CN103509040A - Coordination polymer with high thermal stability and fluorescence properties and preparation method thereof - Google Patents
Coordination polymer with high thermal stability and fluorescence properties and preparation method thereof Download PDFInfo
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- CN103509040A CN103509040A CN201210232821.9A CN201210232821A CN103509040A CN 103509040 A CN103509040 A CN 103509040A CN 201210232821 A CN201210232821 A CN 201210232821A CN 103509040 A CN103509040 A CN 103509040A
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- hfipbb
- carboxylic acid
- dipyridyl
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Abstract
The invention discloses a coordination polymer with high thermal stability and fluorescence properties. The composition of the coordination polymer is shown by a chemical formula [Cd2(hfipbb)2(4,4'-bpy)]n, an asymmetric unit of the coordination polymer consists of three independent metal Cd atoms, two hfipbb ligands and one 4,4'-dipyridyl. All the Cd atoms are connected together to form one-dimensional metal carboxylic acid chains which can be regarded as being formed by connecting linear trinuclear cadmium clusters with mononuclear cadmium through carboxyl. Each one-dimensional metal carboxylic acid chain and the other adjacent six one-dimensional metal carboxylic acid chains are in cross connection through organic hfipbb ligands and the 4,4'-dipyridyl to form a three-dimensional non-interpenetrating compact accumulated network structure. The preparation method of the coordination polymer disclosed by the invention is simple and feasible in process, short in time and low in cost.
Description
Technical field
The invention belongs to the synthesis technical field of metal organic coordination polymer, be specifically related to a kind of ligand polymer with high thermal stability and fluorescence property and preparation method thereof.
Background technology
Metal-organic coordination polymer, as one of important research theme of current inorganic and materials chemistry, not only has aesthetics of structural design and is worth, and has a good application prospect with the field such as separated in luminous, magnetic, absorption, Chu Qing, catalysis.Particularly, by the coordination of metal ion and organic multi-functional part, construct the ligand polymer with high thermal stability structure and extraordinary physical and chemical performance and caused people's very big interest.Yet design and construct the material that this class has special construction and function and belong to innovative technology, has very large challenge, particularly has the material of high thermal stability and fluorescence property concurrently.In recent years, some have high thermal stability, or the ligand polymer with fluorescence property is widely studied, and have obtained certain achievement, but in these ligand polymer, the material that simultaneously has high thermostability and good fluorescence performance concurrently but rarely has report.
Summary of the invention
For the above state of the art, it is gentle that technical problem to be solved by this invention is to provide a kind of reaction conditions, and preparation process is simple, with low cost, has the preparation method of the ligand polymer of fluorescence property and high thermostability simultaneously.
The present invention solves the problems of the technologies described above adopted technical scheme to be:
A ligand polymer for fluorescence property and high thermostability, it forms with chemical formulation is [Cd
2(hfipbb)
2(4,4 '-bpy)]
n,
In formula
Hfipbb is 2, and 2 ' two (4-formic acid phenyl) hexafluoro isopropyl alkane, 4,4 '-bpy is 4,4 '-dipyridyl;
The crystal of above-mentioned ligand polymer belongs to oblique system, and unit cell parameters is:
c=25.091 (8)
α=90.00 °, β=109.93 ° (3), γ=90.00 °; All metal Cd all adopt the octoploids structure of hexa-coordinate, and wherein Cd1 is from six oxygen atom ligands in hfipbb part carboxylic acid from different and form octoploids structure; Cd2 is and two nitrogen-atoms from pyridine and the distortion octoploids structure forming from four oxygen atom ligands in different hfipbb parts; Cd3 forms by a nitrogen-atoms and five carboxyl oxygen atoms the octoploids structure being out of shape.All Cd atoms are connected to form one-dimensional metal carboxylic acid chain,, in this one-dimensional metal carboxylic acid chain, center C d1 atom and other two Cd3 pass through two 1,3-μ
2the carboxyl of-bridging and one 1,1,1,1-μ
4the carboxyl of-bridging has formed three core Cd-O-Cd-O-Cd bunch unit.Therefore, this one-dimensional metal carboxylic acid chain can be regarded linear three core cadmiums bunch as and monokaryon cadmium is formed by connecting by carboxyl.Every one-dimensional metal carboxylic acid chain six the one-dimensional metal carboxylic acid chains adjacent with other pass through organic ligand hfipbb and 4,4'-Bipyridine cross connection, have formed three-dimensional non-interspersed tightly packed network structure.
