CN109180708A - A kind of chiral binuclear copper complex of acetate bridging and preparation method thereof - Google Patents
A kind of chiral binuclear copper complex of acetate bridging and preparation method thereof Download PDFInfo
- Publication number
- CN109180708A CN109180708A CN201811182671.9A CN201811182671A CN109180708A CN 109180708 A CN109180708 A CN 109180708A CN 201811182671 A CN201811182671 A CN 201811182671A CN 109180708 A CN109180708 A CN 109180708A
- Authority
- CN
- China
- Prior art keywords
- chiral
- acetate
- pyridine
- copper complex
- preparation
- 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.)
- Granted
Links
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 title claims abstract description 35
- 150000004699 copper complex Chemical class 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000010949 copper Substances 0.000 claims abstract description 26
- 239000013110 organic ligand Substances 0.000 claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- BJDYCCHRZIFCGN-UHFFFAOYSA-N pyridin-1-ium;iodide Chemical compound I.C1=CC=NC=C1 BJDYCCHRZIFCGN-UHFFFAOYSA-N 0.000 claims description 11
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 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 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical class N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 5
- KMRMUZKLFIEVAO-RKDXNWHRSA-N Myrtenal Natural products C1[C@H]2C(C)(C)[C@@H]1CC=C2C=O KMRMUZKLFIEVAO-RKDXNWHRSA-N 0.000 claims description 5
- 240000005125 Myrtus communis Species 0.000 claims description 5
- 235000019257 ammonium acetate Nutrition 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 150000003222 pyridines Chemical class 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- ZFTKWAVDJBKFCS-UHFFFAOYSA-N iodine;pyridine Chemical compound [I].C1=CC=NC=C1 ZFTKWAVDJBKFCS-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 230000005291 magnetic effect Effects 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 10
- 230000003287 optical effect Effects 0.000 abstract description 9
- 230000008878 coupling Effects 0.000 abstract description 6
- 238000010168 coupling process Methods 0.000 abstract description 6
- 238000005859 coupling reaction Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 abstract description 3
- 239000000696 magnetic material Substances 0.000 abstract description 3
- 238000012805 post-processing Methods 0.000 abstract description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 2
- 230000005290 antiferromagnetic effect Effects 0.000 abstract description 2
- 230000001588 bifunctional effect Effects 0.000 abstract description 2
- 229910001431 copper ion Inorganic materials 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract 1
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 6
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 description 4
- 239000005695 Ammonium acetate Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229940043376 ammonium acetate Drugs 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000002983 circular dichroism Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- 239000000052 vinegar Substances 0.000 description 2
- -1 Dichlorodiphenyl Acetate Chemical compound 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 241000233855 Orchidaceae Species 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005303 antiferromagnetism Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- RDRCCJPEJDWSRJ-UHFFFAOYSA-N pyridine;1h-pyrrole Chemical compound C=1C=CNC=1.C1=CC=NC=C1 RDRCCJPEJDWSRJ-UHFFFAOYSA-N 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005390 triboluminescence Methods 0.000 description 1
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 chiral binuclear copper complex of a kind of acetate bridging and preparation method thereof, the molecular formula of the complex is Cu2(CH3COO)4(L)2, the present invention is by chiral monodentate organic ligand L:[(- containing N) -2- (4 '-pyridyl group) -4,5- firpene-pyridine] and it is reacted with copper acetate, obtain the chiral binuclear copper complex of acetate bridging, simple process, normal-temperature reaction, easy post-processing and yield are high.The complex had not only had chiral optical activity but also had had strong antiferro-magnetic coupling performance, was rare chiral magnetic bifunctional molecule sill.Acetate is as bridge linkage group, since bridging is apart from short, so that the magnetic coupling interaction between two copper ion Cu (II) enhances, cause molecular material that there is very strong magnetic coupling performance, the chirality magnetic materials synthesis mild condition isolates and purifies easy, has broad application prospects in terms of nonlinear optical material, information recording device and light-magnetism molecule.
Description
Technical field
The invention belongs to molecule base chirality function material and its preparation and application technical fields, in particular to a kind of to have
Chiral optical activity has magnetic dicopper complex4-amino-3 and preparation method thereof simultaneously again.
