CN103992341A - Mixed organic carboxylic acid containing rare earth complex as well as preparation method and application of mixed organic carboxylic acid containing rare earth complex - Google Patents
Mixed organic carboxylic acid containing rare earth complex as well as preparation method and application of mixed organic carboxylic acid containing rare earth complex Download PDFInfo
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- CN103992341A CN103992341A CN201410239954.8A CN201410239954A CN103992341A CN 103992341 A CN103992341 A CN 103992341A CN 201410239954 A CN201410239954 A CN 201410239954A CN 103992341 A CN103992341 A CN 103992341A
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Abstract
The invention relates to a 1-naphthoic acid and 2-pyrazinecarboxylic acid mixed ligand containing rare earth metal complex as well as a preparation method and an application of the1-naphthoic acid and 2-pyrazinecarboxylic acid mixed ligand containing rare earth metal complex. The complex has the chemical formula as follows: [Ln(mu3-OH)(NA)(pyzc)], wherein Ln is a lanthanide rare earth ion Dy(III), Gd(III) or Yb(III), NA<-> is the univalent anion of 1-naphthoic acid, and pyzc<-> is the univalent anion of 2-pyrazinecarboxylic acid. The complex is prepared by using a solvothermal method and is relatively high in yield and good in repeatability. A fluorescent material of the complex is the first 1-naphthoic acid and 2-pyrazinecarboxylic acid mixed ligand containing rare earth metal complex, can emit an emission peak with a rare earth ion characteristic or an emission peak of a ligand in a solid state and can be used as a molecular-based fluorescent material to exert a huge application value in the field of material science.
Description
about subsidizing the statement of research or exploitation
21171129 and 21173157) and Tianjin S & T Developmentin High Institutions fund planning item (fund number: subsidy 2012ZD01) the present patent application obtains state natural sciences fund (fund number:.
Technical field
The present invention relates to metal-organic coordination compounds and molecular based fluorescent magnetic material technology field thereof, particularly contain preparation method and the application of the rare earth metal complex of 1-naphthoic acid and 2-pyrazine carboxylic acid mixed ligand.Described compound is the rare earth metal complex that first case contains 1-naphthoic acid and 2-pyrazine carboxylic acid mixed ligand simultaneously, and its optical property makes it can be used as molecular based optical material to be applied at material science.
Background technology
Rare earth compounding is the coordination chemistry thing that a class is formed round center rare earth ion by organic ligand.In recent years, rare earth compounding is because of its abundant topological framework and compositing characteristic, in fields such as catalysis, absorption, lewis' acid identification and optical, electrical, magnetics, have important use or potential application prospect (Zheng Ziqiao, Li Hongying. Rare Earth Functional Materials. Beijing: Chemical Industry Press
2003; B. D. Chandler, D. T. Cramb, G. K. H. Shimizu.
j. Am. Chem. Soc.,
2006, 128 (32): 10403 ~ 10412; H.-L. Gao, L. Yi, B. Zhao, X.-Q. Zhao, P. Cheng, D.-Z. Liao, S.-P.Yan,
inorg. Chem.2006,45,5980 ~ 5988; Q.-Y. Liu, W.-F. Wang, Y.-L. Wang, Z.-M. Shan, M.-S. Wang, J. Tang,
inorg. Chem., 2012,51,2381 ~ 2392; Zhan Wangcheng, Guo Yun, Guo Yanglong, Gong Xueqing, Wang Yanqin, Lu Guanzhong, Chinese science: chemistry, 2012,42 (9): 1289 ~ 1307).
