CN112794863B - Metal organic complex and preparation method and application thereof - Google Patents
Metal organic complex and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 title abstract description 18
- 239000002184 metal Substances 0.000 title abstract description 18
- 238000010668 complexation reaction Methods 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims description 66
- -1 bromo, acetyl Chemical group 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- HPHZVOOLJMXCIA-UHFFFAOYSA-K thiolane;trichlorogold Chemical compound [Cl-].[Cl-].[Cl-].[Au+3].C1CCSC1 HPHZVOOLJMXCIA-UHFFFAOYSA-K 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
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- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 claims description 3
- 238000003384 imaging method Methods 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
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- 239000003513 alkali Substances 0.000 claims 2
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- 238000004020 luminiscence type Methods 0.000 abstract description 27
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- 238000000295 emission spectrum Methods 0.000 description 24
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- 125000002524 organometallic group Chemical group 0.000 description 17
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- SFHYNDMGZXWXBU-LIMNOBDPSA-N 6-amino-2-[[(e)-(3-formylphenyl)methylideneamino]carbamoylamino]-1,3-dioxobenzo[de]isoquinoline-5,8-disulfonic acid Chemical compound O=C1C(C2=3)=CC(S(O)(=O)=O)=CC=3C(N)=C(S(O)(=O)=O)C=C2C(=O)N1NC(=O)N\N=C\C1=CC=CC(C=O)=C1 SFHYNDMGZXWXBU-LIMNOBDPSA-N 0.000 description 9
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- MLCNOCRGSBCAGH-UHFFFAOYSA-N 2,3-dichloropyrazine Chemical compound ClC1=NC=CN=C1Cl MLCNOCRGSBCAGH-UHFFFAOYSA-N 0.000 description 2
- PQYODZZWGVGVJK-UHFFFAOYSA-N 2-n,3-n-dimethylpyrazine-2,3-diamine Chemical compound CNC1=NC=CN=C1NC PQYODZZWGVGVJK-UHFFFAOYSA-N 0.000 description 2
- MKARNSWMMBGSHX-UHFFFAOYSA-N 3,5-dimethylaniline Chemical compound CC1=CC(C)=CC(N)=C1 MKARNSWMMBGSHX-UHFFFAOYSA-N 0.000 description 2
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
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- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 1
- NSXJEEMTGWMJPY-UHFFFAOYSA-N 9-[3-(3-carbazol-9-ylphenyl)phenyl]carbazole Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=CC(C=2C=CC=C(C=2)N2C3=CC=CC=C3C3=CC=CC=C32)=CC=C1 NSXJEEMTGWMJPY-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
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- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
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- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- MOXXPQWMYMUHHV-UHFFFAOYSA-N diethoxymethanol Chemical compound CCOC(O)OCC MOXXPQWMYMUHHV-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
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- 238000000504 luminescence detection Methods 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
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- 150000007530 organic bases Chemical class 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
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- 239000002516 radical scavenger Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/371—Metal complexes comprising a group IB metal element, e.g. comprising copper, gold or silver
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
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Abstract
The invention belongs to the technical field of luminescent materials, and relates to a metal organic complex, a preparation method and an application thereof, in particular to a metal organic complex shown as a formula I, a preparation method and an application thereof. The complex can realize artificial regulation and control of luminescence, ligand-induced intermolecular L' LCT room temperature phosphorescence, metal d-orbit-participated MLCT room temperature phosphorescence and intramolecular charge transfer-induced delayed fluorescence. The metal complex can emit thermal activation delayed fluorescence, and realizes the full-wave-band light emission regulation and control in a visible light region. The metal complex provided by the invention is used for preparing an OLED device, and can realize high electroluminescent efficiency.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to a metal organic complex, and a preparation method and application thereof.
