CN114181232A - Chiral one-dimensional copper chain ferromagnetic molecular base material and preparation method thereof - Google Patents
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- 239000000463 material Substances 0.000 title claims abstract description 58
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 230000005294 ferromagnetic effect Effects 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 112
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 93
- 239000010949 copper Substances 0.000 claims abstract description 67
- 238000003756 stirring Methods 0.000 claims abstract description 33
- 238000001914 filtration Methods 0.000 claims abstract description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000012360 testing method Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 10
- 239000013110 organic ligand Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 15
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 6
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 239000003302 ferromagnetic material Substances 0.000 abstract description 4
- 238000009987 spinning Methods 0.000 abstract description 3
- 238000011914 asymmetric synthesis Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 60
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 28
- DBZAKQWXICEWNW-UHFFFAOYSA-N 2-acetylpyrazine Chemical compound CC(=O)C1=CN=CC=N1 DBZAKQWXICEWNW-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 14
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- KMRMUZKLFIEVAO-UHFFFAOYSA-N 7,7-dimethylbicyclo[3.1.1]hept-3-ene-4-carbaldehyde Chemical compound C1C2C(C)(C)C1CC=C2C=O KMRMUZKLFIEVAO-UHFFFAOYSA-N 0.000 description 10
- KMRMUZKLFIEVAO-RKDXNWHRSA-N Myrtenal Natural products C1[C@H]2C(C)(C)[C@@H]1CC=C2C=O KMRMUZKLFIEVAO-RKDXNWHRSA-N 0.000 description 10
- FHIAPLHUANFKGE-UHFFFAOYSA-N CC(C1=NC=CN=C1C1=NC=CC=C1)=O.I Chemical compound CC(C1=NC=CN=C1C1=NC=CC=C1)=O.I FHIAPLHUANFKGE-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 8
- 230000005291 magnetic effect Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 6
- 239000005695 Ammonium acetate Substances 0.000 description 6
- 229940043376 ammonium acetate Drugs 0.000 description 6
- 235000019257 ammonium acetate Nutrition 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001142 circular dichroism spectrum Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 241000238366 Cephalopoda Species 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003216 pyrazines Chemical class 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
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- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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Abstract
The invention discloses a chiral one-dimensional copper chain ferromagnetic molecular base material and a preparation method thereof, belonging to the technical field of asymmetric synthesis. The molecular formula of the molecular base material is [ Cu (L)) (NO3)2]n. The preparation method of the molecular base material comprises the following steps: will dissolve Cu (NO)3)2·6H2Adding O acetonitrile solution into L-dissolved dichloromethane solution, stirring, filtering, transferring the obtained clear solution into a test tube, placing the test tube in a gas-collecting bottle filled with ether gas, obtaining blue crystals after 5-7 days, filtering, washing and drying to obtain chiral one-dimensional copper chain ferromagnetic molecular base material [ Cu (L) (NO)3)2]n. The molecular-based material has the advantages of mild synthesis conditions, high yield, good stability and easy separation and purification, and has wide application prospect in the aspect of magnetic-optical spinning electronic devices as a novel chiral molecular-based ferromagnetic material.
Description
Technical Field
The invention belongs to the technical field of asymmetric synthesis, and particularly relates to a chiral one-dimensional copper chain ferromagnetic molecular base material and a preparation method thereof.
