CN109180708B - Acetate bridged chiral binuclear copper complex and preparation method thereof - Google Patents
Acetate bridged chiral binuclear copper complex and preparation method thereof Download PDFInfo
- Publication number
- CN109180708B CN109180708B CN201811182671.9A CN201811182671A CN109180708B CN 109180708 B CN109180708 B CN 109180708B CN 201811182671 A CN201811182671 A CN 201811182671A CN 109180708 B CN109180708 B CN 109180708B
- Authority
- CN
- China
- Prior art keywords
- chiral
- acetate
- pyridine
- copper complex
- bridged
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 150000004699 copper complex Chemical class 0.000 title claims abstract description 35
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000013110 organic ligand Substances 0.000 claims abstract description 23
- 239000010949 copper Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- 238000001914 filtration Methods 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- OPXQOHWDOVAEGE-UHFFFAOYSA-N 1-pyridin-1-ium-4-yl-2-pyridin-2-ylethanone iodide Chemical compound [I-].N1=C(C=CC=C1)CC(=O)C1=CC=[NH+]C=C1 OPXQOHWDOVAEGE-UHFFFAOYSA-N 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 8
- WMQUKDQWMMOHSA-UHFFFAOYSA-N 1-pyridin-4-ylethanone Chemical compound CC(=O)C1=CC=NC=C1 WMQUKDQWMMOHSA-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000005695 Ammonium acetate Substances 0.000 claims description 6
- KMRMUZKLFIEVAO-RKDXNWHRSA-N Myrtenal Natural products C1[C@H]2C(C)(C)[C@@H]1CC=C2C=O KMRMUZKLFIEVAO-RKDXNWHRSA-N 0.000 claims description 6
- 229940043376 ammonium acetate Drugs 0.000 claims description 6
- 235000019257 ammonium acetate Nutrition 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 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 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- KMRMUZKLFIEVAO-IUCAKERBSA-N (1s,5r)-6,6-dimethylbicyclo[3.1.1]hept-3-ene-4-carbaldehyde Chemical compound C1[C@@H]2C(C)(C)[C@H]1CC=C2C=O KMRMUZKLFIEVAO-IUCAKERBSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 230000005291 magnetic effect Effects 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 9
- 230000003287 optical effect Effects 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000008878 coupling Effects 0.000 abstract description 5
- 238000010168 coupling process Methods 0.000 abstract description 5
- 238000005859 coupling reaction Methods 0.000 abstract description 5
- 230000005290 antiferromagnetic effect Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000000696 magnetic material Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001588 bifunctional effect Effects 0.000 abstract description 2
- 229910001431 copper ion Inorganic materials 0.000 abstract description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 abstract description 2
- 230000001808 coupling effect Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- -1 4- (pyridylacetyl) pyridine iodate Chemical compound 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001142 circular dichroism spectrum Methods 0.000 description 1
- 150000001879 copper Chemical class 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
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005390 triboluminescence Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/08—Copper compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/42—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of organic or organo-metallic materials, e.g. graphene
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention discloses an acetate bridged chiral binuclear copper complex and a preparation method thereof, wherein the molecular formula of the complex is Cu2(CH3COO)4(L)2The invention uses chiral monodentate N-containing organic ligand L [ (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine]The chiral binuclear copper complex with the bridged acetate is obtained by the reaction with copper acetate, and the method has the advantages of simple process, normal-temperature reaction, easy post-treatment and high yield. The complex has chiral optical activity and strong antiferromagnetic coupling performance, and is a rare chiral magnetic bifunctional molecular base material. The acetate is used as a bridging group, and the bridging distance is short, so that the magnetic coupling effect between two copper ions Cu (II) is enhanced, the molecular material has strong magnetic coupling performance, the chiral magnetic material has mild synthesis conditions and easy separation and purification, and has wide application prospects in the aspects of nonlinear optical materials, information storage devices, optical-magnetic molecular devices and the like.
Description
Technical Field
The invention belongs to the technical field of molecule-based chiral functional materials and preparation and application thereof, and particularly relates to a binuclear copper complex with both chiral optical activity and magnetism and a preparation method thereof.
