CN102702269B - Carbazole group-containing bipyridino [3, 2-a:2', 3'-c] phenazine tricarbonyl rhenium (I) complexes, preparation method and application thereof - Google Patents
Carbazole group-containing bipyridino [3, 2-a:2', 3'-c] phenazine tricarbonyl rhenium (I) complexes, preparation method and application thereof Download PDFInfo
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Abstract
The invention provides carbazole group-containing bipyridino [3, 2-a:2', 3'-c] phenazine tricarbonyl rhenium (I) complexes, a preparation method and an application thereof. Annihilation among triplet states of the two rhenium complexes is less. The rhenium complexes have higher transmission performances and better luminescent properties, and can be used as good materials for manufacturing electroluminescent devices.
Description
Technical field
The present invention relates to the title complex of rhenium, also include organic electroluminescence devices.
Background technology
Organic electroluminescent (Organic Electroluminescence, be called for short EL or OEL) be a kind of phenomenon that is luminous energy by electric energy conversion in device, organic electroluminescence device (Organic Light-emitting Diodes, be called for short OLEDs), claiming again photodiode, is the device of realizing organic electroluminescent.Compare with other flat panel displays such as inorganic EL demonstration, liquid-crystal display, plasma display, ORGANIC ELECTROLUMINESCENCE DISPLAYS is with the feature such as its less energy-consumption, low cost, wide viewing angle, high brightness, big area, light emitting region be wide, and more and more noticeable.
The people such as C. W. Tang of Kodak in 1987 [referring to: Tang, C. W.; Vanslyke, S. A.
appl. Phys. Lett.1987,51,913] utilize ultrathin membrane technology to prepare the double-deck electroluminescent of small molecules organic film (EL) device of the efficient high brightness of low voltage starting, demonstrate the clear superiority of organic electroluminescence device, made the research of organic electroluminescence device and corresponding luminescent material and transport material enter an epoch-making developmental stage.Go through the research of twenties years, the organic electroluminescent that the flat pannel display of take is one of major objective has stepped into industrialization phase substantially, with the colored demonstration of common small size that red, green, blue three primary colours are basis, there is very large market, and had a small amount of commercialization large size display screen to come out.
The structure of carrier transmission material, luminescent material, electrode materials and device that the distinct advantages of OLEDs device and device adopt has relation closely, and wherein luminescent material is the core component of OLEDs device, can be divided into two kinds of fluorescent material and phosphor materials.Fluorescence results from transition of electron between multiplicity of the same race [referring to (a) Baldo, M. A.; O ' Brien, D. F.; You, Y.; Shoustikov, A.; Sibley, S.; Thompson, M. E.; Forrest, S. R.
nature1998,395,151; (b) Li Wenlian work, luminous organic material, device and flat pannel display thereof-a kind of photoelectron technology [M], Science Press, 2002], maximum efficiency only has 25%.And long lifetime phosphorescent transmitting generally comes from excited triplet state to the transition of electron of ground state singlet state, here said excited triplet state is long-life first to excite or excited triplet state, owing to having utilized the energy of singlet state and triplet state, theoretical efficiency can reach 100%, is the most promising material.
The transition of electron of common fluorescent material from triplet excited state to ground state is spin forbidden, cause just not producing transition under room temperature, so the organic and polymer materials of common hydrocarbon polymer is difficult to obtain phosphorescence, so people are devoted to produce obvious spin orbital coupling (spin-orbit coupling) by heavy metal complex, can make singlet excited mix with triplet excited state, increased the chance that triplet excited state forms, this also can be described as heavy atoms effect.There is numerous title complex can launch phosphorescence, particularly there is 4d, the metal complexes of 5d electronic configuration, there is significant Effect of Spin-orbit Coupling, the spin that is no longer limited by simple excited triplet state when causing singlet excited mutually to be mixed with triplet excited state and returning to ground state is forbidden, so these title complexs have higher luminous efficiency and shorter phosphorescent lifetime.Conventional transition metal complex has the title complex of rhenium (I), ruthenium (II), iridium (III).
