CN103130839A - Ferrocene formamide type compound and preparation method and application thereof - Google Patents

Abstract

式（Ⅰ）中：R为苯基、取代苯基、萘基、或苯并噻唑基或取代苯并噻唑基，所述取代苯基上的取代基为卤素、甲基或硝基，所述取代苯并噻唑基上的取代基为卤素、甲基或硝基。The invention discloses a ferrocene carboxamide-type compound represented by formula (I), its preparation method and its application in third-order nonlinear optics; Mild conditions and other advantages, while opening up the application of ferrocene carboxamide compounds in third-order nonlinear optics, which has great implementation value and good social and economic benefits;

In formula (I): R is phenyl, substituted phenyl, naphthyl, or benzothiazolyl or substituted benzothiazolyl, and the substituent on the substituted phenyl is halogen, methyl or nitro, and the The substituent on the substituted benzothiazolyl is halogen, methyl or nitro.

Description

A kind of ferrocene carboxamide type compound and its preparation method and application

(1) Technical field

The invention relates to a ferrocene formamide compound, a preparation method thereof and an application in third-order nonlinear optical materials, belonging to the field of functional materials.

(2) Background technology

Nonlinear optical materials can be used in optical communication, optical computing, optical information processing, optical storage and holography, laser processing, laser medical treatment, laser printing, laser film and television, laser equipment, laser controlled thermonuclear reaction and laser isotope separation, laser guidance , ranging and directed energy weapons and many other aspects.

Since the ferrocene group conforms to the eighteen-electron rule of transition metal bonding, it shows a high degree of stability and aromaticity, and the electrons in its frontier orbitals are fed back by the d electrons of the iron atom, and the d orbitals participate in and expand the metallocene ring. In the π-electron system, the iron atom also has various oxidation states and the entire ferrocene group becomes a very good electron-donating group after the ring is combined. When it is connected to the receptor through the π conjugated system, it is easy to undergo intramolecular charge transfer, and effectively induce the asymmetric polarization of the system, so that the conjugated system can be expanded and extended as much as possible, so the molecule has a large non- linear polarizability. Common π-electron conjugated bridges include carbon-carbon double bonds (—C=C—) and carbon-nitrogen double bonds (—C=N—), among which carbon-carbon double bonds are more reported. The electron-withdrawing part of the push-pull system usually chooses chromophores such as aromatic rings and aromatic heterocycles. Some organic pigment chromophores with large π-conjugated structures are excellent components for constructing organic third-order nonlinear optical materials. Early studies on the nonlinear optical properties of ferrocene metal-organic materials mainly focused on the second-order properties. With the continuous deepening of research, the third-order nonlinear optical properties of ferrocene-based metal-organic materials are gradually becoming a research hotspot.

In 2008, Bin, YJ et al. (Chinese Physics Letters 2008, 25(9), 3257-3259) reported a compound containing a ferrocene structure of phthalocyanine (represented by formula (1)), and used degenerate four-wave mixing Using frequency technology, the third ^- order nonlinear coefficient χ ⁽³⁾ and The molecular hyperpolarizability γ is 6.44×10 ^-14 esu and 1.74×10 ^-30 esu respectively, and compared with the molecular hyperpolarizability γ of related compounds reported in the literature, it is found that the compound with this structure has a higher molecular Hyperpolarizability.

In 2008, Zhou Xiaoli et al. (Acta Chem. Sinica 2008, 66(7), 775-782) synthesized two different complexes of ferrocenemethylenetriazole and transition metal cadmium and nickel, using YAG frequency doubled laser, The pulse width is 7nm, and the Z-scan test technology measures its third-order nonlinear refractive index. And discussed the relationship between the structure and performance of the material, found that the nonlinear optical properties of the material mainly depend on the ligand (chromophore), at the same time, due to the ferrocene group and triazole group of the ligand (chromophore) There is a methylene group between the groups, which blocks the electron transfer between the ferrocene group and the triazole group, and fails to form a larger conjugated system. Therefore, when the metal ion is coordinated to the ligand, the central metal ion will not significantly affect the third-order nonlinear optical properties of the ligand due to the presence of the methylene group, and thus the two compounds have similar nonlinear optical behavior .

