CN1747944A - Blue light-emitting compound, method for producing same and light-emitting device utilizing same - Google Patents

Blue light-emitting compound, method for producing same and light-emitting device utilizing same Download PDF

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CN1747944A
CN1747944A CN 200480003846 CN200480003846A CN1747944A CN 1747944 A CN1747944 A CN 1747944A CN 200480003846 CN200480003846 CN 200480003846 CN 200480003846 A CN200480003846 A CN 200480003846A CN 1747944 A CN1747944 A CN 1747944A
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blue light
emitting compound
compound
aforementioned
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仲矢忠雄
松本良二
飞田道昭
犀川知行
江藤直伸
石飞达郎
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Hirose Engineering Co Ltd
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Abstract

The present invention provides blue-light emitting compounds capable of emitting blue light at a high luminance for a long time upon the application of electric energy, processes of producing the compounds, and luminescent elements including the blue light-emitting compounds. The blue-light emitting compounds according to the present invention have the chemical structure represented by formula (1).

Description

Blue light-emitting compound, its manufacture method and the luminescence component that utilizes this
Technical field
The luminescence component that the present invention relates to a kind of blue light-emitting compound, its manufacture method and utilize this, particularly relate to blue light-emitting compound, its manufacture method and the luminescence component that utilizes this that a kind of supply applies energy (applying energy) and can send out high the blue light of briliancy, fluorescent lifetime length.
Background technology
In the past, advised as the organic luminescent assembly various organic compound of (also being called organic el element).But, high brightness and can be for a long time constantly the organic compound of blue light-emitting still also be not developed now.
Summary of the invention
Purpose of the present invention is providing a kind of blue light-emitting compound exactly, its manufacture method and the luminescence component that utilizes this, the blue light that can send out briliancy high and can be luminous constantly for a long time.
For solving foregoing problems, a kind of blue light-emitting compound of proposition of the present invention (hereinafter referred to as " first kind of blue light-emitting compound ") is characterized in that this blue light-emitting compound has the structural formula shown in the following formula (1),
Figure A20048000384600071
But, the R in the formula (1) 1Be carbon number at 1～15 alkyl (alkyl), carbon number at cycloalkyl (cycloalkyl) or the aryl (aryl) shown in the following formula (1-1)～(1-4), wherein two R of 6～15 1Can be identical or different, R 2Be aryl or the furyl (furyl) in the following formula (1-1)～(1-4), R 3Be base or the hydrogen atom shown in the following formula (2),
Figure A20048000384600072
(the X in the formula 1Be carbon number at 1～10 alkyl, the alkyl or the hydrogen atom of carbon number 1～10 contain fluorine atoms, n is 1～15 integer.)
Figure A20048000384600081
(the X in the formula 1As hereinbefore, Y be carbon number at 1～10 alkyl, the alkyl or the hydrogen atom of carbon number 1～10 contain fluorine atoms, m is 1～3 integer, q is 1～4 integer, and X 1With Y can be identical or different.)
(X 1, Y, m and q as hereinbefore, and X 1With Y can be identical or different.)
Figure A20048000384600083
(X 1, Y, n and q as hereinbefore, and X 1With Y can be identical or different.)
R in the formula (2) 2As hereinbefore, the R that works as formula (1) 3When being basic shown in the formula (2), R 2Can combine or R with oxadiazoles base (oxadiazolyl) on one side 2Can combine with the oxadiazoles base of the other side, and can be mutually identical or different.
The present invention reintroduces a kind of blue light-emitting compound (hereinafter referred to as " second kind of blue light-emitting compound "), it is characterized in that this blue light-emitting compound has the structural formula shown in the following formula (3),
Figure A20048000384600092
R in the formula 1Identical with in first kind of blue light-emitting compound, R 4Be the aryl shown in hydrogen atom or the following formula (3-1)～(3-2), four R wherein 4Can be identical or different.
(the R in the formula (3-1) 5Be hydrogen atom or carbon number at 1～5 alkyl.)
(the R in the formula (3-2) 6Be hydrogen atom or carbon number at 1～5 alkyl, and n is described identical with first kind of blue light-emitting compound.)
The present invention proposes a kind of manufacture method of blue light-emitting compound in addition, comprise that dicarboxylic acid (dicarboxylic acid) compound shown in the following formula (4) and halogen (halogen) are changed chlorination acid compound that the agent reaction obtains to react with hydrazides (hydrazide) compound and obtain the blue light-emitting compound intermediate product shown in the following formula (5), again this kind blue light-emitting compound intermediate product is carried out dehydration reaction, to obtain
Blue light-emitting compound shown in the following formula (6),
Figure A20048000384600101
R in the formula 1Identical with in first kind of blue light-emitting compound.
R in the formula 1, R 2Identical with in first kind of blue light-emitting compound.
Figure A20048000384600103
R 1And R 2As hereinbefore.
The present invention proposes a kind of manufacture method of blue light-emitting compound again, comprising that the chlorination acid compound that the carboxylic acid cpd shown in the following formula (7) and halogen agent reaction is obtained reacts with hydrazide compound obtains the intermediate product shown in the following formula (8), again this intermediate product is carried out dehydration reaction, to obtain the blue light-emitting compound shown in the following formula (9)
R in the formula 1Identical with in first kind of blue light-emitting compound,
Figure A20048000384600112
R in the formula 1, R 2Identical with in first kind of blue light-emitting compound,
Figure A20048000384600113
R 1And R 2As hereinbefore.
The present invention proposes a kind of manufacture method of blue light-emitting compound again, comprise that fluorenes (fluorene) compound shown in the halogenation following formula (10) obtains the aromatic series halogen compounds shown in the following formula (11), make aromatic series halogen compounds and triphenyl phosphine (triphenylphosphine) reaction then, to obtain an organo phosphorous compounds, make the reaction of organo phosphorous compounds and carbonyl (carbonyl) compound again, with the blue light-emitting compound shown in the formula (3) that obtains aforementioned second kind of blue light-emitting compound.
(the R in the formula 1Identical with in first kind of blue light-emitting compound.)
(the R in the formula 1Identical with in first kind of blue light-emitting compound, and Hal is meant halogen atom.)
The present invention proposes a kind of luminescence component again, it is characterized in that this luminescence component comprises a luminescent layer, and luminescent layer contains the blue light-emitting compound shown in aforementioned formula (1) or the formula (3).
The present invention is because of adopting the compound of aforementioned formula (1) or formula (3) blue-light-emitting, therefore utilizes blue light that the luminescence component of this compound can send out briliancy high and can be luminous constantly for a long time.
The present invention compared with prior art has tangible advantage and beneficial effect.Via as can be known above-mentioned, the invention relates to a kind of blue light-emitting compound, its manufacture method and the luminescence component that utilizes this.This blue light-emitting compound, its manufacture method and the luminescence component that utilizes this apply energy and can send out high briliancy, the long blue light of fluorescent lifetime with supply.And blue light-emitting compound of the present invention has following formula (1),
Figure A20048000384600122
Shown structural formula.
Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technique means of the present invention, and can be implemented according to the content of specification sheets, and for above-mentioned and other purposes, feature and advantage of the present invention can be become apparent, below especially exemplified by preferred embodiment, and conjunction with figs., be described in detail as follows.
Description of drawings
Fig. 1 is the explanatory view of the luminescence component of a relevant example of the present invention.
Fig. 2 is the explanatory view of the luminescence component of relevant another example of the present invention.
Fig. 3 is the relevant explanatory view of the luminescence component of an example more of the present invention.
Fig. 4 is the explanatory view of the luminescence component of relevant another example of the present invention.
Fig. 5 is by the nucleus magnetic resonance of the blue light-emitting compound of first embodiment of the present invention gained (nuclear magnetic resource, NMR) figure spectrogram (spectrum chart).
Fig. 6 is by the infrared rays of the blue light-emitting compound of first embodiment of the present invention gained (infrared ray, IR) figure spectrogram.
Fig. 7 is the fluorescence spectrum figure by the blue light-emitting compound of first embodiment of the present invention gained.
Fig. 8 is the NMR figure spectrogram by the blue light-emitting compound of second embodiment of the present invention gained.
Fig. 9 is the IR figure spectrogram by the blue light-emitting compound of second embodiment of the present invention gained.
Figure 10 is the fluorescence spectrum figure by the blue light-emitting compound of second embodiment of the present invention gained.
Figure 11 is the NMR figure spectrogram by the blue light-emitting compound of third embodiment of the present invention gained.
Figure 12 is the IR figure spectrogram by the blue light-emitting compound of third embodiment of the present invention gained.
Figure 13 is the fluorescence spectrum figure by the blue light-emitting compound of third embodiment of the present invention gained.
Figure 14 is the NMR figure spectrogram by the blue light-emitting compound of fourth embodiment of the present invention gained.
