CN105153205B - The phosphonitrile hexacarboxylic acid derivative of copper ring three is coordinated frame material and its preparation and application - Google Patents
The phosphonitrile hexacarboxylic acid derivative of copper ring three is coordinated frame material and its preparation and application Download PDFInfo
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- CN105153205B CN105153205B CN201510572507.9A CN201510572507A CN105153205B CN 105153205 B CN105153205 B CN 105153205B CN 201510572507 A CN201510572507 A CN 201510572507A CN 105153205 B CN105153205 B CN 105153205B
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Abstract
The invention discloses a kind of phosphonitrile hexacarboxylic acid derivative of copper ring three coordination frame material and preparation method and application, the coordination frame material is used and formed including the raw material reaction including copper ion and ligand L, wherein described ligand L is six (4 carboxylic acid phenoxy group) phosphonitriles of ring three, and its chemical formula is C42H30O18N3P3；Additionally, the coordination frame material is three-dimensional framework material, and with one-dimensional linear duct.The present invention is improved by various parameters to being coordinated in the composition of frame material and structure, preparation method etc., it is obtained in that the structurally ordered phosphonitrile hexacarboxylic acid derivative of copper ring three coordination frame material, and the preparation method of the series material can effectively ensure that reaction yield, be easy to useful application.
Description
Technical field
The invention belongs to transition-metal coordination frame material self assembly field, the phosphorus of ring three is utilized more particularly, to one kind
Nitrile derive hexacarboxylic acid part prepare the phosphonitrile hexacarboxylic acid derivative of copper-ring three coordination frame material, with and preparation method and application；
The frame material is the network frame material of gap structure, and with very special absorption property, application prospect is good.
Background technology
Coordination frame material represents excellent application prospect in various application fields due to its specific pore passage structure.But
How to orient and effectively construct the material with specific frame structure and performance, be still the research emphasis of complex material worker.Mesh
Before, the method for effective framing material still concentrates on reasonable selection and builds having with specific connected mode and steric configuration
Machine part aspect, and be generally rigidly and with less connection site.There are some researches show the linking number for increasing part can have
The resistance to overturning of effect lifting material, and then various functions application can be carried out.But the organic ligand for being used at present is mostly two
Connection or four connection sites, and synthesis technique is relatively complicated, cost is higher.[1-2]
Hexachlorocyclotriph,sphazene is a kind of highly stable purely inorganic material, and it is modified very using necleophilic reaction
Convenient, synthesis condition is very simple, therefore, preparing the organic ligand with multi-link pattern as bed material with hexachlorocyclotriph,sphazene should
This is the relatively low route of a whole cost.And such organic ligand obtained as template derivative with the phosphonitrile of ring three can have up to
Six coordination arms, and configuration has certain flexible characteristic, and this feature is higher for assembling topological structure novelty, stability
Frame material be very favorable.[3]
However, further investigations have shown that, although the derivative with hexachlorocyclotriph,sphazene as template has These characteristics,
Often inner molecular structure arrangement is random for these derivatives, it is impossible to form the derivative with ad hoc structure, thus inapplicable right
Molecular arrangement has the application scenario of particular requirement.Additionally, using hexachlorocyclotriph,sphazene reaction generation derivative, the product for often reacting
Rate is not high, influences practical application.
Bibliography 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.Dalton Trans.2013,43,
2558.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, it is an object of the invention to provide a kind of phosphonitrile of copper-ring three
Hexacarboxylic acid derivative be coordinated frame material, with and preparation method and application, wherein by be coordinated frame material composition and
Various parameters (such as raw material type, concentration, reaction temperature and time) in structure, preparation method are improved, with existing skill
Art is compared and can effectively solve the problem that the derivative inner molecular structure with hexachlorocyclotriph,sphazene as template arranges random problem, and
Preparation method corresponding with the phosphonitrile hexacarboxylic acid derivative of copper-ring three coordination frame material effectively ensures reaction yield, is easy to
Useful application.
To achieve the above object, according to one aspect of the present invention, there is provided a kind of phosphonitrile hexacarboxylic acid derivative of copper-ring three
Coordination frame material, it is characterised in that the coordination frame material is used including the raw material reaction shape including copper ion and ligand L
Into wherein the ligand L has following structure：
Preferably, the coordination frame material is three-dimensional framework material, and with one-dimensional linear duct.
As present invention further optimization, the phosphonitrile hexacarboxylic acid derivative of the copper-ring three coordination frame material, with such as
Lower structure：
As present invention further optimization, the phosphonitrile hexacarboxylic acid derivative of the copper-ring three coordination frame material, with such as
Lower structure：
Used as present invention further optimization, the copper ion comes from copper nitrate.
