CN105753845A - Low-symmetry tetradentate pyrazole ligand Ni based metal-organic framework material and preparation method thereof - Google Patents
Low-symmetry tetradentate pyrazole ligand Ni based metal-organic framework material and preparation method thereof Download PDFInfo
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- 239000003446 ligand Substances 0.000 title claims abstract description 26
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000013099 nickel-based metal-organic framework Substances 0.000 title abstract 4
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 49
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000013110 organic ligand Substances 0.000 claims abstract description 18
- 239000013078 crystal Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 26
- 125000003226 pyrazolyl group Chemical group 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- -1 1-(4-methoxybenzyl)-pyrazoles borate Chemical class 0.000 claims description 5
- 150000003217 pyrazoles Chemical class 0.000 claims description 5
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000003682 fluorination reaction Methods 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- ATHHXGZTWNVVOU-UHFFFAOYSA-N monomethyl-formamide Natural products CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims 1
- 239000011148 porous material Substances 0.000 claims 1
- 239000002178 crystalline material Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- FNHISDQCWYSMTO-UHFFFAOYSA-N 1,3,6,8-tetrabromo-9h-carbazole Chemical class C1=C(Br)C=C2C3=CC(Br)=CC(Br)=C3NC2=C1Br FNHISDQCWYSMTO-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000002050 diffraction method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
-
- 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
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention belongs to the technical field of crystalline materials and discloses a low-symmetry tetradentate pyrazole ligand Ni based metal-organic framework material and a preparation method thereof.A chemical formula of the low-symmetry tetradentate pyrazole ligand Ni based metal-organic framework material is [Ni(CTP)], and CTP refers to an organic ligand 1,3,6,8-tetra(-1H-pyrazolyl-4-yl)-9H-pyrazole.The metal-organic framework material is synthesized by that under closed conditions, the 1,3,6,8-tetra(-1H-pyrazolyl-4-yl)-9H-pyrazole is in thermal reaction with nickel chloride in a mixed solution of N,N-dimethylformamide, acetonitrile and water to obtain metal-organic framework crystals.The low-symmetry tetradentate pyrazole ligand Ni based metal-organic framework material has an application potential in gas adsorption and storage.
Description
Technical field
The invention belongs to the technical field of crystalline material, technology relates to metal-organic coordination polymer material, and particularly one
Plant metal-organic frameworks based on novel low symmetrical four tooth Pyrazole Ligands Ni and preparation method thereof.
Background technology
Metal-organic framework (metal-organic frameworks, MOFs) because its in gas absorption and storage, urge
The potential application of the aspects such as change, fluorescence, electrochemistry and charming structure and diversified topology configuration, receive scientific research work
Author pays close attention to widely.Metal-organic framework is to be constructed by coordinate bond by metal ion or metal cluster and organic ligand to form
, the complicated and diversified frame structure of MOFs be mostly derived from the structure that in its structure, organic ligand is various, abundant coordination mode with
And the coordination geometric configuration that metal ion is various.But, when the ligancy of metal ion and geometric configuration are relatively fixed, serve as
The organic ligand of connecting rod plays an important role in framework is formed.
In numerous parts constructing metal-organic framework, the metal-organic framework that pyrazoles part is constructed is confused because of it
The structure of people and special character, be increasingly subject to the extensive concern of researcher.And be currently used for synthesizing metal-organic framework
Pyrazole Ligands be two pyrazoles or the part of three pyrazoles of high degree of symmetry mostly, with asymmetric four Pyrazole Ligands synthesis metals-have
The research of machine skeleton is relatively fewer.Low symmetrical part and metal-complexing, tend to construct out metal-organic bone of novel structure
Frame, shows different performances.
Summary of the invention
It is an object of the invention to provide the synthetic method of a kind of novel low symmetrical four tooth Pyrazole Ligands and construct with it
The preparation method of the metal-organic framework of Ni.