The described preparation method with the ligand polymer of fluorescence property and high thermal stability, comprises the following steps:
1, by four nitric hydrate cadmium (Cd (NO
3) 4H
2o), 4,4 '-dipyridyl and 2,2 ' two (4-formic acid phenyl) hexafluoro isopropyl alkane (hfipbb) is dissolved in the distilled water of 5～10ml;
2, after, at room temperature stir after 10～30 minutes, put into the tetrafluoroethylene inner tube of the stainless steel autoclave of 20ml, sealing;
3, reactor is put into baking oven, under 140～180 ℃ of high temperature, react 24～96h;
4, treat that the temperature in baking oven is down to room temperature, open reactor, obtain yellow bulk crystals, filter, with distilled water wash and dry after can make described ligand polymer.To add the mol ratio of each composition be hfipbb: Cd (NO
3) 4H
2o: 4,4 '-dipyridyl: H
2o=1: 1～3: 1～2: 5～20.
Compared with prior art, advantage of the present invention is as follows:
1, described ligand polymer locates to occur strong emission peak at 390nm (λ=246nm), the fluorescence that its fluorescent emission may mainly cause owing to electronics transmission (MMCL) effect between part itself and metal-ligand;
2, the TG curve display of title complex goes out compound and has high thermostability, and one step Weight lose has only occurred whole process.Organic ligand, since 420 ℃ of weightlessness, causes structural framing to cave in.Contact its structure, we analyze and cause the reason of its high thermostability to have: the existence of (1) carboxylate metal chain, and rigidity is firm more to make structure; (2) the tightly packed 3-d modelling in title complex has strengthened its stability; (3) in structure, there is no solvent molecule;
3, ligand polymer provided by the present invention not only has very strong fluorescence, and has very high thermostability simultaneously;
4, preparation technology of the present invention is simple, and production efficiency is high, and facility investment is few, and whole production process, without any pollution, meets Sustainable development requirement simultaneously.
Accompanying drawing explanation
Fig. 1 is ligand polymer [Cd
2(hfipbb)
2(4,4 '-bpy)]
ncrystalline structure.
Fig. 2 is ligand polymer [Cd
2(hfipbb)
2(4,4 '-bpy)]
nthe non-interspersed tightly packed grid structure sketch of three-dimensional.
Fig. 3 is ligand polymer [Cd
2(hfipbb)
2(4,4 '-bpy)]
ntG curve.
Fig. 4 is ligand polymer [Cd
2(hfipbb)
2(4,4 '-bpy)]
nfluorescence spectrum.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Take 0.1261g (0.40mmol) Cd (NO
3)
24H
2o, 0.0407g (0.25mmol) 4,4 '-dipyridyl and 0.0736g (0.20mmol) 2,2-bis-(4-formic acid phenyl) hexafluoro isopropyl alkane is dissolved in 8ml distilled water, under room temperature, stir after 30min, put into the tetrafluoroethylene inner tube of the stainless steel autoclave of 20ml, after sealing in baking oven 170 ℃ of pyroreaction 75h, treat that the temperature in baking oven is down to room temperature, open reactor, obtain yellow bulk crystals, filter, with distilled water wash dry.With Cd (NO
3)
24H
2the initial amount of O is benchmark, and productive rate is 75%.
Take 0.1898g (0.60mmol) Cd (NO
3)
24H
2o, 0.0657g (0.40mmol) 4,4 '-dipyridyl and 0.1475g (0.40mmol) 2,2-bis-(4-formic acid phenyl) hexafluoro isopropyl alkane is dissolved in 10ml distilled water, under room temperature, stir after 30min, put into the tetrafluoroethylene inner tube of the stainless steel autoclave of 20ml, after sealing in baking oven 170 ℃ of pyroreaction 48h, treat that the temperature in baking oven is down to room temperature, open reactor, obtain yellow bulk crystals, filter, with distilled water wash dry.With Cd (NO
3)
24H
2the initial amount of O is benchmark, and productive rate is 73%.