Figure 15 is the IR figure spectrogram by the blue light-emitting compound of fourth embodiment of the present invention gained.
Figure 16 is the fluorescence spectrum figure by the blue light-emitting compound of fourth embodiment of the present invention gained.
Figure 17 is the NMR figure spectrogram by the blue light-emitting compound of fifth embodiment of the present invention gained.
Figure 18 is the IR figure spectrogram by the blue light-emitting compound of fifth embodiment of the present invention gained.
Figure 19 is the fluorescence spectrum figure by the blue light-emitting compound of fifth embodiment of the present invention gained.
Figure 20 is the NMR figure spectrogram by the blue light-emitting compound of sixth embodiment of the present invention gained.
Figure 21 is the IR figure spectrogram by the blue light-emitting compound of sixth embodiment of the present invention gained.
Figure 22 is the NMR figure spectrogram by the blue light-emitting compound of seventh embodiment of the present invention gained.
Figure 23 is the IR figure spectrogram by the blue light-emitting compound of seventh embodiment of the present invention gained.
Figure 24 is the NMR figure spectrogram by the blue light-emitting compound of eighth embodiment of the present invention gained.
Figure 25 is the IR figure spectrogram by the blue light-emitting compound of eighth embodiment of the present invention gained.
Figure 26 is the NMR figure spectrogram by the blue light-emitting compound of ninth embodiment of the present invention gained.
Figure 27 is the IR figure spectrogram by the blue light-emitting compound of ninth embodiment of the present invention gained.
Figure 28 is the fluorescence spectrum figure by the blue light-emitting compound of tenth embodiment of the present invention gained.
Figure 29 is the NMR figure spectrogram by the blue light-emitting compound of eleventh embodiment of the invention gained.
Figure 30 is the IR figure spectrogram by the blue light-emitting compound of eleventh embodiment of the invention gained.
Figure 31 is the fluorescence spectrum figure by the blue light-emitting compound of eleventh embodiment of the invention gained.
Figure 32 is the NMR figure spectrogram by the blue light-emitting compound of twelveth embodiment of the invention gained.
Figure 33 is the IR figure spectrogram by the blue light-emitting compound of twelveth embodiment of the invention gained.
Figure 34 is the fluorescence spectrum figure by the blue light-emitting compound of twelveth embodiment of the invention gained.
Figure 35 is the fluorescence spectrum figure by the blue light-emitting compound of twelveth embodiment of the invention gained.
1: substrate 2: transparency electrode
3,3a, 3b: luminescent layer 4: electrode layer
5: electric hole transfer layer 6,8: electron supplying layer
A, B, C, D: luminescence component
Embodiment
Reach technique means and the effect that predetermined goal of the invention is taked for further setting forth the present invention, below in conjunction with accompanying drawing and preferred embodiment, blue light-emitting compound, its manufacture method that foundation the present invention is proposed and its embodiment of luminescence component, structure, method, step, feature and the effect thereof of utilizing this, describe in detail as after.
Relevant blue light-emitting compound of the present invention has the structural formula shown in the following formula (1).
Figure A20048000384600141
Blue light-emitting compound shown in the relevant formula of the present invention (1) is a part fluorenes (fluorene) bone lattice with at least one molecule, is that the basic bone lattice of 4-body oxadiazoles (oxadiazole) bone lattice constitute with dimolecular 1,3 ideally.
When there is carbon 9 positions of aforementioned fluorenes bone lattice then in conjunction with the R of a part at least 1, and aforementioned 1,3,4-body oxadiazoles then with different carbon and the R of aforementioned fluorenes institute's bonded carbon 2In conjunction with.
Aforementioned R 1Be carbon number at 1～15 alkyl, carbon number at 6～15 cycloalkyl or the aryl shown in the formula of usefulness (1-1)～(1-4) as an illustration below.In addition, R 2Be aryl or the furyl shown in the formula of usefulness (1-1)～(1-4) as an illustration below, R 3Be base or the hydrogen atom shown in the following formula (2).And, two R 1Can be identical or different.
R shown in aforementioned 1Comprise that carbon number is in 1～15 alkyl, for example usefulness as an example such as methyl, ethyl, propyl group, sec.-propyl, n-butyl, isobutyl-, second butyl, tributyl, n-amyl group, second amyl group, the 3rd amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl.Wherein, be preferably the alkyl that contains 1～10 carbon, as methyl, ethyl, propyl group, sec.-propyl, n-butyl, isobutyl-, second butyl, tributyl, n-amyl group, second amyl group, the 3rd amyl group, hexyl, heptyl, octyl group, nonyl, decyl etc.Better person is the alkyl that contains 1～6 carbon.
And the R shown in aforementioned 1Comprise that also carbon number is in 6～15 cycloalkyl, the metathetical cycloalkyl of for example inner substituent bonded cycloalkyl, inner alkyl etc.Wherein, be preferably cycloalkyl.
Figure A20048000384600142
Aryl shown in the aforementioned formula (1-1) is the basic bone lattice as phenyl.
X in aforementioned formula (1-1) 1Be that carbon number is at 1～10 alkyl, the alkyl or the hydrogen atom of carbon number 1～10 contain fluorine atoms.
X shown in aforementioned 1Being carbon number at 1～10 alkyl, then for example is methyl, ethyl, propyl group, sec.-propyl, n-butyl, isobutyl-, second butyl, tributyl, n-amyl group, second amyl group, the 3rd amyl group, hexyl, heptyl, octyl group, nonyl, decyl etc.Wherein, be preferably methyl, ethyl, propyl group, sec.-propyl, n-butyl, isobutyl-, second butyl, tributyl, n-amyl group, second amyl group, the 3rd amyl group, n-hexyl etc.
X shown in aforementioned 1Being the alkyl of carbon number 1～10 contain fluorine atoms, then is the alkyl that comprises at least one fluorine atom, for example methyl fluoride (fluoromethyl), difluoromethyl, trifluoromethyl, fluoro ethyl, 1,1-two fluoro ethyls, 1,2-two fluoro ethyls, 1,1, the 1-trifluoroethyl, 1,1, the 2-trifluoroethyl, 1,2, the 2-trifluoroethyl, 1,1,2,2-tetrafluoro ethyl, 1,1,1,2, the 2-pentafluoroethyl group, the 1-fluoropropyl, the 2-fluoropropyl, 1,1-two fluoropropyls, 1,2-two fluoropropyls, 1,3-two fluoropropyls, 2,2-two fluoropropyls, 1,1, the 1-trifluoro propyl, 1,1, the 2-trifluoro propyl, 1,2, the 3-trifluoro propyl, 1,2, the 2-trifluoro propyl, 1,3,3-trifluoro propyls etc. wherein are preferably the contain fluorine atoms alkyl that contains 1～3 carbon.
N in aforementioned formula (1-1) is aforementioned X 1In conjunction with the number of phenyl, and aforementioned phenyl contains 1～5 X 1
In addition, aforementioned aryl can be formula (1-2) or the formula (1-3) shown in following.And the numeral 1～8 in these formulas is meant the number of position.
Figure A20048000384600151
Aryl shown in the formula (1-2) is the basic bone lattice of naphthyl (naphthyl), wherein has one at least in 2,3 or 4 position and is and X 1In conjunction with, and in 5,6,7 or 8 position, have at least one to combine with Y.
Figure A20048000384600161
Aryl shown in the formula (1-3) is the basic bone lattice of naphthyl, wherein has one at least in 1,3 or 4 position and is and X 1In conjunction with, and in 5,6,7 or 8 position, have at least one to combine with Y.
The X of aforementioned formula (1-2) and formula (1-3) 1Be the kind described in the aforementioned formula (1-1).
M in aforementioned formula (1-2) and formula (1-3) is aforementioned X 1In conjunction with number, and aforementioned naphthyl contains 1～3 X in the naphthyl bonded 1
Aforementioned Y is the alkyl that 1～10 carbon is arranged, contain fluorine atoms alkyl or the hydrogen atom that 1～10 carbon is arranged.
Y shown in aforementioned is an alkyl, then for example is methyl, ethyl, propyl group, sec.-propyl, n-butyl, isobutyl-, second butyl, tributyl, n-amyl group, second amyl group, the 3rd amyl group, hexyl, heptyl, octyl group, nonyl, decyl etc.
If the alkyl of contain fluorine atoms then for example is a methyl fluoride, difluoromethyl, trifluoromethyl, fluoro ethyl, 1,1-two fluoro ethyls, 1,2-two fluoro ethyls, 1,1, the 1-trifluoroethyl, 1,1, the 2-trifluoroethyl, 1,2, the 2-trifluoroethyl, 1,1,2,2-tetrafluoro ethyl, 1,1,2,2, the 2-pentafluoroethyl group, the 1-fluoropropyl, the 2-fluoropropyl, 1,1-two fluoropropyls, 1,2-two fluoropropyls, 1,3-two fluoropropyls, 2,2-two fluoropropyls, 1,1, the 1-trifluoro propyl, 1,1, the 2-trifluoro propyl, 1,2, the 3-trifluoro propyl, 1,2, the 2-trifluoro propyl, 1,3, the fluorinated alkyl that contains 1～3 carbon of 3-trifluoro propyl etc.