Background
Chirality is a fundamental property of nature and plays an important role in the fields of chemistry, material science, biology, medicine, and the like. Due to the non-centrosymmetry of the molecular structure, the chiral complex has special properties closely related to the non-centrosymmetric structure, such as: non-linear optical activity, second harmonic generation, chiral circular polarization luminescence, triboluminescence, ferroelectricity, piezoelectricity and other interesting physical properties. Especially, chirality is introduced into the molecular structure of the magnetic complex, so that the complex generates interesting magnetic chiral color direction effect. Therefore, the preparation of molecule-based multifunctional materials with both chiral optical activity and magnetic property is the subject of intense research by chemists and materials scientists. However, due to the limited availability of chiral ligands; in addition, chiral ligands are prone to racemization during crystallization of the synthetic complex, resulting in no chiral optical activity of the target product. The preparation of chiral complexes is extremely challenging due to the above factors. At present, no article of an acetate-bridged chiral binuclear copper complex is published, and no related patent exists.
Disclosure of Invention
The invention aims to provide an acetate bridged chiral binuclear copper complex molecular-based magnetic material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
an acetate bridged chiral binuclear copper complex, the molecular formula of which is Cu2(CH3COO)4(L)2Wherein L is [ (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine]Structural formula is
A preparation method of an acetate bridged chiral binuclear copper complex comprises the following steps:
dissolving copper acetate Cu (CH)3COO)2·H2Adding the methanol solution of O into acetonitrile solution dissolved with chiral monodentate N-containing organic ligand L, stirring for 20-25 min, filtering, slowly volatilizing the obtained blue clear solution at room temperature, obtaining blue crystals after one week, filtering, washing with acetonitrile and water respectively, and drying at room temperature to obtain acetic acidRadical-bridged chiral binuclear copper complexes.
The Cu (CH)3COO)2·H2The mass ratio of O to the monodentate nitrogen-containing chiral organic ligand L is 1: 1.
The preparation method of the monodentate nitrogen-containing chiral organic ligand L in the step (1) comprises the following steps:
preparation of 4- (pyridylacetyl) pyridine iodide salt intermediate: adding 4.0 g of 4-acetylpyridine into a 250mL round-bottom flask, dissolving with 15-20 mL of pyridine solution, adding 15-20 mL of pyridine solution dissolved with 12-15 g of iodine into the round-bottom flask, heating the mixture to 100-110 ℃, reacting for 4-4.5 hours, cooling to room temperature, filtering, washing twice with a small amount of pyridine, and drying in vacuum to obtain a gray solid, namely a 4- (pyridylacetyl) pyridine iodide intermediate;
b. synthesizing a chiral monodentate N-containing organic ligand L: weighing 3.5 g of the 4- (pyridine acetyl) pyridine iodide salt intermediate prepared in the step a and 1.8-2.7 g of ammonium acetate (NH)4Ac) is placed in a three-neck flask, and 35-45 mL of formamide (CH) is added3CONH2) 1.8 g of myrtenal (-) -myrtenoal (produced by Bailingwei) is added under continuous stirring, heated to 75-85 ℃ and reacted for 12-12.5 hours under nitrogen. And filtering the product to obtain a milky white solid, washing with water, recrystallizing with ethanol, and drying the solid to obtain the chiral monodentate N-containing organic ligand L.
The invention has the beneficial effects that: (1) the preparation method of the acetate bridged chiral binuclear copper complex has the advantages of simple process, normal-temperature reaction, easy post-treatment and high yield. (2) The acetate-bridged chiral binuclear copper complex prepared by the invention has chiral optical activity and strong antiferromagnetic coupling performance. Is a rare chiral magnetic bifunctional molecular base material. In addition, acetate acts as a bridging group, which enhances the magnetic coupling between the two copper ions Cu (II) due to the short bridging distance. Resulting in a molecular material with strong magnetic coupling properties. At present, the acetate-bridged chiral binuclear copper complex is not reported, so that the invention also fills the blank of the materials. (3) The chiral magnetic material has the advantages of mild synthesis conditions, high yield, strong stability, good reproducibility and easy separation and purification, and has wide application prospects in the aspects of nonlinear optical materials, information storage devices, photo-magnetic molecular devices and the like.