The sign of embodiment 1,2 prepared ligand polymer is detected:
(1) crystalline structure
Choose under the microscope the monocrystalline of suitable size, under room temperature, on Bruker P4 four-circle diffractometer, use the alpha-ray through the Mo-K of graphite monochromator monochromatization
under 293K, collect the diffraction data of crystal; All diffraction datas are used SADABS program to carry out absorption correction; Unit cell parameters is determined by method of least squares; Reduction of data and structure solution folding are used respectively SAINT and SHELXTL program to complete.First by difference functions method and method of least squares, determine whole non-hydrogen atom coordinates, and obtain hydrogen atom position with theoretical hydrogenation method, then by method of least squares, crystalline structure is carried out to refine.The crystalline structure of this ligand polymer and three-dimensional non-interspersed tightly packed grid structure schematic diagram are shown in Fig. 1, Fig. 2.
The partial parameters of the data gathering of crystallography point diffraction and structure refinement sees the following form:
[Cd
2(hfipbb)
2(4,4 '-bpy)]
nthe experiment of main crystallography and refine parameter
(2) differential thermal thermogravimetric analysis characterizes
Adopt Seiko TG/DTA 6300 type Differential Thermal Analysis instrument, with α-Al
2o
3for reference substance, at the N of 200ml/min
2air-flow protection, temperature rise rate is under the condition of 10 ℃/min, to measure the TG-DTA curve of ligand polymer.As shown in Figure 3, only there is a step Weight lose in whole process to the TG curve of this ligand polymer.Organic ligand, since 420 ℃ of weightlessness, causes skeleton construction to be caved in.
(3) Fluorescent Characterization
Common fluorescence optocoupler adopts SHIMADZU RF-540 (Japan produces) to measure, and measures at normal temperatures the emmission spectrum of title complex with HRG-5-90 nitrogen molecular laser and Spex1403 double grating monochromator.The fluorescence spectrum of this ligand polymer as shown in Figure 4.
Claims (2)
1. ligand polymer with high thermal stability and fluorescence property and preparation method thereof, is characterized in that: it forms with chemical formulation is [Cd
2(hfipbb)
2(4,4 '-bpy)]
n, in formula, hfipbb is that 2,2 '-bis-(4-formic acid phenyl) hexafluoro isopropyl alkane, 4,4 '-bpy is 4,4 '-dipyridyl; The crystal of described ligand polymer belongs to oblique system, and unit cell parameters is:
α=90.00 °, β=109.93 ° (3), γ=90.00 °; All metal Cd all adopt the octoploids structure of hexa-coordinate, and wherein Cd1 is from six oxygen atom ligands in hfipbb part carboxylic acid from different and form octoploids structure; Cd2 is and two nitrogen-atoms from pyridine and the distortion octoploids structure forming from four oxygen atom ligands in different hfipbb parts; Cd3 forms by a nitrogen-atoms and five carboxyl oxygen atoms the octoploids structure being out of shape.All Cd atoms are connected to form one-dimensional metal carboxylic acid chain, every one-dimensional metal carboxylic acid chain six the one-dimensional metal carboxylic acid chains adjacent with other pass through organic ligand hfipbb and 4, the cross connection of 4 '-dipyridyl, has formed three-dimensional non-interspersed tightly packed network structure.
2. a kind of ligand polymer with fluorescence property and high thermal stability according to claim 1 and preparation method thereof, is characterized in that comprising the following steps:
(1) by four nitric hydrate cadmium (Cd (NO
3) 4H
2o), 4,4 '-dipyridyl and 2,2 '-bis-(4-formic acid phenyl) hexafluoro isopropyl alkane (hfipbb) is dissolved in the distilled water of 5～10ml;
(2) after, at room temperature stir after 10～30 minutes, put into the tetrafluoroethylene inner tube of the stainless steel autoclave of 20ml, sealing;
(3) reactor is put into baking oven, under 140～180 ℃ of high temperature, react 24～96h;
(4) treat that the temperature in baking oven is down to room temperature, open reactor, obtain yellow bulk crystals, filter, with distilled water wash and dry after can make described ligand polymer.To add the mol ratio of each composition be hfipbb: Cd (NO
3) 4H
2o: 4,4 '-dipyridyl: H
2o=1: 1～3: 1～2: 5～20.
