CN104610285B - N-heterocyclic carbine univalent copper complex and its preparation method and application - Google Patents
N-heterocyclic carbine univalent copper complex and its preparation method and application Download PDFInfo
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- 150000004699 copper complex Chemical class 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003446 ligand Substances 0.000 claims abstract description 18
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 18
- 150000001450 anions Chemical class 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims description 50
- 239000010949 copper Substances 0.000 claims description 31
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 16
- 239000012043 crude product Substances 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 239000013067 intermediate product Substances 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 230000004044 response Effects 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 6
- 229940073608 benzyl chloride Drugs 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical class [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 229910001923 silver oxide Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- IHHFYTBVUOPWLB-UHFFFAOYSA-N C(C)#N.[O] Chemical compound C(C)#N.[O] IHHFYTBVUOPWLB-UHFFFAOYSA-N 0.000 claims 1
- -1 Potassium Hexafluorophosphates Chemical class 0.000 claims 1
- 150000005524 benzylchlorides Chemical class 0.000 claims 1
- 150000004694 iodide salts Chemical class 0.000 claims 1
- OTCVAHKKMMUFAY-UHFFFAOYSA-N oxosilver Chemical class [Ag]=O OTCVAHKKMMUFAY-UHFFFAOYSA-N 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 30
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 6
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 6
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 125000001188 haloalkyl group Chemical group 0.000 description 4
- OTWSURXLBKIUNH-UHFFFAOYSA-N methylidenesilver Chemical compound [Ag]=C OTWSURXLBKIUNH-UHFFFAOYSA-N 0.000 description 4
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 3
- 238000004679 31P NMR spectroscopy Methods 0.000 description 3
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 3
- 238000006862 quantum yield reaction Methods 0.000 description 3
- 150000005762 2-bromopyridine Chemical class 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- JYZIHLWOWKMNNX-UHFFFAOYSA-N benzimidazole Chemical compound C1=C[CH]C2=NC=NC2=C1 JYZIHLWOWKMNNX-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 150000005645 2-bromoquinolines Chemical class 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005286 illumination Methods 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
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/08—Copper 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/371—Metal complexes comprising a group IB metal element, e.g. comprising copper, gold or silver
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
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Abstract
The present invention discloses a kind of ionic N-heterocyclic carbine univalent copper complex, and the coordinate bond of the complex is made up of a N-heterocyclic carbine bidentate ligand and a bidentate phosphine ligandses, and such complex has monokaryon four-coordination structure, and formula is：, in formula, partRepresent N-heterocyclic carbine bidentate ligand, partRepresent bidentate phosphine ligandses, PF6 ‑For complex external world anion.The luminous quantum efficiency of the complex of the present invention reaches as high as more than 70%, is remarkably improved the luminous efficiency of luminescent material, and stability is higher.
Description
Technical field
The invention belongs to technical field of electronic materials, relates generally to aza ring Cabbeen univalent copper complex and its preparation
Methods and applications.
Background technology
Organic electroluminescent LED（OLED）Have the advantages that luminous efficiency is high, Applicable temperature scope is big, device is frivolous,
Had broad application prospects in the field such as FPD and solid-state illumination.Phosphorescent OLED can make full use of production in luminescence process
Raw singlet state and triplet exciton, theoretical internal quantum efficiency 100%, operating efficiency are far above fluorescence OLED（It can only utilize
Singlet excitons, theoretical internal quantum efficiency are only 25%）.At present, Ir3+、Pt2+Exist Deng transient metal complex phosphor material
OLED fields have been widely studied.1999, the scientific research personnel such as horse what light reports first to be prepared with phosphorescence univalent copper complex
OLED；Because relative to noble metals such as iridium, platinum, copper has the advantages that price is low, reserves are big, environmentally friendly, monovalence copper coordinates
Thing phosphor material gradually attracts attention.