Background technique
Chirality is the essential attribute of nature, plays important work in chemistry, material science, biology and medicine and other fields
With.Due to the non-centrosymmetry of molecular structure, chiral coordination compound has the particularity closely related with non-centrosymmetric structure
Can, such as: non-linear optical active, the second harmonic generate, chiral circular polarised luminescence, tribo-luminescence, ferroelectricity and piezoelectricity have
The physical property of interest.Chirality is introduced especially in the molecular structure of magnetic partner, and complex can be made to generate interesting magnetic hand
Property color is to effect.Therefore, preparing while having chiral optical activity again to have molecule Quito functional material of magnetic property is chemistry
The hot research topic of family and material scholars.However, since available chiral ligand is limited;In addition, chiral ligand is closing
At racemization is easy in the crystallization process of complex, cause target product without how chiral optical activity.Due to above-mentioned factor
Influence so that the preparation of chiral coordination compound have it is extremely challenging.Currently, there has been no the chiral binuclear copper of acetate bridging
The article of complex is delivered, and there are no related patents.
Summary of the invention
The object of the present invention is to provide a kind of chiral binuclear copper complex molecule based magnetic materials of acetate bridging and systems
Preparation Method, the preparation method simple process, normal-temperature reaction, easy post-processing and yield are high.
To achieve the above object, the invention adopts the following technical scheme:
A kind of chiral binuclear copper complex of acetate bridging, point of the chiral binuclear copper complex of the acetate bridging
Minor is Cu2(CH3COO)4(L)2, wherein L is [(-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine], and structural formula is
A kind of preparation method of the chiral binuclear copper complex of acetate bridging, steps are as follows:
It will be dissolved with copper acetate Cu (CH3COO)2·H2The methanol solution of O is added to dissolved with chiral monodentate organic ligand containing N L's
In acetonitrile solution, after stirring 20~25 minutes, filtering, gained clear solution blue slowly volatilizees at room temperature, obtains orchid after a week
Color crystal, filtering obtain the chiral binuclear copper complex of acetate bridging with acetonitrile and water washing, drying at room temperature respectively.
Cu (the CH3COO)2·H2The ratio between the amount of substance of O and the nitrogenous chiral organic ligand L of monodentate are 1:1.
In the step (1) monodentate nitrogenous chiral organic ligand L's the preparation method is as follows:
A.4- in the round-bottomed flask of 250mL, 4.0 grams of 4- the preparation of (pyridine acetyl group) pyridinium iodide intermediate: are added
Acetylpyridine is dissolved with 15~20mL pyridine solution, round bottom will be added dissolved with 15~20mL pyridine solution of 12~15 grams of iodine
In flask, mixture is heated to 100~110 DEG C, reacts 4~4.5 hours, then cools to room temperature and filter, with a small amount of pyrrole
Pyridine flushing is secondary, and it is 4- (pyridine acetyl group) pyridinium iodide intermediate that gray solid is obtained after vacuum drying;
B. the synthesis of chiral monodentate organic ligand containing N L: 3.5 grams of 4- (pyridine acetyl group) pyrrole that step a is prepared is weighed
Pyridine salt compounded of iodine intermediate and 1.8~2.7 grams of ammonium acetate (NH4Ac it) is placed in three-neck flask, adds the formamide of 35~45mL
(CH3CONH2), it is stirred continuously lower myrte (-)-myrtenal (Bellingwell company's production) for being added 1.8 grams, is heated to
It 75-85 DEG C, reacts 12-12.5 hours under nitrogen.Off-white solid is obtained by filtration in above-mentioned product, and is rinsed with water, ethyl alcohol is used
Recrystallization, it is then that solid is dry, obtain chiral monodentate organic ligand containing N L.
