CN106188155A - A kind of four core Iron clusters and crystal structure thereof and preparation method - Google Patents
A kind of four core Iron clusters and crystal structure thereof and preparation method Download PDFInfo
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- CN106188155A CN106188155A CN201610601420.4A CN201610601420A CN106188155A CN 106188155 A CN106188155 A CN 106188155A CN 201610601420 A CN201610601420 A CN 201610601420A CN 106188155 A CN106188155 A CN 106188155A
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- 150000002505 iron Chemical group 0.000 title claims abstract description 38
- 239000013078 crystal Chemical group 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 97
- 229910052742 iron Inorganic materials 0.000 claims abstract description 30
- 230000005283 ground state Effects 0.000 claims abstract description 28
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000001768 cations Chemical class 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 238000006467 substitution reaction Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract 2
- 150000001875 compounds Chemical class 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- -1 Iron clusters Cations Chemical class 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 230000005291 magnetic effect Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 238000009792 diffusion process Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 150000002891 organic anions Chemical class 0.000 claims 1
- VLRICFVOGGIMKK-UHFFFAOYSA-N pyrazol-1-yloxyboronic acid Chemical compound OB(O)ON1C=CC=N1 VLRICFVOGGIMKK-UHFFFAOYSA-N 0.000 claims 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 abstract 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008827 biological function Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005404 magnetometry Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- QCVGEOXPDFCNHA-UHFFFAOYSA-N 5,5-dimethyl-2,4-dioxo-1,3-oxazolidine-3-carboxamide Chemical compound CC1(C)OC(=O)N(C(N)=O)C1=O QCVGEOXPDFCNHA-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108010044394 Hemerythrin Proteins 0.000 description 1
- 108010063312 Metalloproteins Proteins 0.000 description 1
- 102000010750 Metalloproteins Human genes 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 102000000505 Ribonucleotide Reductases Human genes 0.000 description 1
- 108010041388 Ribonucleotide Reductases Proteins 0.000 description 1
- 230000005290 antiferromagnetic effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014103 egg white Nutrition 0.000 description 1
- 210000000969 egg white Anatomy 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 150000003278 haem Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 108010009977 methane monooxygenase Proteins 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Compounds Of Iron (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses four core Iron clusters of a kind of ground state spin quantum number S=1 and crystal structure thereof and preparation method.The chemical formula of four described core Iron clusters is [Fe4O2(O2CPh‑NH2)7(bipy‑NH2)2]·HO2CPh‑NH2·(CH3CN)3·C2H5OH OH, wherein bipy NH2=4,4 ' diamino 2,2 ' di Pyridine.Four core ferrum bunch composite cation [Fe4O2(O2CPh‑NH2)7(bipy‑NH2)2]+Crystal structure as follows:Four described core Iron cluster crystal are monoclinic system, No. 9 non-heart space groups Cc, cell parameter: β=130.451 (2) °.Four discrete core ferrum bunch composite cations are by free HO2CPh‑NH2With solvent molecule C2H5OH connects into one-dimensional catenary structure.Four core Iron clusters of the present invention are prepared by a kind of pinpoint substitution reaction, it is shown that the ground state spin quantum number of rare S=1.
Description
Technical field
The invention belongs to ferrum Study on Coordination Clusters compound field, more particularly, to four cores of a kind of ground state spin quantum number S=1
Iron cluster and crystal structure thereof and preparation method.
Background technology
In recent years, by oxygen, the multinuclear Iron cluster of hydroxyl or carboxyl bridging receives much attention.These multinuclear ferrum
The cluster compound a lot of fields in nature all play an important role, and these fields include mineralogy, biology etc..Especially
Being in field of biology, multinuclear Iron cluster is used as inorganic template, investigates metalloprotein or the metal of non-heme
The biological function (Chem.Rev.2004,104,987) of enzyme.
In multinuclear Iron cluster mentioned above.The four core Iron clusters that iron ion is distributed in " butterfly-like " occupy emphatically
The position wanted.Four core Iron clusters, for investigating hemerythrin, methane monooxygenase, ribonucleotide reductase, wait metal egg
White biological function plays an important role (Coord.Chem.Rew.1987,79,195).
