CN114149466A - Chiral one-dimensional manganese nonlinear optical material and preparation method thereof - Google Patents
Chiral one-dimensional manganese nonlinear optical material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a chiral one-dimensional manganese nonlinear optical material and a preparation method thereof, belonging to the technical field of chiral molecular-based functional materials. The molecular formula of the chiral one-dimensional manganese nonlinear optical material is [ Mn2(L)2Cl4]nWherein L is a chiral bidentate N-containing organic ligand of R configuration: (-) -4, 5-pinene-2, 2' -bipyridine. The preparation method of the nonlinear optical material disclosed by the invention comprises the following steps: mixing MnCl2·4H2And adding the methanol solution of O into the tetrahydrofuran solution of L, stirring, filtering, transferring the obtained filtrate into a test tube, placing the test tube into a gas collection bottle of n-hexane gas to obtain yellow crystals, filtering, washing with methanol, and drying to obtain the chiral one-dimensional manganese nonlinear optical material. The preparation method disclosed by the invention has the advantages of simple process, normal temperature and pressure reaction, easiness in post-treatment and high yield, and the invention is based on the SHG and THG response of the crystalline sample test materialThe test process is convenient and fast.
Description
Technical Field
The invention belongs to the technical field of chiral molecule-based functional materials, and particularly relates to a chiral one-dimensional manganese nonlinear optical material and a preparation method thereof.
Background
Prior to the advent of lasers, human knowledge of optical phenomena has only stayed in the "linear optics" phase. By linear optics is meant that when a weak light beam propagates in a medium, the main optical parameters of the medium, such as refractive index, absorption coefficient, etc., are independent of the intensity of the incident light, i.e. these main parameters do not change with the change in the intensity of the light, nor does the frequency of the light change during propagation. However, with the discovery of lasers, linear optics has not been able to account for new optical phenomena, such as when a laser beam passes through a medium to emit a new frequency beam. Therefore, nonlinear optics has been developed as an emerging optical subject, and nonlinear optical (NLO) crystals have a function of amplifying incident laser frequency and play an important role in the fields of laser and photoelectric technology as key materials, so that research on nonlinear optical materials has been a research topic with a high scientific value.
Second Harmonic Generation (SHG) and Third Harmonic Generation (THG) are the most common nonlinear optical processes in materials. The second-order nonlinear optical performance requires that the structure of the second-order nonlinear optical performance is necessarily non-centrosymmetric and crystallized in a non-centrosymmetric space group, a typical molecular structure with second-order nonlinear optical property also conforms to a Donor-pi-Acceptor configuration, an electron Donor (Donor) and an electron Acceptor (Acceptor) are connected together through a conjugate structure, the electron Donor transfers electrons to the electron Acceptor by virtue of a conjugate bridge to generate a second-order nonlinear optical effect, and thus the molecular structure with non-centrosymmetry is a necessary condition for the material to have SHG response; the THG activity is not related to the symmetry of the molecular structure, but compared with the molecular base material with SHG activity, the molecular base material with THG response is more rare in quantity, because most of the third harmonic generation processes are weaker and are not easy to detect. In addition, the study on the third-order nonlinear optical response is usually carried out in a dilute solution by using a Z-scanning technology, the study result is inevitably influenced by the solvent effect, and particularly for the molecular-based materials which are difficult to dissolve in an organic solvent, the THG performance test and study of the molecular-based materials are undoubtedly restricted by the Z-scanning technology.
At present, the nonlinear optical material with both SHG and THG responses has a wide application prospect in the aspects of data storage, optical amplitude limiting, optical communication, optical calculation, all-optical information conversion and the like, so that the material also attracts high attention of related scientific researchers in the fields of chemistry, physics and material science. However, the reported molecular-based materials with both SHG and THG responses are extremely rare, well suggesting that developing such materials faces significant challenges.
