CN116444805B - Supermolecular material with anion-induced stacking mode and chiral change, preparation method and application - Google Patents
Supermolecular material with anion-induced stacking mode and chiral change, preparation method and application Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 84
- 150000001450 anions Chemical class 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000008859 change Effects 0.000 title claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- -1 halogen ions Chemical class 0.000 claims abstract description 36
- 239000003446 ligand Substances 0.000 claims abstract description 22
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 17
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 32
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 30
- 239000013078 crystal Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000013110 organic ligand Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 6
- AWMAOFAHBPCBHJ-UHFFFAOYSA-M sodium;(7,7-dimethyl-3-oxo-4-bicyclo[2.2.1]heptanyl)methanesulfonate Chemical compound [Na+].C1CC2(CS([O-])(=O)=O)C(=O)CC1C2(C)C AWMAOFAHBPCBHJ-UHFFFAOYSA-M 0.000 claims description 6
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 5
- VXWBQOJISHAKKM-UHFFFAOYSA-N (4-formylphenyl)boronic acid Chemical compound OB(O)C1=CC=C(C=O)C=C1 VXWBQOJISHAKKM-UHFFFAOYSA-N 0.000 claims description 4
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 claims description 4
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- MIOPJNTWMNEORI-UHFFFAOYSA-N camphorsulfonic acid Chemical compound C1CC2(CS(O)(=O)=O)C(=O)CC1C2(C)C MIOPJNTWMNEORI-UHFFFAOYSA-N 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- LIGACIXOYTUXAW-UHFFFAOYSA-N phenacyl bromide Chemical compound BrCC(=O)C1=CC=CC=C1 LIGACIXOYTUXAW-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000005049 silicon tetrachloride Substances 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 claims 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical class CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims 1
- 230000006698 induction Effects 0.000 abstract description 7
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- 230000008901 benefit Effects 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000356 contaminant Substances 0.000 abstract description 3
- 239000002178 crystalline material Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000000978 circular dichroism spectroscopy Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical class [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 238000001142 circular dichroism spectrum Methods 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- 238000004791 1D NOESY Methods 0.000 description 1
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000012565 NMR experiment Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
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- 238000002983 circular dichroism Methods 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
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- 238000001819 mass spectrum Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
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- 239000000741 silica gel Substances 0.000 description 1
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- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C08G83/008—Supramolecular polymers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of supermolecular materials, and discloses a supermolecular material with an anion-induced stacking mode and chiral change, a preparation method and application thereof. According to the invention, a trigeminal ligand containing terpyridine is assembled with metal Zn (II) to obtain a tetrahedral structure supermolecule material, and then halogen ions are added to influence the stacking mode of tetrahedral metal cages, so that the stacking mode from initial hexagonal closest stacking to hexagonal stacking to graphene-like stacking is changed. The chiral induction of the tetrahedral metal cage is realized by adding chiral anions. This halide ion-induced hierarchical stacking mode transformation results in different intermolecular channels, and therefore they show potential advantages as an emerging adaptive porous crystalline material for oxygen ion separation, contaminant adsorption, catalysis, and the like.
Description
Technical Field
The invention relates to the field of supermolecular materials, in particular to a supermolecular material with an anion-induced stacking mode and chiral change, a preparation method and application thereof.
Background
Coordination-driven metal cages have gained continuous attention for their delicate structure and diverse functionality, and in recent studies they have been used as efficient building blocks for layered super structures with highly aesthetic and emerging functionality. In positively charged metal cages, they are usually ignored as counter ions due to their strong solubility in solution or high disorder in the solid state. With the intensive research, the important role of anions in the resulting metal cage has been widely studied, but is now focused on the host-guest chemistry and structural transformations of the metal cage. While the regulation of the hierarchical structure of metal cages by anions has not been extensively explored and studied, which is a great challenge, there is a need for a system in which anions are used to induce multistage self-assembly of metal cages with more complex structures and practical functions. Therefore, we designed and synthesized a metal supermolecular cage with tetrahedral configuration, and further studied the influence of halogen ions on the stacking mode of the metal cage.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a tetrahedral supermolecular material with an anion-induced stacking mode and chiral change, a preparation method and application, wherein a metal supermolecular material with a tetrahedral structure is constructed by using a three-fork organic ligand and metal coordination by improving a material structure, and a metal cage constructed after halide ions are added can be self-assembled in an adaptive hierarchical mode, so that huge different superstructure is caused; the chiral induction of the metal cage is realized after the chiral anions are added, so that the technical problems are solved.
