CN106366326B - A kind of yttrium base substituted-phenyl M-phthalic acid metal coordinating polymer and preparation method thereof - Google Patents
A kind of yttrium base substituted-phenyl M-phthalic acid metal coordinating polymer and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of yttrium base substituted-phenyl M-phthalic acid metal coordinating polymer, chemical formula C384H336N12O124Y16, monoclinic system, P21/ c space group, cell parameter are α=90 °, β=133.0950 (10) °, γ=90 °.Compared with prior art, the better heat stability of the metal coordinating polymer, while there is preferable fluorescence property.
Description
Technical field
The invention belongs to coordination polymer technical fields more particularly to a kind of yttrium base substituted-phenyl M-phthalic acid metal to match
Position polymer and preparation method thereof.
Background technique
Structure of the coordination polymer with multiplicity, and the permeability that coordination polymer is excellent, huge specific surface area, controllable
Specific surface area makes it have huge application prospect in fields such as catalysis, gas absorption, ion exchanges, is Material Field primary study
Object.
Metal-organic framework materials have as constructed by imidazoles, the coordination of carboxylic acid Combination because it is with unique structure
Unique property.It is developed so far, metal organic polymer material obtains very big progress, such as is studied using terephthalic acid (TPA) etc.
Synthesize the polymer of a large amount of unique structures, experimental studies have found that, this quasi polymer shows huge in terms of gas absorption performance
Big application value, such as MOF-5.Although the achievement obtained now be it is huge, metal organic complex research on still
So there is huge challenges, such as how to synthesize the polymer with pre- geodesic structure, that is to say, that the structure of polymer is one
Determine to be uncontrollable in degree, this is because up to now we studied on the influence of complex structure it is not deep enough,
Complex structure is influenced by many factors, and the influence degree of many factors is different, such as is reacted in synthetic compound
The influences such as temperature, the pH value of solution, the type of the coordination mode of ion, ligand be all different.Metal is coordinated at this stage
The research of polymer remains in the synthesis and structure analysis of complex.
Summary of the invention
In view of this, studying, finding the purpose of the present invention is by crystallographic method and provide between yttrium base substituted-phenyl
The crystal structure and preparation method thereof of phthalic acid metal coordinating polymer.
The present invention studies, finds and provide yttrium base substituted-phenyl M-phthalic acid metal to match by crystallographic method
The crystal structure of position polymer.
The present invention provides a kind of yttrium base substituted-phenyl M-phthalic acid metal coordinating polymer, the metal coordination polymerizations
The chemical formula of object is C384H336N12O124Y16, monoclinic system, P21/ c space group, cell parameter areα=90 °, β=
133.0950 (10) °, γ=90 °.
Preferably, the unit cell volume of the metal coordinating polymer
Preferably, the Molecules Z=1 in the structure cell of the metal coordinating polymer.
Preferably, the infrared spectroscopy of the metal coordinating polymer is in about 3450cm-1, 640cm-1, 598cm-1, 1306cm-1, 936cm-1, 632cm-1There is characteristic absorption peak at place.
Preferably, the thermal gravimetric analysis curve of the metal coordinating polymer has weightless peak at about 260 DEG C.
The present invention also provides a kind of preparation methods of yttrium base substituted-phenyl M-phthalic acid metal complex, special
Sign is, comprising:
S1) under vacuum conditions, by organic ligand shown in 5- phenylisophthalic acid, formula (I) and yttrium salt in dimethyl
Formamide is reacted with the heating of the in the mixed solvent of water, obtains metal complex；The 5- phenylisophthalic acid, formula
(I) molar ratio of ruthenium ion is (0.028~0.030): (0.025~0.027): 0.050 in organic ligand shown in and yttrium salt；
The volume ratio of the dimethylformamide and water is 1:1；
Preferably, the step S1) specifically:
Organic ligand shown in 5- phenylisophthalic acid, formula (I) and yttrium salt are added in glass tube closed at one end, so
Afterwards be added dimethylformamide and water mixed solvent, glass tube is vacuumized, is sealed, be warming up within 6~10 hours 100 DEG C~
140 DEG C, 70~100h of isothermal reaction, it is finally cooled to 25 DEG C~35 DEG C in 10~15h, obtains metal complex；Institute
The molar ratio for stating ruthenium ion in organic ligand shown in 5- phenylisophthalic acid, formula (I) and yttrium salt is (0.02~0.04):
(0.02~0.04): 0.050；The volume ratio of the dimethylformamide and water is 1:(0.5~2).
