CN107011389A - 11 core Iron clusters and its synthetic method and application - Google Patents
11 core Iron clusters and its synthetic method and application Download PDFInfo
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- CN107011389A CN107011389A CN201710357123.4A CN201710357123A CN107011389A CN 107011389 A CN107011389 A CN 107011389A CN 201710357123 A CN201710357123 A CN 201710357123A CN 107011389 A CN107011389 A CN 107011389A
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- salicyl
- butylene
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 18
- 150000002505 iron Chemical class 0.000 title claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 57
- -1 dimethylamine cations Chemical class 0.000 claims abstract description 26
- JZWFDVDETGFGFC-UHFFFAOYSA-N salacetamide Chemical group CC(=O)NC(=O)C1=CC=CC=C1O JZWFDVDETGFGFC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000012046 mixed solvent Substances 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 9
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 7
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims abstract description 6
- 239000000696 magnetic material Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000376 reactant Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000002425 crystallisation Methods 0.000 claims abstract description 3
- 230000008025 crystallization Effects 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 51
- 229910052757 nitrogen Inorganic materials 0.000 claims description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 abstract description 27
- 230000005316 antiferromagnetic exchange Effects 0.000 abstract description 7
- 230000003993 interaction Effects 0.000 abstract description 6
- 230000005408 paramagnetism Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 31
- 125000004429 atom Chemical group 0.000 description 13
- 239000013078 crystal Substances 0.000 description 13
- 125000004430 oxygen atom Chemical group O* 0.000 description 13
- 230000005291 magnetic effect Effects 0.000 description 10
- XSXYESVZDBAKKT-UHFFFAOYSA-N 2-hydroxybenzohydrazide Chemical group NNC(=O)C1=CC=CC=C1O XSXYESVZDBAKKT-UHFFFAOYSA-N 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 1
- 230000005343 Curie-Weiss law Effects 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910006124 SOCl2 Inorganic materials 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000005290 antiferromagnetic effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing 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
- 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
-
- 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
-
- 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)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
Abstract
The invention discloses a kind of 11 core Iron clusters and its synthetic method and application.The chemical formula of the cluster compound is [Fe11(L)6(DMF)5(H2O)]·4DMF·H2O·3C2H8N0.5Py, L represent N, the hydrazides of N ' two (salicyl) (E) butylene two, and the part sloughs six hydrogen atoms, the negative electrical charge of six units of band, and there be three dimethylamine cations not being coordinated in the external world.The synthetic method of the cluster compound is：Take N, the hydrazides of N ' two (salicyl) (E) butylene two and FeCl3·6H2O mixed solvents are dissolved, and adjust pH=5.3~5.9 of resulting solution with pyridine afterwards, and gained mixed liquor is placed in hydrothermal reaction kettle, and in being reacted under heating condition, reactant cooling stands crystallization, produced.There is anti-ferromagnetic exchange interaction between cluster compound intramolecular iron ion of the present invention, general performance is paramagnetism, available for preparing magnetic material.
Description
Technical field
The present invention relates to a kind of 11 core Iron clusters and its synthetic method and application, belong to technical field of magnetic materials.
Background technology
The synthesis of multinuclear transition metal cluster compound and property are always the popular domain of scientists study.Ferro element is in member
It is located at VIII in plain periodic table, extranuclear strucure is [Ar] 3d64s2.Iron cluster is very important one point in complex
Class, is still the object that many researchers are pursued so far due to the diversity of its structure and with excellent property.
It is the rich and varied multidentate ligand of coordination pattern that N-, which is acylated salicylyl hydrazine part, itself has the life of antibacterial
Thing activity, the molecule cage that the such part of introducing is constructed may produce influence to its potential application performance.But have not yet to see
With N, N '-two (salicyl)-hydrazides of (E)-butylene two is the core Iron cluster [Fe of caged 11 that part is synthesized11(L)6
(DMF)5(H2O)]·4DMF·H2O·3C2H8N0.5Py relevant report.
The content of the invention
The technical problem to be solved in the present invention is to provide 11 novel core Iron clusters of a kind of structure and its synthetic method
And application.
11 core Iron cluster of the present invention, its chemical formula is：[Fe11(L)6(DMF)5(H2O)]·4DMF·
H2O·3C2H8N0.5Py, wherein L represent N, and N '-two (the salicyl)-hydrazides of (E)-butylene two, the part sloughs six hydrogen
There is three dimethylamine cations not being coordinated in atom, the negative electrical charge of six units of band, the external world；
The cluster compound belongs to monoclinic system, C2/ c space groups, cell parameter is： α=90.00 °, β=105.823 (3) °, γ=90.00 °.
