CN102321105B - One-dimensional chain oxalic acid rare earth coordination polymer and preparation method and application thereof - Google Patents
One-dimensional chain oxalic acid rare earth coordination polymer and preparation method and application thereof Download PDFInfo
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- CN102321105B CN102321105B CN201110150598.9A CN201110150598A CN102321105B CN 102321105 B CN102321105 B CN 102321105B CN 201110150598 A CN201110150598 A CN 201110150598A CN 102321105 B CN102321105 B CN 102321105B
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- rare earth
- dimensional chain
- coordination polymer
- oxalic acid
- earth oxalate
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 87
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title claims abstract description 83
- -1 oxalic acid rare earth Chemical class 0.000 title claims abstract description 59
- 235000006408 oxalic acid Nutrition 0.000 title claims abstract description 28
- 239000013256 coordination polymer Substances 0.000 title claims abstract description 26
- 229920001795 coordination polymer Polymers 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000002910 rare earth metals Chemical class 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 150000004686 pentahydrates Chemical class 0.000 claims 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims 1
- 239000004810 polytetrafluoroethylene Substances 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract 1
- 125000004430 oxygen atom Chemical group O* 0.000 abstract 1
- 239000003446 ligand Substances 0.000 description 46
- 229920000642 polymer Polymers 0.000 description 46
- UHTYDNCIXKPJDA-UHFFFAOYSA-H oxalate;praseodymium(3+) Chemical compound [Pr+3].[Pr+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UHTYDNCIXKPJDA-UHFFFAOYSA-H 0.000 description 13
- VKLDOHAGZQSOPP-UHFFFAOYSA-H neodymium(3+);oxalate Chemical compound [Nd+3].[Nd+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VKLDOHAGZQSOPP-UHFFFAOYSA-H 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000005284 excitation Effects 0.000 description 5
- 239000003125 aqueous solvent Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- WCWKKSOQLQEJTE-UHFFFAOYSA-N praseodymium(3+) Chemical compound [Pr+3] WCWKKSOQLQEJTE-UHFFFAOYSA-N 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Luminescent Compositions (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
一维链状草酸稀土配位聚合物及其制备方法和应用，涉及草酸稀土配位聚合物及其制备方法和应用。解决现有近红外发光配位聚合物的种类稀少，且近红外发光寿命短的问题。草酸稀土配位聚合物是以Ln(HC2O4)(C2O4)(H2O)5为结构单元，通过草酸中的氧原子桥连成一维链状结构，其中Ln为Pr3+或者Nd3+。一维链再通过氢键得到三维超分子结构。将稀土硝酸盐和草酸加入水中，溶解后调pH，再在密封反应釜中加热反应。本发明草酸稀土配位聚合物具有近红外发光性质。其以稀土离子为中心形成八配位构型，草酸稀土镨配位聚合物荧光寿命为3.52μs，草酸稀土钕配位聚合物双指数衰减荧光寿命分别为1.07μs和7.86μs。
The invention relates to a one-dimensional chain rare earth oxalate coordination polymer and its preparation method and application, relating to the rare earth oxalate coordination polymer and its preparation method and application. The method solves the problems that the types of existing near-infrared luminescent coordination polymers are scarce and the near-infrared luminescent lifetime is short. Rare earth oxalate coordination polymer is a one-dimensional chain structure with Ln(HC 2 O 4 )(C 2 O 4 )(H 2 O) 5 as the structural unit, which is bridged by oxygen atoms in oxalic acid, where Ln is Pr 3 + or Nd 3+ . The one-dimensional chains then obtain a three-dimensional supramolecular structure through hydrogen bonds. Add rare earth nitrate and oxalic acid into water, adjust the pH after dissolving, and then heat the reaction in a sealed reaction kettle. The rare earth oxalate coordination polymer of the present invention has near-infrared luminescent properties. It forms an eight-coordination structure with rare earth ions as the center. The fluorescence lifetime of rare earth praseodymium oxalate coordination polymer is 3.52μs, and the double exponential decay fluorescence lifetime of rare earth neodymium oxalate coordination polymer is 1.07μs and 7.86μs respectively.
Description
Technical field
The present invention relates to rare earth oxalate ligand polymer and its preparation method and application.
Background technology
Rare earth ion has higher ligancy and good luminescent properties, as luminescent material, in fields such as colour TV and graphoscope, illumination, medical science and military affairs, has a wide range of applications.In recent years, based on the near-infrared luminous extensive concern that causes people of rare earth ion title complex, but due to the weak absorption of rare earth ion f-f, directly excite Ln (III) ion (trivalent rare earth ions) normally invalid, when having used after " antenna effect ", it is more effective that the transmitting of metal just becomes.The kind of the existing rare earth ion title complex with near-infrared luminous performance is few, and the near-infrared luminous life-span is short, still has much room for improvement.