To achieve the above object, according to another aspect of the present invention, there is provided a kind of phosphonitrile hexacarboxylic acid of above-mentioned copper-ring three
Derivative is coordinated the preparation method of frame material, it is characterised in that comprise the following steps：
The synthesis of (1) six (4- methyl formates-phenoxy group) phosphonitrile of ring three：In argon atmosphere, to the third of 50mL~70mL
1.5g hexachlorocyclotriph,sphazenes, 6.5g methyl p-hydroxybenzoates and 1g~3g potassium carbonate are added in ketone, be followed by stirring for 5min~
10min, and the heating that flowed back at 60 DEG C~70 DEG C forms the first mixed solution at least 12 hours；Then, it is evaporated described
Acetone in one mixed solution, obtains white solid；Then, with white solid described in distillation water washing, then filter, then will
The filter residue being filtrated to get is added in 40mL~50mL ethyl acetate, is spin-dried for after stirring and dissolving, that is, obtain six (4- methyl formates-
Phenoxy group) phosphonitrile of ring three；
(2) synthesis of ligand L：To six (the 4- formic acid first obtained in step (1) described in addition 5g in 30mL~50mL methyl alcohol
Ester-phenoxy group) phosphonitrile of ring three and 6g~10g NaOH, then in 65 DEG C~75 DEG C agitating heating reflow treatments at least 12
Hour, then decompressing and extracting methyl alcohol obtains solid I；Then, institute is made to the distilled water of addition 150mL~200mL in the solid I
Solid I dissolvings are stated, is then filtered, then make the pH value of the filtrate be 1~2 to addition hydrochloric acid in the filtrate being filtrated to get, then
Obtain white precipitate；Then refilter, six-(4- carboxylic acids phenoxy group) ring triphosphine nitriles are obtained after the filter residue drying that will be filtrated to get
Ligand L；
(3) synthesis of complex：
8mg~12mg six-(4- carboxylic acids phenoxy group) ring triphosphine nitrile ligand L and 24mg~36mg copper nitrates are added to by going
Ionized water and N, in the mixed solvent that N '-dimethyl formamide is constituted, then the ultrasonic reaction mixing of formation second at least 5 minutes is molten
Liquid, then obtains forerunner to the hydrochloric acid or aqueous solution of nitric acid of addition 0.2mL~0.3mL 2mol/L in second mixed solution
Body；Then, the presoma is obtained into crystal in 48 hours~96 hours in 80 DEG C~100 DEG C reactions, is then filtered, after filtering
To filter residue through deionized water wash after i.e. obtain be coordinated frame material crystal.
To achieve the above object, according to another aspect of the present invention, there is provided a kind of phosphonitrile hexacarboxylic acid of above-mentioned copper-ring three
Derivative is coordinated the preparation method of frame material, it is characterised in that comprise the following steps：
The synthesis of (1) six (4- methyl formates-phenoxy group) phosphonitrile of ring three：In argon atmosphere, to the third of 50mL~70mL
1.5g hexachlorocyclotriph,sphazenes, 6.5g methyl p-hydroxybenzoates and 1g~3g potassium carbonate are added in ketone, be followed by stirring for 5min~
10min, and the heating that flowed back at 60 DEG C~70 DEG C forms the first mixed solution at least 12 hours；Then, it is evaporated described
Acetone in one mixed solution, obtains white solid；Then, with white solid described in distillation water washing, then filter, then will
The filter residue being filtrated to get is added in 40mL~50mL ethyl acetate, is spin-dried for after stirring and dissolving, that is, obtain six (4- methyl formates-
Phenoxy group) phosphonitrile of ring three；
(2) synthesis of ligand L：To six (the 4- formic acid first obtained in step (1) described in addition 5g in 30mL~50mL methyl alcohol
Ester-phenoxy group) phosphonitrile of ring three and 6g~10g NaOH, then in 65 DEG C~75 DEG C agitating heating reflow treatments at least 12
Hour, then decompressing and extracting methyl alcohol obtains solid I；Then, institute is made to the distilled water of addition 150mL~200mL in the solid I
Solid I dissolvings are stated, is then filtered, then make the pH value of the filtrate be 1~2 to addition hydrochloric acid in the filtrate being filtrated to get, then
Obtain white precipitate；Then refilter, obtaining six-(4- carboxylic acids phenoxy group) ring triphosphine nitriles after the filter residue drying being filtrated to get matches somebody with somebody
Body L；
(3) synthesis of complex：
By 16mg~24mg six-(4- carboxylic acids phenoxy group) ring triphosphine nitrile ligand L and 8mg~12mg copper nitrates, 8mg~12mg
4,4'-Bipyridine is added to by deionized water and N, and in the mixed solvent that N '-dimethyl formamide is constituted, then ultrasonic reaction is extremely
The 3rd mixed solution is formed within few 5 minutes, then to the hydrochloric acid that 0.2mL~0.3mL 2mol/L are added in the 3rd mixed solution
Or aqueous solution of nitric acid obtains presoma；Then, the presoma is obtained into crystalline substance in 48 hours~96 hours in 80 DEG C~100 DEG C reactions
Body, then filters, and the filter residue obtained after filtering obtains being coordinated frame material crystal after being washed through deionized water.
Used as present invention further optimization, the methyl p-hydroxybenzoate in the step (1) is prepared as follows：
It is 98% to the methyl alcohol of addition 40mL~60mL, 6g P-hydroxybenzoic acid and 1mL~2mL mass percentage concentrations in round-bottomed flask
The concentrated sulfuric acid forms the first mixed system；Then, first mixed system is heated to reflux at 65 DEG C~75 DEG C processing 4h~6h,
Then it is evaporated methyl alcohol to be precipitated, then is precipitated with described in distillation water washing, product methyl p-hydroxybenzoate is obtained after drying.
As further preferred in the present invention, by deionized water and N in the step (3), N '-dimethyl formamide structure
Into mixed solvent in N, the volume ratio of N '-dimethyl formamide and deionized water is 3：2~2：1.
As further preferred in the present invention, by deionized water and N in the step (3), N '-dimethyl formamide structure
Into mixed solvent in N, the volume ratio of N '-dimethyl formamide and deionized water is 10：1.5~5：1.
