CN102936258B - Seven yuan of melon ring-rare earth tubular polymers of tetrachloro zincic acid root induction and synthetic method - Google Patents
Seven yuan of melon ring-rare earth tubular polymers of tetrachloro zincic acid root induction and synthetic method Download PDFInfo
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- CN102936258B CN102936258B CN201210454578.5A CN201210454578A CN102936258B CN 102936258 B CN102936258 B CN 102936258B CN 201210454578 A CN201210454578 A CN 201210454578A CN 102936258 B CN102936258 B CN 102936258B
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Abstract
The present invention is seven yuan of melon ring-rare earth tubular polymers and the synthetic method of tetrachloro zincic acid root induction, is exactly under tetrachloro zincic acid root exists, seven yuan of melon rings (Cucurbit [7] uril, Q [7]) and rare earth metal salt (Ln (NO
3)
3) in 3 ~ 6M hydrochloric acid soln, form seven yuan of melon ring-rare earth tubulose supermolecule polymers.According to seven yuan of melon rings, the batching mol ratio 1 of rare earth metal salt and zinc chloride?:? (6 ~ 8)?:? (2 ~ 8), heat and mix, at normal temperatures static a couple of days, can form target compound in 3 ~ 6 mole hydrochlorides.The advantage such as synthetic method has that synthetic method is simple, easy and simple to handle, productive rate high (between 50 ~ 70%), cycle are short.
Description
Technical field
Seven yuan of melon ring-rare earth tubulose supermolecule polymers of tetrachloro zincic acid root induction of the present invention and synthetic method belong to metal-organic supermolecular polymkeric substance and synthetic method field thereof.Be exactly seven yuan of melon ring-rare earth tubulose supermolecule polymers and the synthetic method of tetrachloro zincic acid root induction specifically.Seven yuan of melon rings and rare earth element form tubulose supermolecule polymer in the present invention.This structure has nanotubes feature, likely for the application of the aspects such as molecular sieve, molecular wire, Anion-adsorption and exchange.
background technology:
Material and the synthetic method thereof with linear pipelines structure are subject to extensive concern in the numerous areas such as nano material, molecular sieve, ionization sensor, various countries investigator has dropped into extensive work in the pipeline configuration research of the such as organic or inorganic quality such as carbon nanotube, achieves certain progress.But up to the present, people can't control structure and the size of nanotubes effectively.In principle, the pipeline configuration of organic or inorganic quality is all constructed by the supramolecule of molecule and is reached.The report constructed with the biological organic substrate pipeline configuration such as D, L polypeptide, linear gramicidins is compared, the pipeline configuration of inorganic quality, particularly inorganic metal ion and organic ligand construct pipeline configuration by coordination report then phase shape see clumsy.The pipeline configuration being to construct metal ion-organic ligand of tracing it to its cause requires that in process, both carry out reversible mutual matching effect, and this reversible coupling interacts restive in building-up process, and be subject to the impact of factors, as metal ion physicochemical property, to negatively charged ion physicochemical property, medium, synthesis condition etc.