Background
Chirality is a fundamental property of nature and plays an important role in the fields of chemistry, biology, medicine, material science, and the like. Due to the non-central symmetry of the molecular structure, chiral complexes may have unique physical properties based only on non-central or chiral molecular structures, such as non-linear optical activity, second order harmonic generation, circularly polarized luminescence, ferroelectrics, piezoelectricity, and the like. Therefore, the design and preparation of chiral complexes have been the subject of intense research in the fields of chemistry and material science. Especially, chiral information is introduced into the molecular structure of the magnetic complex, so that chirality and magnetism coexist in the same molecule, and the two different physical and chemical properties interact in the molecule to generate an interesting magnetic chiral color direction effect. Therefore, the molecular-based functional material has attractive application prospect in the aspect of magnetic-optical spinning electronic devices, and is always a popular material which is highly concerned by scientific researchers in the fields of chemistry, physics and material science. Because the synthesis difficulty of the chiral organic ligand is high, the yield is not high, and the quantity of the commercially available chiral ligands is limited; in addition, chiral ligands are prone to racemization during crystallization of the synthesized complex, resulting in loss of chiral optical activity of the target product. Due to the above-mentioned multiple factors, the preparation of chiral complexes is extremely challenging. Thus, relatively small numbers of chiral complexes have been reported, with more rare complexes having both chiral and ferromagnetic couplings. At present, no document report of a one-dimensional copper chain complex which has chiral optical activity and simultaneously shows ferromagnetic performance exists, and no patent publication of a chiral one-dimensional copper chain molecule-based ferromagnetic material exists.
Disclosure of Invention
The invention provides a chiral one-dimensional copper chain ferromagnetic molecular base material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a chiral one-dimensional copper chain ferromagnetic molecular base material has a molecular formula of [ Cu (L) (NO)3)2]nWherein L is S configuration chiral mono-bidentate N-containing organic ligand: (+) -2- (4 ', 5' -pinene pyridyl group-2') pyrazines; the chiral one-dimensional copper chain ferromagnetic molecular base material is crystallized in a monoclinic system non-centrosymmetric space group P21The unit cell parameters are as follows: α=γ=90°,β=105.247(2)°,Z=4,Dc=1.657g·cm–1,μ=1.289mm–1,R1=0.0310,wR2=0.0864。
the invention provides a preparation method of a chiral one-dimensional copper chain ferromagnetic molecular base material, which comprises the following steps:
(ii) reacting Cu (NO)3)2·6H2Dissolving O in acetonitrile, and stirring for 2-3min to obtain Cu (NO) solution3)2·6H2A solution of O in acetonitrile;
dissolving the S-configuration chiral mono-bidentate N-containing organic ligand L in dichloromethane, and stirring for 2-3min to obtain a dichloromethane solution in which L is dissolved;
dissolving Cu (NO) in the Cu solution obtained in the step (i)3)2·6H2Adding acetonitrile solution of O into dichloromethane solution dissolved with L obtained in the second step, continuously stirring for 15-20min at room temperature, filtering, transferring the obtained clear solution into a test tube, placing the test tube into a gas collection bottle filled with ether gas, obtaining blue crystals after 5-7 days, filtering, washing twice with acetonitrile, and drying at room temperature to obtain chiral one-dimensional copper chain ferromagnetic molecular base material [ Cu (L) (NO)3)2]n。
Preferably, Cu (NO) in said step (i)3)2·6H2Cu (NO) in O acetonitrile3)2·6H2The concentration of O is 0.02-0.035 mol/L.
Preferably, the concentration of L in the dichloromethane solution of the chiral mono-bidentate N-containing organic ligand L in the step (II) is 0.01-0.015 mol/L.
Preferably, Cu (NO) in said step (i)3)2·6H2The ratio of O to the amount of L in the step (II) is 1: 1.
Preferably, Cu (NO) in step (c)3)2·6H2The volume ratio of the acetonitrile solution of O to the dichloromethane solution of L is (3-5) to (6-10).
The invention has the beneficial effects that:
(1) the invention adopts S-configuration monodentate nitrogen-containing chiral organic ligand L (+) -2- (4 ', 5 ' -pinene pyridyl-2 ') pyrazine and Cu (NO)3)2·6H2And O reacts in a mixed solution of dichloromethane and acetonitrile, and a crystalline target product is synthesized in an ether atmosphere: the chiral one-dimensional copper chain ferromagnetic molecular base material has both chiral optical activity and ferromagnetic coupling performance, and no literature report of the one-dimensional copper chain complex which simultaneously shows the chiral optical activity and the ferromagnetic performance exists at present, so that the chiral metal complex family is enriched, and a foundation is laid for further research on the application of the chiral metal complex family.
