CN106432353B - Enhance ruthenium complex, its preparation method and the application of characteristic with aggregated-state induced phosphorescence - Google Patents
Enhance ruthenium complex, its preparation method and the application of characteristic with aggregated-state induced phosphorescence Download PDFInfo
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- 239000012327 Ruthenium complex Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003446 ligand Substances 0.000 claims abstract description 41
- 230000002708 enhancing effect Effects 0.000 claims abstract description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 150000001555 benzenes Chemical class 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000004440 column chromatography Methods 0.000 claims description 10
- 239000012047 saturated solution Substances 0.000 claims description 8
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 8
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 150000005045 1,10-phenanthrolines Chemical class 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000013067 intermediate product Substances 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 5
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 5
- 150000003303 ruthenium Chemical class 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- OADZHFGJIVKDJN-UHFFFAOYSA-N 3-bromo-1,10-phenanthroline Chemical compound C1=CN=C2C3=NC=C(Br)C=C3C=CC2=C1 OADZHFGJIVKDJN-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000012805 post-processing Methods 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 27
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000002776 aggregation Effects 0.000 abstract description 5
- 238000004220 aggregation Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 150000005041 phenanthrolines Chemical class 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 16
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000003480 eluent Substances 0.000 description 5
- 238000004949 mass spectrometry Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910019891 RuCl3 Inorganic materials 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000011182 sodium carbonates Nutrition 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- -1 eluant Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004020 luminiscence type 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
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
-
- 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
- H10K50/00—Organic light-emitting devices
-
- 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
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
-
- 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
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses a kind of ruthenium complex, its preparation method and applications enhancing characteristic with aggregated-state induced phosphorescence.The ruthenium complex has structure shown in Formulas I：Wherein, N^N bidentate ligands are the first ligand, and X^X bidentate ligands are Ligands, and first ligand includes 2,2 bipyridyls or 1, and 10 phenanthrolines, the Ligands include 2,2 diphenylethyllene benzene derivatives.The ruthenium complex can send out stronger phosphorescence under state of aggregation, when being used to prepare electroluminescent device, it is not necessary to be doped in material of main part as object, so as to simplify device fabrication process, reduce element manufacturing cost, Devices Electroluminescent efficiency is improved, industrialization is conducive to.Meanwhile the method provided by the invention for preparing the ruthenium complex is simple, condition is easily-controllable, is conducive to extensive implement.
Description
Technical field
Present invention relates particularly to a kind of ruthenium complex that there is aggregated-state induced phosphorescence to enhance characteristic, preparation method and answer
With, such as the application in preparing electroluminescent device, belong to optoelectronic materials technology.
Background technology
Traditional luminescent material has stronger emissive porwer and higher quantum yield in weak solution.But in height
In the solution of concentration, especially the state of aggregations such as film, crystal when, since intermolecular strong interaction makes the energy of excited state molecule
Amount is decayed by non-radiative pathway, and the luminous efficiency of luminescent material is caused to reduce.There is seminar to report a series of sila rings more
Ene compound have aggregated-state induced fluorescent emission characteristic, the aggregated-state induced fluorescent material solve to a certain extent by
In caused by concentration quenching effect luminous efficiency reduce the problem of.
Organic electroluminescent phosphorescence luminescent material is a kind of electroluminescent material with high-luminous-efficiency, phosphorescent light-emitting materials reason
4 times higher than fluorescence luminescent material by upper luminous efficiency, internal quantum efficiency can reach 100%.But be widely used at present
Electroluminescent material is still fluorescence luminescent material.Due to the intermolecular strong interaction of phosphorescent light-emitting materials or intermolecular three line
State-triplet state buries in oblivion mechanism and material is made to lead to the problem of concentration quenching in solid-state, keeps luminous efficiency not high.It is asked to solve this
Topic, researcher are entrained in using phosphor material as object in material of main part, increase the complexity and difficulties of device preparation, with
And the problems such as device is easily separated when subsequently using, and device lifetime reduces.The appearance of aggregation inducing phosphor material, certain
The problem of luminous efficiency reduces can effectively be improved caused by concentration quenching effect in degree, it can be with when preparing luminescent device
Material of main part need not be added, simplify device fabrication process, reduce cost of manufacture etc..Therefore, aggregation inducing phosphorescent emissive material
It opens up a new way to design the luminous electromechanical phosphorescent material of efficient main body, there is extensive market application prospect.
Invention content
The main purpose of the present invention is to provide a kind of ruthenium complex with aggregated-state induced phosphorescence enhancing characteristic and answer
With to overcome deficiency in the prior art.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes：
An embodiment of the present invention provides a kind of ruthenium complex enhancing characteristic with aggregated-state induced phosphorescence, the ruthenium cooperation
The general structure of object is shown in formula I：
Wherein, N^N bidentate ligands are the first ligand, and X^X bidentate ligands are Ligands.
First ligand includes 2,2- bipyridyls or 1,10- phenanthrolines.
The Ligands include 2,2- diphenylethyllene benzene derivatives.
In some embodiments, 2, the 2- diphenylethyllenes benzene derivative has in Formula II, formula III, formula IV and Formula V
Structure shown in any one：
In some embodiments, the structural formula of the ruthenium complex such as Formula IV, Formula VII, Formula VIII, Formula IX, Formula X, formula
Shown in XI, Formula XII or Formula XIII：
The embodiment of the present invention additionally provides a kind of preparation side of the ruthenium complex with aggregated-state induced phosphorescence enhancing characteristic
Method comprising：
It is 1 by molar ratio in protective atmosphere：1~3 soluble ruthenium salt is dissolved in the compound as the first ligand
In first solvent, and back flow reaction 6h or more, after being cooled to room temperature, obtain intermediate product；
It is 1 by molar ratio：3~8 intermediate product and the 2,2- diphenylethyllene benzene derivatives as Ligands
It is dissolved in the second solvent, 6h or more is reacted at 100~150 DEG C, obtained reaction mixture is post-treated to obtain the ruthenium complex.
Further, the soluble ruthenium salt, the compound as the first ligand and 2,2- diphenylethyllene benzene derivatives
Molar ratio be 1：1~3：3~8.
More preferred, first solvent includes DMF, but not limited to this.
More preferred, second solvent includes ethylene glycol, but not limited to this.
Further, the saturated solution of sodium perchlorate is added into obtained reaction mixture, is carried using filter, column chromatography
It is pure, obtain the ruthenium complex.
Further, the preparation method of 2, the 2- diphenylethyllenes benzene derivative includes：In protective atmosphere, it will rub
You are than being 1：1~3 bromo phenanthroline and 4- (2,2- diphenylethyllenes) phenyl boric acid is dissolved in tetrahydrofuran or toluene and carbonic acid
The mixed liquor of sodium water solution, under the action of catalyst, 12~36h of back flow reaction obtains 2,2- diphenylethyllene benzene derivatives.
Further, the catalyst includes tetrakis triphenylphosphine palladium.
More preferred, the protective atmosphere includes nitrogen atmosphere, but not limited to this.
It is electric in preparing that the embodiment of the present invention additionally provides the ruthenium complex with aggregated-state induced phosphorescence enhancing characteristic
Application in electroluminescence device.
Compared with prior art, the ruthenium complex provided by the invention with aggregated-state induced phosphorescence enhancing characteristic is dilute molten
Phosphorescence is weaker in liquid, but stronger phosphorescence is sent out under state of aggregation, which is used to prepare electroluminescent device
When, it is not necessary to it is doped to device main body material and can be prepared by device, to simplify the preparation process of device, reduce device
Cost of manufacture, improve Devices Electroluminescent efficiency, be easy to industrialization.
Description of the drawings
Fig. 1 is 3,8- bis- (4- (2,2- diphenylethyllenes) phenyl) -1,10 ferrosins (BDP) in the embodiment of the present invention 3
Uv-visible absorption spectra in DMF solution and launching light spectrogram；
Fig. 2 is 3,8- bis- (4- (2,2- diphenylethyllenes) phenyl) -1,10 ferrosins (BDP) in the embodiment of the present invention 3
Launching light spectrogram in the DMF solution of different moisture content；
Fig. 3 is the ruthenium complex [Ru (bpy) in the embodiment of the present invention 32BDP](ClO4)2In DMF solution it is ultraviolet-can
See absorption spectrum and launching light spectrogram；
Fig. 4 is the ruthenium complex [Ru (bpy) in the embodiment of the present invention 32BDP](ClO4)2It is molten in the DMF of different moisture content
Launching light spectrogram in liquid.
Specific implementation mode
In view of deficiency in the prior art, inventor is able to propose the present invention's through studying for a long period of time and largely putting into practice
Technical solution.The technical solution, its implementation process and principle etc. will be further explained as follows.
An embodiment of the present invention provides a kind of ruthenium complex enhancing characteristic with aggregated-state induced phosphorescence, the ruthenium cooperation
The general structure of object is shown in formula I：
Wherein, N^N bidentate ligands are the first ligand, and X^X bidentate ligands are Ligands；
First ligand includes 2,2- bipyridyls or 1,10- phenanthrolines.
The Ligands include 2,2- diphenylethyllene benzene derivatives.
In some embodiments, 2, the 2- diphenylethyllenes benzene derivative has in Formula II, formula III, formula IV and Formula V
Structure shown in any one：
In some embodiments, the skeleton symbol of the ruthenium complex is as shown in Formula IV, Formula VII, Formula VIII or Formula IX：
In some embodiments, the first ligand N^N is 2,2- bipyridyls, and Ligands X^X is 3- (4- (2,2- hexichol
Vinyl) phenyl) -1,10 ferrosins (DP), the skeleton symbol such as Formula X of the ruthenium complex.
In some embodiments, the first ligand N^N is 1,10- phenanthrolines, and Ligands X^X is 3- (4- (2,2- bis-
Styryl) phenyl) -1,10 ferrosins (DP), the skeleton symbol such as Formula XI of the ruthenium complex.
In some embodiments, the first ligand N^N is 2,2- bipyridyls, and Ligands X^X is the (4- (2,2- of 3,8- bis-
Diphenylethyllene) phenyl) -1,10 ferrosins (BDP), the skeleton symbol such as Formula XII of the ruthenium complex.
In some embodiments, the first ligand N^N be 1,10- phenanthrolines, Ligands X^X be 3,8- bis- (4- (2,
2- diphenylethyllenes) phenyl) -1,10 ferrosins (BDP), the skeleton symbol such as Formula XIII of the ruthenium complex.
The embodiment of the present invention additionally provides a kind of preparation side of the ruthenium complex with aggregated-state induced phosphorescence enhancing characteristic
Method comprising：
It is 1 by molar ratio in protective atmosphere：1~3 soluble ruthenium salt is dissolved in the compound as the first ligand
In first solvent, and back flow reaction 6h or more, after being cooled to room temperature, obtain intermediate product；
It is 1 by molar ratio：3~8 intermediate product and the 2,2- diphenylethyllene benzene derivatives as Ligands
It is dissolved in the second solvent, 6h or more is reacted at 100~150 DEG C, obtained reaction mixture is post-treated to obtain the ruthenium complex.
Further, the soluble ruthenium salt, the compound as the first ligand and 2,2- diphenylethyllene benzene derivatives
Molar ratio be 1：1~3：3~8.
More preferred, first solvent includes DMF, but not limited to this.
More preferred, second solvent includes ethylene glycol, but not limited to this.
Further, described post-process includes：The saturated solution of sodium perchlorate is added into obtained reaction mixture, then passes through
Filtering, column chromatography purification, obtain the ruthenium complex.
In one more specific embodiment, the system of the ruthenium complex with aggregated-state induced phosphorescence enhancing characteristic
Preparation Method includes the following steps：
Under nitrogen protection, by 2, the 2- bipyridyls or 1 of the ruthenium trichloride of 1 molar equivalent and 1-3 molar equivalents, 10- is adjacent
Ferrosin is dissolved in DMF solvent, return stirring 6-12h, after being cooled to room temperature, obtains [Ru (bpy)2Cl2] or [Ru (phen)2Cl2]；Later by [Ru (bpy)2Cl2] or [Ru (phen)2Cl2] with the 2,2- diphenylethyllene benzene derivatives of 3-8 molar equivalents
Assistant ligand is dissolved in ethylene glycol, reacts 6-12h at 100-150 DEG C, and reaction was completed, after the saturated solution of sodium perchlorate is added,
Filtering, is purified with column chromatography, obtains the ruthenium complex, the ruthenium trichloride, 2,2- bipyridyls or 1,10- phenanthrolines and 2,
The molar ratio of 2- diphenylethyllene benzene derivative ligands is 1:1~3:3~8.
Further, the preparation method of 2, the 2- diphenylethyllenes benzene derivative includes：In protective atmosphere, it will rub
You are than being 1：1~3 bromo phenanthroline and 4- (2,2- diphenylethyllenes) phenyl boric acid is dissolved in tetrahydrofuran or toluene and carbonic acid
The mixed liquor of sodium water solution, under the action of catalyst, 12~36h of back flow reaction obtains 2,2- diphenylethyllene benzene derivatives.
The catalyst includes tetrakis triphenylphosphine palladium.
More preferred, the protective atmosphere includes nitrogen atmosphere, but not limited to this.
It is electric in preparing that the embodiment of the present invention additionally provides the ruthenium complex with aggregated-state induced phosphorescence enhancing characteristic
Application in electroluminescence device.
Further, it is produced by the present invention with aggregated-state induced phosphorescence enhancing characteristic ruthenium complex can be used for prepare with
Ruthenium complex is the electroluminescent device of the doped or non-doped single layer of luminescent layer.
Further, it is produced by the present invention with aggregated-state induced phosphorescence enhancing characteristic ruthenium complex can be used for prepare with
Ruthenium complex is the multilayer electroluminescent device of luminescent layer.
Stable state/Instantaneous emission spectrum of the ruthenium complex with aggregated-state induced phosphorescence enhancing characteristic of the present invention shows this
Class material is luminous weaker in weak solution, and luminescence enhancement and shines in the collected state as phosphorescence.The electricity of phosphor material
Photoluminescence quantum efficiency is higher than fluorescent material, is that a kind of one kind for having very much potential using value is organic in electroluminescent field
Material.Therefore, such material can be as the luminescent material of efficient organic electroluminescence device.By the ruthenium complex for making
When standby electroluminescent device, it is not necessary to be doped to device main body material and can be prepared by device, to simplify the preparation of device
Process, the cost of manufacture for reducing device, improve Devices Electroluminescent efficiency, are easy to industrialization.
Below in conjunction with attached drawing and several embodiments the technical solution of the present invention is further explained explanation.
Embodiment 1
(1) synthesis of Ligands 3- (4- (2,2- diphenylethyllenes) phenyl) -1,10 ferrosins (DP)
Under nitrogen protection, by 3- bromines phenanthroline (0.10g, 0.40mmol), 4- (2,2- diphenylethyllene) phenyl boric acid
(0.14g, 0.48mmol), tetrakis triphenylphosphine palladium, 20mL tetrahydrofurans are added in 100mL three neck round bottom flask and are stirred at room temperature
After 10min, 4mL aqueous sodium carbonates (2M) are added into reaction system and are reacted for 24 hours at 70 DEG C, wait steaming after the completion of reacting
Most of tetrahydrofuran, dichloromethane extraction, washing, anhydrous sodium sulfate drying, concentration, column chromatography (SiO2, eluant, eluent：Dichloro
Volume ratio=19 of methane/methanol:1) DP product 0.12g, yield 69.0% are obtained.The DP is analyzed by mass spectrometry：Ms(m/
z):434.1(M+).Reaction equation such as following formula 1.
(2) ruthenium complex [Ru (bpy)2DP](ClO4)2Preparation
Under nitrogen protection, by RuCl3·3H2O (1.56g, 6mmol), 2,2- bipyridyls (1.87g, 12mmol) and chlorination
Lithium (1.68g, 28mmol) is dissolved in 10mL DMF, is heated to reflux 8h.After being cooled to room temperature, add 50mL acetone, freeze overnight.It takes out
Filter, precipitation ice water, after the elution of cold acetone, vacuum drying obtains [Ru (bpy)2Cl2] atropurpureus crystallite, yield 61.6%.
Under nitrogen protection, by [Ru (bpy)2Cl2] (0.048g, 0.1mmol), DP (0.217g, 0.5mmol) is dissolved in 5mL
8h is reacted in ethylene glycol and at 150 DEG C, waits for being cooled to room temperature after reaction, is added 20mL water to dilute, is added sodium perchlorate
Saturated solution is until generate a large amount of precipitations, filtering, column chromatography (neutral Al2O3, volume ratio=1 of eluent toluene/acetonitrile:3)
Product [Ru (bpy)2DP](ClO4)2Ruthenium complex 0.039g, yield 35.3%.The ruthenium complex is analyzed by mass spectrometry：
MALDI-TOF,m/z:calcd for[Ru(bpy)2DP](ClO4)2C52H38N6Ru:847.97,Found:848.32.Reaction side
Formula such as following formula 2.
Embodiment 2
(1) in the synthesis of Ligands 3- (4- (2,2- diphenylethyllenes) phenyl) -1,10 ferrosins (DP) and embodiment 1
It is identical.
(2) ruthenium complex [Ru (phen)2DP](ClO4)2Preparation
Under nitrogen protection, by RuCl3·3H2O (1.56g, 6mmol), 1,10- phenanthroline (2.16g, 12mmol) and
Lithium chloride (1.68g, 28mmol) is dissolved in 10mL DMF, is heated to reflux 8h.After being cooled to room temperature, add 50mL acetone, freeze overnight.
It filters, precipitation ice water, after the elution of cold acetone, vacuum drying obtains [Ru (phen)2Cl2] atropurpureus crystallite, yield
66.46%.
Under nitrogen protection, by [Ru (phen)2Cl2] (0.053g, 0.1mmol), DP (0.217g, 0.5mmol) is dissolved in
8h is reacted in 5mL ethylene glycol and at 150 DEG C, waits for being cooled to room temperature after reaction, is added 20mL water to dilute, is added sodium perchlorate
Saturated solution until generating a large amount of precipitations, filtering, column chromatography (neutral Al2O3, volume ratio=1 of eluent toluene/acetonitrile:3)
Product [Ruphen)2DP](ClO4)2Ruthenium complex.The ruthenium complex is analyzed by mass spectrometry：MALDI-TOF,m/z:
calcd for[Ru(phen)2DP](ClO4)2C56H38N6Ru:896.22,Found:895.97.Reaction equation such as following formula 3.
Embodiment 3
(1) synthesis of 3,8- bis- (4- (2,2- diphenylethyllenes) phenyl) -1,10 ferrosins (BDP)
Under nitrogen protection, 3,8- dibromos phenanthroline (0.135g, 0.40mmol) is added in 100mL three-necked flasks,
4- (2,2- diphenylethyllene) phenyl boric acid (0.30g, 1.00mmol), tetrakis triphenylphosphine palladium, 20mL tetrahydrofurans, 15ml second
Alcohol after 10min is stirred at room temperature, 4mL aqueous sodium carbonates (2M) is added into reaction system, are reacted for 24 hours at 110 DEG C later.
Most of tetrahydrofuran, dichloromethane extraction, washing, anhydrous sodium sulfate drying, concentration, column chromatography are steamed after the completion of reaction
(SiO2, the volume ratio of eluant dichloromethane/ethyl acetate is 1:1) yellow solid BDP 0.15g, yield 73.2% are obtained.
Nuclear magnetic data is：1HNMR(DMSO,400MHz,ppm)δ:9.44(s,2H),8.80(s,2H),8.08(s,2H),7.96(d,J
=16Hz, 4H), 7.53-7.242 (m, 26H).Reaction equation such as following formula 4.
(2) ruthenium complex [Ru (bpy)2BDP](ClO4)2Preparation
First ligand [Ru (bpy)2Cl2] synthesis it is in the same manner as in Example 1.
Under nitrogen protection, [Ru (bpy) is weighed2Cl2] BDP made from (0.048g, 0.1mmol) and step (1) (0.069g,
It 0.5mmol) is dissolved in 15mL ethylene glycol, 8h is reacted at 150 DEG C, obtains red clear liquid.It is cooled to room temperature, it is dilute to add 20mL water
It releases, the saturated solution of sodium perchlorate is added later until generating a large amount of red precipitates.Filtering, filter cake are washed with water, ether respectively
Three times, dry, column chromatography (neutral Al2O3, the volume ratio of eluent toluene/acetonitrile is 1:3) brown ruthenium complex [Ru, is made to obtain
(bpy)2BDP](ClO4)2Product 0.045g, yield 35.25%.The ruthenium complex is analyzed by mass spectrometry：MALDI-
TOF,m/z:calcd for[Ru(bpy)2BDP](ClO4)2C72H52N6Ru:1102.33,Found:1102.19. reaction equation
Such as following formula 5.
It is that 3,8- bis- (4- (2,2- diphenylethyllenes) phenyl) -1,10 ferrosins (BDP) in the present embodiment exist referring to Fig. 1
Uv-visible absorption spectra in DMF solution and launching light spectrogram.
It is that 3,8- bis- (4- (2,2- diphenylethyllenes) phenyl) -1,10 ferrosins (BDP) in the present embodiment exist referring to Fig. 2
Launching light spectrogram in the DMF solution of different moisture content.
It is the ruthenium complex [Ru (bpy) in the present embodiment referring to Fig. 32BDP](ClO4)2In DMF solution it is ultraviolet-can
See absorption spectrum and launching light spectrogram.
It is the ruthenium complex [Ru (bpy) in the present embodiment referring to Fig. 42BDP](ClO4)2In the DMF solution of different moisture content
In launching light spectrogram.
Embodiment 4
(1) synthesis of 3,8- bis- (4- (2,2- diphenylethyllenes) phenyl) -1,10 ferrosins (BDP) is same as Example 3.
(2) ruthenium complex [Ru (phen)2BDP](ClO4)2Preparation
First ligand [Ru (phen)2Cl2] synthesis it is in the same manner as in Example 2.
Under nitrogen protection, [Ru (phen) is weighed2Cl2] BDP made from (0.053g, 0.1mmol) and step (1)
(0.069g, 0.5mmol) is dissolved in 15mL ethylene glycol, and 8h is reacted at 150 DEG C, obtains red clear liquid.It is cooled to room temperature, adds
20mL water dilutes, and the saturated solution of sodium perchlorate is added later until generating a large amount of red precipitates.Filtering, filter cake respectively use water,
Ether washs three times, dry, column chromatography (neutral Al2O3, the volume ratio of eluent toluene/acetonitrile is 1:3) ruthenium, is made to match
Close object [Ru (phen)2BDP](ClO4)2Yield is 36.73%.The ruthenium complex is analyzed by mass spectrometry：MALDI-TOF,m/
z:calcd for[Ru(phen)2BDP](ClO4)2C76H52N6Ru:1150.33,Found:1150.44. reaction equation is as follows
Formula 6.
It should be appreciated that the technical concepts and features of above-described embodiment only to illustrate the invention, its object is to allow be familiar with this
The personage of item technology cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all
According to equivalent change or modification made by spirit of the invention, should be covered by the protection scope of the present invention.
Claims (4)
1. a kind of ruthenium complex with aggregated-state induced phosphorescence enhancing characteristic, it is characterised in that：The structure of the ruthenium complex
Formula is following any：
2. the preparation method of the ruthenium complex described in claim 1 with aggregated-state induced phosphorescence enhancing characteristic, feature exist
In including：
It is 1 by molar ratio in nitrogen atmosphere：It is molten that 1~3 soluble ruthenium salt with the compound as the first ligand is dissolved in first
In agent, and back flow reaction 6h or more, after being cooled to room temperature, intermediate product is obtained, the compound of first ligand joins for 2,2-
Pyridine or 1,10- phenanthrolines；
It is 1 by molar ratio in nitrogen atmosphere：1~3 bromo phenanthroline and 4- (2,2- diphenylethyllenes) phenyl boric acid is dissolved in
The mixed liquor of tetrahydrofuran or toluene and aqueous sodium carbonate, under the action of catalyst, 12~36h of back flow reaction obtains 2,2-
Diphenylethyllene benzene derivative, wherein the catalyst uses tetrakis triphenylphosphine palladium；
Later, it is 1 by molar ratio：3~8 intermediate product and the 2,2- diphenylethyllene benzene derivatives as Ligands
It is dissolved in the second solvent, 6h or more is reacted at 100~150 DEG C, obtained reaction mixture is post-treated to be obtained with aggregated-state induced
Phosphorescence enhances the ruthenium complex of characteristic.
3. preparation method according to claim 2, it is characterised in that：First solvent uses DMF, second solvent
Using ethylene glycol.
4. preparation method according to claim 2, which is characterized in that the post-processing includes：To obtained reaction mixture
The interior saturated solution that sodium perchlorate is added purifies using filter, column chromatography, obtains the ruthenium complex of purifying.
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