Applicant has found that 11 core Iron cluster of the present invention has following magnetic property under study for action：Molecule
There is anti-ferromagnetic exchange interaction between interior iron ion, its general performance is paramagnetism.Therefore, present invention additionally comprises above-mentioned 11 core iron
Application of the cluster compound in magnetic material is prepared.
The synthetic method of 11 core Iron cluster of the present invention is：Take N, N '-two (the salicyl)-acyl of (E)-butylene two
Hydrazine and FeCl3·6H2O mixed solvents dissolve, and adjust pH=5.3~5.9 of resulting solution, gained mixed liquor with pyridine afterwards
It is placed in hydrothermal reaction kettle, in being reacted under heating condition, reactant cooling stands crystallization, produces target product；Described mixing
Solvent is N, N ' dimethylformamides and methanol composition.
In specific building-up process, it is found by the applicant that：
1) mixed liquor only after pH is adjusted, which is placed in hydrothermal reaction kettle to react, can just obtain target product, when using other
Utensil contains the mixed liquor after regulation pH in being reacted under the same terms, has solid powder precipitation after reactant cooling, is not crystal,
By characterizing not an object of the application product.
Although 2) anion in metal salt is not engaged in coordination, key effect is served to generation target product,
When the molysite of our trial different anions, such as Fe (NO3)2·4H2O or Fe (OAc)2·4H2The molysite such as O, are not obtained
Turbid liquid or precipitation, are more generated without crystal.It can be seen that, synthesis of the anion to target product has a major impact.
In above-mentioned synthetic method, N, N '-two (salicyl)-hydrazides of (E)-butylene two and FeCl3·6H2O mol ratio is led to
Often it is stoichiometric proportion, can is specifically 1：2~4, preferably 1：2.
In above-mentioned synthetic method, described in the mixed solvent, N, N ' volume ratio of dimethylformamide and methanol can be
Any proportioning, preferably 1~4：1~4, preferably selection is 1：4、1：3 or 1：2.The consumption of the mixed solvent can be according to need
It was determined that being generally advisable with the raw material that can dissolve participation reaction.Specifically, with 0.1mmol N, N '-two (salicyl)-
(E) calculated on the basis of-hydrazides of butylene two, total consumption of mixed solvent used in whole raw materials is generally 16~18mL.Specific molten
, can be by N, N '-two (salicyl)-hydrazides of (E)-butylene two and FeCl in the step of solution3·6H2O is respectively with the mixed solvent
A kind of composition dissolving, remixes and reacts together, also can be by N, N '-two (salicyl)-hydrazides of (E)-butylene two and FeCl3·
6H2Add mixed solvent dissolving after O mixing again.
In above-mentioned synthetic method, pH=5.5~5.7 of solution are preferably adjusted.
In above-mentioned synthetic method, described hydrothermal reaction kettle is hydrothermal reaction kettle conventional in solvent-thermal method, usually band
The hydrothermal reaction kettle of polytetrafluoroethylsubstrate substrate.The reaction is preferably carried out under the conditions of 60~120 DEG C, in said temperature condition
The lower time reacted will be usually 30~80h, can also be more than 80h；It will preferably control in 60~80h in the reaction time.Instead
It should be more preferably and be carried out under the conditions of 80~100 DEG C.
The N being related in synthetic method of the present invention, N '-two (salicyl)-hydrazides of (E)-butylene two may be referred to existing
There is document (N.Sreenivasachary；D.T.Hickman；D.Sarazin, et al.DyNAs:Constitutional
Dynamic Nucleic Acid Analogues[J].Chemistry,2006,12(33):8581-8588.) synthesized,
Either designed, designed route synthesis.
Compared with prior art, the invention provides 11 novel core Iron cluster [Fe of a kind of structure11(L)6(DMF)5
(H2O)]·4DMF·H2O·3C2H8N0.5Py and its synthetic method, synthetic method are simple, with low cost, reproducible；Shen
Ask someone to find there is antiferromagnetic exchange between the cluster compound intramolecular iron ion under study for action, can be used for preparing magnetic material.