(2) The chiral molecular-based ferromagnetic material has the advantages of mild synthesis conditions, good stability, easy separation and purification, simple synthesis method and process, easy post-treatment and high yield, avoids potential safety hazards possibly caused by a high-temperature and high-pressure solvent thermal method frequently adopted for preparing the complex, is expected to be used as a novel chiral molecular-based ferromagnetic material, and has wide application prospect in the aspect of magnetic-optical spinning electronic devices.
Drawings
FIG. 1 shows example 2 a chiral one-dimensional copper-chain ferromagnetic molecular base material [ Cu (L) (NO)3)2]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 example 2 chiral one-dimensional copper chain ferromagnetic molecular base material [ Cu (L) (NO) ]3)2]nThe one-dimensional copper chain molecular structure diagram of (a) has been omitted for clarity of the H atom.
FIG. 3 shows the chiral one-dimensional copper chain ferromagnetic molecular base material [ Cu (L) (NO) in example 23)2]nSchematic diagram of the right-hand helical structure of the middle nitrate-bridged one-dimensional copper chain.
FIG. 4 shows the chiral one-dimensional copper chain ferromagnetic molecular base material [ Cu (L) (NO) in example 33)2]nSolid state Circular Dichroism (CD) spectra of (a).
FIG. 5 shows example 3 chiral one-dimensional copper chain ferromagnetic molecular base material [ Cu (L) (NO) ]3)2]nThe product of the direct current magnetic susceptibility and the temperature is a graph with the change of the temperature.
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 preparation method of the S-configuration chiral mono-bidentate N-containing organic ligand L comprises the following steps:
A. adding 2-acetylpyrazine into a flask, and dissolving the 2-acetylpyrazine with a pyridine solution, wherein the mass-to-volume ratio of the 2-acetylpyrazine to the pyridine solution is (3.5-3.8) g, (10-15) mL; adding the iodine-dissolved pyridine solution into a flask, wherein the mass volume ratio of iodine to the pyridine solution is (12-15) g (20-25) mL; continuously stirring, heating the mixed solution in the flask to 115-125 ℃ for reaction for 4-5h, then cooling to room temperature, filtering, washing with pyridine twice, and drying in vacuum to obtain a brown 2- (acetylpyrazinyl) pyridine iodide salt intermediate;
B. placing the 2- (acetylpyrazinyl) pyridine iodide salt intermediate prepared in the step A and ammonium acetate into a three-neck flask, adding formamide, stirring, and adding S-configuration myrtenal (+) -myrtenal, wherein the mass-to-volume ratio of the 2- (acetylpyrazinyl) pyridine iodide salt intermediate to the ammonium acetate to the myrtenal (+) -myrtenal is (2.5-3.8) g, (3-4) g, (30-35) mL, (2-2.2) g, heating to 85-88 ℃, reacting for 15-15.5h under nitrogen, cooling to room temperature for 8-10h, filtering to obtain a light gray solid, adding ethyl acetate and ammonium acetate, and stirringAnd recrystallizing the mixed solvent of the methanol, and drying at room temperature to obtain the S-configuration chiral mono-and-bidentate N-containing organic ligand L. The yield was 81% (based on the intermediate). Elemental analysis: according to the formula C16H15N3(molecular weight 249.31): calculated value (%): c, 77.08; h, 6.06; n, 16.85; found (%): c, 76.83; h, 6.19; n, 16.57.
Synthesis of chiral mono-and bidentate N-containing organic ligands of S configuration example 1:
A. 3.5g of 2-acetylpyrazine was added to the flask, dissolved in 10mL of pyridine solution, and 20mL of pyridine solution containing 12g of iodine was added to the flask, with constant stirring, the mixture in the flask was heated to 125 ℃ for 4h, then cooled to room temperature, filtered, washed twice with pyridine, and dried in vacuo to give a brown 2- (acetylpyrazinyl) pyridinium iodide intermediate.
