synthesis of the especially macromolecular third order non-linear optical material of third order non-linear optical material.Because metallo organic material shows good characteristic in optoelectronic device, the organic third-order non-linear material of metal is day by day obvious in the application of photoelectricity and electronic applications.The introducing of metal ion has been strengthened intramolecular transfer transport and has been strengthened the non-linear effect of molecule, so that the research of the organic third-order non-linear material of metal is more active.Organic non linear optical material is generally connect by the π-electron bridging by donor residues and electron withdrawing group and forms, and has the conjugated system of D-π-A, and the molecule of large pi-conjugated electron system can show better nonlinear optical properties.Common π-electron abutment comprises carbon-carbon double bond, and (C=C-), carbon-to-nitrogen double bon (C=N-).Acceptor groups intensity is larger, and non-linear susceptibility is larger; The increase of conjugate length also can make non-linear susceptibility increase.The ferrocene deriv of carbon-carbon double bonds, quinone structure derivative more and more receive people's concern because of its stability to heat, the π-electron structure of self, good NLO performance etc.
The ferrocene metalloid-organic compound is because its unique electrochemistry and optical characteristics and in the potential using value of the high-tech sectors such as optical Information Processing, communication and integrated optics, attract investigator's extensive attention, become rapidly a focus of functional materials research.Some organic pigment color bodiess with large pi-conjugated structure are the good integral parts that make up Developments of Third-order Nonlinear Optical Polymers.
(3) summary of the invention
The object of the invention provides a kind of symmetric form Schiff bases ferrocene deriv and preparation method thereof and application at third order non-linear optical material, the method raw material is easy to get, synthesis technique is simple, reaction conditions is gentle, and prepared compound has good organic third order non-linear optical property.
The technical solution used in the present invention is:
It is a kind of suc as formula the symmetric form Schiff bases ferrocene deriv shown in (I),
A kind of method for preparing symmetric form Schiff bases ferrocene deriv of the present invention is: with the substituted benzoyl aldehyde cpd shown in the diamine compounds shown in the formula (II) and the formula (III) in aprotic solvent, 40～150 ℃, under the lewis-base catalyst effect behind aldimine condensation reaction 5～15h, the reaction solution aftertreatment makes the symmetric form Schiff bases ferrocene deriv shown in the formula (I); The molar ratio that feeds intake of the substituted benzoyl aldehyde cpd shown in the diamine compounds shown in the described formula (II) and the formula (III) is: 1: 1.8～2.5; Described lewis-base catalyst, aprotic solvent and diamine compounds and substituted benzoyl aldehyde cpd total mass ratio are 0.1～0.3: 50～100: 1;
Described aprotic solvent is one of following: methylene dichloride, ethylene dichloride, chloroform, benzene,toluene,xylene, oil of mirbane, chlorobenzene or tetrahydrofuran (THF) are preferably toluene, dimethylbenzene or chlorobenzene.
Described lewis-base catalyst is one of following: triethylamine, sodium bicarbonate, yellow soda ash, salt of wormwood, saleratus, sodium hydroxide, potassium hydroxide or alkaline hydrogen aluminum oxide are preferably triethylamine or alkaline hydrogen aluminum oxide.
Further, described lewis-base catalyst, aprotic solvent and diamine compounds and substituted benzoyl aldehyde cpd total mass ratio are preferably 0.2～0.3: 60～80: 1.
Further, the molar ratio that feeds intake of the substituted benzoyl aldehyde cpd shown in the diamine compounds shown in the described formula (II) and the formula (III) be preferably 1: 2.0～2.2.
Further, described temperature of reaction is preferably 120～140 ℃, and the reaction times is preferably 8～10h.
The preparation method of symmetric form Schiff bases ferrocene deriv of the present invention, described aftertreatment is: reaction finishes, reaction solution is cooled off, underpressure distillation, obtain crude product, with the crude product column chromatography for separation, obtain target product, be symmetric form Schiff bases ferrocene deriv, described column chromatography is take sherwood oil and 2: 1 mixed solution of ethyl acetate volume ratio as eluent.