Trivalent rare earth ions in rare earth compound
f-
ftransition is often by partly shielding effect.Therefore, the intensity of the Absorption and emission spectra of rare earth ion itself is very weak.Yet the fluorescence intensity of rare earth compounding can regulate and control by organic ligand.Desirable organic ligand not only has and has good efficiency of light absorption, and between rare earth ion and organic ligand, needs depositing energy transformation efficiently, and then affects luminous intensity and the efficiency of rare earth ion.As the conjugated system that contains larger p electronics, fragrant organic acid part has stronger uv-absorbing, can, by coordinate bond and rare earth ion bonding, form the coordination compound of novel structure.Meanwhile, organic acid part can sensitization rare earth luminescence.Up to now, contain phenyl polyacid, amino acid, pyridine polyacid and
bthe binary of-diones organic ligand or ternary rare earth complex are obtained (Zhang Hongjie, Ma Jianfang, Yang Kuiyue, Pan Lihua, luminous journal, 1996,17 (1), 79-83 successively; Peak, Niu Chunji, Ni Jiazan, Acta PhySico-Chimica Sinica, 1991,7 (3), 362-365; Tian Jun, Yin Jingqun, Ou Yangke neon, Yao Huiqin, Speciality Petrochemicals progress, 2002,3 (9), 21-23), and its structure and luminescent properties have been carried out to comprehensive research.Yet, take the aromatic carboxylic acid of rigidity and the construction method of the rare earth metal complex that nitrogen heterocyclic ring carboxylic acid is mixed ligand and strategy and the correlative study aspect luminescent properties still shallow, further investigate the relation of the Structure and luminescence performance of its metal complexes, impact and the understanding to its rule particularly the molecular structure of fluorescent chemicals and surrounding environment brought to the behavior of compound spectrum and luminous intensity, must make people utilize fluorescent chemicals as fluorescence dye, electroluminescent material, photoconductive material, the aspect such as energy converslon materials and probe is all of great significance tool.
Summary of the invention
The object of the invention is to provide one to contain 1-naphthoic acid and the rare earth metal complex of 2-pyrazine carboxylic acid mixed ligand and preparation method and the application thereof of this title complex simultaneously.This title complex is the rare earth metal complex that first case contains 1-naphthoic acid and 2-pyrazine carboxylic acid mixed ligand simultaneously, there is the fluorescence emission peak of rare earth ion feature or the characteristic emission peak of organic ligand, can at material science, be used widely as molecular based fluorescent material.
For achieving the above object, the invention provides following technology contents:
The rare earth metal complex that 1-naphthoic acid and 2-pyrazine carboxylic acid be mixed ligand of take with following chemical general formula: [Ln (
m 3-OH) (NA) (pyzc)], wherein Ln is La rear earth ion Dy (III), Gd (III) or Yb (III); NA
-the univalent anion of 1-naphthoic acid, pyzc
-be the univalent anion of 2-pyrazine carboxylic acid, its molecular formula is as follows:
The preparation method of the rare earth metal complex that contains 1-naphthoic acid and 2-pyrazine carboxylic acid mixed ligand of the present invention, it is characterized in that: 1-naphthoic acid, 2-pyrazine carboxylic acid and hydrated rare-earth nitrate are obtained to colourless bulk crystals via solvent thermal reaction in redistilled water and organic solvent, and wherein the mol ratio of 1-naphthoic acid, 2-pyrazine carboxylic acid and hydrated rare-earth nitrate is 2 ~ 2.5:2:1.5 ~ 2; Redistilled water: the volume of organic solvent is 3 ~ 2: 2 ~ 3; The pH value scope of controlling is 4 ~ 5; 160 ~ 170
oClower insulation dropped to room temperature after three days, and then washing is dry; Obtain colourless bulk crystals.
Solvent thermal reaction of the present invention refers in the stainless steel cauldron of inner liner polytetrafluoroethylene, take redistilled water and organic solvent as reaction medium, by temperature control oven, heat (heated perimeter: 100 ~ 300 ℃) and make internal tank produce spontaneous pressure (1 ~ 100 Mpa), make indissoluble or insoluble substance dissolves crystallization under normal conditions.
Organic solvent of the present invention is methyl alcohol, ethanol, DMF or acetonitrile.Preferably water and methyl alcohol or ethanol form mixed solvent.
