CN110157004A - One-dimensional cobalt coordination polymer and preparation method thereof - Google Patents
One-dimensional cobalt coordination polymer and preparation method thereof Download PDFInfo
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- CN110157004A CN110157004A CN201910449591.3A CN201910449591A CN110157004A CN 110157004 A CN110157004 A CN 110157004A CN 201910449591 A CN201910449591 A CN 201910449591A CN 110157004 A CN110157004 A CN 110157004A
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Abstract
The invention discloses a kind of one-dimensional cobalt coordination polymers and preparation method thereof.The complex belongs to monoclinic system,C2/cSpace group has one-dimensional " zigzag " chain structure, includes 0.5 Co in its structural unit2+Ion, 0.5 part deprotonation ligand molecular, 1 hydrone and 1 Pyridine Molecules.The present invention utilizes 1,3- bis- (3,5- dicarboxyl phenol) paraxylene is ligand, cobalt nitrate is source metal, synthesizes subject polymer by hydro-thermal method, preparation process is simple and reproducible, provides certain foundation to synthesize and studying transient metal complex.Have studied the coordination polymer under nitrogen atmosphere, the thermal stability in 20-800 degree Celsius temperature range has preferable thermal stability, can be used as potential heat proof material.
Description
Technical field
The invention belongs to inorganic and organic composite material field, it is related to a kind of one-dimensional cobalt coordination polymer and its preparation side
Method.
Background technique
Coordination polymer is to be passed through to be self-assembly of in the form of coordinate bond by metal ion and organic/inorganic ligand,
With unlimited skeleton structure.The design and synthesis of coordination polymer, essentially consist in the selection of inorganic metal and organic ligand, the two
Property and connection type determine coordination polymer structure and function.It, can will be current from the changeability of coordination angle
Ligand is divided into rigid ligand and flexible ligand two major classes.So far, more most of coordination polymer is matched based on rigidity
Body design synthesis, the coordination polymer constructed based on flexible ligand is relatively fewer.This is because flexible ligand is in self assembly
In the process, vulnerable to the influence of external condition, different configurations is taken, increases the difficulty of construction structure.Utilize flexible ligand structure
When building coordination polymer, response parameter such as temperature, time, pH etc. easily influences the generation of final structure, so as to cause that can not design
With the final structure of prediction coordination polymer.Although constructing coordination polymer there are certain challenge using flexible ligand,
Just due to its influence of the flexible configuration vulnerable to reaction condition, so as to assemble to obtain novel and multiplicity topological structure,
So that having obtained extensive concern to the research of flexible ligand in recent years.
Cobalt is one of required trace element in organism as a kind of important biological element.Cobalt element is the 8th race
Transition element has the coordination geometry of multiplicity, can construct to obtain stable structure and the complex with specific function with ligand.
Summary of the invention
One of the objects of the present invention is to provide a kind of one-dimensional cobalt coordination polymer, which has good thermostabilization
Property.
The second object of the present invention is to provide the preparation method of the one-dimensional cobalt coordination polymer.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of one-dimensional cobalt coordination polymer, it is characterised in that the chemical formula of the one-dimensional cobalt coordination polymer are as follows: [Co (H2L)
(H2O)2(py)2]n, wherein L is the complete deprotonation state of (3, the 5- dicarboxyl phenol) paraxylene of 1,3- bis-, and py is pyridine；It should
Coordination polymer is monoclinic system, and C2/c space group has one-dimensional " zigzag " chain structure,
The basic structural unit of above-mentioned polymer includes 0.5 cobalt ions, 0.5 1,3- bis- (3,5- dicarboxyl phenol)
Paraxylene part deprotonation is negative bi-valent ligand, 1 water of coordination and 1 Pyridine Molecules, and wherein cobalt ions is hexa-coordinate, respectively
With the nitrogen-atoms on the oxygen atom and two Pyridine Molecules on two carboxylic carbonylic oxygen atoms from different ligands, two hydrones
Coordination is in octoploids structure.