The novel four tooth Pyrazole Ligands of one of the present invention, are characterised by that it belongs to low symmetrical part.Additionally, this part center
Carbazole and four pyrazole rings between non-coplanar；The participation coordination of the carbazole ring at part center and two close carbazole atom N
Between pyrazole ring, formed dihedral angle is 35.271o, and two other is away from institute between the pyrazole ring participating in coordination of atom N
The dihedral angle become is 8.390o.
The metal-organic framework materials based on low symmetrical carbazole four Pyrazole Ligands Ni of the present invention, it is characterised in that chemistry
Molecular formula is [Ni (CTP)] Cl2, CTP is organic ligand 1,3,6,8-tetra-(-1H-pyrazoles-4-base)-9H-carbazole.
Connecting from skeleton from the point of view of constructing, the crystal structure of this metal-organic framework belongs to cubic system, and space group is
Pm-3, cell parameter is:α=β=γ=90 °.
In this metal-organic framework, each Ni and 2 Cl and 4 pyrazolyl atom N from different ligands are coordinated, shape
Become octoploids structure；Each part connects 4 W metal.The pyrazolyl of part is with μ 1-η1:η0Coordination mode connect Ni.At this
Metal-organic framework exists the structure of a kind of caged.12 CTP parts and 24 Ni atoms define one 20
Hexahedron cage, 20 hexahedron cage inscribed sphere diameters are about
Each 20 hexahedral cage is connected with six 20 hexahedron cages of surrounding by the face of shared tetragon, structure
Having become three-dimensional framework material, along crystallography a, b, c direction is respectively formed diameter and is aboutWith Two kinds one-dimensional logical
Road.If by the metal node in this metal-organic framework and four tooth asymmetric ligands be simplified to the node of four connections, then
This metal-organic framework be simplified to one four connect network structure, its Shi Laifuli symbol (Symbol) it is
(42·62·82), belong to the topology of rhr type.After removing guest molecule, the enterable hole of this metal-organic framework
Volume is 75.5%, and this numerical value can be calculated according to crystal data by PLATON software.
Wherein the chemical structural formula of organic ligand 1,3,6,8-tetra-(-1H-pyrazoles-4-base)-9H-carbazole (CTP) is
The synthetic method of the novel low symmetrical four tooth Pyrazole Ligands of the present invention, including three below step:
First it is that carbazole reacts with halogen R (R=Br, I), obtains 1,3,6,8-tetra-R-9H-carbazoles.
Secondly 1,3,6,8-tetra-R-9H-carbazole previous step obtained and 1-(4-methoxybenzyl)-pyrazoles borate, fluorine
Change caesium, tetra-triphenylphosphine palladium, glycol dimethyl ether join in reactor, seal, evacuation, inert gas shielding, and heating is anti-
Deserved 1,3,6,8-tetra-(1-(4-methoxybenzyl)-1H-pyrazoles-4-base)-9H-carbazole.
Finally by anti-with trifluoroacetic acid backflow for 1,3,6,8-tetra-(1-(4-methoxybenzyl)-1H-pyrazoles-4-base)-9H-carbazole
Should；After reaction stops, adding deionized water and add ammonia and obtain 1 to without sucking filtration after sinking to the bottom precipitation, 3,6,8-tetra-(1H-pyrazoles-4-
Base)-9H-carbazole.
The synthetic method of metal-organic framework materials of the present invention, comprises the following steps:
Under air-proof condition, organic ligand CTP (1,3,6,8-tetra-(-1H-pyrazoles-4-base)-9H-carbazole) and Nickel dichloride.
(NiCl2) at DMF (N,N-dimethylformamide), ACN (acetonitrile) and H2In the mixed solution of O (deionized water), via solvent thermal
Reaction obtains the crystal of this metal-organic framework.