Brief description of the drawings
The infrared light of the part N, N '-two (salicyl) that Fig. 1 uses for various embodiments of the present invention-hydrazides of (E)-butylene two
Spectrogram；
Fig. 2 is the infrared spectrogram of final product made from the embodiment of the present invention 1；
Fig. 3 is the molecular structure of final product made from the embodiment of the present invention 1；
Fig. 4 is the thermogravimetric curve figure of final product made from the embodiment of the present invention 1；
Fig. 5 is the variable temperature magnetic susceptibility figure of final product made from the embodiment of the present invention 1.
Embodiment
With reference to specific embodiment, the present invention is described in further detail, to more fully understand present disclosure, but
The present invention is not limited to following examples.
The N being related in following embodiment, N '-two (salicyl)-hydrazides of (E)-butylene two (hereinafter referred to as part or
L) synthesized using following methods, its synthetic route is as follows：
Weigh (E)-butene dicarboxylic acid (11mmol, 1.8g) to be added in 250mL round-bottomed flask, 25mL is slowly added dropwise
SOCl2, it is stirred at reflux under the conditions of 95 DEG C after 5 hours and half drop DMF is added dropwise, vacuum distillation obtains yellow thick liquid, then is dissolved
In 15mL THF.Salicylyl hydrazine (23.0mmol, 3.6g) is dissolved in 75mL THF solutions simultaneously, both are mixed under ice bath
Stirring is closed, 2.5mL triethylamines are added dropwise, continues to go to be stirred at room temperature after ice bath stirring 5h to react three days, obtains light-yellow precipitate,
Filtering, with THF, Shao Liangshui, absolute ether washing, crude product DMF and H2O mixed solution recrystallization, vacuum drying is obtained
Target product, yield is 70%.Part (C18H16N4O6) elementary analysis (%) theoretical value：C, 56.25；H, 4.20；N, 14.58.
Experiment value：C, 56.24；H, 4.04；N, 13.98.Infrared spectrum is as shown in figure 1, data are as follows：IR (KBr pellet, cm-1)：
3370 (m), 3539 (m), 3231 (m), 2743 (w), 2590 (w), 1706 (m), 1614 (vs), 1490 (vs), 1316 (m),
1218 (m), 1156 (m), 974 (s), 877 (m), 821 (m), 731 (m).From infrared spectrum, part is in 3539cm-1Place
Absworption peak can be attributed to the stretching vibration ν (HO-H) of hydrone, 3231cm-1The wide absworption peak in place is the ν (N-H) of amide groups
Stretching vibration, 2743cm-1The absworption peak at place is attributed to phenolic hydroxyl group ν (O-H) stretching vibration, in 1706cm-1There is absworption peak at place, can
It is attributed to carbonyl C=O stretching vibration ν (C-O) peak, 1614cm-1The absworption peak at place is attributed to the characteristic absorption of C=C in butylene
Peak, 1316cm-1The absworption peak at place is stretching vibration ν (C-N) peak of-C-NH-NH-C-group, 1218cm-1The absworption peak at place can
It is attributed to phenolic group stretching vibration ν (C-O), 1490cm-1、1156cm-1、974cm-1、877cm-1、731cm-1The absworption peak at place is benzene
The special absworption peak of ring.
Embodiment 1
Weigh part (0.05mmol, 0.0192g) and FeCl3·6H2O (0.1mmol, 0.026g) be dissolved in by 2mL DMF and
8mL CH3The in the mixed solvent of OH compositions, then 3 drop pyridines are instilled, stir (the now pH=5.6 of solution), and gained is molten
Liquid is transferred to volume in hydrothermal reaction kettles of the 25mL with polytetrafluoroethylsubstrate substrate, 72h is reacted under the conditions of being placed in 100 DEG C, takes out,
Room temperature is cooled to, the black feed liquid of gained is filtered, filtrate stands at room temperature grows black strip crystalline substance after volatilization, four weeks
Body, yield：40%.(C141.5H141.5Fe11O47N35.5) elementary analysis (%), theoretical value：C, 45.86；H, 3.86；N, 13.42；
Experiment value：C, 45.80；H, 3.79；N, 13.38.
