CN105153205A - Copper-cyclotriphosphazene hexacarboxylic acid derivative coordination framework material and preparation and application thereof - Google Patents
Copper-cyclotriphosphazene hexacarboxylic acid derivative coordination framework material and preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a copper-cyclotriphosphazene hexacarboxylic acid derivative coordination framework material and a preparation method and application thereof. The coordination framework material is formed by adopting raw materials comprising copper ions and a ligand L through reaction, wherein the ligand L is hexa-(4-carboxylate benzoxy) cyclotriphosphazene and the chemical formula is C42H30O18N3P3; in addition, the coordination framework material is a three-dimensional framework material and has one-dimensional linear pore passages. By improving the composition and structure of the coordination framework material, various parameters in the preparation method and the like, the structurally ordered copper-cyclotriphosphazene hexacarboxylic acid derivative coordination framework materials can be obtained, the preparation method of the series of materials can effectively guarantee the reaction yield and the actual application is facilitated.
Description
Technical field
The invention belongs to transition-metal coordination frame material self-assembly field, more specifically, relate to one utilize ring three phosphonitrile derive hexacarboxylic acid part prepare copper-ring three phosphonitrile hexacarboxylic acid derivative coordination frame material, with and preparation method thereof with application; This frame material is the network frame material of gap structure, and have very special absorption property, application prospect is good.
Background technology
Coordination frame material, due to its specific pore passage structure, represents excellent application prospect in multiple Application Areas.But how orientation effectively constructs the material with specific frame structure and performance, is still the research emphasis of complex material worker.At present, the method for effective framing material still concentrates on choose reasonable and builds the organic ligand aspect with specific mode of connection and sterie configuration, and mostly is rigidity and has less connection site.There are some researches show, the linking number increasing part effectively can promote the resistance to overturning of material, and then can carry out various functionalized application.But mostly current used organic ligand is two connections or four connection site, and synthesis technique is comparatively loaded down with trivial details, cost is higher.[1-2]
Hexachlorocyclotriphosphazene is a kind of highly stable pure inorganic materials, and it is very convenient to utilize nucleophilic reaction to modify it, synthesis condition is very simple, therefore, take hexachlorocyclotriphosphazene as the organic ligand that bed material preparation has a multi-link pattern should be the route that a whole cost is lower.And this type of can have nearly six coordination arms with the organic ligand that ring three phosphonitrile obtains for template derives, and configuration has certain flexible characteristic, and this feature is very favorable for novel, that stability the is higher frame material of assembling topological framework.[3]
But, further research shows, although be that the derivative of template has These characteristics with hexachlorocyclotriphosphazene, often inner molecular structure arrangement is random for these derivatives, the derivative with ad hoc structure cannot be formed, thus inapplicable application scenario molecular arrangement being had to particular requirement.In addition, utilize hexachlorocyclotriphosphazene to react and generate derivative, the productive rate often reacted is not high, affects practical application.
Reference is as follows:
[1]Furukawa,H.；Yaghi,O.M.J.Am.Chem.Soc.2009,131,8875-8883.
[2]Zhang,J.P.；Huang,X.C.；Chen,X.M.Chem.Soc.Rev.2009,38,2385-2396.
[3]Li,B.；Dai,X.；Meng,X.；Zhang,T.；Liu,C.；Yu,K.DaltonTrans.2013,43,2558.
Summary of the invention
For above defect or the Improvement requirement of prior art, the object of the present invention is to provide a kind of copper-ring three phosphonitrile hexacarboxylic acid derivative coordination frame material, with and preparation method thereof with application, wherein pass through the composition to coordination frame material and structure, various parameters in preparation method are (as raw material type, concentration, temperature of reaction and time) etc. improve, compared with prior art can effectively solve with hexachlorocyclotriphosphazene is that the derivative inner molecular structure of template arranges random problem, and the preparation method corresponding with this copper-ring three phosphonitrile hexacarboxylic acid derivative coordination frame material effectively ensures reaction yield, be convenient to useful application.
For achieving the above object, according to one aspect of the present invention, provide a kind of copper-ring three phosphonitrile hexacarboxylic acid derivative coordination frame material, it is characterized in that, this coordination frame material adopts the raw material reaction comprising cupric ion and ligand L to be formed, and wherein said ligand L has following structure:
Preferably, this coordination frame material is three-dimensional framework material, and has one dimension linear duct.
As present invention further optimization, described copper-ring three phosphonitrile hexacarboxylic acid derivative coordination frame material, has following structure:
As present invention further optimization, described copper-ring three phosphonitrile hexacarboxylic acid derivative coordination frame material, has following structure:
As present invention further optimization, described cupric ion is from cupric nitrate.
