CN104356166A - Cobalt-containing compound based on flexible nitrogen-containing and carboxylic acid-containing dual ligands and preparation method thereof - Google Patents
Cobalt-containing compound based on flexible nitrogen-containing and carboxylic acid-containing dual ligands and preparation method thereof Download PDFInfo
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- CN104356166A CN104356166A CN201410672583.2A CN201410672583A CN104356166A CN 104356166 A CN104356166 A CN 104356166A CN 201410672583 A CN201410672583 A CN 201410672583A CN 104356166 A CN104356166 A CN 104356166A
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- cobalt
- carboxylic acid
- preparation
- cobalt compound
- nitrogenous
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 18
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims abstract description 17
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003446 ligand Substances 0.000 title abstract description 14
- 229910017052 cobalt Inorganic materials 0.000 title abstract 6
- 239000010941 cobalt Substances 0.000 title abstract 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title abstract 6
- 230000009977 dual effect Effects 0.000 title abstract 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 3
- 150000001869 cobalt compounds Chemical class 0.000 claims description 26
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 14
- 229940103494 thiosalicylic acid Drugs 0.000 claims description 14
- 150000003217 pyrazoles Chemical class 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 11
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 2
- 239000013110 organic ligand Substances 0.000 claims description 2
- 238000010583 slow cooling Methods 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 abstract description 2
- XAQHXGSHRMHVMU-UHFFFAOYSA-N [S].[S] Chemical compound [S].[S] XAQHXGSHRMHVMU-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000004020 luminiscence type Methods 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000012621 metal-organic framework Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910020647 Co-O Inorganic materials 0.000 description 2
- 229910020704 Co—O Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910020676 Co—N Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000010586 diagram 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
- 229910052751 metal Inorganic materials 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000373 single-crystal X-ray diffraction data Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009466 transformation Effects 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention relates to the field of coordination chemistry, in particular to a cobalt-containing compound based on flexible nitrogen-containing and carboxylic acid-containing dual ligands and a preparation method thereof. The chemical formula of the cobalt-containing compound based on the flexible nitrogen-containing and carboxylic acid-containing dual ligands is C19H19N4SCoO4, the compound is of a tetragonal system in a space group I41/acd, and cell parameters are as follows: a=27.7402(10) angstrom, b=27.7402(10) angstrom, C=25.8807(14) angstrom, alpha=beta=gamma=90 degrees, and V=19915.7(11) angstrom<3>. The synthesis method of the cobalt-containing compound is simple, and the synthesised cobalt-containing compound forms a three-dimensional structure through the flexible nitrogen-containing ligand; therefore, the compound is high in thermostability; mercaptan on the benzene ring forms sulphur-sulphur linking after being dehydrogenated, thus promoting electron conduction. Therefore, the cobalt-containing compound has a great potential application prospect in the fields of molecular magnets, catalysis, sensing, molecular recognition, molecular luminescence and the like.
Description
Technical field
The present invention relates to coordination chemistry field, particularly based on the cobalt compound and preparation method thereof of the two part of the nitrogenous and carboxylic acid of flexibility.
Background technology
In the design and synthesis of metal organic framework compound, not only can construct with single part, but also mixed ligand can be adopted realize, utilize mixed ligand, can be larger in the selection space of part, can go the length designing flexible ligand neatly, the size of adjustment aperture, thus the metal organic framework compound that synthesis is obtained has potential application in gas storage, separation and absorption etc.
Based on a large amount of bibliographical informations, mixed ligand large more options Carboxylic acid ligand and flexible containing n-donor ligand are combined, such one side can regulate the length of Carboxylic acid ligand, the such as Carboxylic acid ligand of select tape phenyl ring, owing to there is π-pi-conjugated, easy formation has the metal organic framework compound of luminosity, can design the length of flexible containing n-donor ligand on the other hand, the metal organic framework compound of formative dynamics porous.
Summary of the invention
Technical problem to be solved by this invention is to provide cobalt compound that is nitrogenous based on flexibility and the two part of carboxylic acid.
Another object of the present invention is the preparation method providing above-mentioned cobalt compound.
Based on a cobalt compound for the two part of the nitrogenous and carboxylic acid of flexibility, chemical formula is C
19h
19n
4sCoO
4, described compound is tetragonal system,
i4 1 / acdspacer, unit cell parameters is
a=27.7402 (10),
b=27.7402 (10),
c=25.8807 (14),
α=
β=
γ=90 o, V=19915.7 (11)
3.
