CN108976429A - A kind of calcium-MOFs complex for fluorescence identifying - Google Patents
A kind of calcium-MOFs complex for fluorescence identifying Download PDFInfo
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- CN108976429A CN108976429A CN201810634577.6A CN201810634577A CN108976429A CN 108976429 A CN108976429 A CN 108976429A CN 201810634577 A CN201810634577 A CN 201810634577A CN 108976429 A CN108976429 A CN 108976429A
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- C—CHEMISTRY; METALLURGY
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/181—Metal complexes of the alkali metals and alkaline earth metals
Abstract
The invention discloses a kind of calcium-MOFs complex for fluorescence identifying, molecular formula is [Ca (L)0.25(H2O)]·DMF2H2O, complex structure belong to rhombic system Pbam space group, and the basic structural unit of crystal is obtained by asymmetric cell by symmetry operation, and symmetry operation code is1-1/2+X,3/2-Y,1-Z;21/2+X,3/2-Y,1-Z;3+X,+Y,1-Z;4-1/2+X,3/2-Y,+Z;5+X,+Y,-Z;62-X,1-Y,-Z;72-X, 1-Y ,+Z have 1/4 ligand, 1 Ca in the asymmetric cell2+Ion, the hydrone of 1 coordination, Ca2+Take eight-coordinate mode, six of them oxygen atom is respectively from four different derivative ligands, other two oxygen atom is come the hydrone that is coordinated.The present invention has the advantages that 1, reaction solvent for use is easy to get, is inexpensive, green non-pollution;2, reaction condition is simple, reaction can be carried out quickly, is energy saving, saving the time;3, yield is high, ligand dosage is low, saves cost.
Description
Technical field
The invention belongs to new material technology fields, specifically disclose a kind of calcium-MOFs complex for fluorescence identifying.
Background technique
Metal-organic framework materials can modify with its advantageous advantage-porosity, aperture easy-regulating, the ratio of superelevation
Surface area etc. is studied by more and more people, all there is pole at many aspects such as fluorescence identifying, the separation of gas, electro-catalysis
Big application.
With getting worse for environmental pollution, excessive heavy metal all becomes now urgently in the improvement of sewage and reduction sewage
Problem to be solved.And traditional detection method limits its in the industry wide due to the disadvantages of its sensitivity is low, at high cost
General application.
Summary of the invention
The object of the present invention is to provide a kind of calcium-MOFs complexs for fluorescence identifying, to solve institute in the prior art
The existing above problem.
A kind of calcium-MOFs complex for fluorescence identifying, molecular formula are [Ca (L)0.25(H2O)]·DMF2H2O matches
It closes object structure and belongs to rhombic system Pbam space group, the basic structural unit of crystal is obtained by asymmetric cell by symmetry operation
It arrives, symmetry operation code is1-1/2+X,3/2-Y,1-Z;21/2+X,3/2-Y,1-Z;3+X,+Y,1-Z;4-1/2+X,3/2-Y,+Z;5
+X,+Y,-Z;62-X,1-Y,-Z;72-X, 1-Y ,+Z have 1/4 ligand, 1 Ca in the asymmetric cell2+Ion, 1 is matched
The hydrone of position, Ca2+Take eight-coordinate mode, six of them oxygen atom respectively from four different derivative ligands,
Other two oxygen atom is the hydrone that is coordinated, the average bond length of Ca-OLigand and Ca2+Ion is with μ1-η1:η1
Mode is coordinated, and connection forms one-dimensional chain SBU, is formed three-dimensional frame structure by the connection of ligand, is formed in a axis direction
?WithThe one-dimensional channels of two kinds of different pore sizes, cell parameter are axial length Shaft angle α=90.00 °, β=90.00 °, γ
=90.00 °, unit cell volume isZ=8, wherein ligand L 4,4', 4 ", 4 " '-(- 1,3,6,8- tetra-
Phenyl) four benzoic acid, structural formula are as follows:
A kind of preparation method for the calcium-MOFs complex being as previously described for fluorescence identifying comprising following steps:
By 0.3mmol calcium nitrate and 0.01mmol ligand H4L is put into the vial of 10mL, and the N, N- of 2mL is then added
The mixed solution of dimethylformamide, second alcohol and water, be ultrasonically treated 10min after, tighten bottle cap, be then placed in baking oven with
It is warming up to 100 DEG C of rate heating in 300min, and keeps the temperature 4320min at 100 DEG C, with 0.1 DEG C/min's after heat preservation
Rate is cooled to room temperature, and obtains glassy yellow bulk crystals, i.e., the described calcium-MOFs complex.