The q of aforementioned formula (1-2) and formula (1-3) be aforementioned Y at naphthyl bonded number, and aforementioned naphthyl contains 1～4 X 1
And, the X of aforementioned formula (1-2) and formula (1-3) 1With Y can be identical or different.
Moreover aforementioned aryl also can be the formula (1-4) shown in following.And the numeral 1～6 and 1 '～6 ' in this formula is meant the number of position.
Aryl shown in the formula (1-4) is the basic bone lattice of xenyl (biphenyl), wherein has one at least in 2 ', 3 ', 5 ' or 6 ' position and is and X 1In conjunction with, and in 2,3,5 or 6 position, have at least one to combine with Y.
Aforementioned X 1, Y, n and q be aforementioned formula (1-1), (1-2) with (1-3) described in kind.
And, the X of aforementioned formula (1-4) 1With Y also can be identical or different.
And aforementioned R 3Be shown in the formula (2).
R in formula (2) 2As hereinbefore.
In addition, relevant blue light-emitting compound of the present invention can also be to have the structural formula shown in the following formula (2).
Figure A20048000384600172
About the blue light-emitting compound shown in the formula of the present invention (3) is by a part fluorenes bone lattice and dimolecular unsaturated double-bond base (CH=C (R 4) 2) basic bone lattice constitute.
When there is carbon 9 positions of aforementioned fluorenes bone lattice then in conjunction with the R of a part at least 1, when there is carbon 2 positions of aforementioned unsaturated double-bond base then in conjunction with the R of a part at least 4
Aforementioned R 1With the R in the formula (1) 1Identical.
Aforementioned R 4It is the aryl shown in hydrogen atom or the formula (3-1)～(3-2).Two R 1Can be identical or different.Four R 4Can be identical or different.
Figure A20048000384600181
R in the formula (3-1) 5Be hydrogen atom or the alkyl that 1～5 carbon is arranged.
Aforementioned R 5Be hydrogen atom or the alkyl that 1～5 carbon is arranged.
R shown in aforementioned 5Be the words that the alkyl of 1～5 carbon is arranged, then for example be methyl, ethyl, propyl group, sec.-propyl, n-butyl, isobutyl-, second butyl, tributyl, n-amyl group, second amyl group, the 3rd amyl group etc., wherein be preferably the alkyl that methyl, ethyl, propyl group, sec.-propyl etc. contain 1～3 carbon.
Figure A20048000384600182
R in the aforementioned formula (3-2) 6Be hydrogen atom or the alkyl that 1～5 carbon is arranged.
Aforementioned the alkyl of 1～5 carbon is arranged for example is methyl, ethyl, propyl group, sec.-propyl, n-butyl, isobutyl-, second butyl, tributyl, n-amyl group, second amyl group, the 3rd amyl group etc., wherein is preferably the alkyl that methyl, ethyl, propyl group, sec.-propyl etc. contain 1～3 carbon.
In addition, the n in the aforementioned formula (3-2) is aforementioned R 6In conjunction with the number of phenyl, and aforementioned phenyl contains 1～5 R 6
R in the blue light-emitting compound shown in formula (1) and the formula (3) 1Be that electronics disengages base (electron-releasing group), R 2With R 4Shown in be in whole (bulk) high aryl, be affected arround fluorenes (fluorene) the bone lattice, thus in the basic bone lattice of blue light-emitting compound matter, because of πDian Zi cloud density improve more stable, so should infer that needing only some energy just can send blue light easily.Relevant blue light-emitting compound of the present invention is according to R 1Disengaging property of electronics base provide the structure of electronics as supplementary features at the πDian Zi cloud aspect the basic bone lattice of blue light-emitting compound.This blue light-emitting compound is because there is stable bone lattice to make, so chemistry is stable, and not under too harsh working conditions, to wearing and tearing aspect performance specificity.
Next be the manufacture method of the blue light-emitting compound shown in the relevant formula of the present invention (1).
That is, make (dicarboxylic acid) compound of the dicarboxylic acid shown in the following formula (4) and halogen (halogen) change the agent reaction.
Figure A20048000384600191
But, the R in the formula 1As described above.
Aforementioned halogen agent is to use general solvent that the hydroxyl (hydroxyl) of carboxyl is replaced as halogen atom.And the example of halogen agent is thionyl chloride (thionyl chloride), SULPHURYL CHLORIDE (sulfonyl chloride), sulfonyl chlorination (sulfuryl chloride), phosphorus oxychloride, phosphorus pentachloride, hydrogen fluoride, chlorine trifluoride, phosphorus trifluoride, iodine pentafluoride, hydrogen bromide, hypobromous acid, thionyl bromide etc. for example.
React in the solvent that dicarboxylic acid compound shown in the aforementioned formula (4) and aforementioned halogen agent are easy to heat.And aforementioned solvents can use aceticanhydride (acetic anhydride), acetic acid, carbon number at the aromatic solvent of the acid anhydrides below 5, benzene and toluene etc., dioxan (dioxane) etc.Temperature of reaction is preferably at 60～90 ℃ usually at 30～120 ℃.After reaction, can obtain the chlorination acid compound shown in the following formula (7) by the purification operations of known techniques and lock out operation.
Figure A20048000384600192
But, the R shown in the aforementioned formula (12) 1Identical with in the formula (1), and Hal is meant halogen atoms such as fluorine atom, chlorine atom, bromine atoms, iodine atom.
Then, make hydrazides (hydrazide) the compound reaction shown in chlorination acid compound shown in the aforementioned formula (12) and the formula (13).
R 2-CONHNH 2 (13)
But, the R shown in the aforementioned formula (13) 2With the R in the formula (1) 2Identical.
The reaction of aforementioned chlorination acid compound and aforementioned hydrazide compound is to react in the solvent that is easy to heat.And solvent can use aceticanhydride, acetic acid, carbon number at the aromatic solvent of the acid anhydrides below 5, benzene and toluene etc., dioxan, pyridine (pyridine), tetrahydrofuran (THF) (tetrahydrofuran) etc.Temperature of reaction is usually at 30～80 ℃.After reaction, can obtain the blue light-emitting compound intermediate product (intermediate) shown in the following formula (5) by the purification operations of known techniques and lock out operation.
But, the R in the formula (5) 1With R 2Identical with the connotation in the formula (1).
Afterwards, begin to carry out dehydration reaction, so that the carbon atom in the solvent of heating of the blue light-emitting compound intermediate product shown in the aforementioned formula (5) is combined with Sauerstoffatom and nitrogen-atoms combines with hydrogen atom, to obtain the blue light-emitting compound shown in the following formula (6).And solvent can use aceticanhydride, acetic acid, carbon number at the aromatic solvent of the acid anhydrides below 5, benzene and toluene etc., dioxan, pyridine, tetrahydrofuran (THF), phosphoryl chloride (phosphoryl chloride) etc.Temperature of reaction is usually at 30～80 ℃.After reaction, can obtain blue light-emitting compound of the present invention by the purification operations of known techniques and lock out operation.
Blue light-emitting compound shown in the relevant formula of the present invention (1) can easily create by heating blue light-emitting compound intermediate product.And this blue light-emitting compound intermediate product can easily create by adding thermal chlorination acid compound and aforementioned hydrazide compound.Moreover heating can be easy to carry out in the reaction of dicarboxylic acid importing halogen atom.Therefore, the manufacture method of this easy blue light-emitting compound can be used as the manufacture method of industry.
It is manufactured too to contain the blue light-emitting compound shown in the following formula (9) in the relevant formula of the present invention (1).
Figure A20048000384600202
R in the formula (9) 1With R 2With aforementioned identical.
Then, with monocarboxylic acid compound shown in the formula (7) and halogen agent reaction.
Figure A20048000384600211
But, the R in the formula (7) 1As hereinbefore.
And aforementioned halogen agent is identical with the halogen agent of the dicarboxylic acid compound reaction shown in the formula (4).
The reaction conditions of the monocarboxylic acid compound shown in the aforementioned formula (7) and aforementioned halogen agent is the same with the reaction conditions of dicarboxylic acid compound shown in the formula (4) and halogen agent, reaction easily.And the solvent during reaction is carried out, temperature of reaction, purification operations and lock out operation are all as hereinbefore.The result obtains the chlorination acid compound shown in the following formula (14).
But, the R in the formula (14) 1Identical with the connotation in the formula (1), and Hal is meant halogen atoms such as fluorine atom, chlorine atom, bromine atoms, iodine atom.