B. And C, placing 3.8g of 2- (acetylpyrazinyl) pyridine iodonium salt intermediate prepared in the step A and 4g of ammonium acetate in a three-neck flask, adding 35mL of formamide, stirring, adding 2.2g of S-configuration myrtenal (+) -myrtenal, heating to 85 ℃, reacting for 15.5h under nitrogen, cooling to room temperature for 10h, filtering to obtain a light gray solid, recrystallizing by using a mixed solvent of ethyl acetate and methanol, and drying at room temperature to obtain the S-configuration chiral mono-bidentate and N-bidentate organic ligand L.
Synthesis example 2 of chiral monodentate N-containing organic ligand of S configuration:
A. adding 3.8g of 2-acetylpyrazine into a flask, dissolving the 2-acetylpyrazine in 15mL of pyridine solution, adding 25mL of pyridine solution in which 15g of iodine is dissolved into the flask, continuously stirring, heating the mixed solution in the flask to 115 ℃ for reaction for 5 hours, then cooling to room temperature, filtering, washing with pyridine twice, and drying in vacuum to obtain a brown 2- (acetylpyrazinyl) pyridine iodonium salt intermediate;
B. placing 2.5g of 2- (acetylpyrazinyl) pyridine iodonium salt intermediate prepared in the step A and 3g of ammonium acetate in a three-neck flask, adding 30mL of formamide, stirring, adding 2g of S-configuration myrtenal (+) -myrtenal, heating to 88 ℃, reacting for 15h under nitrogen, cooling to room temperature for 8h, filtering to obtain a light gray solid, recrystallizing by using a mixed solvent of ethyl acetate and methanol, and drying at room temperature to obtain the S-configuration chiral mono-bidentate and N-bidentate organic ligand L.
Synthesis example 3 of chiral monodentate N-containing organic ligand of S configuration:
A. adding 3.6g of 2-acetylpyrazine into a flask, dissolving the 2-acetylpyrazine in 13mL of pyridine solution, adding 13.5g of iodine in 23mL of pyridine solution into the flask, continuously stirring, heating the mixed solution in the flask to 115 ℃, reacting for 5 hours, cooling to room temperature, filtering, washing with pyridine twice, and drying in vacuum to obtain a brown 2- (acetylpyrazinyl) pyridine iodonium salt intermediate;
B. and C, placing 3.2g of 2- (acetylpyrazinyl) pyridine iodonium salt intermediate prepared in the step A and 3.5g of ammonium acetate in a three-neck flask, adding 33mL of formamide, stirring, adding 2.1g of S-configuration myrtenal (+) -myrtenal, heating to 88 ℃, reacting for 15h under nitrogen, cooling to room temperature for 9h, filtering to obtain a light gray solid, recrystallizing by using a mixed solvent of ethyl acetate and methanol, and drying at room temperature to obtain the S-configuration chiral mono-bidentate and N-bidentate organic ligand L.
Example 1
A chiral one-dimensional copper chain ferromagnetic molecular base material has a molecular formula of [ Cu (L) (NO)3)2]nWherein L is an enantiomerically pure S configuration chiral mono-bidentate N-containing organic ligand: (+) -2- (4 ', 5 ' -pinene pyridyl-2 ') pyrazine.