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| CN106366100A (en) * | 2016-07-27 | 2017-02-01 | 宁波大学 | 5-aminoorotic acid dinuclear cadmium complex |
| CN106832326A (en) * | 2017-03-28 | 2017-06-13 | 河北医科大学 | A kind of high-thermal-stability cerium coordination polymer and its preparation method and application |
| CN106893582A (en) * | 2017-03-10 | 2017-06-27 | 宁波大学 | A kind of broadband fluorescent material and preparation method thereof |
| CN108794760A (en) * | 2018-09-07 | 2018-11-13 | 宁夏大学 | A kind of Cd (II) coordination polymer and preparation method thereof containing 9-Fluorenone -4- carboxylic acids |
| CN108794754A (en) * | 2018-06-05 | 2018-11-13 | 安徽师范大学 | New copper-metal-organic framework material and its preparation method and application |
| CN113480739A (en) * | 2021-07-05 | 2021-10-08 | 重庆师范大学 | Supermolecule polymer containing two-axis chiral structure and preparation method and application thereof |
| CN113797975A (en) * | 2021-10-28 | 2021-12-17 | 中原工学院 | Preparation method and application of cadmium sulfide composite cadmium coordination polymer Cd-CP/PAN catalytic material |
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Cited By (14)
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|---|---|---|---|---|
| CN106366100B (en) * | 2016-07-27 | 2018-06-15 | 宁波大学 | A kind of 5- amino orotic acid Dinuclear cadmium complex |
| CN106366100A (en) * | 2016-07-27 | 2017-02-01 | 宁波大学 | 5-aminoorotic acid dinuclear cadmium complex |
| CN106893582B (en) * | 2017-03-10 | 2019-03-15 | 宁波大学 | A kind of broadband fluorescent material and preparation method thereof |
| CN106893582A (en) * | 2017-03-10 | 2017-06-27 | 宁波大学 | A kind of broadband fluorescent material and preparation method thereof |
| CN106832326A (en) * | 2017-03-28 | 2017-06-13 | 河北医科大学 | A kind of high-thermal-stability cerium coordination polymer and its preparation method and application |
| CN106832326B (en) * | 2017-03-28 | 2019-11-05 | 河北医科大学 | A kind of high-thermal-stability cerium coordination polymer and its preparation method and application |
| CN108794754A (en) * | 2018-06-05 | 2018-11-13 | 安徽师范大学 | New copper-metal-organic framework material and its preparation method and application |
| CN108794754B (en) * | 2018-06-05 | 2021-07-30 | 安徽师范大学 | Copper-metal organic framework material and preparation method and application thereof |
| CN108794760A (en) * | 2018-09-07 | 2018-11-13 | 宁夏大学 | A kind of Cd (II) coordination polymer and preparation method thereof containing 9-Fluorenone -4- carboxylic acids |
| CN108794760B (en) * | 2018-09-07 | 2020-09-04 | 宁夏大学 | Cd (II) coordination polymer containing 9-fluorenone-4-carboxylic acid and preparation method thereof |
| CN113480739A (en) * | 2021-07-05 | 2021-10-08 | 重庆师范大学 | Supermolecule polymer containing two-axis chiral structure and preparation method and application thereof |
| CN113480739B (en) * | 2021-07-05 | 2022-06-28 | 重庆师范大学 | Supermolecule polymer containing two-axis chiral structure and preparation method and application thereof |
| CN113797975A (en) * | 2021-10-28 | 2021-12-17 | 中原工学院 | Preparation method and application of cadmium sulfide composite cadmium coordination polymer Cd-CP/PAN catalytic material |
| CN113797975B (en) * | 2021-10-28 | 2023-07-18 | 中原工学院 | Preparation method and application of cadmium sulfide composite cadmium coordination polymer Cd-CP/PAN catalytic material |
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