Preferably, the step S1) specifically:
Organic ligand shown in 5- phenylisophthalic acid, formula (I) and yttrium salt are added in glass tube closed at one end, so
The mixed solvent of dimethylformamide and water is added afterwards, glass tube is vacuumized, is sealed, is warming up to 120 DEG C within 8 hours, constant temperature is anti-
83h is answered, 30 DEG C are finally cooled in 13h, obtains metal complex；Shown in the 5- phenylisophthalic acid, formula (I)
Organic ligand and yttrium salt in ruthenium ion molar ratio be 0.029:0.026:0.050；The body of the dimethylformamide and water
Product is than being 1:1.
Preferably, the yttrium salt is yttrium nitrate.
Preferably, the ratio of the mixed solvent and yttrium salt of the dimethylformamide and water is (1~1.5) ml:
0.050mmol。
The present invention provides a kind of yttrium base substituted-phenyl M-phthalic acid metal coordinating polymer, chemical formula is
C384H336N12O124Y16, monoclinic system, P21/ c space group, cell parameter are α=90 °, β=133.0950 (10) °, γ=90 °.With the prior art
It compares, the better heat stability of the metal coordinating polymer, while there is preferable fluorescence property.
Detailed description of the invention
Fig. 1 is the dissymmetrical structure unit figure of metal coordinating polymer crystal provided by the invention；
Fig. 2 is the one-dimensional catenary structure figure of metal coordinating polymer provided by the invention；
Fig. 3 is the three-dimensional cation matrix structure chart of metal coordinating polymer provided by the invention；
Fig. 4 is the hydrone of metal coordinating polymer provided by the invention, and DMF molecule and DMF anion are located in duct
Three-dimensional cation matrix figure；
Fig. 5 is the infrared spectrogram of metal coordinating polymer provided by the invention；
Fig. 6 is the thermal gravimetric analysis curve of metal coordinating polymer provided by the invention；
Fig. 7 is the fluorescence spectra of metal coordinating polymer obtained in the embodiment of the present invention 1.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
The chemical formula of yttrium base substituted-phenyl M-phthalic acid metal coordinating polymer of the present invention is
C384H336N12O124Y16, monoclinic system, P21/ c space group, cell parameter are α=90 °, β=133.0950 (10) °, γ=90 °.
The present invention also provides the unit cell volumes of the yttrium base substituted-phenyl M-phthalic acid metal coordinating polymerMolecules Z=1 in the structure cell of the metal complex.
The present invention studies and characterizes the crystalline substance of metal coordinating polymer using X-ray diffraction method (XRD) generally acknowledged in the world
Body structure.Instrument and equipment: Bruker Apex II CCD monocrystalline X-ray diffraction instrument.Choose its ray of graphite monochromatised molybdenum targetWith the scan method of ω -2 θ, collect crystal diffraction data, whole intensity datas require by
SADABS carries out semiempiricalization and absorbs correction.Structure elucidation refine be by the SHELXL data packet of Olex2.0 software program into
Capable, to complete matrix after the operation of least square method, to F2It carries out uninterrupted amendment and has obtained all non-hydrogen atom seats
Mark and their data anisotropic parameters.The hydrogen atom overwhelming majority is all fixed using theoretical plus hydrogen method in data, so
And to add hydrogen mode to give fixed at the residual peak that part hydrogen atom is use.Atomic coordinates, the key of the metal coordinating polymer
The data such as long and bond angle are referring to table 1.
The crystallographic data table of 1 metal coordinating polymer of table
aR1=Σ (| | F0|-|Fc||)/Σ|F0|；bwR2=[Σ w (| F0|2-|Fc|2)2/Σ(F0 2)2]1/2。
Yttrium base substituted-phenyl M-phthalic acid metal coordinating polymer provided by the invention is with 5- phenylisophthalic acid
Assistant ligand and transition metal ions yttrium are used as main ligand, flexible double imidazole ligands formula (I) compounds represented (bmimb)
The diimidazole metalloid coordination polymer that ion obtains, molecular formula are represented by [Y4(1,4-Dio)6DMF(H2O)3]·DMF
HDMFn.X-ray single crystal diffraction is analyzed as the result is shown: metal coordinating polymer provided by the invention belongs to monoclinic system, P21/c
Space group.As shown in FIG. 1, FIG. 1 is the dissymmetrical structure unit figure of metal coordinating polymer crystal, the asymmetrical junctions of the complex
Structure unit includes the independent Y atom of four crystallography, six 5- phenylisophthalic acid molecules, three coordination bmimb molecules with
Three DMF molecules, wherein DMF uses three kinds of different effects, coordination, balance skeleton and template or so.The center of this complex
Y2, Y5 and Y9 are all made of seven coordination modes, six of them oxygen atom from different five 5- phenylisophthalic acid molecules and
One oxygen atom comes from water of coordination molecule, and Y13 equally uses seven coordination modes, the difference is that one of sample comes from DMF molecule.
Specific bond distance's key is shown in Table 2.
The bond distance of coordinate bond in 2 metal coordinating polymer of tableWith bond angle (°)
5- phenylisophthalic acid point in yttrium base substituted-phenyl M-phthalic acid metal coordinating polymer provided by the invention
Sub- ligand molecular uses two different coordination modes, and two carboxyls of 5- phenylisophthalic acid molecule ligand molecule (I) are equal
It is connected using bidentate bridging mode, 5- phenylisophthalic acid molecule ligand molecule (II) chelates mode using bidentate.Adjacent Y
Ion connects into one-dimensional catenary structure by 5- phenylisophthalic acid molecule ligand molecule (I), as shown in Fig. 2, Fig. 2 is one-dimensional
Chain structure figure；Each chain connects four neighbouring one-dimensional chains, shape by 5- phenylisophthalic acid molecule ligand molecule (II)
It is organic framework structured at a three-dimensional cationic metal, as shown in figure 3, Fig. 3 is three-dimensional cation matrix structure chart；Between 5- phenyl
The phenyl ring of phthalic acid molecule ligand molecule (II) is located in duct, free hydrone, and DMF molecule and DMF anion are located at
In duct, as shown in figure 4, Fig. 4 is that hydrone, DMF molecule and DMF anion are located at the three-dimensional cation matrix in duct
Figure.
The present invention uses infra-red sepectrometry (IR) also to study and characterize the crystal of metal coordinating polymer.Instrument:
80 Fourier infrared spectrograph of Vertex (German Brooker).Measuring method: KBr pressed disc method, spectral region 4000cm-1-
500cm-1, resolution ratio 4cm-1。
The infrared spectrogram of metal coordinating polymer provided by the invention is as shown in figure 5, it has the property that its is infrared
Spectrum is in about 3450cm-1, 640cm-1, 598cm-1, 1306cm-1, 936cm-1, 632cm-1There is characteristic absorption peak at place.
It is worth noting that, for the infrared light spectral peak of crystal form described above, between a machine and another machine
And between a sample and another sample, the absorption peak of infrared spectroscopy map may be slightly changed, and numerical value may phase
Poor about 1 unit perhaps differs about 0.8 unit and perhaps differs about 0.3 list of about 0.5 unit or difference
Position, or difference about 0.1 unit, therefore given numerical value cannot be considered as it is absolute.
Crystal can also use technically well known other analytical technologies characterization, such as thermal stability analysis (TGA).Instrument:
The TG209 thermogravimetric analyzer of German Nai Chi company production, sample are heated to 800 DEG C under nitrogen atmosphere with 10 DEG C/min of gradient.
Thermal gravimetric analysis curve such as Fig. 6 institute of yttrium base substituted-phenyl M-phthalic acid metal coordinating polymer provided by the invention
Show, has the property that its thermal gravimetric analysis curve has weightless peak at about 260 DEG C；It will be appreciated from fig. 6 that its its structural framework collapses
260 degree or so are appeared in, occurs weightlessness twice altogether during heating, makes a concrete analysis of as follows: matching in 130 DEG C~230 DEG C metals
There is weightless for the first time, weightlessness 3.57%, the weightlessness as caused by the DMF molecule for losing coordination in position polymer, and calculated value is
2.07%.Make second of weightless, metal occur since organic ligand starts to decompose in 260 DEG C~800 DEG C metal coordinating polymers
The skeleton of coordination polymer collapses when temperature is higher than 260 DEG C.
The present invention also analyzes yttrium base substituted-phenyl M-phthalic acid metal coordinating polymer using elemental analyser,
Have the property that elemental analysis (%): calculated value: C 49.84, H 3.67, O21.44, N 1.82；Experiment value: C 49.99,
H3.49, O21.57, N 1.68.
The better heat stability of metal coordinating polymer provided by the invention, while there is preferable fluorescence property.
The present invention also provides the preparation methods of above-mentioned yttrium base substituted-phenyl M-phthalic acid metal coordinating polymer, including
Following steps: S1) under vacuum conditions, by organic ligand shown in 5- phenylisophthalic acid, formula (I) and yttrium salt in dimethyl
Formamide is reacted with the heating of the in the mixed solvent of water, obtains metal complex；The 5- phenylisophthalic acid, formula
(I) molar ratio of ruthenium ion is (0.02~0.04): (0.02~0.04): 0.050 in organic ligand shown in and yttrium salt；It is described
The volume ratio of dimethylformamide and water is 1:(0.5~2)；
Wherein, the present invention is not particularly limited the source of all raw materials, is commercially available.
Under vacuum conditions, by organic ligand shown in 5- phenylisophthalic acid, formula (I) and yttrium salt in dimethyl formyl
Amine is reacted with the heating of the in the mixed solvent of water；Wherein, the 5- phenylisophthalic acid, organic ligand shown in formula (I)
Molar ratio with ruthenium ion in yttrium salt is preferably (0.028~0.030): (0.025~0.027): 0.050, more preferably
(0.029~0.030): (0.026~0.027): 0.050, it is further preferably 0.029:0.026:0.050；The yttrium salt is ability
Inorganic yttrium salts known to field technique personnel have no special limitation, are preferably yttrium nitrate in the present invention；The dimethyl methyl
The dimethylformamide of the in the mixed solvent of amide and water and the volume ratio of water are preferably 1:(0.5~2), more preferably 1:(1~
It 1.5) is further preferably, 1:1；The ratio of the mixed solvent and yttrium salt of the dimethylformamide and water is preferably (1~1.5) ml:
0.050mmol, more preferably (1.1~1.4) ml:0.050mmol are further preferably (1.1~1.3) ml:0.050mmol, optimal
It is selected as 1.2ml:0.050mmol.
The reaction preferably carries out in a glass tube in the present invention；The process of the reaction is preferably to be warming up to for 6~10 hours
100 DEG C~140 DEG C, 70~100h of isothermal reaction is finally cooled to 25 DEG C~35 DEG C in 10~15h；Wherein, the heating is excellent
It is selected in and is warming up within 7~9 hours 110 DEG C~130 DEG C, be more preferably warming up to 120 DEG C at 8 hours；The time of the isothermal reaction is excellent
It is selected as 80~90h, more preferably 80~85h, is further preferably 83h；The cooling is preferably cooled to 25 DEG C~35 in 11~14h
DEG C, 25 DEG C~35 DEG C are cooled in more preferably 12~14h, further preferably to be cooled to 25 DEG C~35 DEG C in 13h, most preferably
30 DEG C are cooled in 13h.
Preferably, the step S1) specifically: by organic ligand and yttrium salt shown in 5- phenylisophthalic acid, formula (I)
It is added in glass tube closed at one end, the mixed solvent of dimethylformamide and water is then added, glass tube is vacuumized, is sealed
Mouthful, 100 DEG C~140 DEG C are warming up within 6~10 hours, 70~100h of isothermal reaction is finally cooled to 25 DEG C~35 in 10~15h
DEG C, obtain metal complex；Ruthenium ion in organic ligand shown in the 5- phenylisophthalic acid, formula (I) and yttrium salt
Molar ratio be (0.028~0.030): (0.025~0.027): 0.050；The volume ratio of the dimethylformamide and water is
1:1.
It is highly preferred that the step S1) specifically: by organic ligand and yttrium shown in 5- phenylisophthalic acid, formula (I)
Salt is added in glass tube closed at one end, and the mixed solvent of dimethylformamide and water is then added, glass tube is vacuumized, is sealed
Mouthful, 120 DEG C are warming up within 8 hours, isothermal reaction 83h is finally cooled to 30 DEG C in 13h, obtains metal complex；It is described
The molar ratio of ruthenium ion is 0.029:0.026 in organic ligand shown in 5- phenylisophthalic acid, formula (I) and yttrium salt:
0.050；The volume ratio of the dimethylformamide and water is 1:1.
In the present invention, after reaction, it preferably filters, and solid matter is washed, obtain metal coordination polymerization
Object.The solvent of the washing is organic solvent well known to those skilled in the art, has no special limitation, excellent in the present invention
It is selected as acetone.
The crystal of metal coordinating polymer can be obtained by the control of material rate, conditional parameter in preparation by the present invention,
Preparation method is simple and yield is higher.
In order to further illustrate the present invention, with reference to embodiments to a kind of yttrium base substituted-phenyl isophthalic provided by the invention
Dioctyl phthalate metal coordinating polymer and preparation method thereof is described in detail.
Reagent used in following embodiment be it is commercially available, it is raw materials used in the embodiment of the present invention to be shown in Table 3.
It is raw materials used in 3 embodiment of table
Embodiment 1
The 5- phenylisophthalic acid (0.029mmol) of 7.0mg is accurately weighed, the bmimb of 7mg is (organic shown in formula (I)
Ligand, 0.026mmol), 19mg yttrium nitrate (0.050mmol) is added in glass tube closed at one end, then will with syringe
1.2ml mixed solvent (VDMF:VWater=1:1) it is added in glass tube, glass tube is vacuumized, is sintered and is sealed with alcohol blast burner.It will
Glass tube after sealing is put into the baking oven of sequencing temperature control, is slowly raised to 120 DEG C within 8 hours, and constant temperature keeps 83 at this temperature
Hour, then 30 DEG C are slowly decreased to after 13 hours.Glass tube is opened, filters solid matter and with acetone rinsing, obtains colourless crystalline substance
Body, as yttrium base substituted-phenyl M-phthalic acid metal coordinating polymer.It is about 75% based on the yield that Y is calculated.
Yttrium base substituted-phenyl M-phthalic acid metal coordinating polymer obtained in embodiment 1 is divided using luminoscope
Analysis, obtains its fluorescence spectra, as shown in Figure 7.
Embodiment 2
The 5- phenylisophthalic acid (0.029mmol) of 7.0mg is accurately weighed, the bmimb of 7mg is (organic shown in formula (I)
Ligand, 0.026mmol), 19mg yttrium nitrate (0.050mmol) is added in glass tube closed at one end, then will with syringe
1.2ml mixed solvent (VDMF:VWater=1:1) it is added in glass tube, glass tube is vacuumized, is sintered and is sealed with alcohol blast burner.It will
Glass tube after sealing is put into the baking oven of sequencing temperature control, is slowly raised to 130 DEG C within 9 hours, and constant temperature keeps 83 at this temperature
Hour, then 30 DEG C are slowly decreased to after 13 hours.Glass tube is opened, filters solid matter and with acetone rinsing, obtains colourless crystalline substance
Body, as yttrium base substituted-phenyl M-phthalic acid metal coordinating polymer.
