CN101209988B - Phenanthrene series derivatives and organic light-emitting diode containing the same - Google Patents
Phenanthrene series derivatives and organic light-emitting diode containing the same Download PDFInfo
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- CN101209988B CN101209988B CN200610171266A CN200610171266A CN101209988B CN 101209988 B CN101209988 B CN 101209988B CN 200610171266 A CN200610171266 A CN 200610171266A CN 200610171266 A CN200610171266 A CN 200610171266A CN 101209988 B CN101209988 B CN 101209988B
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- HGXTVBQMFBXGOA-MEKGRNQZSA-N Brc(cc1)ccc1-c(cc1)cc([C@](CCC2)(CCC3)[C@]23c2c3)c1-c2ccc3-c(cc1)ccc1Br Chemical compound Brc(cc1)ccc1-c(cc1)cc([C@](CCC2)(CCC3)[C@]23c2c3)c1-c2ccc3-c(cc1)ccc1Br HGXTVBQMFBXGOA-MEKGRNQZSA-N 0.000 description 1
- ZFSNYZKTKTXDJT-UHFFFAOYSA-N CCC1C(CC)OCC2C1C2 Chemical compound CCC1C(CC)OCC2C1C2 ZFSNYZKTKTXDJT-UHFFFAOYSA-N 0.000 description 1
- SXRWSYHMFDHWME-UHFFFAOYSA-N CCCC(CCC)(C1(C)C)c2ccccc2-c2c1cccc2 Chemical compound CCCC(CCC)(C1(C)C)c2ccccc2-c2c1cccc2 SXRWSYHMFDHWME-UHFFFAOYSA-N 0.000 description 1
- HZNWJBLAFRIXEB-RTWAWAEBSA-N CCC[C@@]1([C@]2(C)CCC1)c(cc(cc1)Br)c1-c(cc1)c2cc1Br Chemical compound CCC[C@@]1([C@]2(C)CCC1)c(cc(cc1)Br)c1-c(cc1)c2cc1Br HZNWJBLAFRIXEB-RTWAWAEBSA-N 0.000 description 1
- JTPACTAWYIXPSB-UHFFFAOYSA-O Cl[SH+](c1ccccc1)(c1ccccc1)c1ccccc1 Chemical compound Cl[SH+](c1ccccc1)(c1ccccc1)c1ccccc1 JTPACTAWYIXPSB-UHFFFAOYSA-O 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N c(cc1)ccc1Nc1ccccc1 Chemical compound c(cc1)ccc1Nc1ccccc1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to phenanthrene derivatives that have a structure in formula (I) and formula (II), wherein, A is respectively selected from hetero atoms of nitrogen, silicon, oxygen, phosphor and boric and B is respectively selected from phenyl, naphthyl, phenanthreny base, anthracene base, pyrenyl, heterocyclic radical, polycyclic aromatic base and polycyclic heterocyclic radical that at least have a conjugate base. The phenanthrene derivatives of the invention can effectively prevent aggregation among molecules and can improve the injection efficiency of the carriers (electron/cavity)of components and promote photopeak efficiency when being taken as maternal luminous compound of an organic electroluminescence diode.
Description
Technical field
The present invention relates to a kind of novel phenanthrene and be verivate and containing this phenanthrene is the Organic Light Emitting Diode of verivate as luminescent material.
Background technology
The molecular material that Organic Light Emitting Diode (OLED), organic electroluminescent (EL) assembly or photovoltage (photovoltaic) assembly use structurally belongs to conjugated molecule, and molecular structure is to form mutual linking to each other of the two keys of singly-bound, owing to have SP
2Blend together track, so structure is prone to into the plane; And the unpaired electron of Pz track forms π-π on the carbon atom
*Localization conjugated link(age) not, the transmission of the two keys resonance of electronics singly-bound capable of using form reaches the purpose of conduction.The highest the taking between molecular orbital(MO) (HOMO) and the unappropriated minimum vacant molecular orbital(MO) of electronics (LUMO) that the electronics of this kind conjugated molecule takes has energy gap (E
g), therefore also have characteristic of semiconductor.When being used in electroluminescent, the color that the decision of the size of energy gap is luminous.Yet,,, produce crystalline polamer, and then cause component failures so be prone to cause the molecule storehouse during film forming because its molecule has two dimensional structure.
USP discloses a kind of OLED that utilizes the organophosphorus optical molecule as hotchpotch (dopant) for No. 5756224, and it can obtain high luminous efficiency, has more quickened OLED in flat-panel screens and light source applications.But the absorption spectrum of organophosphorus optical molecule is all in UV-light (< 370nm) scope, therefore needs the conjugated molecule parent (host) of high stability, the transmission of high carrier and high energy gap.
