CN111116932A - Metal organic coordination polymer based on hexanuclear cobalt (II) and preparation method thereof - Google Patents
Metal organic coordination polymer based on hexanuclear cobalt (II) and preparation method thereof Download PDFInfo
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- CN111116932A CN111116932A CN201911419523.9A CN201911419523A CN111116932A CN 111116932 A CN111116932 A CN 111116932A CN 201911419523 A CN201911419523 A CN 201911419523A CN 111116932 A CN111116932 A CN 111116932A
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Abstract
The invention provides a metal organic coordination polymer based on hexacyclic cobalt (II) and a preparation method thereof, wherein the metal coordination polymer based on hexacyclic cobalt (II) has a chemical formula { [ Co ] of6(MIA)5(3,3'‑bpy)(μ3‑OH)2(ethanol)2]·(ethanol)2}nThe polymer consisting of Co (NO)3)2·6H2O、H2MIA and 3,3' -bpy, wherein H2MIA is 5-methoxy isophthalic acid, 3,3' -bpy is 3,3' -dimethyl-4, 4 ' -bipyridine, ethanol is ethanol, and the metal-organic coordination polymer of the hexanuclear cobalt (II) has a three-dimensional supermolecular structure.
Description
Technical Field
The invention relates to the field of metal organic coordination polymers, in particular to a metal organic coordination polymer based on hexacuclear cobalt (II) and a preparation method thereof.
Background
The metal organic coordination polymer 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 coordination polymer 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.
5-methoxy isophthalic acid is a ligand with multiple modes of linkage and coordination, and is very important for constructing the structure of coordination polymers. However, the formation of coordination polymers based on cobalt as a transition metal and 5-methoxyisophthalic acid has been rarely reported.
Disclosure of Invention
In order to solve the problems, the invention provides a metal organic coordination polymer based on six-core cobalt (II) and a preparation method thereof.
The purpose of the invention is realized by adopting the following technical scheme:
a hexanuclear cobalt (II) -based metal-organic coordination polymer having the formula { [ Co ] O6(MIA)5(3,3'-bpy)(μ3-OH)2(ethanol)2]·(ethanol)2}nThe polymer consisting of Co (NO)3)2·6H2O、H2MIA and 3,3' -bpy, wherein H2MIA is 5-methoxy isophthalic acid, 3,3' -bpy is 3,3' -dimethyl-4, 4 ' -bipyridine, ethanol is ethanol, and the metal-organic coordination polymer of the hexanuclear cobalt (II) has a three-dimensional supermolecular structure, belongs to an orthorhombic system, a Pcca space group, and crystal cell parameters are respectively a-2.4100 (2) nm, b-1.08426 (9) nm, c-2.8451 (2) nm, α - β -gamma-90 °;
the infrared spectrum data (KBr) of the metal organic coordination polymer are as follows: 3417(s),3084(w),3005(w),2963(w),2935(w),1628(w),1574(vs),1453(s),1318(vs),1317(m),1262(s),1184(m),1129(s),1054(s),992(w),921(m),888(w),775(vs),713(vs),642(w),597(w),46 (w)0(m)cm-1。
In the metal organic coordination polymer, an MIA ligand has two coordination modes, one is in a bridging mode for connecting four cobalt (II) ions, the other is also in a bridging mode for connecting five cobalt ions, and 3,3' -bpy is used for connecting two cobalt ions, namely mu3-OH links three cobalt ions; the connection mode based on the ligand, EIA, 3,3' -bpy and mu3the-OH ligand connects the six-core cobalt cluster into a three-dimensional supermolecular structure. The cobalt (II) metal organic coordination polymer is purple single crystal at normal temperature, and the repeating structural unit of the cobalt (II) metal organic coordination polymer contains 6 Co2+Cation, 5 MIA2-An anion, 13, 3' -bpy ligand, 2 coordinated ethanol molecules and 2 free ethanol molecules; co1 is a four-coordinate tetrahedral geometry consisting of three carboxylic acid oxygen atoms and one mu in three different MIA ligands3-one oxygen atom in the OH ligand coordinates; co2 is in a hexa-coordinated octahedral configuration, consisting of five carboxylic acid oxygen atoms and one mu in five different MIA ligands3-one oxygen atom in the OH ligand coordinates; co3 is also in a hexa-coordinated octahedral geometry, consisting of three carboxylic acid oxygen atoms, one mu, of three different MIA ligands3One oxygen atom in the-OH ligand, one nitrogen atom in a 3,3' -bpy ligand and one ethanol molecule are coordinated.
