CN103724365A - Transition metal complex based on semirigid bipyridine bisamide organic ligand and terephthalic acid as well as synthetic method and application of transition metal complex - Google Patents
Transition metal complex based on semirigid bipyridine bisamide organic ligand and terephthalic acid as well as synthetic method and application of transition metal complex Download PDFInfo
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Abstract
The invention discloses a transition metal complex based on a semirigid bipyridine bisamide organic ligand and terephthalic acid as well as a synthetic method and application of the transition metal complex. The molecular formula of the transition metal complex is as follows: [Zn(3-bpah)(1,4-BDC)).H2O; [Cd(3-bpah)(1,4-BDC)(H2O)], wherein 3-bpah is N,N'-bi(3-pyridine acylamino)-1 2-cyclohexane. The method comprises the steps of mixing Zb<2+> nitrate or Cd<2+> chloride, the semirigid bipyridine bisamide ligand, terephthalic acid and deionized water, adjusting the pH value of the mixture, pouring the mixture into a high-pressure reaction kettle, performing heat preservation in hydrothermal condition, cooling the mixture to room temperature, and airing the mixture, so as to obtain the target complex. The transition metal complex as well as the synthetic method and application of the transition metal complex have the advantages that the synthetic method is simple, the synthetic yield is high, the synthesized complex has high fluorescence-emission property, fluorescent selectivity to different solvent molecules, and fluorescence identification and detection properties for environmental pollutant nitrobenzene, and can be used as fluorescent material.
Description
Technical field
The invention belongs to fluorescent material synthetic field, particularly a kind of transition metal complex and synthetic method and application based on semi-rigid pair of pyridine bisamide organic ligand and terephthalic acid.
Background technology
Transition metal functional complexes based on organic aromatic carboxylic acid and organic amine mixed ligand has the rich and varied feature of structure, at aspects such as magnetic, catalysis, absorption and fluorescence, has potential using value and is subject to extensive concern.The research of this respect mainly concentrates on the design of novel complexes, fasten pass synthetic and that seek structure and performance, although existing progress of attracting attention, accurately the synthetic title complex that has a fixed structure and performance of expecting, is still very large challenge.And the design of organic amine part of ad hoc structure and the selection of appropriate metal ion are a kind of effective ways of controlling target complex structure and performance.At present, be used for constructing the shared ratio maximum of part that contains pyridine groups in the organic amine part of transition metal functional complexes, but because this type of part is hydrophobic nature, and only pyridine functional groups plays with effect, the hapto of metallic ion coordination limited, cause forming the comparatively harshness of conditional request of title complex, productive rate only has 30%～40%, and productive rate is lower.
Transition metal zinc, cadmium functional complexes demonstrate stronger characteristic fluorescence conventionally, are a kind of potential fluorescent materials, have become an important research content of current fluorescent material aspect.Compared with simple organic compound fluorescence material, this type of zinc, cadmium functional complexes base fluorescent material are because its complex structure is various and operability shows huge advantage.But it is less that zinc, cadmium functional complexes are applied in the research of fluorescence selectivity molecular recognition and fluorescent optical sensor aspect, be especially applied to the selectivity identification of environmental pollutant oil of mirbane and the research detecting and have no especially report.
Summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of synthetic method is simple, synthetic yield is high, synthesis material cost is low, has strong fluorescence emitting characteristics, to different solvents molecule demonstrate fluorescence selectivity, p-nitrophenyl has good selectivity identification and the transition metal complex based on semi-rigid pair of pyridine bisamide organic ligand and terephthalic acid and synthetic method and the application of detection effect.
Technical solution of the present invention is:
Based on a transition metal complex for semi-rigid pair of pyridine bisamide organic ligand and terephthalic acid, the molecular formula of this title complex is as follows:
[Zn(3-bpah)(1,4-BDC)]·H
2O；
[Cd(3-bpah)(1,4-BDC)(H
2O)]；
Wherein, 3-bpah is
n,
n'-bis-(3-picolinamide bases)-1,2-hexanaphthene, Isosorbide-5-Nitrae-BDC is p-phthalic bridge.
A synthetic method for transition metal complex based on semi-rigid pair of pyridine bisamide organic ligand and terephthalic acid, its concrete steps are:
By Zn
2+nitrate or Cd
2+muriate, semi-rigid pair of pyridine bisamide part, terephthalic acid add deionized water, at room temperature stir 20min～40min and form suspended mixture, described semi-rigid pair of pyridine bisamide part is
n,
n'-bis-(3-picolinamide bases)-1,2-hexanaphthene, the mol ratio of described semi-rigid pair of pyridine bisamide part and terephthalic acid is 1:1～1:2, described semi-rigid pair of pyridine bisamide part and Zn
2+nitrate or Cd
2+muriatic mol ratio be 1:1～1:3, with NaOH solution, adjusting pH is 6.5～7.5, pour in autoclave and be warming up to 100 ℃～120 ℃, under hydrothermal condition, be incubated 24h～72h, cool to room temperature and obtain colourless bulk crystals, under room temperature, naturally dry, must based on semi-rigid pair of pyridine bisamide organic ligand and terephthalic acid zinc, cadmium complex.