Wherein rhenium (I) title complex, owing to having good optical physics, spectrochemical property and having higher Eo+, is the material that a class has application prospect very much, has in the world a lot of study group to report series material and device.Yet the rhenium compound of bibliographical information has longer lifetime of excited state, easily occur to bury in oblivion between triplet state-triplet state and between triplet state-polaron, the carrier transmission performance of material does not reach the requirement of organic electroluminescent device OLED s yet.
Summary of the invention
The title complex that the object of this invention is to provide two kinds of rheniums, buries in oblivion lessly between triplet state, carrier transmission performance is higher, has good luminescent properties, is the excellent material of making electroluminescent device.
Another object of the present invention is to provide the preparation method of the title complex of two kinds of rheniums, and the method is simple, and productive rate is high, is suitable for industrial application.
The title complex that another object of the present invention is to provide two kinds of rheniums is in the application of making aspect electroluminescent device.
Two pyridos [3,2-a:2', 3'-c] azophenlyene, three carbonyls that the invention provides a kind of carbazolyl-containing group close rhenium (I) title complex, and its structural formula is as follows:
。
The preparation method that the present invention also provides two pyridos [3,2-a:2', 3'-c] azophenlyene, three carbonyls of described carbazolyl-containing group to close rhenium (I) title complex, comprises the preparation of (1) presoma, the preparation of the preparation of (2) part and (3) title complex,
The preparation process of described step (2) part is as follows:
In the bromo-7-carbazole of presoma 4-[2,1,3]-diazosulfide or 4,7-, bis-carbazoles [2,1,3]-diazosulfide, add NaBH
4, with CoCl
26H
2o is catalyzer, vacuumizes, leads to nitrogen under lucifuge condition, adds dehydrated alcohol, is warmed up to 65 ℃～75 ℃ back flow reaction 40～50 hours; After reaction finishes, be cooled to 20 ℃～25 ℃, add successively ammoniacal liquor, 1, the ethanolic soln of 10-Phendione, is warmed up to 65 ℃～75 ℃ back flow reaction 5～10 hours again; After reaction finishes, reaction mixture is cooled to 20 ℃～25 ℃, isolating product is bromo-13-carbazole two pyridines [3,2-a:2', the 3'-c] azophenlyene of ligand 1 0-or 10,13-, bis-carbazole two pyridines [3,2-a:2', 3'-c] azophenlyene;
The preparation process of described step (3) title complex is as follows:
Described each part is mixed according to equimolar ratio example with chlorination pentacarbonyl rhenium respectively, in dry toluene, be warming up to 100
oc～120
oc back flow reaction 5～7 hours, distills out solvent, and gained solid is purified with column chromatography, and two pyridos [3,2-a:2', 3'-c] azophenlyene, three carbonyls that obtain title complex carbazolyl-containing group close rhenium (I) title complex.
When described presoma is the bromo-7-carbazole [2 of 4-, 1,3]-during diazosulfide, step (2) gained part is bromo-13-carbazole two pyridines [3 of 10-, 2-a:2', 3'-c] azophenlyene, two pyridos [3 of step (3) gained carbazolyl-containing group, 2-a:2', 3'-c] to close rhenium (I) title complex be chlorination three carbonyls to azophenlyene three carbonyls
.[bromo-13-carbazole two pyridines of 10-[3,2-a:2', 3'-c] azophenlyene] closes rhenium (I).
When described presoma is 4,7-bis-carbazoles [2,1,3]-during diazosulfide, step (2) gained part is 10,13-bis-carbazole two pyridines [3,2-a:2', 3'-c] azophenlyene, two pyridos [3 of step (3) gained carbazolyl-containing group, 2-a:2', 3'-c] to close rhenium (I) title complex be chlorination three carbonyls to azophenlyene three carbonyls
.[10,13-, bis-carbazole two pyridines [3,2-a:2', 3'-c] azophenlyene] close rhenium (I).
NaBH described in step (2)
4add-on be 15～25 times of presoma amount of substance, described CoCl
26H
2the consumption of O is the 0.8%-1% of presoma amount of substance, described 1, and in the ethanolic soln of 10-Phendione 1,10-Phendione total content is 3～10 times of presoma amount of substance.
Described in step (2), isolate product containing two pyridines [3 of carbazole, 2-a:2', 3'-c] concrete grammar of azophenlyene is: cooled reaction mixture decompression is steamed to solvent, with dichloromethane extraction, then extract is isolated to product containing two pyridines [3 of carbazole by thin layer chromatography board, 2-a:2', 3'-c] azophenlyene.
The solvent that the described column chromatography of step (3) is used in purifying is sherwood oil and ethyl acetate mixed solvent, is wherein added with the triethylamine that volumetric concentration is 50 ml/l; Described mixed solvent PetroChina Company Limited.'s ether and ethyl acetate volume ratio are 2:1.
Two pyridos [3,2-a:2', 3'-c] azophenlyene, three carbonyls that the present invention also provides described carbazolyl-containing to roll into a ball close the application of rhenium (I) title complex aspect making electroluminescent device
Beneficial effect of the present invention is as follows:
(1) the present invention is from molecular designing and device preparation, synthesized two contain carbazole group based on two pyridos [3,2-a:2', 3'-c] three carbonyls of azophenlyene derivative close rhenium (I) title complex, at intramolecule, the photoelectric properties of title complex regulated and controled.Due to space steric effect, reduced between triplet state and buried in oblivion; The introducing of carrier transport group, can effectively regulate HOMO, the lumo energy of title complex, improves carrier transmission performance, simplifies the structure of device, improves the performance of device.
(2) preparation method of the present invention is simple, and productive rate is high, is suitable for industrial application.
(3) three carbonyls of the present invention close rhenium (I) title complex and are easy to purification, stable in properties in air, can be applicable in organic electroluminescence device, Journal of Molecular Catalysis, colorimetric analysis, molecular recognition, Supramolecular Assembling, optical information storage and organism as fields such as photoluminescence probes.
Accompanying drawing explanation
Fig. 1 is title complex chlorination three carbonyls
.[bromo-13-carbazole two pyridines of 10-[3,2-a:2', 3'-c] azophenlyene] closes rhenium (I) (L1Re) and chlorination three carbonyls
.[10,13-, bis-carbazole two pyridines [3,2-a:2', 3'-c] azophenlyene] close (L2Re) the uv-visible absorption spectra figure in dichloromethane solution of rhenium (I);
Fig. 2 is title complex chlorination three carbonyls
.[bromo-13-carbazole two pyridines of 10-[3,2-a:2', 3'-c] azophenlyene] closes rhenium (I) (L1Re) and chlorination three carbonyls
.[10,13-, bis-carbazole two pyridines [3,2-a:2', 3'-c] azophenlyene] close (L2Re) the utilizing emitted light spectrogram in dichloromethane solution of rhenium (I);
Fig. 3 is title complex
.[bromo-13-carbazole two pyridines of 10-[3,2-a:2', 3'-c] azophenlyene] closes rhenium (I) (L1Re) and chlorination three carbonyls
.[10,13-, bis-carbazole two pyridines [3,2-a:2', 3'-c] azophenlyene] close rhenium (I) (L2Re) at the utilizing emitted light spectrogram of solid state;
Fig. 4 is the synthetic route chart of bromo-13-carbazole two pyridines [3,2-a:2', the 3'-c] azophenlyene of ligand 1 0-(L1);
Fig. 5 is ligand 10, the synthetic route chart of 13-bis-carbazole two pyridines [3,2-a:2', 3'-c] azophenlyene (L2);
Fig. 6 is title complex chlorination three carbonyls
.[bromo-13-carbazole two pyridines of 10-[3,2-a:2', 3'-c] azophenlyene] closes rhenium (I) synthetic route chart (L1Re);
Fig. 7 is title complex chlorination three carbonyls
.[10,13-, bis-carbazole two pyridines [3,2-a:2', 3'-c] azophenlyene] close rhenium (I) synthetic route chart (L2Re).
Embodiment
The preparation of embodiment mono-presoma 4-bromo-7-carbazole [2,1,3]-diazosulfide or 4,7-, bis-carbazoles [2,1,3]-diazosulfide
Reference literature method synthesize presoma [referring to (a) Neto, B.A.D., Lopes, A. S., W ü st, M., Costa, V. E. U., Ebeling, G., Dupont, J.,
tetrahedron Lett., 2005,46,6843; (b) Mancilha, F. S., Neto, B. A. D., Lopes, A. S., Quina, F. H., Goncalves, R. S., Dupont, J.,
eur. J. Org. Chem., 2006,4924; (c) Tao, Y. M., Li, H. Y., Xu, Q. L., Zhu, Y. C., Kang, L. C., Zheng, Y. X., Zuo, J. L., You, X. Z.,
synth. Met., 2011,161,718.].
Specific as follows: in reactor, by carbazole (5.02 g, 30 mmol), 4,7-diazosulfide (2.94 g, 10 mmol), cuprous iodide (0.19 g, 1 mmol), 18-are preced with-6 (0.088 g, 0.33 mmol), salt of wormwood (5.53 g, 40 mol) and 1,3-dimethyl-3,4,5,6-tetrahydrochysene-2 (1H)-pyrimidine dione (DMPU) (0.5 mL) mixes, be filled with after nitrogen, 180
ounder C, heat 24 hours.Be cooled to after room temperature, with the hydrochloric acid soln of 1 mol/L, soak sedimentation and filtration, with ammoniacal liquor, water washing, petroleum ether/ethyl ether (v/v=10/1 ~ 5/1) is done eluent column chromatography for separation and is purified, and obtains the bromo-7-carbazole [2,1 of shallow orange solid 4-, 3]-diazosulfide (0.76 g, productive rate: 20%) and orange solid 4,7-bis-carbazoles [2,1,3]-diazosulfide (0.69g, productive rate: 15%).
Embodiment bis-: bromo-13-carbazole two pyridines [3,2-a:2', the 3'-c] azophenlyene of ligand 1 0-(L1) or 10,13-, bis-carbazole two pyridines [3,2-a:2', 3'-c] azophenlyene (L2) synthetic
(1) synthetic method (seeing Fig. 4 and Fig. 5) is specific as follows:
In 100 mL round-bottomed flasks, add the bromo-7-carbazole of 4-[2,1,3]-diazosulfide or 4,7-, bis-carbazoles [2,1,3]-diazosulfides (0.56 mmol), and then add NaBH
4(11.2 mmol) and CATALYST Co Cl
26H
2o (5 * 10
-3mmol), under lucifuge condition, vacuumize, lead to nitrogen each three times, with syringe, add 30 mL dehydrated alcohols, be warmed up to 70
oc back flow reaction 48 hours.Be cooled to 20-25
oc, adds 5 mL ammoniacal liquor, with syringe, adds 10 mL 1, and 10-Phendione ethanolic soln (total content of 1,10-Phendione is 2.8 mmol), is warmed up to 70 again
oc back flow reaction 8 hours.After reaction finishes, reaction mixture is cooled to 20-25
oc, decompression steams solvent, uses dichloromethane extraction product.By thin layer chromatography board, isolating product is L1 or L2 containing two pyridines [3,2-a:2', the 3'-c] azophenlyene of carbazole.L1, productive rate: 24%; L2, productive rate: 26%.
When described presoma is the bromo-7-carbazole of 4-[2,1,3]-diazosulfide, gained part is bromo-13-carbazole two pyridines [3,2-a:2', the 3'-c] azophenlyene of 10-(L1); When described presoma is 4,7-, bis-carbazoles [2,1,3]-diazosulfide, gained part is 10,13-, bis-carbazole two pyridines [3,2-a:2', 3'-c] azophenlyene (L2).
(2) structure verification of compound L 1 or L2:
compound L 1:
M.p.: >300
oC。
1H NMR (CDCl
3, 500MHz): δ 9.622 (d, J = 9.0 Hz, 1H), 9.220 (d, J = 4.0 Hz, 1H), 9.055 (d, J = 4.0 Hz, 1H), 8.492 (d, J = 9.0 Hz, 1H), 8.405 (d, J = 8.5 Hz, 1H), 8.235 (d, J = 8.5 Hz, 2H), 8.154 (d, J = 7.0 Hz, 1H), 8.103 (t, J = 7.5, 1H), 7.772-7.746 (m, 1H), 7.362-7.333 (m, 2H), 7.307-7.280 (m, 2H) ppm.
Results of elemental analyses: calculated value (%): C, 68.45 H, 3.06 N, 13.30
Measured value (%): C, 67.93 H, 3.04 N, 13.42
MS (MALDI-TOF): m/z 526.455 [M]
+.
IR(KBr) (
v, cm
-1): 3010, 1641, 1450, 1081, 802, 738.
compound L 2:
M.p.: >300
oC。
1H NMR (500 MHz, CDCl
3)： δ 9.195 (d, J = 2.0 Hz, 2H ), 8.554 (d, J = 4.0 Hz, 2H), 8.451 (t, J = 1.0, 2H), 8.352-8.331 (m, 4H), 7.515-7.491 (m, 2H), 7.438-7.414 (m, 8H), 7.370-7.349 (m, 4H) ppm.
Results of elemental analyses: calculated value (%): C, 82.33 H, 3.97 N, 13.72
Measured value (%): C, 82.17 H, 4.05 N, 13.61
MS (MALDI-TOF): m/z 613.434 [M+1]
+.
IR(KBr) (
v, cm
-1): 3047, 1595, 1497, 1448, 1227, 1085, 747。
By above
1h-NMR, ultimate analysis, mass spectrum, infrared detected result, show that the product structure obtaining is correct.
Embodiment tri-: title complex chlorination three carbonyls
.[bromo-13-carbazole two pyridines of 10-[3,2-a:2', 3'-c] azophenlyene] close rhenium (I) (
l1Re) and chlorination three carbonyls
.[10,13-, bis-carbazole two pyridines [3,2-a:2', 3'-c] azophenlyene] close (L2Re) synthetic of rhenium (I)
(1) synthetic method (seeing Fig. 6 and Fig. 7) is specific as follows:
Two pyridines [3,2-a:2', 3'-c] azophenlyene L1 or L2 and chlorination pentacarbonyl rhenium Re (CO) by part containing carbazole
5cl, adds in container according to equimolar ratio example (0.10 mmol), in dry toluene (30 mL), is rapidly heated 110
oc backflow back flow reaction 6 hours, distills out solvent, and gained solid is purified with column chromatography, and two pyridos [3,2-a:2', 3'-c] azophenlyene, three carbonyls that obtain corresponding title complex carbazolyl-containing group close rhenium (I) title complex, i.e. chlorination three carbonyls
.[bromo-13-carbazole two pyridines of 10-[3,2-a:2', 3'-c] azophenlyene] closes rhenium (I) (L1Re) or chlorination three carbonyls
.[10,13-, bis-carbazole two pyridines [3,2-a:2', 3'-c] azophenlyene] close rhenium (I) (L2Re).L1Re, productive rate: 69%; L2Re, productive rate: 67%.The solvent using in column chromatography is sherwood oil and ethyl acetate mixed solvent, is wherein added with the triethylamine that volumetric concentration is 50 ml/l; Described mixed solvent PetroChina Company Limited.'s ether and ethyl acetate volume ratio are 2:1.
When part is bromo-13-carbazole two pyridines [3,2-a:2', the 3'-c] azophenlyene of 10-(L1), it is chlorination three carbonyls that two pyridos [3,2-a:2', 3'-c] azophenlyene, three carbonyls of gained carbazolyl-containing group close rhenium (I) title complex
.[bromo-13-carbazole two pyridines of 10-[3,2-a:2', 3'-c] azophenlyene] closes rhenium (I) (L1Re); When part is 10,13-, bis-carbazole two pyridines [3,2-a:2', 3'-c] azophenlyene (L2), it is chlorination three carbonyls that two pyridos [3,2-a:2', 3'-c] azophenlyene, three carbonyls of gained carbazolyl-containing group close rhenium (I) title complex
.[10,13-, bis-carbazole two pyridines [3,2-a:2', 3'-c] azophenlyene] close rhenium (I) (L2Re).
(2) structure verification of compound L 1 or L2:
L1Re：
M.p.(fusing point): >300
oc.
1H NMR (500 MHz, CDCl
3) δ 9.910 (d, J = 6.5Hz, 1H), 9.498 (d, J = 5.5Hz, 1H ), 9.320 (d, J = 7.0Hz, 1H), 9.645 (d, J = 9.5Hz, 2H), 8.351 (d, J = 8.5Hz, 1H), 8.304 (t, J = 8.0Hz, J = 5.0Hz, 2H), 8.080-8.054(m, 1H), 7.668-7.642 (m, 1H), 7.398-7.315 (m, 4H), 7.710 (d, J = 7.5Hz, 1H), 7.096 (d, J = 8.5Hz, 1H) ppm.
Results of elemental analyses: calculated value (%): C, 47.60 H, 1.94 N, 8.41
Measured value (%): C, 47.32 H, 2.03 N, 8.66
MS (MALDI-TOF): m/z.718.135 [M-Br-Cl]
+.
IR(KBr) (
v, cm
-1): 2020, 1890, 1640, 1448, 1260, 1091, 800, 472.
L2Re：
M.p.: >300
oC。
1H NMR (500 MHz, CDCl
3) δ 3.326 (dd, 2H), 8.675 (dd, 2H), 8.566 (s, 2H), 8.354 (t, J = 5.0Hz, 4H), 7.693-7.666 (m, 2H), 7.453-7.373 (m, 8H), 7.275 (d, J = 8.0Hz, 4H) ppm.
Results of elemental analyses: calculated value (%): C, 54.93 H, 2.63 N, 9.15
Measured value (%): C, 54.82 H, 2.71 N, 9.18
MS (MALDI-TOF): m/z. 883.274 [M-Cl]
+.
IR(KBr) (
v, cm
-1): 2020, 1889, 1624, 1496, 1447, 1093, 799, 750, 724, 464.
Title complex passes through respectively through L1 and L2
1h-NMR, ultimate analysis, mass spectrum, infrared checking, result shows that structure is correct.
Embodiment tetra-: chlorination three carbonyls
.[bromo-13-carbazole two pyridines of 10-[3,2-a:2', 3'-c] azophenlyene] close rhenium (I) (
l1Re) and chlorination three carbonyls
.[10,13-, bis-carbazole two pyridines [3,2-a:2', 3'-c] azophenlyene] close rhenium (I) (
l2Re)fluorescent Characterization
The title complex of above-mentioned rhenium is dissolved in respectively in methylene dichloride and measures (10
-3m), make solution.At room temperature condition, detect respectively the lower column data of each title complex: maximal ultraviolet absorption peak, title complex maximum emission peak, the title complex maximum emission peak under solid state in dichloromethane solution of title complex in dichloromethane solution.Concrete outcome is as follows:
L
absnm 239,275 (seeing Fig. 1)
L
em,
max, nm (in solution) 637 (seeing Fig. 2)
L
em,
max, nm (solid) 633 (seeing Fig. 3)
l2Re:chlorination three carbonyls
.[10,13-, bis-carbazole two pyridines [3,2-a:2', 3'-c] azophenlyene] close rhenium (I)
L
absnm 238,289,335,384 (seeing Fig. 1)
L
em,
max, nm (in solution) 662 (seeing Fig. 2)
L
em,
max, nm (solid) 673 (seeing Fig. 3)
The presentation of results of Fluorescent Characterization material have the application prospect in organic electroluminescent device OLED s, there is good commercial value.
Claims (8)
1. two pyridos [3,2-a:2', 3'-c] azophenlyene, three carbonyls of a carbazolyl-containing group close rhenium (I) title complex, and its structural formula is as follows:
。
2. two pyridos [3 that described in a claim 1, carbazolyl-containing is rolled into a ball, 2-a:2', 3'-c] azophenlyene three carbonyls close the preparation method of rhenium (I) title complex, comprise the preparation of (1) presoma, the preparation of the preparation of (2) part and (3) title complex is characterized in that:
The preparation process of described step (2) part is as follows: in the bromo-7-carbazole of presoma 4-[2,1,3]-diazosulfide or 4,7-, bis-carbazoles [2,1,3]-diazosulfide, add NaBH
4, with CoCl
26H
2o is catalyzer, vacuumizes, leads to nitrogen under lucifuge condition, adds dehydrated alcohol, is warmed up to 65
oc-75
oc back flow reaction 40-50 hour; After reaction finishes, be cooled to 20-25
oc, adds ammoniacal liquor, 1 successively, and the ethanolic soln of 10-Phendione is warmed up to 65 again
oc-75
oc back flow reaction 5-10 hour; After reaction finishes, reaction mixture is cooled to 20-25
oc, isolating product is bromo-13-carbazole two pyridines [3,2-a:2', the 3'-c] azophenlyene of ligand 1 0-or 10,13-, bis-carbazole two pyridines [3,2-a:2', 3'-c] azophenlyene;
The preparation process of described step (3) title complex is as follows: described each part is mixed according to equimolar ratio example with chlorination pentacarbonyl rhenium respectively, be warming up to 100 in dry toluene
oc-120
oc back flow reaction 5-7 hour, distills out solvent, and gained solid is purified with column chromatography, obtains two pyridos [3,2-a:2', 3'-c] azophenlyene three rhenium carbonyls (I) title complex of title complex carbazolyl-containing group.
3. two pyridos [3 that carbazolyl-containing is rolled into a ball according to claim 2,2-a:2', 3'-c] azophenlyene three carbonyls close the preparation method of rhenium (I) title complex, it is characterized in that when described presoma be the bromo-7-carbazole [2 of 4-, 1,3]-during diazosulfide, step (2) gained part is bromo-13-carbazole two pyridine [3, the 2-a:2' of 10-, 3'-c] azophenlyene, two pyridos [3,2-a:2', 3'-c] azophenlyene three rhenium carbonyls (I) title complex of step (3) gained carbazolyl-containing group is chlorination three carbonyls
.[bromo-13-carbazole two pyridines of 10-[3,2-a:2', 3'-c] azophenlyene] closes rhenium (I).
4. the preparation method that two pyridos [3,2-a:2', 3'-c] azophenlyene, three carbonyls of carbazolyl-containing group close rhenium (I) title complex according to claim 2, it is characterized in that working as described presoma is 4,7-, bis-carbazoles [2,1,3]-during diazosulfide, step (2) gained part is 10,13-, bis-carbazole two pyridine [3,2-a:2', 3'-c] azophenlyene, two pyridos [3,2-a:2', 3'-c] azophenlyene three rhenium carbonyls (I) title complex of step (3) gained carbazolyl-containing group is chlorination three carbonyls
.[10,13-, bis-carbazole two pyridines [3,2-a:2', 3'-c] azophenlyene] close rhenium (I).
5. the preparation method who closes rhenium (I) title complex according to two pyridos [3,2-a:2', 3'-c] azophenlyene, three carbonyls of carbazolyl-containing group described in claim 2 or 3 or 4, is characterized in that NaBH described in step (2)
4add-on be presoma amount of substance 15-25 doubly, described CoCl
26H
2the consumption of O is the 0.8%-1% of presoma amount of substance, described 1, in the ethanolic soln of 10-Phendione 1,10-Phendione total content be presoma amount of substance 3-10 doubly.
6. two pyridos [3 that carbazolyl-containing is rolled into a ball according to claim 5,2-a:2', 3'-c] azophenlyene three carbonyls close the preparation method of rhenium (I) title complex, it is characterized in that isolating described in step (2) product containing the concrete grammar of two pyridines [3,2-a:2', the 3'-c] azophenlyene of carbazole is: cooled reaction mixture decompression is steamed to solvent, with dichloromethane extraction, then extract is isolated to product containing two pyridines [3,2-a:2', the 3'-c] azophenlyene of carbazole by thin layer chromatography board.
7. two pyridos [3 that carbazolyl-containing is rolled into a ball according to claim 2,2-a:2', 3'-c] azophenlyene three carbonyls close the preparation method of rhenium (I) title complex, it is characterized in that the solvent using in the described column chromatography purification of step (3) is sherwood oil and ethyl acetate mixed solvent, be wherein added with the triethylamine that volumetric concentration is 50 ml/l; Described mixed solvent PetroChina Company Limited.'s ether and ethyl acetate volume ratio are 2:1.
8. the application of two pyridos [3,2-a:2', 3'-c] azophenlyene three rhenium carbonyls (I) title complex of carbazolyl-containing group aspect making electroluminescent device described in a claim 1.
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