Wherein organic ligand CTP (1,3,6,8-tetra-(-1H-pyrazoles-4-base)-9H-carbazole) and NiCl2Mol ratio be 1:
(1～3), Nickel dichloride. correspondence 1mL of every 0.03mmol～the DMF of 2mL, the acetonitrile of 1mL～2mL, 0.4mL
～the deionized water of 0.8mL, the temperature of described thermal response is 60 DEG C-90 DEG C, and the response time is 12-48 hour.
This metal-organic framework contains the hole (20 hexahedron cage inscribed spheres are taken up space) of a kind of caged, its hole chi
Very little be about
Organic ligand synthesized by the present invention belongs to the low symmetrical Pyrazole Ligands of novel four teeth.Metal synthesized by the present invention-
Organic framework structured novelty, has potential application in terms of gas absorption with storage.
Accompanying drawing explanation
Fig. 1 is the synthetic route chart of the low symmetrical Pyrazole Ligands of four teeth synthesizing this metal-organic framework.
Fig. 2 is the Ni of this metal-organic framework2+Ion coordination environment map.
Fig. 3 is the part connection mode figure of this metal-organic framework.
Fig. 4 is the structural representation in the caged hole of this metal-organic framework.
Fig. 5 is the graphics of this metal-organic framework.
Fig. 6 is the topological diagram of this metal-organic framework.
The wherein virtual ball of the simply symbol of the ball in Figure 4 and 5.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but the present invention is not limited to following example.Embodiment
1:
First it is that carbazole reacts with halogen Br, obtains 1,3,6,8-tetra-bromo-9H-carbazoles；By 5.00g (10.36mmol) 1,
3,6,8-tetra-bromo-9H-carbazoles, 26.03g (82.85mmol) 1-(4-methoxybenzyl)-pyrazoles borate, 12.59g
(82.85mmol) cesium fluoride, 0.60g (0.517mmol) tetra-triphenylphosphine palladium, 320mL glycol dimethyl ether joins 500mL tri-
In mouth bottle, sealing, evacuation, nitrogen is protected, and reacts 24 hours under the conditions of 100 DEG C.After reaction stops, extracting with dichloromethane,
Washing, anhydrous sodium sulfate is dried, filters, decompression distillation, purifies through silicagel column column chromatography for separation, obtains 1,3,6,8-tetra-(1-(4-
Methoxybenzyl)-1H-pyrazoles-4-base)-9H-carbazole 6.85g, yield 72%.1H NMR(400MHz,DMSO-d6)δ3.94(s,
12H),5.56(s,8H),6.89(d,8H),7.15(d,8H),7.88(d,2H),8.18(m,2H),8.32(m,6H),8.57
(s,2H),9.77(s,1H)。
Embodiment 2:
By 6.85g 1,3,6,8-tetra-(1-(4-methoxybenzyl)-1H-pyrazoles-4-base)-9H-carbazole, 200mL trifluoroacetic acid
Join in the there-necked flask of 500mL, after reacting 24 hours under counterflow condition.After reaction stops, adding 100mL after decompression distillation and go
Ionized water, is added dropwise over ammonia and obtains 1 to without sucking filtration after sinking to the bottom precipitation, 3,6,8-tetra-(1H-pyrazoles-4-base)-9H-carbazole.1H
NMR(400MHz,DMSO-d6)δ7.89(d,2H)8.14(d,2H)8.36(m,6H)8.56(s,2H)9.77(s,1H)12.97
(s,2H)13.19(s,2H)
Embodiment 3
By organic ligand CTP (0.01mmol) and Nickel dichloride. (0.03mmol) at the N,N-dimethylformamide of 1mL, 1mL
Acetonitrile and 0.4mL deionized water mixed solution in mix homogeneously, enclose in bottle.Via thermal response 48 hours at 65 DEG C
Obtain the crystal of this metal-organic framework.