The four core Iron clusters that 31 kinds of iron ions are distributed are reported altogether in " butterfly-like " at present.These cluster compounds are all logical
Cross [Fe2O]4+Or [Fe3O]7+Extension obtains, and these extended methods would generally produce substantial amounts of by-product
(Inorg.Chem.2010,49,1).And wherein 30 cluster compounds show the ground state spin quantum number of S=0, only cluster compound
[Fe4O2Cl2(O2CMe)2{(py)2CNO}4] show the ground state spin quantum number of S=1, but this cluster compound mainly passes through
(py)2CNO part bridging (Inorg.Chem.2006,45,7372).The four core Iron clusters not yet having carboxyl bridging at present show
Show the ground state spin quantum number of S=1.
Part introduces the solution that active function groups is a kind of very advantageous.By introducing amino official on part
Can group, it is achieved four core Iron clusters be accurately positioned synthesis, four discrete core ferrum bunch composite cations by free part
With the hydrogen bond action of solvent molecule, connecting into one-dimensional catenary structure, and the ground state spin quantum number of display S=1, this respect is studied
There is not been reported.
Summary of the invention
Technical problem: the technical problem to be solved in the present invention is the ground state spin quantum number overcoming existing four core Iron clusters
S=0, and building-up process has defect and the technical deficiency of a large amount of by-product, it is provided that the four of a kind of ground state spin quantum number S=1
Core Iron cluster and crystal structure thereof and preparation method.
It is an object of the invention to provide four core Iron clusters of a kind of ground state spin quantum number S=1.
It is a further object of the present invention to provide the crystal structure of four core Iron clusters of above-mentioned ground state spin quantum number S=1.
Another object of the present invention is to provide the preparation method of four core Iron clusters of above-mentioned ground state spin quantum number S=1.
Technical scheme: above-mentioned purpose of the present invention is achieved through the following technical solutions:
The invention provides the four core Iron clusters of a kind of ground state white spin quantum S=1, it is joining by amino functional
Body HO2CPh-NH2With mononucleated compound [Fe (H2Bpz2)2(bipy-NH2)] occur substitution reaction to be prepared from.
Composite cation [Fe in the four core Iron clusters of the present invention4O2(O2CPh-NH2)7(bipy-NH2)2]+Crystal knot
Structure is as follows:
The synthesis of four core Iron clusters of above-mentioned ground state spin quantum number S=1 comprises the following steps:
(1) mononucleated compound [Fe (H is synthesized2Bpz2)2(bipy-NH2)]: Fe (BF4)2·6H2O and part KH2Bpz2According to
The ratio of mol ratio 1: 2 is dissolved in alcoholic solution in nitrogen atmosphere, stirs 20 minutes, the white precipitate KBF of generation4Cross and filter
Go.The filtrate obtained is added slowly to dissolved with part bipy-NH2Alcoholic solution in.After stirring 1 hour, obtain lurid
Powder, is [Fe (H2Bpz2)2(bipy-NH2)]。
(2) four core Iron cluster [Fe are synthesized4O2(O2CPh-NH2)7(bipy-NH2)2]·HO2CPh-NH2·(CH3CN)3·
C2H5Coordination compound [Fe (the H of OH OH: above-mentioned synthesis2Bpz2)2(bipy-NH2)] and part HO2CPh-NH2According to mol ratio 1: 2
Ratio be dissolved separately in ethanol and acetonitrile solution, room temperature mix and blend.After stirring 30 minutes, gained brown solution is used for expanding
Eliminating stagnation is brilliant.The four core Iron cluster crystal being suitable for X-ray single crystal diffraction obtain within 2 weeks.
In step (1), alcoholic solution includes methanol, ethanol etc..
In step (2), the diffusion solvent used by diffusion crystallization is ether, propyl ether, butyl ether etc..