Melon ring (Cucurbit [n] urils, Q [n]) is the large ring cage compound that a class is linked up by n glycosides urea unit and 2n methylene bridge." inlay " due to melon ring two ports and a circle carbonylic oxygen atom, there is the ability forming title complex with metallic ion coordination, be used as organic ligand in recent years, in the research field that metal-organic supermolecular polymkeric substance is constructed, receive increasing concern.Melon ring-metal linear pipeline configuration based on coordination can trace back to 1999, the Kim study group of Korea S takes the lead in reporting the supermolecule polymer that the linear pipelines structure of formation is constructed in the first hexa-atomic melon ring (Q [6]) and the direct coordination of Alkali Metal Rb ion, and constructs the supermolecule polymer of the linear pipelines structure of formation in Q [6] and the direct coordination of basic metal potassium ion of report in 2000 subsequently.Several years almost do not have correlative study to report afterwards, until doctor Liu Jingxin of Xiamen University Zheng Lan sweet-smelling grass academician study group in 2009 has synthesized the supermolecule polymer that the linear pipelines structure of formation is constructed in Q [6] and the direct coordination of metal copper ion.But for larger melon ring, the linear pipelines structure supermolecule polymer as seven yuan of melon rings (Q [7]) and eight yuan of melon rings (Q [8]) constructs research so far there are no the report of other study group.This study group once found to adopt Cadmium chloride fine powder (CdCl
2) as induction agent, " cellular effect " of the tetrachloro cadmium acid radical anion utilizing it to be formed in hydrochloric acid medium, induce seven yuan of melon rings (Q [7]) and the direct coordination of serial rare-earth metal ion, synthesize a series of seven yuan of melon rings-rare earth metal tubulose supermolecule polymer, and applied for " seven yuan of melon ring-rare earth metal linear, tubular supermolecule polymers of Cadmium chloride fine powder induction and synthetic method (application number: 201110388587.4 " for this reason.Cadmium chloride fine powder (CdCl
2although) can as induction agent, the seven yuan of melon rings-rare earth metal linear, tubular supermolecule polymer of induction, in addition, cadmium is widely used in the industries such as plating, battery, automobile, aviation, pigment, paint, printing, plastics industry.But widely using of cadmium also pollutes to coenocorrelation.Cadmium belongs to moderate toxicity heavy metal, can suppress the various sulfydryl enzyme systems in body, makes tissue metabolism that obstacle occur, also can damage local organization cell, cause inflammation and oedema.After cadmium is absorbed by the body and enters blood, first the overwhelming majority is combined with oxyphorase and is present in red corpuscle, progresses into the tissue such as liver, kidney afterwards, and the metallothionein(MT) in tissue is combined.Therefore, we are being devoted to the induction agent reagent finding alternative Cadmium chloride fine powder in the research of constructing melon ring-metal supermolecular polymkeric substance always.
Usually, rare earth ion and seven yuan of melon rings (Q [7]) can not be constructed form solid supermolecule polymer at neutral, acidic aqueous solution.But when zinc chloride introduced rare earth ion and seven yuan of melon rings (in the acidic solution (HCl) that Q [7] coexists, owing to defining tetrachloro zincate anion, similar to tetrachloro cadmium acid radical anion, it also can rise " cellular effect ", makes rare earth ion and seven yuan of melon rings (Q [7]) direct coordination can form tubular structure supermolecule polymer rapidly.When concentration of hydrochloric acid is at 3 ~ 6mol/L, the linear structure supermolecule polymer of formation is tubular structure (see accompanying drawing 1).
Be exactly utilize tetrachloro zincate anion in present patent application, make seven yuan of melon rings (Q [7]) and the direct coordination of serial rare-earth metal ion, synthesized a series of seven yuan of melon rings-rare earth metal tubulose supermolecule polymer.Utilize the polymkeric substance with metal-melon ring organic framework, in fractionation by adsorption, have huge application potential.
summary of the invention:the object of the invention is to by tetrachloro zincic acid root (ZnCl
4 2-) inducing action, design and synthesis seven yuan of melon ring-rare earth tubulose supermolecule polymers and synthetic method thereof.
Seven yuan of melon ring-rare earth tubulose supermolecule polymers of tetrachloro zincic acid root induction of the present invention and synthetic method are at zinc chloride (ZnCl
2) under existence, seven yuan of melon rings that seven yuan of melon rings (Cucurbit [7] uril, Q [7]) and rare earth metal salt synthesize under certain condition in hydrochloric acid soln and rare earth tubulose supermolecule polymer.The rare earth metal salt of above-mentioned indication is the nitrate of serial rare-earth metal.
