CN107141259A - A kind of imidazoles with many wolframic acid cocrystallization super molecular compounds and preparation method thereof - Google Patents
A kind of imidazoles with many wolframic acid cocrystallization super molecular compounds and preparation method thereof Download PDFInfo
- Publication number
- CN107141259A CN107141259A CN201710334966.2A CN201710334966A CN107141259A CN 107141259 A CN107141259 A CN 107141259A CN 201710334966 A CN201710334966 A CN 201710334966A CN 107141259 A CN107141259 A CN 107141259A
- Authority
- CN
- China
- Prior art keywords
- imidazoles
- wolframic acid
- molecular compounds
- super molecular
- imi
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention belongs to technical field of chemical material preparation, and in particular to a kind of imidazoles with many wolframic acid cocrystallization super molecular compounds and preparation method and application, the compound has following chemical general formula：(NH4)4(imi)6[H2W12O42]·H2O, wherein imi are neutral glyoxaline cation (C3H5N2), prepared using solvent thermal reaction method.Compound in the present invention prepares higher yield, favorable reproducibility, with higher heat endurance and phase purity using solvent thermal process, molecule base monocrystal material therein is the molecule sill with electrochemical characteristic, have the advantages that small volume, relative density are light, be easy to Compound Machining to be molded, it can use, can also be applied as electricity material in electric scientific domain as potential electrode material.
Description
Technical field
The invention belongs to technical field of chemical material preparation, and in particular to a kind of imidazoles with many wolframic acid cocrystallization supermolecules
Compound and preparation method and application.
Background technology
There are many component co-crystallization compounds of interesting structure and property to be the heat subject studied at present for self assembly, special
It is not that this kind of compound can be used to being catalyzed as functional material, the field such as opto-electronic conversion, magnetic has a wide range of applications.
Turn into the important research direction of multiple fields Disciplinary Frontiers scientific research personnel in the last few years.Polyoxometallic acid salt compound has
There are the characteristics such as the changeable, function admirable of structure, be the important inorganic building block for constructing new function material, while being built as inorganic
Build unit and outstanding electronq donor, can be combined with different types of proton donor, formed with magnetic, light, electric and super
Lead the hybrid material of property.Itrogenous organic substance such as ethylenediamine, bipyridyl, imidazoles, methylimidazole etc., are that good many protons are given
Body, can form a variety of new constructions with polyacid, and its own can also be linked by oxygen key, be that organic secondary building is single well for a class
Member.
From the current study, in multi-component material of the organic cation as counter ion counterionsl gegenions, many acid units are with molybdenum
Based on polyoxoanion and miscellaneous many tungsten acid anions, and it is also very limited with the current report of correlative study of many tungsten acid anions.
Exploring the correlative study in this direction helps to enrich the database of compound polyacid material, and it is compound further to disclose molecule base
The structure-activity relationship of material.
The content of the invention
Present invention aims at provide a kind of imidazoles with many wolframic acid cocrystallization super molecular compounds and preparation method with
Using.
To achieve the above object, the present invention provides following technical scheme：
A kind of imidazoles with many wolframic acid cocrystallization super molecular compounds, with following chemical general formula： (NH4)4(imi)6
[H2W12O42] H2O, wherein imi are neutral glyoxaline cation (C3H5N2).
A kind of imidazoles with many wolframic acid cocrystallization super molecular compounds, the complex crystal is brilliant in anorthic system space group
Born of the same parents' parameter is a=12.5922 (11), b=19.7694 (18), c=22.047 (2) (9), β=93.362 (2), V
= 5478.8(9)Å3, Z = 4。
A kind of imidazoles and the preparation method with many wolframic acid cocrystallization super molecular compounds, using solvent thermal reaction method system
It is standby, specifically include following steps：
（1）By Na10 [H2W12O42] 20H2O (0.35 g, 0.1 mmol), imi (0.034 g, 0.5mmol) with
H2O (12 mL) and ethanol (8mL) mixing, stir 30 min；
（2）PH=3.9 are adjusted with the ammonia spirit and 4MHCl of dilution, 25 ml is then added and carries polytetrafluoroethyllining lining
In stainless steel cauldron, it is heated to 130 DEG C and reacts 2 days, afterwards, be slowly dropped to room temperature；
（3）It is washed out, dries, obtains light yellow crystal.