Disclosure of Invention
Aiming at the background technology, the invention provides a chiral one-dimensional manganese nonlinear optical material and a preparation method thereof. The nonlinear optical material disclosed by the invention has SHG and THG responses at the same time, and the preparation method has the advantages of simple process, normal-temperature and normal-pressure reaction, easy post-treatment and high yield. The invention is based on the crystalline state sample of the material, test SHG and THG response of the material at the same time, the test process is convenient and fast, the test result is not influenced by solvent, it is more favorable to developing extensive and deep theory and application research to SHG and THG response of the material.
In order to achieve the above purpose, the invention provides the following technical scheme:
the molecular formula of the chiral one-dimensional manganese nonlinear optical material is [ Mn ]2(L)2Cl4]nAnd N is any value, wherein L is a chiral bidentate N-containing organic ligand with an R configuration.
Preferably, the chiral bidentate N-containing organic ligand is (-) -4, 5-pinene-2, 2' -bipyridine, and the structural formula is as follows:
preferably, the chiral one-dimensional manganese nonlinear optical material is crystallized in a triclinic system non-centrosymmetric space group P1, and the unit cell parameters are as follows:
α＝98.685(5)°，β＝102.886(5)°，γ＝92.618(4)°，
Z＝1，Dc＝1.483g·cm–1，μ＝1.097mm–1，R1＝0.0386，wR2＝0.0811。
the invention provides a preparation method of a chiral one-dimensional manganese nonlinear optical material, which comprises the following steps:
(1) mixing MnCl2·4H2Dissolving O in methanol to obtain MnCl2·4H2A solution of O in methanol;
(2) dissolving the L in tetrahydrofuran to obtain a tetrahydrofuran solution of the L;
(3) mixing the MnCl obtained in the step (1)2·4H2Adding the methanol solution of O into the tetrahydrofuran solution of L in the step (2), stirring, filtering, transferring the obtained filtrate into a test tube, placing the test tube into a gas collection bottle of n-hexane gas, and standing to obtain yellow crystals;
(4) and (4) filtering the yellow crystal obtained in the step (3), washing with methanol, and drying at room temperature to obtain the chiral one-dimensional manganese nonlinear optical material.
Preferably, MnCl is used in the step (1)2·4H2MnCl in methanol solution of O2·4H2The concentration of O is 0.013-0.025 mol/L.
Preferably, the concentration of L in the tetrahydrofuran solution of the L in the step (2) is 0.02-0.05 mol/L.
Preferably, the MnCl2·4H2The mass ratio of O to L is 1 (1-1.5).
Preferably, the stirring time in the step (3) is 25-30 min.
Preferably, the standing time in the step (3) is 5 to 7 days.
The invention has the beneficial effects that:
1. the invention provides a preparation method of a chiral one-dimensional manganese nonlinear optical material, which has the advantages of mild synthesis conditions, high yield, good stability and easy separation and purification, and has wide application prospect in the technical fields of laser and photoelectricity as a novel nonlinear optical material. The invention is based on the crystalline state sample of the material, test SHG and THG response of the material at the same time, the test process is convenient and fast, the test result is not influenced by solvent, it is more favorable to developing extensive and deep theory and application research to SHG and THG response of the material.
2. The invention adopts R configuration chiral bidentate N-containing organic ligand of (-) -4, 5-pinene-2, 2' -bipyridyl (L) and MnCl2·4H2And (3) performing O reaction to prepare the chiral one-dimensional manganese nonlinear optical material, wherein the following strategy is adopted in the design of the molecular structure:
(i) the introduction of the enantiomer-pure R-configuration bidentate N-containing chiral ligand ensures that the material has a non-centrosymmetric molecular structure, thereby meeting the necessary condition that the material has SHG response; (ii) the molecular structure contains Cl with large electronegativity–Ions (with an electron withdrawing characteristic), and the chiral bidentate N-containing ligand L has an electron donating characteristic, so that the whole molecule has larger polarity, and the THG response is polarity-dependent, thereby meeting the necessary condition that the material has the THG response; (iii) the chiral bidentate N-containing heterocyclic ligand L has a pi electron conjugated system, and researches show that the pi electron conjugated system is favorable for the material to present strong THG response.
