CN107652326B - One inter-species picoline tetrazole copper [I] complex blue light material and preparation method thereof - Google Patents
One inter-species picoline tetrazole copper [I] complex blue light material and preparation method thereof Download PDFInfo
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- CN107652326B CN107652326B CN201711046685.3A CN201711046685A CN107652326B CN 107652326 B CN107652326 B CN 107652326B CN 201711046685 A CN201711046685 A CN 201711046685A CN 107652326 B CN107652326 B CN 107652326B
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- 239000000463 material Substances 0.000 title claims abstract description 39
- RXYPMMHMJUGKQB-UHFFFAOYSA-N [Cu].N1N=NN=C1.N1=C(C=CC=C1)C Chemical compound [Cu].N1N=NN=C1.N1=C(C=CC=C1)C RXYPMMHMJUGKQB-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 150000003536 tetrazoles Chemical class 0.000 claims abstract description 33
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000010949 copper Substances 0.000 claims abstract description 23
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims abstract description 20
- 229910000906 Bronze Inorganic materials 0.000 claims abstract description 14
- 239000010974 bronze Substances 0.000 claims abstract description 14
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims abstract description 13
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims abstract description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 52
- 239000011541 reaction mixture Substances 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000012046 mixed solvent Substances 0.000 claims description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 10
- SPWVRYZQLGQKGK-UHFFFAOYSA-N dichloromethane;hexane Chemical compound ClCCl.CCCCCC SPWVRYZQLGQKGK-UHFFFAOYSA-N 0.000 claims description 10
- 239000003446 ligand Substances 0.000 claims description 10
- 238000001953 recrystallisation Methods 0.000 claims description 10
- SBOQCPPINFMCBH-UHFFFAOYSA-N diphenylphosphane;methane Chemical compound C.C=1C=CC=CC=1PC1=CC=CC=C1.C=1C=CC=CC=1PC1=CC=CC=C1 SBOQCPPINFMCBH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 239000012300 argon atmosphere Substances 0.000 claims description 8
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- RAFKCLFWELPONH-UHFFFAOYSA-N acetonitrile;dichloromethane Chemical compound CC#N.ClCCl RAFKCLFWELPONH-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- ZRYJCBRMUIHLOV-UHFFFAOYSA-N 2-methylpyridine 2H-tetrazole Chemical compound N1N=NN=C1.CC1=NC=CC=C1 ZRYJCBRMUIHLOV-UHFFFAOYSA-N 0.000 claims description 4
- UFITZXXHLWZPNO-UHFFFAOYSA-N perchloric acid;hexahydrate Chemical compound O.O.O.O.O.O.OCl(=O)(=O)=O UFITZXXHLWZPNO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims 1
- -1 chlorate anions Chemical class 0.000 claims 1
- 239000007787 solid Substances 0.000 description 14
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- XGCDBGRZEKYHNV-UHFFFAOYSA-N 1,1-bis(diphenylphosphino)methane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)C1=CC=CC=C1 XGCDBGRZEKYHNV-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- LGGVAPZDPXMQOP-UHFFFAOYSA-N 2-methylpyridine 1H-pyrrole Chemical class CC1=NC=CC=C1.N1C=CC=C1 LGGVAPZDPXMQOP-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- TWWJJVNUZQLCPD-UHFFFAOYSA-N diphenylphosphane;methane Chemical compound C.C=1C=CC=CC=1PC1=CC=CC=C1 TWWJJVNUZQLCPD-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- QATLRIDVUPPCGT-UHFFFAOYSA-N pyridine;2h-tetrazole Chemical compound C1=NN=NN1.C1=CC=NC=C1 QATLRIDVUPPCGT-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
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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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6596—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having atoms other than oxygen, sulfur, selenium, tellurium, nitrogen or phosphorus as ring hetero atoms
-
- 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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- 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
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Pyridine Compounds (AREA)
Abstract
The present invention relates to inter-species picoline tetrazole copper [I] complex blue light materials, it is characterized in that, described picoline tetrazole copper [I] complex blue light material is that [5- [5- methyl -2- pyridyl group] tetrazole base] four [bis- [diphenylphosphine] methane] of perchlorate two close four bronze medals [I] complex, molecular formula are as follows: C114H100Cl2Cu4N10O8P8.The present invention also provides the preparation methods of two inter-species picoline tetrazole copper [I] complex blue light materials.Between picoline tetrazole copper [I] complex blue light material belong to a kind of new blue light emitting material, there is good development prospect.
