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
- oxalic acid
- dimensional chain
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- coordination polymer
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Abstract
The invention discloses a one-dimensional chain oxalic acid rare earth coordination polymer and a preparation method and application thereof, which relate to an oxalic acid rare earth coordination polymer and a preparation method and application thereof and are used for solving the problems of few types and short near infrared luminescent lifetime existing in the conventional near infrared luminescent coordination polymer. The oxalic acid rare earth coordination polymer has a one-dimensional chain structure formed by bridging Ln(HC2O4)(C2O4)(H2O5) serving as a structural unit through an oxygen atom bridge in oxalic acid, wherein Ln is Pr<3+> or Nd<3+>. A three-dimensional super-molecular structure of a one-dimensional chain is realized through a hydrogen bond. The preparation method comprises the following steps of: adding rare earth nitrate and oxalic acid into water; dissolving and adjusting the pH; and heating and reacting in a hermetic reaction kettle. The oxalic acid rare earth coordination polymer has near infrared luminance. An eight-coordination structure is formed by taking a rare earth ion as the center, the fluorescent lifetime of an oxalic acid rare earth praseodymium coordination polymer is 3.52 mus, and the dual-exponential attenuation fluorescent lifetime of an oxalic acid rare earth neodymium coordination polymer is 1.07 mus and 7.86 mus.
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)
1. one-dimensional chain rare earth oxalate ligand polymer, is characterized in that one-dimensional chain rare earth oxalate ligand polymer is with Ln (HC
2o
4) (C
2o
4) (H
2o)
5for structural unit, by oxalic acid, connect into one-dimensional chain structure, wherein Ln is Pr
3+or Nd
3+; Between described one-dimensional chain rare earth oxalate ligand polymer, can be connected to form by hydrogen bond the rare earth oxalate ligand polymer of Magnetic Properties of Three-Dimensional Supramolecular Complex structure.
2. the preparation method of one-dimensional chain rare earth oxalate ligand polymer as claimed in claim 1, the preparation method who it is characterized in that one-dimensional chain rare earth oxalate ligand polymer 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 160 ℃, and insulation reaction 3～5 days obtains one-dimensional chain rare earth oxalate ligand polymer.
3. one-dimensional chain rare earth oxalate ligand polymer as claimed in claim 1 is as the application of near-infrared light-emitting material.
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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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| 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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