The aim of the invention is realized by adopting the following technical scheme:
in a first aspect, the present invention provides a tetrahedral supramolecular material having an anionically induced stacking mode and chiral variation, comprising a unit structure of formula (i):
in a second aspect, the present invention provides a method for preparing a tetrahedral supramolecular material having an anionically induced stacking mode and chiral variation, comprising the steps of:
(1) Preparing a trigeminal terpyridine organic ligand shown in formula (II):
(2) And (3) adding a solvent into the ligand of the formula (II) prepared in the step (1), dissolving, then dropwise adding a metal salt solution, heating for reaction, adding an anion displacer after the reaction is finished, and filtering to obtain a precipitate, thus obtaining the supermolecule material containing tpy-Zn 2+ -tpy groups.
The terpyridine organic ligand used in the step (2) is a tridentate ligand, has unique geometric angles and configurations, and can be spontaneously assembled with different divalent metal ions in a solution system to form a tetrahedral structure with accurate and ordered structure.
Preferably, in step (2), the anionic displacer is selected from ammonium hexafluorophosphate or lithium bistrifluoro-methanesulfonimide. The Cl-or NTf 2 -or the isoanions introduced in the assembly process are replaced by the anion replacement agent, and under the action of ammonium hexafluorophosphate or lithium bistrifluoromethane sulfonyl imide, the supermolecular material can be better separated out from the solvent, thereby being beneficial to the separation and purification of subsequent precipitates.
Preferably, in the step (2), the solvent is at least one of alcohol, chloroform and ether.
More preferably, in step (2), the solvent is a mixed solution of alcohol and chloroform.
More preferably, in the step (2), the solvent is a mixed solution of methanol and chloroform, wherein the volume ratio of methanol to chloroform is 1: (1-1.5). Wherein, the mixed solvent of methanol and chloroform plays an important role in the formation of the supermolecular material, and the three terpyridine ligands have good solubility in the mixed solvent of chloroform and methanol, so that the produced supermolecular material can be well dissolved in acetonitrile.
Preferably, in the step (2), the temperature of the heating reaction is 40-70 ℃, and the reaction time is 5-10h.
More preferably, in the step (2), the temperature of the heating reaction is 45-55 ℃, and the reaction time is 6-10h.
Preferably, the method for preparing the ligand of formula (II) in step (1) comprises the steps of:
(1) Reacting 4-formylphenylboronic acid with 2-acetylpyridine under alkaline conditions to generate 4- (2, 2',6, 2', -terpyridyl) -phenylboronic acid, namely an intermediate 1;
(2) Reacting 2-bromoacetophenone with silicon tetrachloride to obtain an intermediate 2:
(3) Carrying out suzuki coupling reaction on the intermediate 1 and the intermediate 2 to obtain a ligand of the formula (I);
in a third aspect, the present invention provides an application of a tetrahedral supramolecular material in which a stacking manner is changed when different halogen ions are added; wherein the halogen ion is Br-, cl-, I-.
Preferably, the stacking mode of the halogen ion induced tetrahedral supermolecular material is as follows: the stacking mode is hexagonal closest stacking when no halogen ions are added; when Br-or Cl-is added, the stacking mode is converted into hexagonal stacking rather than the most dense mode; when I-is added, the stacking mode is changed into a graphene-like stacking mode.
Preferably, the study of the stacking means is performed by means of a crystal structure, the growth of which is obtained by slowly diffusing an isopropyl ether solution into an N, N Dimethylacetamide (DMF) solution of the tetrahedral supramolecular material.
Preferably, 10mg/mL of a halogen ion solution is added during the growth of the crystal structure, so that the influence of halogen ions on the supermolecular crystal structure is explored.
Preferably, the halogen ion is added by means of tetrabutylammonium salt, including any one of tetrabutylammonium chloride, tetrabutylammonium bromide and tetrabutylammonium iodide.
In a fourth aspect, the invention provides an application of a tetrahedral supermolecular material in generating a PPPP type or MMMM type tetrahedral metal cage when chiral anions are added.
Preferably, the chiral anions are camphorsulfonates of D and L forms; more preferably, the chiral molecules are sodium camphorsulfonate in the D and L forms.
