CN111057113A - Trinuclear metal organic complex based on cobalt (II) and preparation method thereof - Google Patents
Trinuclear metal organic complex based on cobalt (II) and preparation method thereof Download PDFInfo
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- CN111057113A CN111057113A CN201911409379.0A CN201911409379A CN111057113A CN 111057113 A CN111057113 A CN 111057113A CN 201911409379 A CN201911409379 A CN 201911409379A CN 111057113 A CN111057113 A CN 111057113A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 20
- 239000002184 metal Substances 0.000 title claims abstract description 20
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 20
- BKXRBGAQGOLFPW-UHFFFAOYSA-N 6-(4-carboxyphenyl)pyridine-3-carboxylic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=N1 BKXRBGAQGOLFPW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000013256 coordination polymer Substances 0.000 claims abstract description 4
- 229920001795 coordination polymer Polymers 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- -1 organometallic cobalt (ii) complexes Chemical class 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 230000003595 spectral effect Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 125000002524 organometallic group Chemical group 0.000 claims 2
- LBFUKZWYPLNNJC-UHFFFAOYSA-N cobalt(ii,iii) oxide Chemical compound [Co]=O.O=[Co]O[Co]=O LBFUKZWYPLNNJC-UHFFFAOYSA-N 0.000 claims 1
- 239000003446 ligand Substances 0.000 description 14
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 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 description 2
- 238000002050 diffraction method Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- 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 provides a trinuclear metal coordination polymer based on cobalt (II), which has a chemical formula of [ Co [ ]3(cpn)3(dmf)2]nWherein cpn is 6- (4-carboxyphenyl) nicotinic acid, dmf is N, N-dimethylformamide, and the cobalt (II) metal organic complex has a two-dimensional microporous structure.
Description
Technical Field
The invention relates to the field of metal organic complexes, in particular to a trinuclear metal organic complex based on cobalt (II) and a preparation method thereof.
Background
The metal organic complex is a metal organic framework material which is synthesized by self-assembly of metal ions and organic ligands under certain conditions and has a one-dimensional, two-dimensional or three-dimensional structure. As a novel functional material, the metal organic complex has the characteristics of high porosity, plastic structure, uniform pore size and the like. Due to the characteristics of unique porous structure, simple and easy preparation method and the like, the magnetic material has potential application value in the fields of adsorption separation, fluorescence sensing, magnetism, drug sustained and controlled release and the like.
6- (4-carboxyphenyl) nicotinic acid is a ligand with a variety of modes of linkage and coordination, and is important for the construction of coordination polymers. However, based on the transition metals cobalt and H2Formation of coordination compounds by cpn has not been reported.
Disclosure of Invention
Aiming at the problems, the invention provides a trinuclear metal organic complex based on cobalt (II) and a preparation method thereof.
The purpose of the invention is realized by adopting the following technical scheme:
a trinuclear metal-organic complex based on cobalt (II), said metal-organic complex having the chemical formula [ Co [ ]3(cpn)3(dmf)2]nWherein cpn is 6- (4-carboxyphenyl) nicotinic acid and dmf is N, N-dimethylformamide; the metal organic complex has a two-dimensional microporous structure, and belongs to a monoclinic system, P21Space group, unit cell parameters are a-1.2093 (3) nm, b-1.3984 (3) nm, c-2.0354 (4) nm, and β -101.616 (5) °;
the infrared spectrum data (KBr) of the metal organic complex are as follows: 1643(s),1601(vs),1522(m),1496(m),1393(vs),1317(m),1232(s),1132(s),1121(w),1101(w),1001(w),923(w),863(w),738(s),697(m),628(m),607(w),531(w),455(w),408(w) cm-1。
In the metal organic complex, two coordination modes exist for cpn ligand: one bridging mode connects four cobalt (II) ions, and the other bridging-chelating mode connects four cobalt (II) ions; and the dmf molecule as a terminal ligand; based on the above connection scheme, six cpn2-Anion, two dmf end ligands and trinuclear cobalt cluster [ Co ]3(cpn)6(dmf)2]Can be regarded as secondary construction units, and the secondary construction units are further connected with surrounding trinuclear cobalt clusters through cpn ligands to form a two-dimensional network structure; the cobalt (II) metal organic complex is purple single crystal at normal temperature and has a repeated structureThe unit contains 3 Co2+Cation, 3 cpn2-An anion and two dmf ligands; co1 is a penta-coordinated tetragonal pyramid geometry coordinated by four carboxylic acid oxygen atoms in three different cpn ligands and the dmf ligand, while Co2 is a hexa-coordinated, octahedral geometry coordinated by six carboxylic acid oxygen atoms in six different cpn ligands.
