CN102010448A - Copper (I) coordination compound and application thereof - Google Patents

Copper (I) coordination compound and application thereof Download PDF

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CN102010448A
CN102010448A CN 201010542965 CN201010542965A CN102010448A CN 102010448 A CN102010448 A CN 102010448A CN 201010542965 CN201010542965 CN 201010542965 CN 201010542965 A CN201010542965 A CN 201010542965A CN 102010448 A CN102010448 A CN 102010448A
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copper
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CN102010448B (en
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程延祥
刘晓辉
孙伟
李晓
谢志元
王利祥
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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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

Copper (I) title complex and application thereof
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, 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 arranged, its research has been become one of main direction in the organic electroluminescent field.And owing to can make full use 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 fields such as organic electroluminescence device and detection, therefore, the research of copper (I) phosphorescent complexes in the organic electroluminescent field is subjected to extensive attention.But copper (I) ion is owing to the restriction that is subjected to low-oxidation-state and tetrahedral coordination configuration, thereby the present copper of reporting (I) phosphorescent complexes mostly is the ionic title complex that contains counter ion.Ionic copper (I) title complex is owing to contain counter ion, and the migration of counter ion takes place under electric field action the electroluminescent device of preparation, the generation time delay phenomenon, and promptly 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 influence the stability of electroluminescent device.
Compare with the ionic title complex, neutral copper (I) title complex is not owing to there is 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 a part (I) title complex, this copper (I) title complex is part with the imdazole derivatives, form ionic copper (I) title complex and neutral copper (I) title complex simultaneously, and, the neutral imidazoles of document report copper (I) title complex that spreads out easily changes ionic copper (I) title complex into its surrounding environment work, thereby influences 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,
Figure BDA0000032025350000021
Formula I,
Wherein, described
Figure BDA0000032025350000022
For the indole derivatives part, described
Figure BDA0000032025350000023
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.
Preferably, state
Figure BDA0000032025350000024
Structure suc as formula shown in II or the formula III,
Figure BDA0000032025350000025
Formula II,
Figure BDA0000032025350000031
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
Figure BDA0000032025350000032
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,
Figure BDA0000032025350000033
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,
Figure BDA0000032025350000041
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,
Figure BDA0000032025350000042
Formula IV,
Figure BDA0000032025350000043
Formula V,
Figure BDA0000032025350000051
Formula VI,
Figure BDA0000032025350000052
Formula VII,
Figure BDA0000032025350000053
Formula VIII,
Figure BDA0000032025350000054
Formula IX.
Preferably, described
Figure BDA0000032025350000055
Under alkaline condition, show negative electricity.
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 transmitter with formula I structure.
From technique scheme as can be seen, the invention provides a kind of copper (I) title complex, have suc as formula the structure shown in the I, wherein, described
Figure BDA0000032025350000061
For the indole derivatives part, described
Figure BDA0000032025350000062
Be the aryl phosphine bitooth ligand of two independent aryl phosphine parts or bridging, having an aryl substituent, other substituting groups on the described aryl phosphine part on each phosphorus atom at least 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 the ionic title complex, and this neutral compound can improve the luminescent properties of electroluminescent organic material owing to there is not 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 transmitter.
Description of drawings
In order to be illustrated more clearly in the embodiment of the invention or technical scheme of the prior art, to do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art below, apparently, accompanying drawing in describing below only is some embodiments of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain other accompanying drawing according to these accompanying drawings.
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 that the ultraviolet-visible of the disclosed copper of the embodiment of the invention (I) title complex absorbs and emmission spectrum figure [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 the sensing characteristics figure of the embodiment of the invention 4 disclosed [Cu (qi) (POP)] to 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 is obtained 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,
Figure BDA0000032025350000071
Formula I
Wherein, described
Figure BDA0000032025350000072
Be the indole derivatives part,
Described
Figure BDA0000032025350000073
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.
According to the present invention, described
Figure BDA0000032025350000074
Structure optimization suc as formula shown in II or the formula III,
Figure BDA0000032025350000075
Formula II,
Figure BDA0000032025350000081
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
Figure BDA0000032025350000082
More preferably 2,2 '-pyridyl indoles or 2,2 '-quinolyl indoles.Described
Figure BDA0000032025350000083
Show 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,
Figure BDA0000032025350000091
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,
Figure BDA0000032025350000092
Formula IV,
Figure BDA0000032025350000093
Formula V,
Figure BDA0000032025350000101
Formula VI,
Figure BDA0000032025350000102
Formula VII,
Figure BDA0000032025350000103
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
Figure BDA0000032025350000111
For the indole derivatives part, described
Figure BDA0000032025350000112
Be the aryl phosphine bitooth ligand of two independent aryl phosphine parts or bridging, having an aryl substituent, other substituting groups on the described aryl phosphine part on each phosphorus atom at least 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 the ionic title complex, and this neutral compound can improve the luminescent properties of electroluminescent organic material owing to there is not 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 transmitter.Experimental result shows that 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 to further specifying the features and advantages of the present invention, rather than to the restriction of claim of the present invention.
Embodiment 1
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;
Solution among the reaction flask A is filtered, 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, be called for short [Cu (pi) (PPh by liquid-liquid diffusion process 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 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;
Solution among the reaction flask A is filtered, 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 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), and 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 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;
Solution among the reaction flask A is filtered, 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, be called for short [Cu (qi) (PPh by liquid-liquid diffusion process 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 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 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;
Solution among the reaction flask A is filtered, 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 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 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-visible of copper (I) title complex of embodiment 1～4 preparation absorb and emmission spectrum figure as shown in Figure 5, as can be seen from the figure, copper (I) title complex that the embodiment of the invention prepares has strong room temperature phosphorimetry emitting performance.Fig. 6 is [Cu (qi) (POP)] of the embodiment of the invention 4 preparations sensing characteristics figure to oxygen, and as can be seen from the figure, this copper (I) title complex has special susceptibility, can be applicable in the transmitter.
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;
Solution among the reaction flask A is filtered, 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, be called for short [Cu (Mpi) (PPh by liquid-liquid diffusion process 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 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;
Solution among the reaction flask A is filtered, 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 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), and 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
From the foregoing description as can be seen, 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 transmitter.
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 conspicuous concerning those skilled in the art, and defined herein General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.

Claims (9)

1. a copper (I) title complex is characterized in that, have suc as formula the structure shown in the I,
Figure FDA0000032025340000011
Formula I,
Wherein, described
Figure FDA0000032025340000012
For the indole derivatives part, described
Figure FDA0000032025340000013
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.
2. copper according to claim 1 (I) title complex is characterized in that, and is described
Figure FDA0000032025340000014
Structure suc as formula shown in II or the formula III,
Figure FDA0000032025340000015
Formula II,
Figure FDA0000032025340000016
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.
3. copper according to claim 1 (I) title complex is characterized in that, and is described
Figure FDA0000032025340000021
Be 2,2 '-pyridyl indoles or 2,2 '-quinolyl indoles.
4. copper according to claim 1 (I) title complex is characterized in that, the aryl phosphine part is any one in following 1～5 structure in described two independent aryl phosphine parts,
Figure FDA0000032025340000022
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.
5. copper according to claim 1 (I) title complex is characterized in that, the aryl phosphine bitooth ligand of described bridging is any one in following 6～8 structures,
Figure FDA0000032025340000023
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.
6. copper according to claim 1 (I) title complex is characterized in that, has suc as formula the structure shown in IV, formula V, formula VI, formula VII, formula VIII or the formula IX,
Figure FDA0000032025340000031
Formula IV,
Figure FDA0000032025340000032
Formula V,
Formula VI,
Figure FDA0000032025340000041
Formula VII,
Figure FDA0000032025340000042
Formula VIII,
Figure FDA0000032025340000043
Formula IX.
7. according to any described copper of claim 1～5 (I) title complex, it is characterized in that, described
Figure FDA0000032025340000044
Under alkaline condition, show negative electricity.
8. the application of copper (I) title complex in organic electroluminescence device with formula I structure.
9. the application of copper (I) title complex in transmitter with formula I structure.
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CN102851024A (en) * 2012-09-28 2013-01-02 太原理工大学 Organic electroluminescent material based on bis(2-diphenylphosphinophenyl)ether serving as ligand
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CN103626789A (en) * 2013-11-22 2014-03-12 中国计量学院 Binuclear cuprous complex luminescent material and preparation method thereof
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JP2014527033A (en) * 2011-07-08 2014-10-09 サイノーラ・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング Copper (I) complexes for optoelectronic devices
CN104066740A (en) * 2011-11-16 2014-09-24 辛诺拉有限公司 Heteroleptic copper complexes for optoelectronic uses
CN104066740B (en) * 2011-11-16 2017-05-10 辛诺拉有限公司 Heteroleptic copper complexes for optoelectronic uses
CN102746843A (en) * 2012-07-24 2012-10-24 江西理工大学 Novel mononuclear copper (I) complex blue light material and preparation method thereof
CN102851024A (en) * 2012-09-28 2013-01-02 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
CN103570761A (en) * 2013-08-28 2014-02-12 渤海大学 Copper complex/composite luminescent material sensitive to oxygen gas as well as preparation method thereof and application thereof on oxygen sensing device
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
CN104140808A (en) * 2014-06-10 2014-11-12 中国计量学院 Tetrahedral cuprous complex luminescent material containing oxazolyl pyridine ligands
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CN114409699B (en) * 2022-01-24 2023-10-20 南京邮电大学 Novel X-ray luminescent material and preparation method thereof

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