CN103951687A - o-TMeQ[6]-rare earth adduct and synthesis method and applications thereof - Google Patents
o-TMeQ[6]-rare earth adduct and synthesis method and applications thereof Download PDFInfo
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- CN103951687A CN103951687A CN201410202321.XA CN201410202321A CN103951687A CN 103951687 A CN103951687 A CN 103951687A CN 201410202321 A CN201410202321 A CN 201410202321A CN 103951687 A CN103951687 A CN 103951687A
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 65
- 238000001308 synthesis method Methods 0.000 title abstract 3
- -1 rare earth ion Chemical class 0.000 claims abstract description 35
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 28
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 12
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 12
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 12
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 11
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 11
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 10
- 230000007935 neutral effect Effects 0.000 claims abstract description 5
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical group N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 claims description 40
- 241000219112 Cucumis Species 0.000 claims description 26
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 claims description 26
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 17
- 239000013078 crystal Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 15
- 238000010189 synthetic method Methods 0.000 claims description 14
- 238000001338 self-assembly Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 229910052691 Erbium Inorganic materials 0.000 claims description 6
- 229910052689 Holmium Inorganic materials 0.000 claims description 6
- 229910052771 Terbium Inorganic materials 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 5
- 229910052765 Lutetium Inorganic materials 0.000 claims description 5
- 229910052775 Thulium Inorganic materials 0.000 claims description 5
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 abstract description 9
- 229920002677 supramolecular polymer Polymers 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 150000005838 radical anions Chemical class 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000005352 clarification Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052747 lanthanoid Inorganic materials 0.000 description 3
- 150000002602 lanthanoids Chemical class 0.000 description 3
- CGRDBGCYRPGACR-UHFFFAOYSA-J Cl[Cd](Cl)(Cl)Cl Chemical compound Cl[Cd](Cl)(Cl)Cl CGRDBGCYRPGACR-UHFFFAOYSA-J 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- MSBXTPRURXJCPF-DQWIULQBSA-N cucurbit[6]uril Chemical compound N1([C@@H]2[C@@H]3N(C1=O)CN1[C@@H]4[C@@H]5N(C1=O)CN1[C@@H]6[C@@H]7N(C1=O)CN1[C@@H]8[C@@H]9N(C1=O)CN([C@H]1N(C%10=O)CN9C(=O)N8CN7C(=O)N6CN5C(=O)N4CN3C(=O)N2C2)C3=O)CN4C(=O)N5[C@@H]6[C@H]4N2C(=O)N6CN%10[C@H]1N3C5 MSBXTPRURXJCPF-DQWIULQBSA-N 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000001941 electron spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000012217 radiopharmaceutical Substances 0.000 description 1
- 229940121896 radiopharmaceutical Drugs 0.000 description 1
- 230000002799 radiopharmaceutical effect Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 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
- 238000005406 washing Methods 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides an o-TMeQ[6]-rare earth adduct and a synthesis method and applications thereof, belonging to the field of a metallic-organic supramolecular polymer and a synthesis method thereof. In a neutral environment, the o-TMeQ [6] and rare earth are formed into an o-TMeQ[6]-heavy rare earth polymer adduct, the o-TMeQ[6] and light rare earth metals La, Ce, Pr, Nd, Sm, Eu and Gd do not generate adducts, the o-TMeQ[6] water solution is added a certain amount of heavy rare earth ion water solution, and the o-TMeQ6] and heavy rare earth metal ions form a polymer in the water solution. No polymer is produced when an o-TMeQ[6] water solution is added into a water solution of light rare earth ions La<3+>, Ce<3+>, Pr<3+>, Nd<3+>, Sm<3+>, Eu<3+> and Gd<3+>. Due to the obvious property difference, the o-TMeQ[6]-rare earth adduct can be used for separating the light and heavy rare earth metal ions.
Description
Technical field
The present invention utilizes the method for synthetic ortho position Tetramethyl melon ring-rare earth adducts and separated weight rare earth thereof to belong to metal-organic supermolecular polymkeric substance and synthetic method field thereof.Be exactly that ortho position Tetramethyl melon ring and heavy rare earths form adducts specifically, but cannot form adducts with light rare earths (La, Ce, Pr, Nd, Sm, Eu, Gd), and utilize its character that can form adducts and separated weight rare earth.
