CN103386326B - Phosphomolybdic acid-hydroxyl five yuan of melon cyclic group porous heterocomplexs and synthetic method thereof - Google Patents

Phosphomolybdic acid-hydroxyl five yuan of melon cyclic group porous heterocomplexs and synthetic method thereof Download PDF

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CN103386326B
CN103386326B CN201310335249.3A CN201310335249A CN103386326B CN 103386326 B CN103386326 B CN 103386326B CN 201310335249 A CN201310335249 A CN 201310335249A CN 103386326 B CN103386326 B CN 103386326B
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yuan
hydroxyl
pmo
phosphomolybdic acid
melon
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CN103386326A (en
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韩保霞
肖昕
王传增
陶朱
薛赛凤
祝黔江
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Guizhou University
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Guizhou University
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Abstract

Phosphomolybdic acid-hydroxyl of the present invention five yuan of melon cyclic group multi-pore channel heterocomplexs and synthetic method thereof, belong to metal-oxygen cluster-organic supermolecular polymer and synthesis field thereof, is with Keggin-type phosphomolybdic acid [H 3pMo 12o 40] be derivant, hydroxyl five yuan of melon rings (HO) 10q [5] synthesizes a class phosphomolybdic acid-hydroxyl five yuan of melon cyclic group multi-pore channel heterocomplexs in aqueous solution of alkali metal salt, and the general formula of chemical composition is: a{M b(H 2o) c(NO 3) d(HO) 10q [5] } (PMo 12o 40) e (H 3o) f (H 2o).Synthetic method of the present invention is simple, and productive rate is high.

