CN101580521A - Dendritic organic metal composition and electroluminescent device using same - Google Patents
Dendritic organic metal composition and electroluminescent device using same Download PDFInfo
- Publication number
- CN101580521A CN101580521A CNA200910066852XA CN200910066852A CN101580521A CN 101580521 A CN101580521 A CN 101580521A CN A200910066852X A CNA200910066852X A CN A200910066852XA CN 200910066852 A CN200910066852 A CN 200910066852A CN 101580521 A CN101580521 A CN 101580521A
- Authority
- CN
- China
- Prior art keywords
- unsubstituted
- replacement
- dendroid
- chemical formula
- organometallic complex
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
The invention provides a dendritic organic metal composition and an electroluminescent device using same .The dendrite of the dendritic organic metal composition is made from organic radicals with the function of host materials. A central nucleus is a transition metal composition unit with the property of phosphorescent light emission. The formula of the dendritic organic metal composition is (1) or (2). The dendritic organic metal composition can be processed in solution, easy to synthesize, high in stability, good in film forming and fine in current carrier transmission ability, and can be used for preparing efficient doped and non-doped organic electroluminescent light-emitting diode (LED) with the luminous layer and an organic electroluminescent device. The max brightness of the prepared multilayer electroluminescent device is 13608cd/m<2>, the max luminous efficiency thereof is 17.55cd/A, and the max power efficiency thereof is 8.41m/W.
Description
Technical field
The present invention relates to the dendroid organometallic complex and with the electroluminescent device of this title complex.
Technical background
Organic electroluminescent (Electroluminescence EL) material is rapid progressive scientific research field.Human oxine aluminium such as Deng Qingyun from Kodak in 1987 are made luminescent material, obtained since the photodiode of high brightness under low voltage, only short over 20 years, we see that clearly this class material shows the bright prospects that present in (flatpanel display) equipment in development as novel flat-plate, become the object that more and more research institutions and company competitively develop.
Generally speaking, luminous organic material is organic compound or the metal complexes that contains conjugated structure.The luminescent layer that is used for organic electroluminescence device has two kinds of different types.A kind of main body luminescent layer that is called, promptly this luminous organic material not only has luminous power but also have the transmittability of current carrier.This main body luminescent material has plenty of electron transport material, and what have then can make hole mobile material, and what have has a bipolarity, both can be used as the electric transmission luminescent material, can be used as the hole transport luminescent material again.Another kind of type luminescent layer is called the doping type luminescent layer.It is that method by coevaporation or spin coating is scattered among the material of main part as different transport layers hotchpotch, the doping molecule can shift by the energy of main body shiner excited state and excite, and then discharge the light of different tones, have high-level efficiency and high brightness.
According to the difference of principle of luminosity, electroluminescent organic material can be divided into fluorescent material and phosphor material two big classes.Fluorescent material with high-luminous-efficiency widely as the doping molecular application in organic electroluminescence device, but the low theoretical ratio that its quantum yield is compared with triplet excitons (75%) by singlet exciton (25%) limits.And,, increase substantially the efficient of device owing to can make full use of all form of energy that comprise singlet and triplet state for phosphor material, can make the internal quantum efficiency of device reach 100% in theory.Because heavy atoms effect utilizes transition metal complex to become the realization phosphorescent emissions, thereby improve a kind of effective means of device efficiency.(Baldo since first is applied in porphyrin platinum PtOEP in the organic electroluminescence device since people such as Forrest, M.A.et al Nature 395,151 (1998)), the transition metal complex of other kind, title complex as Ir (III), Os (II), Ru (II), Re (I), Cu heavy metals such as (I), also be in the news out in succession, and be proved to be and have high relatively efficient and brightness really.Yet except the organometallic complex of heavy metal Ir (III), the phosphorescent complexes of other kind heavy metals is also less relatively, and quantum yield and efficient are lower, and luminous tone is also incomplete.Therefore, the organo-metallic luminescent material of new kind awaits to research and develop.
In addition, organometallic complex class phosphor material, though can increase substantially device efficiency, but because its exciton life-span is long, be easy to reach luminescent saturation, and triplet excitons (triplet-triplet T-T) can take place during high density bury in oblivion, cause the efficient of device sharply to descend along with the increase of current density, have a strong impact on the practical application of organic electroluminescence device.In order to address this problem, the general employing of device is entrained in it in material of main part, with the vacuum method preparation of evaporation altogether.Material of main part has shielding usually or isolates the effect that energy transmits mutually between the object light emitting molecule, inject or transmit to light emitting molecule transmission energy, electronics injection or transmission, hole.Yet because the existence of phenomenon of phase separation and the film forming unstable of distillation vacuum moulding machine, vacuum is total to the method complicated process of preparation of evaporation simultaneously, the cost height, thus limited the application of metal complexes class phosphor material on large-area flat-plate shows.For this reason, develop efficiently, the organo-metallic phosphor material of the panchromatic demonstration of solution processable seems particularly urgent.
Dendrimer had both had the advantage of small molecules and polymkeric substance: if any micromolecular fixed member amount, and the purity height, structure is clear and definite and be easy to control luminosity; High molecular solution processing means etc.Own special advantages is arranged again: the nuclear of itself, shell, dendritic structure can be regulated its photoelectric properties respectively, and can control intermolecular interaction by the adjusting of algebraically, improve device performance.