Further, described solvent thermal reaction refers in the stainless steel cauldron of inner liner polytetrafluoroethylene, with deionization
Water and organic solvent are reaction medium, make to produce spontaneous pressure inside container by temperature control oven heating, heating-up temperature is 100 DEG C
~ 350 DEG C, pressure is the Mpa of 1 Mpa ~ 100 so that indissoluble or insoluble material dissolve and crystallize precipitation under normal conditions.
A kind of imidazoles and the application with many wolframic acid cocrystallization super molecular compounds in terms of molecular-base electric material is prepared.
Beneficial effects of the present invention are：Imidazoles in the present invention with many wolframic acid cocrystallization super molecular compounds with using solvent
It is prepared by hot method, yield is higher, favorable reproducibility, with higher heat endurance and phase purity, can be as electricity material in electric section
In field be applied；Molecule base monocrystal material therein is the molecule sill with electrochemical characteristic, with small volume,
Relative density is light, be easy to the advantages of Compound Machining is molded, and can be used as potential electrode material.
Brief description of the drawings
Fig. 1 is the crystal structure figure of the super molecular compound of the present invention；
Fig. 2 is the three-dimensional accumulation graph of the super molecular compound of the present invention；
Fig. 3 is the thermogravimetric analysis figure of the super molecular compound of the present invention；
Fig. 4 is the electro-chemical test figure of the super molecular compound of the present invention.
Embodiment
Embodiment 1
A kind of imidazoles with many wolframic acid cocrystallization super molecular compounds, with following chemical general formula： (NH4)4(imi)6
[H2W12O42] H2O, wherein imi are neutral glyoxaline cation (C3H5N2).
Above-mentioned super molecular compound, is prepared using solvent thermal reaction method, specifically includes following steps：
（1）By Na10[H2W12O42]·20H2O (0.35 g, 0.1 mmol), imi (0.034 g, 0.5mmol) and H2O
(12 mL) and ethanol (8mL) are mixed, and stir 30 min；
（2）PH=3.9 are adjusted with the ammonia spirit and 4MHCl of dilution, 25 ml is then added and carries polytetrafluoroethyllining lining
In stainless steel cauldron, it is heated to 130 DEG C and reacts 2 days, afterwards, be slowly dropped to room temperature；
（3）It is washed out, dries, obtains light yellow crystal.
Described solvent thermal reaction refers in the stainless steel cauldron of inner liner polytetrafluoroethylene, with deionized water and organic
Solvent is reaction medium, makes to produce spontaneous pressure inside container by temperature control oven heating, heating-up temperature is 100 DEG C ~ 350 DEG C,
Pressure is the Mpa of 1 Mpa ~ 100 so that indissoluble or insoluble material dissolve and crystallize precipitation under normal conditions.
Embodiment 2
By size be 0.16 × 0.12 × 0.18 mm3Embodiment 1 obtain faint yellow monocrystalline i.e.（Imidazoles with many wolframic acids with being total to
Crystallize super molecular compound）Load in glass capillary.Data are collected with Neo-Confucianism R-AXIS RAPID IP diffractometers,
Using Mo-K α (λ=0.71073), room temperature 296 K, θ scope 1.35< θ < 25.00°.Application experience absorption correction,
Collect altogether 12922 diffraction datas (independent point diffraction 12528, Rint=0.0401), hkl values scope -7≤h≤
15, -24≤k≤24, -26≤l≤20.
The compound crystal structure of the present invention is parsed using direct method, and with least square method F2 refine, is used
SHELXL-97 software kits.The crystal data of the compound exists apart from OW in reconditioning process(water)…O(POM)Short connection,
Show to deposit interaction of hydrogen bond between lattice hydrone and polyanionic.Further, since the imidazoles sun in the compound of the present invention
H atom scattering strength on ion is too low to be determined from Fourier's figure, and therefore, whole C-H atom sites on imidazoles are pressed
Theory mode, which is calculated, to be determined, and participates in final structure refine.The crystallographic data of compound is shown in Table 1.
