CN105440084B - Three metallic core platinum complex phosphor materials and its synthetic method based on triphenylamine - Google Patents
Three metallic core platinum complex phosphor materials and its synthetic method based on triphenylamine Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 51
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 37
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 18
- 238000010189 synthetic method Methods 0.000 title claims abstract description 14
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 15
- 238000001556 precipitation Methods 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000013110 organic ligand Substances 0.000 claims abstract description 13
- 239000012046 mixed solvent Substances 0.000 claims abstract description 11
- 229910020427 K2PtCl4 Inorganic materials 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- 239000003446 ligand Substances 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 36
- 239000003960 organic solvent Substances 0.000 claims description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 12
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 12
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 8
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 6
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 150000003217 pyrazoles Chemical class 0.000 claims description 5
- 150000002460 imidazoles Chemical class 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- -1 Acyl acetone Chemical compound 0.000 claims description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 150000003851 azoles Chemical class 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 26
- 239000002184 metal Substances 0.000 abstract description 24
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 abstract description 17
- 238000005395 radioluminescence Methods 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MREIFUWKYMNYTK-UHFFFAOYSA-N 1H-pyrrole Chemical class C=1C=CNC=1.C=1C=CNC=1 MREIFUWKYMNYTK-UHFFFAOYSA-N 0.000 description 1
- VFMUXPQZKOKPOF-UHFFFAOYSA-N 2,3,7,8,12,13,17,18-octaethyl-21,23-dihydroporphyrin platinum Chemical compound [Pt].CCc1c(CC)c2cc3[nH]c(cc4nc(cc5[nH]c(cc1n2)c(CC)c5CC)c(CC)c4CC)c(CC)c3CC VFMUXPQZKOKPOF-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- BNWQAZVVDQEGQJ-UHFFFAOYSA-N [P].C1(=CC=CC=C1)N(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [P].C1(=CC=CC=C1)N(C1=CC=CC=C1)C1=CC=CC=C1 BNWQAZVVDQEGQJ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 239000000700 radioactive tracer Substances 0.000 description 1
- 238000005059 solid analysis Methods 0.000 description 1
- 125000006617 triphenylamine group Chemical group 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
- C07F15/0086—Platinum compounds
-
- 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
-
- 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
-
- 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
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
-
- 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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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
Three metallic core platinum complex phosphor materials and its synthetic method, its general structure based on triphenylamine are：Using direct synthesis technique or collaboration synthetic method, by organic ligand and K2PtCl4Reaction, adds mixed solvent, and in nitrogen atmosphere, until there is solid precipitation, the solid of precipitation can generate product with heating in assistant ligand nitrogen, contain three metal centers in the present invention for heating, cooling plus water；Such molecular structure causes the ability of singlet to the probability and triplet state radioluminescence of altering jump between triplet state system in organic metal platinum (II) complex to be improved, and plays an important roll for the luminescent properties for improving material.
Description
Technical field
The present invention relates to technical field of organic luminescence materials, the three metallic core platinum complexes more particularly to based on triphenylamine
Phosphor material and its synthetic method.
Background technology
Luminous organic material be it is a kind of can be lighted when ambient light excites or when external electrical field excites organise
Compound, the separate sources to be lighted generally according to it can be divided into organic fluorescence luminescent material and Phosphorescent luminescent material.Have
Machine luminescent material has very extensive application field, such as sensor field, tracer field and electroluminescent field etc..Especially
It is Organic Light Emitting Diode (the Organic Light Emitting based on luminous organic material in electroluminescent field
Diode, OLED) have the advantages that working voltage is low, luminosity is high, luminous color enriches, can be made into flexible ultra-thin device,
The application fields such as high-end new display and white-light illuminating have very prominent advantage.The achievement in research of nearly 30 years refers to
Going out, the Organic Light Emitting Diode theoretical internal quantum efficiency prepared by conventional fluorescent luminescent material only has 25%, and by organic metal
Organic Light Emitting Diode theoretical internal quantum efficiency prepared by complex phosphorescence luminescent material can reach 100%, therefore research is opened
It is always the focus direction in Organic Light Emitting Diode field to send out organometallic complex phosphorescent light-emitting materials all kinds of.Because it has surely
The advantages that qualitative good, luminous efficiency is high and synthesis is simple, since earliest phosphorescence Organic Light Emitting Diode research, You Jijin
Category platinum (II) complex phosphorescence luminescent material is always the study hotspot of organic metal phosphorescent light-emitting materials.It is used for phosphorus from earliest
Octaethylporphyrin platinum (Nature, 1998,395 (6698) of light Organic Light Emitting Diode:It is 151-154) various to what is reported at present
Organic metal platinum (II) complex phosphorescence luminescent material (Platinum Metals Review, 2013,57 (1):2-16；
Dalton Transactions,2015,44(18):8433-8443), its complex molecule has a common structure special
Sign, i.e., generally only containing in platinum (II) metal in these organic metal platinum (II) complex phosphorescence luminescent material molecular structures
The heart.For organometallic complex phosphor material, it can produce phosphorescence at room temperature, crucial in a huge sum of money in complex
Category element presence can strengthen singlet to triplet state be between alter jump probability and strengthen triplet state attenuation ability,
So heavy metal center is significant for the phosphorescent emissions property of luminescent material.In view of organic metal platinum (II) is matched somebody with somebody at present
The research starting point of compound phosphorescent light-emitting materials is essentially confined to the design of organic ligand, for more metal center platinum (II)
The research of complex phosphorescence luminescent material does not almost have.