The dendroid organometallic complex has had the advantage of high-level efficiency and solution processable concurrently, has very big magnetism naturally: 1) introducing of branch has realized that the mode of solution processable deposits film forming, has simplified preparation technology, greatly reduces preparation cost; 2) huge branch has blanketing effect, can avoid self quencher of phosphor material; 3) introduce functional group easily, do not change the electronics and the luminescent properties of intercalated nucleus, subject and object is combined together, and then realize non-doping device.
Yet, the research of this class material also seldom, and material few in number does not give full play of the due advantage of dendroid organometallic complex.It is complexes of red light iridium (Anthopoulos, T.D., the Burn of branch with the phenyl ring that P.L.Burn leader's research group has reported, P.L.etal, Adv.Mater 16,557 (2004)), because of the branch of phenyl ring can not well transmit current carrier, the electroluminescent device efficient of its preparation is low; It is the luminescent material (John of nuclear with porphyrin platinum that P.L.Burn research group uses the toluylene support synthetic as branch again, M.L., Burn, P.L.et al, Adv.Func.Mater 11,287 (2001)), but have the phosphorescence quenching effect because of toluylene supports branch, device efficiency neither be very effective.Therefore, be necessary the exploitation synthetic that are easy to, stability is high more, efficiently, the dendroid organo-metallic phosphorescent complexes of solution processable, with obtain can practical application luminescent material.
Summary of the invention
For solving the problem of prior art, the present invention is intended to develop novel dendroid organometallic complex, and is used to construct adulterated and non-adulterated organic electroluminescence device, to realize high-level efficiency, high brightness and panchromatic luminous.
One of purpose of the present invention provides the dendroid organometallic complex, a kind of dendroid organometallic complex with material of main part function of solution processable; Two of purpose of the present invention provides a kind of electroluminescent device that uses above-mentioned dendroid organometallic complex, a kind of characteristics of luminescence, the good organic electroluminescence device of luminous efficiency.
The branch of a kind of dendroid organometallic complex provided by the invention is made up of the organic group with material of main part function; Centronucleus is the transition metal complex unit, has phosphorescent emissions character; Central metallic ions is selected from platinum, ruthenium, osmium or the rhenium in the precious metal;
The chemical formula of this dendroid organometallic complex (1) or (2) are as follows:
In the formula, M is selected from Pt, Ru, Os or Re;
X
1And X
2In any one be the expression nitrogen-atoms of coordination bonding on metal ion, corresponding another is carbon atom or the nitrogen-atoms of expression covalent bonding on metal ion;
Among ring A and the ring B any one is independently selected from and replaces or unsubstituted C
4-C
60Heterocyclic radical or heteroaryl, corresponding another are independently selected from and replace or unsubstituted C
4-C
60Heterocyclic radical, heteroaryl or aryl, perhaps, for replacing or unsubstituted C
4-C
60Carbocylic radical;
Branch (Dendron) is independently selected from that unconjugated aryl ethers, aryl are silica-based, ester, acid amides, amino or imido grpup, or conjugated aryl alkynes, aryl alkene, heteroaryl acetylenic, heteroaryl alkene, aryl or heteroaryl organic group; Preferred carbazyl, N-carbazyl phenyl, phenylpyridyl, pyridyl phenyl, phenyl, hexichol amido, pentanoic phenyl, benzene oxadiazole base, phenyl is silica-based or N-carbazyl phenyl is silica-based;
L is independently selected from the bidentate chelate part of single anion of bidentate chelate part, the phenol hydroxyl of the single anion of single anion part with beta diketone structure, carboxyl;
R
1Be surface group, be independently selected from C
1-C
30Alkyl, C
2-C
20Alkenyl or C
1-C
20Alkoxyl group;
When M is Ru, Re, Os, m
1=3, m
2=2; When M is Pt, m
1=2, m
2=1; N1 and n2 are independently selected from 0,1,2 or 3;
For above-mentioned chemical formula (1) or (2), by encircling A and the ring core cyclic metal complexes (3) that B constituted:
Cyclic metal complexes shown in preferred chemical formula (4), (5), (6) or (7):
In the formula, X
1And X
2As previously mentioned; R
2, R
3, R
4Be independently selected from hydrogen, halogen atom, replacement or unsubstituted C
1-C
20Alkyl, replacement or unsubstituted C
6-C
20Aromatic base, replacement or unsubstituted C
6-C
20Carbocylic radical, replacement or unsubstituted C
6-C
20Heteroaryl, replacement or unsubstituted C
6-C
20Heterocyclic radical;
For above-mentioned chemical formula (1) or (2), the branch shown in the preferred chemical formula (8) of its branch (Dendron):
In the formula, R
1As previously mentioned;
R
5Be the group that connects branch and Cyclometalated part, be selected from singly-bound, two key, triple bond, C
1-C
8Carbochain, replacement or unsubstituted C
6-C
20Aromatic base, replacement or unsubstituted C
6-C
20Carbocylic radical, replacement or unsubstituted C
6-C
20Heteroaryl perhaps replaces or unsubstituted C
6-C
20Heterocyclic radical; N is independently selected from 0,1,2 or 3;
For above-mentioned chemical formula (2), the part shown in the preferred chemical formula of its second ligand L (9), (10):
In the formula, R
6, R
7, R
8Be independently selected from hydrogen, halogen atom, replacement or unsubstituted C
1-C
8Alkyl, replacement or unsubstituted C
2-C
8Thiazolinyl, replacement or unsubstituted C
6-C
20Aromatic base, replacement or unsubstituted C
6-C
20Carbocylic radical, replacement or unsubstituted C
6-C
20Heteroaryl perhaps replaces or unsubstituted C
6-C
20Heterocyclic radical;
For above-mentioned chemical formula (1) or (2), the preferred Pt of metal M;
In order to obtain high efficiency electroluminescent device, with the dendroid organometallic complex shown in chemical formula (1) and the chemical formula (2), with mix and non-adulterated form as luminescent layer, be used to prepare electro phosphorescent device.