Description
Technical field
The present invention relates to inter-species picoline tetrazole copper [I] complex blue light materials and preparation method thereof, belong to hair
Light new material synthesis technical field.
Background technique
Because of the influence of heavy atoms effect and strong Effect of Spin-orbit Coupling, metal emitting complexes are theoretically using all
Singlet state and triplet energies, are substantially improved luminous efficiency.Currently, the research of metal emitting complexes focus primarily upon the 5th,
Six periods, especially group VIII transition metal, such as ruthenium, osmium, iridium and platinum.The transition metal in the five, the six periods is (except the first and second pair
Outside a few metal of race) content is rare in the earth's crust, and exploitation is difficult, therefore is made based on such noble metal emitting complexes
With higher cost, and it can also bring raw material nervous after large-scale application.In addition, such precious metal chemical complex usually have it is larger
The compounds such as toxicity, especially ruthenium, osmium, rhenium, thus, the luminescent material based on such precious metal chemical complex is after large-scale application
Environmental pollution can also be brought and bring injury to production and application person.The defects of high use cost and unfriendly environment, makes theirs
Large-scale application is extremely restricted, thus people be particularly desirable to look for except the five, the six periods it is other alternative
Metal.
The transition metal in the five, the six periods is compared, the copper metal of period 4 is not only resourceful, and it is cheap, and
Environmentally friendly and luminous uniqueness.In addition, univalent copper complex has the excellent visible phosphorescent emissions of room temperature, shining can be ultraviolet
Change to near-infrared, covers entire visible region.It is resourceful, cheap, shine it is unique and environmentally friendly etc. many excellent
Point is so that monovalence copper emitting complexes are all in luminescent device, intellectual material, optical sensor, nonlinear optics, photovoltaic device etc.
It is multi-field to show good application prospect.
Currently, the copper emitting complexes that document discloses report mainly have monovalence copper mononuclear complex and cluster compound.Monovalence copper
Many advantages, such as cluster compound because of structure novel, geometric configuration is abundant, coordination mode multiplicity, luminosity is unique, it is more next in recent years
More receive much attention.However, constructing multicore copper using the multiple tooth cheland of azacyclo- and organic double phosphine assistant ligands
The document report of [I] complex luminescent material is seldom, especially multicore copper [I] complex blue light emitting material.
It is double using the multiple tooth cheland 5- of pyridine tetrazole [5- methyl -2- pyridyl group] tetrazole and double phosphine assistant ligands
[diphenylphosphine] methane, design four core copper [I] complex blue light emitting materials of synthesis and preparation method thereof, there has been no documents at present
Open report.
Summary of the invention
It is an object of the invention to overcome the defect of the prior art, provides an inter-species picoline tetrazole copper [I] and match
Object blue light material and preparation method thereof is closed, a kind of new blue light emitting material is belonged to.
The present invention is implemented as follows:
The present invention provide inter-species picoline tetrazole copper [I] complex blue light material, it is described between four nitrogen of picoline
Azoles copper [I] complex blue light material is perchlorate two [5- [5- methyl -2- pyridyl group] tetrazole base] four [bis- [hexichol
Base phosphine] methane] close four bronze medals [I] complex, molecular formula are as follows: C114H100Cl2Cu4N10O8P8。
Inter-species picoline tetrazole copper [I] complex blue light material as described in claim 1, it is characterised in that:
[5- [5- methyl -2- pyridyl group] tetrazole base] four [bis- [diphenylphosphine] methane] of perchlorate two close four bronze medals [I] cooperation
Object crystal category monoclinic system, P-1 space group, cell parameter: a=13.604 (6), b=15.258 (7),α=74.624 (10) °, β=67.946 (9) °, γ=66.529 (10) °,
Mr=2682.56, Z=1, Dc=1.440g cm-3, μ=1.058mm-1, GOF=1.038.