The chiral one-dimensional copper chain ferromagnetic molecular base material is crystallized in a monoclinic system non-centrosymmetric space group P21The unit cell parameters are as follows:α=γ=90°,β=105.247(2)°,Z=4,Dc=1.657g·cm–1,μ=1.289mm–1,R1=0.0310,wR2=0.0864。
example 2
A preparation method of a chiral one-dimensional copper chain ferromagnetic molecular base material comprises the following steps:
(ii) reacting Cu (NO)3)2·6H2Dissolving O in acetonitrile, stirring for 2-3min to obtain Cu (NO) with concentration of 0.02-0.035mol/L3)2·6H2A solution of O in acetonitrile;
dissolving the S-configuration chiral mono-bidentate N-containing organic ligand L prepared by the method in dichloromethane, and stirring for 2-3min to obtain a dichloromethane solution of L with the concentration of 0.01-0.015 mol/L;
dissolving Cu (NO) in the Cu solution obtained in the step (i)3)2·6H2Adding acetonitrile solution of O into dichloromethane solution dissolved with L obtained in the step (II), wherein Cu (NO)3)2·6H2The volume ratio of the acetonitrile solution of O to the dichloromethane solution of L is (3-5) to (6-10), stirring for 15-20min at room temperature, filtering, transferring the obtained clear solution into a test tube, placing the test tube into a gas collection bottle filled with ether gas, obtaining blue crystals after 5-7 days, filtering, washing twice with acetonitrile, and drying at room temperature to obtain the chiral one-dimensional copper chain ferromagnetic molecular base material [ Cu (L)) (NO) (3)2]n。
Adopting a Perkin-Elmer 2400 element analyzer to analyze the content of elements C, H and N in the chiral one-dimensional copper chain ferromagnetic molecular base material according to the molecular formula C15H17N5O6Calculated Cu (molecular weight 438.88)% C, 43.79; h, 3.90; and N, 15.96. Found (%): c, 43.61; h, 3.79; and (6) N15.86.
The molecular structure of the chiral one-dimensional copper chain ferromagnetic molecular base material is tested by adopting a Bruker SMART APEX CCD diffractometer single crystal diffractometer at normal temperature. The result of analyzing diffraction data proves that the material presents a one-dimensional copper chain molecular structure, and the asymmetric unit of the material consists of one Cu2+Ion, a chiral mono-bidentate nitrogen-containing organic ligand L and two NO3 –The anionic ligand composition is shown in figure 1; NO3 –Linking Cu in adjacent asymmetric units as bridging ligands2+The molecular structure forming the one-dimensional copper chain is shown in FIG. 2; and the one-dimensional copper chain presents a right-handed helical structure as shown in fig. 3.
Example 3
Based on the synthesis example 1, a preparation method of a chiral one-dimensional copper chain ferromagnetic molecular base material comprises the following steps:
(ii) adding 30mg of Cu (NO)3)2·6H2Dissolving O in 3mL acetonitrile, stirring for 2min to obtain Cu (NO) dissolved in3)2·6H2A solution of O in acetonitrile;
dissolving 25mg of S-configuration chiral mono-bidentate N-containing organic ligand L prepared by the method in 6mL of dichloromethane, and stirring for 2min to obtain a dichloromethane solution in which the L is dissolved;
dissolving Cu (NO) in the Cu solution obtained in the step (i)3)2·6H2Adding acetonitrile solution of O into dichloromethane solution dissolved with L obtained in the step II, continuously stirring for 15min at room temperature, filtering, transferring the obtained clear solution into a test tube, placing the test tube into a 1000mL gas collection bottle filled with ether gas, obtaining blue crystals after 5 days, filtering, washing twice with 3mL acetonitrile, and drying at room temperature to obtain the chiral one-dimensional copper chain ferromagnetic molecular base material [ Cu (L) (NO)3)2]n。
The chiral one-dimensional copper chain ferromagnetic molecular base material [ Cu (L) (NO) of the present example was tested at room temperature using a Biologic MS-500Spectropolarimeter3)2]nThe solid state circular dichroism spectrum of (1) is shown in figure 4, the molecular base material shows a positive Cotton effect peak at the wavelength of lambda of 250nm, and shows a negative Cotton effect peak at the wavelength of lambda of 345nm, and the chiral optical activity of the one-dimensional copper chain molecular base material is confirmed.
