CN104447872A - Manganese-containing dual-core three-dimensional polymer and preparation method thereof - Google Patents
Manganese-containing dual-core three-dimensional polymer and preparation method thereof Download PDFInfo
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- CN104447872A CN104447872A CN201410682734.2A CN201410682734A CN104447872A CN 104447872 A CN104447872 A CN 104447872A CN 201410682734 A CN201410682734 A CN 201410682734A CN 104447872 A CN104447872 A CN 104447872A
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- dimensional polymer
- core
- preparation
- manganese
- double
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- 229920000642 polymer Polymers 0.000 title claims abstract description 34
- 239000011572 manganese Substances 0.000 title claims abstract description 27
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 36
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229960003512 nicotinic acid Drugs 0.000 claims description 15
- 235000001968 nicotinic acid Nutrition 0.000 claims description 15
- 239000011664 nicotinic acid Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 150000002696 manganese Chemical class 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000013110 organic ligand Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000010583 slow cooling Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract description 2
- 238000004020 luminiscence type Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 6
- 239000003446 ligand Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 3
- 150000001875 compounds Chemical group 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910018663 Mn O Inorganic materials 0.000 description 1
- 229910003176 Mn-O Inorganic materials 0.000 description 1
- 229910018648 Mn—N Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000627 niacin group Chemical group 0.000 description 1
- -1 rare earth ion Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
- C07F13/005—Compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention relates to the field of coordination chemistry, in particular to a manganese-containing dual-core three-dimensional polymer and a preparation method thereof. The manganese-containing dual-core three-dimensional polymer has a chemical formula of C26H21N5O9Mn2 and is a triclinic system and a P-1 space group; cell parameters are as follows: a is 10.935(2) angstrom, b is 12.251(3) angstrom, c is 14.637(8) angstrom, alpha is 101.73(1) degrees, beta is 113.02(4) degrees, gamma is 112.83(4) degrees and V is 1941.51(3) angstrom 3. The three-dimensional polymer is easy to prepare and good in chemical stability, and has a very good potential application prospect in the fields of catalysis, gas separation, molecular identification, molecular luminescence and the like; moreover, a solvothermal method adopted for synthesizing the three-dimensional polymer is favorable for growth of perfect crystals with very few defects and good orientation; in addition, the preparation method is simple and pollution-free.
Description
Technical field
The present invention relates to coordination chemistry field, particularly one is containing manganese double-core three-dimensional polymer and preparation method thereof.
Background technology
Now, utilize crystal engineering principle, the ligand polymer of design and synthesis novelty becomes one of focus direction for inorganic chemistry and materials chemistry research field, is not only because they are in the potential using value of Material Field, especially because its charming skeleton structure and topological aesthetic feature.At present, a kind of the easiest also the most effective method of synthetic compound skeleton selects well-designed multi-functional organic bridge ligand and transition metal or rare earth ion or metal cluster to carry out autonomous reaction cartridge exactly under hydro-thermal or solvent thermal condition.The ligand polymer of being constructed by rigid ligand, its skeleton structure is relatively stable, under different coordination environment, substantially noticeable change can not occur, and thus more easily realizes structure control.At present, the research major part of heterocyclic carboxylic acid part is all concentrated on N-heterocyclic carboxylic acid class part, because heterocycle atom N more easily provides electronics than O atom and S atom, effectively can participate in coordination.In addition, this kind of part also has skeleton and stablizes, and the features such as coordination mode is flexible can construct out various coordination compound with novel topology and excellent properties.
Summary of the invention
Technical problem to be solved by this invention be to provide a kind of have N-heterocyclic carboxylic acid class as part containing manganese double-core three-dimensional polymer.
Another object of the present invention is the preparation method providing above-mentioned polymkeric substance.
A kind of containing manganese double-core three-dimensional polymer, chemical formula is C
26h
21n
5o
9mn
2, stating polymkeric substance is triclinic(crystalline)system,
p-1spacer, unit cell parameters is
a=10.935 (2),
b=12.251 (3),
c=14.637 (8),
α=101.73 (1) o,
β=113.02 (4) o,
γ=112.83 (4) o, V=1941.51 (3)
3.
Further, in this polymkeric substance, manganese atom takes the octahedral pattern of hexa-coordinate, each manganese atom respectively with three O atoms on three nicotinic acid, the O atom in a water molecules and the atom N coordination on two other nicotinic acid.