In USP No. 6967255 (Republic of China's patent obtains card I225043), disclosing a kind of phenanthrene with molecule steric barrier is verivate; Verivate and high carrier transmission functional group this phenanthrene are then further disclosed are when synthetic altogether in No. the 20050176953rd, the USP; Promote photoelectric efficiency, and can be used as the effect of the fertile material of other fluorescence molecule object (fluorescence guest).It is synthetic altogether to disclose heterocycle molecule and aromatic molecule in No. the 6967062nd, the USP, can adjust energy gap, is applied to the fertile material of fluorescence molecule object.USP then discloses that nitrogenous amine is conjugated molecule on the main chain for No. 6670052, can increase the transfer rate in hole.USP discloses for No. 6830832 and has utilized the heteroatoms copolymerization to increase fluorescence efficiency and carrier transmission speed.But the neither parent that is enough to be used as the organophosphorus optical molecule of its energy gap of the disclosed material of above-mentioned patent.
Therefore, how developing a kind of phenanthrene that can increase the molecule energy gap is verivate, and when making assembly, can effectively prevent the molecule storehouse and promote the important topic that carrier speed is the luminescent material research of Organic Light Emitting Diode (OLED) always.
Summary of the invention
In view of this; The objective of the invention is to develop a kind of novel phenanthrene is verivate; The phenanthrene that utilization has dicyclo pentane steric barrier is that the conjugated molecule structure is core element; Synthetic altogether with the heteroatoms with electrons/affinity and Ppolynuclear aromatic conjugated molecule, and the phenanthrene that obtains having the organic semiconductor material of specific energy gap and the transmission of high electrons/is a verivate.In addition, another object of the present invention is to utilize this phenanthrene is the OLED that verivate is made high stability, high photoelectric efficiency.
For reaching above-mentioned purpose, it is verivate that the present invention provides a kind of novel phenanthrene, and it has the structure shown in following formula (I) or formula (II):
In the compound of formula (I) and formula (II); A is the heteroatoms that independently is selected from nitrogen, silicon, oxygen, phosphorus and boron separately, and B is selected from phenyl, naphthyl, phenanthryl, anthryl, pyrenyl, heterocyclic radical, many cyclophanes perfume base and the many ring heterocyclic radicals with at least one conjugated radicle independently of one another.
For reaching above-mentioned purpose; The present invention provides a kind of Organic Light Emitting Diode again; It comprises the positive pole that is formed on the base material; Be formed at the electro-luminescent zones on the positive pole, and be formed at the negative pole on the electro-luminescent zones, having like aforesaid phenanthrene of the present invention in the luminescent layer that wherein this electro-luminescent zones comprised is verivate.
Compared to known techniques, though all have luxuriant and rich with fragrance architecture, phenanthrene of the present invention is that verivate is that phenanthrene by three-dimensional pentamidine structure is that conjugated molecule is derived; And it is synthetic altogether with heteroatoms with electrons/affinity and Ppolynuclear aromatic conjugated molecule; Except the core element with steric barrier can keep the electroluminescent colour stability, the present invention more through having the heteroatomic importing of electrons/affinity, promotes the carrier transmission speed; And can be effectively when making the OLED assembly; The parent of being used as the phosphorescent molecules object, compared to known technology, the present invention has preferable electroluminescent efficiency and applicability widely.
For let above-mentioned purpose of the present invention, characteristic, and advantage can be more obviously understandable, following conjunction with figs. specifies as follows.
Description of drawings
The spectrogram that Fig. 1 records with NMR for the luxuriant and rich with fragrance based compound 5 according to the embodiment of the invention 5 gained.
The spectrogram that Fig. 2 records with NMR for the luxuriant and rich with fragrance based compound 6 according to the embodiment of the invention 6 gained.
Fig. 3 is the GC MASS collection of illustrative plates according to the luxuriant and rich with fragrance based compound 6 of the embodiment of the invention 6 gained.
Fig. 4 is according to ultraviolet ray-visible light (UV-Vis) absorption spectrum of the luxuriant and rich with fragrance based compound 5 of the embodiment of the invention 5 gained and photoluminescence spectrum (photoluminescence, PL) figure.
Fig. 5 is with luxuriant and rich with fragrance based compound 5 doping Ir (ppy) according to the embodiment of the invention 10
3The PL figure of phosphorescent molecules, and according to the PL figure of the embodiment of the invention 11 with luxuriant and rich with fragrance based compound 5 doped F IrPic blue light phosphorescent molecules.
Fig. 6 is the PL figure according to the luxuriant and rich with fragrance based compound 6 of the embodiment of the invention 6 gained, and according to the Ir (btp) of the embodiment of the invention 12 with luxuriant and rich with fragrance based compound 6 doping 6 weight %
2(acac) PL of ruddiness phosphorescent molecules figure.
Fig. 7 is the section of structure according to the electroluminescence part of the embodiment of the invention 13 mades.
Fig. 8 tests the photoelectric efficiency figure of gained for being luminophor according to the embodiment of the invention 13 with luxuriant and rich with fragrance based compound 6.
The primary clustering nomenclature
10～substrate;
20～transparency electrode;
30～hole transmission layer;
40～electroluminescence layer;
50～negative electrode;
60～resist.