Preparation method based on the cobalt compound of the two part of the nitrogenous and carboxylic acid of flexibility is: by organic ligand 4-Thiosalicylic acid, 3,3 ', 5,5 '-tetramethyl--4,4 '-Lian pyrazoles and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES are dissolved in the middle of acetonitrile, at room temperature stir formed mixed solution, then by described mixed solution under solvent thermal condition after reacting by heating slow cooling obtain described cobalt compound.
Further, described Heating temperature is 150 DEG C ~ 180 DEG C, and the reacting by heating time is 48 ~ 96 hours.
Further, described cooling is 2 DEG C/h ~ 5 DEG C/h and is down to room temperature.
Further, the mol ratio of described 3,3 ', 5,5 '-tetramethyl--4,4 '-Lian pyrazoles, 4-Thiosalicylic acid and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES is 1 ~ 3:1 ~ 3:2.
Further, the mol ratio of described 3,3 ', 5,5 '-tetramethyl--4,4 '-Lian pyrazoles, 4-Thiosalicylic acid and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES is preferably 2:1:2.
The present invention has following beneficial effect:
Cobalt compound synthetic method of the present invention is simple, and the cobalt compound of synthesis forms three-dimensional structure by flexible containing n-donor ligand, and therefore the thermostability of this compound by force, and forms the distich of sulphur sulphur after mercaptan dehydrogenation on phenyl ring, is conducive to electronic conduction.So this cobalt compound has extraordinary potential application prospect in fields such as molecular magnet, catalysis, sensing, molecular recognition, molecular luminescences.
Accompanying drawing explanation
Fig. 1 is that cobalt compound of the present invention is with the coordination environment figure of metal center Co.
Fig. 2 is the three-dimensional structure schematic diagram of cobalt compound of the present invention.
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
By 0.2 mmol3,3 ', 5,5 '-tetramethyl--4,4 '-Lian pyrazoles, 0.1 mmol4-Thiosalicylic acid and 0.2 mmol Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES are dissolved in the middle of 8mL acetonitrile solvent, at room temperature stir and form mixed solution, then described mixed solution to be inserted in 15mL reactor reacting by heating under solvent thermal 160 DEG C of conditions and be down to room temperature with 5 DEG C/h after 72 hours and obtain described cobalt compound, productive rate is 68.1% (based on Co).
Then above-claimed cpd is carried out structural characterization.
The X ray diffracting data of this compound 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.Compound crystal mathematic(al) parameter is in table 1.Structure is shown in Fig. 1, Fig. 2.
table 1. crystallographic parameter and structure elucidation
Single crystal X-ray diffraction data show that this cobalt compound belongs to centrosymmetric tetragonal system,
i4 1 / acdspacer, as shown in Figure 1, each Co atom respectively with two 3,3 ', N (Co-N bond distance is 2.123 (4)) coordination on 5,5 '-tetramethyl--4,4 '-Lian pyrazoles molecules, two O(Co-O bond distances on a nitrate radical are 2.078 (2)) coordination, and O (Co-O bond distance is 2.142 (7)) coordination on two 4-Thiosalicylic acid molecules.Each 3,3 ', 5,5 '-tetramethyl--4,4 '-Lian pyrazoles molecule bridging, two Co atoms, each 4-Thiosalicylic acid molecule bridging Co atom, S and S distich on two 4-Thiosalicylic acid molecules, finally defines a three-dimensional porous metal organic framework compound (as shown in Figure 2).
embodiment 2
By 0.1 mmol3,3 ', 5,5 '-tetramethyl--4,4 '-Lian pyrazoles, 0.15 mmol4-Thiosalicylic acid and 0.2 mmol Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES are dissolved in the middle of 8mL acetonitrile solvent, at room temperature stir and form mixed solution, then described mixed solution to be inserted in 15mL reactor reacting by heating under solvent thermal 150 DEG C of conditions and be down to room temperature with 4 DEG C/h after 80 hours and obtain described cobalt compound, productive rate is 51.3% (based on Co).
embodiment 3
By 0.3 mmol3,3 ', 5,5 '-tetramethyl--4,4 '-Lian pyrazoles, 0.15 mmol4-Thiosalicylic acid and 0.2 mmol Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES are dissolved in the middle of 8mL acetonitrile solvent, at room temperature stir and form mixed solution, then described mixed solution to be inserted in 15mL reactor reacting by heating under solvent thermal 170 DEG C of conditions and be down to room temperature with 3 DEG C/h after 60 hours and obtain described cobalt compound, productive rate is 40.3% (based on Co).