Background
Luminescence mainly results from the radiative transition of excited photons back to the ground state, accompanied by fluorescence or phosphorescence. In organometallic complexes, luminescence is generally charge transfer induced luminescence (ICT) between ligands generated within a molecule, or charge transfer induced luminescence (L' LCT) between different ligands between molecules, as well as charge transfer transitions involving intra-or intermolecular metals, such as metal-ligand charge transfer (MLCT), metal-ligand charge transfer (MMLCT), metal-metal charge transfer (MMCT). Different transition regimes induce different mechanisms of light emission. In the past, if the light emitting mechanism of molecules is to be changed, the molecular structure is usually changed, but now the light emitting mechanism of molecules can be changed more directly by changing the way of stacking between molecules due to pi-pi stacking between molecules. Different application properties are obtained under different light emitting mechanisms. It is known that a ground state molecule undergoes excited transition to an excited state, but excited excitons exist in both singlet and triplet states due to difference in electron spin multiplicity, and the singlet and triplet states exist in the following proportional relationship, singlet excitons: triplet exciton =1:3. due to spin melody, the transition from triplet state to ground state is forbidden, so that the traditional fluorescent material can only utilize singlet excitons, and the internal quantum efficiency can only reach 25% theoretically, therefore, in the application of OLED devices, the high electroluminescent efficiency is difficult to obtain. The focus and difficulty of recent research has been mainly on how to effectively utilize triplet excitons. Based on this, the second generation OLED can effectively reduce the forbidden coefficient between the triplet state and the ground state by developing a phosphorescent material using a large spin-orbit coupling coefficient, so that the triplet excitons can return to the ground state by radiative transition and be accompanied by phosphorescent emission. However, the triplet lifetime of phosphorescent materials is generally long, and therefore there is a large roll-off in device fabrication, and therefore third generation OLED devices have come into play, mainly by effectively utilizing triplet excitons through a new light emission mechanism, thermal Activated Delayed Fluorescence (TADF). TADF can return triplet excitons to a singlet state through reverse intersystem crossing (RISC) mainly by reducing the energy difference between the triplet state and the singlet state, and then return to the ground state from the singlet state through radiative transition with delayed fluorescence emission. Therefore, the molecular design of TADF has been studied mainly to reduce the energy difference Δ E between singlet and triplet states, and currently Δ E is reduced mainly by reducing the overlap of HOMO-LUMO orbitals. However, the conventional TADF generally has a problem that in the aggregate state, the luminescence is generally accompanied by a decrease in luminescence, which is mainly due to an increase in non-radiative transition by formation of exciplex or the like in the aggregate state, and a decrease in luminescence. However, in the aggregation state, the molecular structure can be fixed through intermolecular interaction, so that luminescence quenching caused by internal rotation of the molecule itself in a solution is reduced, and an effect of enhancing luminescence in the aggregation state is achieved, which is called aggregation induced luminescence (AIE).
Disclosure of Invention
In order to improve the technical problems, the invention firstly provides a metal organic complex shown as the following formula I,
wherein R is 1 Identical or different, independently of one another, from C 1-6 Alkyl, -C 1-6 alkyl-C 6-12 Aryl radical, C 6-12 Aryl radical, -C 6-12 aryl-C 1-6 An alkyl group;
R 2 、R 3 identical or different, independently of one another, from H, halogen, C 1-6 Alkyl, -COC 1-6 An alkyl group.
According to an embodiment of the invention, said R 1 Identical or different, independently of one another, from C 1-3 Alkyl, -C 1-3 alkyl-C 6-12 Aryl radical, C 6-12 Aryl radical, -C 6-12 aryl-C 1-3 An alkyl group;
R 2 、R 3 identical or different, independently of one another, from H, halogen, C 1-3 Alkyl, -COC 1-3 An alkyl group.
According to a preferred embodiment of the invention, R is 1 Identical or different and independently of one another are selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, 1, 3-dimethylphenyl or
Wherein
Is a connection site;
R 2 、R 3 identical or different and independently of one another are selected from H, methyl, bromo, acetyl, ethyl or propyl.
As an example, R in the organometallic complexes of the formula I according to the invention 1 Selected from the group corresponding to A to E, R 2 、R 3 Selected from the groups corresponding to the numbers 1 to 6:
the invention also provides a preparation method of the compound of the formula I, which comprises the following steps:
reacting the compound I-1 with the compound I-2 to obtain a compound I;
wherein R is 1 、R 2 、R 3 Having the definitions as described above.
According to an embodiment of the invention, the reaction is carried out in the presence of a quaternary ammonium salt, for example tetrabutylammonium bromide.
According to an embodiment of the invention, the reaction is carried out in the presence of an acid scavenger selected from organic or inorganic bases, for example in the presence of sodium hydroxide.
According to an embodiment of the invention, the process further comprises the preparation of compound I-1, comprising the steps of:
a) Compounds I-a and R 1 -NH 2 Reacting to obtain a compound I-b;
b) Reacting the compound I-b with triethyl orthoformate and concentrated hydrochloric acid to obtain a compound I-c;
c) Reacting the compound I-c with tetrahydrothiophene gold chloride to obtain a compound I-1;
wherein R is 1 Having the definitions as described above.
The invention also provides the use of the compounds of formula I for the preparation of OLED devices or bio-imaging materials.
The invention can obtain different light-emitting mechanisms by simply grinding the compound of the formula I.
The invention can obtain different accumulation modes by changing the steric hindrance of the receptor part in the compound of the formula I, and can regulate and control the light-emitting mechanism of the compound of the formula I by changing the accumulation modes.
The research result of the compound of the formula I shows that the accumulation enhancement can lead to the enhancement of the intermolecular interaction of the compound of the formula I, so that the luminescence is changed from intramolecular electron transition to intermolecular electron transition, and the luminescence is also changed from TADF to room temperature phosphorescence. At the same time, the stacking is changed by the action of external force, the distance between the metals is reduced, and the interaction between the metals is enhanced. Luminescence may be converted from ligand-dominated phosphorescence to phosphorescence induced by MLCT or MMLCT. The compound of formula I of the invention can be well applied to biological imaging as a phosphorescent material.
According to the different light-emitting mechanisms of the compound shown in the formula I, the advantage of thermal activation delayed fluorescence of the compound can be well applied to the preparation of OLED devices.
Under the condition of keeping the carbene ligand, the compound of the formula I can be regulated and controlled between full visible light regions by changing the donor and the substituent of the donor, the red shift of an emission spectrum is enhanced along with the electron donating performance of the donor or the substituent on the donor, the requirement of an electronic effect is met, and the energy difference between HOMO-LUMO can be effectively reduced by increasing the electron donating performance of the donor, so that the light-emitting wavelength is enhanced, and the emission spectrum shows the red shift. Meanwhile, the system has a solvent discoloration effect, shows a positive solvent effect in an emission spectrum, shows a negative solvent effect in an absorption spectrum, shows a stabilizing effect of a polar solvent on a ground state in the absorption spectrum due to the fact that the directions of ground state dipoles and excited state dipoles are opposite, and shows an opposite effect in the emission spectrum.
The compound of the formula I can effectively realize that the torsion angle between donor and acceptor is from close to 0 degree to close to 90 degrees due to different steric hindrance of the adjacent para substituent on the carbazole substituent. That is, the molecular configuration changes from a coplanar structure to a perpendicular structure. As can be appreciated from the design principles of TADF molecules, some distortion between the donor and acceptor is required to achieve an effective TADF. In this case, the overlap between the HOMO-LUMO orbitals can be made small, thereby narrowing the energy difference between the singlet and triplet states. Thereby enhancing the luminescence quantum efficiency.
The invention has the following beneficial effects:
(1) The invention provides a series of metal complexes, which can realize artificial regulation and control of luminescence, ligand-induced intermolecular L' LCT room-temperature phosphorescence, metal d-track-involved MLCT room-temperature phosphorescence and intramolecular charge transfer-induced delayed fluorescence.
(2) The metal complex provided by the invention can emit thermal activation delayed fluorescence, and realizes full-wave-band light emission regulation in a visible light region.
(3) The series of metal complexes provided by the invention are used for preparing OLED devices, and can realize high electroluminescent efficiency.
Drawings
FIG. 1 shows emission spectra of organometallic complexes A2 and E2 synthesized in example 1 (wherein methyl group means the detection result of A2 and phenyl group means the detection result of E2).
FIG. 2 shows that the organometallic complex E1-5 synthesized in example 1 exhibits different emission spectra and absorption spectra at different substituents (wherein a is the emission spectrum of E1-5 in the state of 1% PMMA film; b is the absorption spectrum of E1-5 in tetrahydrofuran solvent; numeral 1 in the figure represents the result of detection of the compound E1, and the other numerals are the same).
FIG. 3 shows an emission spectrum and an absorption spectrum of an organometallic complex E2 synthesized in example 1 in different solutions (wherein a is an emission spectrum of E2 in different solutions as a function of the polarity of the solutions; and b is an absorption spectrum of E2 in different solutions as a function of the polarity of the solutions).
FIG. 4 shows the temperature-swing lifetime curves of organometallic complexes E1 to 5 synthesized in example 1 and emission spectra of a compound E2 at different temperatures (wherein a is the temperature-swing lifetime curve of E1 to 5; and b is E2 emission spectra at different temperatures; in FIG. 4, experiment-1 refers to obtaining a series of lifetime data through lifetime tests at different temperatures, and fitting-1 refers to obtaining a series of lifetime data according to the formula
Fitting the resulting curve).
FIG. 5 shows the aggregation-induced fluorescence curve of the organometallic complex E2 synthesized in example 1 in a mixed solvent composed of water and tetrahydrofuran (wherein 10% means that the volume fraction of water is 10%, and the other percentages are expressed by the same meaning).
FIG. 6 shows emission spectra before and after the grinding of the organometallic complex A2 synthesized in example 1 (wherein a is an emission spectrum before and after the grinding at room temperature, and b is an emission spectrum before and after the grinding at a low temperature).
FIG. 7 shows the electroluminescence properties of a metal complex E2 synthesized in example 1 (where a is a plot of the electroluminescence spectrum at different doping concentrations, b is the external quantum efficiency of the luminescence at different doping concentrations, c is a plot of the current density as a function of the voltage at different doping concentrations, and d is a plot of the luminance as a function of the voltage at different doping concentrations).
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
In the following examples "low temperature" means 77K.
Example 1
First, a methyl-substituted carbene compound A2 and a phenyl-substituted carbene compound E2 are prepared.
The preparation process of A2 is as follows: 2, 3-dichloropyrazine (0.26g, 4.10mmol) and methylamine (33% aqueous solution, 14 ml) were uniformly stirred, added into a 25ml reaction kettle, placed in an oven to react at 140 ℃ for 10 hours, and placed in a refrigerator to crystallize, so that 2, 3-dimethylaminopyrazine was obtained as a yellowish green needle-shaped solid (2.51 g, yield: 90%).
2, 3-Dimethylaminopyrazine (2.51g, 18mmol), triethyl orthoformate (10 ml) and 37% concentrated hydrochloric acid (1 ml) were mixed and refluxed at 120 ℃ overnight, and after completion of the reaction, 50ml of diethyl ether was added thereto at room temperature, and the product was precipitated as a precipitate. The solid was collected by filtration, 20ml ethanol and activated carbon for decolorization and recrystallization. Filtration, spin-drying of the filtrate and recrystallization of the solid from methanol/ether gave 1, 3-dimethylpyrazinylimidazolium chloride as a yellow solid (1.56 g, yield: 47%).
To 1, 3-dimethylpyrazine imidazolium chloride salt (108mg, 0.60mmol) and silver oxide (70mg, 0.35mmol) was added a mixed solution of dichloromethane (40 ml) and ethanol (20 ml), and stirred under the exclusion of light for 12 hours. After completion of the reaction, the resulting precipitate was filtered, tetrahydrothiophene gold chloride (0.35 mmol) was added to the filtrate, and the mixture was reacted for 6 hours in the absence of light, insoluble matter was filtered, and the solid obtained after spin-drying the filtrate was recrystallized from a methylene chloride/diethyl ether solvent to obtain 1, 3-dimethylpyrazine imidazole gold chloride (100 mg, yield: 75%) as a white solid.
Dissolving 1, 3-dimethylpyrazine imidazole gold chloride (50 mg) and carbazole (16 mg) in 30ml dichloromethane, adding 50% by mass of sodium hydroxide (1 ml) and 0.01mmol tetrabutylammonium bromide to react overnight, separating out solids, removing a water layer by liquid separation, and filtering to obtain a solid A2. A specific synthetic route is shown in scheme a below.
The preparation process of E2 comprises the following steps: 2, 3-dichloropyrazine (5 ml) and 3, 5-dimethylaniline (12 ml) were reacted at 140 ℃ under reflux for 6 hours to produce a solid, 50ml of methylene chloride and 50ml of distilled water were added to the solid, and the mixture was stirred for 2 hours, followed by extraction with methylene chloride, followed by spin-drying of the solvent and precipitation of the solid with n-hexane (7 g, yield: 60%).
The above solid (750 mg) was reacted with 10ml of diethyl orthoformate and 0.2ml of concentrated hydrochloric acid at 120 ℃ under reflux overnight, after completion of the reaction, n-hexane was added to precipitate a solid, which was filtered to obtain a solid (550 mg, yield: 60%).
The above solid (100 mg) was reacted with 40mg cuprous chloride in 15ml dry tetrahydrofuran solution at 60 ℃ overnight to give yellow solid, the solid obtained by filtration was added to 30ml dichloromethane, 30mg tetrahydrothiophene gold chloride and reacted at 40 ℃ under reflux for 6h, the filtrate obtained by filtration was dissolved by adding 3ml dichloromethane after drying the filtrate, and recrystallized with 10ml petroleum ether to give solid which was obtained by filtration as white solid.
Dissolving the solid (50 mg) and carbazole (16 mg) in 30ml dichloromethane, adding 50% by mass of sodium hydroxide 1ml and 0.01mmol tetrabutylammonium bromide to react overnight, adding 30ml distilled water, stirring for 2h, separating, collecting organic layers, extracting with 3X 20ml dichloromethane, combining the organic layers, drying with anhydrous sodium sulfate, spin-drying the filtrate, and recrystallizing with dichloromethane/diethyl ether to obtain the carbene compound E2 as a yellow solid. The specific synthetic route is shown in scheme b below.
E1: 1 H NMR(400MHz,CD 2 Cl 2 )δ8.58(s,2H),7.78(s,2H),7.59(s,4H),7.37(s,2H),7.04(s,2H),7.01(s,2H),2.56(s,12H),2.49(s,6H).
E2: 1 H NMR(400MHz,CD 2 Cl 2 )δ8.59(s,2H),8.02(s,2H),7.40(s,4H),7.37(s,2H),7.19(s,2H),7.05(s,2H),2.56(s,12H).
E3: 1 H NMR(400MHz,CD 2 Cl 2 )δ8.61(s,2H),8.04(s,2H),7.57(s,4H),7.39(s,2H),7.01(s,2H),5.30(s,2H),2.55(s,12H).
E4: 1 H NMR(400MHz,CD 2 Cl 2 )δ8.72(s,2H),8.63(s,2H),7.79(d,2H),7.59(s,4H),7.43(s,2H),7.15(d,2H),2.72(s,6H),2.55(s,12H).
E5: 1 H NMR(400MHz,CD 2 Cl 2 )δ8.56(s,2H),7.43(d,2H),7.37(s,4H),7.22(s,2H),7.16(s,2H),2.61(s,6H),2.46(s,12H).
Route a
Route b
Route c
Referring to the preparation of A2, A1 is also prepared, the synthetic route is shown as the scheme c, A1 is R in the general formula I 1 Is methyl, R 2 Is H and R 3 A compound that is methyl.
Referring to the preparation of A2, A3 is also prepared, the synthetic route is shown as the scheme c, A3 is R in the general formula I 1 Is methyl, R 2 Is H and R 3 A compound which is bromine.
Referring to the preparation of A2, A4 is also prepared, the synthetic route is shown as route c, A4 is R in the general formula I 1 Is methyl, R 2 Is H and R 3 A compound which is acetyl.
Referring to the preparation of A2, A5 is also prepared, the synthetic route is shown as the scheme c, A5 is R in the general formula I 1 ，R 2 Is methyl, and R 3 A compound which is H.
Reference to the preparation of E2 also prepares E1, the synthetic route is shown in scheme c, E1 is R in formula I 1 Is 1, 3-methylphenyl, R 2 Is H and R 3 A compound which is methyl.
Reference to the preparation of E2 also prepares E3, the synthetic route is shown in scheme c, E3 is R in formula I 1 Is 1, 3-methylphenyl, R 2 Is H and R 3 A compound which is bromine.
Reference to the preparation of E2 also prepares E4, the synthetic route is shown in scheme c, E4 is R in formula I 1 Is 1, 3-methylphenyl, R 2 Is H and R 3 A compound which is acetyl.
Reference toThe preparation of E2 also prepares E5, the synthetic route is shown as route c, E5 is R in the general formula I 1 Is 1, 3-methylphenyl, R 2 Is methyl and R 3 A compound which is H.
In order to compare the conditions, the stacking mode is changed by changing the substituents of different acceptors under the same donor, so as to obtain different luminescence mechanisms, thereby realizing the regulation and control of the luminescence mechanisms. Emission spectra and photophysical data of the methyl-substituted carbene compound A2 are compared to the phenyl-substituted carbene compound E2.
The emission spectrum of the methyl-substituted carbene compound A2 and the emission spectrum of the phenyl-substituted carbene compound E2 are shown in fig. 1. As can be seen from fig. 1, the emission spectrum positions of the two compounds are different. In addition, the methyl-substituted carbene compound A2, which is less sterically hindered than the phenyl-substituted carbene compound E2, is more heavily stacked, showing reduced solubility, and also showing intermolecular donor-acceptor pi interaction (less than) in the crystal structure
) Or interaction between C-H-pi (less than
) And the difference of the accumulation also causes the change of the light-emitting mechanism to a great extent, and the change of the light-emitting life is also reflected. The photophysical data for organometallic complexes A2 and E2 are shown in Table 1 below. As can be seen from table 1, the lifetime of compound A2 reached 700 μ s at room temperature, while the lifetime of compound E2 was only around 300 ns. That is, the light emission of the compound A2 is mainly light emission from a triplet state, that is, room temperature phosphorescence expressed as L' LCT. While the luminescence of compound E2 is from the singlet state and appears as delayed fluorescence of ICT. The luminescence property data for A2 and E2 indicate that both compounds can be used to make OLED devices.
TABLE 1 photophysical data for organometallic complexes A2 and E2
| wavelength-Room temperature (nanometer) | wavelength-Low temperature (nanometer) | Life-room temperature (microsecond) | Life-low temperature (microsecond) | |
| A2 | 590 | 500/590 | 745 | 564/14 |
| E2 | 520 | 510 | 0.346 | 40.3 |
The photophysical data of the organometallic complex E1-5 prepared by the above procedure are shown in Table 2 below.
TABLE 2 photophysical data for organometallic complexes E1-5
As can be seen from the data in Table 2, organometallic complexes E1, E3-5 can also be used to prepare OLED devices.
FIG. 2 shows the emission spectrum of the organometallic complex E1-5 in the state of 1% PMMA film and the absorption spectrum in the tetrahydrofuran solvent, and it can be seen from FIG. 2 that both the emission spectrum and the absorption spectrum are blue-shifted with the increase in electron-withdrawing property in the case of different substituents.
The emission spectrum and the absorption spectrum of the organometallic complex E2 in different solutions are shown in FIG. 3, and it is understood from FIG. 3 that the emission spectrum is red-shifted with decreasing quantum yield and the absorption spectrum is blue-shifted with increasing polarity of the solvent.
Example 2
The light-emitting mechanism of the compound can be changed by means of polishing or the like. The change of luminescence can be observed obviously by grinding the metal complex A2, the luminescence spectrum of the metal complex A2 is shown in FIG. 6, and the emission spectrum of the metal complex A2 generates a new emission peak at 540nm after being ground at low temperature according to FIG. 6. The photophysical data of the compound A2 are shown in the following table 3, and the data in table 3 also shows that the lifetime of the compound A2 changes significantly with the grinding, from the original 700 microseconds to about 1 microsecond, the luminescence mechanism changes from the original room temperature phosphorescence induced by L' LCT to the phosphorescence emission induced by MLCT or MMLCT with metal d-orbital participation, and the spin-orbit coupling effect is enhanced due to the metal participation, so the intersystem crossing rate is increased, and the luminescence lifetime is greatly reduced. That is, in the case of fixing the molecular structure, the molecular stacking mode can be changed only by means of friction and the like, so that the interaction between metals is enhanced, and the light emitting mechanism is further regulated.
TABLE 3 photophysical data before and after Compound A2 milling
| wavelength-Room temperature (nanometer) | wavelength-Low temperature (nanometer) | Life-room temperature (nanosecond) | Life-low temperature (microsecond) | |
| Before grinding | 590 | 500/590 | 745 | 564/14 |
| After grinding | 550/600 | 540 | 0.458/2.62 | 5.31 |
Example 3
The compound E1-5 prepared in example 1 realizes the construction of a donor-acceptor structure such that the energy difference between the singlet state and the triplet state of such a compound is less than 0.1eV, thereby realizing the transition of triplet excitons back to singlet excitons through the reverse system, followed by radiative transition back to the ground state via the singlet state, accompanied by delayed fluorescence emission, which can effectively reduce roll-off efficiency due to good utilization of triplet excitons and a short lifetime, and thus the organometallic complex compound E1-5 has TADF properties, which are manifested by a significant increase in emission lifetime at low temperatures, as shown in fig. 4. FIG. 4 is a graph showing that the data on lifetime as a function of temperature for compounds E1-5 fit well to satisfy the formula
And a kit which can well demonstrate the obtained compound E1-5With TADF, it can be used to make OLED devices, while also achieving full wavelength range emission in the visible region by modification of the donor moiety. If the electron donating ability of the donor moiety is increased, the emission spectrum can be red-shifted. Different chromaticity OLED devices can be obtained at different light emitting positions.
The results of luminescence detection of compound E2 in solution and solid are shown in table 4, and it can be seen from table 4 that the luminescence efficiency of compound E2 in solution is very low, but the aggregation state can obtain higher luminescence efficiency, and the same properties as those of E2 are shown in compounds E1-5, and the following conclusions can be obtained through the above experimental study: the compound is enhanced due to aggregation-induced emission, and generally shows aggregation-induced quenching in a general thermally-activated delayed fluorescent material, namely, the luminous efficiency is high in a solution state, but the luminescence is weakened in an aggregation state. In this case, the efficiency of the finished device may be reduced. Therefore, the device prepared by using the TADF performance induced by the AIE of the compound E2 has more application prospect. FIG. 5 is a graph showing aggregation-induced fluorescence of the organometallic complex E2 in a mixed solvent composed of water and tetrahydrofuran. As can be seen from FIG. 5, the AIE thereof was observed to emit light with an increase in the content of water as a poor solvent in the solvent, and a significant increase in the emission was observed with an increase in the content of water up to 90%.
TABLE 4E2 photophysical data in solid films and solutions
| E2 | Quantum yield | Life (nanosecond) |
| Methylene dichloride | 0.002 | 4.66 |
| Tetrahydrofuran (THF) | 0.024 | 31.95 |
| Toluene | 0.081 | 72.08 |
| PMMA film | 0.454 | 307.75 |
| Powder of | 0.301 | 265 |
Example 4
An electroluminescent device was prepared using the Au (I) complex of the structure shown by E2 synthesized in example 1 as a light-emitting host material.
The process for preparing the device by using the compound E2 is as follows: OLED devices were fabricated on pre-patterned ITO-coated glass substrates. Prior to deposition, the substrate was cleaned with soap, rinsed with deionized water and sonicated for 15 minutes. Then, two rinses and 12 minutes of sonication were performed in acetone and isopropanol in sequence. All organic layers as well as the aluminum cathode were deposited in a vacuum thermal evaporator. A5 nm hexaazabenzo-hexacyano-nitrile (HATCN) film is spin-coated on the cleaned surface of the 70nm ITO glass and quenched at 140 ℃ for 20 minutes. The structural compound shown as E2 is doped in 3,3 '-di (9H carbazole-9-yl) -1,1' -biphenyl (mCPB) by 4% of mass fraction, and is coated on the TAPC layer in a spin coating mode to form a 40nm light-emitting layer. At 4X 10 -4 2, 2' - (1, 3, 5-benzenetriyl) -tris (N-phenyl-1-H-benzimidazole) (TPBi) of 10nm and LiQ of 1.2nm were sequentially evaporated under a vacuum degree of Pa, and finally an aluminum electrode of 100nm was evaporated through a mask. The rectangular metallic aluminum cathode and the rectangular ITO anode are mutually verticalGet 3X 4mm 2 The square cross section of (a).
The structure of the resulting device is: ITO/HATCN (5 nm)/4%. The maximum external quantum efficiency was 23.6%.
Device characteristics are shown in fig. 7, with the data summarized in table 5. The maximum emission peak of bright green light emitted by the device was between 540 and 555nm (fig. 7 a), consistent with the photoluminescence spectrum of the dopant. Higher doping concentrations result in a slight red shift of the maximum emission peak due to a combination of aggregation and solvation. The J-V-L (J = current density, L = luminance) characteristics of the device show that the turn-on voltage (defined as luminance of 0.1cd/m 2) increases from 4V to 5V as the doping concentration increases from 4% to 16%. (FIG. 7 c). Device resistance also decreases with increasing dopant concentration. The low resistance at high doping concentrations indicates that complex E2 is an effective charge carrier. When the doping concentration of the device prepared by adopting E2 is 4%, the maximum EQE reaches 23%, and the efficiency of the OLED device is the highest. The highest value is reached at a doping concentration of 4%. (FIG. 7 b).
TABLE 5 electroluminescent property data of the metal complexes E2
Example 5
Under the light emitting mechanism of TADF, the light emitting efficiency can be effectively improved by designing a distorted molecular structure, mainly because the TADF molecular design principle requires a distorted molecular structure to obtain smaller singlet and triplet energy differences. The luminescent group is introduced into the carbazole substituent in an adjacent para position, so that the luminescent position is not changed, and the luminescent quantum efficiency is enhanced. As shown in table 2, E1 and E5 can obtain different quantum yields by varying the position of the methyl substitution to obtain different twist angles. The crystal structure also indicates that there is indeed an increase in the twist angle.
The luminous efficiency can be well increased by increasing the torsion angle, and higher external quantum efficiency can be obtained once the OLED is applied.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A compound of the formula I, wherein,
wherein R is 1 Is selected from C 1-6 An alkyl group;
R 2 、R 3 identical or different, independently of one another, from H, halogen, C 1-6 Alkyl, -COC 1-6 An alkyl group.
2. A compound of claim 1, wherein R is 1 Is selected from C 1-3 An alkyl group;
R 2 、R 3 identical or different, independently of one another, from H, halogen, C 1-3 Alkyl, -COC 1-3 An alkyl group.
3. A compound according to claim 1 or 2, wherein R is 1 Selected from methyl, ethyl, propyl, isopropyl, n-butyl;
R 2 、R 3 identical or different and independently of one another are selected from H, methyl, bromo, acetyl, ethyl or propyl.
4. A compound of claim 3, wherein R is in the compound of formula I 1 Selected from the group corresponding to A to D, R 2 、R 3 Selected from the groups corresponding to the numbers 1 to 6:
5. a process for the preparation of a compound according to any one of claims 1 to 4, comprising the steps of:
reacting the compound I-1 with the compound I-2 to obtain a compound I;
wherein R is 1 、R 2 、R 3 Having the definition set forth in claim 1.
6. The method according to claim 5, wherein the reaction is carried out in the presence of a quaternary ammonium salt.
7. The process according to claim 5 or 6, wherein the reaction is carried out in the presence of an acid-binding agent.
8. The method according to claim 7, wherein the quaternary ammonium salt is tetrabutylammonium bromide;
the acid-binding agent is selected from organic alkali or inorganic alkali.
9. The method of claim 5, further comprising the preparation of compound I-1, comprising the steps of:
a) Compounds I-a and R 1 -NH 2 Reacting to obtain a compound I-b;
b) Reacting the compound I-b with triethyl orthoformate and concentrated hydrochloric acid to obtain a compound I-c;
c) Reacting the compound I-c with tetrahydrothiophene gold chloride to obtain a compound I-1;
wherein R is 1 Having the definition set forth in claim 1.
10. Use of a compound of formula I according to any one of claims 1 to 4 for the preparation of OLED devices or bio-imaging materials.
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