Summary of the invention
The object of the invention is the kind rareness in order to solve existing near-infrared luminous ligand polymer, and short problem of near-infrared luminous life-span, the invention provides one-dimensional chain rare earth oxalate ligand polymer and its preparation method and application.
One-dimensional chain rare earth oxalate ligand polymer of the present invention is with Ln (HC
2o
4) (C
2o
4) (H
2o)
5for structural unit, by the Sauerstoffatom bridging in oxalic acid, become one-dimensional chain structure, wherein Ln is Pr
3+or Nd
3+.
Between one-dimensional chain rare earth oxalate ligand polymer of the present invention, by hydrogen bond, be connected to form the rare earth oxalate ligand polymer of Magnetic Properties of Three-Dimensional Supramolecular Complex structure.
The preparation method of one-dimensional chain rare earth oxalate ligand polymer of the present invention realizes by following steps: one, at room temperature, five hydrated rare-earth nitrate and oxalic acid are added in aqueous solvent, stirring and dissolving, regulate again pH value to 7～9, obtain reaction solution, wherein the mol ratio of five hydrated rare-earth nitrate and oxalic acid is 1: 1, and five hydrated rare-earth nitrate are Pr (NO
3)
35H
2o or Nd (NO
3)
35H
2o; Two, the reaction solution of step 1 is put into the stainless steel cauldron that liner is tetrafluoroethylene, sealed reactor, is then heated to 150～180 ℃, and insulation reaction 3～5 days obtains one-dimensional chain rare earth oxalate ligand polymer.
Preparation method's of the present invention productive rate is in 60% left and right.
One-dimensional chain rare earth oxalate ligand polymer of the present invention is as the application of near-infrared light-emitting material.
One-dimensional chain rare earth oxalate ligand polymer of the present invention is using oxalic acid as chromophore, and wherein the Sauerstoffatom in carboxyl has lone-pair electron and higher electronegativity, and coordination ability is stronger, and easy and rare earth ion forms coordinate bond, has good complexing action.In conjunction with having, luminescent lifetime is long, Stokes shift is large and trivalent rare earth praseodymium ion or the neodymium ion of the characteristic linear excitation band of tool simultaneously, obtains having the rare earth oxalate ligand polymer of one-dimensional chain structure after coordination.
One-dimensional chain rare earth oxalate ligand polymer of the present invention has good near-infrared luminous character, has broad application prospects.Under room temperature solid, take 350nm as excitation wavelength, one-dimensional chain rare earth oxalate praseodymium ligand polymer belongs at the characteristic emission peak of 983nm
1d
2→
3f
4transition, fluorescence life τ=3.52 μ s.The characteristic emission peak that one-dimensional chain rare earth oxalate neodymium coordination polymer occurs under 360nm excitation wavelength be respectively 896nm (
4f
3/2→
4i
9/2) weak peak, 1067nm (
4f
3/2→
4i
11/2) strong peak and very weak peak 1394nm (
4f
3/2→
4i
13/2), two exponential attenuation fluorescence life τs
1, τ
2be respectively 1.07 μ s and 7.86 μ s, corresponding decay factor Rel
1, Rel
2be respectively 45.36% and 54.64%.
The present invention utilizes inexpensive oxalic acid and trivalent rare earth nitrate (Pr
3+and Nd
3+), under hot pressing condition, design has obtained one-dimensional chain and has had the organic backbone ligand polymer of near-infrared luminous performance, has obtained two novel structures, central metal (Pr
3+or Nd
3+) ligancy be eight, two ketonic oxygens and five eight-coordinate configurations that the coordination of water molecules oxygen forms that a ketonic oxygen, another oxalic acid providing with an oxalic acid respectively provides, fluorometric investigation result shows that this ligand polymer is a kind of novel good near-infrared light-emitting material.
Accompanying drawing explanation
Fig. 1 is the structural representation of one-dimensional chain rare earth oxalate ligand polymer of the present invention.Fig. 2 is the structural representation of the rare earth oxalate ligand polymer of the supramolecular structure of embodiment two.Fig. 3 is the near-infrared fluorescent spectrogram of the rare earth oxalate praseodymium ligand polymer of embodiment six.Fig. 4 is the near-infrared luminous life curve figure of the rare earth oxalate praseodymium ligand polymer of embodiment six.Fig. 5 is the near-infrared fluorescent spectrogram of the rare earth oxalate neodymium coordination polymer of embodiment eight.Fig. 6 is the near-infrared luminous life curve figure of the rare earth oxalate neodymium coordination polymer of embodiment eight.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: present embodiment is one-dimensional chain rare earth oxalate ligand polymer, and it is with Ln (HC
2o
4) (C
2o
4) (H
2o)
5for structural unit, by Sauerstoffatom bridging in oxalic acid, become one-dimensional chain structure.Wherein Ln is Pr
3+or Nd
3+.