Embodiment
Phenanthrene of the present invention is that verivate is with between C
1With C
10Between two carbon atoms on then the luxuriant and rich with fragrance based compound of two propylidene (or claiming trimethylene) gained be core element; And luxuriant and rich with fragrance according to this based compound is synthesized into heteroatoms and Ppolynuclear aromatic conjugated molecule with electrons/affinity altogether, and it can reach the purpose that high energy gap and high carrier transmit.According to above-mentioned, phenanthrene of the present invention is that verivate has the structure shown in following formula (I) or formula (II):
Wherein A is the heteroatoms that independently is selected from nitrogen, silicon, oxygen, phosphorus and boron etc. separately, is preferably nitrogen or silicon; B is selected from phenyl, naphthyl, phenanthryl, anthryl, pyrenyl, heterocyclic radical, many cyclophanes perfume base and the many ring heterocyclic radicals with at least one conjugated radicle independently of one another.
Above-mentioned B can be exemplified below:
R wherein
1With R
2Be selected from H, F, CF independently of one another
3, the tertiary butyl, C1-C10 alkyl and C1-C10 alkoxyl group.
In one embodiment of the invention, when B was one of above-mentioned conjugated radicle, the phenanthrene of gained was the scope of the wavelength of fluorescence of verivate radiation about 350～520nm.Can excite indigo plant, red, green and pleochroic electroluminescent material and obtain electricity through other material or synthetic altogether that mixes with other energy gap molecule.
The phenanthrene of above-mentioned formula (I) is that verivate can be following compound:
The phenanthrene of above-mentioned formula (II) is that verivate can be following compound:
Phenanthrene of the present invention is that the core element of verivate can flow process as follows make:
With phenanthrene-9, (phenanthrene-9 is 10-dione) with 2 equivalents 1 for the 10-diketone; (3-acetonedicarboxylate) there is reacting by heating in solvent down in diethyl1 in NaOH, after reacting completely to 3-Bing Tongersuosuan diethyl ester; Neutralize with HCl; Obtain throw out, with the throw out of collecting with acetate dissolution, reacting by heating.Then with NaCO
3Neutralization, after sedimentation and filtration separates, compound that obtains and 2 normal N
2H
4In solvent, heat and react, replace ketone group with hydrogen, forming phenanthrene of the present invention is the verivate core element.With this phenanthrene is the verivate core element can get formula (III) through halogenating reaction dihalo phenanthrene compound.
The dihalo phenanthrene compound of formula (III) can be a verivate via the phenanthrene that Suzuki Coupling Reaction further makes formula of the present invention (II) with the boronic acid compounds with other specified substituent.For example following flow process:
Wherein A such as aforesaid definition, the definition of Ar such as above-mentioned B.
Also can utilize Pd-coupling (coupling), Ullman-coupling or Metal-haloid permutoid reaction synthetic altogether the compound of formula (III) and the heteroatoms of other 2 equivalent band aromatic group in addition, the phenanthrene that obtains formula of the present invention (I) be a verivate.For example following flow process:
Wherein A such as above-mentioned definition, Ar, Ar ' are like the definition of above-mentioned B.In above-mentioned reaction formula; Also can be with the compound elder generation of formula (III) and the heteroatoms reaction of a kind of band aromatic group (Ar); Again with the heteroatoms reaction of another kind band aromatic group (Ar '); The phenanthrene that obtains suc as formula (I) is a verivate, and each A heteroatoms wherein is all independent separately with each B group.
In addition, can be in solvent, in CH with the compound of formula (III) and 2 equivalent hypoboric acid ester (diborate) compounds
3COOK and Pd (dppf) Cl
2Catalyzer reacts under existing, and obtains to have the compound (IV) of hypoboric acid ester.Further making 2 bromine phenanthrene of the present invention with the phenyl of the two halogenic substituents of tool via Suzuki Coupling Reaction again is verivate midbody formula V, and flow process is following:
Utilize Pd-coupling (coupling), Ullman-coupling or Metal-haloid permutoid reaction synthetic altogether the luxuriant and rich with fragrance based compound of 2 bromines of formula V and the heteroatoms of other 2 equivalent band aromatic group, the phenanthrene that can obtain formula of the present invention (II) is a verivate.For example following flow process:
Wherein A is heteroatoms such as aforesaid definition, and Ar, Ar ' are like the definition of above-mentioned B.In above-mentioned reaction formula; Also can be with the compound elder generation of formula (III) and the heteroatoms reaction of a kind of band aromatic group (Ar); Again with the heteroatoms reaction of another kind band aromatic group (Ar '); The phenanthrene that obtains suc as formula (II) is a verivate, and each A heteroatoms wherein is all independent separately with each B group.