The cell parameter determined the following is experiment（Table 1）With selective bond distance's bond angle（Table 2）
The structure cell of table 1 and measurement parameter
The selective bond distance's bond angle of table 2
The simple glyoxaline cation of the present invention and the organic-inorganic composite monocrystal constructed jointly with many wolframic acids, the complex
Crystallize in anorthic system space group, cell parameter isa = 12.5922(11)Å, b = 19.7694(18)Å, c = 22.047
(2)(9)Å, β=93.362(2), V = 5478.8(9)Å3, Z= 4；See Fig. 1.
Surrounded in the compounds of this invention structure cell with many tungsten acid anions by 6 glyoxaline cations, constitute organic-inorganic and surpass
Molecular structure.In [H2W12O42]10-In anion, altogether comprising three class W-O keys, the scope of different type W-O keys is as follows：（a）Hold oxygen
W-O (t) keys distance range is 1.695 (15) -1.858 (14)；（ii）Bridging oxygen W-O (μ) keys distance range be 1.868 (13)-
1.992(14);（iii）The W-O keys distance range that the inside of three tungsten atoms is connected to for key is 2.148 (12) -2.278
(13)Å.These numerical value show octoploids structures of the WO6 for distortion, and the phenomenon is attributable between polyanionic and glyoxaline cation
The result of strong interaction.Further analysis shows, glyoxaline cation is crystallized in polyanionic three by electrostatic attraction and hydrogen bond
Among the space of level structure and Magnetic Properties of Three-Dimensional Supramolecular Complex structure is formed, as shown in Figure 2.
The thermogravimetric curve of the compounds of this invention is in N2Under protection, the rate of heat addition is 10 DEG C of min-1, heating temperature range
For what is determined under conditions of 30-600 DEG C.As shown in figure 3, weightless value of the compounds of this invention compound at 110-290 DEG C
16.1% corresponds to free NH4 +, [IMI]+Cation loses（Theoretical value 15.4%）.
Due to [H2W12O42]10-WO simultaneously containing one end oxygen of band6The WO of the octahedra and cis end oxygen of two, band6Octahedral
Body, therefore anion belongs to group iii polyanionic and with certain electro-chemical activity.We utilize UV-vis spectrum monitorings
The compound is simultaneously determined to the stability to its pH value.As a result show the compound pH value be 1-3.5 between compared with
To be stable, therefore we have selected pH to study its electrochemical properties in the environment of 1.5.
The electrochemical properties of the compounds of this invention are 5 × 10-3Tested in the sulfuric acid solution of M pH=1.5.Sweep
The rate of hastening is retouched for 25mVs-1, preliminary sweep direction is negative electrode.From fig. 4, it can be seen that going out in potential range -700 to 700 mV
3 pairs of redox peaks are showed, it reduces peak position at -595, -399 and -12 mV, and they correspond respectively to [H2W12O42]10-
The three steps reduction at W centers in ion, surface compound has good redox active.
Imidazoles in the present invention with many wolframic acid cocrystallization super molecular compounds using solvent thermal process preparation, yield compared with
Height, favorable reproducibility, with higher heat endurance and phase purity, can be applied as electricity material in electric scientific domain；
Molecule base monocrystal material therein is the molecule sill with electrochemical characteristic, and with small volume, relative density is light, it is multiple to be easy to
The advantages of closing machine-shaping, can use as potential electrode material.
Claims (5)
1. a kind of imidazoles with many wolframic acid cocrystallization super molecular compounds, it is characterised in that with following chemical general formula： (NH4)4
(imi)6[H2W12O42]·H2O, wherein imi are neutral glyoxaline cation (C3H5N2)。
2. a kind of imidazoles according to claim 1 with many wolframic acid cocrystallization super molecular compounds, it is characterised in that the change
Compound is crystallized in anorthic system space group, and cell parameter isa = 12.5922(11)Å, b = 19.7694(18)Å, c =
22.047(2)(9)Å, β=93.362(2), V = 5478.8(9)Å3, Z = 4。
3. the imidazoles described in a kind of claim 1 and the preparation method with many wolframic acid cocrystallization super molecular compounds, its feature exist
In, using solvent thermal reaction method prepare, specifically include following steps：
（1）By Na10[H2W12O42]·20H2O (0.35 g, 0.1 mmol), imi (0.034 g, 0.5mmol) and H2O
(12 mL) and ethanol (8mL) are mixed, and stir 30 min；
（2）PH=3.9 are adjusted with the ammonia spirit and 4MHCl of dilution, 25 ml is then added and carries polytetrafluoroethyllining lining
In stainless steel cauldron, it is heated to 130 DEG C and reacts 2 days, afterwards, be slowly dropped to room temperature；
（3）It is washed out, dries, obtains light yellow crystal.