The products therefrom of embodiment 1 is characterized：
With U.S. Nicolet 360FT-IR types Fourier transformation infrared spectrometer (KBr tablettings), the present embodiment is made
Product carry out infrared analysis, take the photograph 4000~400cm of spectral limit-1, gained infrared spectrum spectrogram is as shown in Fig. 2 data are as follows：
IR (KBr pellet, cm-1)：3456 (m), 1642 (w), 1601 (m), 1571 (w), 1509 (vs), 1407 (s),
1325 (w), 1244 (m), 1155 (w), 920 (w), 847 (w), 755 (m).
2) crystal structure analysis：
By Agilent company SuperNova single crystal diffractometers be measured the intact black bulk crystals of surface texture with
Its mono-crystalline structures is determined, gained crystallographic parameter data see below table 1, and bond distance's bond angle data see below table 2.
Table 1：Cluster compound [Fe11(L)6(DMF)5(H2O)]·4DMF·H2O·3C2H8N0.5Py crystallographic parameter is shown in
Table
Table 2：Cluster compound [Fe11(L)6(DMF)5(H2O)]·4DMF·H2O·3C2H8N0.5Py part bond distanceWith
Part bond angle (°) table
X-ray single crystal diffraction analysis shows, gained black strip crystal belongs to monoclinic system, C2/c space groups.Coordinate
Thing 5 is the core Iron cluster of a caged 11 being built into by 11 iron ions of the coordination N on part and O atom bridging,
Its skeleton is by 11 iron ions, the ligand L of six de- six protons, the DMF molecules and the moisture being coordinated of five coordinations
Son is constituted, and peripheral solvent molecule includes four DMF molecules, a hydrone, three the dimethylamine cations and structure cell that are not coordinated
Between share a Pyridine Molecules.
The molecular structure of gained black strip crystal is as shown in Figure 3.Six of coordination are participated in this implementation products therefrom
The hydrazide ligands H of trans N, N '-two (salicyl) butylene two6L sloughs whole protons, chelates 11 iron ions, and iron ion has
Three kinds of different coordination environments, are hexa-coordinates, all in the octoploids structure of distortion, wherein, the first iron ion (Fe2,
Fe6 coordination environment) is identical, is [FeN3O3], coordination atom source is identical, by taking Fe6 as an example, and it participates in six atoms of coordination
Respectively from the oxygen atom on three salicyls of three parts, three salicylyl hydrazine nitrogen-atoms, six coordination atoms are constituted
The octoploids structure of one distortion, axial location is occupied by the oxygen atom on salicylyl hydrazine nitrogen-atoms and salicyl, equator
In plane occupied by the oxygen atom on salicylyl hydrazine nitrogen-atoms and salicyl.Second iron ion (Fe4, Fe8, Fe10)
Coordination environment is identical, is [FeN2O4], coordination atom source is identical, by taking Fe10 as an example, and its six atom for participating in coordination comes respectively
From a phenolic hydroxyl group oxygen atom of a part, a nitrogen-atoms of salicylyl hydrazine a, oxygen atom on crotonyl is another
An oxygen atom on one phenolic hydroxyl group oxygen atom of individual part, a nitrogen-atoms of salicylyl hydrazine, crotonyl, six coordinations
The octoploids structure of one distortion of atomic building, axial location is occupied by the salicylyl hydrazine nitrogen-atoms on two parts, equator
In plane occupied by the oxygen atom on the phenolic hydroxyl group oxygen atom and crotonyl on two parts.The third iron ion (Fe1,
Fe3, Fe5, Fe7, Fe9, Fe11) coordination environment it is identical, be [FeN2O4], coordination atom source is similar, by taking Fe9 as an example, and it is joined
Six atoms with coordination are respectively from a phenolic hydroxyl group oxygen atom of a part, a nitrogen-atoms of salicylyl hydrazine, butylene
Carbonylic oxygen atom on an oxygen atom on acyl group, another part salicyl, a nitrogen-atoms of salicylyl hydrazine, and one
Oxygen atom on individual coordination DMF, six coordination atoms constitute the octoploids structure of a distortion, and axial location is by salicylyl hydrazine
Occupied by oxygen atom on one nitrogen-atoms and coordination DMF, by a phenolic hydroxyl group oxygen atom of part, salicyloyl on equatorial plane
Occupied by oxygen atom on an oxygen atom on one nitrogen-atoms of hydrazine, crotonyl, another part salicyl.