The invention also provides a preparation method of the trinuclear metal organic complex based on cobalt (II), and the preparation method provided by the invention adopts a solvothermal reaction method commonly used in the field to react 6- (4-carboxyphenyl) nicotinic acid with Co (NO)3)2·6H2O is obtained by reaction under the dmf condition after mixing, and the method specifically comprises the following steps:
s1, mixing Co (NO) with equal molar quantity3)2·6H2O and H2Adding cpn into a certain amount of DMF solvent, and then stirring for 20 minutes;
s2, adding the substances in the step S1 into a 23mL polytetrafluoroethylene reaction kettle, keeping the temperature of 130 ℃ under autogenous pressure for reacting for 72 hours at constant temperature, and then cooling to room temperature according to a certain speed;
s3, filtering the product obtained in the S2, collecting crystals, washing the crystals with DMF, and drying the crystals to obtain the trinuclear metal coordination polymer based on cobalt (II).
The invention has the beneficial effects that:
(1) the product of the invention has wide raw material source and is easy to obtain;
(2) the product synthesis method has mild reaction conditions, high purity and no need of inert gas protection;
drawings
The invention is further illustrated by means of the attached drawings, but the embodiments in the drawings do not constitute any limitation to the invention, and for a person skilled in the art, other drawings can be obtained on the basis of the following drawings without inventive effort.
FIG. 1 shows that Co in the complex2+A coordination environment diagram of ions;
FIG. 2 is a schematic diagram of the coordination pattern of cpn ligands;
FIG. 3 is a two-dimensional block diagram of a cobalt metal organic complex according to the present invention;
FIG. 4 is an XRD powder diffractogram (simulated and synthesized) of the complex;
Detailed Description
The invention is further described with reference to the following examples.
Example 1
A trinuclear metal organic complex based on cobalt (II) is prepared by the following steps:
(1) equimolar amount of Co (NO)3)2·6H2O (0.145g,0.5mmol) and H2cpn (0.12g,0.5mmol) was added to 12mL of dmf solvent, followed by stirring for 20 min; (ii) a
(2) Adding the substances in the step 1 into a polytetrafluoroethylene reaction kettle with the volume of 23mL, keeping the temperature of 130 ℃ under autogenous pressure for reacting for 72 hours at constant temperature, and then reducing the temperature to room temperature at the speed of 5 ℃/h;
(3) the mixture in step 2 is filtered, the crystals are collected, washed with dmf solvent and dried to obtain violet crystals.
(4) The product was filtered, the crystals collected and dried to obtain purple crystals.
According to H2The yield was 48% by cpn calculation.
Product identification of example 1
The identification method comprises element analysis, IR spectrum and X-ray single crystal diffraction analysis identification.
(1) Elemental analysis
C45H35O14N5Co3(ii) a Theoretical value: c, 51.64; h, 3.35; n, 6.69; experimental values: c, 51.32; h, 3.26; and N, 7.01.
(2) Infrared spectrum (KBrpellet)
The spectral data were 1643(s),1601(vs),1522(m),1496(m),1393(vs),1317(m),1232(s),1132(s),1121(w),1101(w),1001(w),923(w),863(w),738(s),697(m),628(m),607(w),531(w),455(w),408(w) cm-1。
(3) Single crystal X-ray diffraction
The crystallographic parameters and partial bond lengths are shown in Table 1And table 2. The X-ray single crystal diffraction result shows that the repeating unit in the cobalt (II) metal organic complex is asymmetric unit, and the repeating structural unit contains 3 Co2+Cation, 3 cpn2-An anion and a dmf ligand. Co1 is a penta-coordinate, tetragonal pyramid geometry, and referring to FIG. 1, Co1 is coordinated by four carboxylic acid oxygen atoms in three different cpn ligands and a dmf ligand, while Co2 is coordinated by six carboxylic acid oxygen atoms in six different cpn ligands to form a hexa-coordinate, octahedral geometry.
