CN114133406A - Conjugated organic complex of europium (III) and its preparation method and application - Google Patents
Conjugated organic complex of europium (III) and its preparation method and application Download PDFInfo
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- LNBHUCHAFZUEGJ-UHFFFAOYSA-N europium(3+) Chemical compound [Eu+3] LNBHUCHAFZUEGJ-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 29
- 239000003446 ligand Substances 0.000 claims abstract description 25
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000007935 neutral effect Effects 0.000 claims abstract description 6
- 125000001725 pyrenyl group Chemical group 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- BBEAQIROQSPTKN-UHFFFAOYSA-N antipyrene Natural products C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 229910052693 Europium Inorganic materials 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- -1 diketone europium ion Chemical class 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- HAJSTFQQUPSESY-UHFFFAOYSA-N 1,10-dibromo-1,10-phenanthroline Chemical compound C1=CN(Br)C2=C3N(Br)C=CC=C3C=CC2=C1 HAJSTFQQUPSESY-UHFFFAOYSA-N 0.000 claims description 3
- HVQSEKGARNNWON-UHFFFAOYSA-N boric acid pyrene Chemical compound OB(O)O.c1cc2ccc3cccc4ccc(c1)c2c34 HVQSEKGARNNWON-UHFFFAOYSA-N 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 3
- AWDWVTKHJOZOBQ-UHFFFAOYSA-K europium(3+);trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Eu+3] AWDWVTKHJOZOBQ-UHFFFAOYSA-K 0.000 claims description 3
- 230000005669 field effect Effects 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000010898 silica gel chromatography Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 238000010668 complexation reaction Methods 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 150000005041 phenanthrolines Chemical class 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 3
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical group C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 abstract description 7
- 230000002776 aggregation Effects 0.000 abstract description 5
- 238000004220 aggregation Methods 0.000 abstract description 5
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000010791 quenching Methods 0.000 abstract description 4
- 230000000171 quenching effect Effects 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 2
- 125000005581 pyrene group Chemical group 0.000 abstract description 2
- 238000006862 quantum yield reaction Methods 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 description 1
- OWDZQVCOYJZNGC-UHFFFAOYSA-N thiophene 4,4,4-trifluoro-3-oxobutanal Chemical compound FC(C(=O)CC=O)(F)F.S1C=CC=C1 OWDZQVCOYJZNGC-UHFFFAOYSA-N 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- 125000006617 triphenylamine group Chemical group 0.000 description 1
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- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
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- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
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Abstract
The invention belongs to the technical field of photoelectric materials, and relates to a conjugated organic complex of europium (III) and a preparation method and application thereof, wherein beta-diketone ligand Dibenzoylmethane (DBM) and neutral ligand 3, 8-dipyrene-1, 10-phenanthroline (PhenPy) symmetrically modified by pyrenyl groups are utilized2) Compounding with europium (III) to synthesize europium (III) quaternary complex [ Eu (DBM)3PhenPy2]The complex is modified by introducing pyrene groups to 3 and 8 positions of 1, 10-phenanthroline of a neutral ligand, so that the space effect is increased, the molecular aggregation quenching is inhibited, and a large-pi conjugated aromatic ring structure is introduced to increase the ligandThe electron cloud density of the medium nitrogen atoms improves the carrier transmission capability, so that the fluorescence quantum yield is improved, and a device prepared by doping the material has excellent performances in the aspects of luminous efficiency, chemical stability, carrier mobility and the like.
Description
Technical Field
The invention belongs to the technical field of photoelectric materials, and particularly relates to a europium (III) conjugated organic complex, a preparation method thereof and application thereof in the field of organic electroluminescent materials.
Background
In the modern times, science and technology are rapidly developed, and electronic information subverts life styles of people. With the progress of science and technology, people have higher expectations and requirements for information display technology. As early as the 50 s of the 20 th century, research on the preparation of electroluminescent devices from organic materials began to emerge. Bernanose et al observed luminescence when a dc voltage of 400V was applied to both sides of an anthracene single crystal sheet, which was the first report on organic electroluminescent devices. In 1987, Tang first developed a low driving voltage organic electroluminescent device with practical value. The device uses an amorphous TPD film as a hole transport layer and an 8-hydroxyquinoline aluminum (Alq) film as a light emitting layer. Driven by a voltage less than 10V, the voltage is more than 100cd/m2The quantum efficiency of the light-emitting luminance of (1) is about 1%. The organic electroluminescent device is successfully leaped greatly, and a new era of research on the organic electroluminescent device is initiated. On the basis, Tang et al propose a new idea: by doping a small amount of high-efficiency fluorescent material in the Alq layer, the quantum efficiency can be improved by 2-3 times. And through different proportions and doping of materials, the emitted light can be smoothly adjusted from blue-green to orange-red, and even white light can be generated.
The research on the luminescence property of the rare earth complex starts late, but develops rapidly. In 1942, Weissman found that Eu was observed when ultraviolet light was used to excite organic ligands of europium complexes3+The fluorescence emission phenomenon of the rare earth fluorescent ligand draws the research on the rare earth luminescent ligand and the luminescent mechanism thereof by people. In 2004, K.Binnemans et al modified organic ligand Phen and introduced into the system, and added second ligand thiophene formyl trifluoroacetone (TTA) to enhance Eu3+The fluorescent property of (1). Shao Guiang et al introduced Phen as an ancillary ligand to synthesize europium ternary complexes. In 1994, J Kido et al first designed a typical threeYuan Eu3+Complex Eu (DBM)3Phen, with a maximum luminance of 460cd/m2. Yu Liu et al synthesized and characterized ternary europium complex for modifying triphenylamine group on phenanthroline ligand at 1.2mA/cm2The maximum external quantum efficiency of the device was 1.8% and the peak current efficiency was 2.6cd/a at current density of (a). At 173.2mA/cm2The maximum luminance at this time was 1333cd/m2。
The main advantages of OLED technology are active light emission, faster response speed than LCD, low driving voltage, high light emitting efficiency, thin structure and light weight. By doping in the light emitting layer, red, green, and blue (RGB) emitting OLEDs can be obtained, satisfying full color large screen flat panel display. Low temperature processing technology enables flexible devices. The organic electroluminescent material (OLED) still faces the problem to be broken through. In order to exhibit advantages in electroluminescence, in addition to the requirement that the material satisfies the photoluminescence property, there are, for example, better carrier transport ability, high thermal stability, good film-forming property, and the like.
In order to solve the problem, the improvement of material molecules is mainly started by optimizing the structure and design of the electroluminescent device. Pyrene is a large pi conjugated aromatic group, has the characteristics of high luminous efficiency and high charge carrier mobility, and shows excellent hole injection capability compared with similar materials. Pyrene is an excellent blue light material, but due to a large planar conjugated structure, chromophore aggregation is easily caused to generate fluorescence quenching, and the luminous efficiency is reduced. Therefore, other groups are often introduced into positions 1,3,6 and 8 of pyrene or pyrene is taken as a group and introduced into other structures to inhibit molecular aggregation, and luminous efficiency and hole injection capability are improved.
Disclosure of Invention
The invention provides a luminescent material europium (III) quaternary complex [ Eu (DBM) ] for an OLED device with high efficiency and long service life3PhenPy2]The pyrene group modification is introduced to the 3 and 8 positions of the neutral ligand 1, 10-phenanthroline, so that the space effect is increased, the molecule aggregation quenching is inhibited, the large-pi conjugated aromatic ring structure is introduced, the electron cloud density of nitrogen atoms in the ligand is increased, and the carrier transmission capacity is improved.The material has a wide application prospect in the fields of organic electroluminescent materials, organic field effect transistors, fluorescent probes, electronic paper materials and the like.
In order to achieve the aim, the invention provides a conjugated organic complex of europium (III), which adopts the chemical structure of a classical ternary diketone europium ion complex, utilizes beta-diketone ligand dibenzoylmethane and neutral ligand 3, 8-dipyrene-1, 10-phenanthroline symmetrically modified by pyrenyl to be matched with europium (III) to synthesize a europium (III) quaternary complex [ Eu (DBM)3PhenPy2]。
The invention also provides a preparation method of the conjugated organic complex of europium (III), which comprises the following steps:
(1) synthesis of pyrene modified phenanthroline ligand
Pyrene is subjected to boric acid esterification to improve the stability and yield of subsequent reaction; synthesizing a 3, 8-dipyrene-1, 10-phenanthroline ligand by adopting Suzuki coupling;
the reaction steps are as follows:
①
②
(2) complexation of conjugated organic complexes of europium (III)
Adding the 3, 8-dipyrene-1, 10-phenanthroline ligand synthesized in the step (1) and europium trichloride hexahydrate into an ethanol system, and adjusting the pH of the system to 7-8 by using sodium hydroxide; heating and refluxing for half an hour at 60 ℃, adding dibenzoyl methane, and continuing to react for 3 hours; the product is extracted and purified to obtain target product europium (III) quaternary complex [ Eu (DBM)3PhenPy2]；
The reaction steps are as follows:
further, in the step (1), the synthesis of the pyrene-modified phenanthroline ligand specifically comprises the following steps:
1) weighing Pd (PPh)3)4Dissolving in toluene, deoxidizing, wrapping with tinfoil paper, protecting from light, and deoxidizing with toluene;
2) adding Ba (OH)2·8H2O, pyrene borate, 1, 10-dibromo phenanthroline and magnetons, sealing the device, vacuumizing, wrapping the device with tinfoil paper, and sequentially adding treated Pd (PPh)3)4The solution and toluene are heated and refluxed for 30 hours at 110 ℃ after the system is completely dissolved;
3) after the reaction is finished, extracting by using dichloromethane and water;
4) separating small polar impurities by silica gel column chromatography with ethyl acetate/petroleum ether as eluent, and separating the product with pyridine/ethyl acetate to obtain yellow powder, wherein the volume ratio of ethyl acetate/petroleum ether is 1:5, and the volume ratio of pyridine/ethyl acetate is 1: 15.
The invention also provides the application of the conjugated organic complex of europium (III) in the fields of OLED device luminescent layer materials or devices serving as main materials of white light and phosphorescent main materials, electron or hole carrier transport materials, organic integrated circuits, semiconductor materials of organic field effect tubes, organic solar cell materials and electronic paper materials.
The invention also provides application of the tetraphenylethylene functionalized oligopolymerization thiophene derivative in the aspect of explosive detection.
Has the advantages that:
1) the synthesis steps of the invention are simple, and the cost is low;
2) pyrene is a large pi conjugated aromatic group, has the characteristics of high luminous efficiency and high charge carrier mobility, and shows excellent hole injection capability compared with similar materials, so that the device efficiency is improved;
3) a hole transport group is introduced into the common neutral ligand phenanthroline, so that the electron cloud density of the phenanthroline nitrogen atom is increased, the improvement of the carrier transport performance is facilitated, and the phenanthroline electron cloud density is suitable for serving as an electron transport material;
4) due to the space effect of the pyrenyl group, the aggregation of the complex is avoided, and the fluorescence quenching is reduced, so that the fluorescence quantum yield is improved.
Drawings
FIG. 1 shows the intermediate product PhenPy of example 12Is/are as follows1HNMR spectrogram;
FIG. 2 shows Eu (DBM) in example 13PhenPy2The ultraviolet-visible absorption spectrogram of the complex;
FIG. 3 shows Eu (DBM) in example 13PhenPy2Cyclic voltammetric reduction curves of the complexes;
FIG. 4 shows Eu (DBM) in example 13PhenPy2Cyclic voltammetric oxidation profile of the complex.
Detailed Description
In order to better understand the contents of the present invention, the following examples are provided to further illustrate the technical solutions of the present invention, including product synthesis, spectroscopy and electrochemical correlation property determination, but the examples are not intended to limit the present invention.
Example 1
(1) Synthesis of 3, 8-Dipyrene-1, 10-phenanthroline (PhenPy)2) Ligands
Before the experiment: weighing Pd (PPh)3)4(76mg, 0.06mmol) is dissolved in 10mL of toluene for deoxidation treatment, and the container needs to be wrapped by tinfoil paper and protected from light; 30mL of toluene was separately deoxygenated.
Experimental reaction steps:
adding Ba (OH)2·8H2Sealing the device by O (1.577g, 5mmol), pyrene borate (2.17g, 6.6mmol), 1, 10-dibromophenanthroline (1g, 2.95mmol) and magnetons, vacuumizing the device, and wrapping the device by using foil paper; sequentially adding the treated Pd (PPh)3)430mL of solution and toluene, heating and refluxing for 30h at 110 ℃ after the system is completely dissolved; after the reaction is finished, extracting by using dichloromethane and water; separating small polar impurities by silica gel column chromatography with ethyl acetate/petroleum ether at volume ratio of 1:5 as eluent, and separating with pyridine/ethyl acetate at volume ratio of 1:15 to obtain yellow powderEnd 1054mg (yield 61.51%). Intermediate product PhenPy2Is/are as follows1The HNMR spectrogram is shown in figure 1,1HNMR(400MHz,Chloroform-d)δ9.29(d,J＝2.3Hz,1H),9.21(d,J＝2.3Hz,1H),8.52(d,J＝2.3Hz,1H),8.44(d,J＝2.3Hz,1H),8.35(d,J＝7.8Hz,1H),8.31–8.27(m,1H),8.19(d,J＝2.2Hz,3H),8.16–8.12(m,2H),8.10(d,J＝7.9Hz,1H),8.01(d,J＝8.8Hz,1H),7.87(d,J＝8.8Hz,1H),7.79(s,1H),1.33(s,2H),1.28(s,1H).
(2) synthesis of europium (III) Quaternary Complex [ Eu (DBM)3PhenPy2]
The ligand PhenPy synthesized in the step (1) is2(58mg, 0.1mmol) in chloroform (4ml), after complete dissolution, adding into an ethanol (5ml) system, slowly adding europium chloride hexahydrate (36.7mg, 0.1mmol) and stirring; titrating the system to pH about 7-8 with sodium hydroxide water solution, deoxidizing the solution system, and vacuumizing the reaction device; adding the solution into a reaction device after deoxidizing for 15min, heating and refluxing for 0.5h at 60 ℃, dissolving dibenzoyl methane (73.92mg, 0.33mmol) in a proper amount of ethanol, deoxidizing for 15min, and slowly dripping the solution into the system to react for 3 h; after the reaction is finished, extracting with dichloromethane and water, performing rotary evaporation, and drying;
to obtain a complex [ Eu (DBM)3PhenPy2]The molecular formula is as follows:
test example 1
For example 1 europium (III) quaternary complex [ Eu (DBM)3PhenPy2]Ultraviolet absorption spectrum and fluorescence spectrum.
Eu (DBM)3PhenPy2Dissolving in dichloromethane diluted solution, and performing ultraviolet visible absorption spectrum measurement by using Shimadzu UV-3150 ultraviolet visible spectrometer. The results are shown in FIG. 2Eu (DBM)3PhenPy2Ultraviolet absorption spectrum of Eu (DBM)3PhenPy2The maximum absorption peak of the solution in the interval of more than 300nm is located at 347 nm.
Test example 2
For example 1 europium (III) quaternary complex [ Eu (DBM)3PhenPy2]The cyclic voltammogram of (a) was measured.
Eu (DBM)3PhenPy2Dissolving in N, N Dimethylformamide (DMF) solution, wherein tetrabutylammonium hexafluorophosphate is adopted as electrolyte, and the scanning speed is 5 mV/s; a standard three-electrode electrochemical cell is adopted, a platinum electrode is a working electrode, a platinum wire is a counter electrode, and Ag/AgCl is a reference electrode; the initial oxidation potential was 0.761eV, and the corresponding HOMO level was calculated to be-5.161 eV; the initial reduction potential was-1.786 eV, the corresponding LUMO level was calculated to be-2.614 eV, and the forbidden band width was 2.547.
The test results are shown in fig. 3 and 4: FIG. 3 shows Eu (DBM)3PhenPy2Reduction curve of (1), reduction peak potential of Ered2.695 eV. FIG. 4 shows Eu (DBM)3PhenPy2Oxidation curve of (2), oxidation potential obtainedox＝1.027eV。
The above are preferred embodiments of the present invention, and all changes made according to the technical scheme of the present invention that produce functional effects do not exceed the scope of the technical scheme of the present invention belong to the protection scope of the present invention.
Claims (4)
1. A conjugated organic complex of europium (iii), characterized in that: adopts the chemical structure of a classical ternary diketone europium ion complex, utilizes beta-diketone ligand dibenzoylmethane and neutral ligand 3, 8-dipyrene-1, 10-o-phenanthroline symmetrically modified by pyrenyl group to be matched with europium (III) to synthesize a europium (III) quaternary complex [ Eu (DBM)3PhenPy2]。
2. A process for the preparation of conjugated organic complexes of europium (iii) as claimed in claim 1, characterized in that: the method comprises the following steps:
(1) synthesis of pyrene modified phenanthroline ligand
Pyrene is subjected to boric acid esterification to improve the stability and yield of subsequent reaction; synthesizing a 3, 8-dipyrene-1, 10-phenanthroline ligand by adopting Suzuki coupling;
the reaction steps are as follows:
①
②
(2) complexation of conjugated organic complexes of europium (III)
Adding the 3, 8-dipyrene-1, 10-phenanthroline ligand synthesized in the step (1) and europium trichloride hexahydrate into an ethanol system, and adjusting the pH of the system to 7-8 by using sodium hydroxide; heating and refluxing for half an hour at 60 ℃, adding dibenzoyl methane, and continuing to react for 3 hours; the product is extracted and purified to obtain target product europium (III) quaternary complex [ Eu (DBM)3PhenPy2]；
The reaction steps are as follows:
3. the method of claim 2, wherein the step of preparing the conjugated organic complex of europium (III) comprises: in the step (1), the synthesis of the pyrene-modified phenanthroline ligand comprises the following specific steps:
1) weighing Pd (PPh)3)4Dissolving in toluene, deoxidizing, wrapping with tinfoil paper, protecting from light, and deoxidizing with toluene;
2) adding Ba (OH)2·8H2O, pyrene borate, 1, 10-dibromo phenanthroline and magnetons, sealing the device, vacuumizing, wrapping the device with tinfoil paper, and sequentially adding treated Pd (PPh)3)4The solution and toluene are heated and refluxed for 30 hours at 110 ℃ after the system is completely dissolved;
3) after the reaction is finished, extracting by using dichloromethane and water;
4) separating small polar impurities by silica gel column chromatography with ethyl acetate/petroleum ether as eluent, and separating the product with pyridine/ethyl acetate to obtain yellow powder, wherein the volume ratio of ethyl acetate/petroleum ether is 1:5, and the volume ratio of pyridine/ethyl acetate is 1: 15.
4. Use of the conjugated organic complexes of europium (III) as claimed in claim 1 in the field of materials for light-emitting layers of OLED devices or as host materials for white light and for phosphorescent devices, for electron or hole carrier transport materials, for organic integrated circuits, for semiconductor materials for organic field effect transistors, for organic solar cells, for electronic paper materials.
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