11 iron ions are repetition with [Fe-N-N-Fe] by the nitrogen-atoms of salicylyl hydrazine in the present embodiment products therefrom
Unit is connected, from the side, and the skeleton of products therefrom is the three-bladed propeller shape that Fe ions and N atoms are connected into, wherein,
Fe1, Fe3 and Fe9, Fe4, Fe8 and Fe10, Fe5, Fe7 and Fe11 form three triangles respectively.
To sum up, it is determined that the black strip crystal of gained is 11 core Iron cluster [Fe of the present invention11(L)6
(DMF)5H2O]·4DMF·H2O·3C2H8N0.5Py, wherein L represent N, N '-two (the salicyl)-hydrazides of (E)-butylene two,
The part sloughs six hydrogen atoms, the negative electrical charge of six units of band, and there be three dimethylamine cations not being coordinated in the external world.
3) thermogravimetric is characterized：
With French C1-esteraseremmer-N La Mu Instrument Ltd. Labsys evo TG-DSC/DTA, to made from the present embodiment 11
Core Iron cluster [Fe11(L)6(DMF)5(H2O)]·4DMF·H2O·3C2H8N0.5Py carries out thermogravimetric test and analysis, test
Condition is：Under nitrogen atmosphere, 1000 DEG C are risen to from room temperature with 10 DEG C/min speed, heat analysis result is as shown in Figure 4.
As shown in Figure 4, the weightlessness of 11 core Iron clusters made from the present embodiment is divided into two main weightless processes, from 35
Occur weightless behavior for the first time to 230 DEG C, 12.1% (theoretical value 12.9%) of gross mass is lost, corresponding to compound middle reaches
From solvent molecule lose；Continue to heat up, at 230-1000 DEG C, occur second of weightless behavior, complex framework is gradually
Cave in.
4) magnetic property is determined：
Take 11 core Iron cluster [Fe made from 28.3mg the present embodiment11(L)6(DMF)5(H2O)]·4DMF·H2O·
3C2H8N0.5Py carries out Magnetic Test after pulverizing on Magnetic Test instrument, is specifically the direct current in 2-300K temperature ranges
External magnetic field is under the conditions of H=1000Oe, measures its molar susceptibility variation with temperature situation, and the alternating temperature of gained cluster compound magnetizes
Rate figure (χM-T,χMT-T curve maps) as shown in Figure 5.
As shown in Figure 5, the χ that cluster compound experiment is measured in 300KMT value is 48.82cm3K mol-1, theoretical value
48.13cm3K mol-1[for 11 S=5/2 Fe (III)], and theoretical value are close, with the reduction χ of temperatureMT slowly drops
It is low, reach 31.46cm in 100K3Kmol-1, then drastically reduce, minimum value 3.37cm reached in 2K3K mol-1.And χM –1-T
Curve defers to Curie-Weiss law, and it is fitted and obtains Weiss constants θ=- 110.33K, and Curie constant is C=
65.70cm3K mol–1。χMT-T curvilinear trends and negative Weiss constants show there is antiferromagnetic friendship in cluster compound between iron ion
The effect of changing.
Embodiment 2
Embodiment 1 is repeated, unlike：
1) by N, N '-two (salicyl)-hydrazides of (E)-butylene two and FeCl3·6H2The ratio between O amount of material is changed to
1：3；
2) in the mixed solvent, 1 is changed to by the volume ratio of DMF and methanol：3；
3) pH value of solution is adjusted to 5.7.
Hydrothermal reaction kettle is taken out, room temperature is cooled to, the black feed liquid of gained is filtered, filtrate stands volatilization at room temperature,
Black strip crystal is grown after four weeks.Yield 42%.
Structural characterization is carried out to products therefrom, it is target product [Fe to determine product11(L)6(DMF)5(H2O)]·4DMF·
H2O·3C2H8N0.5Py, wherein L represent N, and N '-two (the salicyl)-hydrazides of (E)-butylene two, the part sloughs six hydrogen
There is three dimethylamine cations not being coordinated in atom, the negative electrical charge of six units of band, the external world.
Understand there is anti-ferromagnetic exchange interaction iron ion in products therefrom to the Magnetic Characterization of products therefrom.
Embodiment 3
Embodiment 1 is repeated, unlike：
1) in the mixed solvent, 1 is changed to by the volume ratio of DMF and methanol：1；
2) mixed liquor for mixing up pH value is placed under the conditions of 80 DEG C and reacts 48h.
Hydrothermal reaction kettle is taken out, room temperature is cooled to, the black feed liquid of gained is filtered, filtrate stands volatilization at room temperature,
Black strip crystal is grown after four weeks.Yield 39%.