Luminescent layer adopts the method preparation of solution spin coating, its processing condition are as follows: the dendroid organometallic complex that the present invention is obtained, or it is entrained in the material of main part with 6～50wt.%, be dissolved in chloroform, toluene or the chlorobenzene, be spin-coated on the ito glass surface of modifying through 50nm polythiofuran derivative (PEDOT), be prepared into luminescent layer; In device architecture layer combined aspects, direct evaporation metal electrode behind the intact luminescent layer of spin coating is made single layer device; Perhaps, between metal electrode and luminescent layer, add hole blocking layer or electron transfer layer, the structure multilayer device; Described material of main part is carbazoles derivative or electron transport material, comprises the compound of chemical formula (11) to chemical formula (18):
(18)
Beneficial effect: the present invention adopts dendritic cyclic metal complexes to obtain the novel monokaryon dendroid organometallic complex phosphor material of two classes by covalent linkage and coordinate bond and heavy metal bonding, and it has solved the few deficiency of existing phosphor material kind.This class material design provided by the invention is unique, combines the advantage of dendrimer and metal phosphorescent complexes effectively, can realize efficiently luminous based on these dendroid organometallic complex electro phosphorescent devices.The present invention is one of them dendroid Cyclometalated platinum complexes (t-BuCzPBI) Pt (acac), is entrained among the material of main part CBP (chemical formula (11)) with the ratio of 30wt.%, and BCP (chemical formula (16)) is as hole barrier materials, Alq
3(chemical formula (18)) are 13608cd/m as the high-high brightness of the multilayer device of electron transport material preparation
2, maximum luminous efficiency is 17.55cd/A, maximum power efficiency is 8.41m/W.
The present invention is by being designed to the dendritic structure molecule, can regulate the photoelectric properties of this class material easily, can realize efficient panchromatic luminous, thereby refreshed the luminescent properties of such material at organic electro phosphorescent device, to satisfy the application demand of people to electromechanical phosphorescent material.
Description of drawings
Fig. 1 provides the change curve of the luminosity of title complex (t-BuCzPBI) Pt (acac) organic EL device that embodiment 1 makes with voltage;
Fig. 2 provides the luminous efficiency of organic EL device of title complex (t-BuCzPBI) Pt (acac) that embodiment 1 makes with the change curve of current density;
Fig. 3 provides the EL spectrogram of title complex (t-BuCzPBI) Pt (acac) organic EL device of embodiment 1 manufacturing;
Fig. 4 provides the change curve of the luminosity of title complex (t-BuCzCzPBI) Pt (acac) organic EL device that embodiment 1 makes with voltage;
Fig. 5 provides the luminous efficiency of organic EL device of title complex (t-BuCzCzPBI) Pt (acac) that embodiment 1 makes with the change curve of current density;
Fig. 6 provides the EL spectrogram of title complex (t-BuCzCzPBI) Pt (acac) organic EL device of embodiment 1 manufacturing;
Fig. 7 provides the title complex (t-BuCzPBI) that embodiment 1 makes
2The luminosity of Pt organic EL device is with the change curve of voltage;
Fig. 8 provides the title complex (t-BuCzPBI) that embodiment 1 makes
2The luminous efficiency of the organic EL device of Pt is with the change curve of current density;
Fig. 9 provides the title complex (t-BuCzPBI) that embodiment 1 makes
2The EL spectrogram of Pt organic EL device;
Figure 10 provides the title complex (t-BuCzCzPBI) that embodiment 1 makes
2The luminosity of Pt organic EL device is with the change curve of voltage;
Figure 11 provides the title complex (t-BuCzCzPBI) that embodiment 1 makes
2The luminous efficiency of the organic EL device of Pt is with the change curve of current density;
Figure 12 provides the title complex (t-BuCzCzPBI) that embodiment 1 makes
2The EL spectrogram of Pt organic EL device.
Embodiment
Synthesizing of two (diethyl sulfide) platinum of synthetic embodiment 1:trans-two chloro-
Reaction formula 1:
Method synthetic (L.Chassot, A.von Zelewsky, Inorg.Chem.458532 (1983)) according to document.In 50ml three neck round-bottomed flasks, add K
2PtCl
4(0.4151g, 1.0mmol) and 20mL distilled water, be stirred to whole dissolvings after, dropwise drip the sulphur ether (0.1765g, 1.95mmol), drip finish after, room temperature reaction 15min.Filter then, the precipitation that obtains is washed with cold ethanol and cold distilled water respectively, ethyl alcohol recrystallization, and drying obtains glassy yellow needle-like crystal 0.2500g (productive rate 56%).
Synthetic embodiment 2:
1. (PBI)
2Synthesizing of Pt platinum complex
Reaction formula 2:
The anhydrous and oxygen-free operation of employing standard: in 50ml three neck round-bottomed flasks, add part PBI (Chemical formula 1 9) (1.5mmol, 0.5238g) and the 10mL tetrahydrofuran (THF), after stirring all dissolvings, be cooled to-78 ℃, dropwise drip butyllithium (0.1057g, 1.65mmol), after dripping end, reaction 45min.Drip the tetrahydrofuran solution (0.2232g, 0.5mmol, 5ml THF) of the platinum intermediate that synthetic embodiment one obtains then.After dripping end, be raised to room temperature, reaction 2h.Vacuum is removed tetrahydrofuran (THF) then, adds the 3mL ether, filters, and obtains yellow-green precipitate, precipitates further column separating purification, promptly gets product (PBI)
2Pt: yellow-green colour powder 0.276g (productive rate 56%).