Further, the preparation method of symmetric form Schiff bases ferrocene deriv of the present invention recommends to carry out according to the following steps: the substituted benzoyl aldehyde cpd shown in the diamine compounds shown in the formula (II) and the formula (III) is mixed with lewis-base catalyst, be dissolved in the aprotic solvent, behind 120～140 ℃ of lower aldimine condensation reaction 8～10h, reaction finishes reaction solution is cooled off, pressurization is concentrated, obtain crude product, be that eluent carries out column chromatography with crude product through 2: 1 sherwood oil of volume ratio and ethyl acetate mixed solution, elutriant is dry, the symmetric form Schiff bases ferrocene deriv shown in the acquisition formula (I); Described lewis-base catalyst is triethylamine or alkaline hydrogen aluminum oxide; Described aprotic solvent is toluene, dimethylbenzene or chlorobenzene; The molar ratio that feeds intake of the substituted benzoyl aldehyde cpd shown in the diamine compounds shown in the described formula (II) and the formula (III) is: 1: 2.0～2.2; Described lewis-base catalyst, aprotic solvent and diamine compounds and substituted benzoyl aldehyde cpd total mass ratio are 0.2～0.3: 60～80: 1.
The application of symmetric form Schiff bases ferrocene deriv in third-order nonlinear optical shown in a kind of formula of the present invention (I).
The application of symmetric form Schiff bases ferrocene deriv in third-order nonlinear optical shown in the formula of the present invention (I): adopt the test of degeneration four-wave mixing (DFWM) method, take the Ti:Sapphire femto-second laser as light source.
The third-order nonlinear susceptibility χ of sample
s (3)Obtain by Relative detecting method, namely adopt generally acknowledged dithiocarbonic anhydride as a reference under the same conditions, obtain the third-order nonlinear susceptibility χ of sample by the signal magnitude of comparative sample and dithiocarbonic anhydride
s (3), calculated by following formula:
L in the formula (1)
sAnd L
rBe respectively testing sample with reference to the cuvette thickness of sample dithiocarbonic anhydride, n
sAnd n
rBe respectively testing sample with reference to the specific refractory power of sample dithiocarbonic anhydride, χ
sAnd χ
rBe respectively testing sample with reference to the third-order nonlinear susceptibility of sample dithiocarbonic anhydride, I
sAnd I
rBe respectively testing sample with reference to the conjugate beam intensity of sample dithiocarbonic anhydride, α is linear absorption coefficient, according to bibliographical information, with reference to the χ of sample dithiocarbonic anhydride
r (3)Be 6.7 * 10-14esu, n
rBe 1.632.
Testing sample is calculated by following formula by the nonlinear refractive index that the third-order non-linear coefficient causes:
n
2(esu)=12 π χ
(3)/ n
2Formula (2)
In the formula (2), n
2Nonlinear refractive index for test substance; χ
(3)Be the third-order nonlinear susceptibility of test substance, the χ that namely calculates
s (3)N is the linear refractive index of test substance;
The second hyperpolarizabilitieof γ of sample solute molecule can be tried to achieve by formula (3):
N is the molecular density of solute in the formula (3), and N=6.02 * 1023c, c are the volumetric molar concentration of sample solution, f
4Be local fields modifying factor, f
4=[(n
s 2+ 2)/3]
4, wherein n is the linear refractive index of test substance.
Time of response τ (fs) is obtained after Gauss curve fitting by four-wave mixing conjugate beam intensity and mapping time of lag again.
Compared with prior art, beneficial effect of the present invention is mainly reflected in: it is few that the inventive method has reactions steps, the advantages such as raw material is easy to get, synthesis technique is simple, reaction conditions is gentle, open up simultaneously the application of symmetric form Schiff bases ferrocene deriv in third-order nonlinear optical, had larger implementary value and good economic results in society.