The chemical formulation of the one-dimensional chain rare earth oxalate ligand polymer of present embodiment is [Ln (HC
2o
4) (C
2o
4) (H
2o)
5]
n, wherein Ln is Pr
3+or Nd
3+.
The schematic arrangement of the one-dimensional chain rare earth oxalate ligand polymer of present embodiment as shown in Figure 1, rare earth ion (Pr centered by 1 in figure
3+or Nd
3+), 2,3,4,5 and 6 marks be five water molecules oxygen, 7 is ketonic oxygens that an oxalic acid provides, 8 and 9 is two ketonic oxygens that another oxalic acid provides, and forms eight-coordinate configuration.In Fig. 1, in dotted line frame, be a Ln (HC
2o
4) (C
2o
4) (H
2o)
5structural unit.
In the rare earth oxalate ligand polymer of present embodiment, there is [Pr (the HC of one-dimensional chain structure
2o
4) (C
2o
4) (H
2o)
5]
n[Nd (HC
2o
4) (C
2o
4) (H
2o)
5]
ncause the near-infrared luminous analysis of its molecule and explanation relatively clear, be conducive to set up the relation of such ligand polymer molecular structure and near-infrared luminous performance, thereby explain the near-infrared luminous mechanism of such ligand polymer.
Embodiment two: what present embodiment was different with embodiment one is the rare earth oxalate ligand polymer that is connected to form Magnetic Properties of Three-Dimensional Supramolecular Complex structure between one-dimensional chain rare earth oxalate ligand polymer by hydrogen bond.Other parameter is identical with embodiment one.
The structural representation of the rare earth oxalate ligand polymer of the supramolecular structure of present embodiment is as shown in 2.
Embodiment three: present embodiment is the preparation method of the one-dimensional chain rare earth oxalate ligand polymer described in embodiment one, it is realized by following steps: one, at room temperature, five hydrated rare-earth nitrate and oxalic acid are added in aqueous solvent, stirring and dissolving, regulate again pH value to 7～9, obtain reaction solution, wherein the mol ratio of five hydrated rare-earth nitrate and oxalic acid is 1: 1, and five hydrated rare-earth nitrate are Pr (NO
3)
35H
2o or Nd (NO
3)
35H
2o; Two, the reaction solution of step 1 is put into the stainless steel cauldron that liner is tetrafluoroethylene, sealed reactor, is then heated to 150～180 ℃, and insulation reaction 3～5 days obtains one-dimensional chain rare earth oxalate ligand polymer.
The preparation method's of present embodiment productive rate is in 60% left and right.
The preparation method of present embodiment adopts inexpensive oxalic acid and trivalent rare earth nitrate (Pr
3+and Nd
3+), under hot pressing condition, design has obtained one-dimensional chain and has had the organic backbone ligand polymer of near-infrared luminous performance, has obtained two novel structures, central metal (Pr
3+or Nd
3+) ligancy be eight, two ketonic oxygens and five eight-coordinate configurations that the coordination of water molecules oxygen forms that a ketonic oxygen, another oxalic acid providing with an oxalic acid respectively provides, fluorometric investigation result shows that this ligand polymer is a kind of novel good near-infrared light-emitting material.
Embodiment four: what present embodiment was different from embodiment three is to be heated to 160 ℃ in step 2.Other step and parameter are identical with embodiment three.
Embodiment five: present embodiment is the application as near-infrared light-emitting material of one-dimensional chain rare earth oxalate ligand polymer described in embodiment one.
Embodiment six: present embodiment is one-dimensional chain rare earth oxalate praseodymium ligand polymer, and it is with Pr (HC
2o
4) (C
2o
4) (H
2o)
5for structural unit, by Sauerstoffatom bridging in oxalic acid, become one-dimensional chain structure.
The chemical formula of the one-dimensional chain rare earth oxalate praseodymium ligand polymer of present embodiment is [Pr (HC
2o
4) (C
2o
4) (H
2o)
5]
n.Between one-dimensional chain rare earth oxalate praseodymium ligand polymer, by hydrogen bond, connect again, can form the rare earth oxalate ligand polymer of Magnetic Properties of Three-Dimensional Supramolecular Complex structure.