Above-mentioned Co-O key bond distance is distributed inBetween, average bond length isThe key of Co-N key
It is a length of
A method of preparing cobalt coordination polymer material according to claim 1, it is characterised in that this method
With step are as follows:
A. 1,3- bis- (3,5- dicarboxyl phenol) paraxylene is dissolved in n,N-Dimethylformamide and is dissolved in pyridine, obtained
Ligand solution；
B. soluble cobalt is dissolved in deionized water, obtains salting liquid；
It c. is the ratio of 1:1~5 according to the molar ratio of (the 3,5- dicarboxyl phenol) paraxylene of 1,3- bis- and soluble cobalt
Example mixes salting liquid obtained by the resulting ligand solution of step a and step b；Constant temperature holding 48~80 is small at 90~120 DEG C
When, room temperature is then cooled to 10 DEG C per hour of velocity gradient, filters, obtains one-dimensional cobalt coordination polymer.
The present invention provides a kind of one-dimensional cobalt coordination polymer by hydrothermal synthesis method.The flexibility tetrabasic carboxylic acid cobalt coordination polymerization
The structure of object is as shown in Fig. 1.The coordination polymer belongs to monoclinic system, and C2/c space group has one-dimensional " zigzag " chain
Shape structure；Cell parameter:
γ=90,Z=4, Dc=1.442g/cm3, F (000)=1484.
The complex basic structural unit includes 0.5 Co2+Ion, the negative bi-valent ligand of 0.5 part deprotonation, one
Pyridine Molecules and a water of coordination.Co1 is hexa-coordinate, respectively with oxygen atom O1, O1A on the carboxylic acid of two monodentate ligands, two
A oxygen atom O2, O2A and two nitrogen-atoms N1, N1A coordinations from Pyridine Molecules from hydrone, in the octahedral of distortion
Body configuration.Bond distance's range of Co-O key is The bond distance of Co-N key isClosing
It manages within the scope of bond distance.
Heat analysis test is carried out to the complex, thermal analysis experiment is the sample of complex in N2Add in atmosphere from 20 DEG C
Heat is to 1000 DEG C, as shown in Fig. 6.The result shows that complex keeps stablizing in 28-130 DEG C of temperature range, there is not weightlessness.
Slowly weightless after temperature is more than 130 DEG C, skeleton starts to collapse.Prove that the complex has preferable thermal stability.
Compared with prior art, the present invention has the advantage that
First, one-dimensional cobalt coordination polymer of the invention with (3, the 5- dicarboxyl phenol) paraxylene of 1,3- bis- be ligand,
Cobalt nitrate is source metal, has one-dimensional " zigzag " chain structure, and coordination polymer molecular structure stabilized is good.
Second, the thermal stability that one-dimensional cobalt coordination polymer of the invention has had, can be used as heat proof material, have latent
In application value.
Third, the present invention synthesizes subject polymer by hydro-thermal method, have preparation process easy, low in cost, repeated
The advantages that good, provides certain foundation to synthesize and studying transient metal complex.
Detailed description of the invention
Fig. 1 is the minimum unit structure chart of cobalt coordination polymer of the invention.
Fig. 2 is the coordination context diagram of Co1.
Fig. 3 is the polyhedral structure figure of Co1.
Fig. 4 is the one-dimensional chain assembling structure figure of coordination polymer.
Fig. 5 is the one-dimensional accumulation graph of coordination polymer.
Fig. 6 is the thermal analysis experiment figure of coordination polymer of the invention.
Fig. 7 is the main bond distance that table 1 is complexBond angle [°] parameter.
Specific implementation method
Embodiment 1: the synthesis of one-dimensional cobalt coordination polymer:
(1) it weighs 0.10 mM of tetrabasic carboxylic acid ligand to be dissolved in 1 milliliter of n,N-Dimethylformamide (DMF), is added 0.1
The pyridine solution of milliliter moves into solution in the reaction kettle with polytetrafluoroethyllining lining that volume is 15 milliliters；
(2) it weighs 0.10 mM of cobalt nitrate to be dissolved in 7 milliliters of water, and is added in step (1)；
(3) aforesaid reaction vessel is sealed, 100 degrees Celsius lower constant temperature 3 days, then with 10 degrees Celsius per hour of speed ladder
Degree is cooled to room temperature, filters, obtains red acicular crystal, as target cobalt coordination polymer, yield 66%.