TABLE 1 [ Co ]3(cpn)3(dmf)2]nCrystallographic parameters of
R＝∑(||Fo︱－︱Fc||)/∑︱Fo︱.wR＝[∑w(Fo 2–Fc 2)2/∑w(Fo)2]1/2.
TABLE 2 [ Co ]3(cpn)3(dmf)2]nPartial bond length (nm, °)
| Co1-O1 | 0.1945(3) | Co1-O3i | 0.1960(2) |
| Co1-O7 | 0.1994(3) | Co1-O6 | 0.2009(3) |
| Co1-O5 | 0.2290(3) | Co2-O2ii | 0.2040(2) |
| Co2-O4iv | 0.2041(3) | Co2-O5iii | 0.2086(2) |
| O1-Co1-O3i | 116.91(12) | O1-Co1-O7 | 97.62(13) |
| O3i-Co1-O7 | 96.31(13) | O1-Co1-O6 | 122.58(14) |
| O3i-Co1-O6 | 113.64(13) | O7-Co1-O5 | 161.19(11) |
| O2ii-Co2-O2iii | 180.0 | O2iii-Co2-O4iv | 92.18(13) |
| O4-Co2-O5iii | 91.22(11) | O4iv-Co2-O5ii | 88.78(11) |
| O4-Co2-O5ii | 88.78(11) | O5iii-Co2-O5ii | 180.00(12) |
Operation symmetry code i ═ 0.5+ x,0.5-y,0.5+ z; ii-1.5-x, -0.5+ y, 1.5-z; iii-0.5 + x,0.5-y, -0.5-z; iv is 2-x, -y,1-z.
The purple crystals obtained in example 1 were cobalt (II) organometallic complexes based on cpn of 6- (4-carboxyphenyl) nicotinic acid and N, N-dimethylformamide and having the formula of the repeating unit [ Co ] as identified by elemental analysis, IR spectroscopy and X-ray single crystal diffraction analysis3(cpn)3(dmf)2]n。
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is 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 on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (3)
1. A trinuclear metal-organic complex based on cobalt (ii), characterized in that the metal-organic complex has the chemical formula [ Co [ ]3(cpn)3(dmf)2]nWherein cpn is 6- (4-carboxyphenyl) nicotinic acid and dmf is N, N-dimethylformamide; the metal organic complex has a two-dimensional microporous structure, and belongs to a monoclinic system, P21In the space group,/n, unit cell parameters are a ═ 1.2093(3) nm, b ═ 1.3984(3) nm, c ═ 2.0354(4) nm, and β ═ 101.616(5) °.
2. A pentacyclic organometallic complex based on cobalt (ii) according to claim 1, wherein the organometallic complex has infrared spectral data (KBr) of: 1643(s),1601(vs),1522(m),1496(m),1393(vs),1317(m),1232(s),1132(s),1121(w),1101(w),1001(w),923(w),863(w),738(s),697(m),628(m),607(w),531(w),455(w),408(w) cm-1。
3. A process for the preparation of trinuclear organometallic cobalt (ii) complexes as claimed in claim 1, characterized by comprising the following steps:
s1, mixing Co (NO) with equal molar quantity3)2·6H2O and H2Adding cpn into a certain amount of DMF solvent, and then stirring for 20 minutes;
s2, adding the substances in the step S1 into a polytetrafluoroethylene reaction kettle, keeping the temperature of 130 ℃ under autogenous pressure for constant-temperature reaction for 72 hours, and then cooling to room temperature at a certain speed;
s3, filtering the product obtained in the S2, collecting crystals, washing the crystals with DMF, and drying the crystals to obtain the trinuclear metal coordination polymer based on cobalt (II).
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| LING QIN等: "One Metal-Organic Framework with one open nitrogen site as luminescence detections for Fe3+ and Cr2O72-", 《JOURNAL OF MOLECULAR STRUCTURE》 * |
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Application publication date: 20200424 |