CN109897191A - One kind being based on the high-dimensional Zn-MOFs complex and preparation method thereof of column [5] aromatic hydrocarbons skeleton - Google Patents
One kind being based on the high-dimensional Zn-MOFs complex and preparation method thereof of column [5] aromatic hydrocarbons skeleton Download PDFInfo
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- CN109897191A CN109897191A CN201910193432.1A CN201910193432A CN109897191A CN 109897191 A CN109897191 A CN 109897191A CN 201910193432 A CN201910193432 A CN 201910193432A CN 109897191 A CN109897191 A CN 109897191A
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Abstract
The invention discloses a kind of high-dimensional Zn-MOFs complexs and preparation method thereof for being based on column [5] aromatic hydrocarbons skeleton, its main feature is that by column [5] arene derivatives H4L ligand is introduced into the skeleton of metal-organic framework material, and obtaining molecular formula is [Zn2(L)] basic structural unit of the Zn-MOFs complex of DMF, crystal is obtained by asymmetry operation, and symmetry operation code is12-X, -1/2+Y, 3/2-Z；21+X, 3/2-Y, 1/2+Z；31+X ,+Y ,+Z contain DMF molecule, two Zn of a coordination in the asymmetric cell of the complex2+With column [5] arene derivatives ligand.Wherein two Zn2+It is all made of pentacoordinate mode, four oxygen atoms in Zn1 are from different column [5] arene derivatives ligands, DMF molecule of another oxygen atom from coordination, and five oxygen atoms in Zn2 are all from different columns [5] arene derivatives ligand.The present invention has the two-fold advantage of MOFs and macrocycle molecule compared with prior art, substantially increase its practical application value, preparation process is simple, ligand dosage is low, yield is high, production cost is further decreased, is a kind of metal-organic framework materials that are environmentally friendly and having great potential and application prospect.
Description
Technical field
The present invention relates to MOFs skeleton complex technology fields, especially a kind of to be matched based on the more carboxyls of column [5] aromatic hydrocarbons skeleton
High-dimensional Zn-MOFs complex of body and preparation method thereof.
Background technique
Metal-organic framework materials due to structure diversity, got over by the features such as high-specific surface area, porous and aperture easy-regulating
It is studied come more people, is reacted in catalysis, gas separation storage, fluorescence identifying etc. all has greatly application.Base
It gathers around in the MOFs complex that functional macrocyclic ligand is constructed there are two types of duct, a kind of duct is formed from the MOFs skeleton constructed
Duct, another electron rich cavity possessed by macrocycle molecule itself.Functional big ring is introduced into MOFs
Significance be that with specific molecular Host-guest interaction can occur for these functional big rings so that being incorporated to big ring
MOFs has the two-fold advantage of MOFs and macrocycle molecule simultaneously, substantially increases its practical application value.
As that studies metal-organic framework materials deepens continuously and social development need, existing MOFs material
Function is restricted, it is therefore desirable to which it is more various to design structure, the higher novel MOFs material of functionalization degree, by functional column
[5] the big ring of aromatic hydrocarbons, which is introduced into MOFs frame, can expedite the emergence of out many unprecedented functions.
Summary of the invention
The purpose of the present invention is a kind of high-dimensional Zn-MOFs complexs and its system that provide in view of the deficiencies of the prior art
The big ring of functional column [5] aromatic hydrocarbons is introduced into the skeleton of MOFs structure by Preparation Method, and the Zn-MOFs complex of preparation has MOFs
With the two-fold advantage of macrocycle molecule, its practical application value is substantially increased, preparation process is simple, and ligand dosage is low, and yield is high,
Production cost is further decreased, is a kind of environmentally friendly and has the metal-of great potential and application prospect to have machine frame
Frame material.
