CN106349482A - Nickel coordination polymer with imidazole-based ligands and method for preparing nickel coordination polymer - Google Patents
Nickel coordination polymer with imidazole-based ligands and method for preparing nickel coordination polymer Download PDFInfo
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- CN106349482A CN106349482A CN201610655900.9A CN201610655900A CN106349482A CN 106349482 A CN106349482 A CN 106349482A CN 201610655900 A CN201610655900 A CN 201610655900A CN 106349482 A CN106349482 A CN 106349482A
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Abstract
The invention relates to the field of coordination polymer materials, and discloses a nickel coordination polymer with imidazole-based ligands and a method for preparing the nickel coordination polymer. A chemical formula of the nickel coordination polymer with the imidazole-based ligands is C<21>H<31>N<6>O<9>SNi, and the nickel coordination polymer with the imidazole-based ligands belongs to P-1 space groups of triclinic systems; unit-cell parameters include that an a is equal to 8.6910 (4) , a b is equal to 11.7296 (5) , a c is equal to 13.1200 (6) , an alpha is equal to 83.9220 (10) degrees, a beta is equal to 77.8290 (10) degrees, a gamma is equal to 74.0640 (10) degrees, and a V is equal to 1255.53 (10) <3>. The nickel coordination polymer with the imidazole-based ligands and the method have the advantages that the nickel coordination polymer with the imidazole-based ligands is easy prepare, high in yield and good in repeatability, synthesized materials rarely have defects and are high in crystallinity, and the method is easy and convenient to implement and good in stability; the nickel coordination polymer with the imidazole-based ligands has an excellent potential application prospect in the fields of molecular magnets, catalysis, molecular recognition and the like.
Description
Technical field
The present invention relates to coordination polymer material field, a kind of imidazoles ylidene ligands nickel coordination polymer and preparation method thereof.
Background technology
Due to nitrogen-atoms coordination ability, such part has been widely used for constructing new function nitrogenous heterocyclic part by force
Coordination polymer.Particularly imidazole derivatives species part, because on imidazole ring, the angle between two n atoms is about 145 °, this
Closely it is easy to synthesize, there is the zeolite structured coordination polymer of class with the angle of si-o-si in zeolite molecular sieve.With biography
The coordination polymer of system is compared, and has the zeolite structured coordination polymer of class and has good heat stability and chemical stability.
At present, people are constructed with imdazole derivatives part and slaine and have obtained a series of thering is ion exchange, fluorescence, absorption, magnetic
Function coordination polymer etc. property.
Content of the invention
The technical problem to be solved is to provide a kind of imidazoles ylidene ligands nickel coordination polymer.
It is a further object to provide the preparation method of above-mentioned imidazoles ylidene ligands nickel coordination polymer.
The technical problem to be solved is achieved by the following technical programs:
A kind of imidazoles ylidene ligands nickel coordination polymer, chemical formula is c21h31n6o9Sni, described imidazoles ylidene ligands nickel coordination polymer
Belong to anorthic system, p-1 space group, cell parameter isa=8.6910 (4),b=11.7296 (5),c=13.1200
(6), α=83.9220 (10) °, β=77.8290 (10) °, γ=74.0640 (10) °,v=1255.53 (10)3.
Further, ni atom adopts hexa-coordinate to deform octoploids structure, ni atom and three n atoms, three o atoms
Coordination；These three n atoms divide respectively from 3 different 1,3,5- tri- (imidazoles -1- methyl) benzene parts, the bond distance of ni-n key
Not Wei 2.0597 (15), 2.0736 (15), 2.0777 (15), three o atoms respectively from 1 glycol molecule, 1
Individual sulfate ion and 1 water of coordination molecule, the bond distance of ni-o key is respectively 2.0904 (12), 2.1458 (12), 2.1048
(12)å.
Further, 1,3,5- tri- (imidazoles -1- methyl) adjacent ni atom of benzene part bridging forms one-dimensional chain knot
Structure.
Further, adjacent one-dimensional chain passes through intermolecular hydrogen bonding o-h o interaction and forms two dimension further
Supramolecular structure.
A kind of preparation method of imidazoles ylidene ligands nickel coordination polymer: by 1,3,5- tri- (imidazoles -1- methyl) benzene and sulphuric acid
Nickel adds in ethylene glycol and the mixed solution of distilled water, filters, then described filtrate is placed in autoclave after being sufficiently stirred for
In, after carrying out reacting by heating under the conditions of solvent thermal, Slow cooling obtains described imidazoles ylidene ligands nickel coordination polymer.