Then, make the hydrazide compound reaction shown in chlorination acid compound shown in the aforementioned formula (14) and the aforementioned formula (13).And the condition that its reaction conditions and the chlorination acid compound shown in the aforementioned formula (12) and the reaction of hydrazides (hydrazide) compound shown in the formula (13) are carried out is identical.
So, then obtain the intermediate product shown in the formula (8).
Figure A20048000384600213
Afterwards, begin to carry out dehydration reaction, so that the carbon atom in the solvent of heating of the intermediate product shown in the aforementioned formula (8) is combined with Sauerstoffatom and nitrogen-atoms combines with hydrogen atom.And be identical when the dehydration reaction with the blue light-emitting compound intermediate product shown in the formula (5) about the solvent during the dehydration reaction, temperature of reaction etc.
After reaction, can obtain blue light-emitting compound of the present invention by the purification operations of known techniques and lock out operation.
Blue light-emitting compound shown in the relevant formula of the present invention (9) can easily create by the aforementioned intermediate product of heating.And this intermediate product can easily create by adding thermal chlorination acid compound and aforementioned hydrazide compound.Moreover heating can be easy to carry out in the reaction of monocarboxylic acid importing halogen atom.Therefore, the manufacture method of this easy blue light-emitting compound can be used as the manufacture method of industry.
In addition, the blue light-emitting compound shown in the relevant formula of the present invention (3) also can be by ensuing method manufacturing.
That is fluorenes (fluorene) compound shown in the formula (10) below the halogenation.
But, the R in the formula (10) 1As hereinbefore.
And the solution that the aforementioned fluorene compound dissolving in organic solvent obtains is added into after the acid, with this solution heating, to obtain the aromatic series halogen compounds shown in the following formula (11).
Figure A20048000384600222
But, the R in the formula (11) 1As hereinbefore, and Hal is meant halogen atoms such as fluorine atom, chlorine atom, bromine atoms, iodine atom.
And aforementioned organic solvent can be used formaldehyde, acetaldehyde, aceticanhydride, acetic acid, Glacial acetic acid, benzene, toluene, dioxan, pyridine, tetrahydrofuran (THF) etc.
The acid of the available halogen atom-containing of aforementioned acid, there is no particular restriction, for example, hydrogen halide such as hydrogen fluoride, hydrochloric acid, hydrogen bromide, hydrogen iodide or formula hypochlorous acid, chlorous acid, chloric acid, crosses carbonyl acid such as chloric acid, hypobromous acid, bromous acid, bromic acid, perbromic acid.
Temperature of reaction is usually at 50～130 ℃.After reaction, can obtain the aromatic series halogen compounds shown in the formula (11) by the purification operations of known techniques and lock out operation.
Then, make aromatic series halogen compounds shown in the aforementioned formula (11) and triphenyl phosphine (triphenylphosphine) (P (C 6H 5) 3) in organic solvent, dissolve, again solution is heated to react.This reaction is so-called Witter (Witting) reaction.
And aforementioned solvents there is no particular restriction, available aceticanhydride, acetic acid, carbon number are at the aromatic solvent of the acid anhydrides below 5, benzene and toluene etc., dioxan etc.Temperature of reaction is usually at 80～130 ℃.After reaction, can obtain the organo phosphorous compounds shown in the following formula (15) by the purification operations of known techniques and lock out operation.
Figure A20048000384600231
But, the R in the formula (10) 1As hereinbefore.
Afterwards, in solvent, mix organo phosphorous compounds shown in the aforementioned formula (15) and formula (16a) or (16b) shown in carbonyl (carbonyl) compound, to react.
R 4-CH＝0 (16a)
R 4-C(＝O)-R 4 (16)
But, the R in the formula (16a) 4As hereinbefore.In addition, two R in formula (16b) 4Can be identical or different.
And aforementioned solvents there is no particular restriction, available aceticanhydride, acetic acid, carbon number are at the aromatic solvent of the acid anhydrides below 5, benzene and toluene etc., dioxan, pyridine, tetrahydrofuran (THF) etc.Temperature of reaction is usually at 80～130 ℃.After reaction, can obtain the blue light-emitting compound shown in the formula of the present invention (3) by the purification operations of known techniques and lock out operation.
Blue light-emitting compound shown in the relevant formula of the present invention (3) can carry out Witter (Witting) reaction and easily creates by organo phosphorous compounds and carbonyl compound.In addition, aforementioned organo phosphorous compounds can easily create by heating aromatic series halogen compounds and triphenyl phosphine, and aforementioned in addition aromatic series halogen compounds can be easy to carry out by heating in the reaction that imports halogen atom at fluorene compound.Therefore, the manufacture method of this easy blue light-emitting compound can be used as the manufacture method of industry.
It below is the luminescence component that the blue light-emitting compound shown in relevant formula of the present invention (1) and (3) is used in explanation.
Fig. 1 is the profile construction explanatory view of luminescence component of the organic el element of expression one stratotype.Please refer to Fig. 1, this luminescence component A is included on the substrate 1 transparency electrode 2 that forms and the luminescent layer that contains luminescent material 3 and the electrode layer 4 of lamination in order.
Luminescent layer 3 in the luminescence component shown in Figure 1 comprises the good blue light-emitting compound of the present invention of balance, red color emitting compounds and green emitting compound; Transparency electrode 2 in the luminescence component and electrode layer 4 electric current of can having switched on, and the luminescence component coloured light that turns white.For the coloured light that turns white, according to the kind difference of each luminophor, determine to contain in the luminescent layer 3 total content and each content ratio in the place of blue light-emitting compound of the present invention, red color emitting compounds and green emitting compound particularly aptly according to the kind of each luminophor.Moreover, as desire to make luminescence component blue light-emitting, luminescent layer 3 to be preferably to contain blue light-emitting compound of the present invention.If attempt makes the turn white light of look and blue outer random color of luminescence component, then need change the total content and each content ratio of blue light-emitting compound of the present invention, red color emitting compounds and green emitting compound aptly again.For example, when the luminescence component that uses relevant blue light-emitting compound of the present invention turns white coloured light, the cooperation ratio of the blue light-emitting compound in luminescent layer, red color emitting compounds and green emitting compound normally weight ratio is 5～200: 10～100: 50～20000, be preferably 10～100: 50～500: 100～10000.
Aforementioned red color emitting compounds is preferably the Nile shown in the following formula (16) red (Nile red) class red color emitting compounds.
Figure A20048000384600241
Aforementioned green emitting compound for example is tonka bean camphor (Coumarin) class green emitting compound, indophenols (Indophenol) class green emitting compound and indigo (Iindigo) class green emitting compound, and especially the coumarins green emitting compound shown in Xia Mian the formula (17) is preferable.
Figure A20048000384600242
Luminous is to utilize added electric field between transparency electrode 2 and electrode layer 4, and from electrode layer 4 sides injection electronics, from the electric hole of transparency electrode 2 injections, in addition, in the electric hole of luminescent layer 3 again with electronics in conjunction with, when valence band is returned in the conduction band be can rank energy as luminous phenomenon.
Luminescence component A shown in Figure 1 can be that all shapes are made large-area planeform, for example metope or be installed in top ceiling, can be as the planar litillumination devices of white luminous assembly of big area metope and the white luminous assembly of big area ceiling surface etc.Just can utilize this luminescence component replace before the pointolite of line source as the picture fluorescent lamp or bulb as area source.Luminescence component of the present invention can be used as can be luminous or the area source of illumination, particularly to inhabitation usefulness indoor, that affairs are used is indoor, metope, top ceiling or bed surface in the vehicle or the like.In addition, this luminescence component A can be used in the backlight of display screen, the display screen aspect mobile phone of computer aspect, digital display screen of cashing machine aspect or the like.In addition, this luminescence component A can be used for the various light sources of direct lighting, indirect lighting or the like.Again, the light source of this luminescence component A advertising device, teleseme, road sign device and luminous bulletin board of can be used to make noctilucence visibility (visibility) good or the like.And this luminescence component A is because luminescent layer has the blue light-emitting compound of particular chemical structure, so luminescent lifetime is long.Thereby this luminescence component A can be as long-life illuminating source.
Should understand as above-mentioned, contain relevant blue light-emitting compound of the present invention, and when not containing red color emitting compounds and green emitting compound, this luminescence component A sends distinct blue light at the luminescent layer of luminescence component A.
In addition, luminescence component A can be by the transparency electrode 2 of tubular substrate 1, substrate 1 inboard and in order the luminescent layer 3 of lamination become the tubulose twinkler with electrode layer 4.This luminescence component A is not because use mercury, so it uses the fluorescent lamp of mercury as the light source that benefits environment before replacing.
Substrate 1 is to adopt the known substrate that can form transparency electrode 2 in its surface.Substrate 1 for example is metal sheet that is formed with on glass substrate, plastic sheet, pottery, the surface insulativity finished surfaces such as insulation compound layer or the like.