Drawings
FIG. 1 is the acetic acid radical bridged chiral binuclear copper complex Cu of example 12(CH3COO)4(L)2The molecular structure of (1);
FIG. 2 shows the acetate-bridged chiral binuclear copper complex Cu of example 12(CH3COO)4(L)2The chiral circular dichroism spectrum of (1);
FIG. 3 is the acetic acid radical bridged chiral binuclear copper complex Cu of example 12(CH3COO)4(L)2The product of the direct current magnetic susceptibility and the temperature is a graph with the change of the temperature.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.
Example 1
A preparation method of an acetate bridged chiral binuclear copper complex comprises the following steps:
(1) the preparation method of the monodentate nitrogen-containing chiral organic ligand L comprises the following steps:
preparation of 4- (pyridylacetyl) pyridine iodide salt intermediate: adding 4.0 g of 4-acetylpyridine into a 250mL round-bottom flask, dissolving by using 18mL of pyridine solution, adding 18mL of pyridine solution dissolved with 13 g of iodine into the round-bottom flask, heating the mixture to 105 ℃, reacting for 4 hours, cooling to room temperature, filtering, washing twice by using a small amount of pyridine, and drying in vacuum to obtain a gray solid, namely a 4- (pyridylacetyl) pyridine iodate intermediate;
b. synthesis of monodentate nitrogen-containing chiral organic ligand L: weighing the product prepared in step a3.5 g of 4- (pyridylacetyl) pyridiniodide intermediate and 2 g of ammonium acetate (NH)4Ac) is placed in a three-neck flask, and 35-45 mL of formamide (CH) is added3CONH2). 1.8 g of myrtenal (-) -myrtenoal (from Bailingwei) are added with constant stirring. The reaction was heated to 80 ℃ and reacted under nitrogen for 12 hours. The product was filtered to give a milky white solid, washed with water, recrystallized from ethanol, and the solid was dried. The yield was 85% (based on intermediate). Elemental analysis: according to the formula C17H18N2(molecular weight 250.33): calculated value (%): C, 81.56; h, 7.25; n, 11.19; found (%): C, 81.61; h, 7.32; n, 11.27. Infrared spectrum IR (KBr) 2949(s),2992(m),2867(v),1584(m),1457(s),1387(m),782(m), 755(s).
(2) Acetate bridged chiral binuclear copper complex Cu2(CH3COO)4(L)2The preparation of (1): 10mL of Cu (CH)3COO)2·H2Adding methanol solution of O (20mg,0.1mmol) dissolved with chiral monodentate N-containing organic ligand L [ (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine]Stirring the mixture in acetonitrile solution (10mL) (25mg,0.1mmol) for 20 minutes, filtering, naturally volatilizing the obtained clear solution, obtaining blue crystals after one week, filtering, washing with acetonitrile and water respectively, and drying at room temperature to obtain the acetate bridged chiral binuclear copper complex with the calculated yield of 89 percent (calculated according to Cu).
Chiral binuclear copper complex Cu bridged to acetate by adopting Perkin-Elmer 2400 element analyzer2(CH3COO)4(L)2Content analysis of C, H and N was performed according to the formula (C)42H47N4O8Cu2) Calculated value (%): C, 58.46; h, 5.49; and N, 6.49. Found (%): c, 58.37; h, 5.53; and N6.58. The Bruker SMART APEX CCD diffractometer single crystal diffractometer is adopted to measure the Cu of the acetate bridged chiral binuclear copper complex at normal temperature2(CH3COO)4(L)2The molecular structure of (1) (see FIG. 1). In the chiral complex, each Cu atom is respectively coordinated with one N atom in one chiral monodentate N-containing organic ligand L, and two O atoms in 4 acetate groups are simultaneously coordinatedTwo copper atoms are bridged to form a chiral binuclear copper structure. The detection of the acetate bridged chiral binuclear copper complex Cu by using a biological MS-500spectropolarimeter2(CH3COO)4(L)2As shown in fig. 2, the complex shows a positive Cotton effect at λ -214 nm and negative Cotton effect signals at λ -263 and 321nm, respectively, thereby proving its chiral optical activity.