Beneficial effects of the present invention: (1) of the invention by a kind of chiral monodentate organic ligand L:[(- containing N) -2- (4 '-pyridines
Base) -4,5- firpene-pyridine] it is reacted with copper acetate, the preparation method of the chiral binuclear copper complex of obtained acetate bridging,
Simple process, normal-temperature reaction, easy post-processing and yield are high.(2) the chiral binuclear copper of acetate bridging prepared by the present invention is matched
Closing object, i.e. having chiral optical activity again has strong antiferro-magnetic coupling performance.It is rare chiral magnetic bifunctional molecule substrate
Material.In addition, acetate is as bridge linkage group, since bridging is apart from short, so that the magnetic coupling between two copper ion Cu (II) is made
With enhancing.Cause molecular material that there is very strong magnetic coupling performance.The chiral binuclear copper complex of acetate bridging is not yet at present
It appears in the newspapers, therefore, the present invention has also filled up the blank of such material simultaneously.(3) the chirality magnetic material have synthesis condition it is mild,
Yield is high, stability is strong, reproducibility is good, it is easy to isolate and purify, in nonlinear optical material, information recording device and light-magnetic
Molecular device etc. has broad application prospects.
Detailed description of the invention
Fig. 1 is the chiral binuclear copper complex Cu of 1 acetate bridging of embodiment2(CH3COO)4(L)2Molecular structure;
Fig. 2 is the chiral binuclear copper complex Cu of 1 acetate bridging of embodiment2(CH3COO)4(L)2Chiral circular dichroism light
Spectrogram;
Fig. 3 is the chiral binuclear copper complex Cu of 1 acetate bridging of embodiment2(CH3COO)4(L)2DC magnetic susceptibility with
The product variation with temperature relational graph of temperature.
Specific embodiment
Combined with specific embodiments below, the present invention will be further described.It should be understood that following embodiment is merely to illustrate this
The person skilled in the art of the range of invention and is not intended to limit the present invention, the field can make one according to the content of foregoing invention
A little nonessential modifications and adaptations.
Embodiment 1
A kind of preparation method of the chiral binuclear copper complex of acetate bridging, steps are as follows:
(1) monodentate nitrogenous chiral organic ligand L's the preparation method is as follows:
A.4- in the round-bottomed flask of 250mL, 4.0 grams of 4- the preparation of (pyridine acetyl group) pyridinium iodide intermediate: are added
Acetylpyridine is dissolved with 18mL pyridine solution, will be added in round-bottomed flask dissolved with the 18mL pyridine solution of 13 grams of iodine, mixture
105 DEG C are heated to, is reacted 4 hours, is then cooled to room temperature and filter, it is secondary with a small amount of pyridine flushing, after vacuum drying
Gray solid is 4- (pyridine acetyl group) pyridinium iodide intermediate;
B. 3.5 grams of 4- (pyridine acetyl group) that step a is prepared the synthesis of the nitrogenous chiral organic ligand L of monodentate: are weighed
Pyridinium iodide intermediate and 2 grams of ammonium acetate (NH4Ac it) is placed in three-neck flask, adds the formamide of 35~45mL
(CH3CONH2).It is stirred continuously lower myrte (-)-myrtenal (Bellingwell company's production) for being added 1.8 grams.It is heated to
It 80 DEG C, is reacted 12 hours under nitrogen.Off-white solid is obtained by filtration in above-mentioned product, and is rinsed with water, with ethyl alcohol recrystallization, so
It is afterwards that solid is dry.Yield is 85% (calculating by intermediate).Elemental analysis: molecular formula C is pressed17H18N2(molecular weight is
250.33): calculated value (%): C, 81.56;H,7.25;N,11.19;Measured value (%): C, 81.61;H,7.32;N,11.27.
Infrared spectroscopy IR (KBr): 2949 (s), 2992 (m), 2867 (v), 1584 (m), 1457 (s), 1387 (m), 782 (m), 755
(s)。
(2) the chiral binuclear copper complex Cu of acetate bridging2(CH3COO)4(L)2Preparation: by 10mL Cu
(CH3COO)2·H2The methanol solution of O (20mg, 0.1mmol) is added dissolved with chiral monodentate organic ligand L:[(- containing N) -2- (4 ' -
Pyridyl group) -4,5- firpene-pyridine] (25mg, 0.1mmol) acetonitrile solution (10mL) in, stirring after twenty minutes, filtering, gained
Clear solution volatilizees naturally, and a Zhou Tianhou obtains crystal blue, filtering, uses acetonitrile and water washing respectively, and drying at room temperature obtains
The chiral binuclear copper complex of acetate bridging, calculating yield is 89% (calculating by Cu).