Embodiment 2: the synthesis of one-dimensional cobalt coordination polymer:
(1) it weighs 0.02 mM of tetrabasic carboxylic acid ligand to be dissolved in 1 milliliter of n,N-Dimethylformamide, is added 0.1 milliliter
Pyridine solution, it is in 15 milliliters of the reaction kettle with polytetrafluoroethyllining lining that solution, which is moved into volume,；
(2) it weighs 0.10 mM of cobalt nitrate to be dissolved in 7 milliliters of water, and is added in step (1)；
(3) aforesaid reaction vessel is sealed, 100 degrees Celsius lower constant temperature 2 days, then with 10 degrees Celsius per hour of speed ladder
Degree is cooled to room temperature, filters, obtains red acicular crystal, as target cobalt coordination polymer, yield 63%.
Embodiment 3: the synthesis of one-dimensional cobalt coordination polymer:
(1) it weighs 0.05 mM of tetrabasic carboxylic acid ligand to be dissolved in 1 milliliter of n,N-Dimethylformamide, is added 0.1 milliliter
Pyridine solution, it is in 15 milliliters of the reaction kettle with polytetrafluoroethyllining lining that solution, which is moved into volume,；
(2) it weighs 0.10 mM of cobalt nitrate to be dissolved in 7 milliliters of water, and is added in step (1)；
(3) aforesaid reaction vessel is sealed, 100 degrees Celsius lower constant temperature 3 days, then with 10 degrees Celsius per hour of speed ladder
Degree is cooled to room temperature, filters, obtains red acicular crystal, as target cobalt coordination polymer, yield 65%.IR(KBr
pellet,cm-1) major absorbance peak are as follows: 3450s, 2573m, 1646s, 1704s, 1660s, 1563s, 1450s, 1376s,
1271s,1221w,1121s,1056m,1034s,1010w,947w,888w,695s,598w,528w。
The suitable crystal of size is chosen under the microscope carries out Advances in crystal X-ray diffraction test.The single crystal X-ray of complex
Diffraction data measures on Bruker Smart Apex II CCD Advances in crystal X-ray diffraction instrument, with graphite monochromator monochromatization
Mo KαRay collects diffraction data, diffracted intensity warp at 293 (2) K with ω scanning mode
The Lorentz-Polarization factor and SADABS absorption correction.The reduction of all diffraction datas and structure elucidation use respectively
SAINT-5.0 and SHELXL-97 program is completed.The position that non-hydrogen atom is determined using direct method, using complete matrix least square
Method is modified the anisotropy of non-hydrogen atom, and hydrogen atom is found out according to difference Fourier or theoretical plus hydrogen.It is final deviate because
Sub- R1=0.0391, wR2=0.1184, S=0.757.
The structure of the flexibility tetrabasic carboxylic acid cobalt coordination polymer is shown in attached drawing 1, and main bond distance, bond angle are listed in table 1.The complex category
In monoclinic system, C2/c space group, there is one-dimensional " zigzag " chain structure.Its basic structural unit includes 0.5 Co2+From
Son, 0.5 part deprotonation ligand molecular, 1 hydrone and 1 Pyridine Molecules.The coordination environment of cobalt ions is shown in attached drawing 2,
Co1 is hexa-coordinate, respectively with oxygen atom O1, O1A on the carboxylic acid of two monodentate ligands, two oxygen atoms from hydrone
O2, O2A and two nitrogen-atoms N1, N1A coordinations from Pyridine Molecules, in the octoploids structure of distortion.The bond distance of Co-O key
Range isThe bond distance of Co-N key isWithin the scope of reasonable bond distance.