Preferably, the ligand H4L's the preparation method comprises the following steps:
By 4- (methoxycarbonyl) phenyl) boric acid, 1,3,6,8- tetrabromo, tetrakis triphenylphosphine palladium (0) and anhydrous phosphoric acid
After tripotassium mixes, in an argon atmosphere, is reacted at 130 DEG C, obtain 1,3,6,8- tetra- (4- (methoxycarbonyl) phenyl)
Pyrene;
By 1,3,6,8- tetra- (4- (methoxycarbonyl) phenyl) pyrene in the mixed solution of tetrahydrofuran, water and sodium hydroxide
After back flow reaction, adjusting pH value is 1, is filtered, washed, recrystallized and dried, obtains ligand H4L。
A kind of application of calcium-MOFs complex as the aforementioned in heavy metal ion fluorescence identifying.
The present invention has the advantages that
1, reaction solvent for use be easy to get, be inexpensive, green non-pollution;
2, reaction condition is simple, reaction can be carried out quickly, is energy saving, saving the time;
3, yield is high, ligand dosage is low, saves cost;
4, by using mixed solvent, promote ligand hydrolysis, reduce ligand dosage, gained complex yield is high;
5, complex shows good fluorescence property.
Detailed description of the invention
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention,
Objects and advantages will become more apparent upon:
Fig. 1 is the coordination mode structure chart of object derived from the calcium-MOFs complex of the preparation of the embodiment of the present invention 2;
Fig. 2 is calcium ion coordination mode structure chart in the calcium-MOFs complex of the preparation of the embodiment of the present invention 2;
Fig. 3 is the three-dimensional framework figure of calcium-MOFs complex prepared by the embodiment of the present invention 2;
Fig. 4 is the XRD diagram of calcium-MOFs complex prepared by the embodiment of the present invention 2;
Fig. 5 is the thermal multigraph of calcium-MOFs complex prepared by the embodiment of the present invention 2;
Fig. 6 is the infrared spectrum of calcium-MOFs complex prepared by the embodiment of the present invention 2;
Fig. 7 is the solid state fluorescence test chart of calcium-MOFs complex prepared by the embodiment of the present invention 2;
Fig. 8 is that calcium-MOFs complex prepared by the embodiment of the present invention 2 is dispersed in the fluorescence spectrum in different organic solvents;
Fig. 9 is ethyl alcohol emulsion of the calcium-MOFs complex of the preparation of the embodiment of the present invention 2 when containing different metal ions
Relative intensity of fluorescence;
Figure 10 is that Mn is being added in calcium-MOFs complex prepared by the embodiment of the present invention 22+The variation diagram of fluorescence spectrum afterwards;
Figure 11 is that Mn is being added in calcium-MOFs complex prepared by the embodiment of the present invention 22+I afterwards0/ I value and Mn2+Concentration is closed
System's figure;
Figure 12 is that Al is being added in calcium-MOFs complex prepared by the embodiment of the present invention 23+The variation diagram of fluorescence spectrum afterwards;
Figure 13 is that Al is being added in calcium-MOFs complex prepared by the embodiment of the present invention 23+I afterwards0/ I value and Mn2+Concentration is closed
System's figure;
Figure 14 is the Stern-Volmer figure of calcium-MOFs complex prepared by the embodiment of the present invention 2.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Embodiment 1
The present embodiment is related to a kind of method for preparing 4,4', 4 ", 4 " '-(- 1,3,6,8- tetraphenyl) four benzoic acid, tool
Body includes the following steps: (4- (methoxycarbonyl) phenyl) boric acid (1.040g, 5.80mmol), 1,3,6,8- tetrabromo
(0.500g, 0.97mmol), tetrakis triphenylphosphine palladium (0) (0.030g 0.026mmol) and anhydrous phosphoric acid tripotassium (1.100g,
It 5.30mmol) is fitted into and (is placed in glove box) in 20mL microwave vial and cover.Under argon gas by the mixture at 130 DEG C
It is stirred 72 hours in oil bath.Reaction mixture is evaporated to dryness, and solid residue is washed with water to remove inorganic salts.Use chlorine
Imitative extraction insoluble matter (50mL is three times) with magnesium sulfate dry extract, and reduces solvent volume under vacuum.By residue four
2 hours are boiled in hydrogen furans and are filtered;Gained filtrate mainly contains impurity.The program obtains the (4- (first of 0.58g 1,3,6,8- tetra-
Epoxide carbonyl) phenyl) pyrene 0.58g (yield 82%).Then, to contain 1,3,6,8- tetra- (4- of 0.58g (0.78mmol) solid
(methoxycarbonyl) phenyl) 250mL round-bottomed flask in be added containing 1.5g (37.5mmol) be added 100mL tetrahydrofuran/
NaOH in water (ratio 1:1) mixture and by gained suspension vigorous stirring overnight under reflux.Solvent is removed under vacuum
And it adds water in the residue to form clear yellow solution.Clear yellow solution is stirred at room temperature 2 hours, and is made
PH value is adjusted to 1 with dense HCl.The yellow solid being collected by filtration, and be washed with water for several times.Crude product is recrystallized with DMF,
Filtering, with chloroform and is dried in vacuo.This obtains the pure products H of 0.49g (91%)4TBAPy, abbreviation H4L。
Embodiment 2
The present embodiment is related to a kind of preparation method for preparing calcium-MOFs complex, specifically comprises the following steps:
Precise Ca (NO3)2(50mg, 0.3mmol), ligand H4L (5mg, 0.01mmol) is put into the vial of 10mL
In, the n,N-Dimethylformamide of 2mL, the mixed solution (volume ratio=5:2:1) of second alcohol and water, ultrasonic 10min is then added
It is put into electric heating constant-temperature blowing drying box later, tightens bottle cap, be put into baking oven and be warming up to 100 DEG C with 300min, and keep
4320min, then with 0.1 DEG C of min-1Rate reaction system is slowly cooled to room temperature.Obtain glassy yellow bulk crystals.Member
Element analysis test value (theoretical value)/%:C:49.78%, H:5.78%, N:4.51%, elemental analysis actual value/%:C:
47.81%, H:5.57%, N:3.99%.
Under room temperature, powder x-ray diffraction characterization has been carried out to calcium-MOFs complex manufactured in the present embodiment, obtained
PXRD spectrogram as indicated at 4, it can be seen that the powder x-ray diffraction peak and monocrystalline for the calcium-MOFs complex that the present embodiment measures
Powder diffraction peak that digital simulation obtains coincide relatively good, this shows to test calcium-MOFs complex purity obtained higher.
Calcium-MOFs complex belongs to rhombic system, Pbam space group, molecular formula C11H5.5Ca0.5O2.5.Have in its asymmetric cell
A quarter ligand, a Ca2+Ion, the hydrone of a coordination.Ca2+Ion takes eight-coordinate mode, six of them oxygen
Atom is respectively from four different derivative ligands, other two oxygen atom is come the hydrone (Fig. 1, Fig. 2) that is coordinated.
The average bond length of Ca-O isLigand and Ca ion are with μ1-η1:η1Mode is coordinated, and connection forms one-dimensional chain
SBU forms three-dimensional frame structure by the connection of ligand.It is formd in a axis directionWithTwo kinds are not
With the one-dimensional channels in aperture.The porosity of calcium-MOFs complex, about 31.33% are calculated by PLATON software, it is specific brilliant
Body parameter is as shown in Table 1 to Table 3.
Thermogravimetric analysis is carried out to calcium-MOFs complex manufactured in the present embodiment, in N2With 10 DEG C of min in atmosphere-1's
Heating rate DEG C is tested from 40 DEG C to 900, as a result as shown in figure 5, just starting to collapse in 510 DEG C of skeletons, is lost before
20% is that solvent molecule includes a DMF molecule and two hydrones, and 510~580 DEG C of structure collapses have lost 60%.
Infrared spectrum analysis is carried out to calcium-MOFs complex manufactured in the present embodiment, data are by German Bruker
Tensor37 type infrared spectrometer is 400~4000cm in wave number-1The collection of range, using solid sample KBr tabletting, as a result
As shown in fig. 6, the main infrared absorption peak (v/cm of calcium-MOFs complex-1) are as follows: 3408 (s), 2930 (s), 1649 (s), 1602
(w), 1416 (s), 1171 (w), 1102 (w), 1006 (s), 858 (m), 783 (w), 719 (w), 655 (w).Wherein 3408cm-1's
Wide absorption peak belongs to the hydroxyl stretching vibration of water of coordination in calcium-MOFs complex;In 1720~1690cm-1Place does not dissociate
The characteristic absorption peak of carboxyl illustrates that all carboxyls on ligand have all sloughed proton, produces 1649 (s) and 1602 accordingly
(s) two characteristic peaks.
Solid state fluorescence test is carried out to calcium-MOFs complex manufactured in the present embodiment, as a result as shown in fig. 7, ligand
There is a maximum absorption band (λ ex=330nm) at 529nm in absorption spectrum, this is because the electronics transfer of π ... π * causes
's.Calcium-MOFs complex shows strong fluorescence at room temperature, and a maximum absorption band occurs at 470nm in absorption spectrum
(λ ex=330nm).And show blue shift (Δ=590nm).This may be attributed to ligands in metal center, effective increasing
The rigidity and symmetry of ligand are added, to reduce the energy loss of non-radiative decay.
Table 1: crystallographic parameter
The selective bond distance of 2 calcium-MOFs complex 3 of table
The symmetry operation code of asymmetric cell in crystal basic structural unit:
1-1/2+X,3/2-Y,1-Z;21/2+X,3/2-Y,1-Z;3+X,+Y,1-Z;4-1/2+X,3/2-Y,+Z;5+X,+Y,-
Z;62-X,1-Y,-Z;72-X,1-Y,+Z
The selective bond angle (°) of 3 calcium-MOFs complex of table
Embodiment 3
Calcium-MOFs the complex prepared to embodiment 2 conducts further research in terms of fluorescence identifying, such as it is in gold
Belong to the application of detection of ion etc..When MOFs is used as fluorescent sensing material, usually it is dispersed in organic solvent,
Therefore, in order to reach optimal recognition effect, the selected solvent of the present invention should make MOFs material wherein and have very strong glimmering
Luminous intensity.The present invention is dispersed in the fluorescent characteristic in different solvents to calcium-MOFs complex and is studied as a result, specific to grasp
It is as follows to make process: the calcium-MOFs complex for weighing 2mg grinding is added separately in the various organic solvents of 3ml (ethyl alcohol, tetrahydro
Furans, Isosorbide-5-Nitrae-dioxane, methanol, DMA, acetonitrile, DMF, DMSO, acetone, nitrobenzene), ultrasound 15min divides it uniformly later
It dissipates in solvent, then carries out fluorometric investigation.As shown in figure 8, solvent has large effect to the fluorescence of complex 3, as calcium-MOFs
When complex is dispersed in ethanol solution, fluorescence intensity is significantly improved.And when calcium-MOFs complex is dispersed in nitrobenzene
With most weak fluorescent emission when middle.So the present invention selected in next test ethyl alcohol as calcium-MOFs complex into
The dispersion liquid of row metal ion identification.
Calcium cooperation is detected to the recognition capability of metal ion, different metal ions (Mn will be contained2+, Al3+, Cr3+, Fe3+, Ag+Deng) ethanol solution (1mM) in be added gradually in the ethyl alcohol emulsion containing calcium-MOFs complex.As shown in figure 9, part
Ion pair calcium-MOFs complex has the effect of fluorescence enhancement, sub-fraction ion (Ni2+, Cu2+, Co2+, Pb2+, Ca2+) to calcium-
MOFs complex has faint quenching effect.When containing Mn2+And Al3+Ethanol solution when being added into, fluorescence intensity obviously increases
By force, this result shows that calcium-MOFs complex to Mn2+And Al3+There is good selectivity.