2. (PBI)
2The structural analysis of Pt platinum complex
(PBI)
2Pt：
1H?NMR(300MHz，CDCl
3)：δ8.25(d，J＝8.1Hz，1H)，7.89(dd，J＝7.05，1.8Hz，1H)，7.72-7.68(m，3H)，7.59-7.56(m，3H)，7.23(td，J＝6.75，1.5Hz，1H)，7.18(td，J＝7.2，1.2Hz，1H)，7.09(dd，J＝10.0，1.8Hz，1H)，6.82(t，J＝7.2Hz，1H)，6.66(dd，J＝7.65，1.2Hz，1H).
13CNMR(300MHz，CDCl
3)：δ164.5，150.3，141.2，138.1，137.9，136.2，135.8，131.3，130.8，130.5，128.7，125.4，123.7，123.5，122.5，119.4，110.9.Anal.Calcd?for?C
38H
26N
4Pt：C，62.20；H，3.57；N，7.64.Found：C，61.44；H，3.54；N，7.04％.MALDI-TOF(m/z)：733.1[M
++H].
Synthetic embodiment 3:
1. (t-BuCzPBI)
2Synthesizing of Pt platinum complex
Reaction formula 3:
The anhydrous and oxygen-free operation of employing standard: in 50ml three neck round-bottomed flasks, add part (t-BuCz) PBI (Chemical formula 2 0) (1.5mmol, 0.9400g) and the 15mL tetrahydrofuran (THF), after stirring all dissolvings, be cooled to-78 ℃, dropwise drip butyllithium (0.1057g, 1.65mmol), after dripping end, reaction 45min.Drip the tetrahydrofuran solution (0.2232g, 0.5mmol, 5ml THF) of the platinum intermediate that synthetic embodiment one obtains then.After dripping end, be raised to room temperature, reaction 2h.Vacuum is removed tetrahydrofuran (THF) then, adds the 5mL ether, filters, and obtains yellow-green precipitate, precipitates further column separating purification, promptly gets product (t-BuCzPBI)
2Pt: yellow powder 0.217g (productive rate 32%).
2. (t-BuCz)
2The structural analysis of Pt platinum complex
(t-BuCz)
2Pt：
1H?NMR(300MHz，CDCl
3)：δ8.32(d，J＝8.4Hz，1H)，8.20(S，2H)，7.98(d，J＝8.4Hz，1H)，7.93(d，J＝8.7Hz，2H)，7.81(d，J＝8.7Hz，2H)，7.57(d，J＝1.2Hz，4H)，7.35-7.23(m，4H)，6.95(t，J＝7.5Hz，1H)，6.86(dd，J＝9.0，1.2Hz，1H)，1.51(S，18H).
13C?NMR(300MHz，CDCl
3)：δ164.7，150.4，144.2，141.9，141.2，140.4，139.1，138.1，135.7，134.1，131.0，130.1，128.4，125.4，124.4，124.3，124.0，123.8，122.8，119.6，116.9，110.9，109.6，35.2，32.4.Anal.Calcd?for?C
78H
72N
6Pt：C，72.71；H，5.63；N，6.52.Found：C，72.42；H，5.85；N，5.59％.MALDI-TOF(m/z)：1288.7[M
++H].
Synthetic embodiment 4:
1. (t-BuCzCzPBI)
2Synthesizing of Pt platinum complex
Reaction formula 4:
The anhydrous and oxygen-free operation of employing standard: in 50ml three neck round-bottomed flasks, add part t-BuCzCzPBI (Chemical formula 2 1) (1.5mmol, 1.6038g) and the 20mL tetrahydrofuran (THF), after stirring all dissolvings, be cooled to-78 ℃, dropwise drip butyllithium (0.1057g, 1.65mmol), after dripping end, reaction 45min.Drip the tetrahydrofuran solution (0.2232g, 0.5mmol, 5ml THF) of the platinum intermediate that synthetic embodiment one obtains then.After dripping end, be raised to room temperature, reaction 2h.Vacuum is removed tetrahydrofuran (THF) then, adds the 5mL ether, filters, and obtains yellow-green precipitate, precipitates further column separating purification, promptly gets product (PBI)
2Pt: pale yellow powder 0.130g (productive rate 18%).
2. (t-BuCzCzPBI)
2The structural analysis of Pt platinum complex
(t-BuCzCzPBI)
2Pt：
1H?NMR(300MHz，CDCl
3)：δ8.35(d，J＝8.4Hz，1H)，8.30(d，J＝1.8Hz，2H)，8.18(d，J＝1.5Hz，4H)，8.13(d，J＝8.7Hz，2H)，8.02(d，J＝8.4Hz，1H)，7.98(d，J＝8.7Hz，2H)，7.86(d，J＝8.7Hz，2H)，7.74(dd，J＝8.7，1.8Hz，2H)，7.49(dd，J＝8.7，1.8Hz，4H)，7.40-7.29(m，4H)，7.01(t，J＝7.5Hz，1H)，6.94(d，J＝6.9Hz，1H)，1.48(S，36H).