For achieving the above object, according to another aspect of the present invention, provide a kind of preparation method of above-mentioned copper-ring three phosphonitrile hexacarboxylic acid derivative coordination frame material, it is characterized in that, comprise the following steps:
The synthesis of (1) six (4-methyl-formiate-phenoxy group) ring three phosphonitrile: in argon atmosphere, 1.5g hexachlorocyclotriphosphazene, 6.5g methyl p-hydroxybenzoate and 1g ~ 3g salt of wormwood is added in the acetone of 50mL ~ 70mL, then stir 5min ~ 10min, and the heat treated that refluxes at 60 DEG C ~ 70 DEG C forms the first mixing solutions at least 12 hours; Then, the acetone in the first mixing solutions described in evaporate to dryness, obtains white solid; Then, with white solid described in distilled water wash, then filter, then joining filtering the filter residue obtained in 40mL ~ 50mL ethyl acetate, being spin-dried for after stirring and dissolving, namely obtaining six (4-methyl-formiate-phenoxy group) ring three phosphonitrile;
(2) synthesis of ligand L: add six (4-methyl-formiate-phenoxy group) ring three phosphonitrile and the 6g ~ 10g sodium hydroxide obtained in step described in 5g (1) in 30mL ~ 50mL methyl alcohol, then 65 DEG C ~ 75 DEG C stirring heating reflow treatment at least 12 hours, then decompressing and extracting methyl alcohol obtains solid I; Then, the distilled water adding 150mL ~ 200mL in described solid I makes described solid I dissolve, and then filters, then adds hydrochloric acid in the filtrate obtained to filtration and make the pH value of described filtrate be 1 ~ 2, obtains white precipitate subsequently; Then refiltering, namely obtaining six-(4-carboxylic acid phenoxy group) ring triphosphine nitrile ligand L by filtering after the filter residue obtained is dried;
(3) synthesis of title complex:
8mg ~ 12mg six-(4-carboxylic acid phenoxy group) ring triphosphine nitrile ligand L and 24mg ~ 36mg cupric nitrate are joined by deionized water and N, in the mixed solvent that N '-dimethyl methane amide is formed, then ultrasonic reaction forms the second mixing solutions at least 5 minutes, and in described second mixing solutions, then add 0.2mL ~ 0.3mL2mol/L hydrochloric acid or aqueous nitric acid obtain presoma; Then, described presoma is obtained crystal in 48 hours ~ 96 hours 80 DEG C ~ 100 DEG C reactions, and then filter, namely the filter residue obtained after filtration obtains coordination frame material crystal after deionized water wash.
For achieving the above object, according to another aspect of the present invention, provide a kind of preparation method of above-mentioned copper-ring three phosphonitrile hexacarboxylic acid derivative coordination frame material, it is characterized in that, comprise the following steps:
The synthesis of (1) six (4-methyl-formiate-phenoxy group) ring three phosphonitrile: in argon atmosphere, 1.5g hexachlorocyclotriphosphazene, 6.5g methyl p-hydroxybenzoate and 1g ~ 3g salt of wormwood is added in the acetone of 50mL ~ 70mL, then stir 5min ~ 10min, and the heat treated that refluxes at 60 DEG C ~ 70 DEG C forms the first mixing solutions at least 12 hours; Then, the acetone in the first mixing solutions described in evaporate to dryness, obtains white solid; Then, with white solid described in distilled water wash, then filter, then joining filtering the filter residue obtained in 40mL ~ 50mL ethyl acetate, being spin-dried for after stirring and dissolving, namely obtaining six (4-methyl-formiate-phenoxy group) ring three phosphonitrile;
(2) synthesis of ligand L: add six (4-methyl-formiate-phenoxy group) ring three phosphonitrile and the 6g ~ 10g sodium hydroxide obtained in step described in 5g (1) in 30mL ~ 50mL methyl alcohol, then 65 DEG C ~ 75 DEG C stirring heating reflow treatment at least 12 hours, then decompressing and extracting methyl alcohol obtains solid I; Then, the distilled water adding 150mL ~ 200mL in described solid I makes described solid I dissolve, and then filters, then adds hydrochloric acid in the filtrate obtained to filtration and make the pH value of described filtrate be 1 ~ 2, obtains white precipitate subsequently; Then refilter, filter after the filter residue obtained is dried and namely obtain six-(4-carboxylic acid phenoxy group) ring triphosphine nitrile ligand L;
(3) synthesis of title complex:
By 16mg ~ 24mg six-(4-carboxylic acid phenoxy group) ring triphosphine nitrile ligand L and 8mg ~ 12mg cupric nitrate, 8mg ~ 12mg4,4 '-dipyridyl joins by deionized water and N, in the mixed solvent that N '-dimethyl methane amide is formed, then ultrasonic reaction forms the 3rd mixing solutions at least 5 minutes, and in described 3rd mixing solutions, then add 0.2mL ~ 0.3mL2mol/L hydrochloric acid or aqueous nitric acid obtain presoma; Then, described presoma is obtained crystal in 48 hours ~ 96 hours 80 DEG C ~ 100 DEG C reactions, and then filter, namely the filter residue obtained after filtration obtains coordination frame material crystal after deionized water wash.
As present invention further optimization, the methyl p-hydroxybenzoate in described step (1) is prepared as follows: add in round-bottomed flask the methyl alcohol of 40mL ~ 60mL, 6g P-hydroxybenzoic acid and 1mL ~ 2mL mass percentage concentration be 98% the vitriol oil form the first mixed system; Then, by described first mixed system at 65 DEG C ~ 75 DEG C reflux process 4h ~ 6h, then evaporate to dryness methyl alcohol is precipitated, then precipitates with described in distilled water wash, namely obtains product methyl p-hydroxybenzoate after oven dry.
As in the present invention further preferably, by deionized water and N in described step (3), N in the mixed solvent that N '-dimethyl methane amide is formed, the volume ratio of N '-dimethyl methane amide and deionized water is 3:2 ~ 2:1.
As in the present invention further preferably, by deionized water and N in described step (3), N in the mixed solvent that N '-dimethyl methane amide is formed, the volume ratio of N '-dimethyl methane amide and deionized water is 10:1.5 ~ 5:1.
For achieving the above object, according to another aspect of the present invention, provide the application of a kind of above-mentioned copper-ring three phosphonitrile hexacarboxylic acid derivative coordination frame material as sorbing material.