When this substrate 1 was opaque, this luminescence component that the luminescent layer of red color emitting compounds, green emitting compound and blue light-emitting compound of the present invention is arranged was the single face means of illumination to substrate 1 opposite side irradiation white light.Again, when this substrate 1 was transparent, luminescence component was from one side of the substrate 1 of luminescence component and the double-faced lighting device of opposite side irradiation white light.
Aforementioned transparency electrode 2 is to adopt the big and transparent various materials of work function, and can exceed the electric hole person of aforementioned light emission layer 3 injections as anode can apply voltage.Transparency electrode 2 is as ITO, In specifically 2O 3, SnO 2, ZnO, CdO etc., and the compound of those inorganic transparent electro-conductive materials etc., and the conductive polymer material of polyaniline (polyaniline) etc. etc. forms.
This transparency electrode 2 forms with chemical Vapor deposition process, spray pyrolysis (spraypyrolysis), vacuum vapour deposition, electron beam evaporation plating method, sputtering method, ionic fluid sputtering method, ion plating, ion assisted deposition method and other method on aforesaid base plate 1.
In addition, when forming substrate with opaque material, it is transparency electrode that the electrode that forms on the substrate there is no need.
Luminescent layer 3 as when wanting blue light-emitting then contain relevant for blue light-emitting compound of the present invention, and when luminescent layer 3 will turn white coloured light, then it contained red color emitting compounds, green emitting compound and relevant blue light-emitting compound of the present invention.Luminescent layer 3 is polymeric membranes of dispersive blue light-emitting compound of the present invention or red color emitting compounds, green emitting compound and blue light-emitting compound of the present invention in polymer.In addition, luminescent layer 3 is evaporations has blue light-emitting compound of the present invention or red color emitting compounds, green emitting compound and blue light-emitting compound of the present invention and the vapor-deposited film that forms in transparency electrode 2.
Polymer about aforementioned polymeric membrane has polyvinyl carbazole (polyvinylcarbazole) for instance, poly-(3-thiotetrole) (poly (3-alkylenethiophene)), the polyimide (polyimide) that contains arylamines (arylamine), poly-fluorenes (fluorene), polyphenyl two inferior ethene (polyphenylenevinylene), poly--α-vinyltoluene (methylstyrene), vinyl carbazole/α-vinyltoluene (co-polymer etc. of vinylcarbazole/ α-methylstyrene).Wherein, be preferably polyvinyl carbazole.
The total content of the content of the blue light-emitting compound of the present invention in aforementioned polymeric membrane or red color emitting compounds, green emitting compound and blue light-emitting compound of the present invention is usually at 0.01～2 weight %.Be preferably at 0.05～0.5 weight %.
And the thickness of aforementioned polymeric membrane is preferably at 100～300nm normally at 30～500nm.The thin thickness of polymeric membrane then can make the luminance deficiency; And the thickness of polymeric membrane is big, then has bad high driving voltage, has the not good problem of pliability as planar body, tubular body arranged inside, bent bodies, ring bodies in addition.
Aforementioned polymeric membrane be utilize the aforementioned polymer be dissolved in appropriate solvent and blue light-emitting compound of the present invention or with a solution of red color emitting compounds, green emitting compound and blue light-emitting compound of the present invention, by for example (,) coating processes such as rotational casting method (spin casting), coating and dip coating formed.
When luminescent layer 3 was vapor-deposited film, the thickness of this vapor-deposited film was according to the layer that forms on luminescent layer difference to be arranged, and generally is at 0.1～100nm.And the thickness of vapor-deposited film too hour, when perhaps excessive again sometimes, problem as hereinbefore can take place also.
And former electrodes layer 4 is to adopt the little material of work function, and for example the metal or metal alloy of MgAg, aluminium alloy, calcium metal etc. forms.Preferable electrode layer 4 is alloy electrodes of aluminium and lithium in small amounts.Kind electrode layer 4 for example is to form easily with evaporation coating technique on containing the substrate 1 of aforementioned light emission layer 3 on the surface.
Both made form luminescent layer used be coating method and vapour deposition method, between electrode layer and luminescent layer, also can install a buffer layer additional.
And the material that forms aforementioned buffer layer for example is oxide compounds, 4 such as alkaline earth metal compound, aluminum oxide such as alkali metal compound, magnesium fluoride such as lithium fluoride for instance, and 4 '-two carbazole biphenyl (4,4 '-biscarbazolebiphenyl, Cz-TPD).In addition, as the material of the buffer layer that between the anode of ITO etc. and organic layer, forms for example 4,4 '; 4 "-three (3-aminomethyl phenyl anilino) triphenylamine (4,4 '; 4 "-tris (3-methylphenylphenylamino) triphenylamine, m-MTDATA), peptide cyanine (phthalocyanine), polyaniline (polyaniline), polythiofuran derivative (polythiophene derivative), inorganic oxide such as molybdenum oxide, ruthenium oxide, vanadium oxide, lithium fluoride.These buffer layers are according to allowing the driving voltage of organic el element of luminescence component descend, can improve luminous quantum yield and reaching the lifting luminosity and select its material rightly.
Then, the 2nd example of the relevant luminescence component of the present invention of icon.Fig. 2 is the cross sectional illustration figure of expression as the multi-layered type organic el element of luminescence component.
Please refer to Fig. 2, this luminescence component B is the transparency electrode 2 of lamination, electric hole transfer layer 5, luminescent layer 3a, 3b, electron supplying layer 6 and an electrode layer 4 in order on the surface of substrate 1.
Identical about substrate 1, transparency electrode 2 and electrode layer 4 with luminescence component A shown in Figure 1.
Be made of luminescent layer 3a and luminescent layer 3b at the luminescent layer aspect the luminescence component B shown in Figure 2, luminescent layer 3a is the vapor-deposited film that the evaporation luminophor forms, and luminescent layer 3b is the layer that the main material function is arranged.
The aforementioned electric hole transfer layer 5 that contains electric hole conveying material comprises for instance, triphenylamine (triphenylamine) compounds such as N, N '-biphenyl-N, N '-two (m-tolyl)-p-diaminodiphenyl (N, N '-diphenyl-N, N '-di (m-tolyl)-benzidine TPD) carries material etc. with α-NPD, hydrazone (hydrazone) compounds, stilbene (stilbene) compounds, multiple prime ring compounds, the electric hole of πDian Zi class star burst (star-burst).
Electron transport materials in the aforementioned electron supplying layer 6 that contains electron transport materials comprises for instance, 2-(4-the 3rd-butyl phenyl)-5-(4-phenylbenzene)-1,3,4-oxadiazoles (2-(4-tert-butylphenyl)-5-(4-biphenyl)-1,3,4-oxadiazole) wait oxadiazoles derivative and 2, two (the 1-naphthyls)-1 of 5-, 3, and the 4-oxadiazoles (2,5-bis (1-naphthyl)-1,3,4-oxadiazole) and 2, and two (5 '-Di, the three-butyl-2 '-benzoxazolyl) thiophene of 5-(2,5-bis (5 '-tert-butyl-2 '-benzoxazolyl) thiophene) etc.In addition, electron transport materials also be suitable for using quinophenol (oxine) aluminum compound (quinolinolaluminum complex) for example (Alq3), the material of benzoquinoline beryllium (benzquinolinolberyllium) compound metallic compound classes such as (Bebq2).
Electron supplying layer 6 in luminescence component B shown in Figure 2 comprises Alq3.
The thickness of each layer is identical with the organic EL luminescence component of known existing multi-layered type.
Luminescence component B shown in Figure 2 is with luminous with luminescence component A same function shown in Figure 1.Therefore, luminescence component B shown in Figure 2 is identical with the purposes of luminescence component A shown in Figure 1.
Shown in Figure 3 is the 3rd example of relevant luminescence component of the present invention.Fig. 3 is the cross sectional illustration figure of expression as the multi-layered type organic el element of luminescence component.
Luminescence component C shown in Figure 3 is the transparency electrode 2 of lamination, electric hole transfer layer 5, luminescent layer 3, electron supplying layer 8 and an electrode layer 4 in order on the surface of substrate 1.
Luminescence component C shown in Figure 3 is the same with aforementioned luminescence component B.
Shown in Figure 4 is another example of luminescence component.And luminescence component D shown in Figure 4 is substrate 1, electrode 2, electric hole transfer layer 5, luminescent layer 3 and the electrode layer 4 of lamination in order.