Acetate bridged chiral binuclear copper complex Cu2(CH3COO)4(L)2The magnetic property test of (1):
test of an acetate bridged chiral binuclear copper complex Cu by using a Quantum Design MPMS-XL5SQUID megnetometer magnetic measuring instrument2(CH3COO)4(L)2Dc magnetic susceptibility. The test result shows that: acetate bridged chiral binuclear copper complex Cu2(CH3COO)4(L)2Between the temperature of 300 and 100K, the product of the molar magnetic susceptibility and the temperature rapidly decreases with decreasing temperature (shown in FIG. 3), which fully indicates that strong antiferromagnetic coupling exists between the two Cu centers.
Example 2
A preparation method of an acetate bridged chiral binuclear copper complex comprises the following steps:
(1) the preparation method of the chiral monodentate N-containing organic ligand L comprises the following steps:
preparation of 4- (pyridylacetyl) pyridine iodide salt intermediate: adding 4.0 g of 4-acetylpyridine into a 250mL round-bottom flask, dissolving the 4-acetylpyridine by using 15mL of pyridine solution, adding 15mL of pyridine solution dissolved with 12 g of iodine into the round-bottom flask, heating the mixture to 100 ℃, reacting for 4 hours, cooling to room temperature, filtering, washing twice by using a small amount of pyridine, and drying in vacuum to obtain a gray solid, namely a 4- (pyridine acetyl) pyridine iodate intermediate;
b. synthesizing a chiral monodentate N-containing organic ligand L: weighing 3.5 g of the 4- (pyridylacetyl) pyridinium iodide intermediate prepared in step a and 1.8 g of ammonium acetate (NH)4Ac) was placed in a three-necked flask, and 35mL of formamide (CH) was added3CONH2). Adding under stirring1.8 g of myrtenal (-) -myrtenoal (from Bailingwei). The reaction was heated to 75 ℃ and reacted under nitrogen for 12 hours. And filtering the product to obtain a milky white solid, washing with water, recrystallizing with ethanol, and drying the solid to obtain the monodentate nitrogen-containing chiral organic ligand L.
(2) Acetate bridged chiral binuclear copper complex Cu2(CH3COO)4(L)2The preparation of (1): 10mL of Cu (CH)3COO)2·H2Adding methanol solution of O (40mg,0.2mmol) dissolved with chiral monodentate N-containing organic ligand L [ (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine]Stirring (50mg,0.2mmol) in acetonitrile solution (20mL) for 25 minutes, filtering, naturally volatilizing the obtained clear solution, obtaining blue crystals after one week, filtering, washing with acetonitrile and water respectively, and drying at room temperature to obtain the acetate bridged chiral binuclear copper complex.
Example 3
A preparation method of an acetate bridged chiral binuclear copper complex comprises the following steps:
(1) the preparation method of the chiral monodentate N-containing organic ligand L comprises the following steps:
preparation of 4- (pyridylacetyl) pyridine iodide salt intermediate: adding 4.0 g of 4-acetylpyridine into a 250mL round-bottom flask, dissolving the 4-acetylpyridine by using 20mL of pyridine solution, adding 20mL of pyridine solution dissolved with 15 g of iodine into the round-bottom flask, heating the mixture to 110 ℃, reacting for 4.5 hours, cooling to room temperature, filtering, washing twice by using a small amount of pyridine, and drying in vacuum to obtain a gray solid, namely a 4- (pyridylacetyl) pyridine iodide salt intermediate;
b. synthesizing a chiral monodentate N-containing organic ligand L: weighing 3.5 g of the 4- (pyridylacetyl) pyridinium iodide intermediate prepared in step a and 2.7 g of ammonium acetate (NH)4Ac) was placed in a three-necked flask and 45mL of formamide (CH) was added3CONH2). 1.8 g of myrtenal (-) -myrtenoal (manufactured by Alfa) was added with continuous stirring. The reaction was heated to 85 ℃ and reacted under nitrogen for 12.5 hours. And filtering the product to obtain a milky white solid, washing with water, recrystallizing with ethanol, and drying the solid to obtain the chiral monodentate N-containing organic ligand L.
