CN108129504A - A kind of preparation method and applications of the 8-hydroxyquinoline complex with four nuclear structures - Google Patents
A kind of preparation method and applications of the 8-hydroxyquinoline complex with four nuclear structures Download PDFInfo
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Abstract
The invention discloses a kind of preparation method and applications of 8 hydroxyquinoline complexes with four nuclear structures, belong to metal organic coordination technical field of chemistry.Preparation method of the present invention comprises the concrete steps that：By organic ligand (E, E') 2,2 (1,3 divinyl phenyl) double 8 acetoxyl group quinaldines are dissolved in N, N dimethylformamides and methanol, then add in the aqueous solution of metallic aluminium or gallium salt, obtained mixed solution is placed in the container of sealing, 30~80 DEG C of reactions to crystalline products are precipitated, with methanol washed product, drying.Two kind of 8 hydroxy quinazine metal complex that the present invention prepares has good fluorescence property, is preparing the application aspects such as luminescent device with potential economic value.In addition, luminescent material preparation method provided by the invention is simple, raw material sources are extensively, it can be achieved that large-scale production, has wide Commercial Prospect.
Description
Technical field
The invention belongs to metal-organic coordination chemical fields, and in particular to two kinds of 8-hydroxyquinolines with four nuclear structures
The preparation method and application of aluminium plus gallium complex.
Background technology
At present, luminescent material is broadly divided into inorganic material, organic material and Metal-organic complex material etc..It is organic and
Phosphor has shown that out the prospect of being widely applied in illumination, display, molecule sensing and optical device etc., some
Phosphor (such as BaMgAl10O17:Eu2+And GdMgB5O10:Ce3+, Tb3+) or even be converted to commercially produced product, nothing
Machine luminescent material has many advantages, such as that photoluminescent band is narrow, bright in luster, light absorpting ability is strong, high conversion efficiency；And on the other hand, it
Luminosity usually by the influence factors such as atomic structure, ingredient, particle size and pattern, interface restrict.And organic light emission
Material has many advantages, such as the defects of adjustability is good, rich in color, light, flexible strong, compensates for many phosphors.
In order to combine the respective advantage of inorganic and organic materials, Metal-organic complex is as a kind of new organic and inorganic
Hybrid material comes into being.Metal-organic complex be between inorganic matter and organic matter, it is not only good with inorganic matter
Stability also has many advantages, such as that organic matter fluorescence quantum efficiency is high, thus be considered as the widest luminescent material of application prospect it
One.Since metal complex is in the successful application of organic luminescent device and optical sensor etc., make metal complex conduct
A kind of novel luminous organic material is increasingly subject to the attention of researcher.In addition, metal-organic functions complex effectively will
Organic and inorganic two kinds of completely different components are merged and have simultaneously the property of the two, can be produced in field of light emitting materials
Raw novel property.
Metal-organic complex has been applied to the hair of electron transport material, Organic Light Emitting Diode (OLED) extensively
In the cushioning layer material of the material of main part and organic solar batteries (OSC) of light and fluorescent dye.Wherein three (8-hydroxyquinolines)
Aluminium has preferable electron affinity (~3.0eV) and ionization potential (~5.95eV), relatively low highest occupied molecular orbital electricity
Position (~-5.7eV), the advantages that function film is easily prepared, good thermal stability (glass transition temperature is up to 172 DEG C) by into
Work(is applied to OLED fields.By Alq3Inspiration, 8-hydroxyquinoline metalloid organic coordination compound be applied to organic electroluminescence hair
The making of optical device.In recent years, the structure of the 8-hydroxyquinoline metal complexes of people's synthesis is mainly monokaryon MqnType, so
And MqnThe device luminous intensity of type luminescent materials and quantum yield etc. cannot still reach practical stage, and monokaryon
Metal organic complex limitation even hinders the novel 8-hydroxyquinoline metalloid for preparing controlled architecture and good luminous performance
Organic material, in order to further regulate and control and optimize the emission wavelength of 8-hydroxyquinoline metal complexes, service life and quantum yield,
Develop new synthetic method and strategy to obtain with clear and definite structure, cost is relatively low and the 8-hydroxyquinoline class of good luminous performance is more
Core metal organic complex is of great significance.
Invention content
In consideration of it, the technical problems to be solved by the invention are to provide the 8-hydroxyquinoline complex with four nuclear structures
Preparation method, to this method green, low cost, it is easy to operate, while prepare 8-hydroxyquinoline metal organic complex
It shines and cell imaging performance with good.