In recent years, as new phosphorescence univalent copper complex continuously emerges, the OLED performance of such material has obtained
Larger raising.2010, Peters et al. report a kind of maximum lumen efficiency be 47.5 cd/A based on monovalence copper phosphorescence material
The OLED of material, the device employ a kind of double-core univalent copper complex of high rigidity structure { (PNP-tBu) Cu } 2 as hair
Luminescent material.2011, Osawa seminars prepared luminous efficiency highest with three-fold coordination monovalence copper phosphor material (dtpb) CuBr
Up to 65.3 cd/A device, this efficiency has reached Ir3+Complex phosphorescence OLED highest level；The seminar is recently again
The OLED devices that maximum lumen efficiency is 54.1 cd/A have been prepared using univalent copper complex Cu (dppb-CF3) (Ph2Bpz2)
Part.In addition, the seminar such as Wang Lixiang, Thompson, Adachi has also been prepared efficiently using phosphorescence univalent copper complex in succession
The OLED of rate.
However, monovalence copper phosphorescent OLED still suffers from problems at present, device efficiency " roll-offing " is mainly shown as seriously, send out
Brightness is relatively low, mostly green device, and feux rouges, blue-light device are deficient, it is difficult to realize three-color light-emitting etc..Luminescent material is to determine
The key factor of OLED performances.Similar with other phosphorescence transient metal complexes, the performance of univalent copper complex depends primarily on
Part.From document report it can be found that phosphorescence univalent copper complex still mainly uses traditional bidentate nitrogen ligands at present（N^N）
And bidentate phosphine ligandses（P^P）, particularly bidentate phosphine ligandses generally use by high-luminous-efficiency univalent copper complex.And to enter
One step improves the performance of such phosphorescent OLED, it is necessary to develops novel high-performance part.
It is well known that N-heterocyclic carbine（NHC）It is strong sigma electrons donor, meanwhile, its π track can receive metal ion
Feedback electronic, with transition metal ions formed complexes stability it is good [10].Based on this, Tsubomura et al. is in 2009
Synthesize a kind of double-core two with phosphorescence performance year first and be coordinated N-heterocyclic carbine univalent copper complex [Cu2 (μ-Me-mbim)
2] 2+ (PF6-) 2, result of study is shown, the compound can show the blue-green phosphorescence of greater efficiency in solid-state（Φ =
0.43）.Afterwards, Thompson seminars report a series of three-fold coordination N-heterocyclic carbine monovalence copper cooperation of high-luminous-efficiencies
Thing, such as luminous efficiencies of (IPr) Cu (fppz) in solid-state（Φ）Up to 0.62, and the compound heat endurance is good, can be 225
DEG C Decompression Sublimation, possesses the condition applied in OLED.These results of study illustrate that N-heterocyclic carbine is adapted to make
It is standby efficiently, stably, can be applied to OLED univalent copper complex phosphor material.In addition, relative to phosphorescence univalent copper complex mesh
The preceding Phosphine ligands generally used, N-heterocyclic carbine structure is more various, is easy to modify, and this is again further raising, regulation material
Performance provide convenience.
The content of the invention
It is an object of the invention to provide aza ring Cabbeen univalent copper complex and its preparation method and application, such is matched somebody with somebody
The luminous quantum efficiency of compound reaches as high as more than 70%, is remarkably improved the luminous efficiency of luminescent material, and stability is higher.
The present invention realizes that the technical scheme that above-mentioned technical purpose uses is：Ionic N-heterocyclic carbine univalent copper complex,
The coordinate bond of the complex is made up of a N-heterocyclic carbine bidentate ligand and a bidentate phosphine ligandses, and such complex has
Monokaryon four-coordination structure, formula are：
,
In formula, partRepresent N-heterocyclic carbine bidentate ligand, partBidentate phosphine is represented to match somebody with somebody
Body, PF6 -For complex external world anion.
The N-heterocyclic carbine bidentate ligandStructure be：；
Wherein,For、OrIn one kind；
For、OrIn one kind；
Wherein, * represents coordination atom, and # is represented and the atom of the combination of another construction unit；G represent hydrogen atom, alkyl,
Aryl；R1~R8Hydrogen atom, alkyl, alkoxy, halogen atom, haloalkyl, aryl, halogenated aryl, amido, two are represented respectively
One kind in alkyl amine group or diaryl amido.
The bidentate phosphine ligandsesFor one kind in following structure：
、、、、Or；
Wherein, R1And R2One kind in alkyl, haloalkyl, aryl or halogenated aryl is represented respectively；N is 1,2,3,4,5
Or 6.
The preparation method of described ionic N-heterocyclic carbine univalent copper complex, carbenes precursor is molten in acetonitrile
With aoxidizing silver reaction in agent, reaction temperature is 0 DEG C~100 DEG C, obtains carbene silver complex, in acetonitrile solvent, 0 DEG C~100
Under the conditions of DEG C, carbene silver complex is reacted with copper powder and bidentate phosphine ligandses successively, that is, obtains ionic N-heterocyclic carbine monovalence
Copper complex.
Application of the described ionic N-heterocyclic carbine univalent copper complex in electroluminescent device.
Beneficial effect
Complex luminescent material provided by the invention using monovalence copper be used as central metallic ions, abundant raw material, inexpensively；Adopt
With bidentate nitrogen heterocycle carbine ligand, the stability of material can be improved, the advantages that making it have high heat endurance, humidity.Such
Complex is collectively constituted by bidentate nitrogen heterocycle carbine ligand and bidentate phosphine ligandses, is remarkably improved the luminous efficiency of material, this hair
The luminous quantum efficiency of the complex of bright offer reaches as high as more than 70%.In addition, nitrogen heterocycle carbine ligand various structures, are easy to
Modification, it can be used for adjusting the emission wavelength of material.
Brief description of the drawings
Fig. 1 is carbenes precursor P-1 synthetic route chart；
Fig. 2 is the complex [(NHC-1) Cu (POP)] that the embodiment of the present invention 1 obtains+PF6 -Crystal structure figure；
Fig. 3 is the complex [(NHC-1) Cu (POP)] that the embodiment of the present invention 1 obtains+PF6 -Room temperature in the solid state is photic
Luminescent spectrum figure；
Fig. 4 is the complex [(NHC-1) Cu (POP)] that the embodiment of the present invention 1 obtains+PF6 -In the solid state room temperature luminous
Intensity decay curve；
Fig. 5 is carbenes precursor P-2 synthetic route chart；
Fig. 6 is the complex [(NHC-2) Cu (POP)] that the embodiment of the present invention 2 obtains+PF6 -Crystal structure figure；
Fig. 7 is the copper complex [(NHC-2) Cu (POP)] that the embodiment of the present invention 2 obtains+PF6 -Light at room temperature in the solid state
Photoluminescence spectrogram；
Fig. 8 is the complex [(NHC-2) Cu (POP)] that the embodiment of the present invention 2 obtains+PF6 -In the solid state room temperature luminous
Intensity decay curve；
Fig. 9 is carbenes precursor P-3 synthetic route chart；
Figure 10 is the complex [(NHC-3) Cu (POP)] that the embodiment of the present invention 3 obtains+PF6 -Crystal structure figure；
Figure 11 is the complex [(NHC-3) Cu (POP)] that the embodiment of the present invention 3 obtains+PF6 -Room temperature in the solid state is photic
Luminescent spectrum figure；
Figure 12 is the complex [(NHC-3) Cu (POP)] that the embodiment of the present invention 3 obtains+PF6 -In the solid state room temperature luminous
Intensity decay curve.
Embodiment
Ionic N-heterocyclic carbine univalent copper complex, the coordinate bond of the complex are matched somebody with somebody by a N-heterocyclic carbine bidentate
Body and a bidentate phosphine ligandses are formed, and such complex has monokaryon four-coordination structure, and formula is：
,
In formula, partRepresent N-heterocyclic carbine bidentate ligand, partBidentate phosphine is represented to match somebody with somebody
Body, PF6 -For complex external world anion.
The N-heterocyclic carbine bidentate ligandStructure be：；
Wherein,For、OrIn one kind；
For、OrIn one kind；
Wherein, * represents coordination atom, and # is represented and the atom of the combination of another construction unit；G represent hydrogen atom, alkyl,
Aryl；R1~R8Hydrogen atom, alkyl, alkoxy, halogen atom, haloalkyl, aryl, halogenated aryl, amido, two are represented respectively
One kind in alkyl amine group or diaryl amido.
The bidentate phosphine ligandsesFor one kind in following structure：
、、、、Or；
Wherein, R1And R2One kind in alkyl, haloalkyl, aryl or halogenated aryl is represented respectively；N is 1,2,3,4,5
Or 6.
The preparation method of ionic N-heterocyclic carbine univalent copper complex of the present invention is：
First, it is 0 DEG C~100 DEG C with oxidation silver reaction, reaction temperature in acetonitrile solvent by carbenes precursor, obtains
To intermediate product carbene silver complex；Then, in acetonitrile solvent, under the conditions of 0 DEG C~100 DEG C, by carbene silver complex successively
Reacted with copper powder and bidentate phosphine ligandses, you can obtain univalent copper complex of the present invention.
Below in conjunction with the drawings and specific embodiments, the present invention will be further described：
Embodiment 1：
（1）N-heterocyclic carbine bidentate ligand precursor P-1 synthesis
Synthetic route is as shown in Figure 1.By imidazoles（6.8g, 100mmol, 1.0 equivalent）, 2- bromopyridines（15.7g,
100mmol, 1.0 equivalents）, cuprous iodide（0.95g, 5mmol, 5% equivalent）, BTA（1.2g, 10mmol, 10% work as
Amount）, potassium tert-butoxide（15.7g, 140mmol, 1.4 equivalent）In the flask for sequentially adding 250mL, solvent N, N- dimethyl is added
Formamide 100mL, back flow reaction 5 hours under the conditions of 110 DEG C.Question response liquid is cooled to room temperature, filters off insoluble solid, collects filter
Liquid, evaporated under reduced pressure, obtain crude product；Then, crude product is separated with column chromatography, purified, leacheate is dichloromethane/petroleum ether
（1/5）, obtain light yellow viscous liquid（13.5g）, as intermediate product M-1, yield 93%.
By intermediate product M-1（11.6g, 80mmol, 1.0 equivalent）, benzyl chloride（50.4g, 400mmol, 5.0 equivalent）Add
In 150mL flask, back flow reaction 3 hours under the conditions of 100 DEG C.Question response liquid is cooled to room temperature, distillation under pressure, removes excessive
Benzyl chloride, yellow solid is obtained, washed solid to colourless with acetone；Then, gained colorless solid is placed in 500 mL burning
In bottle, acetone 250mL is added, adds Potassium Hexafluorophosphate（29.4g, 160mmol, 2.0 equivalent）, stir 5 hours at room temperature；Filter
Insoluble solid is removed, filtrate is collected, is evaporated；Filter cake distillation water washing, drying, obtains colorless solid（23.1g）, as precursor
P-1, yield 76%.1H NMR (400 MHz, DMSO-d6) δ (ppm): 5.54 (2H, s), 7.38-7.45 (3H,
m), 7.49-7.52 (2H, m), 7.63 (1H, dd, J = 6.5, 5.6 Hz), 8.05 (2H, d, J = 8.2
Hz), 8.20 (1H, dd, J = 8.5, 8.1 Hz), 8.53 (1H, dd, J = 3.0, 2.5 Hz), 8.63-
8.65 (1H, m), 10.28 (1H, s); ESI-MS (m/z) = 236.1 (M-PF6 -).
。
（2）Univalent copper complex [(NHC-1) Cu (POP)]+PF6 -Synthesis
By gained precursor P-1（3.8g, 10mmol, 1.0 equivalent）, silver oxide（1.2g, 5mmol, 50% equivalent）, solvent
Acetonitrile 50mL is sequentially added in 100mL flasks, and 50 DEG C of lucifuges are reacted 12 hours；Filtering, filtrate is collected, is evaporated, obtains colorless solid.
By the solid and copper powder（0.64g, 10mmol, 1.0 equivalent）As in 100 mL flasks, the mL of anhydrous and oxygen-free acetonitrile 50, room are added
Warm stirring reaction 5 hours；Add part POP（4.3g, 8mmol, 80% equivalent）, reaction 3 hours is stirred at room temperature；Filtering, remove not
Soluble solids, filtrate is collected, evaporated under reduced pressure, obtains light green solid, as crude product.Crude product is dissolved in dichloromethane solvent
In, slow solvent flashing, there are a large amount of colourless crystallizations to separate out, filtering obtains pure complex [(NHC-1) Cu (POP)]+PF6 -
（7.2g, 7.3mmol）, yield 73%.1H NMR (500 MHz, CDCl3) δ (ppm): 7.91-7.95 (2H, m),
7.86 (1H, d, J = 4.5 Hz), 7.80 (1H, d, J = 8.5 Hz), 7.28-7.33 (6H, m), 7.19
(9H, s), 7.04-7.12 (8H ,m), 6.92-6.98 (8H ,m), 6.7 (4H, d, J = 7.5 Hz), 4.96
(2H, s); 31P NMR (200 MHz, CDCl3) δ (ppm): -9.0 (s), -144.2 (quint); ESI-MS
(m/z) = 837.2 (M-PF6 -).
Crystal structure：The univalent copper complex [(NHC-1) Cu (POP)] of the present embodiment synthesis+PF6 -Crystal structure such as Fig. 2
It is shown.
Photophysics：At room temperature, [(NHC-1) Cu (POP)]+PF6 -The emission peak of solid powder sample is in 524 nm, hair
Quantum yield is 73%, and luminescent spectrum is as shown in Figure 3；Luminescent lifetime is 39.2 microseconds (μ s), and luminous intensity attenuation curve is as schemed
Shown in 4.
Embodiment 2：
（1）N-heterocyclic carbine bidentate ligand precursor P-2 synthesis
Synthetic route is as shown in Figure 5.By benzimidazole（11.8g, 100mmol, 1.0 equivalent）, 2- bromopyridines（15.7g,
100mmol, 1.0 equivalents）, cuprous iodide（0.95g, 5mmol, 5% equivalent）, BTA（1.2g, 10mmol, 10% work as
Amount）, potassium tert-butoxide（15.7g, 140mmol, 1.4 equivalent）In the flask for sequentially adding 250mL, solvent N, N- dimethyl is added
Formamide 100mL, back flow reaction 5 hours under the conditions of 110 DEG C.Question response liquid is cooled to room temperature, filters off insoluble solid, collects filter
Liquid, evaporated under reduced pressure, obtain crude product；Then, crude product is separated with column chromatography, purified, leacheate is dichloromethane/petroleum ether
（1/5）, obtain light yellow viscous liquid（17.7g）, as intermediate product M-2, yield 91%.
By intermediate product M-2（15.6g, 80mmol, 1.0 equivalent）, benzyl chloride（50.4g, 400mmol, 5.0 equivalent）Add
In 150mL flask, back flow reaction 3 hours under the conditions of 100 DEG C.Question response liquid is cooled to room temperature, distillation under pressure, removes excessive
Benzyl chloride, yellow solid is obtained, washed solid to colourless with acetone；Then, gained colorless solid is placed in 500 mL burning
In bottle, acetone 300mL is added, adds Potassium Hexafluorophosphate（29.4g, 160mmol, 2.0 equivalent）, stir 5 hours at room temperature；Filter
Insoluble solid is removed, filtrate is collected, is evaporated；Filter cake distillation water washing, drying, obtains colorless solid（31.5g）, as precursor
P-2, yield 73%.1H NMR (500 MHz, DMSO-d6) δ (ppm): 5.89 (2H, s), 7.39-7.46 (3H,
m), 7.65-7.66 (2H, d, J = 5.0 Hz), 7.71-7.77 (3H, m), 8.00-8.02 (1H, d, J =
10.0 Hz), 8.10-8.12 (1H, d, J = 10.0 Hz), 8.30-8.33 (1H, t, J =7.5 Hz), 8.49-
8.50 (1H, d, J =5.0 Hz), 8.80-8.81 (1H, d, J =5.0 Hz), 10.72 (1H, s); ESI-MS
(m/z) = 286.1 (M-PF6 -).
。
（2）Univalent copper complex [(NHC-2) Cu (POP)]+PF6 -Synthesis
By gained precursor P-2（4.3g, 10mmol, 1.0 equivalent）, silver oxide（1.2g, 5mmol, 50% equivalent）, solvent
Acetonitrile 50mL is sequentially added in 100mL flasks, and 50 DEG C of lucifuges are reacted 12 hours；Filtering, filtrate is collected, is evaporated, obtains colorless solid.
By the solid and copper powder（0.64g, 10mmol, 1.0 equivalent）As in 100 mL flasks, the mL of anhydrous and oxygen-free acetonitrile 50, room are added
Warm stirring reaction 5 hours；Add part POP（4.3g, 8mmol, 80% equivalent）, reaction 3 hours is stirred at room temperature；Filtering, remove not
Soluble solids, filtrate is collected, evaporated under reduced pressure, obtains light green solid, as crude product.Crude product is dissolved in dichloromethane solvent
In, slow solvent flashing, there are a large amount of faint yellow color crystallizations to separate out, filtering obtains pure complex [(NHC-2) Cu (POP)]+PF6 -
（8.0g, 7.8mmol）, yield 78%.1H NMR (500 MHz, CDCl3) δ (ppm): 8.10-8.21 (3H, m),
8.02-8.03 (1H, d, J = 5.0 Hz), 7.48-7.52 (1H, t, J = 10.0 Hz), 7.18-7.30 (9H,
m), 7.08-7.14 (9H ,m), 6.94-7.06 (8H, m), 6.89-6.92 (6H, m), 6.80-6.82 (2H,
d, J = 10.0 Hz), 6.71-6.72 (2H, m), 5.11 (2H, s); 31P NMR (200 MHz, CDCl3) δ
(ppm): -9.0 (s), -144.2 (quint); ESI-MS (m/z) = 886.1 (M-PF6 -).
Crystal structure：The univalent copper complex [(NHC-2) Cu (POP)] of the present embodiment synthesis+PF6 -Crystal structure such as Fig. 6
It is shown.
Photophysics：At room temperature, [(NHC-2) Cu (POP)]+PF6 -The emission peak of solid powder sample is in 535 nm, hair
Quantum yield is 65%, and luminescent spectrum is as shown in Figure 7；Luminescent lifetime is 41.5 microseconds (μ s), and luminous intensity attenuation curve is as schemed
Shown in 8.
Embodiment 3：
（1）N-heterocyclic carbine bidentate ligand precursor P-3 synthesis
Synthetic route is as shown in Figure 9.By benzimidazole（11.8g, 100mmol, 1.0 equivalent）, 2- bromoquinolines（20.8g,
100mmol, 1.0 equivalents）, cuprous iodide（0.95g, 5mmol, 5% equivalent）, BTA（1.2g, 10mmol, 10% work as
Amount）, potassium tert-butoxide（15.7g, 140mmol, 1.4 equivalent）In the flask for sequentially adding 250mL, solvent N, N- dimethyl is added
Formamide 100mL, back flow reaction 5 hours under the conditions of 110 DEG C.Question response liquid is cooled to room temperature, filters off insoluble solid, collects filter
Liquid, evaporated under reduced pressure, obtain crude product；Then, crude product is separated with column chromatography, purified, leacheate is dichloromethane/petroleum ether
（1/5）, obtain faint yellow solid（21.1g）, as intermediate product M-3, yield 86%.
By intermediate product M-3（19.6g, 80mmol, 1.0 equivalent）, benzyl chloride（50.4g, 400mmol, 5.0 equivalent）Add
In 150mL flask, 100 DEG C of back flow reactions 3 hours.Question response liquid is cooled to room temperature, distillation under pressure, removes excessive chlorination
Benzyl, yellow solid is obtained, washed solid to colourless with acetone；Then, gained colorless solid is placed in 500 mL flask,
Acetone 300mL is added, adds Potassium Hexafluorophosphate（29.4g, 160mmol, 2.0 equivalent）, stir 5 hours at room temperature；Filter off not
Soluble solids, filtrate is collected, is evaporated；Filter cake distillation water washing, drying, obtains colorless solid（34.2g）, as precursor P-3,
Yield is 71%.1H NMR (500 MHz, DMSO-d6) δ (ppm): 5.94 (2H, s), 7.45-7.47 (3H, m),
7.68-7.83 (5H, m), 7.86-8.04 (2H, m), 8.21-8.25 (3H, m), 8.89-8.91 (2H, d, J
= 10.0 Hz), 10.94 (1H, s); ESI-MS (m/z) = 336.3 (M-PF6 -).
。
（2）Univalent copper complex [(NHC-3) Cu (POP)]+PF6 -
By gained precursor P-3（4.8g, 10mmol, 1.0 equivalent）, silver oxide（1.2g, 5mmol, 50% equivalent）, solvent
Acetonitrile 50mL is sequentially added in 100mL flasks, and 50 DEG C of lucifuges are reacted 12 hours；Filtering, filtrate is collected, is evaporated, obtains colorless solid.
By the solid and copper powder（0.64g, 10mmol, 1.0 equivalent）As in 100 mL flasks, the mL of anhydrous and oxygen-free acetonitrile 50, room are added
Warm stirring reaction 5 hours；Add part POP（4.3g, 8mmol, 80% equivalent）, reaction 3 hours is stirred at room temperature；Filtering, remove not
Soluble solids, filtrate is collected, evaporated under reduced pressure, obtains light green solid, as crude product.Crude product is dissolved in dichloromethane solvent
In, slow solvent flashing, there are a large amount of pale yellow crystals to separate out, filtering obtains pure complex [(NHC-3) Cu (POP)]+PF6 -
（8.1g, 7.5mmol）, yield 75%.1H NMR (500 MHz, CDCl3) δ (ppm): 8.67-8.69 (1H, d, J
= 10.0 Hz), 8.16-8.28 (2H, dd, J = 10.0 Hz, 10.0 Hz), 7.84-7.88 (2H, t, J =
10.0 Hz),7.47-7.51 (1H, t, J = 10.0 Hz), 7.33-7.37(1H, t, J = 10.0 Hz), 7.25-
7.28 (4H, m), 7.18-7.22 (3H, m), 7.03-7.13 (14H, m), 6.93-6.97 (7H ,m), 6.86-
6.88 (6H ,m), 6.77-6.79 (2H, d, J = 10.0 Hz), 5.15 (2H, s); 31P NMR (200 MHz,
CDCl3) δ (ppm): -8.79 (s), -144.1 (quint); ESI-MS (m/z) = 936.1 (M-PF6 -).
Crystal structure：The univalent copper complex [(NHC-3) Cu (POP)] of the present embodiment synthesis+PF6 -Crystal structure such as Figure 10
It is shown.
Photophysics：At room temperature, [(NHC-3) Cu (POP)]+PF6 -The emission peak of solid powder sample is in 554 nm, hair
Quantum yield is 58%, and luminescent spectrum is as shown in figure 11；Luminescent lifetime is 49.7 microseconds (μ s), and luminous intensity attenuation curve is such as
Shown in Figure 12.
Claims (1)
- A kind of 1. preparation method of ionic N-heterocyclic carbine univalent copper complex, it is characterised in that：The coordination of the complex Key is made up of a N-heterocyclic carbine bidentate ligand and a bidentate phosphine ligandses, and such complex has monokaryon four-coordination structure, Formula is：,In formula, partRepresent N-heterocyclic carbine bidentate ligand, partRepresent bidentate phosphine ligandses, PF6 -For complex external world anion；The N-heterocyclic carbine bidentate ligandStructure be：；The bidentate phosphine ligandsesStructure be：；The preparation method of complex comprises the following steps：（1）, by 6.8g imidazoles, 15.7g2- bromopyridines, 0.95g cuprous iodides, 1.2g BTAs, 15.7g potassium tert-butoxides according to In secondary addition flask, 100mL solvent DMFs are added, back flow reaction 5 hours, question response under the conditions of 110 DEG C Liquid is cooled to room temperature, filters off insoluble solid, collects filtrate, evaporated under reduced pressure, obtains crude product；Then, by crude product column chromatography Method separation, purification, obtain intermediate product, leacheate 1:5 dichloromethane and petroleum ether；（2）, 11.6g intermediate products, 50.4g benzyl chlorides added in flask, back flow reaction 3 hours under the conditions of 100 DEG C, question response liquid Room temperature is cooled to, distillation under pressure, excessive benzyl chloride is removed, obtains yellow solid, is washed solid to colourless with acetone；So Afterwards, gained colorless solid is placed in flask, sequentially adds 250mL acetone and 29.4g Potassium Hexafluorophosphates, it is small to stir 5 at room temperature When；Insoluble solid is filtered off, filtrate is collected, is evaporated；Filter cake distillation water washing, drying, obtains precursor；（3）, 3.8g precursors, 1.2g silver oxides, 50mL solvent acetonitriles sequentially added in flask, 50 DEG C of lucifuges reactions 12 are small When；Filtering, filtrate is collected, is evaporated, obtains colorless solid, by the solid and 0.64g copper powders as in flask, add the anhydrous nothings of 50mL Oxygen acetonitrile, reaction 5 hours is stirred at room temperature；4.3g bidentate phosphine ligandses are added, reaction 3 hours is stirred at room temperature；Filtering, remove insoluble Solid, filtrate is collected, evaporated under reduced pressure, light green solid is obtained, light green solid is dissolved in dichloromethane solvent, slowly volatilize molten Agent, colourless crystallization separate out, and filtering obtains pure complex.
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