(4) description of drawings
Fig. 1 is for to detect the nonlinear optical response of formula of the present invention (I) structural compounds to scheming time of lag with degeneration four-wave mixing, ordinate zou is four-wave mixing conjugation intensity, X-coordinate is time of lag, the figure mid point is experimental data, solid line is the Gauss curve fitting result, and the peak width at half height of response peak is time of response τ after the match; Peak height is the light intensity I described in the formula (1).
Fig. 2 be the symmetric form Schiff bases ferrocene deriv shown in the formula (I) of embodiment 1 preparation proton nmr spectra (
1H NMR) spectrogram.
Fig. 3 is mass spectrum MS (ESI) spectrogram of the symmetric form Schiff bases ferrocene deriv shown in the formula (I) of embodiment 1 preparation.
(5) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1
Respectively with 2.2g (0.01mol, folding hundred) formula (II) diamine compound, 6.32g (0.02mol, folding hundred) substituted benzoyl aldehyde cpd and the 2.36g alkali alumina shown in the formula (III) is dissolved in the 700g dimethylbenzene, at the lower reaction of reflux temperature (140 ℃) 10h, reaction finishes the afterreaction liquid cooling but, underpressure distillation obtains crude product except removal xylene, separate (sherwood oil: ethyl acetate=2: 1 through column chromatography again, volume ratio), drying obtains red solid 6.95g, be symmetric form Schiff bases ferrocene deriv shown in the formula (I), proton nmr spectra (
1H NMR) spectrogram as shown in Figure 2, mass spectrum MS (ESI) spectrogram as shown in Figure 3, yield is 85.18% (in the diamine compound quality).
Change the quality of the substituted benzoyl aldehyde cpd shown in the formula (III) into 7.89g (0.018mol, folding hundred), all the other operate with embodiment 1, obtain red solid 7.38g, and yield is 90.45% (in diamine compound).
Embodiment 3
Change the quality of the substituted benzoyl aldehyde cpd shown in the formula (III) into 5.68g (0.025mol, folding hundred), all the other operate with embodiment 1, obtain red solid 6.26g, and yield is 76.72% (in diamine compound).
Change 700g dimethylbenzene into the 430g methylene dichloride, at the lower reaction of reflux temperature (40 ℃) 15h, all the other operate with embodiment 1, obtain red solid 5.72g, and yield is 70.11% (in diamine compound).
Embodiment 5
Change 700g dimethylbenzene into the 700g tetrahydrofuran (THF), at the lower reaction of reflux temperature (66 ℃) 15h, all the other operate with embodiment 1, obtain red solid 5.81g, and yield is 71.21% (in diamine compound).
Change 700g dimethylbenzene into the 850g chlorobenzene, at the lower reaction of reflux temperature (131 ℃) 10h, all the other operate with embodiment 1, obtain red solid 6.33g, and yield is 77.58% (in diamine compound).
Embodiment 7
Change 700g dimethylbenzene into 700g oil of mirbane, temperature of reaction is 120 ℃, and all the other operate with embodiment 1, obtain red solid 6.39g, and yield is 78.32% (in diamine compound).
Embodiment 8
Change catalyzer 2.36g alkaline hydrogen aluminum oxide into the 2.0g triethylamine, all the other operate with embodiment 1, obtain red solid 6.82g, and yield is 83.59% (in diamine compound).
Embodiment 9
Change catalyzer 2.36g alkaline hydrogen aluminum oxide into the 1.6g sodium bicarbonate, all the other operate with embodiment 1, obtain red solid 6.12g, and yield is 75.01% (in diamine compound).
Embodiment 10
Change catalyzer 2.36g alkaline hydrogen aluminum oxide into 0.86g salt of wormwood, all the other operate with embodiment 1, obtain red solid 6.27g, and yield is 76.85% (in diamine compound).
Embodiment 11 third order non-linear optical properties detect
The third order non-linear optical property of symmetric form Schiff bases ferrocene deriv of the present invention adopts the test of degeneration four-wave mixing (DFWM) method.