4. a kind of imidazoles according to claim 3 and the preparation method with many wolframic acid cocrystallization super molecular compounds, it is special
Levy and be, described solvent thermal reaction refers in the stainless steel cauldron of inner liner polytetrafluoroethylene, with deionized water and organic
Solvent is reaction medium, makes to produce spontaneous pressure inside container by temperature control oven heating, heating-up temperature is 100 DEG C ~ 350 DEG C,
Pressure is the Mpa of 1 Mpa ~ 100 so that indissoluble or insoluble material dissolve and crystallize precipitation under normal conditions.
5. the imidazoles described in a kind of claim 1 with many wolframic acid cocrystallization super molecular compounds with preparing molecular-base electric material
The application of aspect.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710334966.2A CN107141259A (en) | 2017-05-12 | 2017-05-12 | A kind of imidazoles with many wolframic acid cocrystallization super molecular compounds and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710334966.2A CN107141259A (en) | 2017-05-12 | 2017-05-12 | A kind of imidazoles with many wolframic acid cocrystallization super molecular compounds and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107141259A true CN107141259A (en) | 2017-09-08 |
Family
ID=59778320
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710334966.2A Pending CN107141259A (en) | 2017-05-12 | 2017-05-12 | A kind of imidazoles with many wolframic acid cocrystallization super molecular compounds and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107141259A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109518274A (en) * | 2019-01-07 | 2019-03-26 | 合肥学院 | A kind of 12 tungstate crystal materials and preparation method thereof with two-dimensional nanopore cavity configuration |
| CN109796050A (en) * | 2019-01-25 | 2019-05-24 | 昆明学院 | Miscellaneous more arsenomolybdate compounds of one kind and the preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102000610A (en) * | 2010-09-30 | 2011-04-06 | 常熟理工学院 | Tungsten series or molybdenum series polyoxometallate supermolecular compound as well as preparation method and application thereof |
| CN103266353A (en) * | 2013-01-31 | 2013-08-28 | 昆明学院 | Sandwich-type bismuth tungstate compound with methylimidazole simultaneously as counter ion and modified group and preparation method and application thereof |
| CN103360424A (en) * | 2013-07-03 | 2013-10-23 | 吉林化工学院 | Structure of multi-metal phosphomolybdate organic-inorganic hybrid and preparation method |
| CN104086603A (en) * | 2014-07-08 | 2014-10-08 | 吉林化工学院 | Structure and preparation method of imidazole modified phosphotungstate compound |
-
2017
- 2017-05-12 CN CN201710334966.2A patent/CN107141259A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102000610A (en) * | 2010-09-30 | 2011-04-06 | 常熟理工学院 | Tungsten series or molybdenum series polyoxometallate supermolecular compound as well as preparation method and application thereof |
| CN103266353A (en) * | 2013-01-31 | 2013-08-28 | 昆明学院 | Sandwich-type bismuth tungstate compound with methylimidazole simultaneously as counter ion and modified group and preparation method and application thereof |
| CN103360424A (en) * | 2013-07-03 | 2013-10-23 | 吉林化工学院 | Structure of multi-metal phosphomolybdate organic-inorganic hybrid and preparation method |
| CN104086603A (en) * | 2014-07-08 | 2014-10-08 | 吉林化工学院 | Structure and preparation method of imidazole modified phosphotungstate compound |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109518274A (en) * | 2019-01-07 | 2019-03-26 | 合肥学院 | A kind of 12 tungstate crystal materials and preparation method thereof with two-dimensional nanopore cavity configuration |
| CN109796050A (en) * | 2019-01-25 | 2019-05-24 | 昆明学院 | Miscellaneous more arsenomolybdate compounds of one kind and the preparation method and application thereof |