In 2007, Li, JP et al. (Journal of Organometallic Chemistry 2007, 692 (7), 1584-1592) studied the interaction between m-ferrocenyl benzoic acid and three transition metals lead (Pd), zinc (Zn) and manganese (Mn) respectively. ) third-order nonlinear optical properties of the complex. Using the Z-scan detection method with a pulse width of 8 ns and a wavelength of 532 nm, the third-order nonlinear susceptibility χ ⁽³⁾ of the three complexes measured in DMF solution is 6.19×10 ^-13 esu (Pd), 5.9 × 10 ^-13 esu (Zn) and 5.3 × 10 ^-13 esu (Mn).

In 2003, Rangel-Rojo, R., et al. (Optics Communications 2003, 228 (1-3), 181-186) reported a Schiff base derivative (formula ( 2)), and using Z-scan testing technology, YAG laser with a bandwidth of 10 ps, investigated the third-order nonlinear optical properties of the material at different detection wavelengths. The material was found to exhibit a metal ligand transfer absorption at 560 nm.

(3) Contents of the invention

The object of the present invention is to provide a ferrocene carboxamide type compound, its preparation method and its application in third-order nonlinear optics.

The technical scheme adopted in the present invention is:

The present invention provides a ferrocene carboxamide type compound represented by formula (I),

In formula (I): R is phenyl, substituted phenyl, naphthyl, benzothiazolyl or substituted benzothiazolyl, the substituent on the substituted phenyl is halogen, methyl or nitro, and the substituted The substituent on the benzothiazolyl is halogen, methyl or nitro, preferably R is a substituted phenyl or substituted benzothiazolyl, and the substituent on the substituted phenyl is chlorine, fluorine, methyl or nitro, The substituent on the substituted benzothiazolyl is nitro.

Further, the ferrocene carboxamide compound is preferably one of the following:

The present invention also provides a method for preparing the ferrocenecarboxamide-type compound, the method comprising: dissolving ferrocenecarboxyl chloride represented by formula (II) in an aprotic solvent A to obtain a ferrocenecarboxyl chloride solution; Dissolve the aromatic amine represented by the formula (III) in the aprotic solvent B, in the presence of an acid-binding agent, add the ferrocenecarbonyl chloride solution dropwise at -10-20°C, after the reaction is complete, the reaction solution treatment to obtain the ferrocene carboxamide type compound shown in formula (I); the acid-binding agent is one of the following: sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, pyridine or triethylamine (preferably carbonic acid sodium, sodium bicarbonate, sodium hydroxide or triethylamine); the aprotic solvent A is one of the following: dichloromethane, dichloroethane, chloroform, tetrahydrofuran, dimethylformamide, dimethylsulfoxide , sulfolane or acetonitrile (preferably dichloroethane, chloroform, tetrahydrofuran, dimethyl sulfoxide, sulfolane or acetonitrile), the aprotic solvent B is the same as the aprotic solvent A;

In formula (III): R is phenyl, substituted phenyl, naphthyl, benzothiazolyl or substituted benzothiazolyl, the substituent on the substituted phenyl is halogen, methyl or nitro, and the substituted The substituent on the benzothiazolyl group is halogen, methyl or nitro.

Further, the ratio of the ferrocenecarbonyl chloride to the aromatic amine and the acid-binding agent is 1:1.0-2.0:1.5-3.5, preferably 1:1.2-1.5:2.0-3.0.

Further, the total mass ratio of the ferrocenecarbonyl chloride to the aprotic solvent A and the aprotic solvent B is 1:100-300, preferably 1:150-200, and the respective volumetric amounts of the aprotic solvent A and the aprotic solvent B It only needs to be dissolved, preferably the volume ratio of aprotic solvent A to aprotic solvent B is 1:1.

Further, the reaction is carried out at -10-20°C for 5-10 hours, preferably at -5-5°C for 6-8 hours.

Further, the post-treatment method of the reaction solution is as follows: track and monitor the reaction process with TLC until the ferrocenyl chloride point disappears, that is, the reaction is complete, wash the reaction solution with saturated sodium bicarbonate solution, let it stand for stratification, and wash the water layer with chloroform Extract, take the organic phase and distill off the solvent, then carry out silica gel column chromatography, use the mixed solution of ethyl acetate and petroleum ether with a volume ratio of 1:5 as the eluent, collect the eluate containing the target component, dry, and obtain the formula (I) The shown ferrocene carboxamide type compound.

