CN112694496A - Terbium metal complex constructed by sodium dicyandiamide and pyrimidinecarboxylic acid and preparation method thereof - Google Patents
Terbium metal complex constructed by sodium dicyandiamide and pyrimidinecarboxylic acid and preparation method thereof Download PDFInfo
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- CN112694496A CN112694496A CN201911015708.3A CN201911015708A CN112694496A CN 112694496 A CN112694496 A CN 112694496A CN 201911015708 A CN201911015708 A CN 201911015708A CN 112694496 A CN112694496 A CN 112694496A
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- pyrimidinecarboxylic acid
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- dicyandiamide
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- sodium dicyandiamide
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims abstract description 22
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 title claims abstract description 22
- ZFCHNZDUMIOWFV-UHFFFAOYSA-N pyrimidine-2-carboxylic acid Chemical compound OC(=O)C1=NC=CC=N1 ZFCHNZDUMIOWFV-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 22
- 239000011734 sodium Substances 0.000 title claims abstract description 22
- -1 Terbium metal complex Chemical class 0.000 title claims abstract description 18
- 229910052771 Terbium Inorganic materials 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000003446 ligand Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000012153 distilled water Substances 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- 238000002329 infrared spectrum Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- GFISHBQNVWAVFU-UHFFFAOYSA-K terbium(iii) chloride Chemical compound Cl[Tb](Cl)Cl GFISHBQNVWAVFU-UHFFFAOYSA-K 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 12
- 150000002910 rare earth metals Chemical class 0.000 description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000001638 boron Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 101100518501 Mus musculus Spp1 gene Proteins 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009475 tablet pressing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/42—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of organic or organo-metallic materials, e.g. graphene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
Abstract
The invention relates to a terbium metal complex constructed by sodium dicyandiamide and pyrimidinecarboxylic acid and a preparation method thereof. The chemical composition of the complex contains sodium dicyandiamide and a pyrimidinecarboxylic acid (Hpmc) ligand. The synthesis scheme is that sodium dicyandiamide and TbCl are respectively added according to the metering ratio3·6H2Dissolving O in distilled water, stirring at normal temperature for 30min, adding pyrimidinecarboxylic acid ligand according to a metering ratio, stirring at normal temperature for 1h, filtering the mixed solution after reaction, removing the precipitate, volatilizing the solvent, and separating out the target product after about 3 days. Dicyandiamide sodium, pyrimidinecarboxylic acid and TbCl3·6H2The mass ratio of O is: 1: 4.10: 2.85.
Description
Technical Field
The invention relates to a terbium metal complex constructed by sodium dicyandiamide and pyrimidinecarboxylic acid and a preparation method thereof, belonging to the scientific and technical field of metal complexes.
Technical Field
The metal-organic complex material constructed by metal ions and organic ligands has wide application prospect in the fields of gas storage, photoelectron materials, magnetic materials, catalysis and the like due to various structures and unique properties. Compared with a d-group transition metal organic complex and a main group metal organic complex, the rare earth metal organic complex has obvious difference in properties, and because the rare earth metal ions have the characteristics of large radius and high coordination number, the coordination and activation of a substrate are facilitated. The 4f orbit does not participate in bonding due to the extremely strong shielding effect, the 18 electron rule of the d group is not applicable to the rare earth metal organic chemistry, and the common oxidation addition and reduction elimination reaction in the d group transition metal organic complex chemistry is not easy to occur. Although the rare earth elements belong to subgroup elements, the rare earth-carbon sigma bond and the rare earth-nitrogen sigma bond have strong ionic property and good reaction activity. Rare earth ions belong to hard Lewis acids, are easy to coordinate with a hard base ligand containing N, O atoms, show strong oxygen affinity, and have weak coordination with soft bases such as organic phosphine, olefin, carbon monoxide and the like [ Qianzao et al, journal of chemistry, 2014, 72 (8): 883-905.].
Among rare earth metal organic complexes, complexes formed by rare earth elements and nitrogen-containing heterocyclic ligands are an important research direction. For example, pyridine and its derivatives are used as ligands, Yangxiangdong of Junior university [ Yangxiangdong. Junior university report 2009, No2, 21-24.]Europium ions and terbium ions are selected to synthesize an eight-coordination fluorescent rare earth complex with a bipyridyl unit structure and higher quantum efficiency; pyrrole is used as a ligand, Arnold and the like adopt substituted pyrrole bidentate ligands to synthesize imine pyrrole-based rare earth alkyl complexes, four nitrogen atoms in the two ligands are coordinated with metal ions in an eta 1 mode, the complexes catalyze methyl methacrylate to polymerize by single component high activity and high selectivity, and the isotacticity of the polymer is as high as 94.8% [ Cui, C.Etc. organometallics 2003, 22 and 3357 ].](ii) a Tripyrazole boron salt (Tp) is used as a tridentate nitrogen ligand, and Takats and the like are synthesized to obtain a series of divalent rare earth complexes, trivalent rare earth alkyl complexes, amino complexes and hydrides containing the Tp ligand. Meanwhile, Takats and Anwander et al react with La (AlMe) by Tp potassium salt3)3Lanthanum-bridged carbon carbene complexes [ Litlabo, r.etc. angelw.chem.int.ed.2008, 47, 9560 were synthesized by reaction.]The heterobimetallic complex (Tp) Yb (II) (AlR) is synthesized by amine elimination reaction4)(R=Me,Et)[Litlabo,R.Etc.Organometallics 2009,28,6750.]。
At present, rare earth metal complexes taking sodium dicyandiamide and pyrimidinecarboxylic acid as ligands are less researched, so that the method has a great development space.
Disclosure of Invention
The invention aims to provide a terbium metal complex constructed by sodium dicyandiamide and pyrimidinecarboxylic acid and a preparation method thereof, and the terbium metal complex has good application prospects in the aspects of fluorescence, magnetism and the like.
The chemical composition of the terbium metal complex provided by the invention contains sodium dicyandiamide and a 2-pyrimidinecarboxylic acid (Hpmc) ligand.
The infrared spectrum of the terbium metal complex disclosed by the invention is shown in figure 1, and is characterized in that the infrared spectrum has the following characteristic absorption peaks: 3223(s) cm-1,2295(m)cm-1,2226(w)cm-1,2165(s)cm-1,1637(s)cm-1,1577(m)cm-1,1560(m)cm-1,1452(w)cm-1,1384(s)cm-1,1359(m)cm-1,1285(w)cm-1,1265(w)cm-1,1220(w)cm-1,1193(w)cm-1,1020(w)cm-1,874(w)cm-1。
The preparation method of the invention comprises the following steps:
respectively adding sodium dicyandiamide and TbCl according to the metering ratio3·6H2Dissolving O in distilled water, stirring at normal temperature for 30min, adding pyrimidinecarboxylic acid ligand according to a metering ratio, stirring at normal temperature for 1h, filtering the mixed solution after reaction, removing the precipitate, volatilizing the solvent, and separating out the target product after about 3 days.
Dicyandiamide sodium, pyrimidinecarboxylic acid and TbCl3·6H2The mass ratio of O is: 1: 4.10: 2.85.
Drawings
FIG. 1: infrared spectrogram of the complex;
Detailed Description
Example 1 synthesis of the complex:
sodium dicyandiamide (0.0089g, 0.1mmol) and TbCl are respectively added according to the metering ratio3·6H2Dissolving O (0.0365g, 0.1mmol) in distilled water, stirring at normal temperature for 30min, adding pyrimidinecarboxylic acid ligand (0.0248g, 0.2mmol) according to a metering ratio, stirring at normal temperature for 1h, filtering the mixed solution after reaction, removing precipitate, volatilizing the solvent, and separating out the target product after about 3 days. Dicyandiamide sodium, pyrimidinecarboxylic acid and TbCl3·6H2The mass ratio of O is: 1: 4.10: 2.85.
Example 2 infrared spectroscopic determination of the complex:
the infrared spectrum of the complex is measured by a KBr tablet pressing method and a Nicolet330FT-IR infrared spectrometer at 4000-500 cm-1The specific peaks are recorded in the range shown in FIG. 1.
Claims (5)
1. A terbium metal complex constructed by sodium dicyandiamide and pyrimidinecarboxylic acid and a preparation method thereof are disclosed, wherein the chemical composition of the complex contains sodium dicyandiamide and 2-pyrimidinecarboxylic acid (Hpmc) ligand.
2. The terbium metal complex constructed from sodium dicyandiamide and pyrimidinecarboxylic acid according to claim 1 wherein the infrared spectrum thereof has the following characteristic absorption peaks: 3223(s) cm-1,2295(m)cm-1,2226(w)cm-1,2165(s)cm-1,1637(s)cm-1,1577(m)cm-1,1560(m)cm-1,1452(w)cm-1,1384(s)cm-1,1359(m)cm-1,1285(w)cm-1,1265(w)cm-1,1220(w)cm-1,1193(w)cm-1,1020(w)cm-1,874(w)cm-1。
3. The method for preparing the terbium metal complex jointly constructed by sodium dicyandiamide and pyrimidinecarboxylic acid according to claim 1, characterized in that it comprises the following steps:
1) respectively adding sodium dicyandiamide and TbCl according to the metering ratio3·6H2Dissolving O in distilled water, and stirring at normal temperature for 30 min;
2) then adding the pyrimidinecarboxylic acid ligand according to the metering ratio, and stirring for 1h at normal temperature;
3) and filtering the mixed solution after reaction, removing the precipitate, volatilizing the solvent, and separating out the target product after about 3 days.
4. The method for preparing the terbium metal complex jointly constructed by sodium dicyandiamide and pyrimidinecarboxylic acid according to claim 3, wherein the sodium dicyandiamide, pyrimidinecarboxylic acid and TbCl are used as the metal complex3·6H2The mass ratio of O is: 1: 4.10: 2.85.
5. The process for preparing a terbium metal complex structured by using sodium dicyandiamide and pyrimidinecarboxylic acid according to claim 3 wherein the reaction condition is that the solution volatilizes under normal temperature conditions.
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