3. The chiral one-dimensional manganese nonlinear optical material disclosed by the invention respectively shows emission peaks at 517nm (about 1/3 of the wavelength of incident laser) and 775nm (about 1/2 of the wavelength of the incident laser), proves that the material has SHG and THG responses simultaneously, and is alpha-SiO with a reference material2In comparison, the THG response intensity of the chiral one-dimensional manganese nonlinear optical material is alpha-SiO232 times of the first order, and its third order nonlinear excitation rate (1219.8 pm)2/V2) Is alpha-SiO2Third order nonlinear activation rate (214 pm)2/V2) 5.7 times of the total weight of the powder.
Drawings
In order to illustrate the embodiments of the invention more clearly, the drawings that are needed in the description of the embodiments will be briefly described below, it being apparent that the drawings in the following description are only some embodiments of the invention, and that other drawings may be derived from those drawings by a person skilled in the art without inventive effort.
FIG. 1 shows chiral one-dimensional manganese nonlinear optical material [ Mn ] in example 12(L)2Cl4]nThe molecular composition diagram of the asymmetric unit in the molecular structure of (a), the H atom has been omitted for clarity.
FIG. 2 shows chiral one-dimensional manganese nonlinear optical material [ Mn ] in example 12(L)2Cl4]nThe one-dimensional molecular structure diagram of (1).
FIG. 3 shows chiral one-dimensional manganese nonlinear optical material [ Mn ] in example 12(L)2Cl4]nSecond and third harmonic generation (SHG and THG) spectrograms.
FIG. 4 shows chiral one-dimensional manganese nonlinear optical material [ Mn ] in example 12(L)2Cl4]nWith reference material alpha-SiO2THG and SHG spectra of (a).
FIG. 5 shows chiral one-dimensional manganese nonlinear optical material [ Mn ] in example 12(L)2Cl4]nChiral Circular Dichroism (CD) spectra of (a).
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
The invention discloses a chiral one-dimensional manganese nonlinear optical material, the molecular formula of which is [ Mn ]2(L)2Cl4]nAnd N is any value, wherein L is a chiral bidentate N-containing organic ligand of R configuration: (-) -4, 5-pinene-2, 2' -bipyridine, the structural formula is:
wherein, the chiral one-dimensional manganese nonlinear optical material is crystallized in a triclinic system non-centrosymmetric space group P1, and the unit cell parameters are as follows:
α＝98.685(5)°，β＝102.886(5)°，γ＝92.618(4)°，
Z＝1，Dc＝1.483g·cm–1，μ＝1.097mm–1，R1＝0.0386，wR2＝0.0811。
the invention also provides a preparation method of the chiral one-dimensional manganese nonlinear optical material, which comprises the following steps:
(1) mixing MnCl2·4H2Dissolving O in methanol to obtain MnCl with the concentration of 0.013-0.025mol/L2·4H2A solution of O in methanol;
(2) dissolving the L in tetrahydrofuran to obtain a tetrahydrofuran solution of which the concentration is 0.02-0.05 mol/L;
(3) mixing the MnCl obtained in the step (1)2·4H2Adding the methanol solution of O into the tetrahydrofuran solution of L in the step (2), stirring for 25-30min, filtering, transferring the obtained filtrate into a test tube, and placing the test tube into a gas collection bottle for 5-7 days to obtain yellow crystals;
(4) and (4) filtering the yellow crystal obtained in the step (3), washing with methanol, and drying at room temperature to obtain the chiral one-dimensional manganese nonlinear optical material.
Wherein, MnCl2·4H2The mass ratio of O to L is 1 (1-1.5).