By the above technical scheme that the present invention conceives, compared with prior art, following beneficial effect can be obtained:
1. the present invention constructs formation frame material by deriving hexacarboxylic acid part with ring triphosphine nitrile, self-assembly forms topological framework novelty, frame material that stability is higher, this frame material is prepared by six-(4-carboxylic acid phenoxy group) ring triphosphine nitrile part and cupric ion, copper-ring three phosphonitrile hexacarboxylic acid derivative coordination the frame material formed has one-dimensional tunnel structure, good adsorption performance.
This coordination frame material effectively can increase the linking number (coordination arm number reaches 6) of part, its basic list of coordination units is six core copper bunch secondary construction units, be connected to form three-dimensional network configuration by derivative hexacarboxylic acid part between six core copper bunch, one-dimensional channels is retained in crystalline structure.This copper-ring three phosphonitrile hexacarboxylic acid derivative coordination frame material, structurally ordered, one-dimensional tunnel structure makes it have good specific surface area parameter, material monolithic good stability.
2. preparation method of the present invention is the precursor solution that employing six-(4-carboxylic acid phenoxy group) ring triphosphine nitrile ligand L and cupric nitrate form solvent thermal reaction, by the concentration to precursor solution, the concrete preparation process of each raw material, a series of parameter such as the condition of solvent thermal reaction is optimized, enormously simplify the synthesis technique of copper-ring three phosphonitrile hexacarboxylic acid derivative coordination frame material, have easy, higher and the repeatable strong feature of productive rate, copper-ring three phosphonitrile hexacarboxylic acid derivative coordination frame material of synthesis has one-dimensional tunnel structure, be conducive to expanding the synthesis scope utilizing ring triphosphine nitrile derived ligand to construct the frame material with specific absorption property, and greatly can reduce preparation cost.
The present invention also preferred preparation to methyl p-hydroxybenzoate adjusts, with the preparation requirement making its parameters (as purity, globule size) etc. more meet copper-ring three phosphonitrile hexacarboxylic acid derivative coordination frame material.
3. copper-ring three phosphonitrile hexacarboxylic acid derivative coordination the frame material in the present invention, owing to having one-dimensional tunnel structure, specific surface area is large, can be used as sorbing material (as molecular sieve etc.); Because the one-dimensional channels aperture of copper-ring three phosphonitrile hexacarboxylic acid derivative coordination frame material can reach 0.6nm ~ 0.8nm, well N can be adsorbed
2, H
2, CO
2deng micro-molecular gas; When applying, frame material can be ground into powder, adsorbable micro-molecular gas after vacuumizing in 120 DEG C of baking ovens.
Accompanying drawing explanation
Fig. 1 is the minimum asymmetric cell structural representation of the embodiment of the present invention 1 middle frame material 1;
Fig. 2 is title complex 1 three-dimensional frame structure schematic diagram in the embodiment of the present invention 1;
Fig. 3 is title complex 1 six core copper bunch secondary construction unit schematic diagram in the embodiment of the present invention 1;
Fig. 4 is the minimum asymmetric cell structural representation of title complex 2 in the embodiment of the present invention 2;
Fig. 5 is title complex 2 three-dimensional frame structure schematic diagram in the embodiment of the present invention 2.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.In addition, if below in described each embodiment of the present invention involved technical characteristic do not form conflict each other and just can mutually combine.
The preparation of embodiment 1 title complex 1
Preparation method is as follows for six-(4-carboxylic acid phenoxy group) ring three phosphonitriles:
First synthesize methyl p-hydroxybenzoate, take 6g P-hydroxybenzoic acid with electronic balance, join in 100ml round-bottomed flask, then about 50ml methyl alcohol is added, drip about 15 vitriol oils (mass percentage concentration is 98%), after 70 DEG C of backflow 4h, obtain colourless transparent solution, remove reaction unit, evaporate to dryness methyl alcohol, finally uses distilled water wash, obtains 7g white product (i.e. methyl p-hydroxybenzoate), dry for standby, productive rate is about 93%.Secondly, the hexachlorocyclotriphosphazene (drying 5h at 50 DEG C) after 1.5g (0.0043mol) distillation is added under Ar atmosphere, 6.5g (0.043mol) methyl p-hydroxybenzoate (drying), about 1g salt of wormwood (can dry about 1-2h at 120 DEG C, guarantee drying), then (deoxygenation that needs to dewater is refined to add 50ml acetone, such as, Vanadium Pentoxide in FLAKES can be added in acetone to dewater deoxygenation, and then distill obtain refining after acetone), stir, solution becomes muddy state, after continuing to stir for some time, solution is clarified gradually, be warming up to 65 DEG C of reactions to spend the night, second day, reaction soln clarification is (because product is dissolved in acetone, therefore solution clarification), remove reaction unit, evaporate to dryness acetone, obtain a large amount of white solid, then add a large amount of distilled water and wash away excessive potash solid, filter, obtain crude product, gained crude product is added in the ethyl acetate of 40ml, abundant stirring, obtain settled solution, be spin-dried for (such as, available revolve steam instrument decompression steam solvent ethyl acetate, the temperature used can lower than the boiling point of ethyl acetate, as at 45 DEG C ~ 55 DEG C), obtain 4g six (4-methyl-formiate-phenoxy group) ring three phosphonitrile white solid, productive rate is about 90%.
