CN107652326A - 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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- CN107652326A CN107652326A CN201711046685.3A CN201711046685A CN107652326A CN 107652326 A CN107652326 A CN 107652326A CN 201711046685 A CN201711046685 A CN 201711046685A CN 107652326 A CN107652326 A CN 107652326A
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- Prior art keywords
- tetrazole
- copper
- blue light
- picoline
- dichloromethane
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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 21
- 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
- 238000003756 stirring Methods 0.000 claims description 18
- 239000012046 mixed solvent Substances 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 13
- 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
- TWWJJVNUZQLCPD-UHFFFAOYSA-N diphenylphosphane;methane Chemical compound C.C=1C=CC=CC=1PC1=CC=CC=C1 TWWJJVNUZQLCPD-UHFFFAOYSA-N 0.000 claims description 10
- 238000001953 recrystallisation Methods 0.000 claims description 10
- 238000001914 filtration Methods 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 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 claims description 5
- 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
- -1 Chlorate anions Chemical class 0.000 claims 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 16
- 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
- 239000003446 ligand Substances 0.000 description 4
- 238000004519 manufacturing process Methods 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
- 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
- 238000004458 analytical method Methods 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
- 238000005516 engineering process 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
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 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
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000686 essence Substances 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
- 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
- 238000006467 substitution reaction Methods 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
-
- 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
-
- 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
Landscapes
- 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 material, it is characterized in that, described picoline tetrazole copper [I] complex blue light material is that perchlorate two [5 [pyridine radicals of 5 methyl 2] tetrazole base] four [double [diphenylphosphine] methane] close four bronze medals [I] complex, and its molecular formula is：C114H100Cl2Cu4N10O8P8.The present invention also provides the preparation method 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 material and preparation method thereof, belong to hair
Light new material synthesis technical field.
Background technology
Because of the influence of heavy atoms effect and strong Effect of Spin-orbit Coupling, metal emitting complexes are in theory using all
Singlet state and triplet energies, are substantially improved luminous efficiency.At present, the research of metal emitting complexes focus primarily upon the 5th,
Six cycles, especially group VIII transition metal, such as ruthenium, osmium, iridium and platinum.The transition metal in the five, the six cycles is (except 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
It is higher with cost, and can also bring raw material nervous after large-scale application.In addition, such precious metal chemical complex generally have it is larger
The compound 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, causes theirs
Large-scale application is extremely restricted, thus people be particularly desirable to look for outside the five, the six cycles it is other alternative
Metal.
The transition metal in the five, the six cycles is compared, the copper metal of period 4, not only aboundresources, cheap, and
Environmentally friendly and luminous uniqueness.In addition, univalent copper complex has the visible phosphorescent emissions of excellent room temperature, lighting can be ultraviolet
Change to near-infrared, cover whole visible region.It is aboundresources, cheap, luminous unique and environmentally friendly etc. many excellent
Point make it 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.
At present, the copper emitting complexes that document discloses report mainly have monovalence copper mononuclear complex and cluster compound.Monovalence copper
Cluster compound is because structure is novel, and geometric configuration enriches, and coordination mode is various, more next in recent years many advantages, such as luminosity uniqueness
More receive much attention.However, build multinuclear 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 multinuclear copper [I] complex blue light emitting material.
It is double using the multiple tooth cheland 5- of pyridine tetrazole [5- methyl -2- pyridine radicals] tetrazoles 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 document at present
Open report.
The content of the invention
It is an object of the invention to overcome the defect of prior art, there is provided an inter-species picoline tetrazole copper [I] is matched somebody with somebody
Compound blue light material and preparation method thereof, it belongs to a kind of new blue light emitting material.