Description

Phosphomolybdic acid-hydroxyl five yuan of melon cyclic group porous heterocomplexs and synthetic method thereof
Technical field
The present invention utilizes phosphomolybdic acid-hydroxyl five yuan of melon cyclic group multi-pore channel heterocomplexs and synthetic method thereof to belong to metal-oxygen cluster-organic supermolecular polymer and synthetic method field thereof.Be exactly heteropolyacid anions Induced synthesis one class phosphomolybdic acid-hydroxyl five yuan of melon cyclic group multi-pore channel heterocomplexs and synthetic method thereof specifically.
Background technology
Polyoxometallate or polyacid (polyoxometalates is abbreviated as POMs) by electrostatic interaction or hydrogen bond action, construct the crystalline state porous material with rule or void structure with macrocyclic compound.Along with developing rapidly of the porous material based on inorganic skeleton, the class new material occurred in the crossing domain of inorganic material science and Coordinative Chemistry.This class material not only has the crystal structure similar to zeolite molecular sieve, and its structure has and can design and Scalability, can obtain different size and the duct that need not construct or hole by the rational design of topological structure and organic selection.Generally speaking, they have these features: 1, and stronger electrostatic interaction and hydrogen bond action impart very strong plasticity; The discrete structure of 2, POMs-organic framework material, has Acidity of Aikalinity, oxidisability, spectrochemical property etc.3, the organic matter connecting POMs has diversity, and suitable organic molecule can be selected as required to participate in constructing.
Melon ring (Cucurbit [ n] urils, Q [ n] s) there is the large ring cage compound linked up by n glycosides urea unit and 2n methylene bridge, two edge, openend " is inlayed " and a circle carbonylic oxygen atom, thus there is the ability forming complex with metal ion, the coordination of organic molecule functional group, melon cyclic group covalency organic frame compound (Covalent-Organic Framework, COF) being formed and there is various structures feature is constructed by direct coordinations of effect such as hydrogen bond, Π-Π pile up.Hydroxyl melon ring (perhydroxycucurbit [n] uril, (HO) 2nq [n] s), hydroxyl substituted cucurbituril not only has special hydrophobicity cage body and hydrophily port organization, also there is multiple hydroxyl reactive group, make its better and metal, organic molecule, POMs etc. interact, form multiple multidimensional and multiple-level time self-assembled supermolecular entity, they have good development prospect in the practical applications such as front line science and investigation of materials such as molecular recognition, molecular device, host-guest chemistry and supramolecular chemistry.
Summary of the invention
The object of the invention is to the inducing action by heteropolyacid anions, design and synthesis hydroxyl five yuan of melon rings ((HO) 10q [5]) multi-pore channel heterocomplex and synthetic method thereof.
Hydroxyl five yuan of melon rings (HO) of the present invention one class heteropoly acid induction 10q [5] multi-pore channel heterocomplex is with Keggin-type phosphomolybdic acid [H 3pMo 12o 40] be derivant, hydroxyl five yuan of melon rings synthesize a class phosphomolybdic acid-hydroxyl five yuan of melon cyclic group multi-pore channel heterocomplexs in aqueous solution of alkali metal salt, and the general formula of chemical composition is:
a{M b(H 2O) c(NO 3) d(HO) 10Q[5]}(PMo 12O 40) e (H 3O) f (H 2O)
In formula, a is the quantity that hydroxyl five yuan of melon rings and alkali metal ion form complex; M represents alkali metal ion; B is quantity 0≤a≤2 of coordination alkali metal ion; C is metallic ion coordination hydrone quantity 0≤c≤2; D is by (HO) 10quantity 0≤d≤1 of the nitrate anion of Q [5] inclusion; (HO) 10hydroxyl five yuan of melon rings selected by Q [5] representative; (PMo 12o 40) be Keggin-type phosphomolybdic acid [H 3pMo 12o 40] anion; E is quantity 1≤e≤15 of protonated hydrone; F is crystalline water molecules quantity 28≤f≤55.
Indication alkali metal salt of the present invention is hydrochloride, bromate, as potassium chloride, KBr, sodium bromide etc.
The hydroxyl five yuan of melon ring multi-pore channel heterocomplexs of the class heteropoly acid induction that the present invention has synthesized are:
（1） [C 30H 30N 20O 20] (PMo 12O 40) 3(H 3O) 48(H 2O)
（2） 2{K 2(H 2O)(NO 3)(HO 10Q[5]} + (PMo 12O 40) 2-29(H 2O)
（3） {K(H 2O) 2HO 10Q[5]} 2(PMo 12O 40) (H 3O) 38(H 2O)
（4） 2(HO 10Q[5])·(Mo 12O 40P)·3(H 3O)·55(H 2O)
Hydroxyl five yuan of melon ring multi-pore channel heterocomplexs of a class heteropoly acid induction of the present invention are yellow-green crystal, and to measure related crystalline structural parameters, X-ray powder diffraction and crystal structure basically identical.The crystal thermal analyses of multi-pore channel heterocomplex and infrared analysis confirm further to its structure.
Hydroxyl five yuan of melon rings ((HO) of the present invention one class heteropoly acid induction 10q [5]) multi-pore channel heterocomplex synthetic method is:
(1) by (HO) 10q [5], phosphomolybdic acid and alkali metal salt 1: 1 ~ 6: 0 ~ 10 batch weighings in molar ratio;
(2) said mixture matter be heated to dissolve completely with q.s distilled water and seethe with excitement 2 ~ 3 minutes, solution is yellow green, is cooled to room temperature;
(3) leave standstill about 3 ~ 15 days under normal temperature, in precipitation, separate out microscler yellow-green crystal;