Further, the preparation method of the ferrocene carboxamide type compound is carried out as follows: the ferrocene carboxyl chloride shown in the formula (II) is dissolved in the aprotic solvent A to obtain the ferrocene carboxyl chloride solution; the formula (III ) is dissolved in the aprotic solvent B, and in the presence of an acid-binding agent, the ferrocenecarbonyl chloride solution is added dropwise at -5 to 5°C, reacted for 6 to 8 hours, and tracked and monitored by TLC during the reaction , until the point of ferrocenyl chloride disappears, that is, the reaction is complete. The reaction solution is washed with saturated sodium bicarbonate solution, and the layers are separated. The water layer is extracted with chloroform. A 1:5 mixed solution of ethyl acetate and petroleum ether is used as an eluent, and the eluate containing the target component is collected and dried to obtain a ferrocene carboxamide-type compound shown in formula (I); the acid-binding agent It is one of the following: sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, pyridine or triethylamine; the aprotic solvent A is one of the following: methylene dichloride, ethylene dichloride, chloroform, tetrahydrofuran, Dimethylformamide, dimethyl sulfoxide, sulfolane or acetonitrile, the aprotic solvent B is the same as the aprotic solvent A; the ratio of the amount of the feed material of the ferrocene formyl chloride and aromatic amine and acid-binding agent is 1:1.2～1.5:2.0～3.0, the total mass ratio of the ferrocenecarbonyl chloride to the aprotic solvent A and the aprotic solvent B is 1:150～200.

The present invention also relates to an application of the ferrocene carboxamide type compound in third-order nonlinear optics.

When the ferrocene is connected to the amide group, since the carbon atom on the carbonyl group is directly connected to the nitrogen atom with a lone pair of electrons, the n electron on the nitrogen atom and the π electron on the carbonyl group produce n-π conjugation, resulting in a π orbital The improvement of the energy level reduces the energy level difference with the π* orbital, which is beneficial to increase the molecular bivalent nonlinear hyperpolarizability γ value. At the same time, the lone pair electrons of the N atom can form p-π conjugation with the conjugated system of the material molecule, and the π electrons will delocalize with the aromatic heterocyclic chromophore through the ferrocene center and the double bond, thereby enhancing the entire The electronic mobility of molecules increases the delocalization of electrons and reduces the n-π* and π-π* transition energy of material molecules, thereby improving the nonlinear optical properties of materials.

The ferrocene carboxamide compound represented by the formula (I) of the present invention and its application in the field of third-order nonlinear optics: it is tested by the degenerate four-wave mixing (DFWM) method, and the Ti: Sapphire femtosecond laser is used as the light source.

The third-order nonlinear susceptibility χ _s ⁽³⁾ of the sample is obtained by the relative detection method, that is, the recognized carbon disulfide is used as a reference under the same conditions, and the third-order nonlinear polarizability of the sample is obtained by comparing the signals of the sample and carbon disulfide. The transformation rate χ _s ⁽³⁾ is calculated by the following formula:

${\mathrm{\χ}}_{\mathrm{the\; s}}^{\left(3\right)}={\left(\frac{I_{\mathrm{the\; s}}}{I_r}\right)}^{1/2}\frac{L_r}{L_{\mathrm{the\; s}}}{\left(\frac{{\mathrm{no}}_{\mathrm{the\; s}}}{{\mathrm{no}}_r}\right)}^2\frac{\mathrm{\α\; L\; exp}(\mathrm{\α\; L}/2)}{1-\exp (-\mathrm{\αL})}{\mathrm{\χ}}_r^{\left(3\right)}$ Formula 1)

In formula (1), L _s and L _r are the thicknesses of the cuvettes of the sample to be tested and the reference sample carbon disulfide, respectively, n _s and n _r are the refractive indices of the sample to be tested and the reference sample carbon disulfide, respectively, χ _s and χ _r are The third-order nonlinear polarizability of the sample to be tested and the reference sample carbon disulfide, I _s and I _r are the conjugated light intensities of the sample to be tested and the reference sample carbon disulfide, respectively, α is the linear absorption coefficient, and the χ _r of the reference sample carbon disulfide ^{(3 )} is 6.7×10 ^-14 esu, n _r is 1.632.

The nonlinear refractive index of the sample to be tested caused by the third-order nonlinear coefficient is calculated by the following formula:

n ₂ (esu)=12πχ ⁽³⁾ /n ² formula (2)

In formula (2), n ₂ is the nonlinear refractive index of the substance to be measured; χ ⁽³⁾ is the third-order nonlinear susceptibility of the substance to be measured, that is, the calculated χ _s ⁽³⁾ ; n is the substance to be measured The linear refractive index;

The second-order hyperpolarizability γ of the sample solute molecule can be obtained by formula (3):

$\mathrm{\&gamma;}=\frac{{\mathrm{\&chi;}}^{\left(3\right)}}{{\mathrm{<figure-callout\; id="4"\; label="Nf"\; filenames="HDA00002784656400051.png,HDA00002784656400091.png"\; state="\{\{state\}\}">Nf</figure-callout>}}^4}$ Formula (3)

In the formula (3), N is the molecular density of the solute, N=6.02×10 ²³ c, c is the molar concentration of the sample solution, f ⁴ is the local field correction factor, f ⁴ =[( _ns ² +2)/3 ] ⁴ , where n is the linear refractive index of the substance to be measured.