Finally, six (4-methyl-formiate-phenoxy group) ring three phosphonitrile white solids and excessive sodium hydrate solid are put into flask, add the methyl alcohol of about 30ml, 70 DEG C time, stirring and refluxing is spent the night, decompressing and extracting methyl alcohol, then add a large amount of distilled water to stir, solid dissolves substantially completely, then filter, obtain clear soln, add rare HCl, pH is regulated to make its pH ≈ 2, in adjustment pH process, have a large amount of white precipitate slowly to separate out, last solid collected by filtration (i.e. six-(4-carboxylic acid phenoxy group) ring three phosphonitriles), for subsequent use after drying, productive rate is about 85%.
Six-(4-carboxylic acid phenoxy group) ring three phosphonitriles, its chemical formula is C
42h
30o
18n
3p
3, its structural formula is as follows:
Six-(4-carboxylic acid phenoxy group) ring three phosphonitriles can be used as ring triphosphine nitrile and derive hexacarboxylic acid part.
The synthesis preparation method of title complex 1 of the present invention is as follows:
First take 10mg six-(4-carboxylic acid phenoxy group) ring three phosphonitrile and 30mg cupric nitrate, add 5mL deionized water and 10mLN, N '-dimethyl methane amide, ultrasonic reaction, after 5 minutes, drips 5 2molL
-1aqueous hydrochloric acid, obtain blue clear filtrate (i.e. solvent thermal reaction precursor liquid); This blue clear filtrate is joined in hydrothermal reaction kettle, and this reactor is placed in 80 DEG C of baking ovens, grow blue needle-like crystal after 48 hours, filter and use suitable deionized water wash, the finished product title complex 1 (this title complex 1 i.e. frame material 1) can be obtained.The productive rate of above-mentioned title complex 1 is about 45%, and has following structure:
The preparation of embodiment 2 title complex 2
Six-(4-carboxylic acid phenoxy group) ring three phosphonitrile preparation methods are with embodiment 1.
The synthesis preparation method of title complex 2 is as follows:
First take 20mg six-(4-carboxylic acid phenoxy group) ring three phosphonitrile, 10mg cupric nitrate and 10mg4,4 '-dipyridyl, add 1.5mL deionized water and 10mLN, N '-dimethyl methane amide, ultrasonic reaction, after 5 minutes, drips 5 2molL
-1aqueous nitric acid, obtain solvent thermal reaction precursor liquid; This precursor liquid is added in hydrothermal reaction kettle, and reactor is placed in 100 DEG C of baking oven reactions 4 days, then obtain blue rhabdolith with the cooling of the speed of 5 DEG C/h, filter and use suitable deionized water wash, the finished product title complex 2 (title complex 2 i.e. frame material 2) can be obtained; This title complex 2 has following structure:
In the present invention, the crystal structure determination method of title complex is as follows:
Choose the single crystal samples of 0.20mm × 0.05mm × 0.05mm size, be placed in OxfordGeminiSUltra single crystal diffractometer, utilize Mo-K
α for source-collector crystal data, data empirical absorption is corrected and is then completed from tape program CrysAlisRED by instrument.Manually complete structure elucidation and refine by SHELXS-97 program, utilize complete matrix method of least squares (full-matrixleast-squaresrefinementbasedonF
2) obtain all non-hydrogen atoms and carry out anisotropy refine.On part, hydrogen atom is then manually produced by geometry symmetry
At 298 (2) K temperature, OxfordGeminiSUltradiffractometer uses Mo-K
α collect crystal data, above-mentioned title complex 1 belongs to trigonal system, and spacer is P
-3c1,
z value is 4; Its basic construction unit is six core copper bunch secondary construction units, and be connected to form three-dimensional network configuration by derivative hexacarboxylic acid part between six core copper bunch, one-dimensional channels is retained in crystalline structure.Said frame material 2 belongs to trigonal system, and spacer is PC2/c,
its basic construction unit is six core copper bunch, and be connected to form three-dimensional network configuration by derivative hexacarboxylic acid part between six core copper bunch, one-dimensional channels is retained in crystalline structure.
Middle frame material of the present invention (title complex 1) absorption property result is as follows:
The final frame material of preparation 100mg, methyl alcohol steeps 2 days post-dryings, then steeps oven dry in 2 days with acetone, utilizes ASAP-2020 to measure its nitrogen and carbon dioxide adsorption ability.Frame material described herein is at the adsorbable nitrogen 115cm of 77K
3/ g, Brunauer-Emmett-Teller and Langmuir surface-area can reach 342m
2/ g and 568m
2/ g; During 77K, carbon dioxide adsorption can reach 21cm
3/ g.
The present invention, by the self-assembling technique of transition-metal coordination frame material, forms the frame material of complex form; Find through structural analysis, this three-dimensional framework material prolongs pore passage structure (the i.e. one-dimensional tunnel structure a certain crystal orientation having and runs through up and down; In other directions vertical with this crystal orientation, all there is no the pore passage structure that other run through), there is excellent absorption property.In frame material 1, ring triphosphine nitrile derives six carboxyl functional groups all de-protons of hexacarboxylic acid part, and forms coordinate bond with cupric ion; Plane six core copper bunch secondary construction unit is connected to form by carboxyl functional group between cupric ion; Each six core copper bunch connect 8 different hexacarboxylic acid parts, and each hexacarboxylic acid part takes tetrahedral configuration to connect 4 different six core copper bunch, finally form the three-dimensional network that topological framework is 4,8T11 configurations; One-dimensional channels is retained in crystalline structure.In frame material 2, ring triphosphine nitrile derives six carboxyl functional groups all de-protons of hexacarboxylic acid part, and form coordinate bond with cupric ion, copper in this structure has two kinds of coordination environments, one is pentacoordinate pattern, respectively with the Sauerstoffatom in two water moleculess, and the carboxyl oxygen atom and 4 in two ring three phosphonitrile hexacarboxylic acid parts, nitrogen-atoms coordination in 4 '-dipyridyl, and each hexacarboxylic acid part connects the three-dimensional net structure that a cupric ion formation has one-dimensional channels.