What the present invention was realized in：
The present invention provide inter-species picoline tetrazole copper [I] complex blue light material, it is described between the nitrogen of picoline four
Azoles copper [I] complex blue light material is perchlorate two [5- [5- methyl -2- pyridine radicals] tetrazole base] four [double [hexichol
Base phosphine] methane] four bronze medals [I] complex is closed, its molecular formula is：C114H100Cl2Cu4N10O8P8。
Inter-species picoline tetrazole copper [I] complex blue light material as claimed in claim 1, it is characterised in that：
Perchlorate two [5- [5- methyl -2- pyridine radicals] tetrazole base] four [double [diphenylphosphine] methane] close four bronze medals [I] and coordinated
Thing crystal category monoclinic system, P-1 space groups, 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, mol ratio 2:2:1 [Cu [MeCN]4][ClO4], double [diphenylphosphine] methane,
5- [5- methyl -2- pyridine radicals] tetrazole stirring at normal temperature in dichloromethane reacts 2-4 hours, obtains the first reaction mixture；
Step 2：Added and 5- [5- methyl -2- pyridine radicals] tetrazole part equimolar into first reaction mixture
The sodium hydroxide of amount, and continue stirring at normal temperature reaction 1-2 hours, obtain the second reaction mixture；
Step 3：The solvent of second reaction mixture is evaporated, tied again using dichloromethane-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] are closed for perchlorate two [5- [5- methyl -2- pyridine radicals] tetrazole base] four [double [diphenylphosphine] methane] to match somebody with somebody
Compound.
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 dichloromethane and n-hexane is 1:10.
The preparation method of the invention that inter-species picoline tetrazole copper [I] complex blue light material is also provided, including with
Lower step：
Step 1：Under an argon atmosphere, mol ratio 1:(5-10):2:1 perchlorate hexahydrate's copper, excessive copper powder, double [two
Phenylphosphine] methane, 5- [5- methyl -2- pyridine radicals] tetrazoles acetonitrile-dichloromethane in the mixed solvent stirring at normal temperature react 2-4
Hour, obtain the first reaction mixture；
Step 2：Added and 5- [5- methyl -2- pyridine radicals] tetrazole part equimolar into first reaction mixture
The sodium hydroxide of amount, and continue stirring at normal temperature reaction 1-2 hours, obtain the second reaction mixture；
Step 3：After second reaction mixture is filtered, solvent evaporated, carried out with dichloromethane-n-hexane mixed solvent
Recrystallization, the colourless crystalline products that filtration and recrystallization obtains, is washed 3-4 times with ether, and colorless solid production is obtained after vacuum drying
Thing, as perchlorate two [5- [5- methyl -2- pyridine radicals] tetrazole base] four [double [diphenylphosphine] methane] close four bronze medals
[I] complex.
Further, in step 1, the volume ratio of acetonitrile-dichloromethane in the mixed solvent acetonitrile and dichloromethane 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 dichloromethane and n-hexane is 1:10.
The invention has the advantages that：
The invention provides inter-species picoline tetrazole copper [I] complex blue light material and preparation method thereof, and it belongs to
In a kind of new blue light emitting material.Between the present invention in picoline tetrazole four core copper [I] complex blue light emitting material
From the main purpose and meaning of 5- [5- methyl -2- pyridine radicals] tetrazoles and double [diphenylphosphine] methane：By applying 5- [5-
Methyl -2- pyridine radicals] the multiple tooth cheland of tetrazole and double [diphenylphosphine] methane bridge ligands, regulation copper [I] complex
Space multistory effect and electron density distribution, the solid state blue emission characteristic of copper [I] complex is realized, at normal temperatures, it is solid
State emission wavelength maximum is 459nm, and the solid luminescent life-span is 80 μ s, and solid luminescent quantum efficiency is 65%.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is perchlorate two provided in an embodiment of the present invention [5- [5- methyl -2- pyridine radicals] tetrazole base] four
[double [diphenylphosphine] methane] closes four bronze medals [I] complex crystal structure chart.
Fig. 2 is perchlorate two provided in an embodiment of the present invention [5- [5- methyl -2- pyridine radicals] tetrazole base] four
[double [diphenylphosphine] methane] closes four bronze medals [I] complex solid state fluorescence emission spectrum.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art obtained on the premise of creative work is not made it is all its
Its embodiment, belongs to the scope of protection of the 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
It is [5- [5- methyl -2- pyridine radicals] tetrazole of perchlorate two to state picoline tetrazole copper [I] complex blue light material
Base] four [double [diphenylphosphine] methane] close four bronze medals [I] complex, and its molecular formula is：C114H100Cl2Cu4N10O8P8.Molecular weight
For 2311.0.
Its English name：[Cu4[5-(5-methyl-2-pyridyl)tetrazolate]2[bis
(diphenylphosphino)methane]4][ClO4]2, it is abbreviated as：[Cu4[m-mpytz]2[dppm]4][ClO4]2。
Its molecular structure is：
(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), comprise the following steps：
Step 1：Under an argon atmosphere, mol ratio 2:2:1 [Cu [MeCN]4][ClO4], double [diphenylphosphine] methane,
5- [5- methyl -2- pyridine radicals] tetrazole [abbreviation pytzH] stirring at normal temperature in dichloromethane reacts 2-4 hours, obtains first
Reaction mixture.
Step 2：Added and 5- [5- methyl -2- pyridine radicals] tetrazole part equimolar into first reaction mixture
The sodium hydroxide of amount, and continue stirring at normal temperature reaction 1-2 hours, obtain the second reaction mixture.
Step 3：The solvent of second reaction mixture is evaporated, tied again using dichloromethane-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] are closed for perchlorate two [5- [5- methyl -2- pyridine radicals] tetrazole base] four [double [diphenylphosphine] methane] to match somebody with somebody
Compound.Wherein, the solvent of the second reaction mixture is evaporated using Rotary Evaporators, dichloromethane-n-hexane in the mixed solvent
The volume ratio of dichloromethane and n-hexane is 1:10.
The reaction mechanism of this preparation method is：
The present invention also provides the preparation method of inter-species picoline tetrazole copper [I] complex blue light material, and (this is the
Two kinds of preparation methods), comprise the following steps：
Step 1：Under an argon atmosphere, mol ratio 1:(5-10):2:1 perchlorate hexahydrate's copper [Cu [ClO4]2·
6H2O], excessive copper powder, double [diphenylphosphine] methane [abbreviation dppm], 5- [5- methyl -2- pyridine radicals] tetrazole [referred to as
PytzH] acetonitrile-dichloromethane in the mixed solvent stirring at normal temperature react 2-4 hours, obtain the first reaction mixture.Wherein, second
The volume ratio of nitrile-dichloromethane in the mixed solvent acetonitrile and dichloromethane is 1:2.
Step 2：Added and 5- [5- methyl -2- pyridine radicals] tetrazole part equimolar into first reaction mixture
The sodium hydroxide of amount, and continue stirring at normal temperature reaction 1-2 hours, obtain the second reaction mixture；
Step 3：After second reaction mixture is filtered, solvent evaporated, carried out with dichloromethane-n-hexane mixed solvent
Recrystallization, the colourless crystalline products that filtration and recrystallization obtains, is washed 3-4 times with ether, and colorless solid production is obtained after vacuum drying
Thing, as perchlorate two [5- [5- methyl -2- pyridine radicals] tetrazole base] four [double [diphenylphosphine] methane] close four bronze medals
[I] complex.Wherein, the solvent of the second reaction mixture is evaporated using Rotary Evaporators, dichloromethane-n-hexane mixing is molten
The volume ratio of dichloromethane and n-hexane is 1 in agent:10.
The reaction mechanism of this preparation method is：
Illustrated below by way of two specific embodiments：
Embodiment 1：
Under an argon atmosphere, [Cu [MeCN]4][ClO4] (20.9mg, 0.064mmol), double [diphenylphosphine] methane
(24.6mg, 0.064mmol) and 5- [5- methyl -2- pyridine radicals] tetrazole (5.2mg, 0.032mmol) is in 10mL dichloromethane
Middle stirring at normal temperature is reacted 3 hours, rear toward addition sodium hydroxide (1.28mg, 0.032mmol) in the reaction solution, continues to stir under normal temperature
Mix reaction 1 hour, after solvent is evaporated with Rotary Evaporators, with dichloromethane (1mL)-n-hexane (10mL) mixed solvent [body
Product is than being 1:10] recrystallized.The colourless crystalline products that filtration and recrystallization obtains, are washed 3-4 times, vacuum is done with 10mL ether
Colorless solid product (30.1mg, 0.013mmol), yield 81% are obtained after dry.
Elementary 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 groups, 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 temperatures
Reveal solid state blue emission characteristic, its solid luminescent wavelength maximum is 459nm, and the solid luminescent life-span is 80 μ s, solid luminescent
Quantum efficiency is 65%, and its 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 acetonitriles is reacted 30 minutes, rear to add double [diphenylphosphine] methane
The 10mL dichloromethane solutions of (21.5mg, 0.056mmol), continue stirring reaction and 5- [5- methyl -2- pyridines are added after 1 hour
Base] tetrazole (4.5mg, 0.028mmol), continue stirring reaction under normal temperature 2 hours, it is rear toward adding sodium hydroxide in the reaction solution
(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] recrystallized.Filtration and recrystallization obtains colourless
Crystalline products, are washed 3-4 times with 10mL ether, and colorless solid product (25.4mg, 0.011mmol) is obtained after vacuum drying, production
Rate is 79%.Analysis and characterization experimental data is the same as embodiment 1.
The invention provides inter-species picoline tetrazole copper [I] complex blue light material and preparation method thereof, and it belongs to
In a kind of new blue light emitting material.Between the present invention in picoline tetrazole four core copper [I] complex blue light emitting material
From the main purpose and meaning of 5- [5- methyl -2- pyridine radicals] tetrazoles and double [diphenylphosphine] methane：By applying 5- [5-
Methyl -2- pyridine radicals] the multiple tooth cheland of tetrazole and double [diphenylphosphine] methane bridge ligands, regulation copper [I] complex
Space multistory effect and electron density distribution, the solid state blue emission characteristic of copper [I] complex is realized, at normal temperatures, it is solid
State emission wavelength maximum is 459nm, and the solid luminescent life-span 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 essences in the present invention
God any modification, equivalent substitution and improvements made etc., should be included in the scope of the protection with principle.
Claims (7)
1. inter-species picoline tetrazole copper [I] complex blue light material, it is characterised in that picoline tetrazole between described
Copper [I] complex blue light material is perchlorate two [5- [5- methyl -2- pyridine radicals] tetrazole base] four [double [diphenyl
Phosphine] methane] four bronze medals [I] complex is closed, its molecular formula is：C114H100Cl2Cu4N10O8P8。
2. inter-species picoline tetrazole copper [I] complex blue light material as claimed in claim 1, it is characterised in that：It is high
Chlorate anions two [5- [5- methyl -2- pyridine radicals] tetrazole base] four [double [diphenylphosphine] methane] close four bronze medals [I] complex
Crystal category monoclinic system, P-1 space groups, 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 preparation method of picoline tetrazole copper [I] complex blue light material between 3. one kind is as claimed in claim 1, it is special
Sign is, comprises the following steps：
Step 1：Under an argon atmosphere, mol ratio 2:2:1 [Cu [MeCN]4][ClO4], double [diphenylphosphine] methane, 5-
[5- methyl -2- pyridine radicals] tetrazole stirring at normal temperature in dichloromethane reacts 2-4 hours, obtains the first reaction mixture；
Step 2：Added into first reaction mixture and 5- [5- methyl -2- pyridine radicals] tetrazole part equimolar amounts
Sodium hydroxide, and continue stirring at normal temperature reaction 1-2 hours, obtain the second reaction mixture；
Step 3：The solvent of second reaction mixture is evaporated, recrystallized using dichloromethane-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, is
Perchlorate two [5- [5- methyl -2- pyridine radicals] tetrazole base] four [double [diphenylphosphine] methane] close four bronze medals [I] and coordinated
Thing.
4. the preparation method of picoline tetrazole copper [I] complex blue light material, its feature exist between as claimed in claim 3
In：In step 3, the solvent of the second reaction mixture is evaporated using Rotary Evaporators, dichloromethane-n-hexane mixing is molten
The volume ratio of dichloromethane and n-hexane is 1 in agent:10.
The preparation method of picoline tetrazole copper [I] complex blue light material between 5. one kind is as claimed in claim 1, it is special
Sign is, comprises the following steps：
Step 1：Under an argon atmosphere, mol ratio 1:(5-10):2:1 perchlorate hexahydrate's copper, excessive copper powder, double [diphenyl
Phosphine] methane, 5- [5- methyl -2- pyridine radicals] tetrazoles acetonitrile-dichloromethane in the mixed solvent stirring at normal temperature reaction 2-4 it is small
When, obtain the first reaction mixture；
Step 2：Added into first reaction mixture and 5- [5- methyl -2- pyridine radicals] tetrazole part equimolar amounts
Sodium hydroxide, and continue stirring at normal temperature reaction 1-2 hours, obtain the second reaction mixture；
Step 3：After second reaction mixture is filtered, solvent evaporated, tied again with dichloromethane-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] are closed for perchlorate two [5- [5- methyl -2- pyridine radicals] tetrazole base] four [double [diphenylphosphine] methane] to match somebody with somebody
Compound.
6. the preparation method of picoline tetrazole copper [I] complex blue light material, its feature exist between as claimed in claim 5
In：In step 1, the volume ratio of acetonitrile-dichloromethane in the mixed solvent acetonitrile and dichloromethane is 1:2.
7. the preparation method of picoline tetrazole copper [I] complex blue light material, its feature exist between as claimed in claim 5
In：In step 3, the solvent of the second reaction mixture is evaporated using Rotary Evaporators, dichloromethane-n-hexane mixing is molten
The volume ratio of dichloromethane and n-hexane is 1 in agent:10.
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| CN110699063A (en) * | 2019-11-05 | 2020-01-17 | 江西理工大学 | Application of 6-methylpyridine tetrazole tetranuclear copper [ I ] complex in stimulus response luminescent and photochromic material |
| CN110776532A (en) * | 2019-11-05 | 2020-02-11 | 江西理工大学 | Application of 3-methylpyridine tetrazole tetranuclear copper [ I ] complex in stimulus response luminescent and photochromic material |
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| CN103797017A (en) * | 2011-07-08 | 2014-05-14 | 辛诺拉有限公司 | Copper(I) complexes for optoelectronic devices |
| CN103951683A (en) * | 2014-05-12 | 2014-07-30 | 江西理工大学 | Novel tri/tetra-coordination dual-core copper [I] coordination compound blue-green materials and preparation method thereof |
| CN106349259A (en) * | 2016-08-25 | 2017-01-25 | 江西理工大学 | Organic vapor luminescent off-color material of pyridine pyrazole copper [I] complex and preparation method thereof |
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| CN103459403A (en) * | 2011-04-04 | 2013-12-18 | 默克专利有限公司 | Metal complexes |
| CN103797017A (en) * | 2011-07-08 | 2014-05-14 | 辛诺拉有限公司 | Copper(I) complexes for optoelectronic devices |
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| CN110699063A (en) * | 2019-11-05 | 2020-01-17 | 江西理工大学 | Application of 6-methylpyridine tetrazole tetranuclear copper [ I ] complex in stimulus response luminescent and photochromic material |
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| CN110776532B (en) * | 2019-11-05 | 2022-05-17 | 江西理工大学 | Application of 3-methylpyridine tetrazole tetranuclear copper [ I ] complex in stimulus response luminescent and photochromic material |
| CN110699063B (en) * | 2019-11-05 | 2022-08-05 | 江西理工大学 | Application of 6-methylpyridine tetrazole tetranuclear copper [ I ] complex in stimulus response luminescent and photochromic material |
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