CN101993457A - 2,2'-rhenium (I) bipyridyl complexes containing carbazole or oxadiazole groups as well as preparation method and application thereof - Google Patents
2,2'-rhenium (I) bipyridyl complexes containing carbazole or oxadiazole groups as well as preparation method and application thereof Download PDFInfo
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- CN101993457A CN101993457A CN201010518976.XA CN201010518976A CN101993457A CN 101993457 A CN101993457 A CN 101993457A CN 201010518976 A CN201010518976 A CN 201010518976A CN 101993457 A CN101993457 A CN 101993457A
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- dipyridyl
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- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 title claims abstract description 16
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052702 rhenium Inorganic materials 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims description 8
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 title abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 8
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims abstract description 7
- 238000005660 chlorination reaction Methods 0.000 claims description 38
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 12
- WARCRYXKINZHGQ-UHFFFAOYSA-N benzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1 WARCRYXKINZHGQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 150000003282 rhenium compounds Chemical class 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 4
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- XZBIXDPGRMLSTC-UHFFFAOYSA-N formohydrazide Chemical compound NNC=O XZBIXDPGRMLSTC-UHFFFAOYSA-N 0.000 claims description 3
- 238000006798 ring closing metathesis reaction Methods 0.000 claims description 3
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 claims description 3
- 125000000950 dibromo group Chemical group Br* 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 230000005525 hole transport Effects 0.000 abstract description 2
- 150000003281 rhenium Chemical class 0.000 abstract 1
- OJNBAGCXFHUOIQ-UHFFFAOYSA-N [Re+] Chemical compound [Re+] OJNBAGCXFHUOIQ-UHFFFAOYSA-N 0.000 description 32
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 32
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 8
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 8
- 238000001819 mass spectrum Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000005401 electroluminescence Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 150000001716 carbazoles Chemical class 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ISAKRJDGNUQOIC-UHFFFAOYSA-N Uracil Chemical compound O=C1C=CNC(=O)N1 ISAKRJDGNUQOIC-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
The invention discloses 2,2'-rhenium (I) bipyridyl complexes containing carbazole or oxadiazole groups, which are shown in the following constitutional formulas in specification. The rhenium complexes in the invention can be applied to luminescent layers of electroluminescent devices. The complexes 1 and 2 are prepared through the step of respectively introducing carbazole groups at the different positions of the 2,2'- bipyridyl, wherein the complexes 1 and 2 with the carbazole groups can be used as luminescent layers with good hole transport performance; and complexes 3 and 4 are prepared through the step of respectively introducing oxadiazole groups at the 2,2'-bipyridyl, wherein the complexes 3 and 4 with oxadiazole groups can be used as luminescent layers with good electron transport performance. The invention also discloses a method for preparing the complexes.
Description
Invention field
The present invention relates to rhenium compound and organic electroluminescence device.
Background technology
Organic electroluminescence device (Organic Electroluminescence Devices or Organic Light-emitting Diodes, be called for short OLEDs), claim photodiode again, being to apply voltage therein and electric energy is converted into the device of luminous energy, is display screens such as ideal mobile phone, colour TV.From the Tang of Kodak in 1987 [referring to Tang, C.W.; Vanslyke, S. A.
Appl. Phys. Lett.1987,51,913] delivered since the double-deck electroluminescent of small molecules organic film (EL) device of efficient high brightness of low voltage starting, the research of electroluminescent material and device has caused the very big interest of world technology circle and industry member, and El element is generally believed to have less energy-consumption, wide viewing angle, large-area flat panel display simultaneously concurrently.
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 the transition of electron between multiplicity of the same race, and maximum efficiency has only 25%.From Forrest group in 1998 [referring to Baldo, M. A.; O ' Brien, D. F.; You, Y.; Shoustikov, A.; Sibley, S.; Thompson, M. E.; Forrest, S. R.
Nature1998
,395,151] the report electromechanical phosphorescent material be owing to simultaneously can gather in the crops singlet state and triplet exciton, make the internal quantum efficiency of OLEDs have to reach 100% potential may, the research of heavy metal electromechanical phosphorescent material is increasingly extensive [referring to (a) Bolink, H. J.; Cappelli, L.; Coronado, E.; Gr tzel, M.; Ort í, E.; Costa, R. D.; Viruela, P. M.; Nazeeruddin, M. K.