The content of the invention
The defects of in order to overcome above-mentioned prior art, it is an object of the invention to provide a kind of three metals based on triphenylamine
Core platinum complex phosphor material and its synthetic method, develop organic metal platinum (II) complex phosphorus with more metal centers
Light luminescent material, it is organic metal platinum (II) complex phosphorescence material with three metal centers, platinum can be greatly enriched and matched somebody with somebody
The species of compound phosphor material.
In order to achieve the above object, the technical scheme is that：
The three metallic core platinum complex phosphor materials based on triphenylamine, its general structure are：
In formula,For nitrogenous heteroaromatic, including pyridine, pyrimidine, thiazole, benzothiazole, quinoline, isoquinolin, pyrrole
Azoles, imidazoles；For nitrogenous heteroaromatic, including pyridine, pyrimidine, thiazole, benzothiazole, quinoline, isoquinolin, pyrazoles, miaow
Azoles；For nitrogenous heteroaromatic, including pyridine, pyrimidine, thiazole, benzothiazole, quinoline, isoquinolin, pyrazoles, imidazoles.
The synthetic method of the three metallic core platinum complex phosphor materials based on triphenylamine, direct synthesis technique step are：
By organic ligandWith K2PtCl4According to the amount 1 of material：(3~6)
Ratio input reaction vessel in, under nitrogen atmosphere, added into the reaction vessel can by reactant dissolve it is organic
The volume ratio of the mixed solvent of solvent and water, in the mixed solvent organic solvent and water is (2~5)：1；The organic solvent is four
One or more in hydrogen furans, ethylene glycol ethyl ether, dioxane, glycol dimethyl ether；80 DEG C are heated in nitrogen atmosphere extremely
130 DEG C are reacted 5~24 hours；Stop heating, cold water is added into reaction mixture after being cooled to room temperature, until there is solid analysis
Go out, filter and dry separate out solid, itself and assistant ligand acetylacetone,2,4-pentanedione are dissolved in organic solvent, the solid of precipitation with it is auxiliary
Help part acetylacetone,2,4-pentanedione according to material amount ratio be 1：(3~20), be heated in nitrogen atmosphere 30 DEG C to 130 DEG C reactions 5~
24 hours can generating structure formula beThree metallic core platinum complex phosphorus
Luminescent material.
The synthetic method of the three metallic core platinum complex phosphor materials based on triphenylamine, collaboration synthetic method step are：
By organic ligandWith organic ligand L and K2PtCl4Input reaction
In container, the ratio of input amount is respectively：With organic ligand L according to material
Amount 1：3~1：6；With K2PtCl4According to the amount 1 of material：3~1：6；It is organic herein
Ligand L is
In one
Kind is a variety of, and the mixed solvent of the organic solvent that can dissolve reactant and water is added into the reaction vessel, and mixing is molten
The volume ratio of organic solvent and water is (2~5) in agent：1, the organic solvent is tetrahydrofuran, ethylene glycol ethyl ether, dioxy six
One or more in ring, glycol dimethyl ether, 80 DEG C to 130 DEG C are heated in nitrogen atmosphere and is reacted 5~24 hours, stop plus
Heat, cold water is added into reaction mixture after being cooled to room temperature, until there is solid precipitation, filter and dry the solid separated out, will
It is dissolved in organic solvent with assistant ligand acetylacetone,2,4-pentanedione, the amount of the solid of precipitation with assistant ligand acetylacetone,2,4-pentanedione according to material
Ratio is 1：(3~50), be heated in nitrogen 30 DEG C to 130 DEG C reactions 5~24 hours can generating structure formula beThree metallic core platinum complex phosphor materials.
Compared with existing organic metal platinum (II) complex phosphorescence material for comprising only a metal center, the present invention obtains
There is organic metal platinum (II) complex phosphorescence material of three metal centers, platinum complex phosphor material can be greatly enriched
Species.In addition, the presence of more metal centers causes in organic metal platinum (II) complex singlet to altering jump between triplet state system
Probability and the ability of triplet state radioluminescence be improved, play an important roll for the luminescent properties for improving material.
Brief description of the drawings
Fig. 1 is to synthesize three metallic core organic metal platinum (II) complex phosphorescence material Pt1 by direct synthesis technique of the present invention
Route map.
Fig. 2 is to synthesize three metallic core organic metal platinum (II) complex phosphorescence material Pt2 by present invention collaboration synthetic method
Route map.
Fig. 3 is three metallic core organic metal platinum (II) complex phosphorus of two embodiments synthesis as selected by the present invention
Luminescent material Pt1 and Pt2 luminous spectrogram.
Embodiment
The present invention is further described below in conjunction with the accompanying drawings.
Embodiment one：
Three metallic core organic metal platinum (II) complex Pt1, chemical formula C of the present embodiment48H42N4O6Pt3, structure
Formula isReferring to the drawings 1, the synthetic route of its direct synthesis technique includes following step
Suddenly：
The first step：By 0.48 gram of organic ligandWith 1.21 grams of K2PtCl4Input is anti-
Answer in container, add the mixed solvent of 30 milliliters of ethylene glycol ethyl ethers and water in nitrogen atmosphere, in the mixed solvent ethylene glycol ethyl ether with
The volume ratio of water is 3:1,110 DEG C are heated in nitrogen atmosphere, stirring is cooled to room temperature after 12 hours；
Second step：Into step 1, final reaction mixture adds 50 ml deionized waters, produces precipitation.Pass through suction filtration
Precipitated and dried in vacuum drying chamber, then precipitation is mixed with 0.5 gram of acetylacetone,2,4-pentanedione, returned in nitrogen atmosphere
Stream stirring 12 hours；
3rd step：Into step 2, final reaction mixture adds 50 ml deionized waters, produces precipitation.Pass through suction filtration
Precipitated and in vacuum drying chamber drying can obtain crude product, then by its make by oneself thin layer silica gel chromatosheet on it is pure
Change, finally give 0.25 gram of bright yellow solid Pt1, yield 18.5%.
Its nuclear-magnetism characterize data is：
1H NMR(400MHz,CDCl3):δ (ppm) 8.90 (d, J=4.0Hz, 3H), 7.71 (t, J=8.0Hz, 3H),
7.52-7.47 (m, 6H), 7.33 (d, J=8.0Hz, 3H), 7.01-6.94 (m, 6H), 5.36 (s, 3H), 1.95 (s, 9H),
1.78(s,9H).
According to above-mentioned data, that illustrate the present embodiment synthesis is Pt1.
Embodiment two：
Three metallic core organic metal platinum (II) complex Pt2, chemical formula C of the present embodiment54H42N4O6Pt3S3, structure
Formula isReferring to the drawings 2, its cooperate with synthetic method synthetic route include with
Lower step：
The first step：By 0.64 gram of organic ligandOrganic match somebody with somebody with 0.6 gram
BodyAnd 1.21 grams of K2PtCl4Put into reaction vessel, the mixed of 30 milliliters of ethylene glycol ethyl ethers and water is added in nitrogen atmosphere
The volume ratio of bonding solvent, in the mixed solvent ethylene glycol ethyl ether and water is 3:1,110 DEG C are heated in nitrogen atmosphere, is stirred 12 hours
After be cooled to room temperature；
Second step：Into step 1, final reaction mixture adds 50 ml deionized waters, produces precipitation.Pass through suction filtration
Precipitated and dried in vacuum drying chamber, then precipitation is mixed with 0.5 gram of acetylacetone,2,4-pentanedione, returned in nitrogen atmosphere
Stream stirring 12 hours；
3rd step：Into step 2, final reaction mixture adds 50 ml deionized waters, produces precipitation.Pass through suction filtration
Precipitated and in vacuum drying chamber drying can obtain crude product, then by its make by oneself thin layer silica gel chromatosheet on it is pure
Change, finally give 0.38 gram of yellow solid Pt2, yield 24.9%.
Its nuclear-magnetism characterize data is：1H NMR(400MHz,CDCl3):δ (ppm) 9.10 (d, J=8.4Hz, 3H), 7.75
(d, J=8.0Hz, 3H), 7.57 (s, 3H), 7.51 (t, J=8.0Hz, 3H), 7.41-7.35 (m, 6H), 6.97 (d, J=
8.4Hz,3H),5.42(s,3H),2.01(s,9H),1.77(s,9H).
According to above-mentioned data, that illustrate the present embodiment synthesis is Pt2.
The embodiment of the present invention is described above in association with accompanying drawing, but these explanations can not be understood to limit
The scope of the present invention, protection scope of the present invention are limited by appended claims, any in the claims in the present invention base
Change on plinth is all protection scope of the present invention.
Claims (3)
1. the three metallic core platinum complex phosphor materials based on triphenylamine, it is characterised in that the three metallic cores platinum complex has
There is following general structural formula：
In formula,For nitrogenous heteroaromatic, selected from pyridine, pyrimidine, thiazole, benzothiazole, quinoline, isoquinolin, pyrazoles, miaow
Azoles；For nitrogenous heteroaromatic, selected from pyridine, pyrimidine, thiazole, benzothiazole, quinoline, isoquinolin, pyrazoles, imidazoles；For nitrogenous heteroaromatic, selected from pyridine, pyrimidine, thiazole, benzothiazole, quinoline, isoquinolin, pyrazoles, imidazoles.
2. based on the synthetic method of the three metallic core platinum complex phosphor materials based on triphenylamine described in claim 1, its
It is characterised by,
Direct synthesis technique step is：
By organic ligandWith K2PtCl4According to the amount 1 of material：The ratio of (3~6)
Put into reaction vessel in, under nitrogen atmosphere, added into the reaction vessel can by reactant dissolve organic solvent with
The volume ratio of the mixed solvent of water, in the mixed solvent organic solvent and water is (2~5)：1；The organic solvent be tetrahydrofuran,
One or more in ethylene glycol ethyl ether, dioxane, glycol dimethyl ether；80 DEG C to 130 DEG C are heated in nitrogen atmosphere instead
Answer 5~24 hours；Stop heating, cold water is added into reaction mixture after being cooled to room temperature, until there is solid precipitation, filtering is simultaneously
The solid separated out is dried, itself and assistant ligand acetylacetone,2,4-pentanedione are dissolved in organic solvent, solid and the assistant ligand second of precipitation
Acyl acetone is 1 according to the amount ratio of material：(3~20), 30 DEG C to 130 DEG C reactions are heated in nitrogen atmosphere 5~24 hours i.e.
Can generating structure formula beThree metallic core platinum complex phosphor materials.
3. based on the synthetic method of the three metallic core platinum complex phosphor materials based on triphenylamine described in claim 1, its
It is characterised by,
Collaboration synthetic method step be：
By organic ligandWith organic ligand L and K2PtCl4Put into reaction vessel
In, the ratio of input amount is respectively：Amount 1 with organic ligand L according to material：3
~1：6；With K2PtCl4According to the amount 1 of material：3~1：6；Organic ligand L herein
For In one kind or more
Kind, the organic solvent of reactant dissolving and the mixed solvent of water, in the mixed solvent can be had by being added into the reaction vessel
Solvent and the volume ratio of water are (2~5)：1, the organic solvent is tetrahydrofuran, ethylene glycol ethyl ether, dioxane, second two
One or more in diethylene glycol dimethyl ether, 80 DEG C to 130 DEG C are heated in nitrogen atmosphere and is reacted 5~24 hours, stops heating, is cooled to
Cold water is added after room temperature into reaction mixture, until there is solid precipitation, the solid separated out is filtered and dry, by itself and auxiliary
Part acetylacetone,2,4-pentanedione is dissolved in organic solvent, and the solid and assistant ligand acetylacetone,2,4-pentanedione of precipitation are 1 according to the amount ratio of material：
(3~50), be heated in nitrogen 30 DEG C to 130 DEG C reactions 5~24 hours can generating structure formula beThree metallic core platinum complex phosphor materials.
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| CN113105509B (en) * | 2021-04-02 | 2022-06-21 | 西安交通大学 | Complex phosphorescent material based on electron-deficient functional group |
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| CN102372670A (en) * | 2010-08-20 | 2012-03-14 | 清华大学 | Arylamine compounds containing arylpyridine groups and application of arylamine compounds containing arylpyridine group |
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