Described Zn
2+nitrate be Zn (NO
3)
22H
2o, described Cd
2+muriate be CdCl
22.5H
2o.
During intensification, temperature rise rate is 5 ℃/h～10 ℃/h; During cooling, rate of temperature fall is 5 ℃/h～10 ℃/h.
The add-on of described deionized water is 30%～60% of autoclave volume.
The concentration of described NaOH solution is 0.1mol/L～2.0mol/L.
A kind of transition metal complex based on semi-rigid pair of pyridine bisamide organic ligand and terephthalic acid is as the application in fluorescence selective material.
The present invention is take terephthalic acid as bridging aromatic carboxylic acid part, with
n,
n'-bis-(3-picolinamide bases)-1,2-hexanaphthene is neutral organic amine part, by selecting the different metallic zinc of radius, two kinds of different salt of cadmium to construct the title complex of different structure; The hapto and the coordination ability that by introduce bisamide functional group in pyridine groups, increase part; By introducing hexanaphthene group, as a grid, adjust the snappiness of organic amine part, its hexanaphthene group is to exist with chair form or boat conformation, not in same plane, can there is specific conformational change in six atoms on ring, can construct new network structure; The selection of transition metal zinc, cadmium ion also can increase the wetting ability fluorescence property of title complex, thereby causes zinc, cadmium complex to have good fluorescent characteristic; Transition metal zinc, the cadmium complex of 2 two-dimensional framework structures have been synthesized.Wherein, [Zn (3-bpah) (Isosorbide-5-Nitrae-BDC)] H
2o and [Cd (3-bpah) (Isosorbide-5-Nitrae-BDC) (H
2o)] inorganic-organic title complex skeleton shows two kinds of different two-dimensional layer structures.In Zn complex, semi-rigid couple of pyridine bisamide organic ligand 3-bpah takes double coordination pattern, utilizes nitrogen-atoms and the zinc coordination of two pyridine groups; And in cadmium complex, 3-bpah utilizes a pyridine nitrogen and amide oxygen atom and cadmium metal coordination to realize double coordination pattern.In two kinds of title complexs, terephthalic acid show altogether two kinds of different coordination modes: in Zn complex, only have a kind of two monodentate ligand patterns; In cadmium complex, there are two monodentates and two two kinds of coordination modes of chelating.Its beneficial effect is:
(1) synthetic method is simple, and synthesis material is easy to get, with low cost, and synthetic yield is high, and terephthalic acid shows different coordination modes;
(2) adopt semirigid pair of pyridine bisamide part
n,
n'-bis-(3-picolinamide bases)-1,2-cyclohexane give is neutral organic amine part, not only pyridine nitrogen atom and metallic ion coordination, and amide oxygen atom is also potential hapto, and because the introducing of amide group has increased the wetting ability of part, the crystallisation process while having accelerated synthetic transition metal complex, has shortened synthesis cycle, constant temperature time shortens, and power consumption reduces; Hexanaphthene group can reverse flexibly, and the change of its configuration has increased the coordination adaptive faculty of amide group, thereby the coordination possibility of part is increased, and has improved the productive rate of synthetic compound, has reduced synthetic cost; The poorly water-soluble of the title complex that hydrothermal condition forms, has prevented the secondary pollution to environment;
(3) synthetic zinc, cadmium complex at room temperature have strong solid state fluorescence emission characteristic;
(4) under hydrothermal condition, synthetic zinc, cadmium metal complex is water insoluble and common are machine solvent, has prevented the secondary pollution to environment;
(5) synthetic zinc, cadmium complex are after different solvent molecules is processed, and the fluorescence showing in various degree strengthens and Quenching, can make fluorescence selective material;
(6) synthetic zinc, cadmium complex are after the ethanol-water solution that contains different ratios is processed, and in fluorescence intensity and solution, the content of ethanol is linear, can be applied to the ethanol molecule content detecting in ethanol-water solution;
(7) synthetic zinc, cadmium complex are after benzene, toluene or oil of mirbane are processed, and fluorescence intensity change is obvious, and p-nitrophenyl shows good Molecular Recognization;
(8) synthetic zinc, cadmium complex are after the ethanolic soln that contains different concns oil of mirbane is processed, and in fluorescence intensity and solution, the content of oil of mirbane is linear, can be applied to the nitrobenzene in detection oil of mirbane-ethanolic soln.