In the preparation method of the chiral one-dimensional manganese nonlinear optical material, the preparation method of the chiral bidentate N-containing organic ligand L with the R configuration comprises the following steps:
(a) preparation of 2- (acetylpyridyl) pyridine iodide salt intermediate: adding 2.6g of 2-acetylpyridine into a flask, dissolving the 2-acetylpyridine with 12mL of pyridine solution, adding 10mL of pyridine solution dissolved with 8g of iodine into the flask, heating the mixture to 115 ℃, reacting for 3 hours, cooling to room temperature, filtering, washing with 3mL of pyridine twice, and drying in vacuum to obtain an intermediate 2- (acetylpyridyl) pyridine iodonium salt;
(b) synthesis of a bidentate N-containing organic ligand L of chiral R configuration: weighing 2.2g of the 2- (acetylpyridyl) pyridine iodide salt intermediate prepared in step (a) and 2.1g of ammonium acetate (NH)4Ac) was placed in a three-necked flask, and 20mL of formamide (HCONH) was added2) Adding 1.2g of R-configured myrtenal (-) -myrtenal under stirring, heating to 73 ℃, stirring under nitrogen for reaction for 11 hours, adding the product obtained after the reaction into 160mL of saturated sodium bicarbonate solution, continuously stirring to generate a brown solid, filtering, dissolving the obtained solid with 5mL of ethanol, adding 110mL of water to separate out the solid, repeating the process twice to finally obtain a white flocculent solid, and drying the solid at room temperature to obtain the R-configured chiral bidentate N-containing organic ligand L, wherein the yield is 83% (calculated according to an intermediate), and the elemental analysis: according to the formula C17H18N2(molecular weight 250.33): calculated value (%): c, 81.56; h, 7.25; n, 11.19; found (%): c, 81.43; h, 7.35; n, 11.23. Infrared spectrum ir (kbr): 2943(s), 2992(m), 2865(v), 1582(m), 1457(s), 1385(m), 782(m), 753(s).
The technical solution of the present invention is further illustrated by the following specific examples
Example 1
This example is chiral one-dimensional manganese nonlinear optical material [ Mn2(L)2Cl4]nThe preparation of (1): 3mL of a solution of chiral bidentate N-containing organic ligand L (38mg, 0.15mmol) in R configuration in tetrahydrofuran was added to 7mL of MnCl in solution2·4H2Stirring O (29mg, 0.15mmol) in methanol solution at room temperature for 25min, filtering, transferring the obtained filtrate into a test tube, putting the test tube into a gas collection bottle filled with n-hexane solution, obtaining yellow crystals after 5 days, washing the obtained crystals twice by using 3mL of methanol, and drying at room temperature to obtain the one-dimensional manganese nonlinear optical material with the yield of 87% (calculated according to Mn).
Chiral analysis of this example using a Perkin-Elmer 240C elemental analyzerOne-dimensional manganese nonlinear optical material [ Mn ]2(L)2Cl4]nAnalyzing the content of C, H and N elements according to the formula C34H36N4Cl4Mn2(molecular weight 752.36) calculated (%): c, 54.28; h, 4.82; and N, 7.45. Found (%): c, 54.13; h, 4.71; and (7) N7.67.
The molecular structure of the nonlinear optical material is measured by Bruker SMART APEX II CCD diffractometer single crystal diffractometer at normal temperature, as shown in figure 1, it can be seen that the nonlinear optical material has a one-dimensional chain molecular structure, and the asymmetric unit of the nonlinear optical material comprises two Mn2+Ion, two chiral bidentate N-containing ligands L and four Cl–An anionic ligand; as bridging ligands, each Cl–The anions bridging two different Mn's respectively2+The formation of one-dimensional manganese chains by the ions is shown in figure 2.
Chiral one-dimensional manganese nonlinear optical material [ Mn ] of the present example2(L)2Cl4]nSHG and THG response test of (1): selecting target product and reference substance (alpha-SiO) with particle size of 15-35 μm at room temperature2) The crystal sample of (2) was excited at 1550nm by an ultrafast fiber laser (NPI Lasers, Rainbow 1550OEM), the laser pulse having a repetition rate of 80MHz, a pulse width of 100fs and a power of 100 mW. Image information of the sample is collected by a CCD camera (MI chrome 5Pro), spectral information is obtained by a refrigeration type fiber spectrometer (Ideoplastics, NOVA), the sample is placed on an electric displacement platform (the stepping precision is 0.1 mu m, and the scanning precision is 1 mu m), the appearance of the sample is observed through the CCD, and a scanning area is selected.
The test result shows that: chiral one-dimensional manganese nonlinear optical material [ Mn2(L)2Cl4]nEmission peaks are present at 517nm (about 1/3 at the wavelength of the incident laser) and 775nm (about 1/2 at the wavelength of the incident laser), respectively, corresponding to third and second harmonic generation (THG and SHG) responses, respectively, as shown in fig. 3.
FIG. 4 shows chiral one-dimensional manganese nonlinear optical material [ Mn ]2(L)2Cl4]nWith reference material alpha-SiO2The THG and SHG spectrograms of the same are shown to be the same as the reference material alpha-SiO with the same grain size range2Compared with the results obtained under the same test conditions, the THG response intensity of the chiral one-dimensional manganese nonlinear optical material is alpha-SiO232 times of the first order of the second order of the third order of the fourth order of the fifth order of the fourth order of the fifth order of the fourth order(3)＝1219.8pm2/V2The value is alpha-SiO2Third order nonlinear activation Rate (214 pm)2/V2) 5.7 times of that of THG, such high THG response and large χ(3)In the molecular based NLO material, the fact is rare.
The solid state circular dichroism spectrum (CD spectrum) of the nonlinear optical material of the present embodiment was tested by using a Biologic MS-500 spectrophotometer at room temperature, as shown in FIG. 5, it can be seen that the material shows a positive Cotton effect at a wavelength of λ ═ 235nm, and shows two negative Cotton effect peaks at λ ═ 280 and 325nm, confirming the chiral optical activity of the NLO material.
Example 2
This example is chiral one-dimensional manganese nonlinear optical material [ Mn2(L)2Cl4]nThe preparation of (1): 10mL of a solution of chiral bidentate N-containing organic ligand L (50.67mg, 0.2mmol) in R configuration in tetrahydrofuran was added to 14mL of MnCl in solution2·4H2Stirring O (38.67mg, 0.2mmol) in methanol solution at room temperature for 25min, filtering, transferring the obtained filtrate into a test tube, putting the test tube into a gas collection bottle filled with n-hexane solution, obtaining yellow crystals after 6 days, washing the obtained crystals twice by using 3mL of methanol, and drying at room temperature to obtain the one-dimensional manganese nonlinear optical material.
Example 3
This example is chiral one-dimensional manganese nonlinear optical material [ Mn2(L)2Cl4]nThe preparation of (1): 2.5mL of a solution of chiral bidentate N-containing organic ligand L (25.33mg, 0.1mmol) in R configuration in tetrahydrofuran was added to 5mL of MnCl in solution2·4H2Stirring O (19.33mg, 0.1mmol) in methanol at room temperature for 30min, filtering, transferring the filtrate into a test tube, placing the test tube into a gas collection bottle containing n-hexane solution, collecting yellow crystals after 7 days, and purifying with chloroform to obtain the final productAnd washing the obtained crystals twice by 3mL of methanol, and drying at room temperature to obtain the one-dimensional manganese nonlinear optical material.
Example 4
This example is chiral one-dimensional manganese nonlinear optical material [ Mn2(L)2Cl4]nThe preparation of (1): 10mL of a solution of chiral bidentate N-containing organic ligand L (76mg, 0.3mmol) in R configuration in tetrahydrofuran was added to 13mL of MnCl in solution2·4H2Stirring O (38.67mg, 0.2mmol) in methanol solution at room temperature for 25min, filtering, transferring the obtained filtrate into a test tube, putting the test tube into a gas collection bottle filled with n-hexane solution, obtaining yellow crystals after 7 days, washing the obtained crystals twice with 3mL of methanol, and drying at room temperature to obtain the one-dimensional manganese nonlinear optical material.