The response time τ(fs) is obtained by plotting the four-wave mixing conjugate light intensity and the delay time, and then fitting it by Gaussian.

Compared with the prior art, the beneficial effect of the present invention is mainly reflected in that the method of the present invention has the advantages of few reaction steps, easy to obtain raw materials, simple synthesis process, mild reaction conditions, etc. The application in linear optics has great implementation value and good social and economic benefits.

(4) Description of drawings

Fig. 1 is the nonlinear optical response versus delay time graph of the ferrocene carboxamide type compound shown in formula (I-1) prepared in Example 1 by degenerate four-wave mixing detection, and the ordinate is four-wave mixing conjugate Intensity, the abscissa is the delay time, the dots in the figure are the experimental data, the solid line is the Gaussian fitting result, the half peak width of the response peak after fitting is the response time τ; the peak height is the light intensity described in the formula (1) Strong I.

Fig. 2 is a hydrogen nuclear magnetic resonance ( ¹ HNMR) spectrum of the ferrocene carboxamide type compound represented by formula (I-1) prepared in Example 1.

Fig. 3 is the mass spectrum MS (ESI) spectrum of the ferrocene carboxamide type compound represented by formula (I-1) prepared in Example 1.

Fig. 4 is a graph showing the nonlinear optical response versus delay time of the ferrocene carboxamide-type compound represented by formula (I-2) prepared in Example 2 by using degenerate four-wave mixing detection.

Fig. 5 is a hydrogen nuclear magnetic resonance ( ¹ HNMR) spectrum of the ferrocene carboxamide type compound represented by formula (I-2) prepared in Example 2.

Fig. 6 is the mass spectrum MS (ESI) spectrum of the ferrocene carboxamide type compound represented by formula (I-2) prepared in Example 2.

Fig. 7 is a graph showing the nonlinear optical response versus delay time of the ferrocene carboxamide-type compound represented by formula (I-3) prepared in Example 3 by using degenerate four-wave mixing detection.

Fig. 8 is a hydrogen nuclear magnetic resonance ( ¹ HNMR) spectrum of the ferrocene carboxamide type compound represented by formula (I-3) prepared in Example 3.

Fig. 9 is a mass spectrum MS (ESI) spectrum of the ferrocene carboxamide type compound represented by formula (I-3) prepared in Example 3.

Fig. 10 is a graph showing the nonlinear optical response versus delay time of the ferrocene carboxamide-type compound represented by formula (I-4) prepared in Example 4 by using degenerate four-wave mixing detection.

11 is a hydrogen nuclear magnetic resonance ( ¹ H NMR) spectrum of the ferrocene carboxamide-type compound represented by formula (I-4) prepared in Example 4.

FIG. 12 is a mass spectrum MS (ESI) spectrum of the ferrocene carboxamide-type compound represented by formula (I-4) prepared in Example 4.

Fig. 13 is a graph showing the nonlinear optical response versus delay time of the ferrocene carboxamide-type compound represented by formula (I-5) prepared in Example 5 by degenerate four-wave mixing detection.

Fig. 14 is a hydrogen nuclear magnetic resonance ( ¹ H NMR) spectrum of the ferrocene carboxamide type compound represented by formula (I-5) prepared in Example 5.

Fig. 15 is the mass spectrum MS (ESI) spectrum of the ferrocenecarboxamide-type compound represented by formula (I-5) prepared in Example 5.

Fig. 16 is a graph showing the nonlinear optical response versus delay time of the ferrocene carboxamide-type compound represented by formula (I-6) prepared in Example 6 by using degenerate four-wave mixing detection.

Fig. 17 is a hydrogen nuclear magnetic resonance ( ¹ H NMR) spectrum of the ferrocene carboxamide-type compound represented by formula (I-6) prepared in Example 6.

Fig. 18 is the mass spectrum MS (ESI) spectrum of the ferrocene carboxamide type compound represented by formula (I-6) prepared in Example 6.