Accompanying drawing explanation
Fig. 1 is [Zn (3-bpah) (Isosorbide-5-Nitrae-BDC)] of the present invention H
2o powder diagram;
Fig. 2 is [Cd (3-bpah) (Isosorbide-5-Nitrae-BDC) (H of the present invention
2o)] powder diagram;
Fig. 3 is [Zn (3-bpah) (Isosorbide-5-Nitrae-BDC)] of the present invention H
2o and [Cd (3-bpah) (Isosorbide-5-Nitrae-BDC) (H
2o)] thermogram;
In figure: 1-[Zn (3-bpah) (Isosorbide-5-Nitrae-BDC)] H
2o, 2-[Cd (3-bpah) (Isosorbide-5-Nitrae-BDC) (H
2o)];
Fig. 4 is [Zn (3-bpah) (Isosorbide-5-Nitrae-BDC)] of the present invention H
2the coordination environment figure of O;
Fig. 5 is [Zn (3-bpah) (Isosorbide-5-Nitrae-BDC)] of the present invention H
2the two-dimensional network figure of O;
Fig. 6 is [Zn (3-bpah) (Isosorbide-5-Nitrae-BDC)] of the present invention H
2the two-dimensional network topological diagram of O;
Fig. 7 is [Cd (3-bpah) (Isosorbide-5-Nitrae-BDC) (H of the present invention
2o)] coordination environment figure;
Fig. 8 is [Cd (3-bpah) (Isosorbide-5-Nitrae-BDC) (H of the present invention
2o)] two-dimensional network figure;
Fig. 9 is [Cd (3-bpah) (Isosorbide-5-Nitrae-BDC) (H of the present invention
2o)] two-dimensional network topological diagram;
Figure 10 is the fluorescence emission spectrogram of semi-rigid pair of pyridine bisamide organic ligand using in the present invention and zinc of the present invention, cadmium complex;
Figure 11 is through different solvents [Zn (3-bpah) (Isosorbide-5-Nitrae-BDC)] after treatment H
2the fluorescence emission spectrogram of O;
Figure 12 is through different solvents [Zn (3-bpah) (Isosorbide-5-Nitrae-BDC)] after treatment H
2the fluorescence emission peak Strength Changes histogram of O;
Figure 13 is through the aqueous solution of different ethanol contents [Zn (3-bpah) (Isosorbide-5-Nitrae-BDC)] after treatment H
2the fluorescence emission spectrogram of O;
Figure 14 is through the aqueous solution of different ethanol contents [Zn (3-bpah) (Isosorbide-5-Nitrae-BDC)] after treatment H
2the fluorescence intensity of O and the linear relationship chart of ethanol content;
Figure 15 is [Zn (3-bpah) (Isosorbide-5-Nitrae-BDC)] H after benzene, toluene, oil of mirbane are processed
2the fluorescence emission spectrogram of O;
Figure 16 is through the ethanolic soln of different nitrobenzenes [Zn (3-bpah) (Isosorbide-5-Nitrae-BDC)] after treatment H
2the fluorescence emission spectrogram of O;
Figure 17 is through the ethanolic soln of different nitrobenzenes [Zn (3-bpah) (Isosorbide-5-Nitrae-BDC)] after treatment H
2the fluorescence intensity of O and the linear relationship chart of nitrobenzene;
Figure 18 is through different solvents [Cd (3-bpah) (Isosorbide-5-Nitrae-BDC) (H after treatment
2o)] fluorescence emission spectrogram;
Figure 19 is through different solvents [Cd (3-bpah) (Isosorbide-5-Nitrae-BDC) (H after treatment
2o)] fluorescence emission peak Strength Changes histogram;
Figure 20 is through the aqueous solution of different ethanol contents [Cd (3-bpah) (Isosorbide-5-Nitrae-BDC) (H after treatment
2o)] fluorescence emission spectrogram;
Figure 21 is through the aqueous solution of different ethanol contents [Cd (3-bpah) (Isosorbide-5-Nitrae-BDC) (H after treatment
2o)] fluorescence intensity and the linear relationship chart of ethanol content;
Figure 22 is through benzene, toluene, oil of mirbane [Cd (3-bpah) (Isosorbide-5-Nitrae-BDC) (H after treatment
2o)] fluorescence emission spectrogram.
Figure 23 is through the ethanolic soln of different nitrobenzenes [[Cd (3-bpah) (Isosorbide-5-Nitrae-BDC) (H after treatment
2o)] fluorescence emission spectrogram;
Figure 24 is through the ethanolic soln of different nitrobenzenes [Cd (3-bpah) (Isosorbide-5-Nitrae-BDC) (H after treatment
2o)] fluorescence intensity and the linear relationship chart of nitrobenzene;
In figure: 1-[Zn (3-bpah) (Isosorbide-5-Nitrae-BDC)] H
2o, 2-[Cd (3-bpah) (Isosorbide-5-Nitrae-BDC) (H
2o)], 3-
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene.
Embodiment
Synthetic [Zn (3-bpah) (Isosorbide-5-Nitrae-BDC)] H of embodiment 1
2o, wherein, 3-bpah is
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, structural formula is:
, Isosorbide-5-Nitrae-BDC is p-phthalic bridge
By 0.3mmol Zn (NO
3)
22H
2o, 0.10mmol
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, 0.10mmol terephthalic acid and 8.0mL H
2o joins in 25mL beaker successively, under room temperature, stir 40min, with the NaOH solution of 0.1mol/L, adjust pH to 6.5, pour in the autoclave of 25mL, with the heating rate of 5 ℃/h, be warming up to 100 ℃, under hydrothermal condition, be incubated 48h, rate of temperature fall with 5 ℃/h cools the temperature to room temperature, obtains colourless bulk crystals, under room temperature, naturally dries, obtain [Zn (3-bpah) (Isosorbide-5-Nitrae-BDC)] H
2o, productive rate is 48%, as shown in Figure 4, as shown in Figure 5, the reduced graph of its two-dimensional framework structure is as shown in Figure 6 for its two-dimensional network figure for its coordination environment figure.
Synthetic [Zn (3-bpah) (Isosorbide-5-Nitrae-BDC)] H of embodiment 2
2o, wherein, 3-bpah is
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, Isosorbide-5-Nitrae-BDC is p-phthalic bridge
By 0.2 mmol Zn (NO
3)
22H
2o, 0.10mmol
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, 0.15mmol terephthalic acid and 10.0mL H
2o joins in 25mL beaker successively, under room temperature, stir 30min, with the NaOH solution of 1mol/L, adjust pH to 6.8, pour in the autoclave of 25mL, with the heating rate of 10 ℃/h, be warming up to 110 ℃, under hydrothermal condition, be incubated 36h, rate of temperature fall with 10 ℃/h cools the temperature to room temperature, obtains colourless bulk crystals, under room temperature, naturally dries, obtain [Zn (3-bpah) (Isosorbide-5-Nitrae-BDC)] H
2o, productive rate is 56%, as shown in Figure 4, as shown in Figure 5, the reduced graph of its two-dimensional framework structure is as shown in Figure 6 for its two-dimensional network figure for its coordination environment figure.
Synthetic [Zn (3-bpah) (Isosorbide-5-Nitrae-BDC)] H of embodiment 3
2o, wherein, 3-bpah is
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, Isosorbide-5-Nitrae-BDC is p-phthalic bridge
By 0.2 mmol Zn (NO
3)
22H
2o, 0.10mmol
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, 0.15mmol terephthalic acid and 13.0mL H
2o joins in 25mL beaker successively, under room temperature, stir 20min, with the NaOH solution of 2mol/L, adjust pH to 7.2, pour in the autoclave of 25mL, with the heating rate of 5 ℃/h, be warming up to 120 ℃, under hydrothermal condition, be incubated 24h, rate of temperature fall with 10 ℃/h cools the temperature to room temperature, obtains colourless bulk crystals, under room temperature, naturally dries, obtain [Zn (3-bpah) (Isosorbide-5-Nitrae-BDC)] H
2o, productive rate is 66%, as shown in Figure 4, as shown in Figure 5, the reduced graph of its two-dimensional framework structure is as shown in Figure 6 for its two-dimensional network figure for its coordination environment figure.
Synthetic [Cd (3-bpah) (Isosorbide-5-Nitrae-BDC) (H of embodiment 4
2o)], wherein, 3-bpah is
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, Isosorbide-5-Nitrae-BDC is p-phthalic bridge
By 0.2mmol CdCl
22.5H
2o, 0.10mmol
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, 0.10mmol terephthalic acid and 8.0mL H
2o joins in 25mL beaker successively, under room temperature, stir 20min, with the NaOH solution of 0.1mol/L, adjust pH to 6.7, pour in the autoclave of 25mL, with the heating rate of 10 ℃/h, be warming up to 110 ℃, under hydrothermal condition, be incubated 48h, rate of temperature fall with 10 ℃/h cools the temperature to room temperature, obtains colourless bulk crystals, under room temperature, naturally dries, obtain [Cd (3-bpah) (Isosorbide-5-Nitrae-BDC) (H
2o)], productive rate is 58%, and as shown in Figure 7, as shown in Figure 8, the reduced graph of its two-dimensional framework structure as shown in Figure 9 for its two-dimensional network figure for its coordination environment figure.
Synthetic [Cd (3-bpah) (Isosorbide-5-Nitrae-BDC) (H of embodiment 5
2o)], wherein, 3-bpah is
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, Isosorbide-5-Nitrae-BDC is p-phthalic bridge
By 0.2mmol CdCl
22.5H
2o, 0.10mmol
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, 0.15mmol terephthalic acid and 12.0mL H
2o joins in 25mL beaker successively, under room temperature, stir 40min, with the NaOH solution of 1mol/L, adjust pH to 7.0, pour in the autoclave of 25mL, with the heating rate of 5 ℃/h, be warming up to 120 ℃, under hydrothermal condition, be incubated 56h, rate of temperature fall with 5 ℃/h cools the temperature to room temperature, obtains colourless bulk crystals, under room temperature, naturally dries, obtain [Cd (3-bpah) (Isosorbide-5-Nitrae-BDC) (H
2o)], productive rate is 66%, and as shown in Figure 7, as shown in Figure 8, the reduced graph of its two-dimensional framework structure as shown in Figure 9 for its two-dimensional network figure for its coordination environment figure.
Synthetic [Cd (3-bpah) (Isosorbide-5-Nitrae-BDC) (H of embodiment 6
2o)], wherein, 3-bpah is
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, Isosorbide-5-Nitrae-BDC is p-phthalic bridge
By 0.1mmol CdCl
22.5H
2o, 0.10mmol
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, 0.10mmol terephthalic acid and 15.0mL H
2o joins in 25mL beaker successively, under room temperature, stir 30min, with the NaOH solution of 0.5mol/L, adjust pH to 7.5, pour in the autoclave of 25mL, with the heating rate of 5 ℃/h, be warming up to 100 ℃, under hydrothermal condition, be incubated 72h, rate of temperature fall with 10 ℃/h cools the temperature to room temperature, obtains colourless bulk crystals, under room temperature, naturally dries, obtain [Cd (3-bpah) (Isosorbide-5-Nitrae-BDC) (H
2o)], productive rate is 57%, and as shown in Figure 7, as shown in Figure 8, the reduced graph of its two-dimensional framework structure as shown in Figure 9 for its two-dimensional network figure for its coordination environment figure.
Zinc based on semi-rigid pair of pyridine bisamide organic ligand and terephthalic acid, the sign of cadmium complex
(1) powdery diffractometry characterizes phase purity
On Rigaku Ultima IV powder x-ray diffraction, collect powdered diffraction data, actuating current is 40 mA, and voltage is 40 kV.Adopt copper target X ray.Scanning constant, receiving slit wide is 0.1mm.Density data is collected and is used 2
θ/
θscan pattern, sweep limit 5
oto 60
o, sweep velocity is 5
o/ s, span is 0.02
o/ time.Data fitting is used Cerius2 program, and single crystal structure powdery diffractometry spectrum analog transforms and uses Mercury 1.4.1.
As shown in Fig. 1～Fig. 2, the XRD spectra of the zinc based on semi-rigid pair of pyridine bisamide organic ligand and terephthalic acid, the powder x-ray diffraction spectrogram of cadmium complex and matching is substantially identical, shows that title complex is pure phase.
(2) thermogravimetric exosyndrome material stability
Thermostability adopts PE-Pyris Diamond S-II thermal analyzer to complete, 10 ℃/min of heating rate, 20 ℃～800 ℃ of temperature ranges.Fig. 3 shows that the decomposition temperature scope of the synthetic Zn complex of the present invention is 310 ℃～640 ℃, and the decomposition temperature scope of cadmium complex is 380 ℃～570 ℃.
(3) crystal structure determination
With microscope, choose the monocrystalline of suitable size, under room temperature, adopt Bruker SMART APEX II diffractometer (graphite monochromator, Mo-K
a,
l=0.71073) collect diffraction data.Scan mode
w-φ, diffraction data is used SADABS program to carry out absorption correction.Reduction of data and structure elucidation are used respectively SAINT and SHELXTL program to complete.Method of least squares is determined whole non-hydrogen atom coordinates, and obtains hydrogen atom position with theoretical hydrogenation method.Adopt method of least squares to carry out refine to crystalline structure.Fig. 4～Fig. 9 shows the zinc based on semi-rigid pair of pyridine bisamide organic ligand and terephthalic acid synthetic in embodiment 1～embodiment 6, basic coordination situation and the expansion structure of cadmium complex.The partial parameters of its crystallography point diffraction data gathering and structure refinement is as shown in the table:
| | Embodiment | 1 | |
| Molecular weight | 571.88 | 618.91 | |
| Crystallographic system | Three is oblique | Three is oblique | |
| Spacer | P -1 | |
|
| a (?) | 9.3074(5) | 7.8559(4) | |
| b (?) | 11.8484(6) | 11.5298(6) | |
| c (?) | 13.2041(6) | 16.1232(8) | |
| α (°) | 108.8050(10) | 82.5120(10) | |
| β (°) | 97.7350(10) | 81.0530(10) | |
| γ (°) | 112.4420(10) | 73.3020(10) | |
| V (? 3) | 1217.51(11) | 1376.12(12) | |
|
|
2 | 2 | |
| Theoretical density (g m –3) | 1.560 | 1.494 | |
| Uptake factor (mm -1) | 1.065 | 0.843 | |
| F(000) | 592 | 628 | |
| GOF | 1.038 | 1.008 | |
| R 1 (I > 2σ(I)) | 0.0258 | 0.0192 | |
| wR 2 (I>2σ(I)) | 0.0744 | 0.0555 |
Zinc based on semi-rigid pair of pyridine bisamide organic ligand and terephthalic acid, the test of the photoluminescent property of cadmium complex
[Zn (3-bpah) (Isosorbide-5-Nitrae-BDC)] H synthetic to embodiment 1～embodiment 3
2o(title complex 1), synthetic [Cd (3-bpah) (Isosorbide-5-Nitrae-BDC) (H of embodiment 4～embodiment 6
2o)] (title complex 2), semi-rigid pair of pyridine bisamide organic ligand
n,
n'-bis-(Niacinamide)-1, the solid state fluorescence spectrum under 2-hexanaphthene room temperature is measured, and result shows that title complex 1 and title complex 2 have strong fluorescence emitting characteristics, can be applicable to fluorescent material.
The title complex of 30mg 1, title complex 2 are ground to form respectively to uniform powder in agate mortar, carry out solid state fluorescence spectrum test, and semi-rigid pair of pyridine bisamide organic ligand getting homogenous quantities tested in contrast.As shown in figure 10, the light that is 315nm with wavelength under solid state is as exciting light, semi-rigid couple of pyridine bisamide organic ligand 3-bpah has fluorescent emission feature, and maximum emission wavelength is 386nm, and this emission peak can be summed up as π → π * or the n → π * transfer transport in part.When part and zinc, cadmium ion coordination form after title complex, the solid fluorescence character of its title complex 1, title complex 2 has a very large change.The maximum emission wavelength of title complex 1, title complex 2 is respectively 420nm, 424nm, with respect to 3-bpah part, there is certain red shift, and fluorescence intensity significantly increases, this owing to form after title complex electric charge by part the result to metal transfer (LMCT).Experimental result shows, zinc, cadmium complex have good fluorescent emission character, can be used as fluorescent material.
The powder of the title complex of 30mg 1 is dipped into respectively to methyl alcohol (MeOH), ethanol (EtOH), acetonitrile (MeCN), the methylene dichloride (CH of 30ml
2cl
2), DMF (DMF), methyl-sulphoxide (DMSO), tetrahydrofuran (THF) (THF), ether (Diethyl ether), deionized water (H
2o) or in hexanaphthene (Cyclohexane) solvent, after ultrasonication 2h, by after solution stirring 24h, filtration obtains the powdered sample through solvent molecule title complex 1 after treatment, then by sample powder at 120 ℃ of dry 5h, then the solid state fluorescence spectrum under the different product powder of test specimens room temperature respectively.As shown in figure 11, contrast with the fluorescence spectrum of the title complex 1 without solvent treatment, the fluorescence intensity increase of the title complex 1 after Ethanol Treatment is the most remarkable, and the fluorescence intensity reduction of the title complex 1 soaking through cyclohexane solution is the most obvious, the fluorescence intensity change of other solvent molecules title complex 1 after treatment is relatively little.Figure 12 shows that title complex 1 in different solvents, process after the histogram of fluorescence intensity change, show that title complex 1 has fluorescence selectivity to different solvents molecule.
The powder of the title complex of 30mg 1 is dipped into respectively in the water-ethanol solvent of water, ethanol and 10wt%, 20wt%, 40wt%, 60wt%, 80wt%, ultrasonication 2h, by after solution stirring 24h, filtration obtains the powdered sample of title complex 1, this sample, at 120 ℃ of dry 5h, then is carried out to photoluminescent property test to title complex 1 powder after treatment in the alcohol-water solvent of different ratios respectively.As shown in figure 13, in alcohol-water mixing solutions, along with the increase gradually of alcohol solvent amount, the fluorescence intensity of the title complex 1 of this solution-treated of process increases gradually.Figure 14 has shown the change curve increasing with alcohol solvent ratio through ethanol-water solution title complex 1 fluorescence intensity after treatment of different ratios, result show the fluorescence intensity of title complex 1 and ethanol content linear, therefore according to the fluorescence intensity of different ethanol-water solutions title complex 1 after treatment, can accurately calculate the content of ethanol in this kind of mixing solutions.
The powder of the title complex of 30mg 1 is dipped into respectively in benzene, toluene, oil of mirbane solvent, ultrasonication 2h, by after solution stirring 24h, filtration obtains the powdered sample of title complex 1, by this sample at 120 ℃ of dry 5h, again respectively to carrying out photoluminescent property test through benzene, toluene, oil of mirbane title complex 1 powder after treatment, as shown in figure 15.In Figure 15, curve a, b, c, d are respectively without solvent treatment, through the fluorescence emission spectrum of benzene, toluene, oil of mirbane title complex 1 after treatment.With the title complex 1 without solvent treatment, the fluorescence intensity of the title complex 1 after benzene or O for toluene has enhancing in various degree, and the most remarkable through the fluorescence intensity quencher of oil of mirbane title complex 1 after treatment, show that title complex 1 p-nitrophenyl has good fluorescence recognition reaction.
The powder of the title complex of 30mg 1 is dipped into respectively in the ethanolic soln of different nitrobenzenes, ultrasonication 2h, to under solution stirring, place after 24h, filtration obtains the powdered sample of title complex 1, this sample, at 120 ℃ of dry 5h, then is carried out to photoluminescent property test to title complex 1 powder after treatment in the ethanolic soln of different nitrobenzenes respectively.As shown in figure 16, in oil of mirbane-ethanolic soln, along with the increase gradually of nitrobenzene, the fluorescence intensity of the title complex 1 of this solution-treated of process reduces gradually.Figure 17 has shown the change curve increasing with nitro phenenyl concentration through ethanolic soln title complex 1 fluorescence intensity after treatment of different nitrobenzenes, result show the fluorescence intensity of title complex 1 and the content of oil of mirbane linear.Result shows, title complex 1 has using value in nitrobenzene context of detection.
The powder of the title complex of 30mg 2 is dipped into respectively to methyl alcohol (MeOH), ethanol (EtOH), acetonitrile (MeCN), the methylene dichloride (CH of 30ml
2cl
2), DMF (DMF), methyl-sulphoxide (DMSO), tetrahydrofuran (THF) (THF), ether (Diethyl ether), deionized water (H
2o) or in hexanaphthene (Cyclohexane) solvent, after ultrasonication 2h, by after solution stirring 24h, filtration obtains the powdered sample through solvent molecule title complex 2 after treatment, then by sample powder at 120 ℃ of dry 5h, then test respectively the solid state fluorescence spectrum under different sample powder room temperatures.If figure is as shown in the of 18, with the complex fluorescent spectral comparison without solvent treatment, the fluorescence intensity of the title complex 2 after Ethanol Treatment significantly increases, and title complex 2 fluorescence intensities of soaking through cyclohexane solution significantly reduce, other solvent molecules title complex 2 after treatment shows respectively fluorescence intensity change in various degree.Figure 19 shows that title complex 2 in different solutions, process after the histogram of fluorescence intensity change, show that title complex 2 has fluorescence selectivity to different solvents molecule.
The powder of the title complex of 30mg 2 is dipped into respectively in the water-ethanol solvent of water, ethanol and 10wt%, 20wt%, 40wt%, 60wt%, 80wt%, ultrasonication 2h, by after solution stirring 24h, filtration obtains the powdered sample of title complex 2, this sample, at 120 ℃ of dry 5h, then is carried out to photoluminescent property test to title complex 2 powder after treatment in the alcohol-water solvent of different ratios respectively.As shown in figure 20, in alcohol-water mixing solutions, along with the increase gradually of alcohol solvent amount, the fluorescence intensity of the title complex 2 of this solution-treated of process increases gradually.Figure 21 has shown the change curve increasing with alcohol solvent ratio through ethanol-water solution title complex 2 fluorescence intensities after treatment of different ratios, result show the fluorescence intensity of title complex 2 and ethanol content linear, therefore according to the fluorescence intensity of different ethanol-water solutions title complex 2 after treatment, can accurately calculate the content of ethanol in this kind of mixing solutions.