13C?NMR(300MHz，CDCl
3)：δ164.8，150.4，143.1，141.4，140.5，140.4，139.4，138.0，135.6，135.4，132.1，131.2，130.7，129.2，126.7，124.9，124.0，123.6，122.8，120.0，116.7，111.4，109.5，35.2，32.5.Anal.Calcd?forC
142H
132N
10Pt：C，78.46；H，6.12；N，6.44.Found：C，77.36；H，7.02；N，4.91％.MALDI-TOF(m/z)：2173.1[M
++H].
Synthetic embodiment 5:
1. (PBI) Pt (acac) platinum complex is synthetic
Reaction formula 5:
1) the chlorine bridge is dimeric synthetic
In the single neck round-bottomed flask of 50ml, add K
2PtCl
4(0.2076g; 0.50mmol) and part (Chemical formula 2 2) (0.6mmol 0.1622g), is dissolved in it in mixed solvent of 9mL ethylene glycol monomethyl ether and 3mL distilled water; substitute gas repeatedly 3 times; stirring heating under argon shield is warming up to 80 ℃, behind the back flow reaction 16h; filter; the precipitation that obtains is used ethanol and distilled water wash respectively, drying, and the chlorine bridge dimer that obtains is not purified and is directly used in the next step.
2) (PBI) Pt (acac) platinum complex synthetic
Chlorine bridge dimer, methyl ethyl diketone (0.100g that step 1 is obtained; 1.00mmol), anhydrous sodium carbonate (0.265g, 2.50mmol), ethylene glycol monomethyl ether 5mL joins in the single neck round-bottomed flask of 50ml, substitutes gas repeatedly 3 times; under argon shield, back flow reaction 16h.Cool to room temperature adds distilled water, uses dichloromethane extraction, washing, anhydrous Na
2SO
4Drying is filtered, and rotary evaporation falls solvent, and post separates purifies, and obtains product (PBI) Pt (acac): green powder 0.7314g (productive rate 66%).
2. the nmr analysis of (PBI) Pt (acac) platinum complex
(PBI)Pt(acac)：
1H?NMR(300MHz，CDCl
3)：δ8.55(d，J＝8.1Hz，1H)，7.72-7.67(m，4H)，7.53(d，J＝3.3Hz，1H)，7.51(d，J＝3.45Hz，1H)，7.38(td，J＝7.7，0.6Hz，1H)，7.26(td，J＝8.1，0.9Hz，1H)，7.09(td，J＝8.25，1.5Hz，1H)，7.01(d，J＝8.1Hz，1H)，6.75(td，J＝8.1，0.9Hz，1H)，6.41(d，J＝6.9Hz，1H)，5.54(s，1H)，2.09(s，3H)，2.01(s，3H).
13C?NMR(300MHz，CDCl
3)：δ185.4，183.7，140.5，139.3，136.2，135.2，134.8，131.1，130.8，130.7，129.7，128.5，124.8，124.5，123.8，123.2，117.2，110.8，102.5，28.3，27.7.Anal.Calcd?for?C
24H
20N
2O
2Pt：C，51.15；H，3.58；N，4.97.Found：C，51.44；H，3.70；N，4.68％.MALDI-TOF(m/z)：563.1[M
++H].
Synthetic embodiment 6:
1. (t-BuCz PBI) Pt (acac) platinum complex is synthetic
Reaction formula 6:
1) the chlorine bridge is dimeric synthetic
In the single neck round-bottomed flask of 50ml, add K
2PtCl
4(0.2076g; 0.50mmol) and part (Chemical formula 2 3) (0.6mmol 0.3285g), is dissolved in it in mixed solvent of 12mL ethylene glycol monomethyl ether, 5ml dioxane and 4mL distilled water; substitute gas repeatedly 3 times; stirring heating under argon shield is warming up to 80 ℃, behind the back flow reaction 48h; filter; the precipitation that obtains is used ethanol and distilled water wash respectively, drying, and the chlorine bridge dimer that obtains is not purified and is directly used in the next step.
2) (t-BuCz PBI) Pt (acac) platinum complex is synthetic
Chlorine bridge dimer, methyl ethyl diketone (0.100g that step 1 is obtained; 1.00mmol), anhydrous sodium carbonate (0.265g, 2.50mmol), ethylene glycol monomethyl ether 10mL and 5ml dioxane join in the single neck round-bottomed flask of 50ml, substitutes gas repeatedly 3 times; under argon shield, back flow reaction 24h.Cool to room temperature adds distilled water, uses dichloromethane extraction, washing, anhydrous Na
2SO
4Drying is filtered, and rotary evaporation falls solvent, and post separates purifies, and obtains product (t-BuCzPBI) Pt (acac): yellow powder 0.260g (productive rate 31%).
2. the nmr analysis of (t-BuCz PBI) Pt (acac) platinum complex
(t-BuCz?PBI)Pt(acac)：
1H?NMR(300MHz，CDCl
3)：δ8.86(d，J＝8.1Hz，1H)，8.19(s，2H)，7.91(d，J＝8.4Hz，2H)，7.76-7.74(d，3H)，7.55(s，4H)，7.43(t，J＝7.2Hz，1H)，7.34(t，J＝7.7Hz，1H)，7.18(d，J＝7.8Hz，1H)，7.15(t，J＝7.5Hz，1H)，6.86(t，J＝7.1Hz，1H)，6.63(d，J＝7.5Hz?1H)，5.56(s，1H)，2.11(s，3H)，2.03(s，3H)，1.50(s，18H).