Further, described heating-up temperature is 130 ~ 160 DEG C.
Further, the described reacting by heating time is 24 ~ 72 hours.
Further, described cooling is down to room temperature for 2 DEG C/h ~ 5 DEG C/h.
Further, the volume ratio of described mixed solution ethylene glycol and distilled water is 1:2.
Further, described nickel sulfate and 1,3,5- tri- (imidazoles -1- methyl) benzene mole than for 0.8 ~ 1.2: 0.8 ~
1.2.
Further, described nickel sulfate and 1,3,5- tri- (imidazoles -1- methyl) benzene mole is than preferably 1:1.
The invention has the following beneficial effects:
Under the conditions of solvent thermal, the imidazoles ylidene ligands nickel coordination polymer of synthesis is easily prepared first, yield is high for the present invention, stable
Property is good, and the fault in material being synthesized is few, degree of crystallinity, and preparation method is simple, convenient, favorable reproducibility.This imidazoles ylidene ligands
Nickel coordination polymer has extraordinary potential application prospect in fields such as molecular magnet, catalysis, molecular recognition.
Brief description
Fig. 1 is the coordination context diagram of imidazoles ylidene ligands nickel coordination polymer metal center ni () of the present invention；
Fig. 2 is the connected mode figure of the imidazoles ylidene ligands nickel coordination polymer of the present invention；
Fig. 3 is the two-dimensional layered structure figure of the imidazoles ylidene ligands nickel coordination polymer of the present invention；
Fig. 4 is the thermogravimetric analysis figure of the imidazoles ylidene ligands nickel coordination polymer of the present invention；
Fig. 5 is the xrd figure of the imidazoles ylidene ligands nickel coordination polymer of the present invention；
Fig. 6 is the ir figure of the imidazoles ylidene ligands nickel coordination polymer of the present invention.
Specific embodiment
With reference to embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention,
It is not limitation of the invention.
Embodiment 1:
0.2mmol nickel sulfate and 0.2mmol 1,3,5- tri- (imidazoles -1- methyl) benzene are dissolved in 20ml ethylene glycol/distilled water
(v:v=1:2) in, filter after stirring at normal temperature 20min, filtrate is transferred to the stainless steel reaction making lining with politef
In kettle, put into after stainless steel cauldron is sealed in baking oven, react 72h at 140 DEG C, be down to room temperature with 5 DEG C/h afterwards,
Obtain described nickel coordination polymer, yield is 62.8% (based on ni).
Then above-mentioned imidazoles ylidene ligands nickel coordination polymer is carried out structural characterization
Crystal x-ray diffraction data adopts bruker smart apex ccd single crystal diffractometer to measure.Use graphite under 293k
Monochromatization mo k alpha ray (λ=0.071073nm) as radiation source, collect diffraction data.Scan mode is that φ-ω scans,
And carrying out lp factor correction and empirical absorption correction, absorption correction uses sadabs program.Metallic atom is determined using direct method
And the position coordinateses of non-hydrogen atom, whole non-hydrogen atom coordinates and its anisotropy thermal parameter carry out complete matrix least square method and repair
Just, the hydrogen atom beyond hydrone passes through theoretical hydrogenation and determines, and carries out isotropism refine, and the hydrogen atom on hydrone from
Directly find out on difference Fourier figure.Crystallographic parameter is shown in Table 1, and structure is shown in Fig. 1, Fig. 2, Fig. 3.