The preparation of embodiment 3 title complex 1
(1) part synthesis: in argon atmosphere, add 1.5g hexachlorocyclotriphosphazene, 6.5g methyl p-hydroxybenzoate and 1g salt of wormwood in 50ml acetone, then stir 5min, and be heated to 60 DEG C of reactions, 20 hours formation mixing solutionss; Then, the acetone in mixing solutions described in evaporate to dryness, obtains white solid; Then, with white solid described in distilled water wash, then filter, then joining in 40ml ethyl acetate by filtering the filter residue obtained, being spin-dried for after dissolving after stirring, namely obtaining six (4-methyl-formiate-phenoxy group) ring three phosphonitrile; In 30mL methyl alcohol, add 5g six (4-methyl-formiate-phenoxy group) ring three phosphonitrile and 6g sodium hydroxide then 65 DEG C of stirring heating backflows at least 12 hours, then decompressing and extracting methyl alcohol obtains solid I; Then, in described solid I, add 150mL distilled water described solid I is dissolved, then filter, then add dilute hydrochloric acid in the filtrate obtained to filtration and make the pH value of described filtrate be 2 obtain white precipitate; Then refilter, filter after the filter residue obtained is dried and namely obtain six-(4-carboxylic acid phenoxy group) ring triphosphine nitrile ligand L;
(2) Opacity in lens: 8mg six-(4-carboxylic acid phenoxy group) ring triphosphine nitrile and 24mg cupric nitrate are joined by deionized water and N, in the mixed solvent that N '-dimethyl methane amide volume ratio 1:2 is formed, then ultrasonic reaction forms mixing solutions at least 5 minutes, and the aqueous hydrochloric acid then adding 0.2mL2mol/L in described mixing solutions obtains presoma; Then, described presoma is obtained crystal in 96 hours 80 DEG C of reactions, and then filter, namely the filter residue obtained after filtration obtains coordination frame material crystal after deionized water wash.
The preparation of embodiment 4 title complex 1
(1) part synthesis: in argon atmosphere, add 1.5g hexachlorocyclotriphosphazene, 6.5g methyl p-hydroxybenzoate and 2g salt of wormwood in 60ml acetone, then stir 8min, and be heated to 65 DEG C of reactions, 18 hours formation mixing solutionss; Then, the acetone in mixing solutions described in evaporate to dryness, obtains white solid; Then, with white solid described in distilled water wash, then filter, then joining in 45ml ethyl acetate by filtering the filter residue obtained, being spin-dried for after dissolving after stirring, namely obtaining six (4-methyl-formiate-phenoxy group) ring three phosphonitrile; In 40mL methyl alcohol, add 5g six (4-methyl-formiate-phenoxy group) ring three phosphonitrile and 8g sodium hydroxide then 70 DEG C of stirring heating backflows at least 12 hours, then decompressing and extracting methyl alcohol obtains solid I; Then, in described solid I, add 200mL distilled water described solid I is dissolved, then filter, then add dilute hydrochloric acid in the filtrate obtained to filtration and make the pH value of described filtrate be 2 obtain white precipitate; Then refilter, filter after the filter residue obtained is dried and namely obtain six-(4-carboxylic acid phenoxy group) ring triphosphine nitrile ligand L;
(2) Opacity in lens: 10mg six-(4-carboxylic acid phenoxy group) ring triphosphine nitrile and 30mg cupric nitrate are joined by deionized water and N, in the mixed solvent that N '-dimethyl methane amide volume ratio 1:2 is formed, then ultrasonic reaction forms mixing solutions at least 5 minutes, and the aqueous hydrochloric acid then adding 0.25mL2mol/L in described mixing solutions obtains presoma; Then, described presoma is obtained crystal in 72 hours 90 DEG C of reactions, and then filter, namely the filter residue obtained after filtration obtains coordination frame material crystal after deionized water wash.
The preparation of embodiment 5 title complex 1
(1) part synthesis: in argon atmosphere, add 1.5g hexachlorocyclotriphosphazene, 6.5g methyl p-hydroxybenzoate and 3g salt of wormwood in 70ml acetone, then stir 10min, and be heated to 70 DEG C of reactions, 15 hours formation mixing solutionss; Then, the acetone in mixing solutions described in evaporate to dryness, obtains white solid; Then, with white solid described in distilled water wash, then filter, then joining in 50ml ethyl acetate by filtering the filter residue obtained, being spin-dried for after dissolving after stirring, namely obtaining six (4-methyl-formiate-phenoxy group) ring three phosphonitrile; In 50mL methyl alcohol, add 5g six (4-methyl-formiate-phenoxy group) ring three phosphonitrile and 10g sodium hydroxide then 75 DEG C of stirring heating backflows at least 12 hours, then decompressing and extracting methyl alcohol obtains solid I; Then, in described solid I, add 250mL distilled water described solid I is dissolved, then filter, then add dilute hydrochloric acid in the filtrate obtained to filtration and make the pH value of described filtrate be 1 obtain white precipitate; Then refilter, filter after the filter residue obtained is dried and namely obtain six-(4-carboxylic acid phenoxy group) ring triphosphine nitrile ligand L;
(2) Opacity in lens: 12mg six-(4-carboxylic acid phenoxy group) ring triphosphine nitrile and 36mg cupric nitrate are joined by deionized water and N, in the mixed solvent that N '-dimethyl methane amide volume ratio 1:2 is formed, then ultrasonic reaction forms mixing solutions at least 5 minutes, and the aqueous hydrochloric acid then adding 0.3mL2mol/L in described mixing solutions obtains presoma; Then, described presoma is obtained crystal in 48 hours 100 DEG C of reactions, and then filter, namely the filter residue obtained after filtration obtains coordination frame material crystal after deionized water wash.