Utilize FLSP920 built-up type stable state transient state fluorescent/phosphorescent spectrograph to carry out near-infrared luminous property detection to the rare earth oxalate praseodymium ligand polymer of present embodiment, obtain the near-infrared luminous life curve figure shown in near-infrared fluorescent spectrum and Fig. 4 as shown in Figure 3.Visible, under room temperature solid, take 350nm as excitation wavelength, rare earth oxalate praseodymium ligand polymer belongs at the characteristic emission peak of 983nm
1d
2→
3f
4transition.Fluorescence life τ=3.52 μ s.
Embodiment seven: present embodiment is the preparation method of one-dimensional chain rare earth oxalate praseodymium ligand polymer, and it is realized by following steps: one, at room temperature, by five hydrated rare-earth praseodymium nitrate (Pr (NO
3)
35H
2o) add in aqueous solvent with oxalic acid, stirring and dissolving, then regulate pH value to 7～9, obtain reaction solution, wherein Pr (NO
3)
35H
2the mol ratio of O and oxalic acid is 1: 1; Two, the reaction solution of step 1 is put into the stainless steel cauldron that liner is tetrafluoroethylene, sealed reactor, is then heated to 160 ℃, and insulation reaction 4 days obtains one-dimensional chain rare earth oxalate praseodymium ligand polymer.
Utilize rare earth oxalate praseodymium ligand polymer that X-ray single crystal diffractometer prepares present embodiment to test and determine its molecular structure, be the one-dimensional chain rare earth oxalate praseodymium ligand polymer described in embodiment six.
Embodiment eight: present embodiment is one-dimensional chain rare earth oxalate neodymium coordination polymer, and it is with Nd (HC
2o
4) (C
2o
4) (H
2o)
5for structural unit, by Sauerstoffatom bridging in oxalic acid, become one-dimensional chain structure.
The chemical formula of the one-dimensional chain rare earth oxalate neodymium coordination polymer of present embodiment is [Nd (HC
2o
4) (C
2o
4) (H
2o)
5]
n.Between one-dimensional chain rare earth oxalate neodymium coordination polymer, by hydrogen bond, be connected to form again the rare earth oxalate ligand polymer of Magnetic Properties of Three-Dimensional Supramolecular Complex structure.
Utilize FLSP920 built-up type stable state transient state fluorescent/phosphorescent spectrograph to carry out near-infrared luminous property detection to the rare earth oxalate praseodymium ligand polymer of present embodiment, obtain the near-infrared luminous life curve figure shown in near-infrared fluorescent spectrum and Fig. 6 as shown in Figure 5.Visible, under room temperature solid, the characteristic emission peak occurring under 360nm excitation wavelength be respectively 896nm (
4f
3/2→
4i
9/2) weak peak, 1067nm (
4f
3/2→
4i
11/2) strong peak and very weak peak 1394nm (
4f
3/2→
4i
13/2).Two exponential attenuation fluorescence life τs
1, τ
2be respectively 1.07 μ s and 7.86 μ s, corresponding decay factor Rel
1, Rel
2be respectively 45.36% and 54.64%.
Embodiment nine: present embodiment is the preparation method of one-dimensional chain rare earth oxalate neodymium coordination polymer, and it is realized by following steps: one, at room temperature, by five hydrated rare-earth neodymium nitrate (Nd (NO
3)
35H
2o) add in aqueous solvent with oxalic acid, stirring and dissolving, then regulate pH value to 7～9, obtain reaction solution, wherein Nd (NO
3)
35H
2the mol ratio of O and oxalic acid is 1: 1; Two, the reaction solution of step 1 is put into the stainless steel cauldron that liner is tetrafluoroethylene, sealed reactor, is then heated to 160 ℃, and insulation reaction 4 days obtains one-dimensional chain rare earth oxalate neodymium coordination polymer.
The rare earth oxalate neodymium coordination polymer that utilizes X-ray single crystal diffractometer to prepare present embodiment is tested and is determined its molecular structure, is the one-dimensional chain rare earth oxalate neodymium coordination polymer described in embodiment six.
Claims (3)
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| CN106633096B (en) * | 2017-01-09 | 2019-06-28 | 山西大学 | A kind of Binuclear Europium (III) coordination polymer and the preparation method and application thereof |
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|---|---|---|---|---|
| CN1249754A (en) * | 1997-03-11 | 2000-04-05 | 新日本理化株式会社 | Rareearth complexes |
| CN101798321A (en) * | 2010-04-29 | 2010-08-11 | 江苏兴业塑化股份有限公司 | Tetra-branched rare earth complex and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1249754A (en) * | 1997-03-11 | 2000-04-05 | 新日本理化株式会社 | Rareearth complexes |
| CN101798321A (en) * | 2010-04-29 | 2010-08-11 | 江苏兴业塑化股份有限公司 | Tetra-branched rare earth complex and preparation method thereof |
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