Except the luminescence component shown in the earlier figures 1～4, also enumerating example is included in to be formed at and is used as the anodic transparency electrode on the substrate and is used as between the electrode layer of negative electrode, contain double deck type organic low molecular luminescence component that the electric hole transfer layer of electric hole carrying material and the electron transport luminescent layer lamination that relevant blue light-emitting compound of the present invention contains form (for example between anode and negative electrode, electricity hole transfer layer with as the blue light-emitting compound relevant of the present invention of objective pigment (guest pigment) and contain double deck type coating (dope) the type luminescence component that the luminescent layer lamination of prime pigments (hostpigment) forms), between anode and negative electrode, contain double deck type organic luminescent assembly that the electric hole transfer layer of electric hole carrying material and the electron transport luminescent layer lamination of relevant blue light-emitting compound of the present invention and the common evaporation one-tenth of electron transport material form (for example between anode and negative electrode, electricity hole transfer layer with as the blue light-emitting compound relevant of the present invention of objective pigment and contain the double deck type pigment coating type organic luminescent assembly that the electron transport luminescent layer lamination of prime pigments forms), between anode and negative electrode, electric hole transfer layer, contain the luminescent layer of relevant blue light-emitting compound of the present invention and the three stratotype organic luminescent assemblies that the electron transport laminated layer forms.
In aforementioned light emission layer, be preferably and comprise sensitizing agent (sensitizer) and rubrene (rubrene), particularly comprise rubrene and Alq3 is preferable.
Utilize the blue-light-emitting assembly of blue light-emitting compound of the present invention or utilize the white luminous assembly of red color emitting compounds, green emitting compound and blue light-emitting compound of the present invention also can be used as the organic luminescent assembly of pulsed drive type and the organic luminescent assembly of AC driving type in addition and to use as usually as the organic luminescent assembly use of direct current.
＜embodiment 1 〉
Synthesizing of blue light-emitting compound shown in the formula (18).
Figure A20048000384600281
[synthesizing of hydrazide compound]
In 1L four mouth flasks, put into 1-naphthols chlorine (1-naphthoylchloride) 23.8g, anhydrous hydrazine 20g, pyridine 12.8g and tetrahydrofuran (THF) 250ml.The silicone that is heated to 50 ℃ is bathed solution reaction 2 hours in (silicone oil bath) and the four mouth flasks.After reaction finishes, use vaporizer (evaporator) solvent distillation.With the charging post of the solid filling silica gel that obtains, refining and obtain the hydrazide compound shown in the formula (19) of 20.06g faint yellow solid with chloroform (chloroform) photographic developer.
Figure A20048000384600291
[synthesizing of chlorination acid compound]
Figure A20048000384600292
In the eggplant shape flask (eggplant flask) of 1L, put into the dicarboxylic acid compound 10g shown in the following formula (20), dioxan (dioxane) 230ml and thionyl chloride 150ml.Solution heating with in silicone bath and the eggplant shape flask after arriving 110 ℃, adds the thionyl chloride of 40ml then, comes to heat 2.5 hours in 110 ℃ again.After reaction finishes, use the vaporizer solvent distillation.With the charging post of the solid filling silica gel that obtains, refining and obtain 4.9g yellow ocher solid chlorination acid compound with the chloroform photographic developer.
[synthesizing of blue light-emitting compound intermediate product]
In 500ml four mouth flasks, put into aforementioned faint yellow solid (hydrazide compound) 2.7g, aforementioned yellow ocher solid (chlorination acid compound) 1.55g, pyridine 0.9g and tetrahydrofuran (THF) 33ml.With the silicone that is heated to 70 ℃ bathe with four mouth flasks in solution reaction 1 hour.After reaction finishes, the solids component in the fractionation solution, and water and methanol cleaning.Clean after be drying to obtain the blue light-emitting compound intermediate product of solids component 2.8g.
[synthesizing of blue light-emitting compound]
In the eggplant shape flask of 300ml, put into aforementioned blue light-emitting compound intermediate product 2.8g, phosphoryl chloride 150ml and dioxan 75ml.With the silicone that is heated to 115 ℃ bathe with eggplant shape flask in solution reaction 6 hours.After reaction finishes, lose in the frozen water, the throw out fractionation is come out and with in 10% the sodium hydroxide and after, heavy dissolution precipitation thing in benzene, again the filtered liquid that filtration is obtained concentrate, drying and to obtain fusing point be 310 ℃ white crystals.
Aforementioned crystalline nucleus magnetic resonance (nuclear magnetic resource, NMR) figure spectrogram (spectrum chart) is shown in Figure 5, and its infrared rays (infrared ray, IR) the figure spectrogram is shown in Figure 6.By this, the crystallization of present embodiment gained is the blue light-emitting compound with the structure shown in the aforementioned formula (18) by evaluation.
In addition, after measured, maximum emission wavelength is 412.8nm to the fluorescence spectrum of the blue light-emitting compound of present embodiment gained (F-45000 type spectrofluorophotometer, excitation wavelength 365nm, solvent DMAC, concentration 0.25 weight %).Fluorescence spectrum figure as shown in Figure 7.
[luminous persistence]
And, the solution that the blue light-emitting compound of 5mg present embodiment gained and toluene 10g, Meta Dichlorobenzene (o-dichlorobenzene) 5g, tetrahydrofuran (THF) 2.5g and DMAC2g dissolving are obtained is distinctly through uviolizing, and, estimate with " luminous good ", " luminous dies down ", " can not be luminous " three stages relevant luminous persistence by the luminous light of solution.The result is, as can be known toluene solution greater than 14 days, Meta Dichlorobenzene solution greater than 20 days, tetrahydrofuran solution can be luminous good under greater than 100 days situation for blue light greater than 46 days, DMAC solution.
[using the characteristics of luminescence of the luminescence component of blue light-emitting compound]
Next, make the luminescence component with the blue light-emitting compound of present embodiment gained, this kind luminescence component is made according to the following stated, and studies its characteristics of luminescence.
After with acetone ito substrate (50 * 50mm, three holds vacuum industry limited-liability company systems) ultrasound being cleaned 10 minutes, clean 10 minutes with the propyl alcohol ultrasound, use again nitrogen predrying it.Then, with photosurface treater (photo surface processor) (SEN special light sources limited-liability company system, wavelength are 254nm) ito substrate irradiation ultraviolet ray in 5 minutes is cleaned it again.
The ito substrate of cleaning is in vacuum deposition apparatus (Dare's vacuum skill is ground the UDS-M2-46 type of limited-liability company) and be set in 4 * 10 -6Under the vacuum below the torr, the layer 40nm of the blue light-emitting compound of lamination α-NPD layer 45nm and present embodiment gained (formula (18)) and the luminescent layer that forms, the aluminium alloy system electrode (Al: Li=99: 1 weight ratio, high-purity chemical institute system) of last evaporation 150nm thickness is to produce the blue-light-emitting assembly of lamination structure.
About this blue-light-emitting assembly, slowly improve voltage with the BM-7Fast of Topcon system and measure its briliancy and colourity.Consequently voltage is 3196.00Cd/m in 14V and the electric current briliancy during at 18.47mA 2, colourity X be 0.2366 and colourity Y be 0.3025.
＜embodiment 2 〉
Synthesizing of blue light-emitting compound shown in the formula (21).
Figure A20048000384600301
[synthesizing of hydrazide compound]
In 500ml four mouth flasks, put into 4-trifluoromethyl benzoyl chloride
(4-trifluoromethylbenzoylchloride) 25g, anhydrous hydrazine 38g, pyridine 14g and tetrahydrofuran (THF) 70ml.The solution reacting by heating that 70 ℃ silicones baths (silicone oil bath) and four mouth flasks are interior 17 hours.After reaction finishes, use the vaporizer solvent distillation.With the charging post of the solid filling silica gel that obtains, refining and obtain the hydrazide compound shown in the formula (22) of 7.5g white solid with the chloroform photographic developer.
Figure A20048000384600311
[synthesizing of blue light-emitting compound intermediate product]
In 500ml four mouth flasks, put into hydrazide compound 2.8g, pyridine 1.2g and the tetrahydrofuran (THF) 135ml shown in embodiment 1 resulting chlorination acid compound 2.0g, the aforementioned formula (22).With the silicone that is heated to 50 ℃ bathe with four mouth flasks in solution reaction 18 hours.After reaction finishes, the solids component in the fractionation solution, and water and methanol cleaning.Clean after be drying to obtain the blue light-emitting compound intermediate product of solids component 2.9g.And its productive rate is 70%.
[synthesizing of blue light-emitting compound]
In the three mouth flasks of 300ml, put into aforementioned blue light-emitting compound intermediate product 2.8g, phosphoryl chloride 65ml and dioxan 120ml.With the silicone that is heated to 110 ℃ bathe with three mouth flasks in solution reaction 9 hours.After reaction finishes, the throw out fractionation is come out, heavy dissolution precipitation thing in 150ml toluene, again the filtered liquid that filtration is obtained concentrate, dry and to obtain fusing point be 288 ℃ faint yellow crystallization 1.12g.And productive rate is 79.6%.
Aforementioned crystalline NMR figure spectrogram is shown in Figure 8, and its IR figure spectrogram is shown in Figure 9.By this, the crystallization of present embodiment gained is the blue light-emitting compound with the structure shown in the aforementioned formula (22) by evaluation.
