CN102010448B - Copper (I) coordination compound and application thereof - Google Patents
Copper (I) coordination compound and application thereof Download PDFInfo
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- CN102010448B CN102010448B CN 201010542965 CN201010542965A CN102010448B CN 102010448 B CN102010448 B CN 102010448B CN 201010542965 CN201010542965 CN 201010542965 CN 201010542965 A CN201010542965 A CN 201010542965A CN 102010448 B CN102010448 B CN 102010448B
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- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 150000001875 compounds Chemical class 0.000 title abstract description 14
- -1 aryl phosphine Chemical compound 0.000 claims abstract description 31
- 239000003446 ligand Substances 0.000 claims abstract description 16
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 15
- 239000010949 copper Substances 0.000 claims description 29
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 238000005401 electroluminescence Methods 0.000 claims description 6
- 230000005611 electricity Effects 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 abstract description 17
- 125000003118 aryl group Chemical group 0.000 abstract description 12
- 125000004437 phosphorous atom Chemical group 0.000 abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 5
- 125000004429 atom Chemical group 0.000 abstract description 4
- 150000002475 indoles Chemical class 0.000 abstract description 4
- 229940054051 antipsychotic indole derivative Drugs 0.000 abstract description 3
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 238000009791 electrochemical migration reaction Methods 0.000 abstract 1
- 125000001424 substituent group Chemical group 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 48
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 36
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 24
- 238000002360 preparation method Methods 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000007788 liquid Substances 0.000 description 18
- 229910052786 argon Inorganic materials 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 7
- 239000011368 organic material Substances 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical group C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 4
- 238000005539 phosphorimetry Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000005013 aryl ether group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 125000000101 thioether group Chemical group 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- LCGITQAMTPXTBS-UHFFFAOYSA-N copper;copper(1+) Chemical compound [Cu+].[Cu+2] LCGITQAMTPXTBS-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000007246 mechanism Effects 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
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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Abstract
The invention provides a copper (I) coordination compound. The copper (I) coordination compound has the structure as shown in formula I, wherein the indole derivative ligand is shown in the specification, two individual aryl phosphine ligands or bridging aryl phosphine bidentate ligands are also shown in the specification, and each phosphorus atom of the aryl phosphine ligands at least has one aryl substituent, and the other substituent is one of the aryl and C1-C30 alkyls. The copper (I) coordination compound provided by the invention is the neutral copper (I) coordination compound. Compared with the ionized coordination compound, the neutral copper (I) coordination compound can be used to overcome the time delay effect of the luminescent device caused by the ionic migration resistance due to the fact that the neutral copper (I) coordination compound has no other coordination atoms. In addition, due to the absence of other coordination atoms in the copper (I) coordination compound, the neutral copper (I) coordination compound of the indole derivatives has small possibility of reacting with the surrounding environment to be converted into the ionized copper (I) coordination compound, therefore the copper (I) coordination compound provided by the invention can be used in organic electroluminescent devices and sensors.
Description
Technical field
The present invention relates to the luminescent material technical field, more particularly, relate to a kind of copper (I) title complex and application thereof.
Background technology
Organic electroluminescent is to excite organic materials and luminous phenomenon by electric energy.1998, the people such as S.R.Forrest found first, and phosphorescent complexes is applied to the efficient that electroluminescent organic material can greatly improve device.Because the huge advantage of electroluminescent organic material on device of phosphorescent complexes being arranged, its research has been become one of main direction in the organic electroluminescent field.And owing to can take full advantage of all form of energy that comprise singlet state and triplet state based on the phosphorescent complexes of heavy metal, its maximum internal quantum efficiency is higher, therefore, makes electroluminescent organic material have higher electroluminescent efficiency.
In various phosphorescent complexes based on heavy metal, monovalence copper (copper (I)) phosphorescent complexes because have stronger room temperature phosphorimetry emitting performance, be easy to form coenocytism, luminescence mechanism is various, spectrum peak changes characteristics such as can covering whole visible light, can be applied to the fields such as organic electroluminescence device and detection, therefore, copper (I) phosphorescent complexes is in widespread attention in the research in organic electroluminescent field.But copper (I) ion is owing to the restriction that is subject to low-oxidation-state and tetrahedral coordination configuration, thereby the present copper of reporting (I) phosphorescent complexes mostly is the ionic complex that contains counter ion.Ionic copper (I) title complex is owing to containing counter ion, and the migration of counter ion occurs under electric field action the electroluminescent device of preparation, the generation time delay phenomenon, and namely device brightness needs certain hour just can reach steady state value after applying voltage; Simultaneously, after the counter ion migration, may cause charge balance destroyed, stability of material is reduced, and then affect the stability of electroluminescent device.
Compare with ionic complex, neutral copper (I) title complex is not owing to there being the nucleation of counter ion, the electroluminescent device non-time-delay phenomenon of preparation, and the stability of electroluminescent organic material is improved.Application number is that 200610130886.7 Chinese patent literature discloses the copper that a kind of imdazole derivatives is part (I) title complex, this copper (I) title complex is take imdazole derivatives as part, form simultaneously ionic copper (I) title complex and neutral copper (I) title complex, and, the neutral imidazoles of document report is spread out copper (I) title complex easily and its surrounding environment is done to change ionic copper (I) title complex into, thereby affects the stability of electroluminescent device.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of neutral copper (I) title complex and application thereof, and this copper (I) title complex is not easy to change into ionic copper (I) title complex.
The invention provides a kind of copper (I) title complex, have suc as formula the structure shown in the I,
Formula I,
Wherein, described
For the indole derivatives part, described
Be the aryl phosphine bitooth ligand of two independent aryl phosphine parts or bridging,
At least have an aryl substituent on the described aryl phosphine part on each phosphorus atom, other substituting groups are any one in the alkyl of aryl and C1~C30.
Formula II,
Formula III,
Wherein, described R
1, R
2, R
3, R
4, R
5, R
6And R
7Independent separately is hydrogen, alkyl, cycloalkyl, aralkyl, alkoxyl group, aryl ether group, fragrant thioether group, dialkyl amido, ammonia diaryl base, aryl and hetero-aromatic ring base, halogen, haloalkyl, silyl or siloxanes.
Preferably, described
Be 2,2 '-pyridyl indoles or 2,2 '-quinolyl indoles.
Preferably, the aryl phosphine part is any one in following 1~5 structure in described two independent aryl phosphine parts,
Wherein, described R
8, R
9And R
10Independent separately is in the alkoxyl group of the alkyl of C1~C30 and C1~C20 any one.
Preferably, the aryl phosphine bitooth ligand of described bridging is any one in following 6~8 structures,
Wherein, described R
8, R
9And R
10Independent separately is in the alkoxyl group of the alkyl of C1~C30 and C1~C20 any one;
Described m is 1,2,3,4 or 5.
Preferably, have suc as formula the structure shown in IV, formula V, formula VI, formula VII, formula VIII or the formula IX,
Formula IV,
Formula V,
Formula VI,
Formula VII,
Formula VIII,
Formula IX.
The present invention also provides a kind of application of copper (I) title complex in organic electroluminescence device with formula I structure.
The present invention also provides a kind of application of copper (I) title complex in sensor with formula I structure.
Can find out from technique scheme, the invention provides a kind of copper (I) title complex, have suc as formula the structure shown in the I, wherein, described
For the indole derivatives part, described
Be the aryl phosphine bitooth ligand of two independent aryl phosphine parts or bridging, having at least an aryl substituent, other substituting groups on the described aryl phosphine part on each phosphorus atom is in the alkyl of aryl and C1~C30 any one.Copper provided by the invention (I) title complex is neutral copper (I) title complex, compares with ionic complex, and this neutral compound can improve the luminescent properties of electroluminescent organic material owing to there not being the nucleation of counter ion.And, because this copper (I) but there are not other ligating atoms in title complex, so neutral copper (I) title complex of this indole derivatives class is not easy to the surrounding environment reaction and changes ionic copper (I) title complex into.Simultaneously, neutral copper provided by the invention (I) title complex has enriched the kind of copper (I) phosphorescent complexes, can be applicable in organic electroluminescence device and the sensor.
Description of drawings
In order to be illustrated more clearly in the embodiment of the invention or technical scheme of the prior art, the below will do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art, apparently, accompanying drawing in the following describes only is some embodiments of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the embodiment of the invention 1 disclosed [Cu (pi) (PPh
3)
2] crystalline structure figure;
Fig. 2 is the embodiment of the invention 2 disclosed [Cu (pi) (POP)] CH
2Cl
2Crystalline structure figure;
Fig. 3 is the embodiment of the invention 3 disclosed [Cu (qi) (PPh
3)
2] CH
2Cl
2Crystalline structure figure;
Fig. 4 is the embodiment of the invention 4 disclosed [Cu (qi) (POP)] CH
3The crystalline structure figure of OH;
Fig. 5 is ultraviolet-ray visible absorbing and the utilizing emitted light spectrogram of the disclosed copper of the embodiment of the invention (I) title complex, [Cu (pi) (PPh
3)
2] (1), [Cu (pi) is (POP)] (2), [Cu (qi) (PPh
3)
2] (3), [Cu (qi) is (POP)] (4);
Fig. 6 is that the embodiment of the invention 4 disclosed [Cu (qi) (POP)] is to the sensing characteristics figure of oxygen.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the invention, the technical scheme in the embodiment of the invention is clearly and completely described, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills belong to the scope of protection of the invention not making the every other embodiment that obtains under the creative work prerequisite.
The invention provides a kind of copper (I) title complex, have suc as formula the structure shown in the I,
Formula I
At least have an aryl substituent on the described aryl phosphine part on each phosphorus atom, other substituting groups are any one in the alkyl of aryl and C1~C30.
According to the present invention, described
Structure optimization suc as formula shown in II or the formula III,
Formula II,
Formula III,
Wherein, described R
1, R
2, R
3, R
4, R
5, R
6And R
7Independently be hydrogen, alkyl, cycloalkyl, aralkyl, alkoxyl group, aryl ether group, fragrant thioether group, dialkyl amido, ammonia diaryl base, aryl and hetero-aromatic ring base, halogen, haloalkyl, silyl or siloxanes separately, described
More preferably 2,2 '-pyridyl indoles or 2,2 '-quinolyl indoles.Described
Aobvious negative electricity under alkaline condition, therefore, neutral copper (I) title complex of the present invention's preparation can be used as the environmentally sensitive material.
According to the present invention, the aryl phosphine part is any one in following 1~5 structure in described two independent aryl phosphine parts,
Wherein, described R
8, R
9And R
10Independent separately is in the alkoxyl group of the alkyl of C1~C30 and C1~C20 any one;
The aryl phosphine bitooth ligand of described bridging is any one in following 6~8 structures,
Wherein, described R
8, R
9And R
10Independent separately is in the alkoxyl group of the alkyl of C1~C30 and C1~C20 any one; Described m is 1,2,3,4 or 5.
According to the present invention, described copper (I) title complex preferably has suc as formula the structure shown in IV, formula V, formula VI, formula VII, formula VIII or the formula IX,
Formula IV,
Formula V,
Formula VI,
Formula VII,
Formula VIII,
Formula IX.
The invention provides a kind of copper (I) title complex, have suc as formula the structure shown in the I, wherein, described
For the indole derivatives part, described
Be the aryl phosphine bitooth ligand of two independent aryl phosphine parts or bridging, having at least an aryl substituent, other substituting groups on the described aryl phosphine part on each phosphorus atom is in the alkyl of aryl and C1~C30 any one.Copper provided by the invention (I) title complex is neutral copper (I) title complex, compares with ionic complex, and this neutral compound can improve the luminescent properties of electroluminescent organic material owing to there not being the nucleation of counter ion.And, because this copper (I) but there are not other ligating atoms in title complex, so neutral copper (I) title complex of this indole derivatives class is not easy to the surrounding environment reaction and changes ionic copper (I) title complex into.Simultaneously, neutral copper provided by the invention (I) title complex has enriched the kind of copper (I) phosphorescent complexes, can be applicable in organic electroluminescence device and the sensor.Experimental result shows, copper provided by the invention (I) title complex has strong room temperature phosphorimetry emitting performance and special susceptibility.
In order further to understand technical scheme of the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, but should be appreciated that these describe just as further specifying the features and advantages of the present invention, rather than to the restriction of claim of the present invention.
Under the argon gas condition, in reaction flask A, add 1.0mmol 2,2 '-pyridyl indoles, 0.12g NaH0.12g and 10ml tetrahydrofuran (THF);
Under the argon gas condition, in reaction flask B, add 1.0mmol CuI, 2.0mmol PPh
3With 10ml tetrahydrofuran (THF), stirring at room 2h;
With the solution filter among the reaction flask A, the clear liquid that filtration is obtained adds among the reaction flask B, drain solvent behind the stirring at room 2h, with 10ml dichloromethane extraction residue, the clear liquid that obtains is transferred among the reaction flask C, 10ml methyl alcohol is added on the described dichloromethane solution layer, obtains copper (I) complex crystal 0.65g by liquid-liquid diffusion process, be called for short [Cu (pi) (PPh
3)
2], yield is 84%, and structural formula is suc as formula shown in the IV, and crystalline structure figure is as shown in Figure 1.Utilize the 600MHz nuclear magnetic resonance spectrometer that copper (I) title complex of the present embodiment preparation is detected, the result is: Mp:169 ℃;
1H NMR (600MHz, CDCl
3) δ 6.69-6.73 (t, J=7.01H), 6.83-6.85 (m, 2H), (7.14 t, J=7.0Hz, 12H), 7.21 (dd, J=15.5,7.3Hz, 14H), 7.26 (t, J=7.1Hz, 6H), 7.50 (t, J=7.5Hz, 1H), 7.64-7.66 (m, 1H), (7.84 t, J=7.3Hz, 2H).
Embodiment 2
Under the argon gas condition, in reaction flask A, add 1.0mmol 2,2 '-pyridyl indoles, 0.12NaH and 10ml tetrahydrofuran (THF);
Under the argon gas condition, in reaction flask B, add 1.0mmol CuI, 1.0mmol POP and 10ml tetrahydrofuran (THF), stirring at room 2h;
With the solution filter among the reaction flask A, the clear liquid that filtration is obtained adds among the reaction flask B, drain solvent behind the stirring at room 2h, 10ml dichloromethane extraction residue is transferred to the clear liquid that obtains among another reaction flask C, and 10ml methyl alcohol carefully is added on the dichloromethane solution layer, obtain copper (I) complex crystal 0.57g by liquid-liquid diffusion process, be called for short [Cu (pi) (POP)], yield is 72%, and structural formula is suc as formula shown in the V.Utilize the 600MHz nuclear magnetic resonance spectrometer that copper (I) title complex of the present embodiment preparation is detected, the result is: Mp:210 ℃;
1H NMR (600MHz, CDCl
3) δ 6.57 (t, J=7.5Hz, 1H), 6.73-6.79 (m, 4H), 6.88 (t, J=7.5Hz, 2H), 7.00 (d, J=8.0Hz, 2H), (7.06 dd, J=13.4,5.9Hz, 8H), 7.09-7.21 (m, 14H), 7.22-7.27 (m, 2H), 7.43 (t, J=7.6Hz, 1H), 7.59 (d, J=7.6Hz, 1H), 7.77 (d, J=8.0Hz, 1H), 7.86 (d, J=4.9Hz, 1H).
[Cu (pi) (POP)] CH of the present embodiment preparation
2Cl
2Crystalline structure as shown in Figure 2.
Embodiment 3
Under the argon gas condition, in reaction flask A, add 1.0mmol 2,2 '-quinolyl indoles, 0.12g NaH and 10ml tetrahydrofuran (THF);
Under the argon gas condition, in reaction flask B, add 1.0mmol CuI, 2.0mmol PPh
3With 10ml tetrahydrofuran (THF), stirring at room 2h;
With the solution filter among the reaction flask A, the clear liquid that filtration is obtained joins among the reaction flask B, drain solvent behind the stirring at room 2h, 10ml dichloromethane extraction residue, clear liquid is transferred among the reaction flask C, 10ml methyl alcohol is added on the dichloromethane solution layer, obtains copper (I) complex crystal 0.68g by liquid-liquid diffusion process, be called for short [Cu (qi) (PPh
3)
2], yield is 81%, structural formula is suc as formula shown in the VI.Utilize the 600MHz nuclear magnetic resonance spectrometer that copper (I) title complex of the present embodiment preparation is detected, the result is: Mp:157 ℃;
1HNMR (600MHz, CDCl
3) δ 6.81 (m, 2H), 6.98 (m, 2H), (7.10-7.17 m, 18H), 7.19 (t, J=7.37,7.37Hz, 1H), 7.23-7.29 (m, 12H), (7.32 s, 1H), 7.59 (dd, J=12.73,8.16Hz, 2H), 7.66 (d, J=7.35Hz, 1H), 8.00 (m, 2H).
[Cu (the qi) (PPh of the present embodiment preparation
3)
2] CH
2Cl
2Crystalline structure as shown in Figure 3.
Embodiment 4
Under the argon gas condition, in reaction flask A, add 1.0mmol 2,2 '-quinolyl indoles, 0.12g NaH and 10ml tetrahydrofuran (THF);
Under the argon gas condition, in reaction flask B, add 1.0mmol CuI, 1.0mmol POP and 10ml tetrahydrofuran (THF), stirring at room 2h;
With the solution filter among the reaction flask A, the clear liquid that filtration is obtained adds among the reaction flask B, drain solvent behind the stirring at room 2h, with 10ml dichloromethane extraction residue, the clear liquid that obtains is transferred among the reaction flask C, 10ml methyl alcohol is added on the dichloromethane solution layer, obtain copper (I) complex crystal 0.64g by liquid-liquid diffusion process, be called for short [Cu (qi) is (POP)], yield is 76%), structural formula is suc as formula shown in the VII.Utilize the 600MHz nuclear magnetic resonance spectrometer that copper (I) title complex of the present embodiment preparation is detected, the result is: Mp:196 ℃;
1H NMR (600MHz, CDCl
3) d 6.70 (t, J=7.58,7.58Hz, 1H), 6.79-6.85 (m, 2H), (6.85-7.01 m, 15H), 7.03-7.11 (m, 10H), 7.13-7.21 (m, 3H), (7.30 m, 1H), 7.44-7.49 (m, 1H), 7.52 (t, J=8.74,8.74Hz, 2H), 7.62 (d, J=7.80Hz, 1H), 7.77 (d, J=8.40Hz, 1H), 7.82 (d, J=8.61Hz, 1H), 7.90 (d, J=8.61Hz, 1H).
[Cu (qi) (POP)] CH of the present embodiment preparation
3The OH crystalline structure as shown in Figure 4.
The crystallographic data of copper (I) title complex of embodiment 1~4 preparation is as shown in table 1.Copper (I) title complex (mass percent 10%) in the PMMA film to embodiment 1~4 preparation carries out the optical property detection, and detected result is as shown in table 2.To the ultraviolet-ray visible absorbing of copper (I) title complex of embodiment 1~4 preparation and utilizing emitted light spectrogram as shown in Figure 5, as can be seen from the figure, copper (I) title complex of embodiment of the invention preparation has strong room temperature phosphorimetry emitting performance.Fig. 6 be [Cu (qi) (POP)] of the embodiment of the invention 4 preparation to the sensing characteristics figure of oxygen, as can be seen from the figure, this copper (I) title complex has special susceptibility, can be applicable in the sensor.
Embodiment 5
Under the argon gas condition, in reaction flask A, add 1.0mmol6 '-methyl-2,2 '-pyridyl indoles, 0.12g, NaH and 10ml tetrahydrofuran (THF);
Under the argon gas condition, in reaction flask B, add 1.0mmol CuI, 2.0mmol PPh
3With 10ml tetrahydrofuran (THF), stirring at room 2h;
With the solution filter among the reaction flask A, the clear liquid that filtration is obtained adds among the reaction flask B, drain solvent behind the stirring at room 2h, with 10ml dichloromethane extraction residue, the clear liquid that obtains is transferred among the reaction flask C, 10ml methyl alcohol is added on the dichloromethane solution layer, obtains copper (I) complex crystal 0.45g by liquid-liquid diffusion process, be called for short [Cu (Mpi) (PPh
3)
2], yield is 57%, structural formula is suc as formula shown in the VIII.Utilize the 600MHz nuclear magnetic resonance spectrometer that copper (I) title complex of the present embodiment preparation is detected, the result is: Mp:155 ℃;
1H NMR (600MHz, CDCl
3) δ 3.04 (s, 3H), 6.82-6.86 (m, 2H), (7.12 t, J=7.2Hz, 12H), 7.23 (dd, J=15.2,7.0Hz, 14H), 7.28 (t, J=7.1Hz, 6H), 7.50 (t, J=7.2Hz, 1H), 7.64-7.67 (m, 1H), (7.82 t, J=7.0Hz, 2H).
Embodiment 6
Under the argon gas condition, in reaction flask A, add 1.0mmol 6 '-methyl-2,2 '-pyridyl indoles, 0.12g NaH and 10ml tetrahydrofuran (THF);
Under the argon gas condition, in reaction flask B, add 1.0mmol CuI, 1.0mmol POP and 10ml tetrahydrofuran (THF), stirring at room 2h;
With the solution filter among the reaction flask A, the clear liquid that filtration is obtained adds among the reaction flask B, drain solvent behind the stirring at room 2h, with 10ml dichloromethane extraction residue, the clear liquid that obtains is transferred among the reaction flask C, 10ml methyl alcohol carefully is added on the dichloromethane solution layer, obtain copper (I) complex crystal 0.52g by liquid-liquid diffusion process, be called for short [Cu (pi) is (POP)], yield is 64%, during structure suc as formula shown in the IX.Utilize the 600MHz nuclear magnetic resonance spectrometer that copper (I) title complex of the present embodiment preparation is detected, the result is: Mp:205 ℃;
1H NMR (600MHz, CDCl
3) δ 2.98 (s, 3H), 6.74-6.78 (m, 4H), 6.85 (t, J=7.4Hz, 2H), 7.00 (d, J=7.9Hz, 2H), (7.06 dd, J=13.6,6.0Hz, 8H), 7.09-7.21 (m, 14H), 7.22-7.27 (m, 2H), 7.43 (t, J=7.5Hz, 1H), 7.59 (d, J=7.5Hz, 1H), 7.77 (d, J=7.8Hz, 1H), 7.86 (d, J=5.2Hz, 1H).
The crystallographic data of copper (I) title complex of table 1 embodiment of the invention 1~4 preparation
The photophysics data of copper (I) title complex in the PMMA film of table 2 embodiment of the invention preparation
Can find out from above-described embodiment, the invention provides a kind of copper (I) title complex, this copper (I) title complex has and has strong room temperature phosphorimetry emitting performance and special susceptibility, can be used for organic electroluminescence device and sensor.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be apparent concerning those skilled in the art, and General Principle as defined herein can be in the situation that do not break away from the spirit or scope of the present invention, in other embodiments realization.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (6)
1. a copper (I) title complex is characterized in that, have suc as formula the structure shown in the I,
Formula I,
The aryl phosphine part is any one in following 1~5 structure in described two independent aryl phosphine parts,
Wherein, described R
8, R
9And R
10Independent separately is in the alkoxyl group of the alkyl of C1~C30 and C1~C20 any one;
The aryl phosphine bitooth ligand of described bridging is any one in following 6~8 structures,
Wherein, described R
8Be in the alkoxyl group of the alkyl of C1~C30 and C1~C20 any one; Described m is 1,2,3,4 or 5.
3. the described copper of any one (I) title complex is characterized in that according to claim 1~2, and is described
Aobvious negative electricity under alkaline condition.
4. the application of copper (I) title complex in organic electroluminescence device with formula I structure,
Formula I,
Described
Be the aryl phosphine bitooth ligand of two independent aryl phosphine parts or bridging,
The aryl phosphine part is any one in following 1~5 structure in described two independent aryl phosphine parts,
Wherein, described R
8, R
9And R
10Independent separately is in the alkoxyl group of the alkyl of C1~C30 and C1~C20 any one;
The aryl phosphine bitooth ligand of described bridging is any one in following 6~8 structures,
Wherein, described R
8Be in the alkoxyl group of the alkyl of C1~C30 and C1~C20 any one; Described m is 1,2,3,4 or 5.
5. the application of copper (I) title complex in sensor with formula I structure,
Formula I,
The aryl phosphine part is any one in following 1~5 structure in described two independent aryl phosphine parts,
Wherein, described R
8, R
9And R
10Independent separately is in the alkoxyl group of the alkyl of C1~C30 and C1~C20 any one;
The aryl phosphine bitooth ligand of described bridging is any one in following 6~8 structures,
Wherein, described R
8Be in the alkoxyl group of the alkyl of C1~C30 and C1~C20 any one; Described m is 1,2,3,4 or 5.
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CN102746843B (en) * | 2012-07-24 | 2013-11-06 | 江西理工大学 | Novel mononuclear copper (I) complex blue light material and preparation method thereof |
CN102851024B (en) * | 2012-09-28 | 2014-05-14 | 太原理工大学 | Organic electroluminescent material based on bis(2-diphenylphosphinophenyl)ether serving as ligand |
CN105408447A (en) * | 2013-06-14 | 2016-03-16 | 新泽西鲁特格斯州立大学 | Light emitting hybrid semiconductors based on IB-VII binary compounds |
CN103570761B (en) * | 2013-08-28 | 2016-05-25 | 渤海大学 | A kind of copper complex/composite luminescent material to oxygen sensitive and preparation method thereof and the application on oxygen sensor device |
CN103626789A (en) * | 2013-11-22 | 2014-03-12 | 中国计量学院 | Binuclear cuprous complex luminescent material and preparation method thereof |
CN104140808B (en) * | 2014-06-10 | 2016-02-10 | 中国计量学院 | A kind of cuprous complex luminescent material of tetrahedral of Han oxazolyl pyridine ligand |
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Philip Coppens et al..Geometry Changes of a Cu(I) Phenanthroline Complex on Photoexcitation in a Confining Medium by Time-Resolved X-ray Diffraction.《J. AM. CHEM. SOC.》.2004,第126卷(第19期),第5980-5981页. * |
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