Realizing the specific technical solution of the object of the invention is: one kind is matched based on the high-dimensional Zn-MOFs of column [5] aromatic hydrocarbons skeleton
Object is closed, its main feature is that by column [5] arene derivatives H4L ligand is introduced into the skeleton of MOFs material, obtains flat crystal structure
Zn-MOFs complex, molecular formula be [Zn2(L)] basic structural unit of DMF, the crystal are operated by asymmetry
It arrives, the DMF molecule being coordinated in asymmetric cell containing one, two Zn2+With column [5] arene derivatives ligand；It is described
Two Zn2+It is all made of pentacoordinate mode, wherein four in Zn1 oxygen atom is from different column [5] arene derivatives ligands, separately
Outer DMF molecule of the oxygen atom from coordination, five oxygen atoms in Zn2 are all from different columns [5] arene derivatives and match
Body；The coordination uses carboxylic acid group and Zn2+The SBU of the coordination mode of ion chelating, double-core is unlimited by the connection of ligand
Extend to form the crystal structure of three-dimensional network shape；The crystal structure is monoclinic system P21/ c space group, cell parameter are as follows:
Axial length Shaft angle α=90.00 °；β=
114.501(3)°；γ=90.00 °, unit cell volume areZ=4；Zn-O average bond length is
The asymmetry, which is operated through symmetry operation code, is12-X, -1/2+Y, 3/2-Z；21+X, 3/2-Y, 1/2+Z；31+X ,+Y ,+Z are obtained
To the basic structural unit of crystal；Column [5] the arene derivatives H4L ligand structure formula is as follows:
The preparation method of high-dimensional Zn-MOFs complex of the one kind based on column [5] aromatic hydrocarbons skeleton, its main feature is that by six hydrations
Zinc nitrate and H4L ligand, n,N-Dimethylformamide and deionized water by 0.03~0.1mmol:0.01~0.05mmol:1~
3ml:1~3ml molal volume is than mixing, ultrasonic treatment 30~after sixty minutes with the heating rate of 1 DEG C/min, it is heated to 100~
The Zn-MOFs complex synthesis of 140 DEG C of progress following reaction formulas:
Room temperature is down to the cooling rate of 0.1 DEG C/min after reaction, the product for obtaining faint yellow flat crystal is Zn-
MOFs complex, molecular formula are [Zn2(L)]·DMF。
The H4L ligand is prepared according to the following steps:
A, bis- (carbethoxyl group) phenyl boric acids of 3,5- and bis- (fluoroform sulphonate) -32,35,52,55,72,75 12,15-,
Ten alkane of-five benzo ring of eight methoxyl group -1,3,5,7,9 (1,4) of 92,95-, tetrakis triphenylphosphine palladium (0) and Carbon Dioxide caesium by 1~
The mixing of the molar ratio of 2:1~2:0.1~0.3:3~6, reacts 60~85 hours under the nitrogen atmosphere of 80~120 DEG C of temperature, obtains product
For-five benzo ring of eight methoxyl group -1,3,5,7,9 (1,4) of bis- (peroxide the ethyl) -32,35,52,55,72,75,92,95- of 12,15-
Ten alkane.
It b, is that 20~50wt% sodium hydroxide solution presses 0.3 by the product of above-mentioned a step preparation and tetrahydrofuran and concentration
~1.5mmol:25~60ml:5~20ml molal volume flows back 24~72h hours at a temperature of 40~70 DEG C than mixing, reacts
Liquid is adjusted to be filtered, washed after pH is 1~2 through hydrochloric acid, and it is H4L ligand that product is obtained after dry.
The present invention has the two-fold advantage of MOFs and macrocycle molecule compared with prior art, substantially increases its practical application
Value, preparation process is simple, and synthesis cycle is short, reaction process low toxicity, it is reproducible, reaction solvent for use it is simple and easy to get, it is inexpensive,
Green non-pollution, ligand dosage is low, and yield is high, further decreases production cost, is a kind of environmentally friendly and has huge hair
Open up the metal-organic framework materials of potentiality and application prospect.
Detailed description of the invention
Fig. 1 is Zn-MOFs complex center pillar [5] arene derivatives coordination structure figure prepared by embodiment 2；
Fig. 2 is zinc ion coordination structure chart in the Zn-MOFs complex of the preparation of embodiment 2；
Fig. 3 is Zn-MOFs complex three-dimensional network figure prepared by embodiment 2；
Fig. 4 is Zn-MOFs complex PXRD figure prepared by embodiment 2；
Fig. 5 is Zn-MOFs complex thermal multigraph prepared by embodiment 2；
Fig. 6 is Zn-MOFs complex infrared spectrum prepared by embodiment 2.
Specific embodiment
Below by way of specific embodiment, the present invention is described in further detail.
Embodiment 1
The present invention is prepared according to the following steps H4L ligand:
A, bis- (carbethoxyl group) phenyl boric acids of 1.60g (6.01mmol) 3,5- and 2.00g (2.01mmol) 12,15- bis- (three are taken
Fluorine mesylate) ten alkane of-five benzo ring of eight methoxyl group -1,3,5,7,9 (1,4) of -32,35,52,55,72,75,92,95-,
0.30g (0.26mmol) tetrakis triphenylphosphine palladium and the mixing of 1.00g (3.07mmol) cesium carbonate, in 100 DEG C of temperature and nitrogen item
72h is stirred under part.Reaction solution is revolved except after solvent, solid residue is washed with water and repeatedly removes inorganic salts, and with acetic acid second
Ester extracts insoluble matter, vacuum drying treatment.Extract is subjected to column chromatography for separation, obtaining 1.335g product is the bis- (mistakes of 12,15-
Oxygen ethyl) -32,35,52,55,72,75,92,95- eight methoxyl groups -1,3,5,7,9 (Isosorbide-5-Nitrae)-five benzo ring, ten alkane, yield is
56.8%.