| CN109796050B (en) * | 2019-01-25 | 2021-04-20 | 昆明学院 | Heteropoly-arsenic molybdate compound and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Hydrothermal syntheses and structural characterization of layered vanadium oxides incorporating organic cations: α-, β-(H3N (CH2) 2NH3)[V4O10] and α-, β-(H2N (C2H4) 2NH2)[V4O10] | |
| Zhao et al. | Two Dawson-Templated Three-Dimensional Metal− Organic Frameworks Based on Oxalate-Bridged Binuclear Cobalt (II)/Nickel (II) SBUs and Bpy Linkers | |
| Zhang et al. | Syntheses, structures, and electrochemical properties of three new acetate-functionalized zirconium-substituted germanotungstates: From dimer to tetramer | |
| Wang et al. | A novel 2D→ 3D {Co 6 PW 9}-based framework extended by semi-rigid bis (triazole) ligand | |
| Cao et al. | Proton conductivity resulting from different triazole-based ligands in two new bifunctional decavanadates | |
| Wang et al. | Triol-Ligand Modification and Structural Transformation of Anderson–Evans Oxomolybdates via Modulating Oxidation State of Co-Heteroatom | |
| CN107141259A (en) | A kind of imidazoles with many wolframic acid cocrystallization super molecular compounds and preparation method thereof | |
| Jang et al. | Enabling electrochemical N 2 reduction to NH 3 in the low overpotential region using non-noble metal Bi electrodes via surface composition modification | |
| Xu et al. | Solvent-induced Mn (II)/Zn (II)/Co (II) organopolymolybdate compounds constructed by bis-pyridyl-bis-amide ligands through the Mo–N bond: synthesis, structures and properties | |
| Yu et al. | Assembly of organic–inorganic hybrid supramolecular materials based on {P 2 W 18 O 62} 6− anion and Cu (ii)/Mn (ii) complex | |
| Guo et al. | Two three-dimensional Fe (ii) frameworks based on {P 4 Mo 6} tetrameric clusters exhibiting efficient visible-light photocatalytic properties for the degradation of Cr (vi) and methylene blue | |
| Gui et al. | Developing a unique hydrogen-bond network in a uranyl coordination framework for fuel cell applications | |
| CN104829813B (en) | A kind of ionomeric polymer containing phosphine, preparation method and anion-exchange membrane | |
| Suh et al. | Template synthesis and characterization of a nickel (II) complex with tris (((aminoethyl) amino) methyl) amine:(semisepulchrate) nickel (2+) | |
| Copping et al. | Tetravalent metal complexation by Keggin and lacunary phosphomolybdate anions | |
| CN104910214A (en) | Weakley polyacid compound containing mixed cations, and preparation method and application thereof | |
| Xiu et al. | Fe‐VS2 Electrocatalyst with Organic Matrix‐Mediated Electron Transfer for Highly Efficient Nitrogen Fixation | |
| CN107417928A (en) | A kind of metallic silver coordination polymer containing mixed ligand and preparation method thereof | |
| Ayyappan et al. | New Metal-Intercalated Layered Vanadyl Phosphates, M x VOPO4⊙ yH2O (M= Ag, Cu, Zn) | |
| Yakubovich et al. | An orthorhombic modification of KCoPO4 stabilized under hydrothermal conditions: Crystal chemistry and magnetic behavior | |
| Liu et al. | Assembly of trimeric polyoxovanadate aggregates based on [MnV 13 O 38] 7− building blocks and lanthanide cations | |
| Khavasi et al. | Conformational variety of flexible mono-dentate ligands in coordination compounds: influence of π-involving interactions | |
| Rom et al. | Bifunctional Role of Methyl Viologen in UV and X-ray Sensitive Switchable Organophosphonate Single Crystal | |
| Gao et al. | Design and synthesis of phosphomolybdate coordination compounds based on {P 4 Mo 6} structural units and their proton conductivity | |
| Han et al. | The first polyoxometalate polymer constructed by assembly of the heptamolybdic anion and copper coordination groups |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170908 |
|
| WD01 | Invention patent application deemed withdrawn after publication |