To achieve the above object, according to another aspect of the present invention, there is provided a kind of phosphonitrile hexacarboxylic acid of above-mentioned copper-ring three
Derivative is coordinated application of the frame material as sorbing material.
By the contemplated above technical scheme of the present invention, compared with prior art, following beneficial effect can be obtained：
1. the present invention constructs to form frame material by deriving hexacarboxylic acid part with ring triphosphine nitrile, and self assembly forms topological knot
The frame material that structure is novel, stability is higher, the frame material is by six-(4- carboxylic acids phenoxy group) ring triphosphine nitrile part and copper
Ion is prepared, and the phosphonitrile hexacarboxylic acid derivative of the copper-ring three coordination frame material of formation has one-dimensional tunnel structure, adsorptivity
Can be excellent.
The coordination frame material can be effectively increased the linking number (coordination arm number up to 6) of part, and it matches somebody with somebody substantially
Bit location is to connect to form three-dimensional network structure by derivative hexacarboxylic acid part between six two grades of construction units of core copper cluster, six core copper clusters
Type, one-dimensional channels are retained in crystal structure.The phosphonitrile hexacarboxylic acid derivative of copper-ring three is coordinated frame material, structurally ordered, and one
Dimension pore passage structure makes it have good specific surface area parameter, and material resistance to overturning is good.
2. the preparation method is that forming molten with copper nitrate using six-(4- carboxylic acids phenoxy group) ring triphosphine nitrile ligand Ls
The precursor solution of agent thermal response, by the concentration to precursor solution, the specific preparation process of each raw material, solvent thermal reaction
A series of parameters such as condition are optimized, and enormously simplify the synthesis that the phosphonitrile hexacarboxylic acid derivative of copper-ring three is coordinated frame material
Technique, with it is easy, yield is higher and repeatable strong the characteristics of, the phosphonitrile hexacarboxylic acid derivative of copper-ring three coordination of synthesis
Frame material has one-dimensional tunnel structure, is conducive to expanding and is constructed with specific absorption property using ring triphosphine nitrile derived ligand
The synthesis scope of frame material, and preparation cost can be substantially reduced.
Preparation of the present invention further preferably to methyl p-hydroxybenzoate is adjusted, (such as purity, grain so that its parameters
Degree size) etc. more conform to the phosphonitrile hexacarboxylic acid derivative of copper-ring three be coordinated frame material preparation requirement.
3. the phosphonitrile hexacarboxylic acid derivative of the copper-ring three coordination frame material in the present invention, due to one-dimensional tunnel structure,
Specific surface area is big, can be used as sorbing material (such as molecular sieve)；Because the phosphonitrile hexacarboxylic acid derivative of copper-ring three is coordinated framework
The one-dimensional channels aperture of material can well adsorb N up to 0.6nm~0.8nm2, H2, CO2Deng micro-molecular gas；In use,
Frame material can be ground into powder, adsorbable micro-molecular gas after being vacuumized in 120 DEG C of baking ovens.
Brief description of the drawings
Fig. 1 is the minimum asymmetric cell structural representation of 1 center frame material of the embodiment of the present invention 1；
Fig. 2 is the three-dimensional frame structure schematic diagram of complex 1 in the embodiment of the present invention 1；
Fig. 3 is two grades of construction unit schematic diagrames of core copper cluster of complex 1 six in the embodiment of the present invention 1；
Fig. 4 is the minimum asymmetric cell structural representation of complex 2 in the embodiment of the present invention 2；
Fig. 5 is the three-dimensional frame structure schematic diagram of complex 2 in the embodiment of the present invention 2.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as additionally, technical characteristic involved in invention described below each implementation method
Not constituting conflict each other can just be mutually combined.
The preparation of the complex 1 of embodiment 1
Six-(4- carboxylic acids phenoxy group) the phosphonitrile preparation methods of ring three are as follows：
Synthesize methyl p-hydroxybenzoate first, 6g P-hydroxybenzoic acid is weighed with electronic balance, be added to 100ml round bottoms
In flask, about 50ml methyl alcohol is subsequently adding, is added dropwise 15 and drips the left and right concentrated sulfuric acid (mass percentage concentration is 98%), flow back 4h at 70 DEG C
Afterwards, colourless transparent solution is obtained, reaction unit is removed, methyl alcohol is evaporated, finally with distillation water washing, 7g white products is obtained (i.e.
Methyl p-hydroxybenzoate), dry for standby, yield is about 93%.Secondly, 1.5g (0.0043mol) is added to rise under Ar atmosphere
Hexachlorocyclotriph,sphazene (drying 5h at 50 DEG C) after China, 6.5g (0.043mol) methyl p-hydroxybenzoate (drying), 1g or so
Potassium carbonate (can dry about 1-2h, it is ensured that dry) at 120 DEG C, and being subsequently adding 50ml acetone (needs water removal deoxygenation to refine, example
Such as, phosphorus pentoxide can be in acetone added to remove water deoxygenation, the acetone after then redistillation is out refined), stirring is equal
Even, solution into cloudy state, gradually clarify after continuing to stir a period of time by solution, is warming up to 65 DEG C of reactions overnight, second day, instead
Answer solution to clarify (because product is dissolved in acetone, therefore solution is clarified), remove reaction unit, be evaporated acetone, obtain a large amount of whites
Solid, is subsequently added into a large amount of distilled water and washes away excessive potash solid, filtering, obtains crude product, and gained crude product is added
In the ethyl acetate of 40ml, it is sufficiently stirred for, obtains settled solution, is spin-dried for (for example, can be depressurized with revolving instrument steams solvent acetic acid second
Ester, the temperature for using can be less than the boiling point of ethyl acetate, such as at 45 DEG C~55 DEG C), obtain 4g six (4- methyl formates-phenoxy group)
The phosphonitrile white solid of ring three, yield is about 90%.