Using the chiral binuclear copper complex Cu of 2400 elemental analyser Dichlorodiphenyl Acetate root bridging of Perkin-Elmer2
(CH3COO)4(L)2The content analysis of C, H and N are carried out, by molecular formula (C42H47N4O8Cu2) calculated value (%): C, 58.46;H,
5.49;N,6.49.Measured value (%): C, 58.37;H,5.53;N 6.58.Using Bruker SMART APEX CCD
Diffractometer single crystal diffractometer measures the chiral binuclear copper complex Cu of acetate bridging at normal temperature2(CH3COO)4
(L)2Molecular structure (see Fig. 1).In the chiral coordination compound, each Cu atom is matched with a chiral monodentate containing N is organic respectively
A N Atomic coordinate in body L, two copper atoms of bridging form chiral binuclear copper knots to two O atoms in 4 acetates simultaneously
Structure.The chiral binuclear copper complex Cu of acetate bridging has been measured using Biologic MS-500spectropolarimeter2
(CH3COO)4(L)2Circular dichroism, as shown in Fig. 2, the complex shows positive Cotton effect at λ=214nm, λ=
Negative Cotton effect signal is shown at 263 and 321nm respectively, to demonstrate its chiral optical activity.
The chiral binuclear copper complex Cu of acetate bridging2(CH3COO)4(L)2Magnetism testing:
Acetate bridge is tested using Quantum Design MPMS-XL5SQUID Magnetometer magnetic measurement instrument
The chiral binuclear copper complex Cu of connection2(CH3COO)4(L)2DC magnetic susceptibility.Test result shows: the chirality of acetate bridging
Dicopper complex4-amino-3 Cu2(CH3COO)4(L)2Between temperature 300-100K, the product of molar susceptibility and temperature is with temperature
Reduction and rapid decrease (shown in Fig. 3), absolutely prove that there are very strong anti-ferromagnetism to couple at two centers Cu.
Embodiment 2
A kind of preparation method of the chiral binuclear copper complex of acetate bridging, steps are as follows:
(1) chiral monodentate organic ligand containing N L's the preparation method is as follows:
A.4- in the round-bottomed flask of 250mL, 4.0 grams of 4- the preparation of (pyridine acetyl group) pyridinium iodide intermediate: are added
Acetylpyridine is dissolved with 15mL pyridine solution, will be added in round-bottomed flask dissolved with the 15mL pyridine solution of 12 grams of iodine, mixture
100 DEG C are heated to, is reacted 4 hours, is then cooled to room temperature and filter, it is secondary with a small amount of pyridine flushing, after vacuum drying
Gray solid is 4- (pyridine acetyl group) pyridinium iodide intermediate;
B. the synthesis of chiral monodentate organic ligand containing N L: 3.5 grams of 4- (pyridine acetyl group) pyrrole that step a is prepared is weighed
Pyridine salt compounded of iodine intermediate and 1.8 grams of ammonium acetate (NH4Ac it) is placed in three-neck flask, adds the formamide (CH of 35mL3CONH2)。
It is stirred continuously lower myrte (-)-myrtenal (Bellingwell company's production) for being added 1.8 grams.It is heated to 75 DEG C, under nitrogen
Reaction 12 hours.Off-white solid is obtained by filtration in above-mentioned product, and is rinsed with water, with ethyl alcohol recrystallization, is then done solid
It is dry, obtain the nitrogenous chiral organic ligand L of monodentate.
(2) the chiral binuclear copper complex Cu of acetate bridging2(CH3COO)4(L)2Preparation: by 10mL Cu
(CH3COO)2·H2The methanol solution of O (40mg, 0.2mmol) is added dissolved with chiral monodentate organic ligand L:[(- containing N) -2- (4 ' -
Pyridyl group) -4,5- firpene-pyridine] (50mg, 0.2mmol) acetonitrile solution (20mL) in, stirring 25 minutes after, filtering, gained
Clear solution volatilizees naturally, obtains crystal blue after a week, filtering, uses acetonitrile and water washing respectively, and drying at room temperature obtains vinegar
The chiral binuclear copper complex of acid group bridging.
Embodiment 3
A kind of preparation method of the chiral binuclear copper complex of acetate bridging, steps are as follows:
(1) chiral monodentate organic ligand containing N L's the preparation method is as follows:
A.4- in the round-bottomed flask of 250mL, 4.0 grams of 4- the preparation of (pyridine acetyl group) pyridinium iodide intermediate: are added
Acetylpyridine is dissolved with 20mL pyridine solution, will be added in round-bottomed flask dissolved with the 20mL pyridine solution of 15 grams of iodine, mixture
110 DEG C are heated to, is reacted 4.5 hours, is then cooled to room temperature and filter, it is secondary with a small amount of pyridine flushing, after vacuum drying
Obtaining gray solid is 4- (pyridine acetyl group) pyridinium iodide intermediate;
B. the synthesis of chiral monodentate organic ligand containing N L: 3.5 grams of 4- (pyridine acetyl group) pyrrole that step a is prepared is weighed
Pyridine salt compounded of iodine intermediate and 2.7 grams of ammonium acetate (NH4Ac it) is placed in three-neck flask, adds the formamide (CH of 45mL3CONH2)。
It is stirred continuously lower myrte (-)-myrtenal (production of Alfa company) for being added 1.8 grams.85 DEG C are heated to, it is anti-under nitrogen
It answers 12.5 hours.Off-white solid is obtained by filtration in above-mentioned product, and is rinsed with water, with ethyl alcohol recrystallization, is then done solid
It is dry, obtain chiral monodentate organic ligand containing N L.
(2) the chiral binuclear copper complex Cu of acetate bridging2(CH3COO)4(L)2Preparation: by 15mL Cu
(CH3COO)2·H2The methanol solution of O (60mg, 0.3mmol) is added dissolved with chiral monodentate organic ligand L:[(- containing N) -2- (4 ' -
Pyridyl group) -4,5- firpene-pyridine] (75mg, 0.3mmol) acetonitrile solution (10mL) in, stirring after twenty minutes, filtering, gained
Clear solution volatilizees naturally, obtains crystal blue after a week, filtering, uses acetonitrile and water washing respectively, and drying at room temperature obtains vinegar
The chiral binuclear copper complex of acid group bridging.
Basic principles and main features and advantages of the present invention of the invention have been shown and described above.The skill of the industry
Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the above embodiments and description only describe
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (4)
1. a kind of chiral binuclear copper complex of acetate bridging, the molecule of the chiral binuclear copper complex of the acetate bridging
Formula is Cu2(CH3COO)4(L)2, wherein L is [(-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine], and structural formula is
2. the preparation method of the chiral binuclear copper complex of acetate bridging according to claim 1, it is characterised in that step
It is rapid as follows: will be dissolved with Cu (CH3COO)2·H2It is molten that the methanol solution of O is added to the acetonitrile dissolved with chiral monodentate organic ligand containing N L
In liquid, after stirring 20~25 minutes, filtering, gained clear solution blue slowly volatilizees at room temperature, obtains crystal blue after a week,
Filtering obtains the chiral binuclear copper complex of acetate bridging with acetonitrile and water washing, drying at room temperature respectively.
3. the preparation method of the chiral binuclear copper complex of acetate bridging according to claim 2, it is characterised in that: institute
State Cu (CH3COO)2·H2The ratio between amount of substance of the O and nitrogenous organic ligand L of chiral monodentate is 1:1.