(2) Acetate bridged chiral binuclear copper complex Cu2(CH3COO)4(L)2The preparation of (1): 15mL of Cu (CH)3COO)2·H2Adding methanol solution of O (60mg,0.3mmol) dissolved with chiral monodentate N-containing organic ligand L [ (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine]Stirring the mixture in acetonitrile solution (10mL) (75mg,0.3mmol) for 20 minutes, filtering, naturally volatilizing the obtained clear solution, obtaining blue crystals after one week, filtering, washing with acetonitrile and water respectively, and drying at room temperature to obtain the acetate bridged chiral binuclear copper complex.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (4)
1. An acetate bridged chiral binuclear copper complex, the molecular formula of which is Cu2(CH3COO)4(L)2Wherein L is [ (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine]Structural formula is
2. The method for preparing an acetate-bridged chiral binuclear copper complex according to claim 1, characterized by the following steps: will dissolve Cu (CH)3COO)2·H2Adding the methanol solution of O into acetonitrile solution dissolved with chiral monodentate N-containing organic ligand L, stirring for 20-25 min, filtering, slowly volatilizing the obtained blue clear solution at room temperature to obtain blue crystals after one week, filtering, and respectively using acetonitrile and waterWashing and drying at room temperature to obtain the acetate bridged chiral binuclear copper complex.
3. The method for preparing an acetate-bridged chiral binuclear copper complex according to claim 2, characterized in that: the Cu (CH)3COO)2·H2The ratio of the amount of O to the amount of the substance of the chiral monodentate nitrogen-containing organic ligand L is 1: 1.
4. The method for preparing an acetate-bridged chiral binuclear copper complex according to claim 2, characterized in that: the preparation method of the chiral monodentate nitrogen-containing organic ligand L comprises the following steps:
preparation of 4- (pyridylacetyl) pyridine iodide salt intermediate: adding 4.0 g of 4-acetylpyridine into a 250mL round-bottom flask, dissolving with 15-20 mL of pyridine solution, adding 15-20 mL of pyridine solution dissolved with 12-15 g of iodine into the round-bottom flask, heating the mixture to 100-110 ℃, reacting for 4-4.5 hours, cooling to room temperature, filtering, washing twice with a small amount of pyridine, and drying in vacuum to obtain a gray solid, namely a 4- (pyridylacetyl) pyridine iodide intermediate;
b. synthesizing a chiral monodentate N-containing organic ligand L: weighing 3.5 g of the 4- (pyridine acetyl) pyridine iodonium salt intermediate prepared in the step a and 1.8-2.7 g of ammonium acetate, placing the intermediate and the ammonium acetate in a three-neck flask, adding 35-45 mL of formamide, adding 1.8 g of myrtenal (-) -myrtenal under continuous stirring, heating to 75-85 ℃, reacting for 12-12.5 hours under nitrogen, filtering the product to obtain a milky white solid, washing with water, recrystallizing with ethanol, and drying the solid to obtain the monodentate nitrogen-containing chiral organic ligand L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811182671.9A CN109180708B (en) | 2018-10-11 | 2018-10-11 | Acetate bridged chiral binuclear copper complex and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811182671.9A CN109180708B (en) | 2018-10-11 | 2018-10-11 | Acetate bridged chiral binuclear copper complex and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109180708A CN109180708A (en) | 2019-01-11 |
| CN109180708B true CN109180708B (en) | 2020-12-25 |
Family
ID=64947648
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811182671.9A Active CN109180708B (en) | 2018-10-11 | 2018-10-11 | Acetate bridged chiral binuclear copper complex and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109180708B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114181232A (en) * | 2021-12-06 | 2022-03-15 | 郑州轻工业大学 | Chiral one-dimensional copper chain ferromagnetic molecular base material and preparation method thereof |
-
2018
- 2018-10-11 CN CN201811182671.9A patent/CN109180708B/en active Active
Non-Patent Citations (3)
| Title |
|---|