embodiment 4
By 0.1 mmol3,3 ', 5,5 '-tetramethyl--4,4 '-Lian pyrazoles, 0.3 mmol4-Thiosalicylic acid and 0.2 mmol Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES are dissolved in the middle of 8mL acetonitrile solvent, at room temperature stir and form mixed solution, then described mixed solution to be inserted in 15mL reactor reacting by heating under solvent thermal 180 DEG C of conditions and be down to room temperature with 2 DEG C/h after 48 hours and obtain described cobalt compound, productive rate is 31.8% (based on Co).
embodiment 5
By 0.1 mmol3,3 ', 5,5 '-tetramethyl--4,4 '-Lian pyrazoles, 0.1 mmol4-Thiosalicylic acid and 0.2 mmol Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES are dissolved in the middle of 8mL acetonitrile solvent, at room temperature stir and form mixed solution, then described mixed solution to be inserted in 15mL reactor reacting by heating under solvent thermal 155 DEG C of conditions and be down to room temperature with 5 DEG C/h after 96 hours and obtain described cobalt compound, productive rate is 51.9% (based on Co).
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 (7)
1. a cobalt compound for the two part of and carboxylic acid nitrogenous based on flexibility, is characterized in that: chemical formula is C
19h
19n
4sCoO
4.
2. a kind of cobalt compound based on the two part of the nitrogenous and carboxylic acid of flexibility according to claim 1, it is characterized in that, described compound is tetragonal system,
i4 1 / acdspacer, unit cell parameters is
a=27.7402 (10),
b=27.7402 (10),
c=25.8807 (14),
α=
β=
γ=90 o, V=19915.7 (11).
3. the preparation method of the cobalt compound based on the two part of the nitrogenous and carboxylic acid of flexibility according to claim 1, it is characterized in that: by organic ligand 4-Thiosalicylic acid, 3,3 ', 5,5 '-tetramethyl--4,4 '-Lian pyrazoles and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES are dissolved in the middle of acetonitrile, at room temperature stir formed mixed solution, then by described mixed solution under solvent thermal condition after reacting by heating slow cooling obtain described cobalt compound.
4. the preparation method of the cobalt compound based on the two part of the nitrogenous and carboxylic acid of flexibility according to claim 3, is characterized in that: described Heating temperature is 150 DEG C ~ 180 DEG C, and the reacting by heating time is 48 ~ 96 hours.
5. the preparation method of the cobalt compound based on the two part of the nitrogenous and carboxylic acid of flexibility according to claim 3, is characterized in that: described cooling is 2 DEG C/h ~ 5 DEG C/h and is down to room temperature.
6. the preparation method of the cobalt compound based on the two part of the nitrogenous and carboxylic acid of flexibility according to claim 3, it is characterized in that: described 3,3 ', 5, the mol ratio of 5 '-tetramethyl--4,4 '-Lian pyrazoles, 4-Thiosalicylic acid and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES is 1 ~ 3:1 ~ 3:2.
7. the preparation method of the cobalt compound based on the two part of the nitrogenous and carboxylic acid of flexibility according to claim 6, it is characterized in that: described 3,3 ', 5, the mol ratio of 5 '-tetramethyl--4,4 '-Lian pyrazoles, 4-Thiosalicylic acid and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES is preferably 2:1:2.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410672583.2A CN104356166A (en) | 2014-11-22 | 2014-11-22 | Cobalt-containing compound based on flexible nitrogen-containing and carboxylic acid-containing dual ligands and preparation method thereof |
| CN201510561851.8A CN105153432A (en) | 2014-11-22 | 2015-09-07 | Coordination polymer based on flexible dual ligand containing nitrogen and carboxylic acid and preparation method of coordination polymer |
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| CN201410672583.2A CN104356166A (en) | 2014-11-22 | 2014-11-22 | Cobalt-containing compound based on flexible nitrogen-containing and carboxylic acid-containing dual ligands and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105070497A (en) * | 2015-08-25 | 2015-11-18 | 广西大学 | Cobalt-based single-molecular magnet synthesizing method |
| CN106397788A (en) * | 2016-09-28 | 2017-02-15 | 齐鲁工业大学 | Cobalt coordination polymer of double carboxylate ligand, and preparation method thereof |
-
2014
- 2014-11-22 CN CN201410672583.2A patent/CN104356166A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105070497A (en) * | 2015-08-25 | 2015-11-18 | 广西大学 | Cobalt-based single-molecular magnet synthesizing method |
| CN105070497B (en) * | 2015-08-25 | 2017-08-25 | 广西大学 | Cobalt-based single molecular magnetses synthetic method |
| CN106397788A (en) * | 2016-09-28 | 2017-02-15 | 齐鲁工业大学 | Cobalt coordination polymer of double carboxylate ligand, and preparation method thereof |
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Application publication date: 20150218 |