Embodiment 3
The 5- phenylisophthalic acid (0.029mmol) of 7.0mg is accurately weighed, the bmimb of 7mg is (organic shown in formula (I)
Ligand, 0.026mmol), 19mg yttrium nitrate (0.050mmol) is added in glass tube closed at one end, then will with syringe
1.2ml mixed solvent (VDMF:VWater=1:1) it is added in glass tube, glass tube is vacuumized, is sintered and is sealed with alcohol blast burner.It will
Glass tube after sealing is put into the baking oven of sequencing temperature control, is slowly raised to 120 DEG C within 8 hours, and constant temperature keeps 90 at this temperature
Hour, then 30 DEG C are slowly decreased to after 14 hours.Glass tube is opened, filters solid matter and with acetone rinsing, obtains colourless crystalline substance
Body, as yttrium base substituted-phenyl M-phthalic acid metal coordinating polymer.
The yttrium base substituted-phenyl M-phthalic acid metal coordinating polymer Bruker Apex II that Examples 1 to 3 is obtained
On CCD monocrystalline X-ray diffraction instrument.Choose graphite monochromatised molybdenum target its ray K α With sweeping for ω -2 θ
Method is retouched, crystal diffraction data are collected, whole intensity datas require to carry out semiempiricalization absorption correction by SADABS.Structure
Parsing refine is carried out by the SHELXL data packet of Olex2.0 software program, the fortune to complete matrix Jing Guo least square method
After calculation, to F2It is uninterruptedly corrected us and has obtained all non-hydrogen atom coordinates and their data anisotropic parameters.Number
It is all fixed using theoretical plus hydrogen method according to the middle hydrogen atom overwhelming majority, however the residual peak that part hydrogen atom is use adds
Hydrogen mode gives fixed.
The yttrium base substituted-phenyl M-phthalic acid metal coordinating polymer that Examples 1 to 3 is obtained using infrared spectroscopy into
Row analysis, it is as shown in Figure 5 to obtain its infrared spectrogram.
Using elemental analysis to yttrium base substituted-phenyl M-phthalic acid metal coordinating polymer obtained in Examples 1 to 3
It is analyzed, obtains its elemental analysis result: elemental analysis (%): calculated value: C 61.50, H3.59, O18.21, N 3.99；
Experiment value: C 61.63, H 3.46, O18.34, N3.79.The chemical formula phase that elemental analysis test value is shown with monocrystalline test data
It coincide.
Yttrium base substituted-phenyl M-phthalic acid metal obtained in Examples 1 to 3 is matched using thermal stability analysis (TGA)
Position polymer is analyzed, and sample is heated to 800 DEG C under nitrogen atmosphere with 10 DEG C/min of gradient, obtains its thermal gravimetric analysis curve
Figure, as shown in Figure 6.
Claims (10)
1. a kind of yttrium base substituted-phenyl M-phthalic acid metal coordinating polymer, which is characterized in that the metal coordinating polymer
Chemical formula be C384H336N12O124Y16, monoclinic system, P21/ c space group, cell parameter areα=90 °, β=133.0950
(10) °, γ=90 °；
5- phenylisophthalic acid molecule ligand molecule is adopted in the yttrium base substituted-phenyl M-phthalic acid metal coordinating polymer
Bidentate bridging is all made of with two carboxyls of two different coordination modes, 5- phenylisophthalic acid molecule ligand molecule (I)
Mode connection, 5- phenylisophthalic acid molecule ligand molecule (II) chelate mode using bidentate.
2. yttrium base substituted-phenyl M-phthalic acid metal coordinating polymer according to claim 1, which is characterized in that described
The unit cell volume of metal coordinating polymer
3. yttrium base substituted-phenyl M-phthalic acid metal coordinating polymer according to claim 1, which is characterized in that described
Molecules Z=1 in the structure cell of metal coordinating polymer.
4. yttrium base substituted-phenyl M-phthalic acid metal coordinating polymer according to claim 1, which is characterized in that described
The infrared spectroscopy of metal coordinating polymer is in about 3450cm-1, 640cm-1, 598cm-1, 1306cm-1, 936cm-1, 632cm-1Place has
Characteristic absorption peak.
5. yttrium base substituted-phenyl M-phthalic acid metal coordinating polymer according to claim 1, which is characterized in that described
The thermal gravimetric analysis curve of metal coordinating polymer has weightless peak at about 260 DEG C.
6. the system of yttrium base substituted-phenyl M-phthalic acid metal coordinating polymer described in a kind of Claims 1 to 5 any one
Preparation Method characterized by comprising
S1) under vacuum conditions, by organic ligand shown in 5- phenylisophthalic acid, formula (I) and yttrium salt in dimethyl formyl
Amine is reacted with the heating of the in the mixed solvent of water, obtains metal complex；The 5- phenylisophthalic acid, formula (I)
Shown in organic ligand and yttrium salt the molar ratio of ruthenium ion be (0.02~0.04): (0.02~0.04): 0.050；Described two
Methylformamide and the volume ratio of water are 1:(0.5~2)；
7. preparation method according to claim 6, which is characterized in that the step S1) specifically:
Organic ligand shown in 5- phenylisophthalic acid, formula (I) and yttrium salt are added in glass tube closed at one end, then plus
Glass tube is vacuumized, is sealed by the mixed solvent for entering dimethylformamide and water, is warming up within 6~10 hours 100 DEG C~140 DEG C,
70~100h of isothermal reaction is finally cooled to 25 DEG C~35 DEG C in 10~15h, obtains metal complex；The 5- benzene
The molar ratio of ruthenium ion is (0.028~0.030) in organic ligand shown in base M-phthalic acid, formula (I) and yttrium salt: (0.025
~0.027): 0.050；The volume ratio of the dimethylformamide and water is 1:1.
8. preparation method according to claim 6, which is characterized in that the step S1) specifically:
Organic ligand shown in 5- phenylisophthalic acid, formula (I) and yttrium salt are added in glass tube closed at one end, then plus
Glass tube is vacuumized, is sealed by the mixed solvent for entering dimethylformamide and water, is warming up to 120 DEG C within 8 hours, isothermal reaction
83h is finally cooled to 30 DEG C in 13h, obtains metal complex；Shown in the 5- phenylisophthalic acid, formula (I)
The molar ratio of ruthenium ion is 0.029:0.026:0.050 in organic ligand and yttrium salt；The volume of the dimethylformamide and water
Than for 1:1.
9. preparation method according to claim 6, which is characterized in that the yttrium salt is yttrium nitrate.
10. preparation method according to claim 6, which is characterized in that the mixed solvent of the dimethylformamide and water
Ratio with yttrium salt is (1~1.5) ml:0.050mmol.
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| CN105237574A (en) * | 2015-08-25 | 2016-01-13 | 南阳师范学院 | Pyridine-ligand manganese metal complex with dual functions of magnetic property, and adsorption and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105237574A (en) * | 2015-08-25 | 2016-01-13 | 南阳师范学院 | Pyridine-ligand manganese metal complex with dual functions of magnetic property, and adsorption and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Mechanochemical synthesis of an yttrium based;Niraj K. Singh，等;《Chem. Commun.》;20130201;第49卷(第10期);第972-974页 * |
| Metal–organic hybrid materials built with tetrachlorophthalate acid and different N-donor coligands: Structure diversity and photoluminescence;Zhenyu Xiao，等;《Journal of Solid State Chemistry》;20151130;第234卷;第36-47页 * |
| Syntheses and Structures of Two Complexes Based on Mixing Carboxylate Ligands and Imidazole-containing Ligands;SUN Jie，等;《Chinese J. Struct. Chem.》;20151015;第34卷(第10期);第1546-1552页 * |
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