Finally, six (4- methyl formates-phenoxy group) the phosphonitrile white solids of ring three and excessive sodium hydrate solid are put into burning
In bottle, the methyl alcohol of 30ml or so is added, be stirred at reflux overnight at 70 DEG C, decompressing and extracting methyl alcohol is subsequently added into substantial amounts of distillation
Water is stirred, and solid is substantially completely dissolved, then filters, the solution clarified, and adds dilute HCl, regulation pH to make its pH ≈ 2,
During pH is adjusted, have a large amount of white precipitates and slowly separate out, solid (i.e. six-(4- carboxylic acids phenoxy group) is finally collected by filtration
The phosphonitrile of ring three), standby after drying, yield is about 85%.
Six-(the 4- carboxylic acids phenoxy group) phosphonitriles of ring three, its chemical formula is C42H30O18N3P3, its structural formula is as follows：
Six-(the 4- carboxylic acids phenoxy group) phosphonitriles of ring three can derive hexacarboxylic acid part as ring triphosphine nitrile.
The synthesis preparation method of complex of the present invention 1 is as follows：
10mg six-(4- carboxylic acids phenoxy group) phosphonitrile of ring three and 30mg copper nitrates are first weighed, 5mL deionized waters and 10mL is added
N, N '-dimethyl formamide, ultrasonic reaction is added dropwise 5 and drips 2mol L after 5 minutes-1Aqueous hydrochloric acid solution, obtain blue clear filtrate
(i.e. solvent thermal reaction precursor liquid)；The blue clear filtrate is added in hydrothermal reaction kettle, and the reactor is placed in 80 DEG C
In baking oven, blue acicular crystal is grown after 48 hours, filter and washed with appropriate deionized water, final products complex 1 can be obtained
(complex 1 is frame material 1).The yield of above-mentioned complex 1 is about 45%, and with following structure：
The preparation of the complex 2 of embodiment 2
Six-(4- carboxylic acids phenoxy group) the phosphonitrile preparation methods of ring three are with embodiment 1.
The synthesis preparation method of complex 2 is as follows：
20mg six-(the 4- carboxylic acids phenoxy group) phosphonitrile of ring three, 10mg copper nitrates and 10mg 4,4'-Bipyridines is first weighed, is added
Plus 1.5mL deionized waters and 10mL N, N '-dimethyl formamide, after 5 minutes, 2mol L are dripped in dropwise addition 5 to ultrasonic reaction-1Nitric acid
The aqueous solution, obtains solvent thermal reaction precursor liquid；During the precursor liquid added into hydrothermal reaction kettle, and reactor is placed in 100 DEG C of bakings
Reacted in case 4 days, blue rhabdolith is then obtained with the speed cooling of 5 DEG C/h, filtered and washed with appropriate deionized water, can
Obtain final products complex 2 (complex 2 is frame material 2)；The complex 2 has following structure：
The crystal structure determination method of complex is as follows in the present invention：
The single crystal samples of 0.20mm × 0.05mm × 0.05mm sizes are chosen, Oxford Gemini S Ultra is placed in mono-
Brilliant diffractometer, using Mo-Kα It is source-collector crystal data, data empirical absorption correction then passes through instrument
Device is completed from tape program CrysAlis RED.Structure elucidation and refine are accomplished manually by SHELXS-97 programs, using complete matrix
Least square method (full-matrix least-squares refinement based on F2) obtain all of non-hydrogen original
Son simultaneously carries out anisotropy refine.Hydrogen atom is then either manually or by geometrically symmetric generation on part
At a temperature of 298 (2) K, Mo-K is used on Oxford Gemini S Ultra diffractometerα Crystal data is collected, above-mentioned complex 1 belongs to trigonal system, and space group is P-3c1, Z values are 4；It constructs list substantially
Unit is to connect to form three-dimensional network configuration, one by derivative hexacarboxylic acid part between six two grades of construction units of core copper cluster, six core copper clusters
Dimension duct is retained in crystal structure.Said frame material 2 belongs to trigonal system, and space group is PC2/c, Its is basic
Construction unit is to connect to form three-dimensional network configuration, one-dimensional channels by derivative hexacarboxylic acid part between six core copper clusters, six core copper clusters
It is retained in crystal structure.