The chiral one-dimensional copper chain ferromagnetic molecular base material [ Cu (L) (NO) of the embodiment is tested by using a Quantum Design MPMS-XL5 SQUID Magnetometer magnetic measuring instrument3)2]nThe temperature-changing direct-current magnetic susceptibility is shown in fig. 5, and the test result shows that: molar magnetic susceptibility (chi) of the material at room temperature (300K)M) Product of temperature (χ)MT) is 0.39cm3·K·mol–1This value is close to 1/2 spin of single Cu2+Theoretical value of ion 0.41cm3·K·mol–1(ii) a At a temperature of 300-2.0KThe product of molar magnetic susceptibility and temperature slowly increases along with the decrease of temperature, which fully indicates that Cu in one-dimensional copper chain2+Obvious ferromagnetic coupling exists between ions, and the magnetic coupling constant J is obtained by calculation to be 0.1cm–1。
Example 4
Based on the synthetic example 2, a preparation method of a chiral one-dimensional copper chain ferromagnetic molecular base material comprises the following steps:
(ii) adding 31.5mg of Cu (NO)3)2·6H2Dissolving O in 3.5mL acetonitrile, stirring for 3min to obtain Cu (NO) solution3)2·6H2A solution of O in acetonitrile;
dissolving 26.25mg of S-configuration chiral mono-bidentate N-containing organic ligand L prepared by the method in 7mL of dichloromethane, and stirring for 3min to obtain a dichloromethane solution in which the L is dissolved;
dissolving Cu (NO) in the Cu solution obtained in the step (i)3)2·6H2Adding acetonitrile solution of O into dichloromethane solution dissolved with L obtained in the second step, stirring for 20min at room temperature, filtering, transferring the obtained clear solution into a test tube, placing the test tube into a 1000mL gas collection bottle filled with ether gas, obtaining blue crystals after 6 days, filtering, washing twice with 3mL acetonitrile, and drying at room temperature to obtain chiral one-dimensional copper chain ferromagnetic molecular base material [ Cu (L) (NO)3)2]n。
Example 5
Based on the synthesis example 3, a preparation method of a chiral one-dimensional copper chain ferromagnetic molecular base material comprises the following steps:
(ii) adding 37.5mg of Cu (NO)3)2·6H2Dissolving O in 5mL acetonitrile, stirring for 3min to obtain Cu (NO) dissolved in3)2·6H2A solution of O in acetonitrile;
dissolving 31.25mg of S-configuration chiral mono-bidentate N-containing organic ligand L prepared by the method in 10mL of dichloromethane, and stirring for 3min to obtain a dichloromethane solution in which the L is dissolved;
dissolving Cu (NO) in the Cu solution obtained in the step (i)3)2·6H2O in acetonitrileAdding the obtained solution into dichloromethane solution dissolved with L obtained in the step II, continuously stirring for 20min at room temperature, filtering, transferring the obtained clear solution into a test tube, placing the test tube into a 1000mL gas collection bottle filled with ether gas, obtaining blue crystals after 6 days, filtering, washing twice with 5mL acetonitrile, and drying at room temperature to obtain the chiral one-dimensional copper chain ferromagnetic molecular base material [ Cu (L) (NO)3)2]n。
Example 6
Based on the synthesis example 3, a preparation method of a chiral one-dimensional copper chain ferromagnetic molecular base material comprises the following steps:
(ii) adding 24mg of Cu (NO)3)2·6H2Dissolving O in 4mL acetonitrile, stirring for 3min to obtain Cu (NO) dissolved in3)2·6H2A solution of O in acetonitrile;
dissolving 20mg of S-configuration chiral mono-bidentate N-containing organic ligand L prepared by the method in 8mL of dichloromethane, and stirring for 3min to obtain a dichloromethane solution in which the L is dissolved;
dissolving Cu (NO) in the Cu solution obtained in the step (i)3)2·6H2Adding acetonitrile solution of O into dichloromethane solution dissolved with L obtained in the step II, continuously stirring for 15min at room temperature, filtering, transferring the obtained clear solution into a test tube, placing the test tube into a 1000mL gas collection bottle filled with ether gas, obtaining blue crystals after 7 days, filtering, washing twice with 5mL acetonitrile, and drying at room temperature to obtain the chiral one-dimensional copper chain ferromagnetic molecular base material [ Cu (L) (NO)3)2]n。