Before explanation phenanthrene of the present invention is synthesizing of verivate and spectral quality; Organic Light Emitting Diode (organic light-emitting diode is described earlier; OLED) structure; The structure of OLED assembly can be injected decorative layer, hole transmission layer, electronic barrier layer (electron-blockinglayer), luminescent layer (emitter), hole blocking layer (hole-blocking layer), electron transfer layer (electron-transporting layer) and negative pole by substrate, positive pole, hole in regular turn and form; Its holes is injected decorative layer, electronic barrier layer and hole blocking layer can not be contained in unit construction, looks the demand of assembly and decides.Multilayered structure between positive pole and negative pole is the electro-luminescent zones (electroluminescent medium) of construction components; The luminescent layer that is comprised in the electro-luminescent zones can be independent luminous organic material or comprises luminous organic material as parent luminophor (host compound), and hotchpotch (dopant) is doped in the parent luminophor (host compound).
In Organnic electroluminescent device of the present invention, comprising: be formed at positive pole on the transparent substrate, be formed at the electro-luminescent zones on the positive pole and be formed at the negative pole on the electro-luminescent zones, wherein to contain phenanthrene of the present invention be verivate to electro-luminescent zones.In electro-luminescent zones, contain luminescent layer, its material can be compsn, comprising: (a) 99.99 to 80 weight % phenanthrene of the present invention is a verivate; And (b) 0.01 to 20 weight % organophosphorus optical molecule, being preferably 99 to 90 weight % phenanthrene of the present invention is verivate; And 1 to 10 weight % organophosphorus optical molecule.
Its China and Philippines are that verivate is the parent luminophor as luminescent layer, and the organophosphorus optical molecule then is object luminophor (guest compound), and luminescent layer can produce the light that wavelength region is 420～700nm.
As stated, in electro-luminescent zones, also can comprise hole transmission layer or electronic barrier layer, and its can be selected from following phenanthrene be verivate:
In addition, in electro-luminescent zones, also can comprise electron transfer layer or hole blocking layer, and its can be selected from following phenanthrene be verivate:
Phenanthrene of the present invention is that verivate is a kind of organic semiconductor conjugated molecule, can be applicable to photoelectricity or semiconductor subassembly.When making organic photoelectric assembly; The mode of the hot vapor deposition of vacuum available forms hole injection layer and hole transmission layer earlier on ito substrate; Vapor deposition phenanthrene of the present invention is verivate and electric transmission layer material again; Evaporation metal negative electrode again can be made into organic electroluminescence assembly or photovoltaic module at last, perhaps can use same processing procedure to make OTFT, organic memory subassembly and organic sensor.
Phenanthrene of the present invention is that verivate is to utilize between C
1With C
10Between two carbon atoms on then the luxuriant and rich with fragrance based compound of two propylidene (or claiming trimethylene) gained be that core element is a core element; Synthetic altogether with other heteroatoms with electrons/affinity; Therefore can increase carrier (electrons/) injection efficiency when making electroluminescence part, the photoelectric efficiency of lifting subassembly.In addition, also because of heteroatomic importing, can reduce phenanthrene is the molecular resonance effect of verivate, increases the molecule energy gap thus.
Therefore, disclosed novel phenanthrene is that verivate can effectively prevent the molecule storehouse and promote carrier speed when making assembly, produces the OLED of high stability, high photoelectric efficiency.Simultaneously, also can be made into and send out the short wavelength photochromic (350～520nm) assembly, or doping phosphorescence or fluorescence molecule object are made into that to send out full the light territory photochromic (400～700nm) and the assembly of white light.
Below the phenanthrene that meets formula of the present invention (I) or formula (II) being detailed is the synthesis step and the dependence test result of verivate:
[embodiment 1]
Synthetic compound 1:
9,10:9, two (trimethylene)-9 of 10-, 10-dihydro phenanthrene (9,10:9,10-bis (trimethylene)-9,10-dihydrophenanthrene)
At first the preparation feedback thing 1, and its reaction formula is following:
Reactant 1
With 2 gram NaOH and 200ml methanol mixed, be heated to 60 ℃.After treating that NaOH dissolves fully, add 3 Ke Fei-9,10-diketone and 4 grams 1, (diethyl1,3-acetonedicarboxylate) (ACROS manufactured, 95%) is kept 60 ℃ to 3-Bing Tongersuosuan diethyl ester.React after 36 hours, add the 10%HCl aqueous solution in addition neutralization precipitation filter.To collect throw out with acetate dissolution, add the 300ml 10%HCl aqueous solution again, reacting by heating 18 hours.Remove acetic acid and water, with the sodium bicarbonate aqueous solution neutralization, sedimentation and filtration separates, and gets the product of reactant 1, productive rate 17%.
Follow synthetic compound 1, its reaction formula is following:
Reactant 1 compound 1
3 gram reactants 1 are mixed with 150ml terepthaloyl moietie, add 0.5 gram N
2H
4(Lancaster manufactured, 98%) stirred after 10 minutes, added 0.5 gram KOH, was heated to 180 ℃, reacted 15 hours.After being cooled to room temperature, thin up gets compound 1, obtains white solid, productive rate 48% with distillation mode purifying again.This compound 1 is a verivate synthetic initial monomers for other phenanthrene of the present invention, and obtaining various phenanthrene of the present invention thus is verivate.
[embodiment 2]
Synthetic compound 2:
9,10:9, two (trimethylene)-2 of 10-, 7-two bromo-9,10-dihydro phenanthrene (9,10:9,10-bis (trimethylene)-2,7-dibromo-9,10-dihydrophenanthrene)
Its building-up reactions formula is following:
[embodiment 3]
Synthetic compound 3:
9,10:9, two (trimethylene)-2 of 10-, the two carbazoles-9 of 7-, 10-dihydro phenanthrene (9,10:9,10-bis (trimethylene) 2,7-biscarbazole-9,10-dihydrophenanthrene)
Its building-up reactions formula is following:
Compound 3
Under nitrogen; 0.4 gram carbazole (carbazole) (Aldrich manufactured, 96%) and 0.5 is digested compound 2 be dissolved in the 40ml o-Xylol solvent, add 0.005 gram palladium (II) salt (Palladium (II) acetate) (Aldrich manufactured; 98%) catalyzer, 0.32 gram uncle's fourth sodium oxide (Sodium t-Butoxide) (Aldrich manufactured; 97%) with tri-butyl phosphine (Across manufactured, 99%) (reflux) reaction 12 hours that refluxes, obtains compound 3; It is a white solid, productive rate 90%.This compound 3 is a verivate for novel phenanthrene of the present invention.
Compound 3 records
1H NMR (400MHz, CDCl
3) spectroscopic data is following: δ (ppm) 1.58-1.64 (m, 2H), 1.69-1.75 (m, 2H), 2.15-2.23 (m, 4H), 2.22-2.29 (m, 4H), 7.30-7.33 (t, 4H), 7.44-7.54 (m, 10H), 7.63-7.64 (d, 2H), 8.17-8.18 (d, 2H).
Its UV-light of the film UV that processes with compound 3
MaxAbsorption spectrum is 340nm, pl-PL
MaxSpectrum is 388nm.
[embodiment 4]
Synthetic compound 4:
9,10:9, two (trimethylene)-2 of 10-, two (pentanoic)-9 of 7-, 10-dihydro phenanthrene (9,10:9,10-bis (trimethylene)-2,7-bis (Diphenyl amine)-9,10-dihydrophenanthrene)
Its building-up reactions formula is following:
With 2.43g (14.4mmol) pentanoic (Aldrich, 97%), 0.1123g (0.036mmol) Pd (OAc)
2(Aldrich, 99%), 1.515g (15.8mmol) uncle fourth sodium oxide (Aldrich, 97%) are got test portion ready and are inserted in the three-necked flask, balloon that contains Ar of cover on the prolong, and vacuumizing to make more than 3 times does not have air in the flask, be full of Ar.Get 3g compound 2,0.29g (1.43mmol) (t-Bu) with airtight pin
3P (STREM, 99%) dewaters with nitrogen, the 150ml o-Xylol (TEDIA, 99%) of oxygen (degas) injects the interior temperature reaction (125 ℃) of three-necked bottle and puts and spend the night.Reaction is accomplished and is obtained white solid product compound 4, productive rate 20%.
This compound 4 is a verivate for the phenanthrene of novelty of the present invention.It is measured
1H NMR (400MHz, CDCl
3) spectroscopic data is following: δ (ppm) 7.70 (d, J=8.80tHz, 2H), 7.51 (t, J=3.80Hz, 4H); 7.21-7.09 (m, 16H), 7.03 (s, 2H), 6.92 (d; J=8.00Hz, 2H), 2.17-1.99 (m, 4H), 1.95-1.88 (m; 4H), and 1.60-1.52 (m, 2H), 1.44-1.35 (m, 2H).
Its UV of film that processes with compound 4
MaxAbsorption spectrum is 382nm, PL
MaxSpectrum is 430nm.
[embodiment 5]
Synthetic compound 5:
9,10:9, two (trimethylene)-2 of 10-, two (the triphenyl silyls)-9 of 7-, 10-dihydro phenanthrene (9,10:9,10-bis (trimethylene)-2,7-bis (triphenylsily) 9,10-dihydrophenanthrene)
Its building-up reactions formula is following:
Under nitrogen, 1g (2.4mmol) compound 2 is dissolved in anhydrous THF (ECHO, 100%) 20ml after, add anhydrous 20ml ether (TEDIA, 99.8%).Temperature of reaction is controlled to-78 ℃, add 3ml (7.5mmol) n-BuLi (Chemetall, 2.5M), treat compound 2 complete reactions after, temperature was increased to stirring at room 15 minutes, reduce to-78 ℃ again.Keep-78 ℃ and stir after five minutes, slowly splash into 1.6g (5.4mmol) chlorosilane (Alfa Aesar, 97%) that is dissolved in anhydrous ether, stir and be warming up to room temperature in 2 hours.Add the entry stopped reaction, with HCl (TEDIA) acidifying of 1N, with EA (TEDIA) extraction, the white solid product of gained is a compound 5, productive rate 15%.
This compound 5 is a verivate for novel phenanthrene of the present invention, and it records
1H NMR (400MHz, CDCl
3) spectrum is as shown in Figure 1, spectroscopic data is following: and δ (ppm) 7.90 (d, J=8.0Hz, 2H), 7.62-7.60 (m, 14H), 7.47-7.38 (m, 20H), 2.06-1.99 (m, 4H), 1.96-1.89 (m, 4H), 1.59-1.51 (m, 2H), 1.46-1.38 (m, 2H).
Its UV of film that processes with compound 5
MaxAbsorption spectrum is 296,321nm, PL
MaxSpectrum is 374, and 394nm is as shown in Figure 4, and wherein transverse axis is wavelength (nm), and the longitudinal axis is unitization (normalized) optical absorption intensity (a.u.).
[embodiment 6]
Synthetic compound 6:
9,10:9, two (trimethylene)-2 of 10-, two (phenyl) pentanoic-9 of 7-, 10-dihydro phenanthrene (9,10:9,10-bis (trimethylene)-2,7-bis (phenyl) diphenylamine-9,10-dihydrophenanthrene)
Its building-up reactions formula is following:
Under nitrogen, with 1g (2.4mmol) compound 2,1.46g (5mmol) 4-(diphenyl amino) phenyl-boron dihydroxide (Aldrich, 97%), 1.7g (12.3mmol) salt of wormwood (SHOWA, 99.5%) and 0.12gPd (Pph
3)
4Toluene of catalyzer and 22ml deoxygenation (TEDIA) and 2ml pure water carried out back flow reaction 24 hours, obtained white solid product compound 6, productive rate 75%.
This compound 6 is a verivate for phenanthrene of the present invention, and its measured 1HNMR (400MHz, CDCl3) spectrum is as shown in Figure 2, and spectroscopic data is following: δ (ppm) 7.88 (d, J=8.44Hz, 2H), 7.51 (d; J=1.78Hz, 2H), 7.45 (d, J=8.63Hz, 4H), 7.37 (dd; J=1.73Hz, J=8.21Hz, 2H), 7.21-7.16 (m, 8H), 7.08-7.06 (m; 12H), 6.96 (t, J=7.26Hz, 4H), 2.17-2.11 (m, 4H); 2.03-1.97 (m, 4H), 1.65-1.55 (m, 2H), 1.48-1.38 (m, 2H).GC MASS collection of illustrative plates is as shown in Figure 3, and MS (m/2, EI): 746 (M
+, 0.11).
Its UV of film that processes with compound 6
MaxAbsorption spectrum is 373nm, PL
MaxPrincipal spectrum is 423nm, and shoulder spectrum is 439nm.
[embodiment 7]
Synthetic compound 7:
9,10:9, two (trimethylene)-2 of 10-, two (4,4,5,5-tetramethyl--1,3,2 dioxygen boryls)-9 of 7-, 10-dihydro phenanthrene (9,10:9,10-bis (trimethylene)-2,7-bis (pinacolato boron)-9,10-dihydrophenanthrene)
Its building-up reactions formula is following:
Under nitrogen, with 6.66 grams two (4,4; 5,5-tetramethyl--1,3; 2 dioxygen boron) (Bis (pinacolato) diboron) (Boron molecular manufactured) and 5 digested compound 2 and is dissolved in 100ml toluene (TEDIA) solvent, and (Dichloro [1 for palladium (II) methylene dichloride affixture to add 4.72 gram Potassium ethanoates and 0.1 gram dichloro [1,1 '-two (phenyl phosphino-) phenanthrene]; 1 '-bis (diphenylphosphino) ferrocene] palladium (II) dichloromethane adduct) (Strem Chem manufactured) catalyzer; Under 60 ℃, reacted 48 hours, and obtained white solid product compound 7, productive rate 75%.
This compound 7 is the verivate midbody for phenanthrene of the present invention, and it is measured
1H NMR (400MHz, CDCl
3) spectroscopic data is following: δ (ppm) 1.36 (s, 24H), 1.41～1.49 (m, 2H), 1.7 (m, 2H), 2.01～2.03 (m, 4H), 2.17～2.19 (m, 4H), 7.65～7.67 (d, 2H), 7.82 (s, 2H), 7.92～7.94 (d, 2H).
[embodiment 8]
Synthetic compound 8:
9,10:9, two (trimethylene)-2 of 10-, two (the 4-bromobenzenes)-9 of 7-, 10-dihydro phenanthrene (9,10:9,10-bis (trimethylene)-2,7-bis (4-bromobenzene)-9,10-dihydrophenanthrene)
Its building-up reactions formula is following:
Under nitrogen; 3.48 gram (12.3mmol) 1-bromo-4-iodobenzenes (Aldrich, 98%) and 3 gram (5.86mmol) compounds 7 are dissolved in 75ml toluene (TEDIA) solvent, add 30ml yellow soda ash (SHOWA; 2M) aqueous solution, 0.45 gram (STREM, 95.9%) Pd (Pph
3)
4Catalyzer, (reflux) reaction 2 hours that under 50 ℃, refluxes obtains white solid product compound 8, productive rate 60%.Compound 8 is measured
1H NMR (400MHz, CDCl
3) spectroscopic data is following: δ (ppm) 7.99 (d, J=8.37,2H), 7.60-7.57 (m, 6H), 7.45-7.42 (m, 6H), 2.17-2.11 (m, 4H), 2.03-1.97 (m, 4H), 1.65-1.55 (m, 2H), 1.48-1.38 (m, 2H).
[embodiment 9]
Synthetic compound 9:
9,10:9, two (trimethylene)-2 of 10-, two (triphenyl silyl) phenyl-9 of 7-, 10-dihydro phenanthrene (9,10:9,10-bis (trimethylene)-2,7-bis (triphenylsily) phenyl-9,10-dihydrophenanthrene)
Its building-up reactions formula is following:
Compound 9
Under nitrogen with anhydrous THF (ECHO, 100%) 20ml with 1.37g (2.4mmol) compound 8 dissolving after, add anhydrous 20ml ether (TEDIA, 99.8%).Temperature of reaction is controlled to-78 ℃, add 3ml (7.5mmol) n-BuLi (Chemetall, 2.5M), treat compound 8 complete reactions after, temperature was increased to stirring at room 15 minutes, reduce to-78 ℃ again.Keep-78 ℃ and stir after five minutes, slowly splash into 1.6g (5.4mmol) chlorosilane (Alfa Aesar, 97%) that is dissolved in anhydrous ether, stir and be warming up to room temperature in 2 hours.Add the entry stopped reaction,,, obtain white solid product compound 9, productive rate 15% with EA (TEDIA) extraction with HCl (TEDIA) acidifying of 1N.
This compound 9 is a verivate for phenanthrene of the present invention, and it is measured
1H NMR (400MHz, CDCl
3) spectroscopic data is following: δ (ppm) 8.60 (d, J=20Hz, 4H), 7.91 (d, J=8.0Hz, 2H); 7.63-7.60 (m, 16H), 7.46-7.37 (m, 22H), 2.06-1.99 (m, 4H); 1.96-1.89 (m, 4H), 1.59-1.51 (m, 2H), 1.46-1.38 (m, 2H).
Its UV of film that processes with compound 9
MaxAbsorption spectrum is 345nm, PL
MaxPrincipal spectrum is 384nm, and shoulder spectrum is 405nm.
[embodiment 10]
The PL spectrum test of doping green phosphorescent molecules
With 0.02 the gram compound 5 at N
2Under the environment, be dissolved among the dry toluene solvent 10cc, concentration of ordinary dissolution is 2 weight %.Again respectively with the Ir (ppy) of 0.0004 gram with 0.0016 gram
3Phosphorescent molecules (LumTec., Chun Du>99%, chemical structure is as follows) be dissolved in the toluene solution of compound 5 Ir (ppy) wherein
3The weight percent that accounts for compound 5 is respectively 2 weight % and 8 weight %.
Ir(ppy)
3
This solution is spin-coated on the quartz glass plate that has cleaned, and (HitachiFL-7500) tests its luminescent spectrum with XRF, and test result is as shown in Figure 5, wherein Ir (ppy)
3Be the PL of 2 weight %
MaxSpectrum is 508nm; Ir (ppy)
3Be the PL of 8 weight %
MaxSpectrum is 512nm.Can be known by the PL collection of illustrative plates: the excitation energy of compound 5 can be transferred to Ir (ppy) smoothly
3On the phosphorescent molecules (dopant).
[embodiment 11]
The PL spectrum test of doping blue light phosphorescent molecules
With 0.02 the gram compound 5 at N
2Under the environment, be dissolved among the dry toluene solvent 10cc, concentration of ordinary dissolution is 2 weight %.Again 0.0012 gram FIrPic blue light phosphorescent molecules (Lum Tec, purity>99%, chemical structure is following) is dissolved in compound 5 toluene solutions, wherein to account for the weight percent of compound 5 be 6 weight % to the blue light phosphorescent molecules.
FIrPic
This solution is spin-coated on the quartz glass plate that has cleaned, and (HitachiFL-7500) tests its luminescent spectrum with XRF, and test result is as shown in Figure 5, the PL of compound 5
MaxSpectrum is 374,394nm.Behind the FIrPic blue light phosphorescent molecules of doping 6%, PL
MaxSpectrum moves to 472nm.Can be known by the PL collection of illustrative plates: the excitation energy of compound 5 can be transferred on the FIrPic blue light phosphorescent molecules (dopant) smoothly.
[embodiment 12]
The PL spectrum test of doping ruddiness phosphorescent molecules
With 0.02 the gram compound 6 at N
2Under the environment, be dissolved among the dry toluene solvent 10cc, concentration of ordinary dissolution is 2 weight %.Again with 0.0012 gram Ir (btp)
2(acac) (Lum Tec, Chun Du>99%, chemical structure is following) the ruddiness phosphorescent molecules is dissolved in compound 6 toluene solutions, and wherein to account for the weight percent of compound 6 be 6 weight % to the ruddiness phosphorescent molecules.
Ir(btp)
2(acac)
This solution is spin-coated on the quartz glass plate that has cleaned, and (HitachiFL-7500) tests its luminescent spectrum with XRF, and test result is as shown in Figure 6, the PL of compound 6
MaxSpectrum is 425nm, the Ir (btp) of doping 6%
2(acac) after, PL
MaxSpectrum moves to 614nm.Can be known by the PL collection of illustrative plates: the excitation energy of compound 6 is transferred to Ir (btp)
2(acac) on the ruddiness phosphorescent molecules (dopant).
[embodiment 13]
The making of Organic Light Emitting Diode (OLED) assembly
The OLED unit construction of embodiment 13 is as shown in Figure 7, with compound 6 at N
2Under the environment, be dissolved in the dry toluene solvent, concentration of ordinary dissolution is 2 weight %.PEDOT-PSS 4083 is gathered (Ethylenedioxy Thiophene) (poly (ethylenedioxythiophene); Available from Bayer Co.) be spin-coated on having on transparency electrode ITO 20 glass substrate 10 on it of having cleaned; Be used as hole transmission layer 30, its thickness is 80nm.The solution that is dissolved with compound 6 is spun on the PEDOT layer with the 1500rpm rotating speed, forms the luminescent layer 40 of the about 80nm of thickness, send into again and be evacuated to 10 in the vacuum chamber
-6Holder, the Ca of vapor deposition 50nm thickness is used as cathode electrode 50, then vapor deposition thickness be the A1 of 200nm as resist 60, accomplish the making of assembly again with the deckglass encapsulation.The photoelectric property of last test assembly can be known by Fig. 8, is that verivate is applied on the OLED assembly with phenanthrene of the present invention, and its luminosity can reach 100 nits (candle light number/square centimeter, cd/m
2) more than, current efficiency is about 0.31cd/A at 9.8V.
Though the present invention has disclosed preferred embodiment as above; Right its is not that any those skilled in the art are not breaking away from the spirit and scope of the present invention in order to qualification the present invention; When can doing a little change and retouching, so protection scope of the present invention is when being as the criterion with accompanying claims.
Claims (10)
1. a phenanthrene is a verivate, and its molecular structure is listed as follows:
2. Organnic electroluminescent device comprises:
Be formed at the positive pole on the transparent substrate;
Be formed at the electro-luminescent zones on this positive pole; And
Be formed at the negative pole on this electro-luminescent zones,
Wherein to contain the phenanthrene of claim 1 be verivate to this electro-luminescent zones.
3. the Organnic electroluminescent device of claim 2, wherein this electro-luminescent zones comprises luminescent layer, and this luminescent layer comprises the constituent that the phenanthrene that contains claim 1 is a verivate.
4. the Organnic electroluminescent device of claim 3, wherein this constituent comprises:
(a) 99.99 phenanthrene to the claim 1 of 80 weight percents are verivate; And
(b) the organophosphorus optical molecule of 0.01 to 20 weight percent.
5. the Organnic electroluminescent device of claim 4, wherein this phenanthrene in this constituent is that the weight percent of verivate is 99 to 90, the weight percent of this organophosphorus optical molecule is 1 to 10.
6. the Organnic electroluminescent device of claim 3, when voltage acted on this positive pole and this negative pole, this luminescent layer can produce the light that wavelength region is 350～550nm.
7. the Organnic electroluminescent device of claim 3, wherein this phenanthrene is that verivate is the parent luminophor of this luminescent layer.
8. claim 4 or 5 Organnic electroluminescent device, wherein this phenanthrene is that verivate is the parent luminophor of this luminescent layer, and this organophosphorus optical molecule is the object luminophor, and this luminescent layer can produce the light that wavelength region is 420～700nm.
9. the Organnic electroluminescent device of claim 2, wherein this electro-luminescent zones comprises hole transmission layer or electronic barrier layer.
10. the Organnic electroluminescent device of claim 2, wherein this electro-luminescent zones comprises electron transfer layer or hole blocking layer, and it is verivate that this electron transfer layer or hole blocking layer comprise the phenanthrene that is selected from following molecular structure:
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| CN101654399B (en) * | 2008-08-18 | 2014-06-18 | 财团法人工业技术研究院 | Phenanthrene benzene derivative and polymer thereof, copolymer containing phenanthrene benzene derivative and luminous material composition |
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