Structural characterization is carried out to products therefrom, it is target product [Fe to determine product11(L)6(DMF)5(H2O)]·4DMF·
H2O·3C2H8N0.5Py, wherein L represent N, and N '-two (the salicyl)-hydrazides of (E)-butylene two, the part sloughs six hydrogen
There is three dimethylamine cations not being coordinated in atom, the negative electrical charge of six units of band, the external world.
Understand there is anti-ferromagnetic exchange interaction iron ion in products therefrom to the Magnetic Characterization of products therefrom.
Embodiment 4
Embodiment 1 is repeated, unlike：
1) pH value of solution is adjusted to 5.5.
2) in the mixed solvent, 2 are changed to by the volume ratio of DMF and methanol：1；
3) mixed liquor for mixing up pH value is placed under the conditions of 120 DEG C and reacts 30h.
Hydrothermal reaction kettle is taken out, room temperature is cooled to, the black feed liquid of gained is filtered, filtrate stands volatilization at room temperature,
Black strip crystal is grown after four weeks.Yield 41%.
Structural characterization is carried out to products therefrom, it is target product [Fe to determine product11(L)6(DMF)5(H2O)]·4DMF·
H2O·3C2H8N0.5Py, wherein L represent N, and N '-two (the salicyl)-hydrazides of (E)-butylene two, the part sloughs six hydrogen
There is three dimethylamine cations not being coordinated in atom, the negative electrical charge of six units of band, the external world.
Understand there is anti-ferromagnetic exchange interaction iron ion in products therefrom to the Magnetic Characterization of products therefrom.
Embodiment 5
Embodiment 1 is repeated, unlike：
1) pH value of solution is adjusted to 5.3.
2) mixed liquor for mixing up pH value is placed under the conditions of 60 DEG C and reacts 96h.
Hydrothermal reaction kettle is taken out, room temperature is cooled to, the black feed liquid of gained is filtered, filtrate stands volatilization at room temperature,
Black strip crystal is grown after four weeks.Yield 35%.
Structural characterization is carried out to products therefrom, it is target product [Fe to determine product11(L)6(DMF)5(H2O)]·4DMF·
H2O·3C2H8N0.5Py, wherein L represent N, and N '-two (the salicyl)-hydrazides of (E)-butylene two, the part sloughs six hydrogen
There is three dimethylamine cations not being coordinated in atom, the negative electrical charge of six units of band, the external world.
Understand there is anti-ferromagnetic exchange interaction iron ion in products therefrom to the Magnetic Characterization of products therefrom.
Claims (6)
1. a kind of 11 core Iron clusters, it is characterised in that：
The chemical formula of the cluster compound is：[Fe11(L)6(DMF)5(H2O)]·4DMF·H2O·3C2H8N0.5Py, wherein L are represented
N, N '-two (salicyl)-hydrazides of (E)-butylene two, the part slough six hydrogen atoms, and the negative electrical charge of six units of band is extraneous
Also three dimethylamine cations that are not coordinated；
The cluster compound belongs to monoclinic system, C2/ c space groups, cell parameter is： α=90.00 °, β=105.823 (3) °, γ=90.00 °.
2. the synthetic method of 11 core Iron clusters described in claim 1, it is characterised in that：Take N, N '-two (salicyl)-
(E)-hydrazides of butylene two and FeCl3·6H2O mixed solvents dissolve, afterwards with pyridine adjust resulting solution pH=5.3~
5.9, gained mixed liquor is placed in hydrothermal reaction kettle, and in being reacted under heating condition, reactant cooling stands crystallization, produces target
Product；Described mixed solvent is N, N ' dimethylformamides and methanol composition.
3. synthetic method according to claim 2, it is characterised in that：Described in the mixed solvent, N, N ' dimethyl formyl
The volume ratio of amine and methanol is 1~4：1~4.
4. synthetic method according to claim 2, it is characterised in that：Reaction is carried out under the conditions of 60~120 DEG C.
5. synthetic method according to claim 2, it is characterised in that：The time of reaction is 30~80h or more than 80h.
6. application of the 11 core Iron clusters in magnetic material is prepared described in claim 1.
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| CN110759352A (en) * | 2019-11-15 | 2020-02-07 | 广西师范大学 | Method for synthesizing Beta molecular sieve by adding template agent into seed crystal |
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