As light source, wavelength is 800nm to adopt femto-second laser (Ti:Sapphire, German Nanolayers company produces), and pulsewidth is 80fs, and repetition rate is 1KHz, and single pulse energy is 0.05mJ.
The third-order nonlinear susceptibility χ of sample
s (3)Obtain by relative side chain method, namely adopt under the same conditions the dithiocarbonic anhydride of generally acknowledging as reference, obtain the third-order nonlinear susceptibility χ of sample by the signal magnitude of comparative sample and dithiocarbonic anhydride
s (3)Circular is as follows:
L in the formula (1)
s, L
rRepresent respectively testing sample with reference to the cuvette thickness of sample dithiocarbonic anhydride, n
s, n
rBe respectively testing sample with reference to the specific refractory power of sample dithiocarbonic anhydride, χ
sAnd χ
rBe respectively testing sample with reference to the third-order nonlinear susceptibility of sample dithiocarbonic anhydride, I
sAnd I
rBe respectively testing sample with reference to the conjugate beam intensity of sample dithiocarbonic anhydride, α is linear absorption coefficient, according to bibliographical information, with reference to the χ of sample dithiocarbonic anhydride
r (3)Be 6.7 * 10
-14Esu, n
rBe 1.632.
It is 5 * 10 that symmetric form Schiff bases ferrocene deriv shown in the formula (I) that the embodiment of the invention 1 is prepared is made into concentration
-4The dichloromethane solution of mol/L is as sample.
The nonlinear refractive index that is caused by the third-order non-linear coefficient is calculated by following formula:
n
2(esu)=12 π χ
(3)/ n
2Formula (2)
In the formula (2), n
2Nonlinear refractive index for test substance; χ
(3)(esu) be the third-order nonlinear susceptibility of test substance, namely calculate the χ of gained
s (3)N is the linear refractive index of test substance;
The second hyperpolarizabilitieof γ of sample solute molecule can be tried to achieve by following formula:
N is the molecular density of solute in the formula (3), N=6.02 * 10
23C, c are the volumetric molar concentration of sample solution, f
4Be local fields modifying factor, f
4=[(n
2+ 2)/3]
4, n is the linear refractive index of test substance.
Take four-wave mixing conjugation intensity as ordinate zou, be the X-coordinate mapping time of lag, obtains as shown in Figure 1 curve after Gauss curve fitting, and wherein peak height is conjugation light intensity I, and peak width at half height is time of response τ, and peak height is.
Test sample: it is 5 * 10 that the embodiment of the invention 1 prepared symmetric form Schiff bases ferrocene deriv suc as formula shown in (I) is made into concentration
-4The dichloromethane solution of mol/L is as sample, then adopts degeneration four-wave mixing (DFWM) method to carry out the third order non-linear optical property test, and the result is as shown in table 1, conjugation light intensity and time of lag as shown in Figure 1:
Table 1 symmetric form Schiff bases ferrocene deriv third order non-linear optical property parameter
According to document The Journal of Physical Chemistry, 1990,94 (7): 2847-2851, (light source is the Nd:YAG laser apparatus to the employing femtosecond lasers such as Saswati Ghosal, wavelength 602nm, pulsewidth 400fs), to record the second hyperpolarizabilitieof (γ) of ferrocene molecule be 1.61 ± 0.18 * 10 to DFWM experiment light path
-35Esu contrasts as seen from Table 1, and the present invention is behind ferrocene precursor structure access 2,4 dichloro benzene vinyl, and the molecule second hyperpolarizabilitieof is the very potential third order non-linear optical materials of a class than high 4 orders of magnitude of ferrocene precursor structure.