Fig. 19 is a graph showing the nonlinear optical response versus delay time of the ferrocene carboxamide-type compound represented by formula (I-7) prepared in Example 7 by using degenerate four-wave mixing detection.

Fig. 20 is a hydrogen nuclear magnetic resonance ( ¹ H NMR) spectrum of the ferrocene carboxamide-type compound represented by formula (I-7) prepared in Example 7.

Fig. 21 is the mass spectrum MS (ESI) spectrum of the ferrocene carboxamide type compound represented by formula (I-7) prepared in Example 7.

Fig. 22 is a diagram of the degenerate four-wave mixing detection optical path used in the present invention.

Figure 23 is a plot of the nonlinear optical response versus delay time for the reference sample carbon disulfide.

Fig. 24 is the ultraviolet-visible absorption diagram of seven compounds synthesized in Examples 1-7.

(5) Specific implementation methods

The present invention is further described below in conjunction with specific embodiment, but protection scope of the present invention is not limited thereto:

Example 1

Add 0.1212g (1.0mmol) 3,5-dimethylaniline, 0.3g (2.83mmol) Na ₂ CO ₃ and 20mL (26.51g) anhydrous CH ₂ Cl ₂ into a 100mL three-necked flask and cool to 0～ At 5°C, add dropwise a mixture of 0.28g (1.0mmol) of ferrocenecarbonyl chloride and 20mL (26.51g) of anhydrous CH ₂ Cl ₂ , and react at 0-5°C for 10 hours. TLC tracking and monitoring, until the ferrocenyl chloride point disappears, the reaction is complete, the reaction solution is added to a saturated NaHCO ₃ solution, and the layers are left to stand, the water layer is extracted with CH ₂ Cl ₂ , the combined organic phase is evaporated to remove the solvent, and then silica gel column chromatography is performed , with a mixture of ethyl acetate and petroleum ether at a volume ratio of 1:5 as the eluent, according to the hydrogen spectrum and mass spectrum, the eluate containing the target component was collected and dried to obtain 0.1389g of a yellow solid with a yield of 41.7 %, melting point: 233-234°C, structure as shown in (I-1). The hydrogen nuclear magnetic resonance spectrum ( ¹ H NMR) spectrum is shown in FIG. 2 , and the mass spectrum MS (ESI) spectrum is shown in FIG. 3 . The graph of nonlinear optical response versus delay time for the ferrocene carboxamide type compound represented by the degenerate four-wave mixing detection formula (I-1) is shown in Fig. 1 (the detection method is the same as in Example 8).

Example 2

With o-chloroaniline as raw material, the input amount is 0.2552g (2.0mmol), the acid-binding agent is changed to sodium bicarbonate, the input amount is 0.29g (3.45mmol), the solvent is changed to dichloroethane, and the total input amount is 23mL (28.9g), other synthesis methods were the same as in Example 1, and 0.1875g of a yellow solid was obtained, with a yield of 55.2%, melting point: 167-168°C, and the structure as shown in (I-2). The nonlinear optical response of the ferrocene carboxamide type compound shown in the degenerate four-wave mixing detection formula (I-2) is shown in Figure 4 to the delay time diagram (the detection method is the same as in Example 8), and the proton nuclear magnetic resonance spectrum ( ¹ H NMR) spectrum is shown in Figure 5, and mass spectrum MS (ESI) spectrum is shown in Figure 6.

Example 3

Using m-chloroaniline as raw material, the input amount is 0.1914g (1.5mmol), the acid-binding agent is changed to sodium hydroxide, the input amount is 0.08g (2.0mmol), the total solvent amount is changed to 63mL (83.5g), other synthetic methods Same as Example 1, 0.2139 g of yellow solid was obtained, the yield was 63.0%, melting point: 211-212°C, and the structure was shown in (I-3). The nonlinear optical response of the ferrocene carboxamide compound shown in the degenerate four-wave mixing detection formula (I-3) is shown in Figure 7 on the delay time diagram (the detection method is the same as in Example 8), and the proton nuclear magnetic resonance spectrum ( ¹ H NMR) spectrum is shown in FIG. 8 , and mass spectrum MS (ESI) spectrum is shown in FIG. 9 .