Four core Iron clusters of ground state spin quantum number S=1 of the present invention crystallize at monoclinic system, No. 9 non-heart space groups
Cc, cell parameter:β=130.451 (2) °.
Meanwhile, present invention also offers the preparation method of four core Iron clusters of a kind of ground state spin quantum number S=1.Logical
Cross the part HO of amino functional2CPh-NH2, part replaces mononucleated compound [Fe (H2Bpz2)2(bipy-NH2)] in part
bipy-NH2Replace part H completely2Bpz2, effectively synthesized four core Iron clusters, without the by-product of other Iron clusters.
The four core Iron clusters prepared according to above-mentioned preparation method are also within protection scope of the present invention.
Four core Iron clusters of ground state spin quantum number S=1 of the present invention, in its crystal structure, four core Iron clusters are multiple
Cations [Fe4O2(O2CPh-NH2)7(bipy-NH2)2]+By free HO2CPh-NH2With solvent molecule C2H5The hydrogen bond of OH
Effect, connects into one-dimensional catenary structure, and carries free OH-Ion (Fig. 1).
The four core Iron clusters of the present invention, its magnetic susceptibility measurement result shows, between the iron ion that " butterfly-like " is distributed
Magnetic exchange constant Jwb=-50cm-1, Jbb=-70cm-1, and g=2.02.According to ratio Jbb/Jwb=1.4 are appreciated that
(Inorg.Chem.2006,45,7372), ground state spin quantum number S=1 (Fig. 2) of the four core Iron clusters of the present invention.
Beneficial effect: the invention provides four core Iron cluster and crystal structures thereof of a kind of ground state spin quantum number S=1
And preparation method.Utilize preparation method of the present invention and utilize above-mentioned material to prepare four cores of ground state spin quantum number S=1
Iron cluster, four described core Iron clusters have the advantage that
(1) it is the Carboxylic acid ligand utilizing amino functional first, prepares four cores by pinpoint substitution reaction
Iron cluster.
(2) it is the free part of first passage and the hydrogen bond action of solvent molecule, four core ferrum bunch composite cation bridgings
Become one-dimensional catenary structure.
(3) it is the first four core Iron clusters carrying OH-ion.
(4) it is first carboxylic acid bridging, four core Iron clusters of ground state spin quantum number S=1.
Accompanying drawing explanation
Fig. 1 is four core Iron cluster composite cation [Fe of ground state spin quantum number S=1 of the present invention4O2(O2CPh-
NH2)7(bipy-NH2)2]+By free HO2CPh-NH2With solvent molecule C2HsThe hydrogen bond action of OH, connects into one-dimensional chain
Structure.
Fig. 2 is susceptibility curve and the matching ginseng thereof of four core Iron clusters of ground state spin quantum number S=1 of the present invention
Number, interior illustration is magnetic exchange schematic diagram between " butterfly-like " iron ion.
Detailed description of the invention
This invention is further illustrated below in conjunction with explanation the drawings and specific embodiments.But the present invention is not done by embodiment
Any type of restriction.Unless stated otherwise, the reagent that the present invention uses, method and apparatus is the art conventional reagent,
Method and apparatus.
Unless stated otherwise, material and reagent used by the present invention are commercially available.
Presented below go out some experimental data describe the problem.