The preparation of embodiment 6 title complex 2
Difference from Example 2 is only:
By 16mg six-(4-carboxylic acid phenoxy group) ring triphosphine nitrile and 8mL cupric nitrate, 8mg4,4 '-dipyridyl joins by deionized water and N, N '-dimethyl methane amide volume ratio is in the mixed solvent of 1:5 formation, then ultrasonic reaction forms mixing solutions at least 5 minutes, and the aqueous nitric acid then adding 0.2mL2mol/L in described mixing solutions obtains presoma; Then, described presoma is obtained crystal in 96 hours 80 DEG C of reactions, and then filter, namely the filter residue obtained after filtration obtains coordination frame material crystal after deionized water wash.
The preparation of embodiment 7 title complex 2
Only be with the difference of embodiment 2:
By 24mg six-(4-carboxylic acid phenoxy group) ring triphosphine nitrile and 12mg cupric nitrate, 12mg4,4 '-dipyridyl joins by deionized water and N, in the mixed solvent that N '-dimethyl methane amide volume ratio 1:5 is formed, then ultrasonic reaction forms mixing solutions at least 5 minutes, and the aqueous nitric acid then adding 0.3mL2mol/L in described mixing solutions obtains presoma; Then, described presoma is obtained crystal in 48 hours 100 DEG C of reactions, and then filter, namely the filter residue obtained after filtration obtains coordination frame material crystal after deionized water wash.
The preparation of embodiment 8 title complex 1
Only be with the difference of embodiment 1: take 10mg six-(4-carboxylic acid phenoxy group) ring three phosphonitrile and 30mg cupric nitrate, join by deionized water and N, in the mixed solvent that N '-dimethyl methane amide volume ratio 2:3 is formed, ultrasonic reaction, after 5 minutes, drips 5 2molL
-1aqueous hydrochloric acid, obtain precursor liquid; This precursor liquid is joined in hydrothermal reaction kettle, and this reactor is placed in 80 DEG C of baking ovens, after 48 hours, grow blue needle-like crystal, filter and use suitable deionized water wash, the finished product title complex 1 can be obtained.
Frame material in above-described embodiment can also combine with counter cation and/or guest molecule X, is filled in duct by X, forms [Cu
6(L)
2(H
2o)
6] X, wherein L is six-(4-carboxylic acid phenoxy group) ring triphosphine nitrile parts.
In order to further illustrate technique effect of the present invention, provide following comparative example.
Comparative example 1
Similar with the growth conditions of embodiment 1, to calculate by proportioning and ring three phosphonitrile weighed derives hexacarboxylic acid ligand L and appropriate cadmium nitrate is dissolved in N, in the mixing solutions of N '-dimethyl methane amide and water, ultrasonic rear taking-up adds appropriate amount of acid, then solvent thermal reaction is carried out in 80-100 DEG C, grow two kinds of clear crystals after 3 days, filter and use suitable deionized water wash, can the finished product be obtained.Through crystal structure analysis, a kind of crystalline structure is 3-D solid structure, and another kind of crystalline structure is two-dimension plane structure, and two kinds of crystal are all without one-dimensional channels.
Comparative example 2
Similar with the growth conditions of embodiment 1, to calculate by proportioning and ring three phosphonitrile weighed derives hexacarboxylic acid ligand L and appropriate zinc nitrate is dissolved in N, in N '-dimethyl methane amide, ultrasonic rear taking-up adds appropriate amount of acid, then solvent thermal reaction is carried out in 80 DEG C, grow bulk crystals after 3 days, filter and use suitable deionized water wash, can the finished product be obtained.Through crystal structure analysis, this crystalline structure is 3-D solid structure, but without one-dimensional channels.
Title complex 1 and 2 in the present invention is one-dimensional tunnel structure, the aperture of title complex 1 can reach 0.8nm, the aperture of title complex 2 can reach 0.6nm, also can be used as mesopore molecular sieve as new catalystic material or support of the catalyst, the aperture utilizing it larger increases velocity of diffusion.Its adsorption effect of title complex 1 and 2 in the embodiment of the present invention, for the crystal of comparative example 1,2, has the raising of certain degree, advantages of good adsorption effect.The methyl p-hydroxybenzoate used in the present invention, its preparation parameter, except in embodiment 1, can also be:
The vitriol oil formation mixed system I that the methyl alcohol of 40mL, 6g P-hydroxybenzoic acid and 1mL mass percentage concentration are 98% is added in round-bottomed flask; Then, by described mixed system I at 65 DEG C of reflux process 6h, then evaporate to dryness methyl alcohol is precipitated, then precipitates with described in distilled water wash, namely obtains product methyl p-hydroxybenzoate after oven dry.Or, in round-bottomed flask, add the vitriol oil formation mixed system I that the methyl alcohol of 60mL, 6g P-hydroxybenzoic acid and 2mL mass percentage concentration are 98%; Then, by described mixed system I at 75 DEG C of reflux process 4h, then evaporate to dryness methyl alcohol is precipitated, then precipitates with described in distilled water wash, namely obtains product methyl p-hydroxybenzoate after oven dry.