It b, is 2mol/L sodium hydroxide by the 1.335g product of above-mentioned a step preparation and 40mL tetrahydrofuran and 20mL concentration
Solution flows back 20 hours at 50 °C, removes solvent under vacuum after reaction and adds water to form clear yellow
In the residue of solution, being adjusted to pH value with hydrochloric acid is 1, and the white solid that collected by suction obtains is washed with water repeatedly, obtains
It is 5,5 '-(eight methoxyl groups -1,3,5,7,9 (1,4) of 32,35,52,55,72,75,92,95--pentabenzoyl ring to 1.00g product
Ten alkane -12,15- diyls) diisoamyl diacid, i.e. H4L ligand.
Embodiment 2
Weigh 30mg zinc nitrate hexahydrate (Zn (NO3)2·6H2O) the H prepared with above-described embodiment 14L ligand 50mg, N,
The mixing of dinethylformamide 3mL and 3mL deionized water, is ultrasonically treated after forty minutes with the heating rate of 1 DEG C/min, is heated to
120 DEG C of constant temperature 26h, are down to room temperature after reaction with the cooling rate of 0.1 DEG C/min, obtain faint yellow flat crystal product and are
Zn-MOFs complex, molecular formula C62H57NO18Zn2。
Refering to fig. 1, the Zn-MOFs complex that prepared by embodiment 2 is analyzed through X-ray single crystal diffraction, the complex structure category
In monoclinic system P21/ c space group has the ligand of a coordination, two Zn in dissymmetrical structure unit2+Ion, a coordination
DMF molecule, the cell parameter of the complex are as follows: axial length
Shaft angle α=90.00 °；β=114.501 (3) °；γ=90.00 °；Unit cell volume are as follows:Z=4；Specifically
Crystal parameter see the table below 1:
The crystallographic parameter of 1 Zn-MOFs complex of table
The selective bond distance of Zn-MOFs complex prepared by embodiment 2It see the table below 2:
The selective bond distance of 2 Zn-MOFs complex of table
The symmetry operation code of asymmetric cell in the crystal basic structural unit of Zn-MOFs complex prepared by embodiment 2
Are as follows:12-X, -1/2+Y, 3/2-Z；21+X, 3/2-Y, 1/2+Z；3The selective bond angle (°) of 1+X ,+Y ,+Z, complex see the table below
3:
The selective bond angle (°) of 3 Zn-MOFs complex of table
Referring to Fig.2, Zn-MOFs complex prepared by embodiment 2 is analyzed through X-ray single crystal diffraction, two in the complex
A Zn.It is all made of pentacoordinate mode, wherein four in Zn1 oxygen atom is from different column [5] arene derivatives ligands, in addition
DMF molecule of one oxygen atom from coordination, five oxygen atoms in Zn2 are all from different columns [5] arene derivatives ligand,
The average bond length of Zn-O is
Refering to Fig. 3, Zn-MOFs complex prepared by embodiment 2 is through X-ray single crystal diffraction, all carboxylics in the complex
Acid groups and Zn2+Ion does not take chelating coordination modes, and the SBU of double-core infinitely extends to form three-dimensional by the connection of ligand
Network-like structure.
Refering to Fig. 4, the Zn-MOFs complex prepared to embodiment 2 has carried out powder x-ray diffraction characterization at room temperature,
It can be seen that the powder X-ray diffraction peak of Zn-MOFs complex prepared by embodiment 2 (simulate to obtain by curve b) and single crystal data
(identical relatively good of curve a), shows that the Zn-MOFs complex purity is higher at powder diffraction peak.
Refering to Fig. 5, the Zn-MOFs complex prepared to embodiment 2 is in N2Thermogravimetric test has been carried out under atmosphere, with 10 DEG C/
Min heating rate is raised to 800 DEG C from 25 DEG C, and the solvent molecule which loses in cavity first at 25~90 DEG C or so is matched
Polymer backbone can be stablized at 350~400 DEG C, continue to increase temperature, and complex skeleton starts to collapse, and crystal structure is destroyed,
The oxide of final remaining metal Zn.
Refering to Fig. 6, the Zn-MOFs complex prepared to embodiment 2 has carried out infrared spectrum analysis, wavelength be 500~
4000cm-1It is collected in range, using solid sample KBr tabletting, the main infrared absorption peak (v/cm-1) of Zn-MOFs complex
Are as follows: 3446 (s), 2934 (s), 1716 (s), 1624 (s), 1502 (s), 1400 (s), 1362 (m), 1212 (s), 1041 (s),
780 (s), 720 (s)；In 3446cm-1Wide absorption peak be O-H stretching vibration absworption peak on the carboxyl not being coordinated；?