Embodiment 4
By organic ligand CTP (0.04mmol) and Nickel dichloride. (0.09mmol) at the N,N-dimethylformamide of 3mL, 3mL
Acetonitrile and 1.2mL deionized water mixed solution in mix homogeneously, enclose in bottle.Via thermal response 24 hours at 80 DEG C
Obtain the crystal of this metal-organic framework.
The test result of the product of above-described embodiment gained is identical, is specifically shown in following:
(1) crystal structure determination:
Choose sizeable monocrystalline under the microscope, at a temperature of 100K, utilize Agilent Technologies
Data collected by SuperNova X-ray single crystal diffractometer.Data collection uses the Cu-K α through filter monochromator monochromatizationTarget ray.The absorption correction of data uses SCALE3ABSPACK software to complete.Crystal structure uses
SHELXTL-97 program is resolved by direct method and obtains.First determine that whole non-hydrogen atom is sat by difference functions method and method of least square
Mark, and obtain hydrogen atom position, then with SHELXTL-97, crystal structure being carried out refine with theoretical hydrogenation method.Figure is shown in by structure chart
2 to Fig. 6.Crystallographic data is shown in Table 1.
The crystallographic data of table 1 metal-organic framework
The four tooth Pyrazole Ligands synthetic route charts of Fig. 1 show: be first that carbazole reacts with halogen R (R=Br, I) and obtains 1,
3,6,8-tetra-R-9H-carbazole.Secondly by the product obtained and 1-(4-methoxybenzyl)-pyrazoles borate reaction, 1 is obtained, 3,6,
8-tetra-(1-(4-methoxybenzyl)-1H-pyrazoles-4-base)-9H-carbazole.Finally by 1,3,6,8-tetra-(1-(4-methoxybenzyl)-1H-
Pyrazoles-4-base)-9H-carbazole deprotection base obtain ligand 1,3,6,8-tetra-(1H-pyrazoles-4-base)-9H-carbazole.
The structure chart of Fig. 2 shows: Ni in this metal-organic framework2+Ion and two Cl atoms and four are not from
It is coordinated with part pyrazolyl atom N, forms octoploids structure.
The structure chart of Fig. 3 shows: in this metal-organic framework, and the pyrazolyl of each CTP part uses μ 1-η1:η0Join
Bit pattern connects Ni2+Ion, each CTP connects 4 Ni2+Ion.
The structure chart of Fig. 4 shows: there is the hole of caged in this metal-organic framework.12 CTP parts and 24
Individual Ni atom defines 20 hexahedron cages, and its inscribed sphere diameter is about
The structure chart of Fig. 5 shows: each 20 hexahedral cage is by the face of shared tetragon and six two of surrounding
Ten hexahedron cages are connected, and constitute the framework material of three-dimensional, and along crystallography a, b, c direction forms diameter and is aboutWithOne-dimensional passage.
The structure chart of Fig. 6 shows: by the metal node in this metal-organic framework and CTP part be simplified to four even
The node connect, this metal-organic framework be simplified to one four connect network structure, its Shi Laifuli symbol (
Symbol) it is (42·62·82), belong to the topology of rhr type.
Claims (10)
1. a tooth pyrazoles organic ligand, it is characterised in that described organic ligand is 1,3,6,8-tetra-(-1H-pyrazoles-4-
Base)-9H-carbazole (CTP), chemical structural formula is
2. according to the one four tooth pyrazoles organic ligand described in claim 1, it is characterised in that the carbazole at this part center and four
Between individual pyrazole ring non-coplanar；Between the pyrazole ring participating in coordination of the carbazole ring at part center and two close carbazole atom N
Formed dihedral angle is 35.271 °, and two other is away from dihedral angle formed between the pyrazole ring participating in coordination of atom N
It is 8.390 °.