Example 4

Using o-fluoroaniline as a raw material, the input amount is 0.1111g (1.0mmol), the solvent is changed to tetrahydrofuran, the acid-binding agent is changed to triethylamine, and the input amount is 0.152g (1.5mmol), and the other synthesis methods are the same as in Example 1 to obtain Yellow solid 0.1790g, yield 55.4%, melting point: 231-232°C, structure as shown in (I-4). The nonlinear optical response of the ferrocene carboxamide type compound shown in the degenerate four-wave mixing detection formula (I-4) is shown in Figure 10 (the detection method is the same as in Example 8), and the proton nuclear magnetic resonance spectrum ( ¹ H NMR) spectrum is shown in Figure 11, mass spectrum MS (ESI) spectrum is shown in Figure 12.

Example 5

Using m-nitroaniline as raw material, the input amount is 0.1381g (1.0mmol), the reaction temperature is -10～-5°C, the solvent is changed to DMF (dimethylformamide), and the other synthesis methods are the same as in Example 1 to obtain brown The solid is 0.2378g, the yield is 67.9%, the melting point is 196-197°C, and the structure is shown in (I-5). The nonlinear optical response of the ferrocene carboxamide compound shown in the degenerate four-wave mixing detection formula (I-5) versus the delay time diagram is shown in Figure 13 (the detection method is the same as in Example 8), and the proton nuclear magnetic resonance spectrum ( ¹ H NMR) spectrum is shown in FIG. 14 , and mass spectrum MS (ESI) spectrum is shown in FIG. 15 .

Example 6

Using 2-amino-6-nitrobenzothiazole as raw material, the input amount is 0.1952g (1.0mmol), the reaction temperature is changed to 15-20°C, the reaction time is 5 hours, the solvent is changed to sulfolane, and other synthetic methods are implemented in the same way In Example 1, 0.0831 g of a yellow solid was obtained, the yield was 20.4%, the melting point was greater than 250°C, and the structure was shown in (I-6). The nonlinear optical response of the ferrocene carboxamide compound shown in the degenerate four-wave mixing detection formula (I-6) versus the delay time diagram is shown in Figure 16 (the detection method is the same as in Example 8), and the proton nuclear magnetic resonance spectrum ( ¹ H NMR) spectrum is shown in Figure 17, and mass spectrum MS (ESI) spectrum is shown in Figure 18.

Example 7

Using 3,4,5-trifluoroaniline as raw material, the input amount is 0.1471g (1.0mmol), the reaction time is 7 hours, the solvent is changed to acetonitrile, other synthesis methods are the same as in Example 1, and 0.2331g of dark yellow solid is obtained. The yield is 64.9%, melting point: 185-186°C, and the structure is shown in (I-7). The nonlinear optical response of the ferrocene carboxamide compound shown in the degenerate four-wave mixing detection formula (I-7) versus the delay time diagram is shown in Figure 19 (the detection method is the same as in Example 8), and the proton nuclear magnetic resonance spectrum ( ¹ H NMR) spectrum is shown in Figure 20, and mass spectrum MS (ESI) spectrum is shown in Figure 21.

Embodiment 8 Three-order nonlinear optical performance detection

The third-order nonlinear optical properties of the ferrocene carboxamide compound described in the present invention are tested by a degenerate four-wave mixing (DFWM) method.

A femtosecond laser (Ti: Sapphire, produced by Nanolayers, Germany) was used as the light source, with a wavelength of 800nm, a pulse width of 80fs, a repetition rate of 1KHz, and a single pulse energy of 0.05mJ. The third-order nonlinear susceptibility χ _s ⁽³⁾ of the sample is obtained by the relative side chain method, that is, under the same conditions, the recognized carbon disulfide is used as a reference, and the third-order nonlinearity of the sample is obtained by comparing the signals of the sample and carbon disulfide Polarizability χ _s ⁽³⁾ . The specific calculation method is as follows:

${\mathrm{\&chi;}}_{\mathrm{the\; s}}^{\left(3\right)}={\left(\frac{I_{\mathrm{the\; s}}}{I_r}\right)}^{1/2}\frac{L_r}{L_{\mathrm{the\; s}}}{\left(\frac{{\mathrm{no}}_{\mathrm{the\; s}}}{{\mathrm{no}}_r}\right)}^2\frac{{\mathrm{\&alpha;\; L}}_r\exp (\mathrm{\&alpha;}{L}_r/2)}{1-\exp (-\mathrm{\&alpha;}{L}_r)}{\mathrm{\&chi;}}_r^{\left(3\right)}$ Formula 1)

In formula (1), L _s and L _r represent the thickness of the cuvettes of the sample to be tested and the reference sample carbon disulfide, respectively, n _s and n _r are the refractive indices of the sample to be tested and the reference sample carbon disulfide, respectively, and χ _s and χ _r are respectively The third-order nonlinear polarizability of the sample to be tested and the reference sample carbon disulfide, Is _{and Ir} are the conjugated light intensities of the sample to be tested and the reference sample carbon disulfide, respectively, and α is the linear absorption coefficient. According to literature reports, the reference sample carbon disulfide χ _r ⁽³⁾ is 6.7×10 ^-13 esu, n _r is 1.632.