Example 7
Based on the synthetic example 2, a preparation method of a chiral one-dimensional copper chain ferromagnetic molecular base material comprises the following steps:
(ii) 33.6mg of Cu (NO)3)2·6H2Dissolving O in 4mL acetonitrile, stirring for 3min to obtain Cu (NO) dissolved in3)2·6H2A solution of O in acetonitrile;
dissolving 28mg of S-configuration chiral mono-bidentate N-containing organic ligand L prepared by the method in 8mL of dichloromethane, and stirring for 3min to obtain a dichloromethane solution in which the L is dissolved;
dissolving Cu (NO) in the Cu solution obtained in the step (i)3)2·6H2Adding acetonitrile solution of O into dichloromethane solution dissolved with L obtained in the step II, continuously stirring for 15min at room temperature, filtering, transferring the obtained clear solution into a test tube, placing the test tube into a 1000mL gas collection bottle filled with ether gas, obtaining blue crystals after 7 days, filtering, washing twice with 5mL acetonitrile, and drying at room temperature to obtain the chiral one-dimensional copper chain ferromagnetic molecular base material [ Cu (L) (NO)3)2]n。
The preparation method of the chiral one-dimensional copper chain ferromagnetic molecular base material provided by the invention is 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 (7)
1. A chiral one-dimensional copper chain ferromagnetic molecular base material is characterized in that: the molecular formula of the chiral one-dimensional copper chain ferromagnetic molecular base material is [ Cu (L) (NO)3)2]nWherein L is S configuration chiral mono-bidentate N-containing organic ligand: (+) -2- (4 ', 5 ' -pinene pyridyl-2 ') pyrazine.
2. The chiral one-dimensional copper chain ferromagnetic molecular-based material of claim 1, wherein: the chiral one-dimensional copper chain ferromagnetic molecular base material is crystallized in a monoclinic system non-centrosymmetric space group P21The unit cell parameters are as follows:α=γ=90°,β=105.247(2)°,Z=4,Dc=1.657g·cm–1,μ=1.289mm–1,R1=0.0310,wR2=0.0864。
3. a method for preparing a chiral one-dimensional copper chain ferromagnetic molecular base material is characterized by comprising the following steps: the method comprises the following steps:
(ii) reacting Cu (NO)3)2·6H2Dissolving O in acetonitrile, and stirring for 2-3min to obtain Cu (NO) solution3)2·6H2A solution of O in acetonitrile;
dissolving the S-configuration chiral mono-bidentate N-containing organic ligand L in dichloromethane, and stirring for 2-3min to obtain a dichloromethane solution in which L is dissolved;
dissolving Cu (NO) in the Cu solution obtained in the step (i)3)2·6H2Adding acetonitrile solution of O into dichloromethane solution dissolved with L obtained in the second step, continuously stirring for 15-20min at room temperature, filtering, transferring the obtained clear solution into a test tube, placing the test tube into a gas collection bottle filled with ether gas, obtaining blue crystals after 5-7 days, filtering, washing twice with acetonitrile, and drying at room temperature to obtain chiral one-dimensional copper chain ferromagnetic molecular base material [ Cu (L) (NO)3)2]n。
4. The method for preparing a chiral one-dimensional copper chain ferromagnetic molecular base material according to claim 3, wherein: in the step (i), Cu (NO)3)2·6H2Cu (NO) in O acetonitrile3)2·6H2The concentration of O is 0.02-0.035 mol/L.
5. The method for preparing a chiral one-dimensional copper chain ferromagnetic molecular base material according to claim 3, wherein: in the step (II), the concentration of L in the dichloromethane solution of the chiral mono-bidentate N-containing organic ligand L is 0.01-0.015 mol/L.
6. Method for preparing chiral one-dimensional copper chain ferromagnetic molecular base material according to claim 3, 4 or 5The preparation method is characterized by comprising the following steps: in the step (i), Cu (NO)3)2·6H2The ratio of O to the amount of L in the step (II) is 1: 1.
7. The method for preparing a chiral one-dimensional copper chain ferromagnetic molecular base material according to claim 3, 4 or 5, wherein: step III of Cu (NO)3)2·6H2The volume ratio of the acetonitrile solution of O to the dichloromethane solution of L is (3-5) to (6-10).
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