The invention also provides a preparation method of the metal organic coordination polymer based on the hexacuclear cobalt (II), which adopts a mixed solvent reaction method commonly used in the field to react 5-methoxy isophthalic acid, 3,3' -bpy and Co (NO)3)2·6H2The O is obtained by reacting under the condition of a mixed solvent of ethanol and water after mixing, and the method specifically comprises the following steps:
s1, mixing Co (NO) with equal molar quantity3)2·6H2O，H2Adding EIA and 3,3' -bpy into a certain amount of mixed solvent of ethanol and water, and 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 water and ethanol, and drying the crystals to obtain the metal coordination polymer based on the hexacyclic 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 and high purity, and does not need 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 Co in the coordination polymer2+A coordination environment diagram of ions;
FIG. 2 is a diagram of the coordination pattern of MIA and 3,3' -bpy ligand;
FIG. 3 shows a six-core cobalt cluster [ Co ]6(cpn)10(μ3-OH)2NO]A secondary construction unit;
FIG. 4 is a three-dimensional supramolecular structure diagram of the hexanuclear cobalt metal organic coordination polymer.
Detailed Description
The invention is further described with reference to the following examples.
Example 1
A metal organic coordination polymer based on hexacyclic cobalt (II) is prepared by the following steps:
(1) equimolar amount of Co (NO)3)2·6H2O(0.145g,0.5mmol)，H2MIA (0.098g,0.5mmol)3,3' -bpy (0.092g,0.5mmol) was added to 12mL of a mixed solvent (6mL of distilled water +6mL of ethanol), followed by stirring for 20 minutes;
(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 ethanol and water solvent and dried to obtain purple crystals.
(4) The product was filtered, the crystals collected and dried to obtain purple crystals.
According to H2The yield was 45% by EIA 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
C65H68O31N2Co6(ii) a Theoretical value: c, 45.20; h, 3.94; n, 1.62; experimental values: c, 44.50; h, 4.40; and N, 2.30.
(2) Infrared spectrum (KBr pellet)
The spectral data are 3417(s),3084(w),3005(w),2963(w),2935(w),1628(w),1574(vs),1453(s),1318(vs),1317(m),1262(s),1184(m),1129(s),1054(s),992(w),921(m),888(w),775(vs),713(vs),642(w),597(w),460(m) cm-1。
(3) Single crystal X-ray diffraction
The crystallographic parameters and part of the bond lengths are shown in tables 1 and 2. The X-ray single crystal diffraction result shows that the repeating unit in the cobalt (II) metal organic coordination polymer is an asymmetric unit, and the repeating structural unit contains 1 Co2+Cation, 1 EIA2-An anion, 1 bpy ligand and one free water molecule. Co1 is a hexa-coordinated octahedral geometry, see FIG. 1, Co1 is coordinated by four carboxylic acid oxygen atoms in four different EIA ligands and two nitrogen atoms in two bpy ligands.
TABLE 1 { [ Co ]6(MIA)5(3,3'-bpy)(μ3-OH)2(ethanol)2]·(ethanol)2}nCrystallographic parameters of
R＝∑(||Fo︱－︱Fc||)/∑︱Fo︱.wR＝[∑w(Fo 2–Fc 2)2/∑w(Fo)2]1/2.