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. copper-ring three phosphonitrile hexacarboxylic acid derivative coordination frame material, is characterized in that, this coordination frame material adopts the raw material reaction comprising cupric ion and ligand L to be formed, and wherein said ligand L has following structure:
Preferably, this coordination frame material is three-dimensional framework material, and has one dimension linear duct.
2. copper-ring three phosphonitrile hexacarboxylic acid derivative coordination frame material as claimed in claim 1, it is characterized in that, described copper-ring three phosphonitrile hexacarboxylic acid derivative coordination frame material, has following structure:
3. copper-ring three phosphonitrile hexacarboxylic acid derivative coordination frame material as claimed in claim 1, it is characterized in that, described copper-ring three phosphonitrile hexacarboxylic acid derivative coordination frame material, has following structure:
4. copper-ring three phosphonitrile hexacarboxylic acid derivative coordination frame material as claimed in claim 1, it is characterized in that, described cupric ion is from cupric nitrate.
5. the method for preparation copper-ring three phosphonitrile hexacarboxylic acid derivative coordination frame material as described in claim 1,2 or 4, is characterized in that, comprise the following steps:
The synthesis of (1) six (4-methyl-formiate-phenoxy group) ring three phosphonitrile: in argon atmosphere, 1.5g hexachlorocyclotriphosphazene, 6.5g methyl p-hydroxybenzoate and 1g ~ 3g salt of wormwood is added in the acetone of 50mL ~ 70mL, then stir 5min ~ 10min, and the heat treated that refluxes at 60 DEG C ~ 70 DEG C forms the first mixing solutions at least 12 hours; Then, the acetone in the first mixing solutions described in evaporate to dryness, obtains white solid; Then, with white solid described in distilled water wash, then filter, then joining filtering the filter residue obtained in 40mL ~ 50mL ethyl acetate, being spin-dried for after stirring and dissolving, namely obtaining six (4-methyl-formiate-phenoxy group) ring three phosphonitrile;
(2) synthesis of ligand L: add six (4-methyl-formiate-phenoxy group) ring three phosphonitrile and the 6g ~ 10g sodium hydroxide obtained in step described in 5g (1) in 30mL ~ 50mL methyl alcohol, then 65 DEG C ~ 75 DEG C stirring heating reflow treatment at least 12 hours, then decompressing and extracting methyl alcohol obtains solid I; Then, the distilled water adding 150mL ~ 200mL in described solid I makes described solid I dissolve, and then filters, then adds hydrochloric acid in the filtrate obtained to filtration and make the pH value of described filtrate be 1 ~ 2, obtains white precipitate subsequently; Then refiltering, namely obtaining six-(4-carboxylic acid phenoxy group) ring triphosphine nitrile ligand L by filtering after the filter residue obtained is dried;
(3) synthesis of title complex:
8mg ~ 12mg six-(4-carboxylic acid phenoxy group) ring triphosphine nitrile ligand L and 24mg ~ 36mg cupric nitrate are joined by deionized water and N, in the mixed solvent that N '-dimethyl methane amide is formed, then ultrasonic reaction forms the second mixing solutions at least 5 minutes, and in described second mixing solutions, then add 0.2mL ~ 0.3mL2mol/L hydrochloric acid or aqueous nitric acid obtain presoma; Then, described presoma is obtained crystal in 48 hours ~ 96 hours 80 DEG C ~ 100 DEG C reactions, and then filter, namely the filter residue obtained after filtration obtains coordination frame material crystal after deionized water wash.
6. the method for preparation copper-ring three phosphonitrile hexacarboxylic acid derivative coordination frame material as described in claim 1,3 or 4, is characterized in that, comprise the following steps:
The synthesis of (1) six (4-methyl-formiate-phenoxy group) ring three phosphonitrile: in argon atmosphere, 1.5g hexachlorocyclotriphosphazene, 6.5g methyl p-hydroxybenzoate and 1g ~ 3g salt of wormwood is added in the acetone of 50mL ~ 70mL, then stir 5min ~ 10min, and the heat treated that refluxes at 60 DEG C ~ 70 DEG C forms the first mixing solutions at least 12 hours; Then, the acetone in the first mixing solutions described in evaporate to dryness, obtains white solid; Then, with white solid described in distilled water wash, then filter, then joining filtering the filter residue obtained in 40mL ~ 50mL ethyl acetate, being spin-dried for after stirring and dissolving, namely obtaining six (4-methyl-formiate-phenoxy group) ring three phosphonitrile;
(2) synthesis of ligand L: add six (4-methyl-formiate-phenoxy group) ring three phosphonitrile and the 6g ~ 10g sodium hydroxide obtained in step described in 5g (1) in 30mL ~ 50mL methyl alcohol, then 65 DEG C ~ 75 DEG C stirring heating reflow treatment at least 12 hours, then decompressing and extracting methyl alcohol obtains solid I; Then, the distilled water adding 150mL ~ 200mL in described solid I makes described solid I dissolve, and then filters, then adds hydrochloric acid in the filtrate obtained to filtration and make the pH value of described filtrate be 1 ~ 2, obtains white precipitate subsequently; Then refilter, filter after the filter residue obtained is dried and namely obtain six-(4-carboxylic acid phenoxy group) ring triphosphine nitrile ligand L;
(3) synthesis of title complex:
By 16mg ~ 24mg six-(4-carboxylic acid phenoxy group) ring triphosphine nitrile ligand L, 8mg ~ 12mg cupric nitrate and 8mg ~ 12mg4,4 '-dipyridyl joins by deionized water and N, in the mixed solvent that N '-dimethyl methane amide is formed, then ultrasonic reaction forms the 3rd mixing solutions at least 5 minutes, and in described 3rd mixing solutions, then add 0.2mL ~ 0.3mL2mol/L hydrochloric acid or aqueous nitric acid obtain presoma; Then, described presoma is obtained crystal in 48 hours ~ 96 hours 80 DEG C ~ 100 DEG C reactions, and then filter, namely the filter residue obtained after filtration obtains coordination frame material crystal after deionized water wash.