The predominant crystal data of the imidazoles ylidene ligands nickel coordination polymer of table 1 preparation
| empirical formula | c21h31n6o9sni |
| formular weight | 602.29 |
| crystal size / mm | 0.30×0.25×0.20 |
| crystal system | triclinic |
| space group | p |
| a/ å | 8.6910(4) |
| b/ å | 11.7296(5) |
| c/ å | 13.1200(6) |
| α/ (º) | 83.9220(10) |
| β/ (º) | 77.8290(10) |
| γ/ (º) | 74.0640(10) |
| v/ å3 | 1255.53(10) |
| z | 2 |
| d c / (g·cm-3) | 1.593 |
| λ/ nm | 0.071073 |
| temperature / k | 223.15 |
| θ range / (º) | 3.62～27.48 |
| collected reflections | 10288 |
| unique reflections | 5701 |
| observed reflection | 5107 |
| r int | 0.0145 |
| f (000) | 630.0 |
| μ/ mm-1 | 0.920 |
| r 1 | 0.0306 |
| wr 2 | 0.0761 |
Two-dimentional supramolecular structure.Fig. 1 depicts the coordination environment of metal center ni atom, it can be seen that metal center
Ni atom is located at symmetrical centre, using the octoploids structure of hexa-coordinate deformation, with three n atoms, three o Atomic coordinates.This three
Individual n atom comes from the imidazole group of 3 different 1,3,5- tri- (imidazoles -1- methyl) benzene parts, and (bond distance of ni-n key is
2.0597 (15) -2.0777 (15)), three o atoms are respectively from 1 glycol molecule (ni-o=2.0904 (12)
), 1 sulfate ion (ni-o=2.1458 (12)) and 1 water of coordination molecule (ni-o=2.1048 (12)).
1,3, the 5- tri- adjacent nickel center of (imidazoles -1- methyl) benzene part bridging, forms one-dimensional chain structure, as shown in Figure 2.On
The chain stated passes through sulfate ion and water of coordination molecule mutually can be built into two dimension by excessively intermolecular h o h hydrogen bond further
Supramolecular structure is as shown in Figure 3.
The nickel coordination polymer taking preparation in the present embodiment carries out thermogravimetric analysiss, and its spectrogram is as shown in Figure 4.In figure shows:
This nickel coordination polymer main body framework structure can be stablized to 400 DEG C.
The nickel coordination polymer taking preparation in the present embodiment carries out xrd test, and its spectrogram is as shown in Figure 5.In figure shows: real
This nickel coordination polymer testing synthesis is consistent with the analogue value, and phase purity is preferable.
The nickel coordination polymer taking preparation in the present embodiment carries out infrared spectrum characterization, and its spectrogram is as shown in Figure 6.
Embodiment 2:
0.18mmol nickel sulfate and 0.2mmol 1,3,5- tri- (imidazoles -1- methyl) benzene are dissolved in 20ml ethylene glycol/distillation
Water (v:v=1:2) in, after stirring at normal temperature 20min filter, by filtrate be transferred to politef make lining rustless steel anti-
Answer in kettle, put into after stainless steel cauldron is sealed in baking oven, react 72h at 140 DEG C, be down to room with 10 DEG C/h afterwards
Temperature, obtains described nickel coordination polymer, and yield is 58.7% (based on ni).
Embodiment 3:
0.22mmol nickel sulfate and 0.2mmol 1,3,5- tri- (imidazoles -1- methyl) benzene are dissolved in 20ml ethylene glycol/distillation
Water (v:v=1:2) in, after stirring at normal temperature 20min filter, by filtrate be transferred to politef make lining rustless steel anti-
Answer in kettle, put into after stainless steel cauldron is sealed in baking oven, react 36h at 130 DEG C, be down to room with 5 DEG C/h afterwards
Temperature, obtains described nickel coordination polymer, and yield is 56.4% (based on ni).
Embodiment 4:
0.2mmol nickel sulfate and 0.16mmol 1,3,5- tri- (imidazoles -1- methyl) benzene are dissolved in 20ml ethylene glycol/distillation
Water (v:v=1:2) in, after stirring at normal temperature 20min filter, by filtrate be transferred to politef make lining rustless steel anti-
Answer in kettle, put into after stainless steel cauldron is sealed in baking oven, react 24h at 150 DEG C, be down to room with 2 DEG C/h afterwards
Temperature, obtains described nickel coordination polymer, and yield is 53.5% (based on ni).
Embodiment 5:
0.2mmol nickel sulfate and 0.2mmol 1,3,5- tri- (imidazoles -1- methyl) benzene are dissolved in 20ml ethylene glycol/distilled water
(v:v=1:2) in, filter after stirring at normal temperature 20min, filtrate is transferred to the stainless steel reaction making lining with politef
In kettle, put into after stainless steel cauldron is sealed in baking oven, react 36h at 160 DEG C, be down to room temperature with 4 DEG C/h afterwards,
Obtain described nickel coordination polymer, yield is 60.8% (based on ni).