13C?NMR(300MHz，CDCl
3)：δ185.5，183.8，164.0，144.2，140.6，139.5，139.1，136.2，134.8，133.0，131.3，130.1，129.9，128.3，125.1，124.4，124.0，123.4，117.3，117.0，110.8，109.5，102.6，35.2，32.4，28.3，27.7.Anal.Calcd?forC
44H
43N
3O
2Pt：C，62.85；H，5.15；N，5.00.Found：C，62.86；H，5.27；N，4.03％.MALDI-TOF(m/z)：840.3[M
++H].
Synthetic embodiment 7:
1. (t-BuCzCzPBI) Pt (acac) platinum complex is synthetic
Reaction formula 5:
1) the chlorine bridge is dimeric synthetic
In the single neck round-bottomed flask of 50ml, add K
2PtCl
4(0.2076g; 0.50mmol) and part (Chemical formula 2 4) (0.6mmol 0.7713g), is dissolved in it in mixed solvent of 15mL ethylene glycol monomethyl ether, 10ml dioxane and 5mL distilled water; substitute gas repeatedly 3 times; stirring heating under argon shield is warming up to 80 ℃, behind the back flow reaction 72h; filter; the precipitation that obtains is used ethanol and distilled water wash respectively, drying, and the chlorine bridge dimer that obtains is not purified and is directly used in the next step.
2) (t-BuCzCzPBI) Pt (acac) platinum complex synthetic
Chlorine bridge dimer, methyl ethyl diketone (0.100g that step 1 is obtained; 1.00mmol), anhydrous sodium carbonate (0.265g, 2.50mmol), ethylene glycol monomethyl ether 15mL and 10ml dioxane join in the single neck round-bottomed flask of 50ml, substitutes gas repeatedly 3 times; under argon shield, back flow reaction 48h.Cool to room temperature adds distilled water, uses dichloromethane extraction, washing, anhydrous Na
2SO
4Drying is filtered, and rotary evaporation falls solvent, and post separates purifies, and obtains product (t-BuCzCzPBI) Pt (acac): pale yellow powder 0.320g (productive rate 25%).
2. the nmr analysis of (t-BuCzCzPBI) Pt (acac) platinum complex
(t-BuCzCzPBI)Pt(acac)：
1H?NMR(300MHz，CDCl
3)：δ8.64(d，J＝8.1Hz，1H)，8.30(d，J＝1.8Hz，2H)，8.18(d，J＝1.5Hz，4H)，8.11(d，J＝8.4Hz，2H)，7.91(d，J＝8.4Hz，2H)，7.82(d，J＝8.7Hz，2H)，7.78(d，J＝7.5Hz，1H)，7.71(dd，J＝8.6，1.95Hz，2H)，7.50-7.43(m，5H)，7.40-7.35(m，5H)，7.24(d，J＝7.2Hz，1H)，7.17(td，J＝7.5，1.2Hz，1H)，6.91(td，J＝7.61，1.2Hz，1H)，6.72(d，J＝7.2Hz，1H)，5.58(s，1H)，2.13(s，3H)，2.04(s，3H)，1.47(s，36H).
13C?NMR(300MHz，CDCl
3)：δ185.5，183.8，164.0，143.2，140.7，140.5，140.2，139.7，139.6，136.1，134.7，134.3，132.1，131.4，130.6，130.1，129.0，126.7，125.2，125.0，124.3，124.2，124.0，123.6，123.4，120.0，117.5，116.7，111.4，110.7，109.4，102.6，35.2，32.5，28.3，27.7.Anal.Calcd?for?C
76H
73N
2O
2Pt：C，71.12；H，5.73；N，5.46.Found：C，70.29；H，6.02；N，4.24％.MALDI-TOF(m/z)：1283.7[M
++H].
El element embodiment 1:
For the embodiment that provides, dendroid organometallic complex (t-BuCzPBI) Pt (acac) is entrained among the material of main part CBP (Chemical formula 1 1) with the ratio of 30wt.%, the preparation multilayer device, the structure of device is:
Ito glass/conducting polymer polythiofuran derivative (PEDOT) (50nm)/dendroid organometallic complex (t-BuCzPBI) Pt (acac): material of main part (30nm)/BCP (20nm)/Alq
3(30nm)/LiF (1nm)/Al (100nm).
Device preparing process is as follows:
1, after conducting polymer polythiofuran derivative (PEDOT) is spin-coated on the ito glass surface of cleaning in advance with 3000 rev/mins speed,, forms the thick hole of 50nm and inject two-layer electrode, and improve the planarization on ito glass surface at 120 ℃ of baking 30min down.
2, dendroid organometallic complex and material of main part are dissolved in the toluene, are made into the solution of 10 mg/ml, are spin-coated on PEDOT with 2000 rev/mins speed and go up as luminescent layer (30nm).
3, on luminescent layer evaporation 20nm thick 2,9-dimethyl 4,7-phenylbenzene 1,10-phenanthroline (BCP) is as hole blocking layer.
4, the oxine aluminium (Alq that evaporation 30nm is thick on hole blocking layer
3) as electron transfer layer.
5, the LiF/Al electrode is LiF (1nm)/Al (100nm) on evaporation on the electron transfer layer.
Title complex (t-BuCzPBI) Pt (acac) (30wt.%) maximum luminous efficiency of the El element of gained is 17.55cd/A, and maximum power efficiency is 8.41m/W, high-high brightness 13608cd/m
2, emission peak is 410nm, 542nm, chromaticity coordinates CIE value x=0.39, y=0.56;
El element embodiment 2:
Use dendroid organometallic complex (t-BuCzCzPBI) Pt (acac), be entrained among the material of main part CBP (Chemical formula 1 1) the preparation multilayer device with the ratio of 40wt.%.The structure of device and the processing condition of preparation are with embodiment 1.