Heat analysis test is carried out to the complex, thermal analysis experiment is the sample of complex in N2Add in atmosphere from 20 DEG C
Heat is to 1000 DEG C, as shown in Fig. 6.The result shows that complex keeps stablizing in 28-130 DEG C of temperature range, there is not weightlessness.
Slowly weightless after temperature is more than 130 DEG C, skeleton starts to collapse.Prove that the complex has preferable thermal stability.
Claims (4)
1. a kind of one-dimensional cobalt coordination polymer, it is characterised in that the chemical formula of the one-dimensional cobalt coordination polymer are as follows: [Co (H2L)
(H2O)2(py)2]n, wherein L is the complete deprotonation state of (3, the 5- dicarboxyl phenol) paraxylene of 1,3- bis-, and py is pyridine；It should
Coordination polymer is monoclinic system,C2/C space group has one-dimensional " zigzag " chain structure.
2. one-dimensional cobalt coordination polymer according to claim 1, it is characterised in that the basic structural unit packet of the polymer
Containing 0.5 cobalt ions, 0.5 1,3- bis- (3,5- dicarboxyl phenol) paraxylene part deprotonation is negative bi-valent ligand, and 1 is matched
Position water and 1 Pyridine Molecules, wherein cobalt ions is hexa-coordinate, respectively with two carboxylic carbonylic oxygen atoms from different ligands, two
Nitrogen-atoms coordination on oxygen atom and two Pyridine Molecules on a hydrone, is in octoploids structure.
3. one-dimensional cobalt coordination polymer according to claim 2, it is characterised in that the Co-O key bond distance is distributed in
Between 2.082 ~ 2.155, average bond length 2.119；The bond distance of Co-N key is 2.142.
4. a kind of method for preparing cobalt coordination polymer material according to claim 1, it is characterised in that the tool of this method
There is step are as follows:
A. 1,3- bis- (3,5- dicarboxyl phenol) paraxylene is dissolved in n,N-Dimethylformamide and is dissolved in pyridine, obtain ligand
Solution；
B. soluble cobalt is dissolved in deionized water, obtains salting liquid；
It c. is the ratio of 1:1 ~ 5 according to the molar ratio of (3, the 5- dicarboxyl phenol) paraxylene of 1,3- bis- and soluble cobalt, it will
The resulting ligand solution of step a and step b gained salting liquid mixing；At 90 ~ 120 DEG C constant temperature keep 48 ~ 80 hours, then with
10 DEG C of velocity gradient is cooled to room temperature per hour, and filtering obtains one-dimensional cobalt coordination polymer.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110437465A (en) * | 2019-08-30 | 2019-11-12 | 武汉大学 | A kind of cobalt complex and preparation method thereof and application as proton-conducting material |
| CN111825850A (en) * | 2020-06-15 | 2020-10-27 | 上海大学 | Preparation method of three-dimensional manganese coordination polymer |
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| CN107417740A (en) * | 2017-05-18 | 2017-12-01 | 东北大学秦皇岛分校 | A kind of one-dimensional cobalt complex and its preparation method and application |
| CN108586768A (en) * | 2018-06-11 | 2018-09-28 | 上海大学 | Two-dimentional zinc coordination polymer and preparation method thereof |
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- 2019-05-28 CN CN201910449591.3A patent/CN110157004A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107417740A (en) * | 2017-05-18 | 2017-12-01 | 东北大学秦皇岛分校 | A kind of one-dimensional cobalt complex and its preparation method and application |
| CN108586768A (en) * | 2018-06-11 | 2018-09-28 | 上海大学 | Two-dimentional zinc coordination polymer and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110437465A (en) * | 2019-08-30 | 2019-11-12 | 武汉大学 | A kind of cobalt complex and preparation method thereof and application as proton-conducting material |
| CN111825850A (en) * | 2020-06-15 | 2020-10-27 | 上海大学 | Preparation method of three-dimensional manganese coordination polymer |
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Application publication date: 20190823 |