Embodiment 1 mononucleated compound [Fe (H2Bpz2)2(bipy-NH2)] synthesis
Fe (the BF of 0.4mmol4)2·6H2The part KH of O (135mg) and 0.8mmol2Bpz2(149mg) in nitrogen atmosphere
It is dissolved in 20mL methanol solution, stirs 20 minutes, the white precipitate KBF of generation4It is filtered to remove.The filtrate obtained adds slowly
Enter to 10mL dissolved with 0.4mmol part bipy-NH2(72.5mg) in methanol solution.After stirring 1 hour, obtain lurid
Powder 187mg, is mononucleated compound [Fe (H2Bpz2)2(bipy-NH2)]。
Embodiment 2 four core Iron cluster [Fe4O2(O2CPh-NH2)7(bipy-NH2)2]·HO2CPh-NH2·(CH3CN)3·
C2H5OH OH synthesizes
Mononucleated compound [Fe (the H of 0.2mmol2Bpz2)2(bipy-NH2)] be dissolved in 20mL alcoholic solution, this solution
Join 10mL, dissolved with 0.4mmol HO2CPh-NH2In the acetonitrile solution of part, stirring at normal temperature 1h, obtain the solution of brown, brown
Material in color solution is four core Iron cluster [Fe4O2(O2CPh-NH2)7(bipy-NH2)2]·HO2CPh-NH2·
(CH3CN)3·C2H5OH·OH。
Embodiment 3 four core Iron cluster [Fe4O2(O2CPh-NH2)7(bipy-NH2)2]·HO2CPh-NH2·(CH3CN)3·
C2H5OH OH single crystal cultivation
The four core Iron cluster solution 5mL obtained in Example 2, are placed in the vial that specification is 8mL, this glass
Bottle is placed on containing 15mL diethyl ether solution, and specification is in the closed glass bottle of 50mL, and room temperature environment stands.It is suitable for monocrystalline to spread out
Brown bulk-shaped monocrystal [the Fe penetrated4O2(O2CPh-NH2)7(bipy-NH2)2]·HO2CPh-NH2·(CH3CN)3·C2H5OH·OH
Separate out within 2 weeks.
Embodiment 4 four core Iron cluster [Fe4O2(O2CPh-NH2)7(bipy-NH2)2]·HO2CPh-NH2·(CH3CN)3·
C2H5OH OH single crystal cultivation
Four core Iron cluster solution 5mL in Example 2, are placed in the vial that specification is 8mL, and this vial is placed
Containing 10mL propyl ether solution, specification is in the closed glass bottle of 50mL, and room temperature environment stands.It is suitable for the brown of single crystal diffraction
Color bulk-shaped monocrystal [Fe4O2(O2CPh-NH2)7(bipy-NH2)2]·HO2CPh-NH2·(CH3CN)3·C2H5OH OH is within 3 weeks
Separate out.
Embodiment 5 variable temperature magnetic susceptibility is tested
Take 12mg tetra-core Iron cluster [Fe4O2(O2CPh-NH2)7(bipy-NH2)2]·HO2CPh-NH2·(CH3CN)3·
C2H5OH OH monocrystalline, in 2000Oe magnetic field intensity, has carried out magnetic susceptibility measurement within the temperature range of 300-3K, rate of temperature fall is
2K/min.Susceptibility curve (the χ of samplemTvs T) as shown in Figure 2.Four core Iron clusters show strong antiferromagnetic mutually
Effect, and the ground state spin quantum number of S=1.
Claims (8)
1. a core Iron cluster, it is characterised in that this four core Iron cluster is the four of a kind of ground state spin quantum number S=1
Core Iron cluster, organic anion is as counter ion counterionsl gegenions, and its chemical formula is [Fe4O2(O2CPh-NH2)7(bipy-NH2)2]·
HO2CPh-NH2·(CH3CN)3·C2H5OH OH, wherein bipy-NH2=4,4 '-diamino-2,2 '-diPyridine.
2. the crystal structure of four core Iron clusters as claimed in claim 1, it is characterised in that multiple in four core Iron clusters
Cations [Fe4O2(O2CPh-NH2)7(bipy-NH2)2]+Crystal structure as follows:
The crystal structure of four core Iron clusters the most according to claim 2, it is characterised in that this crystal structure is a kind of gold
Belong to albumen inorganic template, the cell parameter of this template: β=
130.451(2)°。
The crystal structure of four core Iron clusters the most according to claim 2, it is characterised in that described composite cation
[Fe4O2(O2CPh-NH2)7(bipy-NH2)2]+By free HO2CPh-NH2With solvent molecule C2H5The hydrogen bond action of OH, even
It is connected into one-dimensional catenary structure, and carries free OH-ion.