Title complex (t-BuCzCzPBI) Pt (acac) (40wt.%) maximum luminous efficiency of the El element of gained is 8.2cd/A, and maximum power efficiency is 4.51m/W, high-high brightness 8251cd/m
2, emission peak is 544nm, chromaticity coordinates CIE value x=0.39, y=0.56;
El element embodiment 3:
Use dendroid organometallic complex (t-BuCzPBI)
2Pt is entrained among the material of main part CBP (Chemical formula 1 1) with the ratio of 20wt.%, the preparation multilayer device.The structure of device and the processing condition of preparation are with embodiment 1.
Title complex (t-BuCzPBI)
2The maximum luminous efficiency of the El element of Pt (20wt.%) gained is 1.0cd/A, and maximum power efficiency is 0.401m/W, high-high brightness 1876cd/m
2, emission peak is 538nm, chromaticity coordinates CIE value x=0.36, y=0.54;
El element embodiment 4:
Use dendroid organometallic complex (t-BuCzCzPBI)
2Pt is entrained among the material of main part CBP (Chemical formula 1 1) with the ratio of 20wt.%, the preparation multilayer device.The structure of device and the processing condition of preparation are with embodiment 1.
Title complex (t-BuCzCzPBI)
2The maximum luminous efficiency of the El element of Pt (20wt.%) gained is 1.37cd/A, and maximum power efficiency is 0.451m/W, high-high brightness 4342cd/m
2, emission peak is 521nm, chromaticity coordinates CIE value x=0.36, y=0.53.
Claims (6)
1, a kind of dendroid organometallic complex is characterized in that, the branch of dendroid organometallic complex is made up of the organic group with material of main part function; Centronucleus is the transition metal complex unit, has phosphorescent emissions character; Central metallic ions is selected from platinum, ruthenium, osmium or the rhenium in the precious metal;
The chemical formula of this dendroid organometallic complex (1) or (2) are as follows:
In the formula, M is selected from Pt, Ru, Os or Re;
X
1And X
2In any one be the expression nitrogen-atoms of coordination bonding on metal ion, corresponding another is carbon atom or the nitrogen-atoms of expression covalent bonding on metal ion;
Among ring A and the ring B any one is independently selected from and replaces or unsubstituted C
4-C
60Heterocyclic radical or heteroaryl, corresponding another are independently selected from and replace or unsubstituted C
4-C
60Heterocyclic radical, heteroaryl or aryl, perhaps, for replacing or unsubstituted C
4-C
60Carbocylic radical; Branch (Dendron) is independently selected from that unconjugated aryl ethers, aryl are silica-based, ester, acid amides, amino or imido grpup, or conjugated aryl alkynes, aryl alkene, heteroaryl acetylenic, heteroaryl alkene, aryl or heteroaryl organic group; Preferred carbazyl, N-carbazyl phenyl, phenylpyridyl, pyridyl phenyl, phenyl, hexichol amido, pentanoic phenyl, benzene oxadiazole base, phenyl is silica-based or N-carbazyl phenyl is silica-based;
L is independently selected from the bidentate chelate part of single anion of bidentate chelate part, the phenol hydroxyl of the single anion of single anion part with beta diketone structure, carboxyl;
R
1Be surface group, be independently selected from C
1-C
30Alkyl, C
2-C
20Alkenyl or C
1-C
20Alkoxyl group;
When M is Ru, Re, Os, m
1=3, m
2=2; When M is Pt, m
1=2, m
2=1; N1 and n2 are independently selected from 0,1,2 or 3.
2, a kind of dendroid organometallic complex as claimed in claim 1 is characterized in that, in described chemical formula (1) or (2), by encircling A and the ring core cyclic metal complexes that B constituted:
Be the cyclic metal complexes shown in chemical formula (4), (5), (6) or (7):
In the formula, X
1And X
2As previously mentioned; R
2, R
3, R
4Be independently selected from hydrogen, halogen atom, replacement or unsubstituted C
1-C
20Alkyl, replacement or unsubstituted C
6-C
20Aromatic base, replacement or unsubstituted C
6-C
20Carbocylic radical, replacement or unsubstituted C
6-C
20Heteroaryl, replacement or unsubstituted C
6-C
20Heterocyclic radical.
3, a kind of dendroid organometallic complex as claimed in claim 1 is characterized in that, in described chemical formula (1) or (2), branch (Dendron) is the branch shown in the chemical formula (8):
In the formula, R
1As previously mentioned;
R
5Be the group that connects branch and Cyclometalated part, be selected from singly-bound, two key, triple bond, C
1-C
8Carbochain, replacement or unsubstituted C
6-C
20Aromatic base, replacement or unsubstituted C
6-C
20Carbocylic radical, replacement or unsubstituted C
6-C
20Heteroaryl perhaps replaces or unsubstituted C
6-C
20Heterocyclic radical; N is independently selected from 0,1,2 or 3.
4, a kind of dendroid organometallic complex as claimed in claim 1 is characterized in that, in the described chemical formula (2), second ligand L is the part shown in chemical formula (9) or (10):
In the formula, R
6, R
7, R
8Be independently selected from hydrogen, halogen atom, replacement or unsubstituted C
1-C
8Alkyl, replacement or unsubstituted C
2-C
8Thiazolinyl, replacement or unsubstituted C
6-C
20Aromatic base, replacement or unsubstituted C
6-C
20Carbocylic radical, replacement or unsubstituted C
6-C
20Heteroaryl perhaps replaces or unsubstituted C
6-C
20Heterocyclic radical.