The powder of the title complex of 30mg 2 is dipped into respectively in benzene, toluene, oil of mirbane solvent, ultrasonication 2h, to under solution stirring, place after 24h, filtration obtains the powdered sample of title complex 2, by this sample at 120 ℃ of dry 5h, again respectively to carrying out photoluminescent property test through benzene, toluene, oil of mirbane title complex 2 powder after treatment, as shown in figure 22.In Figure 22, curve a, b, c, d are respectively without solvent treatment, through the fluorescence emission spectrum of benzene, toluene, oil of mirbane title complex 1 after treatment.With the title complex 2 without solvent treatment, the fluorescence intensity of the title complex 2 after benzene or O for toluene has enhancing in various degree, and the most remarkable through the fluorescence intensity quencher of oil of mirbane title complex 2 after treatment, show that title complex 2 p-nitrophenyls have good fluorescence recognition reaction.
The powder of the title complex of 30mg 2 is dipped into respectively in the ethanolic soln of different nitrobenzenes, ultrasonication 2h, by after solution stirring 24h, filtration obtains the powdered sample of title complex 2, this sample, at 120 ℃ of dry 5h, then is carried out to photoluminescent property test to title complex 2 powder after treatment in the ethanolic soln of different nitrobenzenes respectively.As shown in figure 23, in oil of mirbane-ethanolic soln, along with the increase gradually of nitrobenzene, the fluorescence intensity of the title complex 2 of this solution-treated of process reduces gradually.Figure 24 has shown the change curve increasing with nitro phenenyl concentration through ethanolic soln title complex 2 fluorescence intensities after treatment of different nitrobenzenes, result show the fluorescence intensity of title complex 2 and the content of oil of mirbane linear.Result shows, title complex 2 has using value in nitrobenzene context of detection.
Claims (7)
1. the transition metal complex based on semi-rigid pair of pyridine bisamide organic ligand and terephthalic acid, is characterized in that: the molecular formula of this title complex is as follows:
[Zn(3-bpah)(1,4-BDC)]·H
2O；
[Cd(3-bpah)(1,4-BDC)(H
2O)]；
Wherein, 3-bpah is
n,
n'-bis-(3-picolinamide bases)-1,2-hexanaphthene, Isosorbide-5-Nitrae-BDC is p-phthalic bridge.
2. the synthetic method of a kind of transition metal complex based on semi-rigid pair of pyridine bisamide organic ligand and terephthalic acid as claimed in claim 1, is characterized in that: concrete steps are as follows:
By Zn
2+nitrate or Cd
2+muriate, semi-rigid pair of pyridine bisamide part, terephthalic acid add deionized water, at room temperature stir 20min～40min and form suspended mixture, described semi-rigid pair of pyridine bisamide part is
n,
n'-bis-(3-picolinamide bases)-1,2-hexanaphthene, the mol ratio of described semi-rigid pair of pyridine bisamide part and terephthalic acid is 1:1～1:2, described semi-rigid pair of pyridine bisamide part and Zn
2+nitrate or Cd
2+muriatic mol ratio be 1:1～1:3, with NaOH solution, adjusting pH is 6.5～7.5, pour in autoclave and be warming up to 100 ℃～120 ℃, under hydrothermal condition, be incubated 24h～72h, cool to room temperature and obtain colourless bulk crystals, under room temperature, naturally dry, must based on semi-rigid pair of pyridine bisamide organic ligand and terephthalic acid zinc, cadmium complex.
3. the synthetic method of the transition metal complex based on semi-rigid pair of pyridine bisamide organic ligand and terephthalic acid according to claim 2, is characterized in that: described Zn
2+nitrate be Zn (NO
3)
22H
2o, described Cd
2+muriate be CdCl
22.5H
2o.
4. the synthetic method of the transition metal complex based on semi-rigid pair of pyridine bisamide organic ligand and terephthalic acid according to claim 2, is characterized in that: during intensification, temperature rise rate is 5 ℃/h～10 ℃/h; During cooling, rate of temperature fall is 5 ℃/h～10 ℃/h.
5. the synthetic method of the transition metal complex based on semi-rigid pair of pyridine bisamide organic ligand and terephthalic acid according to claim 2, is characterized in that: the add-on of described deionized water is 30%～60% of autoclave volume.
6. the synthetic method of the transition metal complex based on semi-rigid pair of pyridine bisamide organic ligand and terephthalic acid according to claim 2, is characterized in that: the concentration of described NaOH solution is 0.1mol/L～2.0mol/L.
7. a kind of transition metal complex based on semi-rigid pair of pyridine bisamide organic ligand and terephthalic acid as claimed in claim 1 is as the application in fluorescence selective material.
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