5. the preparation method of four core Iron clusters as claimed in claim 1, it is characterised in that its preparation method is a kind of
Pinpoint substitution reaction, passes through HO2CPh-NH2Replace mononucleated compound [Fe (H2Bpz2)2(bipy-NH2)] in H2Bpz2
Part is prepared into H2Bpz2=dihydrobis (1-pyrazolyl) borate)；Four cores of above-mentioned ground state spin quantum number S=1
Preparing of Iron cluster is specific as follows:
1). synthesize mononucleated compound [Fe (H2Bpz2)2(bipy-NH2)]: Fe (BF4)2·6H2O and part KH2Bpz2According to mole
Ratio than 1: 2 is dissolved in alcoholic solution in nitrogen atmosphere, stirs 20 minutes, the white precipitate KBF of generation4It is filtered to remove,
The filtrate obtained is added slowly to dissolved with part bipy-NH2Alcoholic solution in, after stirring 1 hour, obtain lurid powder
End, is [Fe (H2Bpz2)2(bipy-NH2)]；
2). synthesize four core Iron cluster [Fe4O2(O2CPh-NH2)7(bipy-NH2)2]·HO2CPh-NH2·(CH3CN)3·
C2H5Coordination compound [Fe (the H of OH OH: above-mentioned synthesis2Bpz2)2(bipy-NH2)] and part HO2CPh-NH2According to mol ratio 1: 2
Ratio be dissolved separately in ethanol and acetonitrile solution, room temperature mix and blend, after stirring 30 minutes, gained brown solution is used for expanding
Eliminating stagnation is brilliant, and the four core Iron cluster crystal being suitable for X-ray single crystal diffraction obtain within 2 weeks.
The preparation method of four core Iron clusters the most according to claim 5, it is characterised in that described step 1) in, alcohol is molten
Liquid is methanol or ethanol.
The preparation method of four core Iron clusters the most according to claim 5, it is characterised in that step 2) in, described diffusion
Crystallization, diffusion solvent used is ether, propyl ether or butyl ether.
Four core Iron clusters the most according to claim 1, it is characterised in that the four of described ground state spin quantum number S=1
Core Iron cluster, is in 2000Oe magnetic field intensity, the extent of alternating temperature of 305-3K, and the susceptibility of the rate of temperature fall of 2K/min is surveyed
Amount result indicates the ground state spin quantum number of S=1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108129520A (en) * | 2018-01-17 | 2018-06-08 | 南京理工大学 | N6β phase polymorphisms of type monokaryon Fe (II) Spin crossover and preparation method thereof |
| CN108129521A (en) * | 2018-01-17 | 2018-06-08 | 南京理工大学 | N6α phase polymorphisms of type monokaryon Fe (II) Spin crossover and preparation method thereof |
| CN113801100A (en) * | 2021-10-26 | 2021-12-17 | 四川省产品质量监督检验检测院 | Tetranuclear copper complex and preparation method and application thereof |
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| EP2072062B1 (en) * | 2007-12-22 | 2012-06-06 | Karlsruher Institut für Technologie | The use of the spin crossover complex [M*+ (L2) Hw]AN)2 as a magnetic resonance imaging contrast agent |
| JP2009212164A (en) * | 2008-02-29 | 2009-09-17 | Univ Of Tokyo | Electronic element, display device, storage element, optical sensor, gas sensor, and electronic element manufacturing method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108129520A (en) * | 2018-01-17 | 2018-06-08 | 南京理工大学 | N6β phase polymorphisms of type monokaryon Fe (II) Spin crossover and preparation method thereof |
| CN108129521A (en) * | 2018-01-17 | 2018-06-08 | 南京理工大学 | N6α phase polymorphisms of type monokaryon Fe (II) Spin crossover and preparation method thereof |
| CN108129521B (en) * | 2018-01-17 | 2020-04-28 | 南京理工大学 | N6α homogeneous polycrystal of type mononuclear Fe (II) spin cross complex and preparation method thereof |
| CN113801100A (en) * | 2021-10-26 | 2021-12-17 | 四川省产品质量监督检验检测院 | Tetranuclear copper complex and preparation method and application thereof |
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