Preferably, the chiral change is studied in a solution of the supramolecular material by dissolving the supramolecular material in DMF solution, dropwise adding a solution of sodium camphorsulfonate in D and L forms thereto, and by circular dichroism spectrum and 1 H NMR.
Preferably, the concentration of the solution of the supermolecular material is 10 -6 mol/L, and the solvent is N, N Dimethylacetamide (DMF).
The beneficial effects of the invention are as follows:
(1) The tetrahedral supermolecular material T with anion-induced stacking mode and chiral variation can be used as an effective component of a layered multilevel structure, and has an obvious adaptability packaging mode of a halide ion-induced crystal structure. Not only is the intermolecular interaction between the metal cage T and PF 6-changed by adding different halide ions, three different layered multi-stage structures are realized, but also the controllable self-assembly of the enantiomer pure metal cage T is realized by adding chiral anions.
(2) The preparation method of the supermolecular material provided by the invention is constructed by self-assembly of a tridentate terpyridine organic ligand and metal Zn through coordination bond guiding, and has stable structure.
(3) The tetrahedral supermolecular material T with the anion-induced stacking mode changed, provided by the invention, has the controllable layered structure transformation accompanied by the change of the intramolecular channel, and shows potential advantages as an adaptive crystalline porous material.
(4) The anion-induced chiral change tetrahedral supermolecular material T provided by the invention opens up new opportunities for exploring circularly polarized luminescent materials, chiral separation, asymmetric catalysis and the like for the enantiomerically pure supermolecular assembly.
(5) The preparation method of the supermolecular material provided by the invention is simple, the reaction condition is mild, and the large-scale industrial production is facilitated.
Drawings
The invention will be further described with reference to the accompanying drawings, in which embodiments do not constitute any limitation of the invention, and other drawings can be obtained by one of ordinary skill in the art without inventive effort from the following drawings.
FIG. 1 is a schematic structural diagram of a supramolecular material T prepared in example 2 of the present invention;
FIG. 2 is a flow chart of the preparation of ligands according to example 2 of the present invention;
FIG. 3 is a flow chart of the preparation of a supramolecular material T according to example 2 of the present invention;
FIG. 4 is a 1 H NMR spectrum of the ligand prepared in example 2 of the present invention;
FIG. 5 is a 13 C NMR spectrum of the ligand prepared in example 2 of the present invention;
FIG. 6 is a 1 H NMR spectrum of a supermolecular material T prepared in example 2 of the present invention;
FIG. 7 is a COSYNMR spectrum of a supermolecular material T prepared in example 2 of the present invention;
FIG. 8 is a NOESY NMR spectrum of a supermolecular material T prepared in example 2 of the present invention
FIG. 9 is a mass spectrum of a supermolecular material T prepared in example 2 of the present invention;
FIG. 10 is a photograph showing a crystal of a supermolecular material T according to example 2 of the present invention;
FIG. 11 is a photograph showing a crystal of a supermolecular material T-Br prepared in example 3 of the present invention;
FIG. 12 is a photograph showing the crystal of the supramolecular material T-I according to example 3 of the present invention;
FIG. 13 is a schematic stacking diagram of the hierarchical structure of the supramolecular material T according to example 2 of the present invention;
FIG. 14 is a schematic stacking diagram of the hierarchical structure of the supermolecular material T-Br prepared in example 3 of the present invention;
FIG. 15 is a schematic stacking diagram of the hierarchical structure of the supramolecular material T-I prepared in example 3 of the present invention;
FIG. 16 is a schematic diagram showing chiral induction of a supramolecular material T according to example 4 of the present invention;
FIG. 17 is a chiral induction 1 H NMR spectrum of a supramolecular material T prepared in example 4 of the present invention;
FIG. 18 is a graph showing a chiral induced 2D DOSY of the supramolecular material T prepared in example 4 of the present invention;
FIG. 19 is a chiral induction ultraviolet spectrum of a supramolecular material T prepared in example 4 of the present invention;
FIG. 20 is a chiral inducing circular dichroism spectrum of a supramolecular material T prepared in example 4 of the present invention.
Detailed Description
The technical features, objects and advantages of the present invention will be more clearly understood from the following detailed description of the technical aspects of the present invention, but should not be construed as limiting the scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
The invention will be further described with reference to the following examples.