As shown in Figure 10, a small amount of Mn is being added2+When, fluorescence just has apparent enhancing, at 120 microlitres of addition containing 1mM
When the ethanol solution of Mn2+, fluorescence intensity has become original 2.25 times, and the linear growth of its reinforcing effect, illustrates calcium-
MOFs complex is to Mn2+There is good recognition effect.As shown in Figure 12, fluorescence intensity is with Al3+Increase increasing degree it is more slow
Slowly, at 300 microlitres of addition containing 1mMAl3+Ethanol solution when, fluorescence intensity has become original 1.77 times, reinforcing effect
It also is linear increase, calcium-MOFs complex is to Al3+Recognition effect be slightly worse than to Mn2+Recognition effect, but still have higher
Ion recognition character.
Pass through Stern-Volmer (SV) formula: (I0/I)=Ksv [A]+1 calculates its enhancing rate, as a result as shown in figure 14.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (4)
1. a kind of calcium-MOFs complex for fluorescence identifying, it is characterised in that: its molecular formula is [Ca (L)0.25(H2O)]·
DMF 2H2O, complex structure belong to rhombic system Pbam space group, and the basic structural unit of crystal is passed through by asymmetric cell
Symmetry operation obtains, and symmetry operation code is1-1/2+X,3/2-Y,1-Z;21/2+X,3/2-Y,1-Z;3+X,+Y,1-Z;4-1/2+
X,3/2-Y,+Z;5+X,+Y,-Z;62-X,1-Y,-Z;72-X, 1-Y ,+Z, there is 1/4 ligand in the asymmetric cell, and 1
Ca2+Ion, the hydrone of 1 coordination, Ca2+Take eight-coordinate mode, six of them oxygen atom is different respectively from four
Derivative ligand, other two oxygen atom is the hydrone that is coordinated, the average bond length of Ca-OLigand and Ca2+From
Son is with μ1-η1:η1Mode is coordinated, and connection forms one-dimensional chain SBU, forms three-dimensional frame structure by the connection of ligand,
It is formd in a axis directionWithThe one-dimensional channels of two kinds of different pore sizes, cell parameter are axial lengthShaft angle α=90.00 °, β=90.00 °, γ=
90.00 °, unit cell volume isZ=8, wherein (- 1,3,6,8- tetra- benzene of ligand L 4,4', 4 ", 4 " '-
Base) four benzoic acid, structural formula are as follows:
2. a kind of preparation method for the calcium-MOFs complex of fluorescence identifying as described in claim 1, which is characterized in that
Include the following steps:
By 0.3mmol calcium nitrate and 0.01mmol ligand H4L is put into the vial of 10mL, and the N of 2mL, N- dimethyl is then added
The mixed solution of formamide, second alcohol and water is tightened bottle cap, is put into baking oven to be warming up in 300min after being ultrasonically treated 10min
100 DEG C of rate heating, and 4320min is kept the temperature at 100 DEG C, it is cooled to room temperature after heat preservation with the rate of 0.1 DEG C/min,
Glassy yellow bulk crystals are obtained, i.e., the described calcium-MOFs complex.
3. the preparation method for the calcium-MOFs complex of fluorescence identifying as claimed in claim 2, which is characterized in that described
Ligand H4L's the preparation method comprises the following steps:
By 4- (methoxycarbonyl) phenyl) boric acid, 1,3,6,8- tetrabromo, tetrakis triphenylphosphine palladium (0) and anhydrous phosphoric acid tripotassium
It after mixing, in an argon atmosphere, is reacted at 130 DEG C, obtains 1,3,6,8- tetra- (4- (methoxycarbonyl) phenyl) pyrenes;
1,3,6,8- tetra- (4- (methoxycarbonyl) phenyl) pyrene is flowed back in the mixed solution of tetrahydrofuran, water and sodium hydroxide
After reaction, adjusting pH value is 1, is filtered, washed, recrystallized and dried, obtains ligand H4L。
4. a kind of application of calcium-MOFs complex as described in claim 1 in heavy metal ion fluorescence identifying.
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