A kind of preparation method containing manganese double-core three-dimensional polymer: organic ligand nicotinic acid and soluble manganese salt are dissolved in the mixed solvent of acetonitrile and water, at room temperature stir formed mixed solution, then by described mixed solution under solvent thermal condition after reacting by heating slow cooling obtain described three-dimensional polymer.
Further, described Heating temperature is 150 DEG C ~ 170 DEG C, and the reacting by heating time is 36 ~ 72 hours.
Further, described cooling is 2 DEG C/h ~ 5 DEG C/h and is down to room temperature.
Further, described soluble manganese salt is at least one in manganous nitrate, Manganous chloride tetrahydrate.
Further, the mol ratio of described nicotinic acid and soluble manganese salt is 1.8 ~ 2.2:1 ~ 1.2.
Further, the mol ratio of described nicotinic acid and soluble manganese salt is preferably 2:1.
Further, the volume ratio of described acetonitrile and water is 3.5 ~ 5:3.
The present invention has following beneficial effect:
Three-dimensional polymer of the present invention is easy to preparation, and chemical stability is good, has extraordinary potential application prospect in fields such as catalysis, gas delivery, molecular recognition, molecular luminescences.And the solvent-thermal method synthesizing the employing of this three-dimensional polymer is conducive to growing few defect, good, the perfect crystal of orientation, and preparation method is simple, pollution-free.
Accompanying drawing explanation
Fig. 1 is of the present invention containing manganese double-core three-dimensional polymer C
26h
21n
5o
9mn
2with the double-core coordination environment figure of metal center Mn.
Fig. 2 is of the present invention containing manganese double-core three-dimensional polymer C
26h
21n
5o
9mn
2tomograph.
Embodiment
Below in conjunction with embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention, is not limitation of the invention.
embodiment 1
0.1mmol organic ligand nicotinic acid and 0.05mmol manganous nitrate are dissolved in (volume ratio of acetonitrile and water is 4:3) in the mixed solvent of 14mL acetonitrile and water, at room temperature stir and form mixed solution, then described mixed solution to be inserted in 25mL reactor reacting by heating under solvent thermal 160 DEG C of conditions to be down to room temperature with 5 DEG C/h after 72 hours and to obtain described three-dimensional polymer, productive rate is 63.3% (based on Mn).
Then above-mentioned polymkeric substance is carried out structural characterization.
The X ray diffracting data of this polymkeric substance visits on diffractometer in Bruker Smart Apex CCD face, uses MoK
αradiation (λ=0.71073), collects with ω scan mode and carries out Lp factor correction, and absorption correction uses SADABS program.Use direct method solution structure, then obtain whole non-hydrogen atom coordinate by difference Fourier method, and obtain hydrogen atom position (C H 1.083) with theoretical hydrogenation method, by method of least squares, structure is revised.Evaluation work completes with SHELXTL routine package on PC.Polymer crystals mathematic(al) parameter is in table 1.Structure is shown in Fig. 1, Fig. 2.
the crystallographic parameter of table 1. polymkeric substance and structure elucidation
From crystalline structure, this polymkeric substance belongs to triclinic(crystalline)system,
p-1spacer, wherein, each asymmetric cell comprises two Mn (II) ions, four nicotinic acid parts, a bridging water molecules.Mn (II) ion is hexa-coordinate, adopt a kind of octahedral coordination geometric configuration of distortion, be 2.1841-2.1890 with the N(Mn-N bond distance on two niacin molecule respectively), O(Mn-O bond distance on three carboxylic acids is 2.0328-2.1613), and a water molecule coordination (as shown in Figure 1).Mn1 and Mn2 ion constitutes a kind of double-core unit by two carboxyls and a water molecules, and these double-core unit are interconnected the three-dimensional polymer (as shown in Figure 2) finally defining a kind of uniqueness.
embodiment 2
0.11mmol organic ligand nicotinic acid and 0.05mmol manganous nitrate are dissolved in (volume ratio of acetonitrile and water is 3.5:3) in the mixed solvent of 13mL acetonitrile and water, at room temperature stir and form mixed solution, then described mixed solution to be inserted in 25mL reactor reacting by heating under solvent thermal 150 DEG C of conditions to be down to room temperature with 4 DEG C/h after 60 hours and to obtain described three-dimensional polymer, productive rate is 59.7% (based on Mn).