Hydroxyl five yuan of melon rings are under the inducing action of heteropolyacid anions in the present invention, form heteropoly acid acid-hydroxyl five yuan of melon cyclic group multi-pore channel heterocomplexs.This kind of heterocomplex has technology such as can be used for absorption, separation, catalysis.Because the Nature comparison of heteropoly acid is special, Application comparison is extensive, so after heteropoly acid and hydroxyl five yuan of melon effects, in conjunction with both characteristic, can be used as the novel nano-material with functions such as selective absorption, trapping, separation, catalytic reaction, medium sensors.
It is simple that the present invention has synthetic method, the feature that productive rate is high.
Accompanying drawing explanation
Fig. 1 (HO) 10the structural representation of Q [5].
Under Fig. 2 derivant Keggin-type phosphomolybdic acid existence condition, (a) (HO) 10q [5]-[PMo 12o 40] 3 –supramolecular self assembly top view, (b) 2 hydroxyls five yuan of melon rings and 3 [PMo 12o 40] 3 –ionization defines the subunit structure with nano-pore, (c) 1 hydroxyl five yuan of melon rings ((HO) 10q [5]) there are 6 [PMo around 12o 40] 3 –ionization figure, (d) 1 [PMo 12o 40] 3 –ion and 6 hydroxyls, five yuan of melon rings ((HO) 10q [5]) action diagram.(e) two-dimensional network structure and (HO) 10q [5] and [PMo 12o 40] 3 –, [PMo 12o 40] 3 –with [PMo 12o 40] 3 –between effect (f) (HO) 10q [5]-[PMo 12o 40] 3 –the stacking chart of supermolecule network
Fig. 3 (a) (HO) 10q [5]-[PMo 12o 40] 3 –two-dimensional network structure, (b) removes [PMo 12o 40] 3 –after " honeycomb " structure, (c ~ e) further describes the interphase interaction of hydroxyl melon toroidal molecule and heteropolyacid anions
(f, g) Supramolecular Assembling two-dimensional network structure (removing [PMo 12o 40] 3 –)
Fig. 4 [PMo 12o 40] 3 –-(HO) 10q [5], [PMo 12o 40] 3 –-(HO) 10q [5]-KNO 3, [PMo 12o 40] 3 –-(HO) 10q [5]-KBr, [PMo 12o 40] 3 –-(HO) 10the X-ray powder diffraction of Q [5]-NaBr supermolecule polymer, experiment value and theoretical value basically identical.
Fig. 5 [PMo 12o 40] 3 –-(HO) 10q [5], [PMo 12o 40] 3 –-(HO) 10q [5]-KNO 3, [PMo 12o 40] 3 –-(HO) 10q [5]-KBr, [PMo 12o 40] 3 –-(HO) 10differential thermal (DTA) and the thermogravimetric (TG) of the crystal of Q [5]-NaBr supermolecule polymer analyze collection of illustrative plates.
Fig. 6 (HO) 10q [5] and [PMo 12o 40] 3 –-(HO) 10q [5], [PMo 12o 40] 3 –-(HO) 10q [5]-KNO 3, [PMo 12o 40] 3 –-(HO) 10q [5]-KBr, [PMo 12o 40] 3 –-(HO) 10the IR collection of illustrative plates that Q [5]-NaBr supermolecule polymer compares.
Detailed description of the invention
Embodiment 1: heteropoly acid [PMo 12o 40] 3 –induction hydroxyl five yuan of melon rings ((HO) 10q [5]) duct Supramolecular self assembly entity synthesis implementation method.
(HO) 10q [5] (10 mg, 0.0085 mmol), Keggin-type phosphomolybdic acid (93 mg, 0.051 mmol) (mol ratio 1:6), add 3mL distilled water, ebuillition of heated is to dissolving, solution presents yellow green, under cool to room temperature, grow yellowish green microscler crystal after 20 days in precipitation, productive rate is 31%.Its structural formula is: [C 30h 30n 20o 20] (PMo 12o 40) 3 (H 3o) 48 (H 2o).Chemistry skeleton symbol and crystal parameters see attached list 1.
Embodiment 2: heteropoly acid [PMo 12o 40] 3 –induce the substituted five-membered melon ring ((HO) of full hydroxyl 10q [5]) " honeycomb " Supramolecular self assembly entity synthesis implementation method.With KNO 3for example illustrates: (HO) 10q [5] (10 mg, 0.0085 mmol), KNO 3(8.6 mg, 0.085 mmol), Keggin-type phosphomolybdic acid (15.6 mg, 0.0085 mmol) (mol ratio is 1:1:10), in this mixture, add 2ml distilled water add 2-3 and drip 6molHCl, ebuillition of heated 3-5 minute, solution presents yellow green, is suspended on solution top layer after cooling latter 3 hours with regard to having microscler yellow-green crystal.Productive rate is 55%.Its structural formula is: 2{K 2(H 2o) (NO 3) (HO 10q [5] } +(PMo 12o 40) 2-29 (H 2o).Chemistry skeleton symbol and crystal parameters see attached list 1.
Embodiment 3: heteropoly acid [PMo 12o 40] 3 –induction hydroxyl five yuan of melon rings ((HO) 10q [5]) " honeycomb " Supramolecular self assembly entity synthesis implementation method.Illustrate for KBr: (HO) 10q [5] (20 mg, 0.017 mmol), KBr (8 mg, 0.067 mmol), Keggin-type phosphomolybdic acid (31.2 mg, 0.017 mmol) (mol ratio is 1:1:4), in this mixture, add 3ml distilled water add 2-3 and drip 6molHCl, ebuillition of heated 3-5 minute, solution presents yellow green, is suspended on solution top layer after cooling after 1-2 days interior hour with regard to having microscler yellow-green crystal.Productive rate is 47%.Its structural formula is: { K (H 2o) 2hO 10q [5] } 2(PMo 12o 40) (H 3o) 38 (H 2o).Chemistry skeleton symbol and crystal parameters see attached list 1.
Embodiment 4: heteropoly acid [PMo 12o 40] 3 –induction hydroxyl five yuan of melon rings ((HO) 10q [5]) " honeycomb " Supramolecular self assembly entity synthesis implementation method.Illustrate for NaBr: (HO) 10q [5] (20 mg, 0.017 mmol), NaBr (7 mg, 0.068 mmol), Keggin-type phosphomolybdic acid (0.0312 mg, 0.017 mmol) (mol ratio is 1:1:4), in this mixture, add 3ml distilled water add 2-3 and drip 6molHCl, ebuillition of heated 3-5 minute, solution is yellow green, after cooling, microscler yellow-green crystal within 4 days, will be had in precipitation to be suspended on solution top layer.Productive rate is 31%.Its structural formula is: 2 (HO 10q [5]) (Mo 12o 40p) 3 (H 3o) 55 (H 2o).Chemistry skeleton symbol and crystal parameters see attached list 1.
table 1. the crystal of 4 heterocomplexs and measurement parameter
The embodiment of the present invention is aided with explanation technical scheme of the present invention, and the content of embodiment is not limited thereto.