Background technology
Lanthanon conventionally presents similar chemical property and originates from lanthanide contraction, most parts are combined complex structure, the character of formation with serial rare-earth very similar, particularly lanthanide metal ion presents high ligancy and easy commutativity in water medium, causes lanthanon and title complex thereof all to face the problem that is difficult to separating-purifying.On the other hand, different lanthanon presents again separately unique character, as lanthanum and alloy thereof have storage hydrogen and catalysis; Nd and samarium show unique magnetic property; Europium receives much concern with its abundant spectral quality; The huge magnetostriction of terbium and dysprosium can be used as the main raw of micro-actuator; And can showing Solid State Laser function, the rare earth such as the heavy lanthanide such as holmium, erbium make them can be used for the relaxation reagent in nuclear magnetic resonance technique, biology fluorescent probe, and DNA cuts catalyzer.Nearest research shows that rare earth element also can be used for radiopharmaceuticals to treat cancer etc.Therefore, the rare earth of taking as the leading factor with lanthanon is playing the part of at aspects such as communication information, oil catalysis, colored demonstration, hydrogen storage material and superconducting materials the role who can not be substituted, the title that has industry " VITAMIN ", and quilt is beautiful, Deng state classifies 21 century as " strategic element ".
Since the structure of the hexa-atomic melon ring of 1981 first member of Nian Qi family (Cucurbituril, Q[6]) is determined, melon ring (Cucurbit[
n] urils, Q[
n] s) family has a growing family, associated melon ring chemical research has also been obtained the progress attracting people's attention.From melon ring structure, melon ring (Cucurbit[
n] urils, Q[
n]) be that a class is by n glycosides urea unit and 2n the large ring cage compound that methylene bridge links up.Due to two ports of melon ring, " inlay " and a circle carbonylic oxygen atom, there is the ability that forms title complex with metallic ion coordination, be used as in recent years organic ligand, in the research field of constructing at metal-organic supermolecular polymkeric substance, receive increasing concern.In recent years, we find in the research of the interaction of research melon ring and serial rare-earth and supramolecule self-assembly thereof, and different melon rings can have different coordination situations from serial rare-earth effect, form different title complexs and supramolecule self-assembly.As we once found to adopt Cadmium chloride fine powder (CdCl
2) as induction reagent, utilize " the honeycomb effect " of its tetrachloro cadmium acid radical anion forming in hydrochloric acid medium, induction melon ring and the direct coordination of serial rare-earth metal ion, synthesize a series of melon ring-rare earth metal tubulose supermolecule polymers, and applied for the linear tubulose supermolecule polymer of seven yuan of melon rings-rare earth metal and the synthetic method (application number: 201110388587.4 > > of the induction of < < Cadmium chloride fine powder for this reason.Find again recently with tetrachloro cadmium acid group ([CdCl
4]
2-) be eight yuan of melon rings of inductor induction (Q[8]), the eight yuan melon ring-light rare earth metal supramolecule self-assemblies synthetic with serial rare-earth metal ion, and the difference of eight yuan of melon ring-heavy rare earth metal three-dimensional meshed super molecular polymkeric substance, can be used for the separation of weight rare earth metal.We have applied for mono-kind eight yuan melon ring-rare earth metal supermolecule polymers of < < and synthetic method and application (application number: 201310218642.4) > > for this reason.Even if same melon ring, under different condition, also can have different coordination situations, form different title complexs and supramolecule self-assembly.As our recent findings, under cadmium nitrate existence condition, ortho position Tetramethyl melon ring and light rare earth metal (Nd, Sm, Eu) and heavy rare earth metal form supramolecule self-assembly polymkeric substance, but cannot induce ortho position Tetramethyl melon ring and light rare earths (La, Ce, Pr) metal to form supramolecule self-assembly polymkeric substance, and utilize it can form supramolecule self-assembly polymkeric substance and the method for separated weight rare earth.We have applied for < < ortho position Tetramethyl melon ring-rare earth supermolecule polymer and synthetic method and application (application number: 201310218642.4) > > for this reason.And discovery in present patent application to be ortho position Tetramethyl melon ring and heavy rare earths form adducts, but cannot form adducts with light rare earths (La, Ce, Pr, Nd, Sm, Eu, Gd), and utilize the separated weight rare earth of its nature difference that can form adducts.
Present patent application in neutral environment, make exactly ortho position Tetramethyl melon ring (
o-TMeQ[6]) with serial rare-earth Action of Metal Ions, synthesized the adducts of a series of ortho positions Tetramethyl melon ring-heavy rare earth metal ionized water compound.Utilize ortho position Tetramethyl melon ring and heavy rare earths (Tb, Dy, Ho, Er, Tm, Yb, Lu) metal ion hydrate to form adducts, but cannot form the different of adducts from light rare earths (La, Ce, Pr, Nd, Sm, Eu, Gd) metal, can be used for the separation of weight rare earth ion.
Summary of the invention
The object of the invention is to synthesize a series of ortho positions Tetramethyl melon ring-heavy rare earths adducts, disclose its synthetic method.Utilize ortho position Tetramethyl melon ring and heavy rare earths Tb, Dy, Ho, Er, Tm, Yb, Lu metal to form adducts, but cannot form the difference of adducts with light rare earths La, Ce, Pr, Nd, Sm, Eu, Gd metal, for the separation of weight rare earth ion.
Ortho position of the present invention Tetramethyl melon ring-rare earth adducts is with ortho position Tetramethyl melon ring
o-TMeQ[6] with rare earth metal salt synthetic ortho position Tetramethyl melon ring-heavy rare earths Tb, Dy, Ho, Er, Tm, Yb, Lu adducts in the aqueous solution, the ortho position Tetramethyl melon ring of indication with the chemical constitution general formula of heavy rare earths formation adducts is:
{[Ln(H
2O)
8 o-TMeQ[6]]·2(NO
3)·Cl·xH
2O}
Ln represents rare earth ion, and x is crystal water molecular amounts 9 or 10.
2. ortho position Tetramethyl melon ring-rare earth adducts that nothing according to claim 1 is induced, is characterized in that the ortho position Tetramethyl melon ring-heavy rare earths adducts forming in indication neutral environment is:
(
1)?{Tb(H
2O)
8 o-TMeQ[6]}·2(NO
3)·Cl·9H
2O
(
2)?{Dy(H
2O)
8 o-TMeQ[6]}·2(NO
3)·Cl·10H
2O
(
3)?{Ho(H
2O)
8 o-TMeQ[6]}·2(NO
3)·Cl·10H
2O
(
4)?{Er(H
2O)
8 o-TMeQ[6]}·2(NO
3)·Cl·9H
2O
(
5)?{Tm(H
2O)
8 o-TMeQ[6]}·2(NO
3)·Cl·9H
2O
(
6)?{Yb(H
2O)
8 o-TMeQ[6]}·2(NO
3)·Cl·9H
2O
Above-mentioned indication ortho position Tetramethyl melon ring
o-TMeQ[6] chemical formula be C
40h
44n
24o
12, crystalline structure is as accompanying drawing 1.
Ortho position Tetramethyl melon ring-rare earth adducts synthetic method described above, its synthetic method follows these steps to carry out:
(1) will
o-TMeQ[6] with the aqueous solution, dissolve obtain solution A completely;
(2) by Ln (NO
3)
3with the aqueous solution, dissolve obtain solution B completely;
(3) solution A and B are pressed
o-TMeQ[6]: Ln (NO
3)
3equal the mixed in molar ratio of 1:7～9;
(4) standing.For light rare earths La, Ce, Pr, Nd, Sm, Eu, Gd cannot grow crystal; And for heavy rare earths Tb and the later heavy rare earths of ordination number,, larger according to ordination number, crystal grows the faster rule of speed and grows corresponding adducts crystal.
A kind of ortho position of the present invention Tetramethyl melon ring-rare earth adducts synthetic method, its solution is the aqueous solution.
A kind of ortho position of the present invention Tetramethyl melon ring-rare earth adducts synthetic method, its rare earth metal salt is rare earth nitrate.
A kind of ortho position of the present invention Tetramethyl melon ring-rare earth adducts synthetic method is to work as
o-TMeQ[6], Ln (NO
3)
31: 7 in molar ratio～9 o'clock, grow the fastest of crystal, productive rate is the highest.
The application of ortho position of the present invention Tetramethyl melon ring-rare earth adducts, to utilize ortho position Tetramethyl melon ring and light rare earth metal La, Ce, Pr, Nd, Sm, Eu, Gd cannot form adducts and ortho position Tetramethyl melon ring can form the different of adducts from heavy rare earth metal, can be used for the separation of weight rare earth ion.
In the present invention, the melon cyclic group supermolecule polymer of synthesized is adopted the analysis means such as X-ray single crystal diffraction, IR, DSC-TG to carry out structural characterization.
Patent 1 of the present invention) synthetic method of using has simple to operate, productive rate high.2) utilize the difference that can form supramolecule self-assembly polymkeric substance, can be used for the separation of weight rare earth ion.
Accompanying drawing explanation
Fig. 1 ortho position Tetramethyl melon ring
o-TMeQ[6] crystalline structure figure.
Fig. 2 in the aqueous solution, (a) heavy rare earth metal ion (Dy
3+), ortho position Tetramethyl melon ring (
o-TMeQ[6]) title complex that forms; (b) each
o-TMeQ[6]/Dy
3+title complex is by three nitric acid acid radical anion (NO
3 -) around; (c) each nitric acid acid radical anion by three ortho position Tetramethyl melon rings around; (d)
o-TMeQ[6]/Dy
3+title complex and nitric acid acid radical anion (NO
3 -) the b axle vertical view of alternate accumulation.(e)
o-TMeQ[6]/Dy
3+title complex and nitric acid acid radical anion (NO
3 -) the b axis side view of alternate accumulation.
The supramolecule self-assembly that other heavy rare earth metal and ortho position Tetramethyl melon ring form has similar structures, is allomeric.Heavy rare earths is: Tb, Ho, Er, Tm, Yb, Lu.
Fig. 3
o-TMeQ[6] the X-ray powder diffraction pattern of/Ln system (represents 7
o-TMeQ[6]/Ln system);
Fig. 4
o-TMeQ[6] differential thermal (DTA) of/Ln system crystal analyzes collection of illustrative plates.
Fig. 5
o-TMeQ[6] thermogravimetric (TG) of/Ln system crystal analyzes collection of illustrative plates.
Fig. 6 with
o-TMeQ[6] relatively
o-TMeQ[6] the IR collection of illustrative plates of/Ln system.
Fig. 7 is from containing the Nd that mol ratio is 1:1
3+and Dy
3+in mixing solutions, obtain the electron spectroscopy analysis result of crystal.
specific implementation method
Embodiment 1:
In the neutral environment existing without inductor, heavy rare earths (nitrate) metal ion and ortho position Tetramethyl melon ring effect form supramolecule self-assembly implementation method.With Dy (NO
3)
3for example illustrates:
Embodiment 1: take respectively Dy (NO
3)
36H
2o 27.49 mg (0.0567 mmol), in a beaker, add the 1.0 mL aqueous solution, are heated to and are sufficiently uniformly dissolved.Take
o-TMeQ[6] 10 mg (0.0081 mmol), add the 1.0 mL aqueous solution to be heated to 70 ℃, shake several minutes, make solution clarification.Will
o-TMeQ[6] solution injects above-mentioned mixing solutions, shakes up.Standing 1 to a couple of days, occurs colourless transparent crystal, and productive rate is 50～60%.Its structural formula is { Dy (H
2o)
8q[6] } 2 (NO
3) Cl10 (H
2o).
Embodiment 2: take respectively Dy (NO
3)
36H
2o 35.33 mg (0.0731 mmol), in a beaker, add the 1.0 mL aqueous solution, are heated to and are sufficiently uniformly dissolved.Take
o-TMeQ[6] 10 mg (0.0081 mmol), add the 1.0 mL aqueous solution to be heated to 70 ℃, shake several minutes, make solution clarification.Will
o-TMeQ[6] solution injects above-mentioned mixing solutions, shakes up.Standing 1 to a couple of days, occurs colourless transparent crystal, and productive rate is 55～70%.Its structural formula is { Dy (H
2o)
8q[6] } 2 (NO
3) Cl10 (H
2o).Under similarity condition, it is homeomorphic supermolecule polymer that ortho position Tetramethyl melon ring and other heavy rare earth metals form structure, and its general structure is { [Ln (H
2o)
8q[6]] 2 (NO
3) ClxH
2o}.
Embodiment 3: utilize ortho position Tetramethyl melon ring and heavy rare earth metal to form supramolecule self-assembly polymkeric substance, but cannot form the different of supramolecule self-assembly polymkeric substance from light rare earths (La, Ce, Pr, Nd, Sm, Eu, Gd) metal, carry out separated weight rare earth ion.With separated Nd
3+with Dy
3+for example illustrates:
Take respectively Nd (NO
3)
36H
2o 33.62 mg (0.0081 mmol), Dy (NO
3)
35H
2o 35.33 mg (0.0081 mmol) y, in same beaker, adds the 2 mL aqueous solution, is heated to 70 ℃, makes it to be sufficiently uniformly dissolved.Take
o-TMeQ[6] 20 mg (0.016 mmol), add the 2.0 mL aqueous solution to be heated to 70 ℃, shake several minutes, make solution clarification.Will
o-TMeQ[6] solution injects above-mentioned mixing solutions, shakes up.Standing 5 days, the precipitate and separate washing producing is to be measured, and productive rate was 55～70%.
Claims (5)
- Ortho position Tetramethyl melon ring ( o-TMeQ[6])-rare earth adducts, it is characterized in that ortho position Tetramethyl melon ring and rare earth metal salt synthetic ortho position Tetramethyl melon ring-heavy rare earths Tb, Dy, Ho, Er, Tm, Yb or Lu adducts in the aqueous solution, the adducts chemical constitution general formula that the ortho position Tetramethyl melon ring of indication and heavy rare earth metal form supramolecule self-assembly is:{[Ln(H 2O) 8 o-TMeQ[6]]·2(NO 3)·Cl·xH 2O}Ln represents rare earth ion, and x is crystal water molecular amounts 9 or 10.
- 2. ortho position according to claim 1 Tetramethyl melon ring-rare earth adducts, is characterized in that the ortho position Tetramethyl melon ring-heavy rare earths adducts forming in indication neutral environment is:( 1)?{Tb(H 2O) 8 o-TMeQ[6]}·2(NO 3)·Cl·9H 2O( 2)?{Dy(H 2O) 8 o-TMeQ[6]}·2(NO 3)·Cl·10H 2O( 3)?{Ho(H 2O) 8 o-TMeQ[6]}·2(NO 3)·Cl·10H 2O( 4)?{Er(H 2O) 8 o-TMeQ[6]}·2(NO 3)·Cl·9H 2O( 5)?{Tm(H 2O) 8 o-TMeQ[6]}·2(NO 3)·Cl·9H 2O( 6)?{Yb(H 2O) 8 o-TMeQ[6]}·2(NO 3)·Cl·9H 2O。
- 3. the ortho position Tetramethyl melon ring-rare earth adducts as described in one of claim 1-2, is characterized in that synthetic method follows these steps to carry out:(1) will o-TMeQ[6] water dissolves obtain solution A completely;(2) by Ln (NO 3) 3water dissolves obtain solution B completely;(3) solution A and B are pressed o-TMeQ[6]: Ln (NO 3) 3equal the mixed in molar ratio of 1:7 ~ 9;(4) standing, for rare earth La, Ce, Pr, Nd, Sm, Eu, Gd cannot grow crystal; And for heavy rare earths Tb and the later heavy rare earths of ordination number, larger according to ordination number, crystal grows the faster rule of speed and grows corresponding adducts crystal.
- 4. ortho position according to claim 3 Tetramethyl melon ring-rare earth adducts synthetic method, is characterized in that: when o-TMeQ[6], Ln (NO 3) 31: 7 in molar ratio ~ 9 o'clock, grow the fastest of crystal, productive rate is the highest.
- 5. the application of the ortho position Tetramethyl melon ring-rare earth adducts as described in one of claim 1 to 2, it is characterized in that utilizing ortho position Tetramethyl melon ring and light rare earth metal La, Ce, Pr, Nd, Sm, Eu, Gd cannot form adducts and the ortho position Tetramethyl melon ring heavy rare earth metal later from ordination number Tb can form the different of polymkeric substance, can be used for the separation of weight rare earth ion.
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|---|---|
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| CN103951687B CN103951687B (en) | 2017-11-14 |
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| CN104230969A (en) * | 2014-10-10 | 2014-12-24 | 贵州大学 | Symmetrical tetramethyl cucurbituril and rare earth coordination compound and addition compound, synthetic method and application |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151338A (en) * | 2014-08-12 | 2014-11-19 | 贵州大学 | Symmetric octamethyl cucurbituril Q[6]-rare earth adduct, and synthesis method and application thereof |
| CN104387408A (en) * | 2014-09-29 | 2015-03-04 | 贵州大学 | Hexamethyl hexahydroxy cucurbit[6]uril-rare earth adduct, synthetic method and application |
| CN104387408B (en) * | 2014-09-29 | 2016-04-13 | 贵州大学 | The hexa-atomic melon ring-rare earth adducts of hexamethyl hexahydroxy-and synthetic method and application |
| CN104230969A (en) * | 2014-10-10 | 2014-12-24 | 贵州大学 | Symmetrical tetramethyl cucurbituril and rare earth coordination compound and addition compound, synthetic method and application |
| CN108484490A (en) * | 2018-05-23 | 2018-09-04 | 贵州大学 | Detect the fluorescence probe and its preparation method and application of various metals ion in water |
| CN108484490B (en) * | 2018-05-23 | 2021-06-15 | 贵州大学 | Fluorescent probe for detecting multiple metal ions in water and preparation method and application thereof |
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Application publication date: 20140730 Assignee: Hechi Product Quality Inspection Institute Assignor: Hechi Yizhou District Food Inspection and Testing Center Contract record no.: X2023980045469 Denomination of invention: Orthotetramethylhexamembered guar ring rare earth adduct and its synthesis method and application Granted publication date: 20171114 License type: Common License Record date: 20231103 |