J. Am. Chem. Soc.2006,128,14786; (b) Reger, D. L.; Watson, R. P.; Smith, M. D.; Pellechia, P. J.
Organomet.2005,24,1544; (c) Wei, Q. H.; Yin, G. Q.; Zhang, L. Y.; Chen, Z. N.
Inorg. Chem.2006,45,10371].Re (I) is the transition metal ion with 6 d electronics, and the title complex that it and dipyridyl or derivatives thereof part form is (as Re (CO)
3Cl (L)) be that the MLCT luminescent ligand compound of a quasi-representative is [referring to (a) Ranjan, S.; Lin, S. Y.; Hwang, K. C.; Chi, Y.; Ching, W. L.; Liu, C. S.; Tao, Y. T.; Chien, C. H.; Peng, S. M.; Lee, G. H.
Inorg. Chem. 2003,42, and 1248; (b) Lee, J. K.; Yoo, D. S.; Handy, E. S.; Rubner, M. F. Appl. Phys. Lett.1996,69,1686.].This class title complex is owing to exist heavy atoms effect, and quantum yield can reach 100% in theory, has unique optical physics, spectrochemical property, is the good alternative materials of OLEDs luminescent layer, and very big researching value is arranged.
Yet the Re that is used for OLEDs (I) title complex of a lot of bibliographical informations takes place to bury in oblivion between triplet state-triplet state and between triplet state-polaron easily, and the carrier transmission performance of material does not reach the requirement of organic electroluminescent device OLED s yet.
Summary of the invention
The present invention has designed the four kinds of novel Re that contains the dipyridyl derivatives part (I) title complexs, promptly in dipyridyl, introduce functional group with better carrier transmission performance, as carbazole with the oxadiazole group, at intramolecule the photoelectric properties of title complex are regulated and control, itself and central ion Re (I) energy level are complementary, simultaneously also can improve Re (I) title complex, improve the performance of electroluminescent device as the carrier transport of luminescent layer material in OLEDs.
Technical scheme of the present invention is as follows:
Contain 2 of carbazole or oxadiazole group, 2 '-dipyridyl closes the title complex of rhenium, and they have following structural formula:
A kind of method for preparing above-mentioned rhenium compound, it is made up of the following step:
Synthesizing of step 1, part
1. the part of carbazolyl-containing group is synthetic
In reactor, 2 of carbazole and dibromo replacement, 2 '-dipyridyl is done under the catalyzer condition at cuprous iodide C is taken place, and the linked reaction of N key obtains 2 of carbazolyl-containing group, 2 '-dipyridyl derivatives part;
2. the part of Han oxadiazole group is synthetic
With 2 of dicarboxyl replacement, 2 '-dipyridyl and benzoyl hydrazine are at POCl
3Middle dehydration ring closure obtains 2 of Han oxadiazole group, and 2 '-dipyridyl derivatives part is replaced by benzoyl hydrazine to behind the tert.-butylbenzene formyl hydrazine, and the solubleness of product in chloroform obviously increases.
Synthesizing of step 2, title complex
With chlorination pentacarbonyl rhenium and corresponding part reflux in dry toluene, separation can obtain rhenium compound after purifying
1-
4
Rhenium compound among the present invention can be used for the luminescent layer in the electroluminescent device.Title complex wherein
1,
22, the different positions of 2 '-dipyridyl has been introduced carbazole group respectively, will be hole transport performance luminescent layer preferably.Title complex
3,
42,2 '-dipyridyl is introduced oxadiazole group respectively, will be electronic transmission performance luminescent layer preferably.
With
1H NMR, mass spectrum, ultimate analysis (C, H, N), infrared, structure that ultraviolet characterized and confirmed the title complex of these rheniums, detecting used instrument is Bruker DRX 500 type nuclear magnetic resonance analyser, Perkin-Elmer240C type elemental analyser, Bruker Autoflex II TOF/TOF spectrometer mass spectrum workstation, UV-3100 ultraviolet-visible spectrophotometer and Hitachi F4600 luminoscope.
Description of drawings
Fig. 1 a title complex chlorination three carbonyls (5,5 '-two carbazyls-2,2 '-dipyridyl) close rhenium (I) (
1), chlorination three carbonyls (4,4 '-two carbazyls-2,2 '-dipyridyl) close rhenium (I) (
2) uv-visible absorption spectra;
Fig. 1 b title complex chlorination three carbonyls (4,4 '-two (5-phenyl-1,3,4-oxadiazoles-2-yl)-2,2 '-dipyridyl) close rhenium (I) (
3), chlorination three carbonyls (4,4 '-two (5-(the 4-tertiary butyl)-phenyl-1,3,4-oxadiazoles-2-yl)-2,2 '-dipyridyl) close rhenium (I) (
4) uv-visible absorption spectra;
Fig. 2 a title complex chlorination three carbonyls (5,5 '-two carbazyls-2,2 '-dipyridyl) close rhenium (I) (
1), chlorination three carbonyls (4,4 '-two carbazyls-2,2 '-dipyridyl) close rhenium (I) (
2) emmission spectrum;
Fig. 2 b title complex chlorination three carbonyls (4,4 '-two (5-phenyl-1,3,4-oxadiazoles-2-yl)-2,2 '-dipyridyl) close rhenium (I) (
3) emmission spectrum;
Fig. 2 c title complex chlorination three carbonyls (4,4 '-two (5-(the 4-tertiary butyl)-phenyl-1,3,4-oxadiazoles-2-yl)-2,2 '-dipyridyl) close rhenium (I) (
4) emmission spectrum.
Embodiment
Title complex of the present invention can synthesize according to following equation:
Annotate: (i) CuI, 18-Crown-6, K
2CO
3, DMPU; (ii) POCl
3, reflux; (iii) Re (CO)
5Cl, toluene refluxes.
Embodiment one: chlorination three carbonyls (5,5 '-two carbazyls-2,2 '-dipyridyl) close rhenium (I) (
1), chlorination three carbonyls (4,4 '-two carbazyls-2,2 '-dipyridyl) close rhenium (I) (
2) preparation.
1.5,5 '-two carbazyls-2,2 '-dipyridyl and 4,4 '-two carbazyls-2, the preparation of 2 '-dipyridyl.
In reactor, with 9 mmol carbazoles, 3 mmol, 5,5 '-two bromo-2,2 '-dipyridyl, 0.6 mmol cuprous iodide, 0.2 mmol 18-hat-6,18 mmol salt of wormwood and 0.2 mL 1,3-dimethyl-3,4,5,6-tetrahydrochysene-2 (1H)-pyrimidine dione (DMPU) mixes, charge into nitrogen after, 235
oC heated 38 hours down.After being cooled to room temperature,, filtering and obtain throw out with the hydrochloric acid soln immersion of 1 mol, with ammoniacal liquor, water washing, use methylene dichloride and normal hexane (volume ratio is 1:1) to do elutriant then, column chromatography is purified, get light yellow solid 5,5 '-two carbazyls-2,2 '-dipyridyl.Productive rate: 36%.With 9 mmol carbazoles and 3 mmol, 4,4 '-two bromo-2, the reaction of 2 '-dipyridyl obtains 4,4 '-two carbazyls-2 of white, 2 '-dipyridyl with identical method.Productive rate: 46%.The compound warp
1H NMR, ultimate analysis, mass spectrum, the infrared checking, the result shows that structure is correct, data are as follows:
5,5 '-two carbazyls-2,2 '-dipyridyl:
1H?NMR?(CDCl
3,?500MHz):?d?9.048?(d,?2H,?
J?=?2?Hz),?8.807?(d,?2H,?
J?=?8?Hz),?8.214?(d,?4H,?
J?=?8?Hz),?8.150?(m,?2H),?7.545-7.491?(m,?8H),?7.387?(t,?4H,?
J?=?7.5?Hz).
Results of elemental analyses:
Calculated value: C (%): 83.93 H (%): 4.56 N (%): 11.51
Measured value: C (%): 83.91 H (%): 4.65 N (%): 11.54
MS(MALDI-TOF):?m/z?487.256?[M+H]
+
IR?(KBr,?cm
-1):?1594,?1490,?1238,?844,?746,?720.
4,4 '-two carbazyls-2,2 '-dipyridyl:
1H?NMR?(CDCl
3,?500?MHz)?δ?9.16?(d,?
J?=?6.1?Hz,?2H),?8.57?(d,?
J?=?1.8?Hz,?2H),?8.23?–?8.13?(m,?6H),?7.77?(d,?
J?=?8.2?Hz,?4H),?7.51?(ddd,?
J?=?26.5,?11.5,?4.1?Hz,?8H).
Results of elemental analyses:
Calculated value: C (%): 83.93 H (%): 4.56 N (%): 11.51
Measured value: C (%): 83.94 H (%): 4.51 N (%): 11.47
MS(MALDI-TOF):?m/z?487.013?[M+H]
+
IR?(KBr,?cm
-1):?1584,?1448,?1334,?1218,?740,?717,?568。
Chlorination three carbonyls (5,5 '-two carbazyls-2,2 '-dipyridyl) close rhenium (I) (
1), chlorination three carbonyls (4,4 '-two carbazyls-2,2 '-dipyridyl) close rhenium (I) (
2) preparation.
To wait 5,5 '-two carbazyls-2 of amount of substance, 2 '-dipyridyl and chlorination pentacarbonyl rhenium refluxed in dry toluene 6 hours, were cooled to room temperature, and suction filtration gets yellow solid.Use methylene dichloride (add 1%(volume ratio) methyl alcohol then) be elutriant, silica gel column chromatography is purified, chlorination three carbonyls (5,5 '-two carbazyls-2,2 '-dipyridyl) close rhenium (I) (
1).With with quadrat method with 4,4 '-two carbazyls-2, the reaction of 2 '-dipyridyl and chlorination pentacarbonyl rhenium can get chlorination three carbonyls (4,4 '-two carbazyls-2,2 '-dipyridyl) close rhenium (I) (
2).The compound warp
1H NMR, ultimate analysis, mass spectrum, the infrared checking, the result shows that structure is correct, data are as follows:
Chlorination three carbonyls (5,5 '-two carbazyls-2,2 '-dipyridyl) close rhenium (I) (
1):
1H?NMR?(DMSO-
d 6 ,?500MHz):?d9.408?(d,?2H,?
J?=?1.5?Hz),?9.179?(d,?2H,?
J?=?8.5?Hz?),?8.841?(m,?2H),?8.356?(d,?4H,?
J?=?6.5?Hz),?7.637-7.584?(m,?8H),?7.428?(t,?4H,?
J?=?6.5?Hz).
Results of elemental analyses:
Calculated value: C (%): 56.09 H (%): 2.80 N (%): 7.07
Measured value: C (%): 56.11 H (%): 2.92 N (%): 7.04
MS(MALDI-TOF):?m/z?757.166?[M-Cl]
+
IR?(KBr,?cm
-1):?2021,?1918,?1891.
Chlorination three carbonyls (4,4 '-two carbazyls-2,2 '-dipyridyl) close rhenium (I) (
2):
1H?NMR?(CDCl
3,?500?MHz)?δ?9.27?(d,?
J?=?6.0?Hz,?1H),?8.42?(s,?1H),?8.15?(d,?
J?=?7.7?Hz,?2H),?7.88?(d,?
J?=?5.0?Hz,?1H),?7.67?(d,?
J?=?8.2?Hz,?2H),?7.50?(t,?
J?=?7.4?Hz,?2H),?7.42?(t,?
J?=?7.4?Hz,?2H).
Results of elemental analyses: calculated value: C (%): 56.09 H (%): 2.80 N (%): 7.07
Measured value: C (%): 55.91 H (%): 2.79 N (%): 6.91
MS(MALDI-TOF):?m/z?757.348?[M-Cl]
+
IR?(KBr,?cm
-1):?2017,?1910,?1879。
Embodiment two: chlorination three carbonyls (4,4 '-two (5-phenyl-1,3,4-oxadiazoles-2-yl)-2,2 '-dipyridyl) close rhenium (I) (
3), chlorination three carbonyls (4,4 '-two (5-(the 4-tertiary butyl)-phenyl-1,3,4-oxadiazoles-2-yl)-2,2 '-dipyridyl) close rhenium (I) (
4) preparation.
1. 4,4 '-two (5-phenyl-1,3,4-oxadiazoles-2-yl)-2,2 '-dipyridyl and 4,4 '-two (5-(the 4-tertiary butyl)-phenyl-1,3,4-oxadiazoles-2-yl)-2, the preparation of 2 '-dipyridyl.
With 2 mmol 4,4 '-dicarboxyl-2,2 '-dipyridyl and 4 mmol benzoyl hydrazines are at 20 mL POCl
3Middle reflux 5 hours.After being cooled to room temperature, underpressure distillation goes out most of POCl
3, residuum is poured in the cold water, filter crude product.Gained crude product CH
2Cl
2(adding the 1%(volume ratio) methyl alcohol) column chromatography gets white solid 4,4 '-two (5-phenyl-1,3,4-oxadiazole-2-yl)-2,2 '-dipyridyl.With with quadrat method with 2 mmol 4,4 '-dicarboxyl-2,2 '-dipyridyl and 4 mmol can get 4,4 '-two (5-(the 4-tertiary butyl)-phenyl-1,3,4-oxadiazoles-2-yl)-2,2 '-dipyridyl to tert.-butylbenzene formyl hydrazine reaction.These compound warps
1H NMR, ultimate analysis, mass spectrum, the infrared checking, the result shows that structure is correct, data are as follows:
4,4 '-two (5-phenyl-1,3,4-oxadiazoles-2-yl)-2,2 '-dipyridyl:
1H?NMR?(CDCl
3,?500?MHz)?δ?9.42?(s,?2H),?9.25?(d,?
J?=?5.4?Hz,?2H),?8.58?(d,?
J?=?5.0?Hz?2H),?8.25?(d,?
J?=?7.8?Hz,?4H),?7.78?(t,?
J?=?7.3?Hz,?2H),?7.69?(t,?
J?=?7.6?Hz,?4H).
Results of elemental analyses:
Calculated value: C (%): 70.26 H (%): 3.63 N (%): 18.91
Measured value: C (%): 70.17 H (%): 3.66 N (%): 18.94
MS(MALDI-TOF):?m/z?445.388?[M+H]
+
IR?(KBr,?cm
-1):?1606,?1542,?1485,?1454,?1066,?723,?687.
4,4 '-two (5-(the 4-tertiary butyl)-phenyl-1,3,4-oxadiazoles-2-yl)-2,2 '-dipyridyl:
1H?NMR?(CDCl
3,?500?MHz)?δ?9.37?(s,?2H),?9.25?(d,?
J?=?5.5?Hz,?2H),?8.56?(dd,?
J?=?5.5,?1.2?Hz,?2H),?8.17?(d,?
J?=?8.5?Hz,?4H),?7.70?(d,?
J?=?8.5?Hz,?4H),?1.43?(s,?18H).
Results of elemental analyses:
Calculated value: C (%): 73.36 H (%): 5.79 N (%): 15.10
Measured value: C (%): 73.28 H (%): 5.80 N (%): 15.19
MS(MALDI-TOF):?m/z?557.463?[M+H]
+
IR?(KBr,?cm
-1):?1606,?1489,?1454,?1390,?1265,?1067,?1016,?847,?744,?716。
Chlorination three carbonyls (4,4 '-two (5-phenyl-1,3,4-oxadiazoles-2-yl)-2,2 '-dipyridyl) close rhenium (I) (
3), chlorination three carbonyls (4,4 '-two (5-(the 4-tertiary butyl)-phenyl-1,3,4-oxadiazoles-2-yl)-2,2 '-dipyridyl) close rhenium (I) (
4) preparation.
With waiting 4,4 '-two (5-phenyl-1,3,4-oxadiazole-2-yl)-2, the 2 '-dipyridyls and the chlorination pentacarbonyl rhenium of amount of substance in dry toluene, to reflux 6 hours, be cooled to room temperature, suction filtration gets yellow solid.Solid is with methylene dichloride (add 1%(volume ratio) methyl alcohol) be elutriant, silica gel column chromatography is purified, must chlorination three carbonyls (4,4 '-two (5-phenyl-1,3,4-oxadiazoles-2-yl)-2,2 '-dipyridyl) close rhenium (I) (
3).Use the same method, respectively with 4,4 '-two (5-(the 4-tertiary butyl)-phenyl-1,3,4-oxadiazoles-2-yl)-2,2 '-dipyridyl and the reaction of chlorination pentacarbonyl rhenium, can obtain chlorination three carbonyls (4,4 '-two (5-(the 4-tertiary butyl)-phenyl-1,3,4-oxadiazole-2-yl)-2,2 '-dipyridyl) close rhenium (I) (
4).These compound warps
1H NMR, ultimate analysis, mass spectrum, the infrared checking, the result shows that structure is correct, data are as follows:
Chlorination three carbonyls (4,4 '-two (5-phenyl-1,3,4-oxadiazoles-2-yl)-2,2 '-dipyridyl) close rhenium (I) (
3):
1H?NMR?(DMSO-
d 6 ,?500?MHz)?δ?9.64?(s,?2H),?9.33?(d,?
J?=?5.7?Hz,?2H),?8.44?(d,?
J?=?4.5?Hz,?2H),?8.34?(d,?
J?=?6.4?Hz,?4H),?7.73-7.77?(m,?6H).
Results of elemental analyses:
Calculated value: C (%): 46.43 H (%): 2.15 N (%): 11.20
Measured value: C (%): 46.33 H (%): 2.15 N (%): 11.12
MS(MALDI-TOF):?m/z?715.095?[M-Cl]
+.
IR?(KBr,?cm
-1):?2019,?1906.
Chlorination three carbonyls (4,4 '-two (5-(the 4-tertiary butyl)-phenyl-1,3,4-oxadiazoles-2-yl)-2,2 '-dipyridyl) close rhenium (I) (
4):
1H?NMR?(CDCl
3,?500?MHz)?δ?9.34?(d,?
J?=?5.7?Hz,?2H),?9.30?(s,?2H),?8.28?(d,?
J?=?5.5?Hz,?2H),?8.16?(d,?
J?=?8.3?Hz,?4H),?7.70?(d,?
J?=?8.4?Hz,?4H),?1.43?(s,?18H).
Results of elemental analyses:
Calculated value: C (%): 51.53 H (%): 3.74 N (%): 9.74
Measured value: C (%): 51.51 H (%): 3.84 N (%): 9.78
MS(MALDI-TOF):?m/z?827.065?[M-Cl]
+
IR?(KBr,?cm
-1):?2023,?1927,?1902。
Embodiment four: title complex chlorination three carbonyls of the present invention (5,5 '-two carbazyls-2,2 '-dipyridyl) close rhenium (I) (
1), chlorination three carbonyls (4,4 '-two carbazyls-2,2 '-dipyridyl) close rhenium (I) (
2), chlorination three carbonyls (4,4 '-two (5-phenyl-1,3,4-oxadiazoles-2-yl)-2,2 '-dipyridyl) close rhenium (I) (
3) and chlorination three carbonyls (4,4 '-two (5-(the 4-tertiary butyl)-phenyl-1,3,4-oxadiazoles-2-yl)-2,2 '-dipyridyl) close rhenium (I) (
4) fluorescence characterize.
Testing tool is a Hitachi F4600 luminoscope, and the title complex of above-mentioned rhenium is dissolved in the methylene dichloride (10
-4M) measure, at ambient temperature, emission peak positions is respectively:
Chlorination three carbonyls (5,5 '-two carbazyls-2,2 '-dipyridyl) close rhenium (I) (
1):
l
Em,
Max, nm 622(sees accompanying drawing 2a);
Chlorination three carbonyls (4,4 '-two carbazyls-2,2 '-dipyridyl) close rhenium (I) (
2):
l
Em,
Max, nm 620(sees accompanying drawing 2a);
Chlorination three carbonyls (4,4 '-two (5-phenyl-1,3,4-oxadiazoles-2-yl)-2,2 '-dipyridyl) close rhenium (I) (
3)
l
Em,
Max, nm 593(sees accompanying drawing 2b);
Chlorination three carbonyls (4,4 '-two (5-(the 4-tertiary butyl)-phenyl-1,3,4-oxadiazoles-2-yl)-2,2 '-dipyridyl) close rhenium (I) (
4)
l
Em,
Max, nm 666(sees accompanying drawing 2c).
Claims (3)
1. contain 2 of carbazole or oxadiazole group, 2 '-dipyridyl closes the title complex of rhenium, it is characterized in that: they have following structure:
。
2. a method for preparing the title complex of the described rhenium of claim 1 is characterized in that it comprises the following steps:
Synthesizing of step 1, part
1). synthesizing of the part of carbazolyl-containing group
In reactor, 2 of carbazole and dibromo replacement, 2 '-dipyridyl is done under the catalyzer condition at cuprous iodide C is taken place, and the linked reaction of N key obtains 2 of carbazolyl-containing group, 2 '-dipyridyl derivatives part;
2). contain part synthetic of oxadiazole group
With 2 of dicarboxyl replacement, 2 '-dipyridyl and benzoyl hydrazine are at POCl
3Middle dehydration ring closure obtains 2 of Han oxadiazole group, 2 '-dipyridyl derivatives part;
3) benzoyl hydrazine is replaced with to tert.-butylbenzene formyl hydrazine and benzoyl hydrazine at POCl
3Middle dehydration ring closure obtains containing 2 of Shu Ding oxadiazole group, 2 '-dipyridyl derivatives part;
Synthesizing of step 2, title complex
With chlorination pentacarbonyl rhenium and corresponding part reflux in dry toluene, separation can obtain the described rhenium compound of claim 1 after purifying
1-
4
3. the application of the title complex of the described rhenium of claim 1 in the preparation electroluminescent device.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690292A (en) * | 2012-05-24 | 2012-09-26 | 南京信息工程大学 | Substituted tricarbonyl chloride 2, 2', 4, 2'-terpyridyl rhenium (I) coordination compound, preparation method and functions thereof |
| CN102702269A (en) * | 2012-05-24 | 2012-10-03 | 南京信息工程大学 | Carbazole group-containing bipyridino [3, 2-a:2', 3'-c] phenazine tricarbonyl rhenium (I) complexes, preparation method and application thereof |
| CN102891258A (en) * | 2011-07-18 | 2013-01-23 | 吉林师范大学 | Re(I) complex phosphor material-based organic light detector |
| CN108822294A (en) * | 2018-07-09 | 2018-11-16 | 国家纳米科学中心 | A kind of more pyridyl group polycarbazole polymer and its preparation method and application |
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| CN101215300A (en) * | 2008-01-16 | 2008-07-09 | 南京大学 | Rhenium(I) tricarbonyl polypyridyl complex and its preparation method and use |
| CN101698672A (en) * | 2009-11-06 | 2010-04-28 | 南京大学 | Tricarbonal rhenium (I) complexes containing carrier-transporting groups (oxadiazole or carbazole), preparation method and application thereof |
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| CN101215300A (en) * | 2008-01-16 | 2008-07-09 | 南京大学 | Rhenium(I) tricarbonyl polypyridyl complex and its preparation method and use |
| CN101698672A (en) * | 2009-11-06 | 2010-04-28 | 南京大学 | Tricarbonal rhenium (I) complexes containing carrier-transporting groups (oxadiazole or carbazole), preparation method and application thereof |
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| CN102891258A (en) * | 2011-07-18 | 2013-01-23 | 吉林师范大学 | Re(I) complex phosphor material-based organic light detector |
| CN102891258B (en) * | 2011-07-18 | 2015-07-08 | 吉林师范大学 | Re(I) complex phosphor material-based organic light detector |
| CN102690292A (en) * | 2012-05-24 | 2012-09-26 | 南京信息工程大学 | Substituted tricarbonyl chloride 2, 2', 4, 2'-terpyridyl rhenium (I) coordination compound, preparation method and functions thereof |
| CN102702269A (en) * | 2012-05-24 | 2012-10-03 | 南京信息工程大学 | Carbazole group-containing bipyridino [3, 2-a:2', 3'-c] phenazine tricarbonyl rhenium (I) complexes, preparation method and application thereof |
| CN102702269B (en) * | 2012-05-24 | 2014-11-26 | 南京信息工程大学 | Carbazole group-containing bipyridino [3, 2-a:2', 3'-c] phenazine tricarbonyl rhenium (I) complexes, preparation method and application thereof |
| CN102690292B (en) * | 2012-05-24 | 2014-12-03 | 南京信息工程大学 | Substituted tricarbonyl chloride 2, 2', 4, 2'-terpyridyl rhenium (I) coordination compound, preparation method and application thereof |
| CN108822294A (en) * | 2018-07-09 | 2018-11-16 | 国家纳米科学中心 | A kind of more pyridyl group polycarbazole polymer and its preparation method and application |
| CN108822294B (en) * | 2018-07-09 | 2020-12-01 | 国家纳米科学中心 | Polypyridyl polycarbazole polymer and preparation method and application thereof |
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