CN110804189B - Three-dimensional lutetium polymer and preparation method thereof - Google Patents
Three-dimensional lutetium polymer and preparation method thereof Download PDFInfo
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- 229910052765 Lutetium Inorganic materials 0.000 title claims abstract description 26
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229920000642 polymer Polymers 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 26
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 claims abstract description 26
- LSPHULWDVZXLIL-UHFFFAOYSA-N Camphoric acid Natural products CC1(C)C(C(O)=O)CCC1(C)C(O)=O LSPHULWDVZXLIL-UHFFFAOYSA-N 0.000 claims abstract description 15
- LSPHULWDVZXLIL-QUBYGPBYSA-N camphoric acid Chemical compound CC1(C)[C@H](C(O)=O)CC[C@]1(C)C(O)=O LSPHULWDVZXLIL-QUBYGPBYSA-N 0.000 claims abstract description 15
- APRNQTOXCXOSHO-UHFFFAOYSA-N lutetium(3+);trinitrate Chemical compound [Lu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O APRNQTOXCXOSHO-UHFFFAOYSA-N 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010439 graphite Substances 0.000 claims abstract description 12
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 239000000376 reactant Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 3
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 20
- 239000003446 ligand Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 229910052768 actinide Inorganic materials 0.000 description 2
- 150000001255 actinides Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- GAPRPFRDVCCCHR-UHFFFAOYSA-N 3-bromoprop-1-ynyl(trimethyl)silane Chemical compound C[Si](C)(C)C#CCBr GAPRPFRDVCCCHR-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 150000001169 Lutetium Chemical class 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JZOSHHPCDNLKFK-UHFFFAOYSA-H lutetium(3+);oxalate;tetrahydrate Chemical compound O.O.O.O.[Lu+3].[Lu+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O JZOSHHPCDNLKFK-UHFFFAOYSA-H 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002714 mellitic acid derivatives Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- SJOQNHYDCUXYED-UHFFFAOYSA-K trichlorolutetium;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Lu+3] SJOQNHYDCUXYED-UHFFFAOYSA-K 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/54—Organic compounds
- C30B29/58—Macromolecular compounds
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention discloses a three-dimensional lutetium polymer and a preparation method thereof. The molecular formula of the three-dimensional lutetium polymer is [ C ]6H6O9Lu]nN is an integer and n is not less than 1; the lutetium polymer belongs to the orthorhombic, Pnnm space group. The preparation method of the lutetium polymer comprises the following steps: dissolving lutetium nitrate hexahydrate, camphoric acid or pyridine-2, 6-dicarboxylic acid in water, placing the obtained mixed solution in an open container, inserting an anode and a cathode, electrifying and electrolyzing, filtering the obtained material after electrolysis, collecting filtrate, reacting under heating or non-heating conditions, standing the reactant, separating out crystals, and collecting the crystals to obtain the lutetium nitrate hexahydrate, camphoric acid or pyridine-2, 6-dicarboxylic acid; wherein, the anode and the cathode both adopt graphite electrodes. The preparation method of the invention has the advantages of simplicity, easy control, safety, mild reaction conditions, low cost and good repeatability.
Description
Technical Field
The invention relates to a three-dimensional lutetium polymer and a preparation method thereof, belonging to the technical field of materials.
Background
Mellitic acid (also known as 1,2,3,4,5, 6-mellitic acid or mellitic acid) is richThe carboxyl functional group has strong coordination capacity, can be used as a ligand of a metal complex, particularly an actinide complex thereof, and has good fluorescence property. However, the mellitic acid salt in nature is usually present in the beeswax, is a rare organic mineral, and the price is very expensive, and the price is 900 yuan/g in the market at present, so that the use of the carboxylic acid ligand is greatly limited. In the prior art, graphite oxide and fuming nitric acid are also used for carrying out a co-thermal reaction to generate mellitic acid, but the product obtained by the method has a lot of impurities and is difficult to purify, and NO is generated2And the like, are easy to explode and pollute the air.
The prior actinide complex using mellitic acid as ligand is usually prepared by directly reacting mellitic acid with corresponding metal salt to generate a target compound, but the method has the defects of high cost, difficult purification and the like caused by obtaining mellitic acid, and has the defects of low reaction condition because the temperature is usually above 120 ℃ during direct reaction. At present, no relevant report that camphoric acid or pyridine-2, 6-dicarboxylic acid is electrolyzed by a graphite electrode to obtain mellitic acid, and the mellitic acid reacts with metal salt under mild conditions to obtain a lutetium mellitic acid complex is found.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides a three-dimensional lutetium polymer with a novel structure and a preparation method thereof.
The molecular formula of the three-dimensional lutetium polymer is as follows: [ C ]6H6O9Lu]nN is an integer and n is not less than 1; the three-dimensional lutetium polymer belongs to an orthorhombic system, Pnmm space group and has the unit cell parameter of
α＝90.00°,β＝90.00°,γ＝90.00°。
The third aspect of the inventionThe repeating unit of the vitamin lutetium polymer is a mononuclear lutetium complex with the molecular formula of C6H6LuO9Molecular weight is 397.08, and the ligand is 1,2,3,4,5, 6-mellitic acid.
The invention also provides a preparation method of the three-dimensional lutetium polymer, which comprises the following steps: dissolving lutetium nitrate hexahydrate, camphoric acid or pyridine-2, 6-dicarboxylic acid in water, placing the obtained mixed solution in an open container, inserting an anode and a cathode, electrifying and electrolyzing, filtering the obtained material after electrolysis, collecting filtrate, reacting under a heating condition, standing the reactant, separating out crystals, and collecting the crystals to obtain the lutetium nitrate hexahydrate and camphoric acid or pyridine-2, 6-dicarboxylic acid; wherein, the anode and the cathode both adopt graphite electrodes.
In the above preparation method, the molar ratio of lutetium nitrate hexahydrate to camphoric acid or pyridine-2, 6-dicarboxylic acid is a stoichiometric ratio, specifically 2: 1. in actual practice, the lutetium nitrate hexahydrate may be in relative excess.
In the above preparation method, the amount of water is preferably such that most of the camphoric acid is dissolved but slightly precipitated. Specifically, the amount of water used for the whole raw materials participating in the reaction is usually 15 to 20mL based on 0.5mmol of camphoric acid or pyridine-2, 6-dicarboxylic acid. In the specific dissolving step, the lutetium nitrate hexahydrate and the camphoric acid or the pyridine-2, 6-dicarboxylic acid are mixed and then dissolved in distilled water, or the camphoric acid or the pyridine-2, 6-dicarboxylic acid is dissolved in water and stirred for several minutes and then the lutetium nitrate hexahydrate is added.
In the preparation method, the graphite electrode is a commercial electrode, and further processing is not needed before use. The power supply for electrolysis is a direct current power supply, and is usually between 5 and 20V. The period of the electrolysis is preferably at least 5 hours or more, and it is preferable to stop the electrolysis when there is a substance falling off from the graphite electrode as the anode during the electrolysis, and the period of time required for this is generally 18 to 24 hours.
In the above production method, the reaction is preferably carried out at not less than 50 ℃, preferably not less than 70 ℃, and more preferably 90 to 100 ℃. When the reaction is carried out at 70 ℃ or higher, the reaction time is usually controlled to 18-24 h.
Compared with the prior art, the invention adopts the cheap camphoric acid or pyridine-2, 6-dicarboxylic acid as the raw material to obtain the three-dimensional lutetium polymer with a novel structure in a mild environment, and compared with the prior art that the lutetium complex is directly synthesized by taking mellitic acid as a ligand at the temperature of more than 120 ℃, the preparation method is simple and easy to control, safe, mild in reaction condition, low in cost and good in repeatability.
Drawings
FIG. 1 shows [ C ] obtained in example 1 of the present invention6H6O9Lu]nThe metal coordination environment diagram of (1);
FIG. 2 shows [ C ] obtained in example 1 of the present invention6H6O9Lu]nThe ligand coordination environment diagram of (1);
FIG. 3 shows [ C ] obtained in example 1 of the present invention6H6O9Lu]nThe three-dimensional structure of (1).
Detailed Description
The present invention will be better understood from the following detailed description of specific examples, which should not be construed as limiting the scope of the present invention.
Example 1
Mixing 100mg (0.5mmol) camphoric acid and 457mg (1mmol) Dy (NO)3)3·6H2Adding O into a 50mL beaker, adding 20mL of distilled water, stirring at normal temperature for 10min, stopping stirring, inserting two graphite electrodes (one is used as an anode and the other is used as a cathode), electrifying for 24h under 12V direct current voltage (at the moment, the graphite electrode as the anode is observed to have substance falling off), stopping electrifying, filtering out impurities such as graphite slag and the like, collecting filtrate, filling into a 20mL sample bottle, covering the sample bottle with a cover, putting the sample bottle into a 100 ℃ oven for reaction for 24h, taking out, standing and cooling, separating out brown yellow needle-shaped crystals at the bottom of the sample bottle, collecting the crystals, and drying. The yield was 27.3% (based on lutetium nitrate hexahydrate). Elemental analysis (% () C6H6O9Lu), the experimental values are C, 18.61, H, 1.55; theoretical values C,18.15, H, 1.52.
The crystals with moderate size obtained in the embodiment are placed in Su of AgilentMonochromating with graphite on a perNova single crystal diffractometer
And (4) performing single crystal test by using rays. Under the condition of 295K, the method comprises
The diffraction points are collected in a scanning mode within the range of more than or equal to 2.9 degrees and less than or equal to 25.0 degrees. The initial crystal structures of the products obtained in the embodiment are solved by adopting a SHELXS-97 and Olex-2 direct method, the geometric hydrogenation is carried out, and the non-hydrogen atom coordinates and the anisotropic thermal parameters are refined by adopting a SHELXL-97 full matrix least square method. The obtained crystallographic data are shown in the following table 1, partial bond length and bond angle data are shown in the following table 2, and the three-dimensional polymerization diagram of the obtained brown yellow crystal is shown in fig. 3, wherein fig. 1 is a metal coordination environment diagram of the obtained brown yellow crystal, and fig. 2 is a ligand coordination environment diagram of the obtained brown yellow crystal. Thus, it was confirmed that the crystal obtained in this example was a three-dimensional lutetium polymer [ C ]6H6O9Lu]nThe repeating unit of the polymer is a mononuclear lutetium complex with the molecular formula of C6H6LuO9Molecular weight is 397.08, and the ligand is 1,2,3,4,5, 6-mellitic acid.
Table 1: [ C ]6H6O9Lu]nCrystallographic data of
Table 2: [ C ]6H6O9Lu]nPartial bond length of
Key angle (degree) table
Comparative example 1
Example 1 was repeated except that water was changed to a single solvent such as methanol, acetonitrile, dichloromethane, chloroform, DMF or DMSO, or water and the above single solvent were changed in a ratio of 1: 1, and the volume ratio of the mixed solvent to the mixed solvent. As a result, no crystalline or other shaped (e.g., powdery) product is formed.
Comparative example 2
Example 1 was repeated except that lutetium acetate, lutetium oxalate tetrahydrate, or lutetium trichloride hexahydrate was used in place of lutetium nitrate hexahydrate, and a molecule of acetic acid (or CH) was desired3COO-) Oxalic acid molecule (or C)2O4 2-) Or Cl-The ions can replace the water molecules participating in coordination, or the complex with a new structure is obtained through bridging of acetate or perchlorate, but no crystal is obtained, which indicates that the thermodynamic conditions for forming lutetium polymer and crystallizing cannot be achieved by other lutetium salts.
Example 2
Example 1 was repeated except that pyridine-2, 6-dicarboxylic acid was used instead of camphoric acid.
As a result, brown yellow needle crystals were obtained. Yield 27.2% (based on lutetium nitrate hexahydrate).
The product obtained in this example was analyzed by single crystal diffraction to determine that the resulting brown-yellow needle crystals were three-dimensional lutetium polymer [ C ]6H6O9Lu]n。
Example 3
Example 1 was repeated except that the collected filtrate was reacted at room temperature for 7 days.
As a result, brown yellow needle crystals were obtained. Yield 26.5% (based on lutetium nitrate hexahydrate).
The product obtained in this example was analyzed by single crystal diffraction to determine that the resulting brown-yellow needle crystals were three-dimensional lutetium polymer [ C ]6H6O9Lu]n。
Example 4
Example 1 was repeated, except that the reaction temperature was changed to 50 ℃.
As a result, brown yellow needle crystals were obtained. Yield 24.3% (based on lutetium nitrate hexahydrate).
The product obtained in this example was analyzed by single crystal diffraction to determine that the resulting brown-yellow needle crystals were three-dimensional lutetium polymer [ C ]6H6O9Lu]n。
Claims (3)
1. The preparation method of the three-dimensional lutetium polymer is characterized by comprising the following steps:
the molecular formula of the three-dimensional lutetium polymer is as follows: [ C ]6H6O9Lu]nN is an integer and n is not less than 1; the three-dimensional lutetium polymer belongs to an orthorhombic system,Pnnmspace group, cell parameter ofa = 6.6133(3) Å，b = 13.4654(5) Å，c = 10.1414(3) Å，α= 90.00o, β = 90.00o, γ = 90.00o；
The preparation method of the three-dimensional lutetium polymer comprises the following steps: dissolving lutetium nitrate hexahydrate, camphoric acid or pyridine-2, 6-dicarboxylic acid in water, placing the obtained mixed solution in an open container, inserting an anode and a cathode, electrifying and electrolyzing, filtering the obtained material after electrolysis, collecting filtrate, reacting under a heating condition, standing the reactant, separating out crystals, and collecting the crystals to obtain the lutetium nitrate hexahydrate and camphoric acid or pyridine-2, 6-dicarboxylic acid; wherein, the anode and the cathode both adopt graphite electrodes; the reaction is carried out at 50-100 ℃.
2. The method of claim 1, wherein: the time of electrifying and electrolyzing is more than or equal to 5 hours.
3. The method of claim 1, wherein: during the electrolysis by energization, the energization is stopped when the graphite electrode as the anode is stripped of the substance.
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