TABLE 2 { [ Co ]6(MIA)5(3,3'-bpy)(μ3-OH)2(ethanol)2]·(ethanol)2}nPartial bond length (nm, °)
| Co1-O1 | 0.1961(3) | Co1-O2 | 0.1937(3) |
| Co1-O7 | 0.1957(3) | Co1-O13 | 0.1940(3) |
| Co2-O1 | 0.2110(3) | Co2-O5 | 0.1992(3) |
| Co2-O8i | 0.2222(3) | Co2-O8ii | 0.2180(3) |
| Co2-O12iii | 0.2014(3) | Co2-O14ii | 0.2081(3) |
| Co3-O1 | 0.2093(3) | Co3-O3iv | 2.057(3) |
| Co3-O6v | 0.2134(3) | Co3-N1 | 0.2213(4) |
| O1-Co1-O2 | 113.12(13) | O2-Co1-O7 | 98.70(14) |
| O7-Co1-O1 | 114.80(12) | O13-Co1-O7 | 114.04(15) |
| O8i-Co2-O1 | 92.41(10) | O8ii-Co2-O1 | 82.47(10) |
| O5-Co2-O1 | 90.31(12) | O8ii-Co2-O5 | 163.42(12) |
| O1-Co3-O6v | 91.37(11) | O1-Co3-O11 | 175.79(14) |
| O1-Co3-N1 | 97.83(14) | O3iv-Co3-O6v | 84.68(14) |
An operation symmetry code i ═ x +1, y, -z + 1/2; ii-x, -y, z-1/2; iii-x +1, y-1, -z + 1/2; x, y +1, z; v-x +1, y +1, -z + 1/2.
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 metal organic coordination polymer based on hexacyclic cobalt (II), characterized in that the metal organic coordination polymer has the chemical formula { [ Co ] Co6(MIA)5(3,3'-bpy)(μ3-OH)2(ethanol)2]·(ethanol)2}nThe polymer consisting of Co (NO)3)2·6H2O、H2MIA and 3,3' -bpy, wherein H2MIA is 5-methoxy isophthalic acid, 3,3' -bpy is 3,3' -dimethyl-4, 4 ' -bipyridine, ethanol is ethanol, the metal-organic coordination polymer of the hexanuclear cobalt (II) has a three-dimensional supermolecular structure, the metal-organic coordination polymer belongs to an orthorhombic system, a Pcca space group, unit cell parameters are respectively a-2.4100 (2) nm, b-1.08426 (9) nm, c-2.8451 (2) nm, α - β -gamma-90°。
2. The metal organic coordination polymer based on six-nuclear cobalt (II), according to claim 1, characterized in that the infrared spectrum data of the metal organic coordination polymer, namely KBr, is: 3417(s),3084(w),3005(w),2963(w),2935(w),1628(w),1574(vs),1453(s),1318(vs),1317(m),1262(s),1184(m),1129(s),1054(s),992(w),921(m),888(w),775(vs),713(vs),642(w),597(w),460(m) cm-1。
3. The method for preparing the metal-organic coordination polymer based on the hexacyclic cobalt (II) as claimed in claim 1, which comprises the following steps:
s1, mixing Co (NO) with equal molar quantity3)2·6H2O,H2MIA and 3,3' -bpy are added into a certain amount of mixed solvent of ethanol and water, and then stirred 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 ethanol and water, and drying the crystals to obtain the metal-organic coordination polymer based on the hexacyclic cobalt (II).
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| CN112759769A (en) * | 2020-12-29 | 2021-05-07 | 山西大学 | Hexa-nuclear copper coordination polymer and preparation method and application thereof |
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| JP2010158617A (en) * | 2009-01-07 | 2010-07-22 | Japan Science & Technology Agency | Organometallic complex, and molding and method for separating gas |
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| JP2010158617A (en) * | 2009-01-07 | 2010-07-22 | Japan Science & Technology Agency | Organometallic complex, and molding and method for separating gas |
Non-Patent Citations (2)
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| PENG YAN等: "C2H2/CH4 and CO2/CH4 separations on a ethoxyl-functionalized Cobalt(II)-Organic framework with open metal sites", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
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| CN112759769A (en) * | 2020-12-29 | 2021-05-07 | 山西大学 | Hexa-nuclear copper coordination polymer and preparation method and application thereof |
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Application publication date: 20200508 |