5, a kind of dendroid organometallic complex as claimed in claim 1 is characterized in that, in described chemical formula (1) or (2), metal M is Pt.
6, a kind of dendroid organometallic complex as claimed in claim 1 electroluminescent device of being used to prepare is characterized in that, described dendroid organometallic complex with mix and non-adulterated form as luminescent layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910066852A CN101580521B (en) | 2009-04-21 | 2009-04-21 | Dendritic organic metal composition and electroluminescent device using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910066852A CN101580521B (en) | 2009-04-21 | 2009-04-21 | Dendritic organic metal composition and electroluminescent device using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101580521A true CN101580521A (en) | 2009-11-18 |
| CN101580521B CN101580521B (en) | 2012-09-05 |
Family
ID=41362857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910066852A Expired - Fee Related CN101580521B (en) | 2009-04-21 | 2009-04-21 | Dendritic organic metal composition and electroluminescent device using same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101580521B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103262283A (en) * | 2010-12-09 | 2013-08-21 | 新日铁住金化学株式会社 | Organic electroluminescent element |
| CN108292709A (en) * | 2015-12-07 | 2018-07-17 | 住友化学株式会社 | Light-emitting component |
| CN108658948A (en) * | 2017-03-29 | 2018-10-16 | 中国科学院长春应用化学研究所 | A kind of dendroid organometallic complex, preparation method and application |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4533015B2 (en) * | 2004-06-15 | 2010-08-25 | キヤノン株式会社 | Compound and organic electroluminescence device using the same |
| CN100362006C (en) * | 2005-09-16 | 2008-01-16 | 中国科学院长春应用化学研究所 | Dendritic iridium complex and organic electroluminescent device therewith |
| CN101108964B (en) * | 2007-08-21 | 2010-05-26 | 中国科学院长春应用化学研究所 | Arborization glowing iridium complex and organic EL device of the compound |
-
2009
- 2009-04-21 CN CN200910066852A patent/CN101580521B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103262283A (en) * | 2010-12-09 | 2013-08-21 | 新日铁住金化学株式会社 | Organic electroluminescent element |
| CN103262283B (en) * | 2010-12-09 | 2016-01-20 | 新日铁住金化学株式会社 | Organic electroluminescent device |
| CN108292709A (en) * | 2015-12-07 | 2018-07-17 | 住友化学株式会社 | Light-emitting component |
| CN108658948A (en) * | 2017-03-29 | 2018-10-16 | 中国科学院长春应用化学研究所 | A kind of dendroid organometallic complex, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101580521B (en) | 2012-09-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102615336B1 (en) | Organic light-emitting materials based on platinum tetradentate ONCN complex, preparation method, and application thereof in organic light-emitting diodes | |
| CN105237557B (en) | Metal complexes with boron-nitrogen heterocycle containing ligands for use in organic light emitting devices | |
| CN103122007B (en) | Host materials for phosphorescent oleds | |
| CN101010405B (en) | New compound and organic light emitting device using the same(8) | |
| CN104053665B (en) | Metal complex and the light-emitting component comprising the metal complex | |
| CN101679856B (en) | Novel organometallic complexes that emit light in the red to green spectral range and their use in OLEDs | |
| CN104603111A (en) | Fluorenes and electronic devices containing them | |
| CN105198868A (en) | Novel 3, 9-Linked Oliogocarbazole-Based Hosts, Containing DBT and DBF Fragments, Separated by Aromatic Spacers | |
| DE112019005124B4 (en) | Organic light-emitting materials of the tetradentate platinum (II) ONNO complexes, their production process and their application in organic light-emitting diodes | |
| CN104447880A (en) | Aza-carbazole OLED phosphor material as well as preparation method and application thereof | |
| CN103380191B (en) | Compound for electronic device | |
| CN107445996B (en) | Pterene-modified pyridazine iridium complex phosphorescent material and preparation method and application thereof | |
| CN100362006C (en) | Dendritic iridium complex and organic electroluminescent device therewith | |
| CN113563325B (en) | ESIPT luminescent material with high exciton utilization rate and preparation method and application thereof | |
| CN101580521B (en) | Dendritic organic metal composition and electroluminescent device using same | |
| Wang et al. | Self-host blue-emitting iridium dendrimer for solution-processed non-doped phosphorescent organic light-emitting diodes with flat efficiency roll-off and less phase segregation | |
| CN101504972B (en) | Electroluminescent device made from rare-earth terbium complex | |
| CN107722059A (en) | Cyclophane base iridium complex compound and the Organnic electroluminescent device using the compound | |
| CN101265407A (en) | Polymer electroluminescence material containing amides iridium metal complexes and preparation method thereof | |
| CN105777809B (en) | Electroluminescent organic material and organic electroluminescence device | |
| CN101440088B (en) | Metal organic complexes, preparation thereof, luminescent material and luminescent device | |
| CN104004509A (en) | Organo-boron group-containing phosphorescent organic electroluminescent material and preparation method thereof | |
| CN108530490A (en) | A kind of metal complex and its organic luminescent device | |
| CN105085579B (en) | N hexyl carbazole substituted-phenyl benzothiazole iridium (III) complexs and its preparation | |
| Cho et al. | Phosphorescent, green-emitting Ir (III) complexes with carbazolyl-substituted 2-phenylpyridine ligands: Effect of binding mode of the carbazole group on photoluminescence and electrophosphorescence |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120905 Termination date: 20180421 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |