CN107201222A - A kind of two-dimentional rare earth coordination polymer fluorescent material and preparation method thereof - Google Patents
A kind of two-dimentional rare earth coordination polymer fluorescent material and preparation method thereof Download PDFInfo
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- CN107201222A CN107201222A CN201710304674.4A CN201710304674A CN107201222A CN 107201222 A CN107201222 A CN 107201222A CN 201710304674 A CN201710304674 A CN 201710304674A CN 107201222 A CN107201222 A CN 107201222A
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Abstract
The invention belongs to rare earth metal coordination polymer field, more particularly to a kind of two-dimentional rare earth coordination polymer fluorescent material, its chemical formula is [Sm (Hcit) (H2O)2·2H2O]n, wherein H4Cit is citric acid；Crystal belongs to monoclinic system,P21/cSpace group, cell parameter is：A=10.4392 (8), b=10.0983 (7), c=11.8967 (9), α=90 °, β=111.03 (10) °, γ=90 °.The two-dimentional rare earth coordination polymer fluorescent material that the present invention is provided is after measured：Pure red light is shown at room temperature, and fluorescence decay experiment shows that average life span is 6.45 μ s, shows the good characteristics of luminescence, it is had good application prospect in fluorescent material field；And preparation technology is simple, high income.
Description
Technical field
The invention belongs to rare earth metal complex field of material technology, and in particular to a kind of two-dimentional rare earth coordination polymer is glimmering
Luminescent material（The flexible hydroxycarboxylic acid part samarium complex constituted is alternately arranged by left-and-right spiral chain）And preparation method thereof.
Background technology
In recent years, because rare earth ion complex has higher luminous excitation, high quantum efficiency and phase
The advantages of to longer fluorescence lifetime, it is had in terms of sensing material, photovoltaic device, bio-medical analysis and widely should
With value, and one of important research field as metal luminous organic material, and also achieve in these areas certain
Progress.[de Melo, E. F.; Santana, N. D. C.; Alves, K. G. B.; de Sá, G. F.; de
Melo, C. P.; Rodrigues, M. O.; Júnior, S. A. J. Mater. Chem. C, 2013,45,
7574; Rocha, J.; Carlos, L. D.; Paz, F. A. A.; Ananias, D. Chem. Soc. Rev.,
2011, 40, 926; White, K. A.; Chengelis, D. A.; Gogick, K. A.; Stehman, J.;
Rosi, N. L.; Petoud, S. J. Am. Chem. Soc., 2009,131, 18069; Hao, J. N.; Yan,
B. Chem. Commun. 2015, 51, 7737; Chen, Z.; Sun, Y.; Zhang, L.; Sun, D.; Liu,
F.; Meng, Q.; Wang, R.; Sun, D. Chem. Commun. 2013, 49, 11557].However, lanthanide series metal
The stability and mechanical strength of ionic complex are relatively low, how to select suitable ligand and then make up these defects and further
The fluorescence property of complex is improved, makes it as fluorescent material and obtains the challenge that practical application is also faced with arduousness.Therefore, for lanthanum
It is the research and exploration of metal coordinating polymer fluorescent material, tool is of great significance.
The content of the invention
It is an object of the invention to provide a kind of two-dimentional rare earth coordination polymer fluorescent material（Flexible hydroxycarboxylic acid part samarium
Coordination polymer）And preparation method thereof.
To achieve the above object, the technical solution adopted by the present invention is as follows：
A kind of two-dimentional rare earth coordination polymer fluorescent material, its chemical formula is [Sm (Hcit) (H2O)2·2H2O]n, wherein H4cit
For citric acid；Crystal belongs to monoclinic system,P21/cSpace group, cell parameter is：A=10.4392 (8), b=10.0983
(7), c=11.8967 (9), α=90 °, β=111.03 (10) °, γ=90 °.The two-dimentional rare earth coordination polymer
The molecular structure of fluorescent material is as shown in figure 1, one dimensional helical chain structure is as shown in Fig. 2 two-dimension plane structure is as shown in Figure 3.
Present invention also offers the preparation method of above-mentioned two-dimentional rare earth coordination polymer fluorescent material, it is using water as molten
Agent, citric acid, melamine and Sm (NO3)3·6H2Reacted under hydrothermal conditions after O mixing and the two-dimensional coordination polymer is made
Fluorescent material.
Specifically, can be by citric acid, melamine and Sm (NO3)3·6H2O is added to the water, and mixes 30-40
Min, then constant-temperature enclosed 3 days at 110-130 DEG C, is cooled to room temperature, is coordinated through filtering, washing, being drying to obtain the two dimension
Polymeric fluorescent material.
It is further preferred that citric acid and melamine, Sm (NO3)3·6H2O amount of substance ratio is 0.5-0.7：0.5-
0.7：1, every mM of Sm (NO3)3·6H2The corresponding volumes for adding water of O are 5-7 mL.
Relative to prior art, the present invention has advantages below：
The two-dimentional rare earth coordination polymer fluorescent material that the present invention is provided is after measured：Pure red light is shown at room temperature,
Fluorescence decay experiment shows that average life span is 6.45 μ s, shows the good characteristics of luminescence, it is had in fluorescent material field
Good application prospect；And preparation technology is simple, high income.
Brief description of the drawings
Fig. 1 is [Sm (Hcit) (H2O)2·2H2O]nMolecular structure；
Fig. 2 is [Sm (Hcit) (H2O)2·2H2O]nOne dimensional helical chain structure chart；
Fig. 3 is [Sm (Hcit) (H2O)2·2H2O]nTwo-dimension plane structure figure；
Fig. 4 is [Sm (Hcit) (H2O)2·2H2O]nInfrared spectrogram；
Fig. 5 is [Sm (Hcit) (H2O)2·2H2O]nColor coordinates；
Fig. 6 is [Sm (Hcit) (H2O)2·2H2O]nSolid state fluorescence spectrogram；
Fig. 7 is [Sm (Hcit) (H2O)2·2H2O]nFluorescence decay figure.
Embodiment
Technical scheme is further discussed in detail with reference to embodiments, but protection scope of the present invention
It is not limited thereto.
Embodiment 1
A kind of preparation method of two-dimentional rare earth coordination polymer fluorescent material, be specially：Take citric acid（0.7mmol）, melamine
Amine (0.5mmol）, Sm (NO3)3·6H2O (1mmol) is added in 5 milliliters of water, is stirred 40 minutes, is then sealed in 25 milliliters
In ptfe autoclave, constant temperature three days, are cooled to room temperature at 110 DEG C, through filtering, washing, be dried to obtain pale yellow color lump
Shape crystal, yield is 30.2%.
Embodiment 2
A kind of preparation method of two-dimentional rare earth coordination polymer fluorescent material, be specially：Take citric acid（0.5mmol）, melamine
Amine (0.5mmol）, Sm (NO3)3·6H2O (1mmol) is added in 6 milliliters of water, is stirred 40 minutes, is then sealed in 25 milliliters
In ptfe autoclave, constant temperature three days, are cooled to room temperature at 120 DEG C, through filtering, washing, be dried to obtain pale yellow color lump
Shape crystal, yield is 51.5%.
Embodiment 3
A kind of preparation method of two-dimentional rare earth coordination polymer fluorescent material, be specially：Take citric acid（0.5mmol）, melamine
Amine (0.7mmol）, Sm (NO3)3·6H2O (1mmol) is added in 7 milliliters of water, is stirred 40 minutes, is then sealed in 25 milliliters
In ptfe autoclave, constant temperature three days, are cooled to room temperature at 130 DEG C, through filtering, washing, be dried to obtain pale yellow color lump
Shape crystal, yield is 34%.
Light yellow bulk crystal obtained by preparation is tested as follows.
1）Crystal structure determination：
Choose suitable monocrystalline and carry out X-ray diffraction analysis on Bruker Apex-II CCD diffractometers, test temperature is
296(2)K.Use graphite monochromatised MoKαRay (λ=0.071073 nm), in the range of 2.09 ° of 28.26 ° of ＜ θ ＜
Crystal diffraction point data is collected, data are reduced by empirical method and absorption correction.Pass through SHELXS-97 and SHELXL-
97 laws of procedure are parsed and refine to structure.The coordinate of hydrogen atom is closed by theory hydrogenation or difference Fourier in complex
Obtained into method, the coordinate of non-hydrogen atom carries out anisotropic temperature factor amendment with complete matrix least square method.The crystalline substance of complex
Body data see the table below 1, molecular structure as shown in figure 1, one dimensional helical chain structure is as shown in Fig. 2 two-dimension plane structure such as Fig. 3 institutes
Show.
The crystallographic data of table 1, complex
。
2）Infrared spectrum measurement：
With pellet technique in 400 ~ 4000cm–1In the range of use Germany's BrukerVERTEX70 Fourier infrared spectrographs
Determine.The main infrared absorption peak of gained complex（See Fig. 4）For：3585 cm–1, 3425 cm–1, 3207 cm–1, 2809
cm–1, 2707 cm–1, 2606 cm–1, 1568 cm–1, 1387 cm–1, 1250 cm–1, 1069 cm–1, 924 cm–1。
Wherein, 3425 cm–1Come from O-H stretching vibration absworption peak, and 1568 cm–1, 1387 cm–1The absworption peak at place should belong to
Asymmetric stretching vibration and symmetrical stretching vibration absworption peak in carboxylate radical.
3）Solid fluorescene spectrum is determined：
Fluorescence spectrum is measured by Britain's Edinburgh Instruments FLS980 XRFs.When exciting
Wavelengthλ exDuring=402 nm, complex shows pure red light（See Fig. 5）, and with four characteristic fluorescence emission peaks：
560th, 596,642 and 706 nm, is respectively belonging to4G5/2→6H5/2、4G5/2→6H7/2、4G5/2→6H9/2With4G5/2→6H11/2Jump
Move.Wherein, positioned at 642 nm's4G5/2→6H9/2Launch peak intensity highest（See Fig. 6）.Therefore, it is used as launch wavelength using 642 nm
The test of Fluorescence decay curve has been carried out to complex.The test draws by carrying out double exponential fitting to it, the longevity of complex
Order and beτ 1= 3.58 μs（54.58 %）Withτ 2= 9.91 μs（45.42 %）, average life span is 6.45 μ s（See Fig. 7）.Test
As a result show the coordination polymer at room temperature have the good characteristics of luminescence, therefore its have in fluorescent material field it is larger
Potential using value.
Above-described embodiment is the preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes made without departing from the present invention should be equivalent substitute mode, be included in the guarantor of the present invention
Within the scope of shield.
Claims (4)
1. a kind of two-dimentional rare earth coordination polymer fluorescent material, it is characterised in that its chemical formula is [Sm (Hcit) (H2O)2·
2H2O]n, wherein H4Cit is citric acid；Crystal belongs to monoclinic system,P21/cSpace group, cell parameter is：a = 10.4392
(8), b=10.0983 (7), c=11.8967 (9), α=90 °, β=111.03 (10) °, γ=90 °.
2. the preparation method of two-dimentional rare earth coordination polymer fluorescent material described in claim 1, it is characterised in that using water as molten
Agent, citric acid, melamine and Sm (NO3)3·6H2Reacted under hydrothermal conditions after O mixing and the two-dimensional coordination polymer is made
Fluorescent material.
3. the preparation method of two dimension rare earth coordination polymer fluorescent material as claimed in claim 2, it is characterised in that by lemon
Acid, melamine and Sm (NO3)3·6H2O is added to the water, and mixes 30-40 min, then constant temperature is close at 110-130 DEG C
Close 3 days, be cooled to room temperature, through filtering, washing, being drying to obtain the two-dimensional coordination polymer fluorescent material.
4. the preparation method of two dimension rare earth coordination polymer fluorescent material as claimed in claim 3, it is characterised in that citric acid
With melamine, Sm (NO3)3·6H2O amount of substance ratio is 0.5-0.7：0.5-0.7：1, every mM of Sm (NO3)3·6H2O institutes
The volume that correspondence adds water is 5-7 mL.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108467493A (en) * | 2018-06-12 | 2018-08-31 | 河南大学 | A kind of Ni- bases three-dimensional coordination polymer and preparation method thereof |
| CN111995758A (en) * | 2019-05-11 | 2020-11-27 | 商丘师范学院 | Rare earth coordination polymer probe for detecting guanylic acid and preparation method and application thereof |
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| WO2006113998A1 (en) * | 2005-04-26 | 2006-11-02 | University Of Victoria Innovation And Development Corporation | Production of light from sol-gel derived thin films made with lanthanide doped nanoparticles, and preparation thereof |
| CN102964389A (en) * | 2012-12-04 | 2013-03-13 | 河南大学 | Two-dimensional coordination polymer magnetic material and preparation method thereof |
| CN103864827A (en) * | 2014-03-28 | 2014-06-18 | 中国科学院长春应用化学研究所 | Citric acid and rare earth complex as well as preparation method and application of rare earth catalyst |
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2017
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108467493A (en) * | 2018-06-12 | 2018-08-31 | 河南大学 | A kind of Ni- bases three-dimensional coordination polymer and preparation method thereof |
| CN111995758A (en) * | 2019-05-11 | 2020-11-27 | 商丘师范学院 | Rare earth coordination polymer probe for detecting guanylic acid and preparation method and application thereof |
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