Example 1
The tetrahedral supermolecular material with anion-induced stacking mode and chiral change provided by the embodiment of the invention comprises a unit structure shown in a formula (I):
the preparation method of the tetrahedral supermolecular material with the anion-induced stacking mode and chiral change comprises the following steps:
(1) Preparing a trigeminal terpyridine organic ligand shown in formula (II):
(2) And (3) adding a solvent into the terpyridine organic ligand shown in the formula (II) prepared in the step (1), dissolving, then dropwise adding a metal salt solution, heating for reaction, adding an anion displacer after the reaction is finished, and filtering to obtain a precipitate, namely the supermolecular material. The terpyridine organic ligand used in the step has unique geometric angles and configurations, and can be spontaneously assembled with different divalent metal ions in a solution system to form a tetrahedral supermolecular structure with precise, ordered and unique structure.
The anionic displacer in step (2) is selected from one of ammonium hexafluorophosphate or lithium bistrifluoromethylsulfonimide. The anions such as Cl-or NTf 2 -introduced in the assembly process are replaced by the anion replacement agent, and under the action of ammonium hexafluorophosphate or lithium bistrifluoromethylsulfonylimide (preferably ammonium hexafluorophosphate), the supermolecular material can be better separated out from the solvent, thereby being beneficial to the separation and purification of subsequent precipitates.
The solvent in the step (2) is a mixed solution of methanol and chloroform, wherein the volume ratio of the methanol to the chloroform is 1: (1-1.5) (the volume ratio of methanol to chloroform is preferably 1:1). The mixed solvent of the methanol and the chloroform plays an important role in forming the supermolecular material, the terpyridine ligand has good solubility in the mixed solvent of the chloroform and the methanol, and the produced supermolecular material can be well dissolved in acetonitrile.
The temperature of the heating reaction in the step (2) is 45-55 ℃, and the reaction time is 6-10h.
The preparation method of the terpyridine organic ligand shown in the formula (II) in the step (1) comprises the following steps:
(1) Reacting 4-formylphenylboronic acid with 2-acetylpyridine under alkaline conditions to generate 4- (2, 2',6, 2', -terpyridyl) -phenylboronic acid, namely an intermediate 1;
(2) Reacting 2-bromoacetophenone with silicon tetrachloride to obtain an intermediate 2:
(3) Performing a suzuki coupling reaction on the intermediate 1 and the intermediate 2 to prepare a ligand;
Example 2
This embodiment is substantially the same as embodiment 1 except that:
A tetrahedral supramolecular material having an anionically induced stacking mode and chiral variation, said supramolecular material comprising a unit structure of formula (i):
The preparation method of the above-mentioned supermolecule material includes the following steps:
(1) Preparation of 4- (2, 2',6, 2', -terpyridyl) -phenylboronic acid (intermediate 1):
Into a 500mL round bottom flask was added ethanol (200 mL), followed by NaOH (9.6 g,240 mmol) and stirring to dissolve. 4-formylphenylboronic acid (6.0 g,40 mmol) and 2-acetylpyridine (10.6 g,88 mmol) were added in this order, and the mixture was stirred at room temperature for 24 hours, NH 3·H2 O (28%, 150 mmol) was added, and the mixture was heated under reflux for 20 hours. Cooling the reaction solution to room temperature, suction filtering, washing the filter residue with ice isopropanol and chloroform to obtain light purple powder (11.96g,84.7％).1H NMR(500MHz,CD3OD,300K,ppm):δ8.71–8.68(m,2H,tpy-H3',5'),8.68–8.62(m,4H,tpy-H6,6"and tpy-H3,3"),8.01(td,J＝7.7,1.8Hz,2H,tpy-H4,4"),7.78(d,J＝7.8Hz,2H,Ph-Hj),7.73(d,J＝8.0Hz,2H,Ph-Hk),7.48(ddd,J＝7.5,4.8,1.1Hz,2H,tpy-H5,5").13C NMR(125MHz,CD3OD,300K,ppm):δ157.46,156.84,153.10,149.87,138.57,135.29,134.99,125.75,125.11,122.82,119.40.
(2) Preparation of intermediate 2
In a 500mL three-necked flask was added 2-bromoacetophenone (20.0 g,100 mmol) and dissolved in 164mL EtOH solution. The flask was cooled to 0deg.C and silicon tetrachloride (34.5 mL,301 mmol) was added dropwise over 1 minute. The resulting yellow mixture was stirred at 0 ℃ for 1.5 hours and then allowed to warm to ambient temperature. After 24 hours, the mixture was cooled again to 0 ℃ and quenched with water (800 mL). The resulting orange-yellow slurry was extracted with CH 2Cl2 (3X 250 mL). The combined organic phases were dried over MgSO 4, filtered and concentrated in vacuo. The red solution obtained was sonicated with n-hexane (100 ml) and suction filtered to give the product as a yellow flaky solid (16g,90％).1H NMR(400MHz,CDCl3,300K)δ7.72–7.67(m,3H,Ph-He),7.50(d,J＝6.1Hz,3H,Ph-Ha),7.47(dd,J＝7.6,1.6Hz,3H,Ph-Hb),7.38(td,J＝7.5,0.9Hz,3H,Ph-Hd),7.22(td,J＝7.7,1.7Hz,3H,Ph-Hc);13C NMR(101MHz,CDCl3,300K)δ142.30,142.24,140.79,140.73,133.54,131.95,131.87,129.96,129.87,129.25,127.77,122.99.
(3) Preparation of ligands
Intermediate 2 (1.08 g,2.00 mmol), intermediate 1 (3.18 g,4.50 mmol), pd (PPh 3)4 (346.5 mg,0.30 mmol) and sodium carbonate (1.91 g,18.0 mmol) were added to a 500mL three-necked flask, 80mL toluene, 30mL H 2 O and 20mL t-butanol were added under an atmosphere of N 2 the mixture was stirred at 85℃for 3 days, cooled to room temperature, extracted with CH 2 Cl2, the combined organic layers were washed with brine, dried over anhydrous Na 2 SO4, then concentrated in vacuo, and the residue was purified by chromatography (silica gel) with CH 2Cl2:CH3 OH (100:1, v/v) to give a white solid (1.80g,73％).1H NMR(400MHz,CDCl3)δ8.79(s,2H,Tpy-H3'5'),8.60(dd,J＝13.8,6.0Hz,4H,Tpy-H3,3",6,6"),7.97(d,J＝8.2Hz,2H,Ph-Hb),7.81(t,J＝6.9Hz,2H,Tpy-H4,4"),7.38(d,J＝7.3Hz,1H,Ph-Hc),7.28(d,J＝7.8Hz,4H,Tpy-H5,5",Ph-Ha),7.25–7.20(m,2H,Ph-Hd,e),6.85(d,J＝6.2Hz,2H,Ph-Hf,g).13C NMR(101MHz,CDCl3)δ156.34,155.96,149.96,149.21,142.76,140.71,140.26,139.93,136.89,127.99,127.55,127.01,123.85,121.42.
(4) Preparation of supramolecules T
The final ligand (10 mg, 8.14. Mu. Mol) was dissolved in CHCl 3 (510 ml) and a solution of Zn (NO 3)2·4H2 O (3.63 mg, 12.21. Mu. Mol) in CH 3 OH was added, then the mixture was stirred at 60℃for 8 hours. Subsequently, NH 4PF6 was added to give a white precipitate, which was filtered with H 2 O and CH 3 OH to give 11.3mg of a white solid (yield 98％).ESI-TOF(m/z):864.53[M-7PF6 -]7+(calcd m/z:864.53),1029.26[M-6PF6 -]6+(calcd m/z:1029.26),1264.69[M-5PF6 -]5+(calcd m/z:1264.69),1616.35[M-4PF6 -]4+(calcd m/z:1616.35),2203.47[M-3PF6 -]3+(calcdm/z:2203.47);1H NMR(500MHz,CD3OD)δ8.87(s,18H,Tpy-H3'5'),8.48(d,J＝8.1Hz,18H,Tpy-Hb),8.31(d,J＝8.1Hz,18H,Tpy-H3,3"),7.85(t,J＝7.5Hz,18H,Tpy-H4,4"),7.77(d,J＝8.4Hz,18H,Tpy-Ha),7.69(d,J＝4.8Hz,18H,Tpy-H6,6"),7.55(d,J＝7.9Hz,9H,Ph-Hc),7.43–7.39(m,18H,Ph-Hd,e),7.33(d,J＝8.5Hz,9H,Ph-Hf),7.17–7.13(m,18H,Tpy-H5,5"),7.04(s,9H,Ph-Hg).
Example 3
This example is a test and verification of anion-induced stacking mode changes performed on the supramolecular materials prepared in examples 1 and 2, and includes the following steps:
(1) Stacking mode analysis of supermolecular structure T
Crystals were obtained by slowly diffusing an isopropyl ether solution into a DMF solution of supermolecule T (fig. 10), and test analysis was performed using X-ray diffraction, and the obtained results are shown in fig. 13. First the crystal structure shows a tetrahedral structure with C3 symmetry, where 4 ligands have been mapped to the four vertices of the tetrahedron. In ligand L, there is either a clockwise (P) or counterclockwise (M) twist of the three terpyridine moieties due to the massive steric hindrance of the orthogonal substitution. Each ligand located at the apex proved to adopt a homeotropic twist direction (P or M), with a pair of conformational enantiomers with opposite helical chirality in one unit cell (PPPP-T and MMMM-T). As can be seen from FIG. 13a, only one PF 6-is hydrogen bonded within the cavity of the cage T via the C-H-F hydrogen bond.
Two metal cages T (primary structures) are assembled into one supramolecular dimer in one unit cell by employing a "head-to-head" pattern (fig. 13 b). PF 6-does not connect two metal cages T, but serves as counter ion. There is also no CH- -pi interaction between the two metal cages T. These dimers (secondary structures) are packed into a staggered helical column (tertiary structure). Then, a four-level supramolecular structure was further assembled by a hexagonal close packed arrangement of triangular intermolecular channels of 10.4 angstroms in diameter (fig. 13 e).
(2) Stacking mode analysis of supermolecular structure T by adding Br ˉ
Crystals were obtained by slowly diffusing an isopropyl ether solution into a DMF solution of supermolecule T added with tetrabutylammonium bromide (fig. 11), and test analysis was performed using X-ray diffraction, and the obtained results are shown in fig. 14. When Br ˉ is added, no encapsulation or structural transformation of the halide ions is found due to the rigid structure of the metal cage T. Instead, it crystallizes into another well-defined triclinic phase structure. First, the addition of Br ˉ or results in more packages of PF6 ˉ (five total, four PFs ˉ in the corners, one in the center) in the cavity of the metal cage T (fig. 14 a). Next, PF 6-was found to link two metal cages T in one cell, resulting in one "side-to-side" dimer (FIG. 14 b). In contrast to the cells of the metal cage T,The two cages were brought close to each other by the two C-H-F hydrogen bonds (fig. 14C). Finally, the addition of Br ˉ is packed in a more compact hexagonal packing, with negligible intermolecular channels.
(3) Stacking mode analysis by adding I-supermolecular structure T
First, crystals were obtained by slowly diffusing an isopropyl ether solution into a DMF solution of supermolecule T to which tetrabutylammonium bromide was added (fig. 12), and test analysis was performed using X-ray diffraction, and the obtained results are shown in fig. 15. Furthermore, the addition of I-results in a transition of another hierarchy. In terms of the main structure, five PF 6-are also incorporated in the metal cage T chamber (FIG. 15 a). In terms of single unit cell, exceptIn the presence of a strong negative-pi interaction between the central pyridine ring and the benzene ring of the dimer of the two cages, ranging from/>Between them. The two cages within the unit cell are stacked in an "edge-to-edge" fashion (fig. 15 b) and further self-organize into a graphite-like hierarchical structure, which results in a three-dimensional porous framework with large, infinite, diameter/>Is shown (fig. 15 f).
Example 4
This example is a test and verification of anion induced chiral changes performed on the supramolecular materials prepared in examples 1,2, comprising the steps of:
(1) Firstly, through the crystal structure of the supermolecular material T, the remarkable space limitation in the ligand L causes the three terpyridine parts to rotate around the central benzene ring, so that the symmetry of the achiral molecules on the supermolecular level is broken, and a racemic mixture is obtained. Thus, circular dichroism and 1 H NMR experiments were performed by adding D-form or L-form sodium camphorsulfonate to DMF solution of metal cage T (FIG. 16).
(2) First, the binding of supermolecule T to D-or L-form sodium camphorsulfonate was studied by 1 H NMR, and from 1 H NMR spectrum, a significant high field shift was observed in the peaks belonging to camphorsulfonate, strongly indicating the formation of host-guest complexes (FIG. 17). For example, H c、Hg of D-form camphorsulfonate shows two methyl proton peaks, single peaks at 1.11ppm and 0.85ppm,To 1.03ppm and 0.74ppm, respectively, toward the upper field of the high field. In addition, other proton resonances belonging to H a、Hb、Hd、He、Hf have been shown to exhibit significantly higher field up-shifts. Two-dimensional DOSY nmr spectra show (fig. 18) that the proton signals assigned to the host (log d= -9.7) and the guest (log d= -9.2) lie in two distinct bands, strongly indicating the external binding of the guest to the supermolecule T.
(3) The chirality in guest-induced supramolecular solutions was investigated by circular dichroism spectroscopy (CD) (fig. 20). Initially, the racemic metal cage T had no CD signal. After addition of chiral guest, the solution of host-guest complex showed strong CD signal in the wavelength range of 330-380nm, which is completely consistent with uv absorption (fig. 19). It is to be noted that, Has a positive cotton effect, while its enantiomer/>It is shown to have a negative cotton effect. Furthermore, it was confirmed that the generated CD signal was derived from supramolecular chirality, since chiral objects (D-, L-SCS) exhibited opposite CD signals in the wavelength range of 280-320nm (FIG. 19).
The tetrahedral supermolecular material T with anion-induced stacking mode and chiral variation provided by the embodiment of the invention is assembled with metal Zn (II) by using trigeminal ligand containing terpyridine to obtain the supermolecular material T with tetrahedral configuration, and then halogen ions are added to influence the stacking mode of the tetrahedral metal cage, so that the tetrahedral supermolecular material T is stacked from initial hexagonal closest stacking to hexagonal stacking to graphene-like stacking. Furthermore, chiral induction of tetrahedral metal cages is achieved by the addition of chiral anions (sodium camphorsulfonate). This halide ion-induced hierarchical stacking mode transformation results in different intermolecular channels, and therefore they show potential advantages as an emerging adaptive porous crystalline material for oxygen ion separation, contaminant adsorption, catalysis, and the like.
In the embodiment of the invention, the trigeminal ligand containing terpyridine is assembled with metal Zn (II) to obtain the tetrahedral supermolecular material, and then halogen ions are added to influence the stacking mode of the tetrahedral metal cage, so that the initial hexagonal close-packed mode is changed into the hexagonal stacked mode to be similar to the graphene stacked mode. The chiral induction of the tetrahedral metal cage is realized by adding chiral anions. This halide ion-induced hierarchical stacking mode transformation results in different intermolecular channels, and therefore they show potential advantages as an emerging adaptive porous crystalline material for oxygen ion separation, contaminant adsorption, catalysis, and the like.
In other embodiments of the present invention, the technical effects described in the present invention may be achieved by selecting different schemes in the ranges of the steps, components, proportions and process parameters described in the present invention, so that the present invention is not listed one by one.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The application of the tetrahedral supermolecular material in the change of stacking mode when different halogen ions are added is characterized in that the tetrahedral supermolecular material has anion-induced stacking mode and chiral change, and comprises a unit structure shown in a formula (I):
formula (I);
the stacking mode of the tetrahedral supermolecular material is changed when different halogen ions are added, wherein the halogen ions are Br < - >, I < - >; the stacking mode of the halogen ion induced tetrahedral supermolecular material is as follows: when no halogen ions are added, the stacking mode of the supermolecular materials is hexagonal closest stacking; upon addition of Br-, the stacking mode of the supramolecular material is converted into hexagonal stacking rather than the most dense mode; when I-is added, the stacking mode of the supermolecular material is changed into a graphene-like stacking mode.
2. The use of a tetrahedral supramolecular material according to claim 1, wherein the addition of the halide ions is by way of tetrabutylammonium salts, including any one of tetrabutylammonium bromide and tetrabutylammonium iodide.
3. The use of a tetrahedral supramolecular material according to claim 2, wherein the study of the stacking means is performed by means of a crystal structure obtained by slow diffusion of isopropyl ether solution into N, N dimethylacetamide solution of the tetrahedral supramolecular material when different halogen ions are added.
4. The use of a tetrahedral supramolecular material according to claim 3, wherein the effect of halide ions on the supramolecular crystal structure is investigated by adding 10mg/mL of halide ion solution during the growth of the crystal structure.
5. The use of a tetrahedral supramolecular material according to claim 1, wherein the preparation of the tetrahedral supramolecular material comprises the following steps:
(1) Preparing a trigeminal terpyridine organic ligand shown in formula (II):
Formula (II)
(2) And (3) adding a solvent into the ligand of the formula (II) prepared in the step (1), dissolving, then dropwise adding a metal salt solution, heating for reaction, adding an anion displacer after the reaction is finished, and filtering to obtain a precipitate, thus obtaining the supermolecule material containing tpy-Zn 2+ -tpy groups.
6. The use of a tetrahedral supramolecular material according to claim 5, wherein in step (2) the anionic displacer is selected from ammonium hexafluorophosphate or lithium bistrifluoro methanesulfonimide; the solvent is at least one of alcohol, chloroform and ether.
7. The use of the tetrahedral supramolecular material according to claim 6, wherein in step (2), the solvent is a mixed solution of methanol and chloroform, wherein the volume ratio of methanol to chloroform is 1: (1-1.5); the temperature of the heating reaction is 40-70 ℃, and the reaction time is 5-10 h.
8. The use of tetrahedral supramolecular material according to claim 5, wherein the preparation of ligand of formula (II) in step (1) comprises the steps of:
(1) Reacting 4-formylphenylboronic acid with 2-acetylpyridine under alkaline conditions to generate 4- (2, 2',6, 2', -terpyridyl) -phenylboronic acid, namely an intermediate 1;
Intermediate 1
(2) Reacting 2-bromoacetophenone with silicon tetrachloride to obtain an intermediate 2:
Intermediate 2
(3) And carrying out a suzuki coupling reaction on the intermediate 1 and the intermediate 2 to obtain the ligand of the formula (II).
9. The application of a tetrahedral supermolecular material in generating a PPPP type or MMMM type tetrahedral metal cage when chiral anions are added is characterized in that the tetrahedral supermolecular material has an anion-induced stacking mode and chiral changes, and comprises a unit structure shown in a formula (I):
The chiral anions are D-type or L-type camphorsulfonate.
10. Use of a tetrahedral supramolecular material according to claim 9 to create a tetrahedral metal cage of PPPP-type or MMMM-type upon addition of chiral anions, wherein the chiral change is performed in a solution of the supramolecular material by dissolving the supramolecular material in DMF solution, to which a solution of sodium camphorsulfonate of D-type or L-type is added dropwise.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104744497A (en) * | 2015-03-09 | 2015-07-01 | 天津师范大学 | One-dimensional triazole-Zn (II) fluorescent complex and synthesis method thereof and application in anionic fluorescent probe |
| WO2017099110A1 (en) * | 2015-12-08 | 2017-06-15 | 国立大学法人熊本大学 | Circularly polarized light-emitting composition, production method therefor, and circularly polarized light-emitting method |
| CN111875642A (en) * | 2020-08-11 | 2020-11-03 | 中南大学 | Poly-terpyridyl metal organic ligand compound, five-membered flower ring-shaped supramolecule assembled by same and preparation method of five-membered flower ring-shaped supramolecule |
| CN114289070A (en) * | 2022-01-07 | 2022-04-08 | 扬州大学 | Supermolecule chiral nano catalyst and preparation method and application thereof |
| CN115449082A (en) * | 2022-08-09 | 2022-12-09 | 广州大学 | Metal organic coordination supermolecule sphere, preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104744497A (en) * | 2015-03-09 | 2015-07-01 | 天津师范大学 | One-dimensional triazole-Zn (II) fluorescent complex and synthesis method thereof and application in anionic fluorescent probe |
| WO2017099110A1 (en) * | 2015-12-08 | 2017-06-15 | 国立大学法人熊本大学 | Circularly polarized light-emitting composition, production method therefor, and circularly polarized light-emitting method |
| CN111875642A (en) * | 2020-08-11 | 2020-11-03 | 中南大学 | Poly-terpyridyl metal organic ligand compound, five-membered flower ring-shaped supramolecule assembled by same and preparation method of five-membered flower ring-shaped supramolecule |
| CN114289070A (en) * | 2022-01-07 | 2022-04-08 | 扬州大学 | Supermolecule chiral nano catalyst and preparation method and application thereof |
| CN115449082A (en) * | 2022-08-09 | 2022-12-09 | 广州大学 | Metal organic coordination supermolecule sphere, preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 刘颖.具有重金属吸附性能的三联吡啶类3D超分子构筑及性质研究.《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2022,(第11期),B014-140. * |
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