The monocrystalline of the organic rare earth carboxylate metal complexes of mixing of the present invention, is characterized in that this complex crystal is in tetragonal system
i spacer, unit cell parameters is
a=
b=18.885 (7) ~ 19.0364 (14),
c=8.222 (3) ~ 8.3437 (12),
v=2932.3 (19) ~ 3023.6 (5)
3,
z=8; See Fig. 1.In rare earth metal complex of the present invention, four discrete rare earth ions are by four
m 3-OH
-form the subelement of four core cubanes bunch with the naphthoic acid anionic aggregated of four bidentate bridgings.Four adjacent core cubane bunch subelements are further expanded and are formed one-dimensional chain structure by the carboxyl oxygen atom in the 2-pyrazine carboxylic acid of single deprotonation.The characteristic infrared absorption peak of this rare earth compounding optical material is 3631 ± 5 cm
-1, 1649 ± 5 cm
-1, 1622 ± 3 cm
-1, 1560 ± 5 cm
-1, 1420 cm
-1, 1382 cm
-1, 1264 cm
-1, 1160 cm
-1, 1031 ± 2 cm
-1, 859 ± 3 cm
-1, 796 cm
-1, 777 cm
-1, 647 cm
-1(seeing Fig. 2); Title complex has higher thermostability, and its one dimension skeleton is 325
oCdecompose afterwards (seeing Fig. 3); This title complex has reliable phase purity (seeing Fig. 4).
The preparation method of rare earth metal complex single crystal of the present invention is as follows:
1-naphthoic acid, 2-pyrazine carboxylic acid and rare earth nitrate are obtained to colourless bulk crystals via solvent thermal reaction in redistilled water and organic solvent, and wherein the mol ratio of 1-naphthoic acid, 2-pyrazine carboxylic acid and rare earth nitrate is 2 ~ 2.5:2:1.5 ~ 2; Redistilled water: the volume of organic solvent is 3 ~ 2: 2 ~ 3; The pH value scope of controlling is 4 ~ 5; 160 ~ 170
oClower insulation dropped to room temperature after three days, and then washing is dry; Obtain colourless bulk crystals.The following examples 1-3 all adopts this method, and spy is illustrated.
The present invention further discloses and take the application aspect preparation molecular based fluorescent material of rare earth metal complex that 1-naphthoic acid and 2-pyrazine carboxylic acid be mixed ligand, wherein said molecular based fluorescent material refers to that fluorescent material, glo-stick, fluorescent plastic, fluorescent ink, fluorescent needle are weaved cotton cloth, fluorescence dye and embedded photoluminescent material.
The distinguishing feature of the rare earth metal complex that contains 1-naphthoic acid and 2-pyrazine carboxylic acid mixed ligand prepared by the present invention is:
(1) the present invention is a rare earth metal complex that simultaneously contains 1-naphthoic acid and 2-pyrazine carboxylic acid mixed ligand.
(2) magneticsubstance in the present invention adopts solvent thermal process preparation, and productive rate is higher, and favorable reproducibility has higher thermostability and phase purity, can in material science, be applied as solid fluorescence material.
Accompanying drawing explanation
Fig. 1 title complex [Ln (
m 3-OH) (NA) (pyzc)] crystalline structure figure (a-b);
Fig. 2 title complex [Ln (
m 3-OH) (NA) (pyzc)] infrared spectrogram;
Fig. 3 title complex [Ln (
m 3-OH) (NA) (pyzc)] thermogravimetric analysis figure;
Fig. 4 title complex [Ln (
m 3-OH) (NA) (pyzc)] powder diagram;
Fig. 5 title complex [Ln (
m 3-OH) (NA) (pyzc)] fluorescence spectrum figure.
Embodiment
For simple and object clearly, below appropriate omission the description of known technology, in order to avoid those unnecessary details impact descriptions to the technical program.Below in conjunction with preferred embodiment, the present invention will be further described, is illustrated especially, prepares initial substance 1-naphthoic acid, 2-pyrazine carboxylic acid and the hydration group of the lanthanides nitrate of the compounds of this invention and all can buy from the market.
embodiment 1
The rare earth metal complex that is mixed ligand based on 1-naphthoic acid and 2-pyrazine carboxylic acid
asynthetic:
By 1-naphthoic acid (0.2 mmole, 34.4 milligrams), 2-pyrazine carboxylic acid (0.2 mmole, 24.8 milligrams) and Dysprosium nitrate hexahydrate (0.15 mmole, 68.5 milligrams) be dissolved in redistilled water (6.0 mL) and methyl alcohol (4.0 mL), with triethylamine, regulating pH is 4, after stirred for several minute, encloses in water heating kettle.170
ounder C, be incubated after three days, with 3.0 ° of Ch
– 1speed programmed cooling to room temperature, obtain colourless bulk crystals, then use methanol wash, air drying.
embodiment 2
The rare earth metal complex that is mixed ligand based on 1-naphthoic acid and 2-pyrazine carboxylic acid
bsynthetic:
By 1-naphthoic acid (0.2 mmole, 34.4 milligrams), 2-pyrazine carboxylic acid (0.2 mmole, 24.8 milligrams) and gadolinium nitrate hexahydrate (0.2 mmole, 90.3 milligrams) be dissolved in redistilled water (6.0 mL) and methyl alcohol (4.0 mL), with triethylamine, regulating pH is 4, after stirred for several minute, encloses in water heating kettle.At 160 ℃, be incubated after three days, with 3.0 ℃ of h
– 1speed programmed cooling to room temperature, obtain colourless bulk crystals, then use methanol wash, air drying.
embodiment 3
The rare earth metal complex that is mixed ligand based on 1-naphthoic acid and 2-pyrazine carboxylic acid
csynthetic:
By 1-naphthoic acid (0.25 mmole, 43.0 milligrams), 2-pyrazine carboxylic acid (0.2 mmole, 24.8 milligrams) and five nitric hydrate ytterbium (0.15 mmoles, 74.9 milligrams) be dissolved in redistilled water (4.0 mL) and methyl alcohol (6.0 mL), with triethylamine, regulating pH is 5, after stirred for several minute, encloses in water heating kettle.At 170 ℃, be incubated after three days, with 3.0 ° of Ch
– 1speed programmed cooling to room temperature, obtain colourless bulk crystals, then use methanol wash, air drying.
The present invention prepare (embodiment 1-3,
a-
c) contain 1-naphthoic acid and 2-pyrazine carboxylic acid mixed ligand the structural characterization of rare earth metal complex as follows:
(1) crystal structure determination (Fig. 1)
Choose under the microscope the monocrystalline of the suitable size of size, under 173 or 296 K, on Bruker APEX II CCD diffractometer, use through the Mo-K of graphite monochromatization alpha-ray (λ=0.71073), with
j-
ωmode is collected diffraction data.All diffraction datas carry out semiempirical absorption correction by SADABS software by multi-scan method.Unit cell parameters is determined by method of least squares.Reduction of data and structure elucidation are used respectively SAINT and SHELXL routine package to complete.All non-hydrogen atoms carry out anisotropy refine by complete matrix method of least squares.Structure is shown in Fig. 1.The partial parameters of the data gathering of crystallography point diffraction and structure refinement is in Table 1.
The rare earth metal complex that table 1. contains 1-naphthoic acid and 2-pyrazine carboxylic acid mixed ligand
Main crystallographic data and refine parameter
| ? | A | B | C |
| Molecular formula | C 16H 11DyN 2O 5 | C 16H 11GdN 2O 5 | C 16H 11YbN 2O 5 |
| Molecular weight | 473.77 | 468.52 | 484.31 |
| Theoretical density (g cm –3) | 2.115 | 2.058 | 2.194 |
| Uptake factor (mm –1) | 5.052 | 4.417 | 6.409 |
| Crystalline size (mm) | 0.18 × 0.17 × 0.15 | 0.18 × 0.17 × 0.16 | 0.18 × 0.17 × 0.15 |
| Crystallographic system | tetragonal | tetragonal | tetragonal |
| Spacer | I | I | I |
| a (?) | 18.9363(12) | 19.0364(14) | 18.885(7) |
| b (?) | 18.9363(12) | 19.0364(14) | 18.885(7) |
| c (?) | 8.2997(10) | 8.3437(12) | 8.222(3) |
| V (? 3) | 2976.1(4) | 3023.6(5) | 2932.3(19) |
| Z | 8 | 8 | 8 |
| F(000) | 1816 | 1800 | 1848 |
| GOF on F 2 | 1.050 | 1.022 | 1.090 |
| R (int) | 0.0435 | 0.0168 | 0.0763 |
| R 1 a , wR 2 b ( I >2 σ( I)) | 0.0235, 0.0440 | 0.0126, 0.0272 | 0.0347, 0.0861 |
| R 1, wR 2(all data) | 0.0246, 0.0445 | 0.0131, 0.0274 | 0.0352, 0.0865 |
a R 1?=?Σ(||
F o|-|
F c||)/Σ|
F o|.?
b wR 2?=?[Σ
w(|
F o|
2-|
F c|
2)
2 /Σ
w(
F o 2)
2]
1/2
(2) infrared measurement (Fig. 2)
Infrared spectra adopts pellet technique to measure on the infrared spectrometer of Nicolet FT-IR – 200.
(3) (Fig. 3) measured in thermogravimetric analysis
The thermogravimetric analysis experiment of rare earth compounding is to complete on the thermogravimetric analyzer of Shimadzu simultaneous DTG – 60A, under nitrogen protection with 5
oCthe speed of/min is heated to 800 from room temperature
oCmeasure.Result shows that the one dimension skeleton of rare earth metal complex is 325
oCbefore can stable existence.After temperature continues to raise, the skeleton of title complex starts to decompose, and residual residue is rare earth oxide.
(4) powdery diffractometry characterizes phase purity (Fig. 4)
Powder diffraction data is collected on Bruker D8 ADVANCE diffractometer and measures.Instrumentation voltage is 40 kV, and electric current is 40 mA.Use the Cu target X ray of graphite monochromatization.Divergent slit width is 0.6 mm, and anti-scatter slit width is 3 mm, and Soller slit is 4
o; Data gathering is used 2
q/
qscan pattern, 5
oto 50
oin scope, continuous sweep completes, and sweep velocity is 0.1
o/ second, step-length is 0.01
o.Single crystal structure powdery diffractometry Spectrum simulation transforms and uses Mercury 1.4.1 software package.Rare earth compounding
a-
cpowdery diffractometry result (Fig. 4) show that it has reliable phase purity, for its application as fluorescent material provides assurance.
embodiment 4
The present invention prepare (embodiment 1-3,
a-
c) research of rare earth metal complex optical property is as follows:
By after the prepared complex crystal enrichment of embodiment 1-3, through further milled processed, in Jobin Yvon (Horiba) Fluorolog-3 fluorescence spectrophotometer, carry out the test of solid fluorescence.Test result shows due to the transmission ofenergy of mixed ligand to rare earth ion, makes title complex sample A obtain strong emission peak at 460,571 and 688 nm places; Title complex sample C obtains strong emission peak at 380 and 458 nm places.Because part is subject to rare earth ion perturbation, make title complex sample B at 408 and 491 nm places, show the emission peak of part, fluorometric investigation the results are shown in Figure 5.
The rare earth metal complex that the present invention proposes is a kind of senior fluorescent material that can stable existence under standard state, there is structure capable of regulating, prepare simple, the obvious advantage of fluorescence photosensitive effect, can be used for making fluorescent material (such as fluorescence paint, fluorescent ink, glo-stick, fluorescent needle fabric etc.), be expected to be applied in fluorescence chemical field.
Claims (9)
1. the rare earth metal complex that 1-naphthoic acid and 2-pyrazine carboxylic acid be mixed ligand of take with following chemical general formula:
[Ln(
m 3-OH)(NA)(pyzc)]；
Wherein Ln is La rear earth ion, Ln=Dy (III), Gd (III) or Yb (III); NA
-1-naphthoic acid univalent anion, pyzc
-be 2-pyrazine carboxylic acid univalent anion, its molecular formula is as follows:
。
2. rare earth metal complex described in claim 1, the main infrared absorption peak that it is characterized in that title complex is 3631 ± 5 cm
-1, 1649 ± 5 cm
-1, 1622 ± 3 cm
-1, 1560 ± 5 cm
-1, 1420 cm
-1, 1382 cm
-1, 1264 cm
-1, 1160 cm
-1, 1031 ± 2 cm
-1, 859 ± 3 cm
-1, 796 cm
-1, 777 cm
-1, 647 cm
-1, there is infrared spectrogram as shown in Figure 2; The one dimension skeleton of title complex can stable existence before 325 ℃, has thermogravimetric analysis figure as shown in Figure 3.
3. the monocrystalline of rare earth metal complex described in claim 1, is characterized in that this complex crystal is in tetragonal system, and spacer is
i , unit cell parameters is
a=
b=18.885 (7) ~ 19.0364 (14),
c=8.222 (3) ~ 8.3437 (12),
v=2932.3 (19) ~ 3023.6 (5)
3,
z=8; Basic structure is one, and to take four core cubanes bunch be basic architecture unit, the one-dimensional chain structure of expanding by the 2-pyrazine carboxylic acid of single deprotonation, as shown in Figure 1.
4. described in claim 1, take the preparation method of the rare earth metal complex that 1-naphthoic acid and 2-pyrazine carboxylic acid be mixed ligand, it is characterized in that: 1-naphthoic acid, 2-pyrazine carboxylic acid and hydrated rare-earth nitrate are obtained to colourless bulk crystals via solvent thermal reaction in redistilled water and organic solvent, and wherein the mol ratio of 1-naphthoic acid, 2-pyrazine carboxylic acid and hydrated rare-earth nitrate is 2 ~ 2.5:2:1.5 ~ 2; Redistilled water: the volume ratio of organic solvent is 3 ~ 2: 2 ~ 3; The pH value scope of controlling is 4 ~ 5; After being incubated three days at 160 ~ 170 ℃, drop to room temperature, then washing, dry, obtain colourless bulk crystals.
5. preparation method claimed in claim 4, wherein said solvent thermal reaction refers in the stainless steel cauldron of inner liner polytetrafluoroethylene, take redistilled water and organic solvent as reaction medium, by temperature control oven, heat 100 ~ 300 ℃ and make internal tank produce spontaneous 1 ~ 100 Mpa pressure, make indissoluble or insoluble substance dissolves crystallization under normal conditions.
6. preparation method claimed in claim 4, wherein said organic solvent is one or more mixed solvents of methyl alcohol, ethanol, DMF, acetonitrile.
7. preparation method claimed in claim 4, wherein said organic solvent is that water and methyl alcohol or ethanol form mixed solvent.
8. claimed in claim 1ly take the application aspect preparation molecular based fluorescent material of rare earth metal complex that 1-naphthoic acid and 2-pyrazine carboxylic acid be mixed ligand.
9. application claimed in claim 1, molecular based fluorescent material wherein refers to that fluorescent material, glo-stick, fluorescent plastic, fluorescent ink, fluorescent needle are weaved cotton cloth, fluorescence dye and embedded photoluminescent material.
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| CN106243055A (en) * | 2016-07-29 | 2016-12-21 | 渤海大学 | Triazine radical tricarboxylic acids heavy rare earth coordination compounds and preparation method, characterizing method and application |
| CN115141381A (en) * | 2022-08-16 | 2022-10-04 | 河西学院 | Rare earth metal praseodymium (III) complex and preparation method thereof |
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