Claims (5)

1. a class phosphomolybdic acid-hydroxyl five yuan of melon cyclic group multi-pore channel heterocomplexs, is characterized in that indication is with Keggin-type phosphomolybdic acid [H 3pMo 12o 40] be derivant, hydroxyl five yuan of melon rings (HO) 10q [5] synthesizes a class phosphomolybdic acid-hydroxyl five yuan of melon cyclic group multi-pore channel heterocomplexs in aqueous solution of alkali metal salt, and the general formula of chemical composition is:
a{M b(H 2O) c(NO 3) d(HO) 10Q[5]}(PMo 12O 40) e (H 3O) f (H 2O)
In formula, a is quantity 0 < a≤2 that hydroxyl five yuan of melon rings and alkali metal ion form complex; M represents alkali metal ion; B is quantity 0 < b≤2 of coordination alkali metal ion; C is metallic ion coordination hydrone quantity 0≤c≤2; D is by (HO) 10quantity 0≤d≤1 of the nitrate anion of Q [5] inclusion; (HO) 10hydroxyl five yuan of melon rings selected by Q [5] representative; (PMo 12o 40) be Keggin-type phosphomolybdic acid [H 3pMo 12o 40] anion; E is quantity 1≤e≤15 of protonated hydrone; F is crystalline water molecules quantity 28≤f≤55.
2. phosphomolybdic acid-hydroxyl according to claim 1 five yuan of melon cyclic group multi-pore channel heterocomplexs, is characterized in that the alkali metal salt of indication is hydrochloride, bromide.
3. a class phosphomolybdic acid-hydroxyl according to claim 1 and 2 five yuan of melon cyclic group multi-pore channel heterocomplexs, is characterized in that the multi-pore channel heterocomplex synthesized is:
（1） [C 30H 30N 20O 20] (PMo 12O 40) 3(H 3O) 48(H 2O)
（2） 2{K 2(H 2O)(NO 3)(HO 10Q[5]} + (PMo 12O 40) 2-29(H 2O)
（3） {K(H 2O) 2HO 10Q[5]} 2(PMo 12O 40) (H 3O) 38(H 2O)
（4） 2(HO 10Q[5])·(Mo 12O 40P)·3(H 3O)·55(H 2O)。
4. a class phosphomolybdic acid-hydroxyl according to claim 3 five yuan of melon cyclic group multi-pore channel heterocomplexs, it is characterized in that the compound synthesized is yellow-green crystal, and to measure related crystalline structural parameters, X-ray powder diffraction and crystal structure basically identical, the crystal thermal analyses of multi-pore channel heterocomplex and infrared analysis confirm further to its structure.
5. the synthetic method of a class phosphomolybdic acid-hydroxyl as claimed in claim 1 five yuan of melon cyclic group multi-pore channel heterocomplexs, is characterized in that synthetic method follows these steps to carry out: (1) is by (HO) 10q [5], phosphomolybdic acid and alkali metal salt 1: 1 ~ 6: 0 ~ 10 batch weighings in molar ratio;
(2) said mixture matter be heated to dissolve completely with q.s distilled water and seethe with excitement 2 ~ 3 minutes, solution is yellow green, is cooled to room temperature;
(3) leave standstill 3 ~ 15 days under normal temperature, in precipitation, separate out microscler yellow-green crystal.
CN201310335249.3A 2013-08-05 2013-08-05 Phosphomolybdic acid-hydroxyl five yuan of melon cyclic group porous heterocomplexs and synthetic method thereof Expired - Fee Related CN103386326B (en)

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