Embodiment described above only have expressed embodiments of the present invention, and its description is more concrete and detailed, but can not
Therefore it is interpreted as the restriction to the scope of the claims of the present invention, as long as the skill being obtained in the form of equivalent or equivalent transformation
Art scheme, all should fall within the scope and spirit of the invention.
Claims (5)
1. a kind of imidazoles ylidene ligands nickel coordination polymer it is characterised in that: chemical formula be c21h31n6o9Sni, described coordination polymerization
Thing belongs to anorthic system, p-1 space group, and cell parameter isa=8.6910 (4),b=11.7296 (5),c=13.1200
(6), α=83.9220 (10) °, β=77.8290 (10) °, γ=74.0640 (10) °,v=1255.53 (10)3.
2. according to claim 1 a kind of imidazoles ylidene ligands nickel coordination polymer it is characterised in that: described imidazoles ylidene ligands nickel
Ni atom in coordination polymer is using deformation octoploids structure.
3. according to claim 2 a kind of imidazoles ylidene ligands nickel coordination polymer it is characterised in that: the octahedra structure of described deformation
Type is ni atom and three n atoms, three o Atomic coordinates；These three n atoms are respectively from 3 different 1,3,5- tri- (miaows
Azoles -1- methyl) benzene part imidazole group, the bond distance of ni-n is respectively 2.0597 (15), 2.0736 (15), 2.0777
(15), three o atoms are respectively from 1 glycol molecule, 1 sulfate ion and 1 water of coordination molecule, the bond distance of ni-o
It is respectively 2.0904 (12), 2.1458 (12), 2.1048 (12).
4. according to claim 1 a kind of preparation method of imidazoles ylidene ligands nickel coordination polymer it is characterised in that: by 1,3,
5- tri- (imidazoles -1- methyl) benzene and nickel sulfate add in ethylene glycol and the mixed solution of distilled water, filter, so after being sufficiently stirred for
Afterwards described filtrate is placed in autoclave, after carrying out reacting by heating under the conditions of solvent thermal, Slow cooling obtains described imidazoles
Ylidene ligands nickel is coordinated polymers.
5. according to claim 4 a kind of preparation method of imidazoles ylidene ligands nickel coordination polymer it is characterised in that: described sulfur
Sour nickel and 1,3,5- tri- (imidazoles -1- methyl) benzene mole are than for 0.8 ~ 1.2: 0.8 ~ 1.2;Preferably, described nickel sulfate and
1,3,5- tri- (imidazoles -1- methyl) benzene mole is than preferably 1:1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586498A (en) * | 2017-12-14 | 2018-09-28 | 南京科技职业学院 | One kind is containing flexible imidazoles ylidene ligands Cu (II) three-dimensional coordination polymer and preparation method thereof |
| CN111116929A (en) * | 2019-12-02 | 2020-05-08 | 西北大学 | Nickel coordination polymer material with wide-temperature-zone reversible thermochromic property and preparation method and application thereof |
-
2016
- 2016-08-11 CN CN201610655900.9A patent/CN106349482A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| GUANO-CHENG XU ET AL.,: "Coordination Polymers with Varied Metal Centers and Flexible Tripodal Ligand 1,3,5-Tris(imidazol-1-ylmethyl)benzene: Synthesis, Structure, and Reversible Anion Exchange Property", 《CRYSTAL GROWTH & DESIGN》 * |
| HONG-KE LIU ET AL.,: "Assembly of a 3D nanoporous framework [Cu6(OH)4(tib)8]n 8+ from Cu(II) and the flexible tripodal ligand tib", 《CHEMCOMM COMMUNICATION》 * |
| LI LUO ET AL.;: "Zinc(II) and Cadmium(II) Complexes with 1,3,5-Benzenetricarboxylate and Imidazole-Containing Ligands: Structural Variation via Reaction Temperature and Solvent", 《CRYSTAL GROWTH & DESIGN》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586498A (en) * | 2017-12-14 | 2018-09-28 | 南京科技职业学院 | One kind is containing flexible imidazoles ylidene ligands Cu (II) three-dimensional coordination polymer and preparation method thereof |
| CN111116929A (en) * | 2019-12-02 | 2020-05-08 | 西北大学 | Nickel coordination polymer material with wide-temperature-zone reversible thermochromic property and preparation method and application thereof |
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