因此，式（1）可以简化为：The ultraviolet-visible absorption spectra of compounds I-1-I-7 prepared in Examples 1-7 were measured at 200-800 nm, as shown in FIG. 24 . From the UV-Vis absorption spectra of the seven compounds measured in Figure 24, it can be seen that the measured materials have no absorption at the laser wavelength of 800nm, indicating that their third-order nonlinear optical properties will not be enhanced by electronic resonance in the DFWM experiment, that is to say The conjugate optical signal detected at the detection wavelength is a third-order nonlinear optical signal under non-resonant conditions. In formula (1) for

Therefore, formula (1) can be simplified as:

${{\mathrm{\&chi;}}_{\mathrm{the\; s}}}^{\left(3\right)}={\left(\frac{I_S}{I_r}\right)}^{1/2}\frac{L_r}{L_{\mathrm{the\; s}}}{\left(\frac{{\mathrm{no}}_{\mathrm{the\; s}}}{{\mathrm{no}}_r}\right)}^2{{\mathrm{\&chi;}}_r}^{\left(3\right)}$ Formula (1-1)

At the same time, since the thickness of the cuvette is L _s =L _r =1mm, formula (5) can be simplified as:

${{\mathrm{\&chi;}}_{\mathrm{the\; s}}}^{\left(3\right)}={\left(\frac{I_S}{I_r}\right)}^{1/2}{\left(\frac{{\mathrm{no}}_{\mathrm{the\; s}}}{{\mathrm{no}}_r}\right)}^2{{\mathrm{\&chi;}}_r}^{\left(3\right)}$ Formula (1-2)

The linear absorption n _s of the sample in the formula (1-2) is measured by Abbe refractometer, and the n _r of the reference CS ₂ is 1.632.

Figure 23 The nonlinear optical response of carbon disulfide versus the delay time. The peak height is the conjugated light intensity I _s of carbon disulfide. The peak height in the graph of nonlinear optical response versus delay time of the measured sample is the conjugated light intensity I _r of each material. The third-order nonlinear susceptibility χ _s ⁽³⁾ of the measured material can be obtained by substituting the above data into formula (1-2). The nonlinear refractive index caused by the third-order nonlinear coefficient is calculated by:

n ₂ (esu)=12πχ ⁽³⁾ /n ² formula (2)

In formula (2), n ₂ is the nonlinear refractive index of the substance to be measured; χ ⁽³⁾ (esu) is the third-order nonlinear susceptibility of the substance to be measured, that is, the calculated χ _s ⁽³⁾ ; n is The linear refractive index of the substance to be measured;

The second-order hyperpolarizability γ of the sample solute molecule can be obtained by the following formula:

$\mathrm{\&gamma;}=\frac{{\mathrm{\&chi;}}^{\left(3\right)}}{{\mathrm{Nf}}^4}$ Formula (3)

In the formula (3), N is the molecular density of the solute, N=6.02×10 ²³ c, c is the molar concentration of the sample solution, f ⁴ is the local field correction factor, f ⁴ =[(n ² +2)/3] ⁴ , n is the linear refractive index of the substance to be measured.

Test sample: DMF with a concentration of 5×10 ^-4 mol/L was prepared from the ferrocene carboxamide compounds shown in formulas (I-1) to (I-7) prepared in Examples 1 to 7 of the present invention (dimethylformamide) solution as a sample, and then use the degenerate four-wave mixing (DFWM) method to test the third-order nonlinear optical properties. The results are shown in Table 1. Compound (I-1) conjugate light intensity and delay time as shown in Figure 1:

Table 1 The third-order nonlinear optical performance parameters of ferrocene carboxamide compounds

According to the literature The Journal of Physical Chemistry, 1990,94(7):2847-2851, Saswati Ghosal et al. used femtosecond laser (Nd:YAG laser light source, wavelength 602nm, pulse width 400fs), DFWM experimental light path measured ferrocene The second-order hyperpolarizability (γ) of the molecule is 1.61±0.18×10 ^-35 esu. From Table 1, it can be seen that the second-order hyperpolarizability of the ferrocene carboxamide compound of the present invention is 4 times higher than that of the parent structure of ferrocene It is an order of magnitude, which is a class of third-order nonlinear optical materials with great potential.