The present invention is achieved by the following technical programs.
The present invention provides a kind of 8-hydroxyquinoline complex with four nuclear structures, which has
Four nuclear structures shown in formula (I), wherein：M is Al or Ga；
Invention also provides the preparation methods of above-mentioned 8-hydroxyquinoline complex, specifically include following steps：
By (E, E') -2, the double -8- acetoxyl groups quinaldine dissolvings of 2- (1,3- divinyl phenyl) in organic solvent, will
The aqueous solution of Metal aluminum salt or gallium salt is added drop-wise to wherein, and mixed solution is sealed in the reaction kettle of 80mL, keeps 30~80
DEG C reaction 20 hours, yellow bulk crystals are obtained by filtration, is washed with methanol and ether and dried in air.
The dosage of the double -8- acetoxyl groups quinaldines of (E, the E') -2,2- (1,3- divinyl phenyl) and organic solvent
Compare 10mmol:10~20mL.
Double -8- acetoxyl groups the quinaldines of (E, the E') -2,2- (1,3- divinyl phenyl) and Metal aluminum salt or gallium
The molar ratio of salt is 1:1~6.Further, the double -8- acetoxyl groups quinolines of described (E, E') -2,2- (1,3- divinyl phenyl)
Which pyridine and Metal aluminum salt or the molar ratio of gallium salt are 1:2.
Further, mixed solution of the organic solvent for n,N-Dimethylformamide and methanol, the two volume ratio 1：2
~10.
Further, the Metal aluminum salt is aluminum nitrate.
Further, the gallium salt is gallium nitrate.
The 8-hydroxyquinoline complex with four nuclear structures that above-mentioned preparation method obtains can made as luminescent material
It is applied in preparation optical device.
Compared with prior art, the present invention has following technique effect：
1st, 8-hydroxyquinoline aluminium plus gallium complex prepared by the present invention has four nuclear structures shown in (I), this two kinds cooperations
Object all has good luminescent properties in solution and solid-state.
2nd, the preparation method of 8-hydroxyquinoline complex of the present invention with four nuclear structures is simple, and raw material sources are extensive, into
This is low, environmental pollution is small, it can be achieved that large-scale production, has wide Commercial Prospect.
Description of the drawings
Fig. 1 is the mono-crystalline structures figure of the 8-hydroxyquinoline aluminium with four nuclear structures.
Fig. 2 is the mono-crystalline structures figure of the 8-hydroxyquinoline gallium with four nuclear structures.
Fig. 3 is the PXRD figures of two kinds of complexs；
Wherein：1 represents 8-hydroxyquinoline aluminum complex；2 represent 8-hydroxyquinoline gallium complex.
Fig. 4 is the fluorescence spectra of organic ligand and two kinds of tetranuclear complex in the solution；
Wherein：1 represents 8-hydroxyquinoline aluminum complex；2 represent 8-hydroxyquinoline gallium complex.
Fig. 5 is the fluorescence spectra of organic ligand and two kinds of tetranuclear complex in solid phase；
Wherein：1 represents 8-hydroxyquinoline aluminum complex；2 represent 8-hydroxyquinoline gallium complex.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It is it should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides the 8-hydroxyquinoline aluminium plus gallium complex that two kinds have four nuclear structures, wherein, the tool
Shown in the structure such as formula (I) for having the metal aluminium plus gallium complex of four nuclear structures：
Wherein M is Al or Ga.
Specifically, the 8-hydroxyquinoline aluminium plus gallium complex is crystalline material, X-ray single crystal diffraction determines
The crystal structure of two kinds of Metal-organic complexes, the crystal parameter of 8-hydroxyquinoline aluminium are as follows：Space group P-1, Z=2,α=89.790 (5) °, β=80.165
(4) °, γ=82.219 (5) °,The crystal parameter of 8-hydroxyquinoline gallium is as follows：Space group P-1, Z=2,α=88.895 (9) °, β=80.445
(10) °, γ=81.18 (1) °,Above two complex is four metal centers, the three ligand cluster of electroneutral
Close object, peripheral three metal centers are coordinated respectively with two organic ligand molecules and two methanol molecules, central metal from
The octahedral coordination configuration of distortion, central metallic ions and periphery three is presented by being coordinated with six methanol molecules in son
Metal ion is linked together by methanol molecules.