4. the preparation method of the chiral binuclear copper complex of acetate bridging according to claim 2, it is characterised in that: institute
State chiral monodentate nitrogenous organic ligand L's the preparation method is as follows:
A.4- in the round-bottomed flask of 250mL, 4.0 grams of 4- acetyl the preparation of (pyridine acetyl group) pyridinium iodide intermediate: are added
Yl pyridines are dissolved with 15~20mL pyridine solution, round-bottomed flask will be added dissolved with 15~20mL pyridine solution of 12~15 grams of iodine
In, mixture is heated to 100~110 DEG C, reacts 4~4.5 hours, then cools to room temperature and filter, and is rushed with a small amount of pyridine
Wash it is secondary, after vacuum drying gray solid be 4- (pyridine acetyl group) pyridinium iodide intermediate;
B. the synthesis of chiral monodentate organic ligand containing N L: 3.5 grams of 4- (pyridine acetyl group) pyridine iodine that step a is prepared is weighed
Salt intermediate and 1.8~2.7 grams of ammonium acetates are placed in three-neck flask, are added the formamide of 35~45mL, are stirred continuously down
1.8 grams myrte (-)-myrtenal is added, is heated to 75-85 DEG C, is reacted 12-12.5 hours under nitrogen, it will be above-mentioned
Off-white solid is obtained by filtration in product, and is rinsed with water, then that solid is dry that the nitrogenous chirality of monodentate has with ethyl alcohol recrystallization
Machine 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 true CN109180708A (en) | 2019-01-11 |
CN109180708B 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) |
Cited By (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
Cited By (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 |
Also Published As
Publication number | Publication date |
---|---|
CN109180708B (en) | 2020-12-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Pinkowicz et al. | Multifunctional magnetic molecular {[MnII (urea) 2 (H2O)] 2 [NbIV (CN) 8]} n system: magnetization-induced SHG in the chiral polymorph | |
Shang et al. | Six Ln (III) coordination polymers with a semirigid tetracarboxylic acid ligand: bifunctional luminescence sensing, NIR-luminescent emission, and magnetic properties | |
CN103724365A (en) | Transition metal complex based on semirigid bipyridine bisamide organic ligand and terephthalic acid as well as synthetic method and application of transition metal complex | |
CN104230968B (en) | Cadmium-containing dual-core polymer with mixed-ligand and preparation method of cadmium-containing dual-core polymer | |
CN107417927A (en) | The synthetic method of porous metals organic framework materials with glyoxaline structure | |
CN104262372B (en) | A kind of chirality monokaryon nine is coordinated neodymium beta diketone coordination compound and preparation method thereof | |
CN107445902A (en) | A kind of preparation, structure and the photoluminescent property of benzimidazole sulfate | |
CN109180708A (en) | A kind of chiral binuclear copper complex of acetate bridging and preparation method thereof | |
CN109096314A (en) | (-) -4,5- firpene-bipy 2,2' bipyridyl copper nitrate monokaryon chiral coordination compound and preparation method thereof | |
CN105884805A (en) | Cd (II) mixed ligand polymer and preparation method thereof | |
Wang et al. | Structures and magnetic properties of two series of Ln2 complexes: Tb2 complexes showing distinct slow magnetic relaxation | |
CN111116343B (en) | Dy (III) -Cu (II) eutectic single-molecule magnet and preparation method thereof | |
CN108358955A (en) | A kind of double-core Dy monomolecular magnetic materials and preparation method thereof | |
CN102827194B (en) | With rare earth organic coordination polymer that 2,2 '-dipyridyl is assistant ligand and template and preparation method thereof and application | |
Liu et al. | Rung-defected ladder of azido-bridged Cu (II) chains linked by [Cu (picolinate) 2] units | |
Zhang et al. | A 3D supramolecular network constructed from {Ni9} cluster and benzotriazole | |
Okubo et al. | Synthesis, structure, and magnetic properties of one-dimensional copper (II) coordination polymer,[Cu (pyrazine-2, 3-dicarboxylate)(H2O) 2]· 2H2On | |
CN104292247A (en) | Cadmium-containing two dimensional polymer having mixed ligand, and its preparation method | |
Biswas et al. | A one-pot synthesis of a paramagnetic high-nuclearity nickel (ii) cluster: an octadecanuclear Ni II 16 Na I 2 metal aggregate | |
CN109081854A (en) | (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine hexafluoroacetylacetone manganese complex and preparation method | |
Uma et al. | Synthesis, structure, spectra and redox interconversions in copper (II) complexes of 5, 6-diphenyl-3-(2-pyridyl)-1, 2, 4-triazine | |
CN104744499A (en) | Trifluoromethyl quinoline-containing cadmium complex tetramer as well as preparation method and application thereof | |
CN109180709A (en) | (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine hexafluoroacetylacetone copper complex and preparation method | |
CN108299509A (en) | A kind of ruthenium-diimine type complex, preparation method and its usage | |
CN114195833A (en) | Crystalline molecular base material generated by chiral mononuclear nickel third-order harmonic 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 |