CN108129385A - A kind of compound quaternary ammonium salt nonlinear optics crystalline state material and preparation method thereof - Google Patents
A kind of compound quaternary ammonium salt nonlinear optics crystalline state material and preparation method thereof Download PDFInfo
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- CN108129385A CN108129385A CN201810061795.5A CN201810061795A CN108129385A CN 108129385 A CN108129385 A CN 108129385A CN 201810061795 A CN201810061795 A CN 201810061795A CN 108129385 A CN108129385 A CN 108129385A
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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Abstract
The invention belongs to fine chemistry synthesis technical fields, and in particular to a kind of compound quaternary ammonium salt nonlinear optics crystalline state material, for the compound that picratol anion and 1 benzyl, 4 dimethylamino naphthyridine quaternary ammonium salt cationic form, chemical constitution such as formula（Ⅰ）It is shown, it is abbreviated as [BzDMAP] [PIC].Preparation method includes：Preparation, the preparation of silver picrate and the preparation of compound quaternary ammonium salt of 1 benzyl, 4 dimethylamino naphthyridine salt.Compound quaternary ammonium salt crystalline material of the present invention has more excellent non-linear optical active, and first-order hyperpolarizability is 86.58 × 10‑31Esu, about 12.64 times of reference crystal KDP, and it is apparently higher than picrate anion and quaternary ammonium salt cationic, there are electrostatic interactions and a large amount of C-HO hydrogen bond actions especially between anion and cation, it plays an important role in terms of the generation of crystal structure and the enhancing of stability and optical characteristics.
Description
Technical field
The invention belongs to fine chemistry synthesis technical fields, and in particular to a kind of compound quaternary ammonium salt nonlinear optics crystalline state material
Material and preparation method thereof.
Background technology
At present, the electric charge transfer of organic crystal has many different applications, burn as bitter taste acid derivative is used for treatment,
Anti-corrosion, hemostasis etc., the organic crystal partly containing bitter taste acid acceptor also shows very excellent non-linear optical property.
Nonlinear optical material has been extensively studied in fields such as telecommunications, can be applied to optical oomputing, optical data storage and light
Information processing etc..Organic molecule with notable non-linear optical active is generally replaced by conjugated structure one end electronic donor group
α-electron conjugated group and the other end form the electron accepting groups composition of " push-and-pull " conjugation, donor and acceptor groups, which provide, to be divided
The ground state charge of son is asymmetric, this is the necessary condition of second nonlinear.The nonlinear optical property of organic crystal with they
Inorganic counterparts, which are compared, has advantage, and in general, the requirement of second harmonic, material should have centrosymmetric structure, cause
Larger nonlinear second-order optical susceptibility, material also must be non-centrosymmetrical.Due to the organic crystal of the acid acceptor containing bitter taste
Second nonlinear degree it is high, optical transparence is wide, band gap is big and the ionic bond between nitro phenonium ion and organic ligand
It is relatively strong, therefore be suitable.
A large amount of organic molecule transfer crystal picric acid（Donor）Go out special application with organic receptor molecule displays.Scientific research people
Member has studied the crystallization picrate of picric acid formation and various organic compounds, including its ion energy, hydrogen bond and π-π
Effect.Recently, also the crystal structure and optical property of a collection of picrate adduct are studied, finds these compounds
Combination be largely dependent upon the property of affiliate.So bitter taste acid anion and substituted benzyl dimethylamino pyrrole
The introducing of pyridine ion has great importance to synthesizing various structural motifs, and especially its optical property greatly promotes, and makes people
Generate new interest.
Invention content
The purpose of the present invention is to provide a kind of compound quaternary ammonium salt crystalline material with more excellent non-linear optical active,
And provide preparation method.
To achieve these goals, the invention is realized by the following technical scheme：
A kind of compound quaternary ammonium salt nonlinear optics crystalline state material is designed, is picratol anion and 1- benzyl -4- dimethylaminos
The compound of pyridine quaternary ammonium salt cation composition, chemical constitution such as formula（Ⅰ）It is shown：
（Ⅰ）.
The preparation method of compound quaternary ammonium salt nonlinear optics crystalline state material of the present invention, includes the following steps：
（1）A certain amount of 4-dimethylaminopyridine and benzyl bromide are taken in container, adding in proper amount of acetone makes fully to dissolve, then stirring
It is heated to reflux under the conditions of mixing 18~30 hours, is then down to room temperature and is filtered, then wash filter with proper amount of acetone and ether successively
Cake, it is dry, obtain white solid powder, as 1- benzyls -4-dimethylaminopyridine salt；The 4-dimethylaminopyridine and benzyl
The molar ratio of bromine is 1:0.8~1.2；
（2）A certain amount of silver nitrate is taken in container, suitable quantity of water is added to make fully to dissolve, adds a certain amount of sodium hydroxide（It is complete immediately
Into reaction）, filtration drying；Obtained solid and a certain amount of picric acid are added in proper amount of methanol and fully dissolved, and stir at room temperature
Mix 18~30 hours, then staticly settled, filtered successively, ether washing filter cake, drying, obtain silver picrate, be protected from light guarantor
It deposits；The silver nitrate, sodium hydroxide and picric molar ratio are 1:0.8~1.2:1.6~2.4；
（3）The a certain amount of 1- benzyls -4-dimethylaminopyridine salt is taken, is dissolved in proper amount of methanol, one is added under stirring condition
The methanol solution of the quantitative silver picrate, is heated to reflux 1~2h, stands filtrate after filtering and volatilizees, pale yellow crystals are precipitated,
Up to compound quaternary ammonium salt nonlinear optics crystalline state material of the present invention；1- benzyls -4-dimethylaminopyridine the salt and silver picrate
Molar ratio be 1:0.8~1.2.
The present invention has following positive beneficial effect：
Compound quaternary ammonium salt crystalline material of the present invention has more excellent non-linear optical active, first-order hyperpolarizability (βtot) be
86.58 × 10-31Esu, about reference crystal KDP（βKDP = 6.85 × 10-31esu）12.64 times, it is and apparent
Higher than picrate anion [PIC]-With cationic [BzDMAP]+, there are electrostatic phases especially between anion and cation
Interaction and a large amount of C-HO hydrogen bond actions, not only play important work in terms of the generation of crystal structure and stability
With, and be also such in terms of its optical characteristics is enhanced.
Description of the drawings
Fig. 1 is the crystal structure figure of 1 compound quaternary ammonium salt of the embodiment of the present invention.
Fig. 2 is the infrared spectrum of 1 compound quaternary ammonium salt of the embodiment of the present invention.
Fig. 3 is the Raman spectrum of 1 compound quaternary ammonium salt of the embodiment of the present invention.
Fig. 4 is the fluorescence pattern of 1 compound quaternary ammonium salt of the embodiment of the present invention.
Fig. 5 is the PXRD collection of illustrative plates of 1 compound quaternary ammonium salt of the embodiment of the present invention.
Fig. 6 is the hot weight-differential heat of 1 compound quaternary ammonium salt of the embodiment of the present invention（TG-DTA）Collection of illustrative plates.
Fig. 7 is the thermogravimetric mass spectrum of 1 compound quaternary ammonium salt of the embodiment of the present invention（TG-MS）Collection of illustrative plates.
Fig. 8 is the solid UV absorption of 1 compound quaternary ammonium salt of the embodiment of the present invention（SS-UV）Collection of illustrative plates.
Fig. 9 is the solid transmitted spectrum collection of illustrative plates of 1 compound quaternary ammonium salt of the embodiment of the present invention.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, below in conjunction with specific embodiment, to this
Invention is further described.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.Involved raw material, is commercially available unless otherwise instructed, involved detection method is such as without spy in following embodiment
It does not mentionlet alone bright, is then conventional method.
Embodiment 1
A kind of compound quaternary ammonium salt nonlinear optics crystalline state material, is prepared with following steps：
（1）The 4-dimethylaminopyridine of 0.01mol and the benzyl bromide of 0.01mol are taken in 100mL ground conical flasks, adds in 30mL
Acetone makes fully to dissolve, then is heated to reflux under agitation 24 hours, and white powder is gradually formed in reaction process, is then dropped
It is filtered to room temperature, then washs filter cake with 40mL acetone and 40mL ether successively, be dried in vacuo, obtain white solid powder,
As 1- benzyls -4-dimethylaminopyridine salt；
（2）0.01mol silver nitrates are taken in beaker, 20mL water is added to make fully to dissolve, adds 0.01mol sodium hydroxides（It is put into
It can react rapidly）, filtration drying；Filtration drying obtained solid and 0.02mol picric acid are added in fully molten in 40mL methanol
Solution, and is stirred at room temperature 24 hours, then staticly settled, filtered successively, ether washing filter cake, drying, obtain bitter taste
Sour silver, is kept in dark place；
（3）1- benzyls -4-dimethylaminopyridine salt described in 1mmol is taken, is dissolved in 10mL methanol, is added under stirring condition described
Containing silver picrate（1mmol）10mL methanol solutions, be heated to reflux 1h, after filtering by filtrate stand volatilize, light yellow crystalline substance is precipitated
Body is to get compound quaternary ammonium salt nonlinear optical material of the present invention.
Gained pale yellow crystals are subjected to coherent detection, specific data are as follows：
Crystal structure：At room temperature, on Bruker Smart CCD X-ray single crystal diffractometers, with through graphite monochromator monochrome
The Mo of changeKαIt radiates as light source（λ= 0.71073Å）, diffraction is collected in the range of certain angle with β-ω scan modes under room temperature
Data.Total data restores and structure elucidation SHELX-97 programs, coordinate and anisotropy physochlaina infudibularis to whole non-hydrogen atoms
Number has carried out complete matrix least square method refine, and all hydrogen atoms are using theoretical plus hydrogen.Compound quaternary ammonium salt belongs to anorthic system,P-
1 space group, it is cationic [BzDMAP] containing 1 1- benzyl -4-dimethylaminopyridine in an asymmetric cell+With a bitter taste
Acid anion [PIC]-.Crystal structure is shown in Fig. 1, and crystallographic data is shown in Table 1：
1 compound quaternary ammonium salt crystallographic data of table
。
Infrared [IR (cm-1)]：ν (phenyl ring C-H)：3080；ν(C=C)：1629、1480；ν(NO2)：1560、1440、
1330；ν(C–C)：1280；ν(C–O)：1160；ν(C–N)：1080、934、906；Refer to attached drawing 2.
Raman [Raman (cm-1)]：ν (phenyl ring C-H)：3072；νCH2(C–H)：2929；ν(NO2)：1567、1367；ν(C
=C)：1463；ν(NO2)：1305；ν(C–O)：1151；ν(C–N)：1000、815、738；Refer to attached drawing 3.
Fluorescence analysis：When being excited with maximum 240 nm of excitation wavelength, quaternary ammonium salt is 386,396,428,450,467
There is strong emission peak at nm, refer to attached drawing 4.
X ray diffraction [PXRD]:Prepare the powder x-ray diffraction of material（λ= 1.5406Å）Collection of illustrative plates uses day at room temperature
The model RigakU-Ultima IV tests of this Neo-Confucianism company production.
Determination condition is pipe pressure：40 kV, Guan Liu：400 mA, Cu KαRadiation scanning speed：2º·min−1, between stepping
Every：0.02 °, scanning range（2ϴ）：2-50o, scan mode are continuous scanning, see attached drawing 5.As can be seen from Figure 5, it tests
The XRD peaks observed coincide very well with the XRD spectrum being fitted by crystal structural data, show that quaternary ammonium salt has preferable knot
Crystalline substance and purity.
Hot weight-differential heat [TG-DTA]:The fusing point of compound quaternary ammonium salt is 125.5 DEG C, can be stabilized before 293.6 DEG C.
Start rapid decomposition at 293.6 DEG C, decomposed rapidly at 293.6 DEG C -376.1 DEG C, the loss of quality later tends to be steady and no longer becomes
Change.Refer to attached drawing 6.
Thermogravimetric-mass spectrum（TG-MS）:During thermogravimetric analysis is done, substance when decomposition temperature is 357.7 DEG C does mass spectrum
Analysis, by mass-to-charge ratio in gained mass spectrogram（m/z）It is fragment ion H for 182O+·Composition, it is fragment ion that mass-to-charge ratio, which is 28,
CO+·Composition, it is fragment ion NO that mass-to-charge ratio, which is 30,+Composition, it is fragment ion C that mass-to-charge ratio, which is 44,2H6N+Composition, mass-to-charge ratio
It is fragment ion C for 776H5 +Composition, it is fragment ion C that mass-to-charge ratio, which is 105,6H5N2 +Composition.
Solid ultraviolet spectra (Solid state UV):Ultraviolet-ray visible absorbing in the range of 200 ~ 800 nm, wherein
The π of phenyl ring conjugated system is absorbed as at 258 nmπ*Transition, 288 nm are the characteristic ultraviolet absorption of bitter taste acid compounds
Peak refers to attached drawing 8.
Solid transmitted spectrum：Transmitance of the prepared quaternary ammonium salt in the range of 400 ~ 800 nm is more than 70%, shows quaternary ammonium
Salt has preferable optical application, refers to attached drawing 9.
And further study its electric dipole momentμ tot(D), polarizabilityα (×10-24) and first-order hyperpolarizability esuβ
(×10-31Esu), it is shown in Table 2.
2 electric dipole moment of tableμ tot, polarizabilityαAnd first-order hyperpolarizabilityβ
。
Table 3 show DFT/B3LYP/6-31G (d, p) calculate gained crystal electric dipole moment (μ i), polarizability (α ij) and
First-order hyperpolarizability (β ijk ).The dipole moment being calculated is 17.22D.xOn direction, the absolute value highest of dipole moment, point
Amountμ x Value is equal to 13.15D.Be calculated polarizability (α tot ) it is 86.58 × 10-24 esu。
It further uses DFT/B3LYP/6-31G (d, p) and does the ingredient calculating of gained crystal and to the first hyperpolarization
Rate, polarizability and dipole moment are compared, and are shown in Table 3.
3 crystalline component optical parameter of table compares
Note：[PIC]-For bitter taste acid anion, [BzDMAP]+For 1- benzyls -4-dimethylaminopyridine cation.
3 data of table show the first-order hyperpolarizability (β of crystaltot) it is 86.58 × 10-31Esu, about reference crystal
KDP（βKDP = 6.85 × 10-31esu）12.64 times.The above result shows that compound quaternary ammonium salt of the present invention is a kind of fine
Nonlinear optics crystalline state material, the value of crystal first-order hyperpolarizability be apparently higher than picrate anion and quaternary ammonium salt sun from
Son, electrostatic interaction and a large amount of C-HO hydrogen bond actions especially between anion and cation, not only in crystalline substance
It plays an important role in terms of the generation of body structure and stability, and is also such in terms of its optical characteristics is enhanced.
Embodiment 2
A kind of compound quaternary ammonium salt nonlinear optics crystalline state material, is prepared with following steps：
（1）The 4-dimethylaminopyridine of 0.01mol and the benzyl bromide of 0.008mol are taken in 100mL ground conical flasks, is added in
30mL acetone makes fully to dissolve, then is heated to reflux under agitation 24 hours, white powder is gradually formed in reaction process, so
After be down to room temperature and filtered, then wash filter cake with 40mL acetone and 40mL ether successively, be dried in vacuo, obtain white solid powder
End, as 1- benzyl -4-dimethylaminopyridine salt；
（2）0.01mol silver nitrates are taken in beaker, 20mL water is added to make fully to dissolve, adds 0.008mol sodium hydroxides（It is put into
It can react rapidly）, filtration drying；Filtration drying obtained solid and 0.024mol picric acid are added in fully molten in 40mL methanol
Solution, and is stirred at room temperature 24 hours, then staticly settled, filtered successively, ether washing filter cake, drying, obtain bitter taste
Sour silver, is kept in dark place；
（3）1- benzyls -4-dimethylaminopyridine salt described in 1mmol is taken, is dissolved in 10mL methanol, is added under stirring condition described
Containing silver picrate（0.8mmol）10mL methanol solutions, be heated to reflux 1h, after filtering by filtrate stand volatilize, be precipitated it is light yellow
Crystal is to get compound quaternary ammonium salt nonlinear optical material of the present invention.
Embodiment 3
A kind of compound quaternary ammonium salt nonlinear optics crystalline state material, is prepared with following steps：
（1）The 4-dimethylaminopyridine of 0.01mol and the benzyl bromide of 0.012mol are taken in 100mL ground conical flasks, is added in
30mL acetone makes fully to dissolve, then is heated to reflux under agitation 24 hours, white powder is gradually formed in reaction process, so
After be down to room temperature and filtered, then wash filter cake with 40mL acetone and 40mL ether successively, be dried in vacuo, obtain white solid powder
End, as 1- benzyl -4-dimethylaminopyridine salt；
（2）0.01mol silver nitrates are taken in beaker, 20mL water is added to make fully to dissolve, adds 0.012mol sodium hydroxides（It is put into
It can react rapidly）, filtration drying；Filtration drying obtained solid and 0.016mol picric acid are added in fully molten in 40mL methanol
Solution, and is stirred at room temperature 24 hours, then staticly settled, filtered successively, ether washing filter cake, drying, obtain bitter taste
Sour silver, is kept in dark place；
（3）1- benzyls -4-dimethylaminopyridine salt described in 1mmol is taken, is dissolved in 10mL methanol, is added under stirring condition described
Containing silver picrate（1.2mmol）10mL methanol solutions, be heated to reflux 1h, after filtering by filtrate stand volatilize, be precipitated it is light yellow
Crystal is to get compound quaternary ammonium salt nonlinear optical material of the present invention.
Embodiment 4
A kind of compound quaternary ammonium salt nonlinear optics crystalline state material, is prepared with following steps：
（1）The 4-dimethylaminopyridine of 0.01mol and the benzyl bromide of 0.01mol are taken in 100mL ground conical flasks, adds in 25mL
Acetone makes fully to dissolve, then is heated to reflux under agitation 18 hours, and white powder is gradually formed in reaction process, is then dropped
It is filtered to room temperature, then washs filter cake with 50mL acetone and 50mL ether successively, be dried in vacuo, obtain white solid powder,
As 1- benzyls -4-dimethylaminopyridine salt；
（2）0.01mol silver nitrates are taken in beaker, 25mL water is added to make fully to dissolve, adds 0.01mol sodium hydroxides（It is put into
It can react rapidly）, filtration drying；Filtration drying obtained solid and 0.02mol picric acid are added in fully molten in 50mL methanol
Solution, and is stirred at room temperature 24 hours, then staticly settled, filtered successively, ether washing filter cake, drying, obtain bitter taste
Sour silver, is kept in dark place；
（3）1- benzyls -4-dimethylaminopyridine salt described in 1mmol is taken, is dissolved in 8mL methanol, is added under stirring condition described
Containing silver picrate（1mmol）8mL methanol solutions, be heated to reflux 1h, after filtering by filtrate stand volatilize, light yellow crystalline substance is precipitated
Body is to get compound quaternary ammonium salt nonlinear optical material of the present invention.
Embodiment 5
A kind of compound quaternary ammonium salt nonlinear optics crystalline state material, is prepared with following steps：
（1）The 4-dimethylaminopyridine of 0.01mol and the benzyl bromide of 0.01mol are taken in 100mL ground conical flasks, adds in 35mL
Acetone makes fully to dissolve, then is heated to reflux under agitation 30 hours, and white powder is gradually formed in reaction process, is then dropped
It is filtered to room temperature, then washs filter cake with 30mL acetone and 30mL ether successively, be dried in vacuo, obtain white solid powder,
As 1- benzyls -4-dimethylaminopyridine salt；
（2）0.01mol silver nitrates are taken in beaker, 18mL water is added to make fully to dissolve, adds 0.01mol sodium hydroxides（It is put into
It can react rapidly）, filtration drying；Filtration drying obtained solid and 0.02mol picric acid are added in fully molten in 30mL methanol
Solution, and is stirred at room temperature 24 hours, then staticly settled, filtered successively, ether washing filter cake, drying, obtain bitter taste
Sour silver, is kept in dark place；
（3）1- benzyls -4-dimethylaminopyridine salt described in 1mmol is taken, is dissolved in 15mL methanol, is added under stirring condition described
Containing silver picrate（1mmol）15mL methanol solutions, be heated to reflux 1h, after filtering by filtrate stand volatilize, light yellow crystalline substance is precipitated
Body is to get compound quaternary ammonium salt nonlinear optical material of the present invention.
Claims (9)
1. a kind of compound quaternary ammonium salt nonlinear optics crystalline state material, it is characterised in that：For picratol anion and 1- benzyls -4-
The compound of dimethylamino naphthyridine quaternary ammonium salt cationic composition.
2. compound quaternary ammonium salt nonlinear optics crystalline state material according to claim 1, it is characterised in that：The compound
Chemical constitution such as formula（Ⅰ）It is shown：
（Ⅰ）.
3. the preparation method of compound quaternary ammonium salt nonlinear optics crystalline state material described in claim 2, which is characterized in that including following
Step：
（1）A certain amount of 4-dimethylaminopyridine and benzyl bromide is taken to be placed in container, adding in proper amount of acetone makes fully to dissolve, then
It is heated to reflux under stirring condition 18~30 hours, is then down to room temperature and is filtered, then washed successively with proper amount of acetone and ether
Filter cake, it is dry, obtain white solid powder, as 1- benzyls -4-dimethylaminopyridine salt；
（2）A certain amount of silver nitrate is taken to be placed in container, suitable quantity of water is added to make fully to dissolve, adds a certain amount of sodium hydroxide, is filtered
It is dry, obtained solid and a certain amount of picric acid are added in proper amount of methanol and fully dissolved, and be stirred at room temperature 18~30 hours,
Then staticly settled, filtered successively, ether washing filter cake, drying, obtain silver picrate；
（3）The a certain amount of 1- benzyls -4-dimethylaminopyridine salt is taken, is dissolved in proper amount of methanol, one is added under stirring condition
The methanol solution of the quantitative silver picrate, is heated to reflux 1~2h, stands filtrate after filtering and volatilizees, pale yellow crystals are precipitated,
Up to compound quaternary ammonium salt nonlinear optics crystalline state material of the present invention.
4. preparation method according to claim 3, it is characterised in that：Step（1）4-dimethylaminopyridine used and benzyl
The molar ratio of bromine is 1:0.8~1.2.
5. preparation method according to claim 4, it is characterised in that：Step（1）4-dimethylaminopyridine used and benzyl
The molar ratio of bromine is 1:1.
6. preparation method according to claim 3, it is characterised in that：Step（2）Silver nitrate used, sodium hydroxide and bitter taste
The molar ratio of acid is 1:0.8~1.2:1.6~2.4.
7. preparation method according to claim 6, it is characterised in that：Step（2）Silver nitrate used, sodium hydroxide and bitter taste
The molar ratio of acid is 1:1:2.
8. preparation method according to claim 3, it is characterised in that：Step（3）1- benzyls -4-dimethylaminopyridine used
The molar ratio of salt and silver picrate is 1:0.8~1.2.
9. preparation method according to claim 8, it is characterised in that：Step（3）1- benzyls -4-dimethylaminopyridine used
The molar ratio of salt and silver picrate is 1:1.
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| CN109761887A (en) * | 2019-01-29 | 2019-05-17 | 华南农业大学 | Degradation of organic dyes catalyst, composite catalyzing material and preparation method thereof |
| CN112011331A (en) * | 2020-07-30 | 2020-12-01 | 华南农业大学 | Novel antimonate bromide luminescent material, luminescent film and preparation method thereof |
| CN112142650A (en) * | 2020-10-12 | 2020-12-29 | 华南农业大学 | Novel bismuth iodide, preparation method thereof and application thereof in fluorescence and photodegradation |
| CN115057812A (en) * | 2022-07-11 | 2022-09-16 | 华南农业大学 | Tetrachloromanganese composite quaternary ammonium salt, fiber film material and preparation method thereof |
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| CN101823995A (en) * | 2010-03-31 | 2010-09-08 | 北京科技大学 | 4-(4-dimethylaminostyryl) picoline3-carboxyl-4-hydroxy benzene sulfonate, nonlinear optical crystal and preparation method thereof |
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| CN109761887A (en) * | 2019-01-29 | 2019-05-17 | 华南农业大学 | Degradation of organic dyes catalyst, composite catalyzing material and preparation method thereof |
| CN112011331A (en) * | 2020-07-30 | 2020-12-01 | 华南农业大学 | Novel antimonate bromide luminescent material, luminescent film and preparation method thereof |
| CN112011331B (en) * | 2020-07-30 | 2021-06-15 | 华南农业大学 | Novel antimonate bromide luminescent material, luminescent film and preparation method thereof |
| CN112142650A (en) * | 2020-10-12 | 2020-12-29 | 华南农业大学 | Novel bismuth iodide, preparation method thereof and application thereof in fluorescence and photodegradation |
| CN115057812A (en) * | 2022-07-11 | 2022-09-16 | 华南农业大学 | Tetrachloromanganese composite quaternary ammonium salt, fiber film material and preparation method thereof |
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