The present invention provides the preparation method of inter-species picoline tetrazole copper [I] complex blue light material, including following
Step:
Step 1: under an argon atmosphere, molar ratio is the [Cu [MeCN] of 2:2:14][ClO4], bis- [diphenylphosphine] methane,
5- [5- methyl -2- pyridyl group] tetrazole in methylene chloride react 2-4 hours by stirring at normal temperature, obtains the first reaction mixture；
Step 2: it is added and 5- [5- methyl -2- pyridyl group] tetrazole ligand equimolar into first reaction mixture
The sodium hydroxide of amount, and continue stirring at normal temperature and react 1-2 hours, obtain the second reaction mixture；
Step 3: the solvent of the second reaction mixture is evaporated, and is tied again using methylene chloride-n-hexane mixed solvent
Crystalline substance, filtration and recrystallization obtain colourless crystalline products, are washed 3-4 times using ether, colorless solid product are obtained after vacuum drying, i.e.,
Four bronze medals [I] is closed for [5- [5- methyl -2- pyridyl group] tetrazole base] four [bis- [diphenylphosphine] methane] of perchlorate two to match
Close object.
Further, in step 3, the solvent of the second reaction mixture is evaporated using Rotary Evaporators, dichloromethane
The volume ratio of alkane-n-hexane in the mixed solvent methylene chloride and n-hexane is 1:10.
The present invention also provides the preparation methods of inter-species picoline tetrazole copper [I] complex blue light material, including with
Lower step:
Step 1: under an argon atmosphere, molar ratio 1:(5-10): perchlorate hexahydrate's copper of 2:1, excessive copper powder, bis- [two
Phenylphosphine] methane, 5- [5- methyl -2- pyridyl group] tetrazole acetonitrile-dichloromethane in the mixed solvent stirring at normal temperature react 2-4
Hour, obtain the first reaction mixture；
Step 2: it is added and 5- [5- methyl -2- pyridyl group] tetrazole ligand equimolar into first reaction mixture
The sodium hydroxide of amount, and continue stirring at normal temperature and react 1-2 hours, obtain the second reaction mixture；
Step 3: after the filtering of the second reaction mixture, solvent evaporated is carried out with methylene chloride-n-hexane mixed solvent
Recrystallization, the colourless crystalline products that filtration and recrystallization obtains are washed 3-4 times with ether, and colorless solid production is obtained after vacuum drying
Object, as perchlorate two [5- [5- methyl -2- pyridyl group] tetrazole base] four [bis- [diphenylphosphine] methane] close four bronze medals
[I] complex.
Further, in step 1, the volume ratio of acetonitrile-dichloromethane in the mixed solvent acetonitrile and methylene chloride is 1:
2。
Further, in step 3, the solvent of the second reaction mixture is evaporated using Rotary Evaporators, dichloromethane
The volume ratio of alkane-n-hexane in the mixed solvent methylene chloride and n-hexane is 1:10.
The invention has the following advantages:
The present invention provides inter-species picoline tetrazole copper [I] complex blue light materials and preparation method thereof, belong to
In a kind of new blue light emitting material.Between of the invention in picoline tetrazole four core copper [I] complex blue light emitting material
Select the main purpose and meaning of 5- [5- methyl -2- pyridyl group] tetrazole and bis- [diphenylphosphine] methane: by applying 5- [5-
Methyl -2- pyridyl group] the multiple tooth cheland of tetrazole and bis- [diphenylphosphine] methane bridge ligands, adjusting copper [I] complex
Space multistory effect and electron density distribution realize the solid state blue emission characteristic of copper [I] complex, at normal temperature, Gu
State emission wavelength maximum value is 459nm, and the solid luminescent service life is 80 μ s, and solid luminescent quantum efficiency is 65%.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
Other attached drawings are obtained according to these attached drawings.
Fig. 1 is two [5- [5- methyl -2- pyridyl group] tetrazole base] four of perchlorate provided in an embodiment of the present invention
[bis- [diphenylphosphine] methane] closes four bronze medals [I] complex crystal structure chart.
Fig. 2 is two [5- [5- methyl -2- pyridyl group] tetrazole base] four of perchlorate provided in an embodiment of the present invention
[bis- [diphenylphosphine] methane] closes four bronze medals [I] complex solid state fluorescence emission spectrum.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art without making creative work it is obtained it is all its
Its embodiment, shall fall within the protection scope of the present invention.
Such as Fig. 1 and Fig. 2, the embodiment of the present invention provides inter-species picoline tetrazole copper [I] complex blue light material, institute
Stating picoline tetrazole copper [I] complex blue light material is [5- [5- methyl -2- pyridyl group] tetrazole of perchlorate two
Base] four [bis- [diphenylphosphine] methane] conjunction four bronze medals [I] complex, molecular formula are as follows: C114H100Cl2Cu4N10O8P8.Molecular weight
It is 2311.0.
Its English name: [Cu4[5-(5-methyl-2-pyridyl)tetrazolate]2[bis
(diphenylphosphino)methane]4][ClO4]2, write a Chinese character in simplified form are as follows: [Cu4[m-mpytz]2[dppm]4][ClO4]2。
Its molecular structure are as follows:
(this is first to the preparation method of the present invention one inter-species picoline tetrazole copper [I] complex blue light material of offer
Kind preparation method), comprising the following steps:
Step 1: under an argon atmosphere, molar ratio is the [Cu [MeCN] of 2:2:14][ClO4], bis- [diphenylphosphine] methane,
5- [5- methyl -2- pyridyl group] tetrazole [abbreviation pytzH] in methylene chloride react 2-4 hours by stirring at normal temperature, obtains first
Reaction mixture.
Step 2: it is added and 5- [5- methyl -2- pyridyl group] tetrazole ligand equimolar into first reaction mixture
The sodium hydroxide of amount, and continue stirring at normal temperature and react 1-2 hours, obtain the second reaction mixture.
Step 3: the solvent of the second reaction mixture is evaporated, and is tied again using methylene chloride-n-hexane mixed solvent
Crystalline substance, filtration and recrystallization obtain colourless crystalline products, are washed 3-4 times using ether, colorless solid product are obtained after vacuum drying, i.e.,
Four bronze medals [I] is closed for [5- [5- methyl -2- pyridyl group] tetrazole base] four [bis- [diphenylphosphine] methane] of perchlorate two to match
Close object.Wherein, the solvent of the second reaction mixture is evaporated using Rotary Evaporators, methylene chloride-n-hexane in the mixed solvent
The volume ratio of methylene chloride and n-hexane is 1:10.
The reaction mechanism of this preparation method are as follows:
The present invention also provides the preparation method of inter-species picoline tetrazole copper [I] complex blue light material, (this is
Two kinds of preparation methods), comprising the following steps:
Step 1: under an argon atmosphere, molar ratio 1:(5-10): perchlorate hexahydrate's copper [Cu [ClO of 2:14]2·
6H2O], excessive copper powder, bis- [diphenylphosphine] methane [abbreviation dppm], 5- [5- methyl -2- pyridyl group] tetrazole [referred to as
PytzH] it is reacted 2-4 hours in acetonitrile-dichloromethane in the mixed solvent stirring at normal temperature, obtain the first reaction mixture.Wherein, second
The volume ratio of nitrile-methylene chloride in the mixed solvent acetonitrile and methylene chloride is 1:2.
Step 2: it is added and 5- [5- methyl -2- pyridyl group] tetrazole ligand equimolar into first reaction mixture
The sodium hydroxide of amount, and continue stirring at normal temperature and react 1-2 hours, obtain the second reaction mixture；
Step 3: after the filtering of the second reaction mixture, solvent evaporated is carried out with methylene chloride-n-hexane mixed solvent
Recrystallization, the colourless crystalline products that filtration and recrystallization obtains are washed 3-4 times with ether, and colorless solid production is obtained after vacuum drying
Object, as perchlorate two [5- [5- methyl -2- pyridyl group] tetrazole base] four [bis- [diphenylphosphine] methane] close four bronze medals
[I] complex.Wherein, the solvent of the second reaction mixture is evaporated using Rotary Evaporators, methylene chloride-n-hexane mixing is molten
The volume ratio of methylene chloride and n-hexane is 1:10 in agent.
The reaction mechanism of this preparation method are as follows:
It is illustrated below by way of two specific embodiments:
Embodiment 1:
Under an argon atmosphere, [Cu [MeCN]4][ClO4] (20.9mg, 0.064mmol), bis- [diphenylphosphine] methane
(24.6mg, 0.064mmol) and 5- [5- methyl -2- pyridyl group] tetrazole (5.2mg, 0.032mmol) is in 10mL methylene chloride
Middle stirring at normal temperature is reacted 3 hours, and sodium hydroxide (1.28mg, 0.032mmol) is added into the reaction solution afterwards, continues to stir under room temperature
Mix reaction 1 hour, after solvent is evaporated with Rotary Evaporators, with methylene chloride (1mL)-n-hexane (10mL) mixed solvent [body
Product is than being 1:10] it is recrystallized.The colourless crystalline products that filtration and recrystallization obtains, are washed 3-4 times with 10mL ether, and vacuum is dry
Colorless solid product (30.1mg, 0.013mmol), yield 81% are obtained after dry.
Elemental analysis calculated value (C114H100Cl2Cu4N10O8P8) it is (%): C 59.25, H 4.36, N 6.06；Measured value:
C 59.27,H 4.38,N 6.03。
X-ray single crystal diffraction: crystal category anorthic system, P-1 space group, cell parameter: a=13.604 (6), b=
15.258 (7),α=74.624 (10) °, β=67.946 (9) °, γ=66.529 (10) °,Mr=2682.56, Z=1, Dc=1.440g cm-3, μ=1.058mm-1, GOF=1.038, crystal knot
Composition is as shown in Figure 1.
Photoluminescence performance test result shows this picoline tetrazole four core copper [I] complex table at normal temperature
Reveal solid state blue emission characteristic, solid luminescent wavelength maximum is 459nm, and the solid luminescent service life is 80 μ s, solid luminescent
Quantum efficiency is 65%, and solid state fluorescence emission spectrum is as shown in Figure 2.
Embodiment 2:
Under an argon atmosphere, perchlorate hexahydrate's copper [Cu [ClO4]2·6H2O] (10.4mg, 0.028mmol) and excessive copper powder
(12.0mg, 0.189mmol) stirring at normal temperature in 5mL acetonitrile is reacted 30 minutes, rear that bis- [diphenylphosphine] methane are added
The 10mL dichloromethane solution of (21.5mg, 0.056mmol) continues that 5- [5- methyl -2- pyridine is added after being stirred to react 1 hour
Base] tetrazole (4.5mg, 0.028mmol), continues to be stirred to react 2 hours under room temperature, sodium hydroxide is added into the reaction solution afterwards
(1.12mg, 0.028mmol), and continue stirring at normal temperature and react 1 hour, solvent is evaporated with Rotary Evaporators after filtering, with two
Chloromethanes (1mL)-n-hexane (10mL) mixed solvent [volume ratio 1:10] is recrystallized.Filtration and recrystallization obtains colourless
Crystalline products, are washed 3-4 times with 10mL ether, are obtained after vacuum drying colorless solid product (25.4mg, 0.011mmol), are produced
Rate is 79%.Experimental data is analyzed and characterized with embodiment 1.
The present invention provides inter-species picoline tetrazole copper [I] complex blue light materials and preparation method thereof, belong to
In a kind of new blue light emitting material.Between of the invention in picoline tetrazole four core copper [I] complex blue light emitting material
Select the main purpose and meaning of 5- [5- methyl -2- pyridyl group] tetrazole and bis- [diphenylphosphine] methane: by applying 5- [5-
Methyl -2- pyridyl group] the multiple tooth cheland of tetrazole and bis- [diphenylphosphine] methane bridge ligands, adjusting copper [I] complex
Space multistory effect and electron density distribution realize the solid state blue emission characteristic of copper [I] complex, at normal temperature, Gu
State emission wavelength maximum value is 459nm, and the solid luminescent service life is 80 μ s, and solid luminescent quantum efficiency is 65%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (7)
1. inter-species picoline tetrazole copper [I] complex blue light material, which is characterized in that picoline tetrazole between described
Copper [I] complex blue light material is perchlorate two [5- [5- methyl -2- pyridyl group] tetrazole base] four [bis- [diphenyl
Phosphine] methane] close four bronze medals [I] complex, molecular formula are as follows: C114H100Cl2Cu4N10O8P8。
2. inter-species picoline tetrazole copper [I] complex blue light material as described in claim 1, it is characterised in that: high
[5- [5- methyl -2- pyridyl group] tetrazole base] four [bis- [diphenylphosphine] methane] of chlorate anions two close four bronze medals [I] complex
Crystal category monoclinic system, P-1 space group, cell parameter: a=13.604 (6), b=15.258 (7),α
=74.624 (10) °, β=67.946 (9) °, γ=66.529 (10) °,Mr=2682.56, Z=1, Dc
=1.440g cm-3, μ=1.058mm-1, GOF=1.038.
3. the preparation method of picoline tetrazole copper [I] complex blue light material between one kind is as described in claim 1, special
Sign is, comprising the following steps:
Step 1: under an argon atmosphere, molar ratio is the [Cu [MeCN] of 2:2:14][ClO4], bis- [diphenylphosphine] methane, 5-
[5- methyl -2- pyridyl group] tetrazole in methylene chloride react 2-4 hours by stirring at normal temperature, obtains the first reaction mixture；
Step 2: it is added into first reaction mixture and 5- [5- methyl -2- pyridyl group] tetrazole ligand equimolar amounts
Sodium hydroxide, and continue stirring at normal temperature and react 1-2 hours, obtain the second reaction mixture；
Step 3: the solvent of the second reaction mixture is evaporated, and is recrystallized using methylene chloride-n-hexane mixed solvent,
Filtration and recrystallization obtains colourless crystalline products, is washed 3-4 times using ether, colorless solid product is obtained after vacuum drying, as
[5- [5- methyl -2- pyridyl group] tetrazole base] four [bis- [diphenylphosphine] methane] of perchlorate two close four bronze medals [I] cooperation
Object.
4. the preparation method of picoline tetrazole copper [I] complex blue light material, feature exist between as claimed in claim 3
In: in step 3, the solvent of the second reaction mixture is evaporated using Rotary Evaporators, methylene chloride-n-hexane mixing is molten
The volume ratio of methylene chloride and n-hexane is 1:10 in agent.
5. the preparation method of picoline tetrazole copper [I] complex blue light material between one kind is as described in claim 1, special
Sign is, comprising the following steps:
Step 1: under an argon atmosphere, molar ratio 1:(5-10): perchlorate hexahydrate's copper of 2:1, excessive copper powder, bis- [diphenyl
Phosphine] methane, 5- [5- methyl -2- pyridyl group] tetrazole acetonitrile-dichloromethane in the mixed solvent stirring at normal temperature reaction 2-4 it is small
When, obtain the first reaction mixture；
Step 2: it is added into first reaction mixture and 5- [5- methyl -2- pyridyl group] tetrazole ligand equimolar amounts
Sodium hydroxide, and continue stirring at normal temperature and react 1-2 hours, obtain the second reaction mixture；
Step 3: after the filtering of the second reaction mixture, solvent evaporated is tied again with methylene chloride-n-hexane mixed solvent
Crystalline substance, the colourless crystalline products that filtration and recrystallization obtains, is washed 3-4 times with ether, colorless solid product is obtained after vacuum drying, i.e.,
Four bronze medals [I] is closed for [5- [5- methyl -2- pyridyl group] tetrazole base] four [bis- [diphenylphosphine] methane] of perchlorate two to match
Close object.
6. the preparation method of picoline tetrazole copper [I] complex blue light material, feature exist between as claimed in claim 5
In: in step 1, the volume ratio of acetonitrile-dichloromethane in the mixed solvent acetonitrile and methylene chloride is 1:2.
7. the preparation method of picoline tetrazole copper [I] complex blue light material, feature exist between as claimed in claim 5
In: in step 3, the solvent of the second reaction mixture is evaporated using Rotary Evaporators, methylene chloride-n-hexane mixing is molten
The volume ratio of methylene chloride and n-hexane is 1:10 in agent.
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