Claims (10)
1. symmetric form Schiff bases ferrocene deriv shown in formula I,
2. method for preparing symmetric form Schiff bases ferrocene deriv as claimed in claim 1, it is characterized in that described method is: with the substituted benzoyl aldehyde cpd shown in the diamine compounds shown in the formula (II) and the formula (III) in aprotic solvent, 40～150 ℃, under the lewis-base catalyst effect behind aldimine condensation reaction 5～15h, the reaction solution aftertreatment makes the symmetric form Schiff bases ferrocene deriv shown in the formula (I); The molar ratio that feeds intake of the substituted benzoyl aldehyde cpd shown in the diamine compounds shown in the described formula (II) and the formula (III) is: 1 ︰ 1.8～2.5; Described lewis-base catalyst, aprotic solvent and diamine compounds and substituted benzoyl aldehyde cpd total mass ratio are 0.1～0.3 ︰, 50～100 ︰ 1;
3. the preparation method of symmetric form Schiff bases ferrocene deriv as claimed in claim 2 is characterized in that described aprotic solvent is one of following: methylene dichloride, ethylene dichloride, chloroform, benzene,toluene,xylene, oil of mirbane, chlorobenzene or tetrahydrofuran (THF).
4. the preparation method of symmetric form Schiff bases ferrocene deriv as claimed in claim 2 is characterized in that described lewis-base catalyst is one of following: triethylamine, sodium bicarbonate, yellow soda ash, salt of wormwood, saleratus, sodium hydroxide, potassium hydroxide or alkaline hydrogen aluminum oxide.
5. the preparation method of symmetric form Schiff bases ferrocene deriv as claimed in claim 2 is characterized in that described lewis-base catalyst, aprotic solvent and diamine compounds and substituted benzoyl aldehyde cpd total mass ratio are 0.2～0.3 ︰, 60～80 ︰ 1.
6. the preparation method of symmetric form Schiff bases ferrocene deriv as claimed in claim 2, the molar ratio that feeds intake that it is characterized in that the substituted benzoyl aldehyde cpd shown in the diamine compounds shown in the described formula (II) and the formula (III) is 1 ︰ 2.0～2.2.
7. the preparation method of symmetric form Schiff bases ferrocene deriv as claimed in claim 2 is characterized in that described temperature of reaction is 120～140 ℃, and the reaction times is 8～10h.
8. the preparation method of symmetric form Schiff bases ferrocene deriv as claimed in claim 2, it is characterized in that described aftertreatment is: reaction finishes, reaction solution is cooled off, underpressure distillation obtains crude product, with the crude product column chromatography for separation, elutriant is dry, obtain target product, i.e. symmetric form Schiff bases ferrocene deriv, described column chromatography is take the mixed solution of sherwood oil and ethyl acetate volume ratio 2:1 as eluent.
9. the preparation method of symmetric form Schiff bases ferrocene deriv as claimed in claim 2, it is characterized in that described preparation method is: the substituted benzoyl aldehyde cpd shown in the diamine compounds shown in the formula (II) and the formula (III) is mixed with lewis-base catalyst, be dissolved in the aprotic solvent, behind 120～140 ℃ of lower aldimine condensation reaction 8～10h, reaction finishes reaction solution is cooled off, pressurization is concentrated, obtain crude product, be that eluent carries out column chromatography with crude product through sherwood oil and the ethyl acetate mixed solution of volume ratio 2:1, elutriant is dry, the symmetric form Schiff bases ferrocene deriv shown in the acquisition formula (I); Described lewis-base catalyst is triethylamine or alkaline hydrogen aluminum oxide; Described aprotic solvent is toluene, dimethylbenzene or chlorobenzene; The molar ratio that feeds intake of the substituted benzoyl aldehyde cpd shown in the diamine compounds shown in the described formula (II) and the formula (III) is: 1 ︰ 2.0～2.2; Described lewis-base catalyst, aprotic solvent and diamine compounds and substituted benzoyl aldehyde cpd total mass ratio are 0.2～0.3 ︰, 60～80 ︰ 1.
10. the application of symmetric form Schiff bases ferrocene deriv in third-order nonlinear optical shown in the formula I as claimed in claim 1.
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| 六氯环三磷腈基类聚合物的合成;高坡等，;《哈尔滨工业大学学报》;20060531;第38卷(第5期);第770-772页 * |
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