The inductor of above-mentioned indication is tetrachloro zincate anion.The chemical formula of seven yuan of melon rings (Q [7]) is
c 42 h 42 n 28 o 14 , structural formula is as follows:
The seven yuan of melon rings-rare earth tubulose supermolecule polymer of the present invention one class tetrachloro zincic acid root induction is with Cadmium chloride fine powder (ZnCl
4 2-) be inductor, seven yuan of melon rings-rare earth tubulose supermolecule polymer that seven yuan of melon rings (Cucurbit [7] uril, Q [7]) are synthesized in hydrochloric acid soln with rare earth metal salt, this polymkeric substance can adsorb volatile substances.Seven yuan of melon rings of indication and serial rare-earth metal form supermolecule polymer chemical constitution general formula:
{[Ln
n(H
2O)
y(Q[7])
m]·aZnCl
4·bClc·H
2O}
Ln represents rare earth ion, and n is rare earth ion quantity (1<n<2); Y is rare earth ion coordinated water molecular amounts (9<y<12); M is the quantity (1<m<2) of seven yuan of melon rings; A is tetrachloro zincate anion quantity (1<a<3); B is chlorion quantity (0<b<4); C is crystalline water molecules quantity (32<c<55), and hydrochloric acid soln is 3 ~ 6 moles.
The seven yuan of melon rings-rare earth tubulose supermolecule polymer of the class tetrachloro zincic acid root induction that the present invention has synthesized is:
1）{La
2(H
2O)
12Q[7]}2(ZnCl
4)2Cl31(H
2O)
2）{Ce
2(H
2O)
12Q[7]}2(ZnCl
4)2Cl25(H
2O)
3）{Pr
2(H
2O)
12Q[7]}2(ZnCl
4)2Cl29(H
2O)
4）{Nd
2(H
2O)
12Q[7]}2(ZnCl
4)2Cl25(H
2O)
5）{Sm
2(H
2O)
10Q[7]}2(ZnCl
4)2Cl24(H
2O)
6）{Eu
2(H
2O)
10Q[7]}2(ZnCl
4)2Cl29(H
2O)
7）{Gd
2(H
2O)
10Q[7]}2(ZnCl
4)2Cl27(H
2O)
8）{Tb
2(H
2O)
10Q[7]}2(ZnCl
4)2Cl27(H
2O)
9）{Dy
2(H
2O)
10Q[7]}ZnCl
44Cl46(H
2O)
10）{Ho
2(H
2O)
10Q[7]}ZnCl
44Cl41(H
2O)
11）{Er
2(H
2O)
10Q[7]}2(ZnCl
4)2Cl33(H
2O)
12）{Tm
2(H
2O)
10Q[7]}2(ZnCl
4)2Cl27(H
2O)
13）{Yb
2(H
2O)
10Q[7]}2(ZnCl
4)2Cl18(H
2O)
14）{Lu
2(H
2O)
10Q[7]}2(ZnCl
4)2Cl29(H
2O)
The present invention's seven yuan of melon rings and serial rare-earth metal are at zinc chloride (ZnCl
2) under induction, form the supermolecule polymer with linear structure, seven yuan of melon rings and serial rare-earth metal form the synthetic method of the supermolecule polymer with tubular structure under certain condition, follow these steps to carry out:
1) it is dissolved with 1mL3 ~ 6 molar hydrochloric acid solution by Q [7] completely, zinc chloride (ZnCl
2) and Ln (NO
3)
3with 1.5mL3 ~ 6 molar hydrochloric acid solution, this mixture is dissolved in mixing and same container;
(2) respectively respective solution is heated to 50 DEG C ~ 80 DEG C;
(3) while hot by zinc chloride (ZnCl
2) and Ln (NO
3)
3mixing solutions, under whipped state, inject Q [7] solution;
(4) be cooled to normal temperature, leave standstill 1 ~ 5 day, crystallize out.
Q [7], Ln (NO
3)
3with zinc chloride (ZnCl
2) mol ratio 1: 6 ~ 8: 2 ~ 8.
The synthetic method of the seven yuan of melon rings-rare earth tubulose supermolecule polymer of tetrachloro zincic acid root induction of the present invention is Q [7], Ln (NO
3)
3with zinc chloride (ZnCl
2) mol ratio is when being 1:8:6, grow the fastest of crystal, productive rate is the highest.
The analysis means such as X-ray single crystal diffraction, IR, DSC-TG is adopted to carry out structural characterization to synthesized melon cyclic group supermolecule polymer in the present invention.