| Synthesis and thermal behavior of 4,4"-bipyridyl and 2,4"-bipyridyl complexes of Co(II), Ni(II) and Cu(II) thiocyanates;Czakis-Sulikowska, D et al.;《Journal of Thermal Analysis》;19961231;第1763-1776页 * |
| Tetra-μ-acetato-κ8O:O"-bis{[2-methylsulfanyl-4-(pyridin-4-yl- κN)pyrimidine]copper(II)}(Cu-Cu);Hai-Bin Zhu et al.;《Acta Crystallographica, Section E: Structure Reports Online》;20111231;第m1168页 * |
| 具有光、磁和铁电性质的手性分子基稀土功能材料的构筑与研究;和来福;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20120615;第B014-333页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109180708A (en) | 2019-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Min et al. | One-dimensional copper–pyridinedicarboxylate polymer containing square-planar Cu (II) centers exhibiting antiferromagnetic coupling | |
| Konar et al. | Crystal structure and magnetic behavior of a copper (II)-(pyrazine 2, 3-dicarboxylate) coordination polymer: 3D architecture stabilized by H-bonding | |
| CN104230968B (en) | Cadmium-containing dual-core polymer with mixed-ligand and preparation method of cadmium-containing dual-core polymer | |
| Yoshinari et al. | Parity-Controlled Self-Assembly of Supramolecular Helices in a Gold (I)–Copper (II) Coordination System with Penicillamine and Bis (diphenylphosphino) alkane | |
| Khalaji et al. | Two different 1D-chains in the structures of the copper (I) coordination polymers based on bidentate Schiff-base building units and thiocyanate anions as bridging ligands | |
| CN109180708B (en) | Acetate bridged chiral binuclear copper complex and preparation method thereof | |
| Yadav et al. | Spontaneous resolution upon crystallization and preferential induction of chirality in a discrete tetrahedral zinc (II) complex comprised of achiral precursors | |
| Wu et al. | An S= 3 cyanide-bridged tetranuclear Fe III 2 Ni II 2 square that exhibits slow relaxation of magnetization: synthesis, structure and magnetic properties | |
| González et al. | Magnetic studies on hexahalorhenate (IV) salts of ferrocenium cations [Fe (C5R5) 2] 2 [ReX6](R= H, CH3; X= Cl, Br, I) | |
| Milway et al. | Trinuclear complexes of a series of ‘tritopic’hydrazide ligands—structural and magnetic properties | |
| CN109096314A (en) | (-) -4,5- firpene-bipy 2,2' bipyridyl copper nitrate monokaryon chiral coordination compound and preparation method thereof | |
| CN109180709B (en) | (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine hexafluoroacetylacetone copper complex and preparation method thereof | |
| Han et al. | Adduct effects on structure and luminescence in a series of new dithiocarbamatogold (I) complexes | |
| Okubo et al. | Synthesis, structure, and magnetic properties of one-dimensional copper (II) coordination polymer,[Cu (pyrazine-2, 3-dicarboxylate)(H2O) 2]· 2H2On | |
| Karadağ et al. | Preparation, structural, magnetic and thermal properties of two heterobimetallic cyano-bridged nickel (II)–copper (II)/platinum (II) coordination polymers | |
| CN109081854A (en) | (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine hexafluoroacetylacetone manganese complex and preparation method | |
| JP7079494B2 (en) | New compound and its synthesis method | |
| CN102827169B (en) | Novel porphyrin ligand and metal complex, preparation method and application for novel porphyrin ligand | |
| Delgado et al. | Structural diversity of copper complexes with angular and linear dipyridyl ligands | |
| CN109232616B (en) | (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex and preparation method thereof | |
| Wu et al. | Infinite chiral single-helical structures formed by the self-assembly of Cu (II)-N-(2-pyridylmethyl)-aspartate complexes | |
| CN109456344B (en) | (-) -2- (4 ', 5 ' -pinene pyridyl-2 ') pyrazine beta-diketone samarium complex and preparation method thereof | |
| CN114181232A (en) | Chiral one-dimensional copper chain ferromagnetic molecular base material and preparation method thereof | |
| CN109265447B (en) | (+) -2, 6-di (4, 5-pinene-2-pyridyl) pyridine chiral mononuclear manganese complex and preparation method thereof | |
| CN108912180B (en) | (-) -2- (4 ', 5 ' -pinene pyridyl-2 ') pyrazine azide cobalt (III) complex and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |