CN102690292B - Substituted tricarbonyl chloride 2, 2', 4, 2'-terpyridyl rhenium (I) coordination compound, preparation method and application thereof - Google Patents
Substituted tricarbonyl chloride 2, 2', 4, 2'-terpyridyl rhenium (I) coordination compound, preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a substituted tricarbonyl 2, 2', 4, 2'- terpyridyl rhenium (I) coordination compound, a preparation method and functions thereof. The preparation method for the rhenium (I) coordination compound includes steps of preparing a ligand and preparing the coordination compound. The rhenium (I) coordination compound has the advantages that triplet state annihilation is reduced, charge carrier transmission performance is improved, and an organic light-emitting device made of the provided rhenium (I) coordination compound can be simplified in structure and improved in performance. The rhenium (I) coordination compound is simple in synthesizing, quite high in yield, easy to purify and stable in property in the air.
Description
Technical field
The present invention relates to the title complex of rhenium, also include organic electroluminescence devices.
Background technology
Organic electroluminescence device (Organic Light-emitting Diodes, be called for short OLEDs), claim again photodiode, be that realization is luminous energy (organic electroluminescent by electric energy conversion in device, Organic Electroluminescence, is called for short EL or OEL) device.Compared 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 the 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 more than ten years, the organic electroluminescent taking flat pannel display as one of major objective has stepped into industrialization phase substantially.
Luminescent material is the core component of OLEDs device, long lifetime phosphorescent transmitting generally come from long-life first excite or excited triplet state to the transition of electron of ground state singlet 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 forbids, therefore 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.But the rhenium compound of bibliographical information has longer lifetime of excited state, easily occurs 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 five rheniums, has reduced between triplet state and has buried in oblivion, and improves carrier transmission performance, for being manufactured with organic electroluminescence devices, and the tender structure of enough simplifying device, the performance of raising device.
Chlorination three carbonyls 2,2 ', 4 that the invention provides a kind of replacement, 2 '-terpyridyl closes rhenium (I) title complex, has following structure:
，
Wherein
。
The present invention also provides a kind of chlorination three carbonyls 2,2 ', 4 of preparing described replacement, and 2 '-terpyridyl closes the method for rhenium (I) title complex, and concrete steps are as follows:
(1) preparation of part:
By carbazole, pentanoic, two (the 4-tertiary butyl) aniline, (N phenyl-1-naphthalene) amine or (N phenyl-2-naphthalene) amine 2.5～3.5 mmol and 4-Cl-2,2 ', 4,2 '-tri-pyridine 0.6～1.0 mmol, potassium tert.-butoxide 1.5～2.5 mmol and 1,3-dimethyl-3,4,5,6-tetrahydrochysene-2 (1H)-pyrimidine dione 0.08～0.12 mL mixes, under pure nitrogen gas environment, 190
oc～220
oc reaction 10～15 hours; After reaction finishes, reaction mixture is cooled to 20
oc-25
oc, extracts part 4-carbazole-2,2 '; 4,2 '-terpyridyl, pentanoic-2,2 '; 4,2 '-tri-pyridines, 4-bis-(the 4-tertiary butyl) anilino-2,2 '; 4,2 '-terpyridyl, 4-(N phenyl-1-naphthalene) amido-2,2 '; 4,2 '-terpyridyl or 4-(N phenyl-2-naphthalene) amido-2,2 '; 4,2 '-terpyridyl;
(2) preparation of title complex:
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 4-8 hour, after reaction finishes, solvent in reaction mixture is distilled out, gained yellow solid obtains described title complex chlorination three carbonyls (4-carbazole-2 after purifying, 2 ', 4, 2 '-terpyridyl) close rhenium (I), chlorination three carbonyls (4-hexichol amido-2, 2 ', 4, 2 '-terpyridyl) close rhenium (I), chlorination three carbonyls (4-bis-(the 4-tertiary butyl) anilino-2, 2 ', 4, 2 '-terpyridyl) close rhenium (I), chlorination three carbonyls (4-N phenyl-1-naphthalene) amido-2, 2 ', 4, 2 '-terpyridyl) close rhenium (I) or chlorination three carbonyls (4-(N phenyl-2-naphthalene) amido-2, 2 ', 4, 2 '-terpyridyl) close rhenium (I).
Described in step (1), extracting method is: described reaction mixture hydrochloric acid soln is soaked, after leaving standstill, cross leaching filter residue, use successively ammoniacal liquor, water washing, then purify with column chromatography, after being desolventized, the elutriant steaming that contains described part obtains part 4-carbazole-2,2 ', 4,2 '-terpyridyl, pentanoic-2,2 ', 4,2 '-tri-pyridines, 4-bis-(the 4-tertiary butyl) anilino-2,2 ', 4,2 '-terpyridyl, 4-(N phenyl-1-naphthalene) amido-2,2 ', 4,2 '-terpyridyl or 4-(N phenyl-2-naphthalene) amido-2,2 ', 4,2 '-terpyridyl; The filler using in described column chromatography is silica gel, and eluent is the mixed solvent of sherwood oil and ethyl acetate, and the volume ratio of described sherwood oil and ethyl acetate is 1:3.
The method of purifying described in step (2) is: adopt column chromatography, filler is silica gel, eluent is the mixed solution of ethyl acetate and sherwood oil, wherein add the triethylamine of described mixed solution 5% volume, the volume ratio of described ethyl acetate and sherwood oil is 2:1, after the elutriant steaming that contains described title complex is desolventized, obtains described title complex.
In the time using carbazole to react in step (1), obtain part 4-carbazole-2,2 ', 4,2 '-terpyridyl, through step (2), reaction obtains title complex chlorination three carbonyls (4-carbazole-2,2 ', 4,2 '-terpyridyl) and closes rhenium (I); In the time using pentanoic to react in step (1), obtain part pentanoic-2,2 ', 4,2 '-tri-pyridines, through step (2), reaction obtains title complex chlorination three carbonyls (4-hexichol amido-2,2 ', 4,2 '-terpyridyl) and closes rhenium (I); When using two (the 4-tertiary butyl) aniline to obtain part 4-bis-(the 4-tertiary butyl) anilino-2 while reaction in step (1), 2 ', 4,2 '-terpyridyl, through step (2), reaction obtains title complex chlorination three carbonyls (4-bis-(the 4-tertiary butyl) anilino-2,2 ', 4,2 '-terpyridyl) close rhenium (I); When using (N phenyl-1-naphthalene) amine to obtain part 4-(N phenyl-1-naphthalene while reaction in step (1)) amido-2,2 ', 4,2 '-terpyridyl, through step (2), reaction obtains title complex chlorination three carbonyls (4-N phenyl-1-naphthalene) amido-2,2 ', 4,2 '-terpyridyl) close rhenium (I); When using (N phenyl-2-naphthalene) amine to obtain part 4-(N phenyl-2-naphthalene while reaction in step (1)) amido-2,2 ', 4,2 '-terpyridyl, through step (2), reaction obtains title complex chlorination three carbonyls (4-(N phenyl-2-naphthalene) amido-2,2 ', 4,2 '-terpyridyl) close rhenium (I).
The present invention also provides chlorination three carbonyls 2,2 ', 4 of described replacement, and 2 '-terpyridyl closes rhenium (I) title complex and applies being manufactured with in organic electroluminescence devices.
the present invention compared to existing technology tool has the following advantages:
The present invention is from molecular designing and device preparation, synthesized five contain carrier transport group (carbazole, pentanoic, to di-t-butyl pentanoic, phenyl naphthalidine, phenyl 2-naphthylamines) based on 2,2 ', 4, three rhenium carbonyls (I) title complex of 2 '-terpyridyl derivative, regulates and controls the photoelectric properties of title complex at intramolecule.Due to space steric effect, reduce 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.
Three rhenium carbonyls of the present invention (I) title complex is synthetic simple, productive rate is higher, be easy to purify, 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.
Brief description of the drawings
Fig. 1 title complex chlorination three carbonyls (4-carbazole-2, 2 ', 4, 2 '-terpyridyl) close rhenium (I) (Re1), chlorination three carbonyls (4-hexichol amido-2, 2 ', 4, 2 '-terpyridyl) close rhenium (I) (Re2), chlorination three carbonyls (4-bis-(the 4-tertiary butyl) anilino-2, 2 ', 4, 2 '-terpyridyl) close rhenium (I) (Re3), chlorination three carbonyls (4-(N phenyl-1-naphthalene) amido-2, 2 ', 4, 2 '-terpyridyl) close rhenium (I) (Re4), chlorination three carbonyls (4-(N phenyl-2-naphthalene) amido-2, 2 ', 4, 2 '-terpyridyl) close (Re5) uv-visible absorption spectra in dichloromethane solution of rhenium (I).
Fig. 2 title complex chlorination three carbonyls (4-carbazole-2, 2 ', 4, 2 '-terpyridyl) close rhenium (I) (Re1), chlorination three carbonyls (4-hexichol amido-2, 2 ', 4, 2 '-terpyridyl) close rhenium (I) (Re2), chlorination three carbonyls (4-bis-(the 4-tertiary butyl) anilino-2, 2 ', 4, 2 '-terpyridyl) close rhenium (I) (Re3), chlorination three carbonyls (4-(N phenyl-1-naphthalene) amido-2, 2 ', 4, 2 '-terpyridyl) close rhenium (I) (Re4), chlorination three carbonyls (4-(N phenyl-2-naphthalene) amido-2, 2 ', 4, 2 '-terpyridyl) close (Re5) excitation and emission spectra in dichloromethane solution of rhenium (I).
Fig. 3 title complex chlorination three carbonyls (4-carbazole-2, 2 ', 4, 2 '-terpyridyl) close rhenium (I) (Re1), chlorination three carbonyls (4-hexichol amido-2, 2 ', 4, 2 '-terpyridyl) close rhenium (I) (Re2), chlorination three carbonyls (4-bis-(the 4-tertiary butyl) anilino-2, 2 ', 4, 2 '-terpyridyl) close rhenium (I) (Re3), chlorination three carbonyls (4-(N phenyl-1-naphthalene) amido-2, 2 ', 4, 2 '-terpyridyl) close rhenium (I) (Re4), chlorination three carbonyls (4-(N phenyl-2-naphthalene) amido-2, 2 ', 4, 2 '-terpyridyl) close rhenium (I) (Re5) at the emmission spectrum of solid state.
Embodiment
Embodiment mono-: the preparation of part and structure verification
Part is respectively: 4-carbazole-2, and 2 ', 4,2 '-terpyridyl (
l1), 4-hexichol amido-2,2 ', 4,2 '-terpyridyl (
l2), 4-bis-(the 4-tertiary butyl) anilino-2,2 ', 4,2 '-terpyridyl (
l3), 4-(N phenyl-1-naphthalene) amido-2,2 ', 4,2 '-terpyridyl (
l4), 4-(N phenyl-2-naphthalene) amido-2,2 ', 4,2 '-terpyridyl (
l5).
1. the preparation method of part: in reactor, by carbazole, pentanoic, two (the 4-tertiary butyl) aniline, (N phenyl-1-naphthalene) amine or (N phenyl-2-naphthalene) amine (3.0 mmol) and 4-Cl-2,2 ', 4,2 '-tri-pyridines (0.22 g, 0.82 mmol), potassium tert.-butoxide (0.22 g, 2.0 mmol) and 1,3-dimethyl-3,4,5,6-tetrahydrochysene-2 (1H)-pyrimidine dione (DMPU) (0.1 mL) mixes, under pure nitrogen gas environment, 205
oc reacts 10-15 hour, after reaction finishes, reaction mixture is cooled to 20
oc-25
oC, extract part 4-carbazole-2, 2 ', 4, (code name is L1 to 2 '-terpyridyl, obtain 0.12 g, 39%) or pentanoic-2 productive rate:, 2 ', 4, ((code name is L2 to 2 '-tri-pyridines, obtain 0.16 g, productive rate: 50%), 4-bis-(the 4-tertiary butyl) anilino-2, 2 ', 4, (code name is L3 to 2 '-terpyridyl, obtain 0.19 g, productive rate: 51%), 4-(N phenyl-1-naphthalene) amido-2, 2 ', 4, (code name is L4 to 2 '-terpyridyl, obtain 0.17 g, productive rate: 34%), 4-(N phenyl-2-naphthalene) amido-2, 2 ', 4, (code name is L5 to 2 '-terpyridyl, obtain 0.09 g, productive rate: 22%).
Product extracting method is: by described hydrochloric acid soln (1 mol/L) immersion for reaction mixture, after leaving standstill, cross leaching filter residue, use successively ammoniacal liquor, water washing, then purify with column chromatography, after the elutriant steaming that contains described part is desolventized, after desolventizing, steaming must obtain white solid L1, L2, L3, L4 or L5; In described column chromatography, use filler for silica gel, eluent is the mixed solvent of sherwood oil and ethyl acetate, and the volume ratio of described sherwood oil and ethyl acetate is 1:3.
In the time using carbazole to react in step (1), obtain part 4-carbazole-2,2 ', 4,2 '-terpyridyl; In the time using pentanoic to react in step (1), obtain part pentanoic-2,2 ', 4,2 '-tri-pyridines; When using two (the 4-tertiary butyl) aniline to obtain part 4-bis-(the 4-tertiary butyl) anilino-2,2 ', 4,2 '-terpyridyl while reaction in step (1); When using (N phenyl-1-naphthalene) amine to obtain part 4-(N phenyl-1-naphthalene while reaction in step (1)) amido-2,2 ', 4,2 '-terpyridyl; When using (N phenyl-2-naphthalene) amine to obtain part 4-(N phenyl-2-naphthalene while reaction in step (1)) amido-2,2 ', 4,2 '-terpyridyl.
2. the structure verification of part
ligand L 1:
M.p.(fusing point): 263 ~ 266
oc.
1H?NMR?(CDCl
3,?500MHz):?δ?8.83?(s,?2H),?8.80?–?8.70?(m,?4H),?8.19?(d,?J?=?7.6?Hz,?2H),?7.94?(t,?J?=?7.2?Hz,?2H),?7.76?(d,?J?=?8.1?Hz,?2H),?7.52?(s,?2H),?7.39?(t,?J?=?12.3?Hz,?4H)?ppm.
Results of elemental analyses: calculated value (%): C, 81.39 H, 4.55 N, 14.06
Measured value (%): C, 81.41 H, 4.63 N, 14.04
MS?(ESI):?m/z?399.44?[M+H]
+。
ligand L 2:
M.p.(fusing point): 213 ~ 218
oc.
1H?NMR?(CDCl
3,?500MHz):?δ?8.60?(dd,?J?=?10.6,?6.1?Hz,?4H),?8.02?(s,?2H),?7.84?(s,?2H),?7.39?(s,?4H),?7.28?(d,?J?=?8.4?Hz,?6H),?7.22?(s,?2H)?ppm.
Results of elemental analyses: calculated value (%): C, 80.98 H, 5.03 N, 13.84
Measured value (%): C, 80.84 H, 5.03 N, 13.99
MS?(ESI):?m/z?401.51?[M+H]
+.
ligand L 3:
M.p.(fusing point): 208 ~ 213
oc.
1H?NMR?(CDCl
3,?500MHz):?δ?8.62?(s,?2H),?8.56?(s,?2H),?7.95?(s,?2H),?7.85?(s,?2H),?7.38?(s,?4H),?7.33?–?7.29?(m,?2H),?7.20?(s,?4H),?1.36?(s,?18H)?ppm.
Results of elemental analyses: calculated value (%): C, 81.99 H, 7.08 N, 10.93
Measured value (%): C, 81.97 H, 7.07 N, 10.89
MS?(ESI):?m/z?513.64?[M+H]
+.
ligand L 4:
M.p.(fusing point): 237 ~ 239
oc.
1H?NMR?(CDCl
3,?500MHz):?δ?8.56?(t,?J?=?7.3?Hz,?4H),?8.01?(d,?J?=?8.5?Hz,?1H),?7.92?(q,?J?=?7.9?Hz,?4H),?7.81?(td,?J?=?7.8,?1.5?Hz,?2H),?7.57?(t,?J?=?7.7?Hz,?1H),?7.54?–?7.47?(m,?2H),?7.40?(t,?J?=?7.4?Hz,?1H),?7.32?(dt,?J?=?15.7,?7.8?Hz,?4H),?7.26?(dd,?J?=?6.4,?5.1?Hz,?2H),?7.14?(t,?J?=?7.1?Hz,?1H)?ppm.
Results of elemental analyses: calculated value (%): C, 82.64 H, 4.92 N, 12.44
Measured value (%): C, 82.78 H, 4.95 N, 12.42
MS?(ESI):?m/z?451.58?[M+H]
+.
part
l5:
M.p.(fusing point): 210 ~ 212
oc.
1H?NMR?(CDCl
3,?500MHz):?δ?8.59?(s,?4H),?8.09?(s,?2H),?7.90?–?7.81?(m,?4H),?7.74?–?7.69?(m,?1H),?7.65?(s,?1H),?7.44?(d,?J?=?38.5?Hz,?5H),?7.30?(d,?J?=?16.7?Hz,?4H),?7.23?(s,?1H)?ppm.
Results of elemental analyses: calculated value (%): C, 82.64 H, 4.92 N, 12.44
Measured value (%): C, 82.69 H, 5.06 N, 12.41
MS?(ESI):?m/z?451.56?[M+H]
+.
Above-mentioned each part process
1h-NMR, ultimate analysis, mass spectrum verify, result shows that structure is correct.
Embodiment bis-: the preparation of title complex and structure verification
Title complex is that chlorination three carbonyls (4-carbazole-2,2 ', 4,2 '-terpyridyl) close rhenium (I) (code name is made as
re1), chlorination three carbonyls (4-hexichol amido-2,2 ', 4,2 '-terpyridyl) close rhenium (I) (code name are made as
re2), (code name is made as chlorination three carbonyls (4-bis-(the 4-tertiary butyl) anilino-2,2 ', 4,2 '-terpyridyl) to close rhenium (I)
re3), chlorination three carbonyls (4-(N phenyl-1-naphthalene) amido-2,2 ', 4,2 '-terpyridyl) (code name is made as to close rhenium (I)
re4), chlorination three carbonyls (4-(N phenyl-2-naphthalene) amido-2,2 ', 4,2 '-terpyridyl) (code name is made as to close rhenium (I)
re5).
1. the preparation of title complex
By each part respectively with chlorination pentacarbonyl rhenium (i.e. (Re (CO)
5cl) mix (0.10 mmol) according to equimolar ratio example, in dry toluene (30 mL), be warming up to 110
oc back flow reaction 6 hours, after reaction finishes, solvent in reaction mixture is distilled out, and gained yellow solid obtains title complex Re1(productive rate and reaches 41% after purifying), Re2 (productive rate reaches 68%), Re3 (productive rate reaches 31%), Re4 (productive rate reaches 37%) or Re5 (productive rate reaches 45%).
The method of above-mentioned purification is: adopt column chromatography, filler is silica gel, eluent is the mixed solution of ethyl acetate and sherwood oil, wherein add the triethylamine of described mixed solution 5% volume, the volume ratio of described ethyl acetate and sherwood oil is 2:1, after the elutriant steaming that contains described title complex is desolventized, obtains several faint yellow solid product Re1-ReL5.
When using part 4-carbazole-2 in step (2), 2 ', 4,2 '-terpyridyl, reaction obtains title complex chlorination three carbonyls (4-carbazole-2,2 ', 4,2 '-terpyridyl) and closes rhenium (I); When using part pentanoic-2 in step (2), 2 ', 4,2 '-tri-pyridines, reaction obtains title complex chlorination three carbonyls (4-hexichol amido-2,2 ', 4,2 '-terpyridyl) and closes rhenium (I); When using part 4-bis-(the 4-tertiary butyl) anilino-2 in step (2), 2 ', 4,2 '-terpyridyl, reaction obtains title complex chlorination three carbonyls (4-bis-(the 4-tertiary butyl) anilino-2,2 ', 4,2 '-terpyridyl) and closes rhenium (I); When using part 4-(N phenyl-1-naphthalene in step (2)) amido-2,2 ', 4,2 '-terpyridyl, reaction obtains title complex chlorination three carbonyls (4-N phenyl-1-naphthalene) amido-2,2 ', 4,2 '-terpyridyl) close rhenium (I); When using part 4-(N phenyl-2-naphthalene in step (2)) amido-2,2 ', 4,2 '-terpyridyl, reaction obtains title complex chlorination three carbonyls (4-(N phenyl-2-naphthalene) amido-2,2 ', 4,2 '-terpyridyl) close rhenium (I).
2. the structure verification of title complex
title complex Re1:
M.p.(fusing point): 263 ~ 266
oc.
1H?NMR?(500?MHz,?CDCl
3)?δ?9.15?(s,?1H),?8.89?(s,?1H),?8.47?(s,?1H),?8.21?(s,?1H),?8.11?(d,?J?=?32.0?Hz,?6H),?7.74?(s,?2H),?7.59?(s,?2H),?7.52?(s,?2H),?7.41?(s,?2H)?ppm.
Results of elemental analyses: calculated value (%): C, 51.17 H, 2.58 N, 7.96
Measured value (%): C, 51.13 H, 2.60 N, 7.99
MS?(MALDI-TOF):?m/z.?669.961?[M-Cl]
+.
title complex Re2:
M.p.(fusing point): 272 ~ 275
oc.
1H?NMR?(500?MHz,?CDCl
3)?δ?9.06?(s,?1H),?8.75?(s,?1H),?7.91?(d,?J?=?38.5?Hz,?3H),?7.75?(s,?1H),?7.49?(s,?7H),?7.35?(s,?6H),?7.01?(s,?1H)?ppm.
Results of elemental analyses: calculated value (%): C, 51.03 H, 2.85 N, 7.93
Measured value (%): C, 50.98 H, 2.87 N, 7.95
MS?(MALDI-TOF):?m/z.?671.638?[M-Cl]
+.
title complex Re3:
M.p.(fusing point): >300
oc.
1H?NMR?(500?MHz,?CDCl
3)?δ?9.07?(d,?J?=?5.1?Hz,?1H),?8.76?(d,?J?=?4.5?Hz,?1H),?7.95?(t,?J?=?7.4?Hz,?1H),?7.86?(t,?J?=?7.1?Hz,?1H),?7.80?(d,?J?=?7.7?Hz,?1H),?7.74?(d,?J?=?8.1?Hz,?1H),?7.54?–?7.40?(m,?7H),?7.24?(t,?J?=?11.3?Hz,?4H),?6.98?(d,?J?=?2.3?Hz,?1H),?1.37?(s,?18H)?ppm.
Results of elemental analyses: calculated value (%): C, 55.77 H, 4.33 N, 6.85
Measured value (%): C, 55.73 H, 4.36 N, 6.88
MS?(MALDI-TOF):?m/z.?783.753?[M-Cl]
+.
title complex Re4:
M.p.(fusing point): 215 ~ 218
oc.
1H?NMR?(500?MHz,?CDCl
3)?δ?9.04?(d,?J?=?4.6?Hz,?1H),?8.72?(dd,?J?=?14.3,?4.1?Hz,?1H),?7.98?(td,?J?=?16.8,?8.1?Hz,?4H),?7.83?(td,?J?=?11.8,?4.9?Hz,?2H),?7.75?(t,?J?=?8.4?Hz,?1H),?7.64?–?7.53?(m,?5H),?7.43?(dd,?J?=?15.7,?4.9?Hz,?8H)?ppm.
Results of elemental analyses: calculated value (%): C, 54.00 H, 2.93 N, 7.41
Measured value (%): C, 53.95 H, 2.97 N, 7.46
MS?(MALDI-TOF):?m/z.?720.771?[M-Cl]
+.
title complex Re5:
M.p.(fusing point): 214 ~ 217
oc.
1H?NMR?(500?MHz,?CDCl
3)?δ?9.07?(d,?J?=?5.0?Hz,?1H),?8.73?(d,?J?=?4.3?Hz,?1H),?7.97?(d,?J?=?8.7?Hz,?1H),?7.91?(s,?2H),?7.86?–?7.77?(m,?4H),?7.73?(d,?J?=?8.1?Hz,?1H),?7.56?(dd,?J?=?11.1,?6.5?Hz,?4H),?7.51?–?7.47?(m,?2H),?7.45?–?7.36?(m,?6H)?ppm.
Results of elemental analyses: calculated value (%): C, 54.00 H, 2.93 N, 7.41
Measured value (%): C, 53.97 H, 2.94 N, 7.45
MS?(MALDI-TOF):?m/z.?720.772?[M-Cl]
+.
Each title complex warp
1h-NMR, ultimate analysis, mass spectrum checking, result shows that structure is correct.
The Fluorescent Characterization of embodiment tri-title complexs
Title complex comprises: chlorination three carbonyls (4-carbazole-2, 2 ', 4, 2 '-terpyridyl) close rhenium (I) Re1), chlorination three carbonyls (4-hexichol amido-2, 2 ', 4, 2 '-terpyridyl) close rhenium (I) (Re2), chlorination three carbonyls (4-bis-(the 4-tertiary butyl) anilino-2, 2 ', 4, 2 '-terpyridyl) close rhenium (I) (Re3), chlorination three carbonyls (4-(N phenyl-1-naphthalene) amido-2, 2 ', 4, 2 '-terpyridyl) close rhenium (I) (Re4) and chlorination three carbonyls (4-(N phenyl-2-naphthalene) amido-2, 2 ', 4, 2 '-terpyridyl) close rhenium (I) (Re5).
Taking methylene dichloride as solvent, it is 10 that the title complex of above-mentioned rhenium is made respectively to concentration
-3the solution of M.At room temperature condition, measure respectively the lower column data of each title complex:
Chlorination three carbonyls (4-carbazole-2,2 ', 4,2 '-terpyridyl) close rhenium (I) (
re1)
L
abs, nm 224,277,295,397 (seeing Fig. 1)
L
ex,
max, nm 459,578 (seeing Fig. 2)
L
em,
max, nm 551 (seeing Fig. 3)
Chlorination three carbonyls (4-hexichol amido-2,2 ', 4,2 '-terpyridyl) close rhenium (I) (
re2)
L
abs, nm 219,282,380 (seeing Fig. 1)
L
ex,
max, nm 444,600 (seeing Fig. 2)
L
em,
max, nm 554 (Fig. 3)
Chlorination three carbonyls (4-bis-(the 4-tertiary butyl) anilino-2,2 ', 4,2 '-terpyridyl) close rhenium (I) (
re3)
L
abs, nm 220,256,281,383 (seeing Fig. 1)
L
ex,
max, nm 454,593 (seeing Fig. 2)
L
em,
max, nm 532 (seeing Fig. 3)
Chlorination three carbonyls (4-(N phenyl-1-naphthalene) amido-2,2 ', 4,2 '-terpyridyl) close rhenium (I) (
re4)
L
abs, nm 220,279,378 (seeing Fig. 1)
L
ex,
max, nm 442,601 (seeing Fig. 2)
L
em,
max, nm 546 (seeing Fig. 3)
Chlorination three carbonyls (4-(N phenyl-2-naphthalene) amido-2,2 ', 4,2 '-terpyridyl) close rhenium (I) (
re5)
L
abs, nm 219,255,280,384 (seeing Fig. 1)
L
ex,
max, nm 450,605 (seeing Fig. 2)
L
em,
max, nm 551 (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 (5)
1. chlorination three carbonyls 2,2 ', 4 of a replacement, 2 '-terpyridyl closes rhenium (I) title complex, has following structure:
，
Wherein
。
2. prepare chlorination three carbonyls 2,2 ', 4 that replace described in claim 1 for one kind, 2 '-terpyridyl closes the method for rhenium (I) title complex, and concrete steps are as follows:
(1) preparation of part:
By carbazole, pentanoic, two (the 4-tertiary butyl) aniline, (N-phenyl-1-naphthalene) amine or (N-phenyl-2-naphthalene) amine 2.5～3.5 mmol and 4-Cl-2,2 ', 4,2 '-tri-pyridine 0.6～1.0 mmol, potassium tert.-butoxide 1.5～2.5 mmol and 1,3-dimethyl-3,4,5,6-tetrahydrochysene-2 (1H)-pyrimidine dione 0.08～0.12 mL mixes, under pure nitrogen gas environment, at 190 DEG C-220 DEG C reaction 10-15 hour; After reaction finishes, reaction mixture is cooled to 20 DEG C-25 DEG C, extracts part 4-carbazole-2; 2 ', 4,2 '-terpyridyl, 4-pentanoic-2; 2 ', 4,2 '-tri-pyridines, 4-bis-(the 4-tertiary butyl) anilino-2; 2 ', 4,2 '-terpyridyl, 4-(N-phenyl-1-naphthalene) amido-2; 2 ', 4,2 '-terpyridyl or 4-(N-phenyl-2-naphthalene) amido-2; 2 ', 4,2 '-terpyridyl;
(2) preparation of title complex:
Each part is mixed according to equimolar ratio example with chlorination pentacarbonyl rhenium respectively, in dry toluene, be warming up to 100～120 DEG C of back flow reaction 4-8 hour, after reaction finishes, solvent in reaction mixture is distilled out, gained yellow solid obtains described title complex chlorination three carbonyls (4-carbazole-2 after purifying, 2 ', 4, 2 '-terpyridyl) close rhenium (I), chlorination three carbonyls (4-hexichol amido-2, 2 ', 4, 2 '-terpyridyl) close rhenium (I), chlorination three carbonyls (4-bis-(the 4-tertiary butyl) anilino-2, 2 ', 4, 2 '-terpyridyl) close rhenium (I), chlorination three carbonyls (4-(N-phenyl-1-naphthalene) amido-2, 2 ', 4, 2 '-terpyridyl) close rhenium (I) or chlorination three carbonyls (4-(N-phenyl-2-naphthalene) amido-2, 2 ', 4, 2 '-terpyridyl) close rhenium (I).
3. chlorination three carbonyls 2 that preparation replaces according to claim 2, 2 ', 4, 2 '-terpyridyl closes the method for rhenium (I) title complex, it is characterized in that the method for extracting part described in step (1) is: described reaction mixture hydrochloric acid soln is soaked, after leaving standstill, cross leaching filter residue, use successively ammoniacal liquor, water washing, then purify with column chromatography, after being desolventized, the elutriant steaming that contains described part obtains part 4-carbazole-2, 2 ', 4, 2 '-terpyridyl, 4-pentanoic-2, 2 ', 4, 2 '-tri-pyridines, 4-bis-(the 4-tertiary butyl) anilino-2, 2 ', 4, 2 '-terpyridyl, 4-(N-phenyl-1-naphthalene) amido-2, 2 ', 4, 2 '-terpyridyl or 4-(N-phenyl-2-naphthalene) amido-2, 2 ', 4, 2 '-terpyridyl, the filler using in described column chromatography is silica gel, and eluent is the mixed solvent of sherwood oil and ethyl acetate, and the volume ratio of described sherwood oil and ethyl acetate is 1:3.
4. according to chlorination three carbonyls 2 of preparation replacement described in claim 2 or 3,2 ', 4,2 '-terpyridyl closes the method for rhenium (I) title complex, it is characterized in that the method for purifying described in step (2) is: adopt column chromatography, filler is silica gel, eluent is the mixed solution of ethyl acetate and sherwood oil, wherein add the triethylamine of described mixed solution 5% volume, the volume ratio of described ethyl acetate and sherwood oil is 2:1, after the elutriant steaming that contains described title complex is desolventized, obtains described title complex.
5. chlorination three carbonyls 2,2 ', 4 that replace described in a claim 1,2 '-terpyridyl closes rhenium (I) title complex and applies being manufactured with in organic electroluminescence devices.
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| 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 |
| CN101993457A (en) * | 2010-10-26 | 2011-03-30 | 南京大学 | 2,2'-rhenium (I) bipyridyl complexes containing carbazole or oxadiazole groups as well as preparation method and application thereof |
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| 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 |
| CN101993457A (en) * | 2010-10-26 | 2011-03-30 | 南京大学 | 2,2'-rhenium (I) bipyridyl complexes containing carbazole or oxadiazole groups as well as preparation method and application thereof |
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| A Rhenium Tricarbonyl 4′-Oxo-terpy Trimer as a Luminescent Molecular Vessel with a Removable Silver Stopper;Michael P. Coogan等,;《Angewandte Chemie》;20090622;第121卷(第27期);第5065-5068页 * |
| Andrew Gelling等,.Synthesis and dynamic NMR studies of fluxionality in rhenium(I), platinum(II) and platinum(IV) complexes of ‘back-to-back’ 2,2′∶6′,2″-terpyridine ligands.《J. Chem. Soc.,Dalton Trans.》.1998,第3479-3488页. * |
| JP特开2002-173674A 2002.06.21 * |
| Michael P. Coogan等,.A Rhenium Tricarbonyl 4′-Oxo-terpy Trimer as a Luminescent Molecular Vessel with a Removable Silver Stopper.《Angewandte Chemie》.2009,第121卷(第27期),第5065-5068页. * |
| Synthesis and dynamic NMR studies of fluxionality in rhenium(I), platinum(II) and platinum(IV) complexes of ‘back-to-back’ 2,2′∶6′,2″-terpyridine ligands;Andrew Gelling等,;《J. Chem. Soc.,Dalton Trans.》;19980101;第3479-3488页 * |
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