Example 5
This example is chiral one-dimensional manganese nonlinear optical material [ Mn2(L)2Cl4]nThe preparation of (1): 5mL of a solution of chiral bidentate N-containing organic ligand L (63.33mg, 0.25mmol) in R configuration in tetrahydrofuran was added to 10mL of MnCl in solution2·4H2Stirring O (48.33mg, 0.25mmol) in methanol solution at room temperature for 30min, filtering, transferring the obtained filtrate into a test tube, putting the test tube into a gas collection bottle filled with n-hexane solution, obtaining yellow crystals after 7 days, washing the obtained crystals twice with 3mL of methanol, and drying at room temperature to obtain the one-dimensional manganese nonlinear optical material.
The chiral one-dimensional manganese nonlinear optical material and the preparation method thereof provided by the invention are described in detail above. The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (9)
1. The chiral one-dimensional manganese nonlinear optical material is characterized in that: the molecular formula of the chiral one-dimensional manganese nonlinear optical material is [ Mn2(L)2Cl4]nAnd N is any value, wherein L is a chiral bidentate N-containing organic ligand with an R configuration.
2. The chiral one-dimensional manganese nonlinear optical material of claim 1, wherein: the chiral bidentate N-containing organic ligand is (-) -4, 5-pinene-2, 2' -bipyridine, and the structural formula is as follows:
3. the chiral one-dimensional manganese nonlinear optical material of claim 1, wherein: the chiral one-dimensional manganese nonlinear optical material is crystallized in a triclinic system noncentrosymmetric space group P1, and the unit cell parameters are as follows:
α＝98.685(5)°，β＝102.886(5)°，γ＝92.618(4)°，
Z＝1，Dc＝1.483g·cm–1，μ＝1.097mm–1，R1＝0.0386，wR2＝0.0811。
4. the method for preparing chiral one-dimensional manganese nonlinear optical material as recited in any one of claims 1 to 3, comprising the steps of:
(1) mixing MnCl2·4H2Dissolving O in methanol to obtain MnCl2·4H2A solution of O in methanol;
(2) dissolving the L in tetrahydrofuran to obtain a tetrahydrofuran solution of the L;
(3) mixing the MnCl obtained in the step (1)2·4H2Adding the methanol solution of O into the tetrahydrofuran solution of L in the step (2), stirring and filteringTransferring the obtained filtrate to a test tube, placing the test tube into a gas collection bottle of n-hexane gas, and standing to obtain yellow crystals;
(4) and (4) filtering the yellow crystal obtained in the step (3), washing with methanol, and drying at room temperature to obtain the chiral one-dimensional manganese nonlinear optical material.
5. The method for preparing the chiral one-dimensional manganese nonlinear optical material as claimed in claim 4, wherein the method comprises the following steps: MnCl in the step (1)2·4H2MnCl in methanol solution of O2·4H2The concentration of O is 0.013-0.025 mol/L.
6. The method for preparing the chiral one-dimensional manganese nonlinear optical material as claimed in claim 4, wherein the method comprises the following steps: the concentration of L in the tetrahydrofuran solution of L in the step (2) is 0.02-0.05 mol/L.
7. The method for preparing the chiral one-dimensional manganese nonlinear optical material according to claim 5 or 6, wherein the chiral one-dimensional manganese nonlinear optical material comprises the following steps: the MnCl2·4H2The mass ratio of O to L is 1 (1-1.5).
8. The method for preparing the chiral one-dimensional manganese nonlinear optical material as claimed in claim 4, wherein the method comprises the following steps: and (4) stirring for 25-30min in the step (3).
9. The method for preparing the chiral one-dimensional manganese nonlinear optical material as recited in claim 8, wherein: and (4) standing for 5-7 days in the step (3).
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