7. the preparation method of copper-ring three phosphonitrile hexacarboxylic acid derivative coordination frame material as described in claim 5 or 6, it is characterized in that, the methyl p-hydroxybenzoate in described step (1) is prepared as follows: add in round-bottomed flask the methyl alcohol of 40mL ~ 60mL, 6g P-hydroxybenzoic acid and 1mL ~ 2mL mass percentage concentration be 98% the vitriol oil form the first mixed system; Then, by described first mixed system at 65 DEG C ~ 75 DEG C reflux process 4h ~ 6h, then evaporate to dryness methyl alcohol is precipitated, then precipitates with described in distilled water wash, namely obtains product methyl p-hydroxybenzoate after oven dry.
8. the preparation method of copper-ring three phosphonitrile hexacarboxylic acid derivative coordination frame material as claimed in claim 5, it is characterized in that, by deionized water and N in described step (3), N in the mixed solvent that N '-dimethyl methane amide is formed, the volume ratio of N '-dimethyl methane amide and deionized water is 3:2 ~ 2:1.
9. the preparation method of copper-ring three phosphonitrile hexacarboxylic acid derivative coordination frame material as claimed in claim 6, it is characterized in that, by deionized water and N in described step (3), N in the mixed solvent that N '-dimethyl methane amide is formed, the volume ratio of N '-dimethyl methane amide and deionized water is 10:1.5 ~ 5:1.
10. as described in claim 1-4 any one copper-ring three phosphonitrile hexacarboxylic acid derivative coordination frame material as the application of sorbing material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108752637A (en) * | 2018-08-01 | 2018-11-06 | 河北大学 | A kind of ZIF-8 encapsulation hexachlorocyclotriph,sphazene fire retardant, preparation method and application and fire retarding epoxide resin |
| CN108948088A (en) * | 2018-06-28 | 2018-12-07 | 江汉大学 | A kind of nickel-two-fold penetration metal organic frame and its preparation method and application |
| CN112885614A (en) * | 2021-01-19 | 2021-06-01 | 广东工业大学 | Nickel-based metal organic framework derived nitrogen-phosphorus-oxygen co-doped nickel/carbon composite material and preparation method and application thereof |
| CN113372529A (en) * | 2021-04-26 | 2021-09-10 | 北京化工大学 | Preparation method of polyphosphazene self-repairing elastomer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1669165A (en) * | 2002-06-19 | 2005-09-14 | 株式会社普利司通 | Supporting electrolyte for cell and method for production thereof, and cell |
| CN104478934A (en) * | 2014-12-11 | 2015-04-01 | 三峡大学 | Cyclotriphosphonitrile phenanthrene flame retardant containing bisoxacyclocaprolactone phosphate as well as preparation method and application thereof |
| CN104478935A (en) * | 2014-12-15 | 2015-04-01 | 四川大学 | Preparation method of nitrophenoxy cyclotriphosphazene flame retardant |
| CN104788495A (en) * | 2015-04-14 | 2015-07-22 | 淄博蓝印化工有限公司 | Fluorination method for phosphonitrilic chloride trimer and derivatives thereof |
-
2015
- 2015-09-10 CN CN201510572507.9A patent/CN105153205B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1669165A (en) * | 2002-06-19 | 2005-09-14 | 株式会社普利司通 | Supporting electrolyte for cell and method for production thereof, and cell |
| CN104478934A (en) * | 2014-12-11 | 2015-04-01 | 三峡大学 | Cyclotriphosphonitrile phenanthrene flame retardant containing bisoxacyclocaprolactone phosphate as well as preparation method and application thereof |
| CN104478935A (en) * | 2014-12-15 | 2015-04-01 | 四川大学 | Preparation method of nitrophenoxy cyclotriphosphazene flame retardant |
| CN104788495A (en) * | 2015-04-14 | 2015-07-22 | 淄博蓝印化工有限公司 | Fluorination method for phosphonitrilic chloride trimer and derivatives thereof |
Non-Patent Citations (1)
| Title |
|---|
| BAO LI等: "Luminescent Response of One Anionic Metal−Organic Framework Based on Novel Octa-nuclear Zinc Cluster to Exchanged Cations", 《CRYST. GROWTH DES.》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108948088A (en) * | 2018-06-28 | 2018-12-07 | 江汉大学 | A kind of nickel-two-fold penetration metal organic frame and its preparation method and application |
| CN108752637A (en) * | 2018-08-01 | 2018-11-06 | 河北大学 | A kind of ZIF-8 encapsulation hexachlorocyclotriph,sphazene fire retardant, preparation method and application and fire retarding epoxide resin |
| CN108752637B (en) * | 2018-08-01 | 2020-02-14 | 河北大学 | ZIF-8 packaged hexachlorocyclotriphosphazene flame retardant, preparation method and application thereof, and flame-retardant epoxy resin |
| CN112885614A (en) * | 2021-01-19 | 2021-06-01 | 广东工业大学 | Nickel-based metal organic framework derived nitrogen-phosphorus-oxygen co-doped nickel/carbon composite material and preparation method and application thereof |
| CN113372529A (en) * | 2021-04-26 | 2021-09-10 | 北京化工大学 | Preparation method of polyphosphazene self-repairing elastomer |
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