embodiment 3
0.10mmol organic ligand nicotinic acid and 0.06mmol Manganous chloride tetrahydrate are dissolved in (volume ratio of acetonitrile and water is 5:3) in the mixed solvent of 16mL acetonitrile and water, at room temperature stir and form mixed solution, then described mixed solution to be inserted in 25mL reactor reacting by heating under solvent thermal 170 DEG C of conditions to be down to room temperature with 3 DEG C/h after 36 hours and to obtain described three-dimensional polymer, productive rate is 43.7% (based on Mn).
embodiment 4
0.10mmol organic ligand nicotinic acid and 0.05mmol Manganous chloride tetrahydrate are dissolved in (volume ratio of acetonitrile and water is 4:3) in the mixed solvent of 14mL acetonitrile and water, at room temperature stir and form mixed solution, then described mixed solution to be inserted in 25mL reactor reacting by heating under solvent thermal 155 DEG C of conditions to be down to room temperature with 3 DEG C/h after 48 hours and to obtain described three-dimensional polymer, productive rate is 51.6% (based on Mn).
The above embodiment only have expressed embodiments of the present invention; it describes comparatively concrete and detailed; but therefore can not be interpreted as the restriction to the scope of the claims of the present invention; in every case the technical scheme adopting the form of equivalent replacement or equivalent transformation to obtain, all should drop within protection scope of the present invention.
Claims (10)
1., containing a manganese double-core three-dimensional polymer, it is characterized in that: chemical formula is C
26h
21n
5o
9mn
2.
2. one according to claim 1 is containing manganese double-core three-dimensional polymer, and it is characterized in that, described polymkeric substance is triclinic(crystalline)system,
p-1spacer, unit cell parameters is
a=10.935 (2),
b=12.251 (3),
c=14.637 (8),
α=101.73 (1) o,
β=113.02 (4) o,
γ=112.83 (4) o, V=1941.51 (3)
3.
3. one according to claim 2 is containing manganese double-core three-dimensional polymer, it is characterized in that, in this polymkeric substance, manganese atom takes the octahedral pattern of hexa-coordinate, each manganese atom respectively with three O atoms on three nicotinic acid, the O atom in a water molecules and the atom N coordination on two other nicotinic acid.
4. a kind of preparation method containing manganese double-core three-dimensional polymer according to claim 1, it is characterized in that: organic ligand nicotinic acid and soluble manganese salt are dissolved in the mixed solvent of acetonitrile and water, at room temperature stir formed mixed solution, then by described mixed solution under solvent thermal condition after reacting by heating slow cooling obtain described three-dimensional polymer.
5. a kind of preparation method containing manganese double-core three-dimensional polymer according to claim 4, is characterized in that: described Heating temperature is 150 DEG C ~ 170 DEG C, and the reacting by heating time is 36 ~ 72 hours.
6. a kind of preparation method containing manganese double-core three-dimensional polymer according to claim 4, is characterized in that: described cooling is 2 DEG C/h ~ 5 DEG C/h and is down to room temperature.
7. a kind of preparation method containing manganese double-core three-dimensional polymer according to claim 4, is characterized in that: described soluble manganese salt is at least one in manganous nitrate, Manganous chloride tetrahydrate.
8. a kind of preparation method containing manganese double-core three-dimensional polymer according to claim 4, is characterized in that: the mol ratio of described nicotinic acid and soluble manganese salt is 1.8 ~ 2.2:1 ~ 1.2.
9. a kind of preparation method containing manganese double-core three-dimensional polymer according to claim 8, is characterized in that: the mol ratio of described nicotinic acid and soluble manganese salt is preferably 2:1.
10. a kind of preparation method containing manganese double-core three-dimensional polymer according to claim 4, is characterized in that: the volume ratio of described acetonitrile and water is 3.5 ~ 5:3.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106831879A (en) * | 2017-01-19 | 2017-06-13 | 东南大学 | 1,1 2 pyrazoles methane double-core manganese polymers and its decarboxylation synthetic method in situ and application |
-
2014
- 2014-11-25 CN CN201410682734.2A patent/CN104447872A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106831879A (en) * | 2017-01-19 | 2017-06-13 | 东南大学 | 1,1 2 pyrazoles methane double-core manganese polymers and its decarboxylation synthetic method in situ and application |
| CN106831879B (en) * | 2017-01-19 | 2018-11-06 | 东南大学 | Bis- pyrazoles methane double-core manganese polymers of 1,1- and its decarboxylation synthetic method in situ and application |
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Application publication date: 20150325 |
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