Claims (9)

1. A ferrocene carboxamide type compound shown in formula (I),

In formula (I): R is phenyl, substituted phenyl, naphthyl, benzothiazolyl or substituted benzothiazolyl, the substituent on the substituted phenyl is halogen, methyl or nitro, and the substituted The substituent on the benzothiazolyl group is halogen, methyl or nitro. 2. ferrocene carboxamide type compound as claimed in claim 1, is characterized in that described compound is one of following:

3. A preparation method for the ferrocene carboxamide type compound according to claim 1, characterized in that the method is: dissolving the ferrocene carboxyl chloride shown in the formula (II) in the aprotic solvent A to obtain the ferrocene Ferroformyl chloride solution; the aromatic amine represented by formula (III) is dissolved in an aprotic solvent B, and in the presence of an acid-binding agent, the ferroceneformyl chloride solution is added dropwise at -10 to 20°C. After the reaction is complete, The reaction solution is post-treated to obtain the ferrocene carboxamide type compound shown in formula (I); the acid-binding agent is one of the following: sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, pyridine or triethyl Amine; the aprotic solvent A is one of the following: dichloromethane, ethylene dichloride, chloroform, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, sulfolane or acetonitrile, the aprotic solvent B and non-protic The protic solvent A is the same; In formula (III): R is phenyl, substituted phenyl, naphthyl, benzothiazolyl or substituted benzothiazolyl, the substituent on the substituted phenyl is halogen, methyl or nitro, and the substituted The substituent on the benzothiazolyl group is halogen, methyl or nitro. 4. the preparation method of ferrocene carboxamide type compound as claimed in claim 3, it is characterized in that the ratio of the amount of feed material of described ferrocene carboxyl chloride and aromatic amine and acid-binding agent is 1:1.0～2.0:1.5～ 3.5. 5. The preparation method of ferrocene carboxamide compound as claimed in claim 3, characterized in that the total mass ratio of ferrocene carboxyl chloride to aprotic solvent A and aprotic solvent B is 1:100-300. 6. The preparation method of the ferrocene carboxamide type compound as claimed in claim 3, characterized in that the reaction is carried out at -10-20° C. for 5-10 h. 7. the preparation method of ferrocene carboxamide type compound as claimed in claim 3, it is characterized in that described reaction solution aftertreatment method is: track and monitor with TLC in the reaction process, until ferrocenyl chloride point disappears and promptly reacts completely, will The reaction solution was washed with saturated sodium bicarbonate solution, left to stand and separated, the aqueous layer was extracted with chloroform, the organic phase was evaporated to remove the solvent, and then subjected to silica gel column chromatography, the mixture of ethyl acetate and petroleum ether with a volume ratio of 1:5 As an eluent, the eluate containing the target component is collected and dried to obtain a ferrocene carboxamide compound represented by formula (I). 8. the preparation method of ferrocene carboxamide type compound as claimed in claim 3, is characterized in that described reaction is carried out as follows: ferrocene carboxyl chloride shown in formula (II) is dissolved in aprotic solvent A, obtains Ferrocenecarbonyl chloride solution: Dissolve the aromatic amine represented by formula (III) in the aprotic solvent B, in the presence of an acid-binding agent, add the ferrocenecarbonyl chloride solution dropwise at -5 to 5°C, and react 6 ~8h, track and monitor with TLC during the reaction, until the point of ferrocenyl chloride disappears, the reaction is complete, wash the reaction solution with saturated sodium bicarbonate solution, let stand to separate layers, extract the water layer with chloroform, take the organic phase and evaporate the solvent Then perform silica gel column chromatography, use ethyl acetate and petroleum ether mixture with a volume ratio of 1:5 as the eluent, collect the eluate containing the target component, dry it, and obtain the dioxane represented by the formula (I) Iron formamide compound; the acid-binding agent is one of the following: sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, pyridine or triethylamine; the aprotic solvent A is one of the following: methylene chloride , dichloroethane, chloroform, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, sulfolane or acetonitrile, the aprotic solvent B is the same as the aprotic solvent A; The ratio of the amount of the feeding material of the acid agent is 1:1.2-1.5:2.0-3.0, and the total mass ratio of the ferrocenecarbonyl chloride to the aprotic solvent A and the aprotic solvent B is 1:150-200. 9. The application of the ferrocene carboxamide compound according to claim 1 in third-order nonlinear optics.

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