3. the preparation method of four tooth pyrazoles organic ligands described in claim 1, it is characterised in that step is as follows:
First it is that carbazole reacts with halogen R (R=Br, I), obtains 1,3,6,8-tetra-R-9H-carbazoles；
Secondly 1,3,6,8-tetra-R-9H-carbazole previous step obtained and 1-(4-methoxybenzyl)-pyrazoles borate, fluorination
Caesium, tetra-triphenylphosphine palladium, glycol dimethyl ether join in reactor, seal, evacuation, inert gas shielding, reacting by heating
Obtain 1,3,6,8-tetra-(1-(4-methoxybenzyl)-1H-pyrazoles-4-base)-9H-carbazole；
Finally by 1,3,6,8-tetra-(1-(4-methoxybenzyl)-1H-pyrazoles-4-base)-9H-carbazole and trifluoroacetic acid back flow reaction；
After reaction stops, adding deionized water and add ammonia and obtain 1 to without sucking filtration after sinking to the bottom precipitation, 3,6,8-tetra-(1H-pyrazoles-4-
Base)-9H-carbazole.
4. a metal-organic framework materials based on low symmetrical carbazole four Pyrazole Ligands Ni, it is characterised in that chemical molecular formula
For [Ni (CTP)] Cl2, CTP is organic ligand 1,3,6,8-tetra-(-1H-pyrazoles-4-base)-9H-carbazole.
5. according to a kind of based on low symmetrical carbazole four Pyrazole Ligands Ni the metal-organic framework materials described in claim 4, its
Being characterised by, connecting from skeleton from the point of view of constructing, the crystal structure of this metal-organic framework belongs to cubic system, space group
For Pm-3, cell parameter is: α=β=γ=90 °.
6. according to a kind of based on low symmetrical carbazole four Pyrazole Ligands Ni the metal-organic framework materials described in claim 4, its
Being characterised by, in this metal-organic framework materials, each Ni and 2 Cl and 4 pyrazolyl atom N from different ligands are joined
Position, forms octoploids structure；Each part connects 4 W metal, and the pyrazolyl of part is with μ1-η1:η0Coordination mode connect
Ni；The structure of a kind of caged is there is in this metal-organic framework.
7. according to a kind of based on low symmetrical carbazole four Pyrazole Ligands Ni the metal-organic framework materials described in claim 6, its
It is characterised by, 20 hexahedrons that the structure of described caged is 12 CTP parts and 24 Ni atoms surround
Cage；Each 20 hexahedral cage is connected with six 20 hexahedron cages of surrounding by the face of shared tetragon, constitutes
Three-dimensional framework material.
8. according to a kind of based on low symmetrical carbazole four Pyrazole Ligands Ni the metal-organic framework materials described in claim 6, its
Be characterised by, if by the metal node in this metal-organic framework and four tooth asymmetric ligands be simplified to the joint of four connections
Point, then this metal-organic framework be simplified to one four connect network structure, its Shi Laifuli symbol (symbol)
For (42·62·82), belong to the topology of rhr type；After removing guest molecule, this metal-organic framework is enterable
Pore volume is 75.5%.
9. the preparation of a kind of based on low symmetrical carbazole four Pyrazole Ligands Ni the metal-organic framework materials described in claim 4
Method, it is characterised in that comprise the following steps:
Under air-proof condition, organic ligand CTP (1,3,6,8-tetra-(-1H-pyrazoles-4-base)-9H-carbazole) and Nickel dichloride. (NiCl2)
In DMF (DMF), ACN (acetonitrile) and the mixed solution of deionized water, obtain this gold via solvent thermal reaction
The crystal of genus-organic backbone.
The most in accordance with the method for claim 9, it is characterised in that organic ligand CTP (1,3,6,8-tetra-(-1H-pyrazoles-4-
Base)-9H-carbazole) and NiCl2Mol ratio be 1:(1～3), Nickel dichloride. correspondence 1mL of every 0.03mmol～the N of 2mL, N-bis-
Methylformamide, the acetonitrile of 1mL～2mL, the deionized water of 0.4mL～0.8mL, the temperature of described thermal response is 60 DEG C-90 DEG C,
Response time is 12-48 hour.
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