The present invention also provides a kind of preparations of the 8-hydroxyquinoline aluminium plus gallium complex with four nuclear structures described above
Method, wherein, the preparation method includes：By the organic ligand of formula (II) structure, metal salt (aluminium salt or gallium salt) it is water-soluble
Liquid and organic solvent hybrid reaction prepare two kinds of crystalline state complexs of structure (I) structure.
In the reaction of two kinds of crystalline state complexs of structure (I) structure is prepared, the organic ligand of formula (II) structure is used
Source be not particularly limited, can buy or be made by oneself according to existing literature, the preferred aluminum nitrate of the metal salt and gallium nitrate,
The concentration of the aqueous metal salt is preferably 0.02~0.1mol/L, more preferably 0.08mol/L；The organic solvent is preferred
For N,N-dimethylformamide and methanol；The volume ratio preferably 1 of the organic solvent N,N-dimethylformamide and methanol：(2~
10), more preferably 1：(3~6), most preferably 1:5；The volume ratio of the organic solvent N,N-dimethylformamide and water is preferred
For (30~50)：1；Double -8- acetoxyl groups the quinaldines of organic ligand (E, the E') -2,2- (1,3- divinyl phenyl) and institute
The amount ratio for stating N,N-dimethylformamide is preferably 10mmol:(10~20) mL, more preferably 10mmol:(12~17) mL；
The molar ratio of the double -8- acetoxyl groups quinaldines of organic ligand (E, the E') -2,2- (1,3- divinyl phenyl) and metal salt
Preferably 1:(1~6), most preferably 1:2.
In the present invention, the hybrid reaction carries out preferably in closed reactor, wherein, the reaction solution of hybrid reaction with it is anti-
Volume of a container is answered than preferably 1:(4~6)；The reaction temperature is 30~80 DEG C, most preferably 70 DEG C；During the reaction
Between be 12~30 hours.
In the present invention, in order to make to be mixed fully between each raw material, the present invention preferably by the organic ligand of formula (II) structure and has
Solvent first mixes, and then adds the aqueous solution of metal salt, obtains uniformly mixed reaction solution.
The present invention also provides two kinds of luminescent materials, the luminescent material is the 8- hydroxyl quinolines with structure shown in formula (I)
Quinoline aluminium plus gallium complex.
The present invention will be described in detail by way of examples below.
Embodiment 1
The preparation of formula (II) compound：8- hydroxyls quinaldine (10mmol), m-terephthal aldehyde (5mmol) are weighed in drying
In 25mL twoport round-bottomed flasks, acetic anhydride (10mL), N are added in into reaction bulb2Under protection, it is heated to 120 DEG C of reaction 72h.It is cold
But to room temperature, yellow solid is obtained, is washed with distilled water respectively 3 times, drying obtains target product, yield：2.05g 82%.It will
It is molten to weigh (E, E') -2,2- obtained above (1,3- divinyl phenyl) double -8- acetoxyl groups quinaldines (2.0g, 4mmol)
In 60mL pyridines, 15mL distilled water is then added in into reaction bulb, is heated to flowing back, reaction is overnight.It is cooled to room temperature, depressurizes
Pyridine is distilled off, adds in 200mL distilled water, yellow solid is obtained by filtration, is washed with distilled water, vacuum drying obtains target production
Object (E, E') -2,2- (1,3- divinyl phenyl) double -8-hydroxyquinoline.Yield 1.4g, 84%.1HNMR(DMSO-d6,
400MHz)δ：7.100 (dd, J=7.2Hz, 2H), 7.378 (m, 4H), 7.560 (d, J=16Hz, 2H), 7.805 (d, J=
7.2Hz, 6H), 8.181 (d, J=16Hz, 2H), 8.310 (d, J=8.4Hz, 2H), 9.609 (s, 2H)；13C NMR(DMSO-
d6, 400MHz)：153.1,152.8,138.0,136.9,136.4,133.8,129.3,128.4,127.5,127.3,126.9,
125.3,120.8,117.4,11.0；ESI-MS m/z：417.15([M+1]+)。
Embodiment 2
The synthesis of 8-hydroxyquinoline aluminum complex (1) shown in formula (I)：By (E, E') -2,2- (1,3- divinyl phenyl)
Double -8-hydroxyquinoline (10mmol) is dissolved in N,N-dimethylformamide and methanol mixed solvent (12mL, V/V=1:It 5), will in
Al(NO3)3·9H2The aqueous solution (0.08mol/L) of O (20mmol) is added drop-wise in solution, and mixed solution is sealed in the anti-of 80mL
It answers in kettle, is kept for 70 DEG C react 20 hours, yellow bulk crystals are obtained by filtration, is washed with methanol and ether and done in air
It is dry.Yield is 5.45g, 85%.ESI-MS m/z：1537([M+1]+)；C88H68O12N6Al4Elemental analysis calculated value：C
70.02, H 4.54, N 5.57；Measured value：C 69.98, H 4.48, N 5.54.FTIR (KBr tablettings)：3443.64 (s),
2836.42 (w), 1669.54 (w), 1599.93 (m), 1558.08 (s), 1505.81 (s), 1455.43 (s), 1384.61 (s),
1344.48 (m), 1307.51 (m), 1279.84 (w), 1163.43 (w), 1106.94 (s), 1059.35 (w), 969.55 (m),
886.40 (w), 832.04 (m), 804.50 (w), 753.91 (s), 700.06 (w), 666.55 (w).
Embodiment 3
The synthesis of 8-hydroxyquinoline gallium complex (2) shown in formula (I)：By (E, E') -2,2- (1,3- divinyl phenyl)
Double -8-hydroxyquinoline (10mmol) is dissolved in N,N-dimethylformamide and methanol mixed solvent (12mL, V/V=1:It 5), will in
Ga(NO3)3The aqueous solution (0.08mol/L) of (20mmol) is added drop-wise in solution, and mixed solution is sealed in the reaction kettle of 80mL
In, it is kept for 70 DEG C react 16 hours, yellow bulk crystals is obtained by filtration, is washed with methanol and ether and dried in air.Production
Rate is 4.9g, 87%.ESI-MS m/z：1679([M+1]+)；C89H69O12N6Ga4Elemental analysis calculated value：C 63.12, H
4.11, N 4.96；Measured value：C 63.98, H 4.28, N 4.74.FTIR (KBr tablettings)：3419.97 (s), 1632.00 (m),
1551.86 (m), 1501.02 (s), 1440.45 (s), 1381.94 (w), 1337.98 (w), 1303.54 (w), 1159.03 (w),
1102.45 (m), 1058.28 (w), 967.27 (m), 832.46 (w), 744.59 (m), 699.06 (w).
Characterization of The Products and luminescent properties test
Mono-crystalline structures characterize：Crystal structure is measured using Germany's Brooker X- single crystal diffractometers.X- single crystal diffraction data analyses
Show that two kinds of 8-hydroxyquinoline complexs have similar mono-crystalline structures, be all four-core metal complex., 8-hydroxyquinoline aluminium
Crystal parameter is as follows：Space group P-1, Z=2, α
=89.790 (5) °, β=80.165 (4) °, γ=82.219 (5) °,The crystal ginseng of 8-hydroxyquinoline gallium
Number is as follows：Space group P-1, Z=2, α=
88.895 (9) °, β=80.445 (10) °, γ=81.18 (1) °,The mono-crystalline structures of two kinds of complexs are such as
Shown in Fig. 1 and 2.
Phase purity characterizes：The phase purity of two kinds of complexs is characterized by X-ray powder diffraction (PXRD), such as Fig. 3
Shown, the PXRD experiment values and match value of complex can coincide well, show the crystal of the sample and complex largely prepared
Structure is consistent.In PXRD spectrograms, the difference of the intensity at experiment value and some peaks of match value may be because powder sample preferentially
Orientation.
Fluorescence property in solution：Two kinds of complexs are made into 1.0 × 10 respectively-4Mol/L dimethyl sulphoxide solutions, research
Their fluorescence property, using 360nm wavelength as exciting light, such as Fig. 4, ligand and two kinds of complexs (1：8-hydroxyquinoline aluminium
Complex；2：8-hydroxyquinoline gallium complex) maximum emission wavelength be respectively 486,557 and 542nm.With ligand H2L1It compares,
Different degrees of red shift has occurred in the maximum emission wavelength of two kinds of complexs.This may be due to after metal ion and ligands
Improve the mobility of electron transition in skeleton, reduce ligand internal charge transfer electron transition energy, meanwhile, ligand with
Metal ion forms five-membered ring, this ring and quinoline ring are coplanar, the coplanarity of π-π * conjugacy and conformation are increased, so as to reduce
Red shift has occurred in energy between ligand π and π * tracks, the fluorescence emission peak for eventually leading to complex.
Fluorescence property in solid-state：At room temperature, to the fluorescence property of the free ligand under solid state and two kinds of complexs
It is studied (as shown in Figure 5).When with the excitation of 360nm, free ligand shows very strong at 455 and 466nm
Emission peak, this is because ligand internal charge transfer caused by.When with the excitation of similary wavelength, two kinds of complexs
Maximum emission peak is 566 and 568nm respectively.There are different variations from the launch wavelength in solution, this is because two kinds of cooperations
Object causes in solution and the intermolecular force difference in solid phase.
Complex fluorescent quantum yield：Fluorescence quantum yield is a basic and important ginseng in many performances of fluorescent material
Number, it represents that the luminous energy of absorption is converted into the ability of fluorescence, relative quantum production of the complex 1 and 2 in tetrahydrofuran by substance
Rate is calculated using following methods.The standard items of selection are quinine sulfate, are dissolved in 0.5M H2SO4In, ultraviolet
Solution to be measured is filled for the quartz colorimetric utensil of 1cm using width in fluorescence experiments.Two kinds are can be calculated using public formula (III)
The Relative quantum yields of complex, subscript s is standard sample in formula, and x is treats test sample, and Φ is Relative quantum yields, and n is the folding of solvent
Light rate, A are UV absorption intensity, and D is fluorescence integral area.N in formulas, nxRespectively 1.33,1.405；Φ s are 0.55.Two kinds
The Relative quantum yields of complex are respectively 0.13 and 0.07.
The 8-hydroxyquinoline ring with four nuclear structures produced by the present invention can be seen that by above-described embodiment, application examples
Aluminium plus gallium complex has good fluorescence property, and reaction condition requirement is low, and reaction is simple, and then can be seen that it
Realize at low cost, easy to operate, the small effect of environmental pollution.
Claims (6)
1. a kind of preparation method of the 8-hydroxyquinoline complex with four nuclear structures, which is characterized in that the 8-hydroxyquinoline is matched
Object is closed with four nuclear structures shown in formula (I), wherein：M is Al or Ga；
The preparation of above-mentioned 8-hydroxyquinoline complex includes the following steps：
By (E, E') -2, the double -8- acetoxyl groups quinaldines of 2- (1,3- divinyl phenyl) are dissolved in organic solvent, by metal
The aqueous solution of aluminium salt or gallium salt is added drop-wise to wherein, and mixed solution is sealed in the reaction kettle of 80mL, is kept for 30~80 DEG C instead
It answers 20 hours, yellow bulk crystals is obtained by filtration, washed with methanol and ether and dry in air；
The amount ratio of the double -8- acetoxyl groups quinaldines of (E, the E') -2,2- (1,3- divinyl phenyl) and organic solvent
10mmol:10~20mL；
Double -8- acetoxyl groups the quinaldines of (E, the E') -2,2- (1,3- divinyl phenyl) and Metal aluminum salt or gallium salt
Molar ratio is 1:1~6.
2. the preparation method of the 8-hydroxyquinoline complex with four nuclear structures according to claim 1, which is characterized in that
The organic solvent is n,N-Dimethylformamide and the mixed solution of methanol, and the two volume ratio is 1：2~10.
3. the preparation method of the 8-hydroxyquinoline complex with four nuclear structures according to claim 1, which is characterized in that
Double -8- acetoxyl groups the quinaldines of (E, the E') -2,2- (1,3- divinyl phenyl) and mole of Metal aluminum salt or gallium salt
Than being 1:2.
4. the preparation method of the 8-hydroxyquinoline complex with four nuclear structures according to claim 1, which is characterized in that
The Metal aluminum salt is aluminum nitrate.
5. the preparation method of the 8-hydroxyquinoline complex with four nuclear structures according to claim 1, which is characterized in that
The gallium salt is gallium nitrate.
6. the 8-hydroxyquinoline complex with four nuclear structures that preparation method obtains according to claim 1 is as the material that shines
Expect the application in luminescent device is prepared.
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| CN114621753A (en) * | 2022-03-03 | 2022-06-14 | 青岛大学 | Cyan fluorescent material prepared from aluminum complex and preparation method thereof |
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| ANTONI KUNICKI等: "Studies on the Reaction of Triethylaluminium with Methyl Alcohol", 《BULLETIN OF THE POLISH ACADEMY OF SCIENCES, CHEMISTRY》 * |
| 张奇 等: "8-羟基喹啉类多核结构以及发光性能的构筑与调控", 《中国化学会第七届全国结构化学学术会议论文摘要》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114621753A (en) * | 2022-03-03 | 2022-06-14 | 青岛大学 | Cyan fluorescent material prepared from aluminum complex and preparation method thereof |
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