2934cm-1For C-H stretching vibration absworption peak on phenyl ring skeleton, in 1716cm-1For C=O stretching vibration absworption peak in carboxyl；?
1362cm-1And 780cm-1For the bending vibration absorption peak of O-H in carboxyl；In 1212cm-1It is absorbed for C-H bending vibration on phenyl ring
Peak.
Only the present invention will be further described for the above various embodiments, is not intended to limit the invention patent, all is this hair
Bright equivalence enforcement, is intended to be limited solely by within the scope of the claims of the invention patent.
Claims (3)
1. the high-dimensional Zn-MOFs complex that one kind is based on column [5] aromatic hydrocarbons skeleton, it is characterised in that by column [5] arene derivatives
H4L ligand is introduced into the skeleton of MOFs material, obtains the Zn-MOFs complex of flat crystal structure, and molecular formula is [Zn2
(L)] basic structural unit of DMF, the crystal are obtained by asymmetry operation, are coordinated in asymmetric cell containing one
DMF molecule, two Zn2+With column [5] arene derivatives ligand；Described two Zn2+It is all made of pentacoordinate mode, wherein Zn1
In four oxygen atoms from different column [5] arene derivatives ligands, DMF molecule of another oxygen atom from coordination,
Five oxygen atoms in Zn2 are all from different columns [5] arene derivatives ligand；The coordination uses carboxylic acid group and Zn2+From
The coordination mode of son chelating, the SBU of double-core infinitely extend to form the crystal structure of three-dimensional network shape by the connection of ligand；Institute
Stating crystal structure is monoclinic system P21/ c space group, cell parameter are as follows: axial lengthShaft angle α=90.00 °；β=
114.501(3)°；γ=90.00 °, unit cell volume areZ=4；Zn-O average bond length isThe asymmetry, which is operated through symmetry operation code, is12-X, -1/2+Y, 3/2-Z；21+X, 3/2-Y, 1/2+Z；31+
X ,+Y ,+Z obtain the basic structural unit of crystal；Column [5] the arene derivatives H4L ligand structure formula is as follows:
2. a kind of preparation method of the high-dimensional Zn-MOFs complex described in claim 1 based on column [5] aromatic hydrocarbons skeleton, special
Sign is zinc nitrate hexahydrate and H4L ligand, n,N-Dimethylformamide and deionized water press 0.03~0.1mmol:0.01
~0.05mmol:1~3ml:1~3ml molal volume is than mixing, ultrasonic treatment 30~fast with the heating of 1 DEG C/min after sixty minutes
Rate is heated to the Zn-MOFs complex synthesis of 100~140 DEG C of progress following reaction formulas:
Room temperature is down to the cooling rate of 0.1 DEG C/min after reaction, the product for obtaining faint yellow flat crystal is Zn-MOFs
Complex, molecular formula are [Zn2(L)]·DMF。
3. the preparation method of the high-dimensional Zn-MOFs complex based on column [5] aromatic hydrocarbons skeleton according to claim 2, special
Sign is the H4L ligand is prepared according to the following steps:
A, bis- (carbethoxyl group) phenyl boric acids of 3,5- and bis- (the fluoroform sulphonate) -32,35,52,55,72,75,92,95- of 12,15-
Ten alkane of-five benzo ring of eight methoxyl groups -1,3,5,7,9 (1,4), tetrakis triphenylphosphine palladium (0) and Carbon Dioxide caesium by 1~2:1~
The mixing of the molar ratio of 2:0.1~0.3:3~6, reacts 60~85 hours under the nitrogen atmosphere of 80~120 DEG C of temperature, and obtaining product is 12,
Ten alkane of-five benzo ring of bis- (peroxide ethyl) eight methoxyl groups -1,3,5,7,9 (1,4) of -32,35,52,55,72,75,92,95- of 15-；
B, by the product of above-mentioned a step preparation and tetrahydrofuran and concentration be 20~50wt% sodium hydroxide solution by 0.3~
1.5mmol:25~60ml:5~20ml molal volume flows back 24~72h hours at a temperature of 40~70 DEG C than mixing, reaction solution
It is adjusted to be filtered, washed after pH is 1~2 through hydrochloric acid, it is H that product is obtained after dry4L ligand.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110935196A (en) * | 2019-12-17 | 2020-03-31 | 湖北大学 | Based on Zn5Metal cluster copolymerization monolithic column and preparation method and application thereof |
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| CN110935196A (en) * | 2019-12-17 | 2020-03-31 | 湖北大学 | Based on Zn5Metal cluster copolymerization monolithic column and preparation method and application thereof |
| CN110935196B (en) * | 2019-12-17 | 2021-11-16 | 湖北大学 | Based on Zn5Metal cluster copolymerization monolithic column and preparation method and application thereof |
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Application publication date: 20190618 |