The synthetic method that patent of the present invention uses has simple to operate, productive rate high, is this kind of zinc chloride (ZnCl
2) seven yuan of melon rings-the carrying out of rare earth metal wire supermolecule polymer practical application of Induced synthesis lay a good foundation.
accompanying drawing explanation:
Fig. 1 is in acidic solution (HCl), and (a) zine ion forms tetrachloro zincate anion (ZnCl
4 2-) " cellular effect " inducing action, impel rare earth ion (Ln
3+) form tubular structure supermolecule polymer with seven yuan of melon rings (Q [7]).
Fig. 2 (a) [ZnCl
4]
2-ion around Ln
3+-Q [7] " it " tubulose supermolecule polymer (side-looking); Zn in (b) tubular polymer
2+ion and Q [7] coordination schematic diagram; C () is around [ZnCl
4]
2-the accumulation graph (overlooking) of ion and wire supermolecule polymer.
Other [ZnCl
4]
2-ion around Ln-Q [7] tubulose supermolecule polymer there is similar structures.Ln is: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.
Fig. 3 Q [7]-La
3+-[ZnCl
4]
2-[7]-Gd
3+-[ZnCl
4]
2-the DSC(of (tubulose) crystal is left)-TG(the right side) collection of illustrative plates, at ZnCl
2induction under, Q [7] and La (NO
3)
3with Gd (NO
3)
3the decomposition temperature forming tubulose supermolecule polymer all obviously increases than Q [7].
At ZnCl
2induction under, Q [7] and Ln (NO
3)
3form the lowest decomposition temperature of wire supermolecule polymer as following table:
Fig. 4 (a) Q [7] and (b) Q [7]-La
3+-[ZnCl
4]
2-the IR collection of illustrative plates of tubular crystal.The IR spectrogram of both contrasts finds, carbonyl peak red shift can occur and moved on to Q [7]-La by 1733 in Q [7]
3+-[ZnCl
4]
2-in (tubulose) crystal 1728.
Other [ZnCl of Fig. 5
4]
2-ion around Ln-Q [7] tubulose supermolecule polymer there is similar IR collection of illustrative plates.Ln is followed successively by: (1) La, (2) Ce, (3) Pr, (4) Nd, (5) Sm, (6) Eu, (7) Gd, (8) Tb, (9) Dy, (10) Ho, (11) Er, (12) Tm, (13) Yb and (14) Lu.
Fig. 6 map interlinking 5, illustrates same Fig. 5.
specific implementation method:
Embodiment 1: transition metal ZnCl
2induce seven yuan of melon rings and rare earth metal to form tubular structure supermolecule polymer and synthesize implementation method.With La (NO
3)
3for example illustrates:
Take Q [7] 20mg (0.015mmol), dissolve with 1.0mL3.0mol/LHCl and be heated to 60 DEG C, shake several minutes, solution is clarified.Take lanthanum nitrate 51.62mg (0.12mmol) respectively, ZnCl
212.19mg (0.09mmol), in same container, dissolves with 1.5mL3.0mol/LHCl, is heated to 60 DEG C, makes it to be sufficiently uniformly dissolved.Q [7] solution is injected into La (NO
3)
3and CdCl
2mixing solutions in, shake up.Leave standstill 1-5 days, occur colourless transparent crystal, productive rate is 50 ~ 70%.Its structural formula is { La
2(H
2o)
12q [7] } 2 (ZnCl
4) 2Cl31 (H
2o).The analysis means such as X-ray single crystal diffraction, IR, DSC-TG is adopted to carry out structural characterization to synthesized melon cyclic group supermolecule polymer in the present invention.
Under similarity condition, transition metal ZnCl
2induce seven yuan of melon rings and other rare earth metal to form the structure that structure is homeomorphic tubulose supermolecule polymer, its general structure is { [Ln
n(H
2o)
y(Q [7])
m] aCdCl
4bClcH
2o}.The surrounding of each oversubscription subchain is also regular around 6 [ZnCl
4]
2-structural unit, is connected by a rare earth metal between melon ring with melon ring.
Claims (3)
1. the seven yuan of melon rings-rare earth tubulose supermolecule polymer of a class tetrachloro zincic acid root induction, is characterized in that the seven yuan of melon rings-rare earth tubulose supermolecule polymer of the class tetrachloro zincic acid root induction synthesized is:
1）{La
2(H
2O)
12Q[7]}2(ZnCl
4)2Cl31(H
2O)
2）{Ce
2(H
2O)
12Q[7]}2(ZnCl
4)2Cl25(H
2O)
3）{Pr
2(H
2O)
12Q[7]}2(ZnCl
4)2Cl29(H
2O)
4）{Nd
2(H
2O)
12Q[7]}2(ZnCl
4)2Cl25(H
2O)
5）{Sm
2(H
2O)
10Q[7]}2(ZnCl
4)2Cl24(H
2O)
6）{Eu
2(H
2O)
10Q[7]}2(ZnCl
4)2Cl29(H
2O)
7）{Gd
2(H
2O)
10Q[7]}2(ZnCl
4)2Cl27(H
2O)
8）{Tb
2(H
2O)
10Q[7]}2(ZnCl
4)2Cl27(H
2O)
9）{Dy
2(H
2O)
10Q[7]}ZnCl
44Cl46(H
2O)
10）{Ho
2(H
2O)
10Q[7]}ZnCl
44Cl41(H
2O)
11）{Er
2(H
2O)
10Q[7]}2(ZnCl
4)2Cl33(H
2O)
12）{Tm
2(H
2O)
10Q[7]}2(ZnCl
4)2Cl27(H
2O)
13）{Yb
2(H
2O)
10Q[7]}2(ZnCl
4)2Cl18(H
2O)
14) { Lu
2(H
2o)
10q [7] } 2 (ZnCl
4) 2Cl29 (H
2o), in formula, indication Q [7] is seven yuan of melon rings.
2. the synthetic method of the seven yuan of melon rings-rare earth tubulose supermolecule polymer of tetrachloro zincic acid root induction as claimed in claim 1, is characterized in that synthetic method follows these steps to carry out:
(1) it is dissolved with 1ml3 ~ 6 molar hydrochloric acid solution by Q [7] completely, zinc chloride ZnCl
2with Ln (NO
3)
3be mixed in same container and with 1.5ml3 ~ 6 molar hydrochloric acid solution, this mixture dissolved;
(2) respectively respective solution is heated to 50 DEG C ~ 80 DEG C;
(3) while hot by zinc chloride ZnCl
2with Ln (NO
3)
3mixing solutions, under whipped state, inject Q [7] solution;
(4) be cooled to normal temperature, leave standstill 1 ~ 5 day, crystallize out,
Q [7], Ln (NO
3)
3with zinc chloride ZnCl
2mol ratio 1: 6 ~ 8: 2 ~ 8, Ln is the rare earth ion occurred in power 1.
3., according to the synthetic method of the seven yuan of melon rings-rare earth tubulose supermolecule polymer of tetrachloro zincic acid root induction according to claim 2, it is characterized in that: Q [7], Ln (NO
3)
3with zinc chloride ZnCl
2mol ratio 1:8:6.
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| CN103265568B (en) * | 2013-06-04 | 2015-12-02 | 贵州大学 | A kind of eight yuan of melon ring-rare earth metal supermolecule polymers and synthetic method and application |
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|---|---|---|---|---|
| CN102060996A (en) * | 2010-11-26 | 2011-05-18 | 贵州大学 | Multi-dimensional porous Cucurbit[n]uril-based metal-organic framework polymer synthesized by organic molecule induction and synthesis method thereof |
| CN102516550A (en) * | 2011-11-30 | 2012-06-27 | 贵州大学 | Seven-membered cucurbituril-rare earth metal linear tubular supramolecular polymer, preparation and application thereof |
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| CN102060996A (en) * | 2010-11-26 | 2011-05-18 | 贵州大学 | Multi-dimensional porous Cucurbit[n]uril-based metal-organic framework polymer synthesized by organic molecule induction and synthesis method thereof |
| CN102516550A (en) * | 2011-11-30 | 2012-06-27 | 贵州大学 | Seven-membered cucurbituril-rare earth metal linear tubular supramolecular polymer, preparation and application thereof |
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