Center frame material (complex 1) absorption property result of the present invention is as follows：
The final frame materials of 100mg are prepared, methyl alcohol is dried after steeping 2 days, then steeps drying in 2 days with acetone, using ASAP-2020
Determine its nitrogen and carbon dioxide adsorption ability.Frame material described herein is in the adsorbable nitrogen 115cm of 77K3/ g,
Brunauer-Emmett-Teller and Langmuir surface areas are up to 342m2/ g and 568m2/g；Carbon dioxide adsorption during 77K
Up to 21cm3/g。
The self-assembling technique that the present invention passes through transition-metal coordination frame material, forms the frame material of complex form；
Found through structural analysis, the three-dimensional framework material prolongs pore passage structure (the i.e. one-dimensional channels knot for having in a certain crystal orientation and running through up and down
Structure；In other directions vertical with the crystal orientation, without the pore passage structure that other run through), with excellent absorption property.Framework
In material 1, ring triphosphine nitrile derives six carboxyl functional groups whole deprotonation of hexacarboxylic acid part, and forms coordination with copper ion
Key；The two grades of construction units of core copper cluster of plane six are formed by the connection of carboxyl functional group between copper ion；Each six core copper cluster connects
8 different hexacarboxylic acid parts are connect, and each hexacarboxylic acid part takes tetrahedral configuration to connect 4 six different core copper clusters, most
End form into topological structure for 4,8T11 configurations three-dimensional network；One-dimensional channels are retained in crystal structure.In frame material 2,
Ring triphosphine nitrile derives six carboxyl functional groups whole deprotonation of hexacarboxylic acid part, and forms coordinate bond, this structure with copper ion
In copper have two kinds of coordination environments, one kind is pentacoordinate pattern, respectively with two hydrones in oxygen atom, two phosphonitriles of ring three
Nitrogen-atoms coordination in carboxyl oxygen atom and 4,4'-Bipyridine in hexacarboxylic acid part, and each hexacarboxylic acid part connection one
Individual copper ion forms the three-dimensional net structure with one-dimensional channels.
The preparation of the complex 1 of embodiment 3
(1) part synthesis：In argon atmosphere, to addition 1.5g hexachlorocyclotriph,sphazenes, 6.5g in 50ml acetone to hydroxyl
Methyl benzoate and 1g potassium carbonate, are followed by stirring for 5min, and be heated to 60 DEG C of reactions, 20 hours formation mixed solutions；Then, steam
The acetone in the mixed solution is done, white solid is obtained；Then, with white solid described in distillation water washing, then filter, connect
The filter residue that will be filtrated to get to be added in 40ml ethyl acetate, be spin-dried for after being dissolved after stirring, that is, obtain six (4- methyl formates-
Phenoxy group) phosphonitrile of ring three；To addition (4- methyl formates-phenoxy group) phosphonitriles of ring three of 5g six and 6g hydroxides in 30mL methyl alcohol
Sodium then flows back at least 12 hours in 65 DEG C of agitating heatings, and then decompressing and extracting methyl alcohol obtains solid I；Then, to the solid I
Middle addition 150mL distilled water dissolves the solid I, then filters, then makes institute to addition watery hydrochloric acid in the filtrate being filtrated to get
The pH value of filtrate is stated for 2 obtain white precipitate；Then refilter, six-(4- carboxylic acid benzene is obtained after the filter residue drying being filtrated to get
Epoxide) ring triphosphine nitrile ligand L；
(2) Opacity in lens：8mg six-(4- carboxylic acids phenoxy group) ring triphosphine nitrile and 24mg copper nitrates are added to by deionization
Water and N, N '-dimethyl formamide volume ratio 1：In 2 mixed solvents for constituting, then ultrasonic reaction forms mixing at least 5 minutes
Solution, then obtains presoma to the aqueous hydrochloric acid solution of addition 0.2mL2mol/L in the mixed solution；Then, before will be described
Drive body and obtain crystal within 96 hours in 80 DEG C of reactions, then filter, the filter residue obtained after filtering is obtained after being washed through deionized water
Coordination frame material crystal.
The preparation of the complex 1 of embodiment 4
(1) part synthesis：In argon atmosphere, to addition 1.5g hexachlorocyclotriph,sphazenes, 6.5g in 60ml acetone to hydroxyl
Methyl benzoate and 2g potassium carbonate, are followed by stirring for 8min, and be heated to 65 DEG C of reactions, 18 hours formation mixed solutions；Then, steam
The acetone in the mixed solution is done, white solid is obtained；Then, with white solid described in distillation water washing, then filter, connect
The filter residue that will be filtrated to get to be added in 45ml ethyl acetate, be spin-dried for after being dissolved after stirring, that is, obtain six (4- methyl formates-
Phenoxy group) phosphonitrile of ring three；To addition (4- methyl formates-phenoxy group) phosphonitriles of ring three of 5g six and 8g hydroxides in 40mL methyl alcohol
Sodium then flows back at least 12 hours in 70 DEG C of agitating heatings, and then decompressing and extracting methyl alcohol obtains solid I；Then, to the solid I
Middle addition 200mL distilled water dissolves the solid I, then filters, then makes institute to addition watery hydrochloric acid in the filtrate being filtrated to get
The pH value of filtrate is stated for 2 obtain white precipitate；Then refilter, six-(4- carboxylic acid benzene is obtained after the filter residue drying being filtrated to get
Epoxide) ring triphosphine nitrile ligand L；
(2) Opacity in lens：10mg six-(4- carboxylic acids phenoxy group) ring triphosphine nitrile and 30mg copper nitrates are added to by deionization
Water and N, N '-dimethyl formamide volume ratio 1：In 2 mixed solvents for constituting, then ultrasonic reaction forms mixing at least 5 minutes
Solution, then obtains presoma to the aqueous hydrochloric acid solution of addition 0.25mL 2mol/L in the mixed solution；Then, will be described
Presoma obtains crystal in 72 hours in 90 DEG C of reactions, then filters, and the filter residue obtained after filtering is obtained final product after being washed through deionized water
To coordination frame material crystal.
The preparation of the complex 1 of embodiment 5
(1) part synthesis：In argon atmosphere, to addition 1.5g hexachlorocyclotriph,sphazenes, 6.5g in 70ml acetone to hydroxyl
Methyl benzoate and 3g potassium carbonate, are followed by stirring for 10min, and be heated to 70 DEG C of reactions, 15 hours formation mixed solutions；Then, steam
The acetone in the mixed solution is done, white solid is obtained；Then, with white solid described in distillation water washing, then filter, connect
The filter residue that will be filtrated to get to be added in 50ml ethyl acetate, be spin-dried for after being dissolved after stirring, that is, obtain six (4- methyl formates-
Phenoxy group) phosphonitrile of ring three；To addition (4- methyl formates-phenoxy group) phosphonitriles of ring three of 5g six and 10g hydroxides in 50mL methyl alcohol
Sodium then flows back at least 12 hours in 75 DEG C of agitating heatings, and then decompressing and extracting methyl alcohol obtains solid I；Then, to the solid I
Middle addition 250mL distilled water dissolves the solid I, then filters, then makes institute to addition watery hydrochloric acid in the filtrate being filtrated to get
The pH value of filtrate is stated for 1 obtains white precipitate；Then refilter, six-(4- carboxylic acid benzene is obtained after the filter residue drying being filtrated to get
Epoxide) ring triphosphine nitrile ligand L；
(2) Opacity in lens：12mg six-(4- carboxylic acids phenoxy group) ring triphosphine nitrile and 36mg copper nitrates are added to by deionization
Water and N, N '-dimethyl formamide volume ratio 1：In 2 mixed solvents for constituting, then ultrasonic reaction forms mixing at least 5 minutes
Solution, then obtains presoma to the aqueous hydrochloric acid solution of addition 0.3mL2mol/L in the mixed solution；Then, before will be described
Drive body and obtain crystal within 48 hours in 100 DEG C of reactions, then filter, the filter residue obtained after filtering is obtained after being washed through deionized water
Coordination frame material crystal.
The preparation of the complex 2 of embodiment 6
Difference from Example 2 is only that：
16mg six-(4- carboxylic acids phenoxy group) ring triphosphine nitrile and 8mL copper nitrates, 8mg 4,4 '-bipyridyl are added to by going
Ionized water and N, N '-dimethyl formamide volume ratio are 1:In 5 mixed solvents for constituting, then at least 5 minutes shapes of ultrasonic reaction
Into mixed solution, then presoma is obtained to the aqueous solution of nitric acid of addition 0.2mL2mol/L in the mixed solution；Then, will
The presoma obtains crystal in 96 hours in 80 DEG C of reactions, then filters, after the filter residue obtained after filtering is washed through deionized water
Obtain being coordinated frame material crystal.
The preparation of the complex 2 of embodiment 7
With the difference is that only for embodiment 2：
By 24mg six-(4- carboxylic acids phenoxy group) ring triphosphine nitrile and 12mg copper nitrates, 12mg 4,4 '-bipyridyl be added to by
Deionized water and N, N '-dimethyl formamide volume ratio 1:In 5 mixed solvents for constituting, then at least 5 minutes shapes of ultrasonic reaction
Into mixed solution, then presoma is obtained to the aqueous solution of nitric acid of addition 0.3mL2mol/L in the mixed solution；Then, will
The presoma obtains crystal in 48 hours in 100 DEG C of reactions, then filters, after the filter residue obtained after filtering is washed through deionized water
Obtain being coordinated frame material crystal.
The preparation of the complex 1 of embodiment 8
With the difference is that only for embodiment 1：Weigh 10mg six-(4- carboxylic acids phenoxy group) phosphonitrile of ring three and 30mg nitric acid
Copper, is added to by deionized water and N, N '-dimethyl formamide volume ratio 2：In 3 mixed solvents for constituting, ultrasonic reaction 5 minutes
Afterwards, 5 are added dropwise and drip 2mol L-1Aqueous hydrochloric acid solution, obtain precursor liquid；The precursor liquid is added in hydrothermal reaction kettle, and should
Reactor is placed in 80 DEG C of baking ovens, and blue acicular crystal is grown after 48 hours, is filtered and is washed with appropriate deionized water, can be obtained most
Finished product complex 1.
Frame material in above-described embodiment can also be combined with counter cation and/or guest molecule X, be filled in by X
In duct, [Cu is formed6(L)2(H2O)6] X, wherein L is six-(4- carboxylic acids phenoxy group) ring triphosphine nitrile parts.
In order to further illustrate technique effect of the invention, there is provided following comparative example.
Comparative example 1
Growth conditions with embodiment 1 is similar, and the phosphonitrile of ring three that will be calculated and weighed by proportioning derives hexacarboxylic acid ligand L
N is dissolved in appropriate cadmium nitrate, in N '-dimethyl formamide and the mixed solution of water, taken out after ultrasound and add appropriate amount of acid, then
Solvent thermal reaction is carried out in 80-100 DEG C, two kinds of clear crystals are grown after 3 days, filtered and washed with appropriate deionized water, can obtained
Final products.Through crystal structure analysis, a kind of crystal structure is 3-D solid structure, and another crystal structure is two dimensional surface knot
Structure, two kinds of crystal are without one-dimensional channels.
Comparative example 2
Growth conditions with embodiment 1 is similar, and the phosphonitrile of ring three that will be calculated and weighed by proportioning derives hexacarboxylic acid ligand L
N is dissolved in appropriate zinc nitrate, is taken out in N '-dimethyl formamide, after ultrasound and is added appropriate amount of acid, then carry out solvent in 80 DEG C
Thermal response, bulk crystals are grown after 3 days, are filtered and are washed with appropriate deionized water, can obtain final products.Through crystal structure point
Analysis, the crystal structure is 3-D solid structure, but without one-dimensional channels.
Complex 1 and 2 in the present invention is one-dimensional tunnel structure, and the aperture of complex 1 is up to 0.8nm, the hole of complex 2
Footpath is alternatively arranged as mesopore molecular sieve as new catalyst material or catalyst carrier, using its larger aperture up to 0.6nm
Increase diffusion velocity.Its adsorption effect of complex 1 and 2 in the embodiment of the present invention has for the crystal of comparative example 1,2
There are considerable degree of raising, advantages of good adsorption effect.The methyl p-hydroxybenzoate used in the present invention, its preparation parameter is except implementing
It is outer in example 1, can also be：
To added in round-bottomed flask the methyl alcohol of 40mL, 6g P-hydroxybenzoic acid and 1mL mass percentage concentrations be 98% it is dense
Sulfuric acid forms mixed system I；Then, the mixed system I is heated to reflux at 65 DEG C processing 6h, is then evaporated methyl alcohol and is sunk
Form sediment, then precipitated with described in distillation water washing, product methyl p-hydroxybenzoate is obtained after drying.Or, in round-bottomed flask
The methyl alcohol of 60mL, 6g P-hydroxybenzoic acid and the concentrated sulfuric acid that 2mL mass percentage concentrations are 98% is added to form mixed system I；Connect
, the mixed system I is heated to reflux at 75 DEG C to process 4h, be then evaporated methyl alcohol and be precipitated, then with distilling water washing institute
Precipitation is stated, product methyl p-hydroxybenzoate is obtained after drying.
As it will be easily appreciated by one skilled in the art that the foregoing is only presently preferred embodiments of the present invention, it is not used to
The limitation present invention, all any modification, equivalent and improvement made within the spirit and principles in the present invention etc., all should include
Within protection scope of the present invention.
Claims (9)
1. a kind of phosphonitrile hexacarboxylic acid derivative of copper-ring three is coordinated frame material, it is characterised in that the coordination frame material is using bag
Include copper ion and ligand L to be formed in interior raw material reaction, wherein the ligand L has following structure：
The coordination frame material is three-dimensional framework material, and with one-dimensional linear duct；
The phosphonitrile hexacarboxylic acid derivative of the copper-ring three coordination frame material belongs to trigonal system, and space group is P-3c1,
In the coordination frame material, ring triphosphine nitrile derives six carboxyl functional groups whole deprotonation of hexacarboxylic acid part, and and copper
Ion forms coordinate bond；The two grades of construction units of core copper cluster of plane six are formed by the connection of carboxyl functional group between copper ion；Often
Individual six core copper cluster connects 8 different hexacarboxylic acid parts, and each hexacarboxylic acid part take tetrahedral configuration connect 4 it is different
Six core copper clusters, ultimately form the three-dimensional net structure with one-dimensional channels；
The minimum asymmetric cell structural representation of the coordination frame material is shown in Figure of description 1, three-dimensional frame structure schematic diagram
See Figure of description 2, six two grades of construction unit schematic diagrames of core copper cluster are shown in Figure of description 3.
2. a kind of phosphonitrile hexacarboxylic acid derivative of copper-ring three is coordinated frame material, it is characterised in that the coordination frame material is using bag
Include copper ion and ligand L to be formed in interior raw material reaction, wherein the ligand L has following structure：
The coordination frame material is three-dimensional framework material, and with one-dimensional linear duct；
The phosphonitrile hexacarboxylic acid derivative of the copper-ring three coordination frame material belongs to trigonal system, and space group is PC2/c,
In the coordination frame material, ring triphosphine nitrile derives six carboxyl functional groups whole deprotonation of hexacarboxylic acid part, and and copper
Ion forms coordinate bond, and the copper in this structure has two kinds of coordination environments, and one of which is pentacoordinate pattern, respectively with two moisture
Oxygen atom in son, the carboxyl oxygen atom in two phosphonitrile hexacarboxylic acid parts of ring three and the nitrogen-atoms in 4,4'-Bipyridine are matched somebody with somebody
Position, and each hexacarboxylic acid part connects a copper ion and forms the three-dimensional net structure with one-dimensional channels；
The minimum asymmetric cell structural representation of the coordination frame material is shown in Figure of description 4, three-dimensional frame structure schematic diagram
See Figure of description 5.
3. the phosphonitrile hexacarboxylic acid derivative of copper-ring as claimed in claim 1 or 2 three is coordinated frame material, it is characterised in that the copper
Ion comes from copper nitrate.
4. the method that the phosphonitrile hexacarboxylic acid derivative of copper-ring as claimed in claim 1 three is coordinated frame material is prepared, and its feature exists
In comprising the following steps：
The synthesis of (1) six (4- methyl formates-phenoxy group) phosphonitrile of ring three：In argon atmosphere, in the acetone of 50mL~70mL
1.5g hexachlorocyclotriph,sphazenes, 6.5g methyl p-hydroxybenzoates and 1g~3g potassium carbonate are added, 5min~10min is followed by stirring for,
And the heating that flowed back at 60 DEG C~70 DEG C forms the first mixed solution at least 12 hours；Then, it is evaporated first mixing
Acetone in solution, obtains white solid；Then, with white solid described in distillation water washing, then filter, will then filter
To filter residue be added in 40mL~50mL ethyl acetate, be spin-dried for after stirring and dissolving, that is, obtain six (4- methyl formates-phenoxy group)
The phosphonitrile of ring three；
(2) synthesis of ligand L：To added in 30mL~50mL methyl alcohol obtained in step (1) described in 5g six (4- methyl formates-
Phenoxy group) phosphonitrile of ring three and 6g~10g NaOH are then small in 65 DEG C~75 DEG C agitating heating reflow treatments at least 12
When, then decompressing and extracting methyl alcohol obtains solid I；Then, make to the distilled water of addition 150mL~200mL in the solid I described
Solid I dissolves, and then filters, then makes the pH value of the filtrate be 1~2 to addition hydrochloric acid in the filtrate being filtrated to get, subsequent
To white precipitate；Then refilter, obtaining six-(4- carboxylic acids phenoxy group) ring triphosphine nitriles after the filter residue drying that will be filtrated to get matches somebody with somebody
Body L；
(3) synthesis of complex：
8mg~12mg six-(4- carboxylic acids phenoxy group) ring triphosphine nitrile ligand L and 24mg~36mg copper nitrates are added to by deionization
Water and N, in the mixed solvent that N '-dimethyl formamide is constituted, then ultrasonic reaction forms the second mixed solution at least 5 minutes,
Then presoma is obtained to the hydrochloric acid or aqueous solution of nitric acid of addition 0.2mL~0.3mL 2mol/L in second mixed solution；
Then, the presoma is obtained into crystal in 48 hours~96 hours in 80 DEG C~100 DEG C reactions, is then filtered, obtained after filtering
Filter residue through deionized water wash after i.e. obtain be coordinated frame material crystal.
5. the method that the phosphonitrile hexacarboxylic acid derivative of copper-ring as claimed in claim 2 three is coordinated frame material is prepared, and its feature exists
In comprising the following steps：
The synthesis of (1) six (4- methyl formates-phenoxy group) phosphonitrile of ring three：In argon atmosphere, in the acetone of 50mL~70mL
1.5g hexachlorocyclotriph,sphazenes, 6.5g methyl p-hydroxybenzoates and 1g~3g potassium carbonate are added, 5min~10min is followed by stirring for,
And the heating that flowed back at 60 DEG C~70 DEG C forms the first mixed solution at least 12 hours；Then, it is evaporated first mixing
Acetone in solution, obtains white solid；Then, with white solid described in distillation water washing, then filter, will then filter
To filter residue be added in 40mL~50mL ethyl acetate, be spin-dried for after stirring and dissolving, that is, obtain six (4- methyl formates-phenoxy group)
The phosphonitrile of ring three；
(2) synthesis of ligand L：To added in 30mL~50mL methyl alcohol obtained in step (1) described in 5g six (4- methyl formates-
Phenoxy group) phosphonitrile of ring three and 6g~10g NaOH are then small in 65 DEG C~75 DEG C agitating heating reflow treatments at least 12
When, then decompressing and extracting methyl alcohol obtains solid I；Then, make to the distilled water of addition 150mL~200mL in the solid I described
Solid I dissolves, and then filters, then makes the pH value of the filtrate be 1~2 to addition hydrochloric acid in the filtrate being filtrated to get, subsequent
To white precipitate；Then refilter, six-(4- carboxylic acids phenoxy group) ring triphosphine nitrile parts are obtained after the filter residue drying being filtrated to get
L；
(3) synthesis of complex：
By 16mg~24mg six-(4- carboxylic acids phenoxy group) ring triphosphine nitrile ligand L, 8mg~12mg copper nitrates and 8mg~12mg 4,
4 '-bipyridyl is added to by deionized water and N, and in the mixed solvent that N '-dimethyl formamide is constituted, then ultrasonic reaction is at least
Form the 3rd mixed solution within 5 minutes, then to the hydrochloric acid that 0.2mL~0.3mL 2mol/L are added in the 3rd mixed solution or
Aqueous solution of nitric acid obtains presoma；Then, the presoma is obtained into crystalline substance in 48 hours~96 hours in 80 DEG C~100 DEG C reactions
Body, then filters, and the filter residue obtained after filtering obtains being coordinated frame material crystal after being washed through deionized water.
6. the phosphonitrile hexacarboxylic acid derivative of copper-ring three is coordinated the preparation method of frame material, its feature as described in claim 4 or 5
It is that the methyl p-hydroxybenzoate in the step (1) is prepared as follows：To addition 40mL~60mL in round-bottomed flask
Methyl alcohol, 6g P-hydroxybenzoic acid and the concentrated sulfuric acid that 1mL~2mL mass percentage concentrations are 98% form the first mixed system；Connect
, first mixed system is heated to reflux at 65 DEG C~75 DEG C to process 4h~6h, be then evaporated methyl alcohol and be precipitated, then use
Precipitated described in distillation water washing, product methyl p-hydroxybenzoate is obtained after drying.
7. the phosphonitrile hexacarboxylic acid derivative of copper-ring as claimed in claim 4 three is coordinated the preparation method of frame material, and its feature exists
In, by deionized water and N in the step (3), N, N '-dimethyl formyl in the mixed solvent that N '-dimethyl formamide is constituted
Amine is 3 with the volume ratio of deionized water：2~2：1.
8. the phosphonitrile hexacarboxylic acid derivative of copper-ring as claimed in claim 5 three is coordinated the preparation method of frame material, and its feature exists
In, by deionized water and N in the step (3), N, N '-dimethyl formyl in the mixed solvent that N '-dimethyl formamide is constituted
Amine is 10 with the volume ratio of deionized water：1.5~5：1.
9. the phosphonitrile hexacarboxylic acid derivative of copper-ring three as described in claim 1-3 any one is coordinated frame material as adsorption material
The application of material.
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