In addition, after measured, maximum emission wavelength is 405.8nm to the fluorescence spectrum of the blue light-emitting compound of present embodiment gained (F-45000 type spectrofluorophotometer, excitation wavelength 365nm, solvent DMAC, concentration 0.25 weight %).Fluorescence spectrum figure as shown in figure 10.
＜embodiment 3 〉
Synthesizing of blue light-emitting compound shown in the formula (23).
[synthesizing of hydrazide compound]
Obtain the hydrazide compound shown in the identical formula (19) of 1.22g and embodiment 1.
[synthesizing of chlorination acid compound]
Figure A20048000384600321
In the eggplant shape flask of 200ml, put into dicarboxylic acid compound 2.25g shown in the following formula (24) and thionyl chloride 30ml.With silicone bathe with eggplant shape flask in 80 ℃ of solution heating after 1 hour, reheat to 90 ℃ 0.5 hour, reheat to 100 ℃ 0.5 hour.After reaction finishes, the solids component of gained is dissolved among the tetrahydrofuran (THF) 30ml, and after filtering this solution, uses the vaporizer solvent distillation and obtain the dark red purple solid of 2.0g chlorination acid compound.
[synthesizing of blue light-emitting compound intermediate product]
In 500ml four mouth flasks, put into aforementioned hydrazide compound 1.22g, aforementioned chlorination acid compound 1g, pyridine 0.4g and tetrahydrofuran (THF) 15ml.With the silicone that is heated to 70 ℃ bathe with four mouth flasks in solution reaction 1 hour.After reaction finishes, the solids component in the fractionation solution, and water and methanol cleaning.Clean after be drying to obtain 1.4g Sandy solid blue light-emitting compound intermediate product.
[synthesizing of blue light-emitting compound]
In the eggplant shape flask of 500ml, put into aforementioned blue light-emitting compound intermediate product 1.4g and phosphoryl chloride 60ml.With the silicone that is heated to 115 ℃ bathe with eggplant shape flask in solution reaction 10 hours.Reaction obtains solids with the chloroform extraction resultant after finishing.Then, with the heavy dissolved solids thing of mixed solution of benzene and hexanaphthene 1 to 1, again the filtered liquid that filtration is obtained concentrate, drying and obtain faint yellow crystallization.
Aforementioned crystalline NMR figure spectrogram is shown in Figure 11, and its IR figure spectrogram is shown in Figure 12.By this, the crystallization of present embodiment gained is the blue light-emitting compound with the structure shown in the aforementioned formula (23) by evaluation.
In addition, after measured, maximum emission wavelength is 414.0nm to the fluorescence spectrum of the blue light-emitting compound of present embodiment gained (F-45000 type spectrofluorophotometer, excitation wavelength 365nm, solvent DMAC, concentration 0.25 weight %).Fluorescence spectrum figure as shown in figure 13.
＜embodiment 4 〉
Synthesizing of blue light-emitting compound shown in the formula (25).
Figure A20048000384600331
[synthesizing of hydrazide compound]
In 300ml four mouth flasks, put into 4-the 3rd-butyl diphenyl chlorination acid 17g, anhydrous hydrazine 27.7g, pyridine 10.3g and the tetrahydrofuran (THF) 50ml shown in the following formula (26).With 70 ℃ silicones bathe with four mouth flasks in solution reacting by heating 5 hours.After reaction finishes, use the vaporizer solvent distillation.With the charging post of the solid filling silica gel that obtains, refining and obtain the hydrazide compound of 3g with the chloroform photographic developer.
Figure A20048000384600332
[synthesizing of chlorination acid compound]
Obtain the identical chlorination acid compound of 1.62g and embodiment 1.
[synthesizing of blue light-emitting compound intermediate product]
In 500ml four mouth flasks, put into aforementioned hydrazide compound 3g, aforementioned chlorination acid compound 1.62g, pyridine 0.96g and tetrahydrofuran (THF) 100ml.With the silicone that is heated to 50 ℃ bathe with four mouth flasks in solution reaction 17 hours.After reaction finishes, the solids component in the fractionation solution, and water and methanol cleaning.Clean after be drying to obtain 3.8g blue light-emitting compound intermediate product.
[synthesizing of blue light-emitting compound]
In the eggplant shape flask of 300ml, put into aforementioned blue light-emitting compound intermediate product 3.8g and phosphoryl chloride 30ml.With the silicone that is heated to 110 ℃ bathe with eggplant shape flask in solution reaction 14.5 hours.After reaction finishes, fractionate out throw out and clean with chloroform.Then, with the heavy dissolution precipitation thing of toluene 300ml, again the filtered liquid that filtration is obtained concentrate, dry and to obtain fusing point be 330 ℃ the faint yellow crystallization of 0.54g.
Aforementioned crystalline NMR figure spectrogram is shown in Figure 14, and its IR figure spectrogram is shown in Figure 15.By this, the aforementioned crystallization of present embodiment gained is the blue light-emitting compound with the structure shown in the aforementioned formula (25) by evaluation.
In addition, after measured, maximum emission wavelength is 414.0nm to the fluorescence spectrum of the blue light-emitting compound of present embodiment gained (F-45000 type spectrofluorophotometer, excitation wavelength 365nm, solvent DMAC, concentration 0.25 weight %).Fluorescence spectrum figure as shown in figure 16.
＜embodiment 5 〉
Synthesizing of blue light-emitting compound shown in the formula (27).
Figure A20048000384600341
[synthesizing of hydrazide compound]
In 300ml four mouth flasks, put into 4-the 3rd-butyl halogenation twenty base (4-tert-butylbenzylchloride) 17g, anhydrous hydrazine 27.7g, pyridine 10.3g and tetrahydrofuran (THF) 50ml.With 70 ℃ silicones bathe with four mouth flasks in solution reacting by heating 5 hours.After reaction finishes, use the vaporizer solvent distillation.With the charging post of the solid filling silica gel that obtains, refining and obtain the hydrazide compound of 10.75g with the chloroform photographic developer.
[synthesizing of chlorination acid compound]
Obtain the identical chlorination acid compound of 2g and embodiment 1.
[synthesizing of blue light-emitting compound intermediate product]
In 500ml three mouth flasks, put into aforementioned hydrazide compound 2.65g, aforementioned chlorination acid compound 2g, pyridine 1.2g and tetrahydrofuran (THF) 50ml.With the silicone that is heated to 50 ℃ bathe with three mouth flasks in solution reaction 18 hours.After reaction finishes, the solids component in the fractionation solution, and water and methanol cleaning.Clean after be drying to obtain 3.5g blue light-emitting compound intermediate product.
[synthesizing of blue light-emitting compound]
In the four mouth flasks of 500ml, put into aforementioned blue light-emitting compound intermediate product 3.4g, phosphoryl chloride 30ml and dioxan 100ml.With the silicone that is heated to 110 ℃ bathe with four mouth flasks in solution reaction 9 hours.After reaction finishes, fractionate out throw out, and with the heavy dissolution precipitation thing of toluene 40ml, again the filtered liquid that filtration is obtained concentrate, drying and obtain faint yellow crystallization.
Aforementioned crystalline NMR figure spectrogram is shown in Figure 17, and its IR figure spectrogram is shown in Figure 180.By this, the aforementioned crystallization of present embodiment gained is the blue light-emitting compound with the structure shown in the aforementioned formula (19) by evaluation.
In addition, after measured, maximum emission wavelength is 401.2nm to the fluorescence spectrum of the blue light-emitting compound of present embodiment gained (F-45000 type spectrofluorophotometer, excitation wavelength 365nm, solvent DMAC, concentration 0.25 weight %).Fluorescence spectrum figure as shown in figure 19.
＜embodiment 6 〉
Synthesizing of blue light-emitting compound shown in the formula (28).
[synthesizing of aromatic series halogen compounds]
Put into 9 in 300ml four mouth flasks, 9-dimethyl fluorine (9,9-dimethyl fluorine) 2.00g, polyphosphoric acid 12.3g, formaldehyde 1.59g, Glacial acetic acid 14.7g are with hydrochloric acid 15.2ml.After the solution stirring in the four mouth flasks, bathe reaction 7 hours with the silicone that is heated to 115 ℃.After reaction finishes, with ice-cooled solution and filter it.The solid that obtains is cleaned with the chloroform of 300ml, cleaned with the pure water of 200ml again.Afterwards, the solid of cleaning is heavily dissolved, and use the vaporizer solvent distillation and obtain the aromatic series halogen compounds of the faint yellow gluey material of 3.1g with chloroform.
[synthesizing of organo phosphorous compounds]
In 200ml three mouth flasks, put into aforementioned aromatic series halogen compounds 3.0g, triphenyl phosphine 8.11g and toluene 80ml.After the solution stirring in the three mouth flasks, bathe reaction one the whole night with the silicone that is heated to 120 ℃.After reaction finishes, with ice-cooled solution and filter it, to obtain solid.Then, after the solid that obtains cleaned with the benzene of 10ml, use moisture eliminator (desiccator) dry and obtain the 5.29g white crystals.
[synthesizing of blue light-emitting compound]
In the eggplant shape flask of 500ml, put into aforementioned organo phosphorous compounds 1.6g, diphenylketone (benzophenone) 0.9g and tetrahydrofuran (THF) 250ml.This solution of water-cooled, use n-butyllithium (n-butyllithium) 6ml to splash into this solution again after, with its stirring and place one the whole night.Then, concentrate this solution after, be dried and obtain the crystallization of 3.87g brown.
Aforementioned crystalline NMR figure spectrogram is shown in Figure 20, and its IR figure spectrogram is shown in Figure 21.By this, the aforementioned crystallization of present embodiment gained is the blue light-emitting compound with the structure shown in the aforementioned formula (28) by evaluation.
＜embodiment 7 〉
Synthesizing of blue light-emitting compound shown in the formula (29).
[synthesizing of blue light-emitting compound]
In the eggplant shape flask of 500ml, put into method synthetic organo phosphorous compounds 1.1g, 4,4 '-dimethyl diphenyl ketone (4,4 '-dimethylbenzophenone) 0.85g and tetrahydrofuran (THF) 275ml with previous embodiment 6.This solution of water-cooled splashes into behind this solution its stirring with n-butyllithium 2.88ml again.Then, filter this solution, to obtain solid.Extract this solid with chloroform 125ml again, concentrate then after drying it, to obtain the 1.41g yellow crystal.
Aforementioned crystalline NMR figure spectrogram is shown in Figure 22, and its I R figure spectrogram is shown in Figure 23.By this, the aforementioned crystallization of present embodiment gained is the blue light-emitting compound with the structure shown in the aforementioned formula (29) by evaluation.
＜embodiment 8 〉
Synthesizing of blue light-emitting compound shown in the formula (30).
Figure A20048000384600362
[synthesizing of blue light-emitting compound]
In the eggplant shape flask of 500ml, put into method synthetic organo phosphorous compounds 1.3g, terephthalaldehyde (terephthalaldehyde) 0.16g and tetrahydrofuran (THF) 275ml with previous embodiment 6.This solution of water-cooled splashes into behind this solution its stirring with n-butyllithium 3.4ml again.Then, filter this solution, to obtain solid.Extract this solid with chloroform 125ml again, use the vaporizer solvent distillation then, to obtain the 1.22g yellow crystal.
Aforementioned crystalline NMR figure spectrogram is shown in Figure 24, and its IR figure spectrogram is shown in Figure 25.By this, the aforementioned crystallization of present embodiment gained is the blue light-emitting compound with the structure shown in the aforementioned formula (30) by evaluation.
＜embodiment 9 〉
Synthesizing of blue light-emitting compound shown in the formula (31).
Figure A20048000384600371
[synthesizing of blue light-emitting compound]
In the eggplant shape flask of 500ml, put into method synthetic organo phosphorous compounds 1.3g, N-ethyl carbazole-3-carboxylic aldehyde (N-ethylcarbazole-3-carboxyaldehyde) 0.82g and tetrahydrofuran (THF) 275ml with previous embodiment 6.This solution of water-cooled splashes into behind this solution its stirring with n-butyllithium 3.4ml again.Then, filter this solution, to obtain solid.Extract this solid with chloroform 125ml again, use the vaporizer solvent distillation then, to obtain the crystallization of 2.31g sorrel.
Aforementioned crystalline NMR figure spectrogram is shown in Figure 26, and its IR figure spectrogram is shown in Figure 27.By this, the aforementioned crystallization of present embodiment gained is the blue light-emitting compound with the structure shown in the aforementioned formula (31) by evaluation.
＜embodiment 10 〉
Synthesizing of blue light-emitting compound shown in the formula (32).
[synthesizing of 2-furoyl hydrazine (2-furoylhydrazide)]
In the three mouth flasks of 500ml, put into anhydrous hydrazine 1.34mol and pyridine 0.192mol, use ice that its cooling back is stirred, in the tetrahydrofuran (THF) of 250ml, it is dissolved again, and slowly splash into the 2 furoyl chloride thing (2-furoylchloride) of 0.192mol.After dripping off, the mixture in the aforementioned three mouth flasks is returned back to room temperature, reheat get back to 50 ℃ about 2 hours, return back to room temperature afterwards again, then the content of three mouth flasks is injected ice.Inject the solution of icing gained with chloroform 500ml extraction, after distilling with chloroform the more yellow mucus of 2.78g is arranged, and obtain the 2-furoyl hydrazine shown in the formula (33).
Figure A20048000384600381
[synthesizing of chlorination acid compound]
Same with previous embodiment 1, the dicarboxylic acid compound inductive chlorination acid compound shown in the synthesis type (20).
[synthesizing of intermediate product]
In the three mouth flasks of 300ml, put into 2-furoyl hydrazine 1.102 * 10 -2Mol (1.76g) and pyridine 1.10 * 10 -2Mol (0.86g) stirs its cooling back with ice.In the tetrahydrofuran (THF) of 100ml,, and slowly splash into 5.61 * 10 with its dissolving -3The 9.9-dimethyl fluorene of mol (1.76g)-2.7-dicarbapentaborane muriate (9.9-dimethylated fluorene-2.7-dicarbonyl chloride).After dripping off with the temperature retrieval in the aforementioned three mouth flasks to room temperature, reheat get back to 85 ℃ about 2 hours, return back to room temperature afterwards again, then with its concentrate drying.Wash the solid substance of gained with water, use methanol cleaning again, to obtain the intermediate product shown in the formula (34).
Figure A20048000384600382
[synthesizing of blue light-emitting compound]
Under nitrogen atmosphere, the intermediate product shown in aforementioned (34) with the about 100ml thermal backflow one the whole night of Phosphorus Oxychloride after, return back to room temperature, reinject in the ice, use chloroform extraction afterwards, then with chloroform distillation, to obtain the purpose compound shown in the 0.90g formula (32).
After measured, maximum emission wavelength is 409.8nm to the fluorescence spectrum of the blue light-emitting compound shown in the formula (32) (F-45000 type spectrofluorophotometer, excitation wavelength 365nm, solvent dioxan, concentration 0.25 weight %).Fluorescence spectrum figure as shown in figure 28.
＜embodiment 11 〉
Synthesizing of blue light-emitting compound shown in the formula (35).
Figure A20048000384600391
[Friedel-Crafts reaction]
Synthesizing of ketone compound shown in the formula (36).
Figure A20048000384600392
Fluorenes 1mol (25g), Acetyl Chloride 98Min. (acetyl chloride) 1mol (25g), aluminum chloride 1.1mol (19g) and dithiocarbonic anhydride 200ml pack in the three mouth flasks of 500ml, slowly heat the content to 60 ℃ in the flask, and thermal backflow 2 hours under this temperature.Then, with in the content input in the flask ice, and with the tetrahydrofuran (THF) extraction of 700ml, remove solvent in the extract with vaporizer again, then be heated to 45 ℃ of also vacuum-dryings and obtain the pink stickies shown in the 30.85g formula (36).
[synthesizing of acyl chlorides]
Pack in 20001 three mouth flasks aforementioned pink thing 16.5g and methyl alcohol 250ml then, mix the clorox (effectively chlorine dose 5%) of 500ml.Content in 65～90 ℃ of heating flasks 3.5 hours.Heating is cooled to room temperature and refilters it after finishing, and adds concentrated hydrochloric acid again in the filtered liquid of gained, to produce white precipitate.
Then, containing sedimentary liquid filtering, again filtrate is collected with glass filter, and through the whole night a vacuum-drying, to obtain the monocarboxylic acid compound shown in the 7.5g formula (37).
Figure A20048000384600401
In the eggplant shape flask of 500ml, put into the monocarboxylic acid compound 10g (4.2 * 10 shown in the aforementioned formula (37) -2Mol) and thionyl chloride 75ml.110 ℃ of heating and through thermal backflow in 2 hours.Afterwards, slowly cool off and concentrate with aspirator (aspirator).
With tetrahydrofuran (THF) enriched material is dissolved, refilter and filtered liquid is vacuumized, after solvent is removed, residue is statically placed in the refrigerating chamber, to obtain the chlorination acid compound shown in the formula (38) with vacuum pump.
[synthesizing of intermediate product]
In the three mouth flasks of 500ml, put into the chlorination acid compound 3.5g (1.37 * 10 shown in the above-mentioned formula (38) -2Mol) with hydrazide compound 2.55g and the tetrahydrofuran (THF) 150ml shown in the formula (19).With the silicone that is heated to 70 ℃ bathe with flask in solution reaction 1 hour.Reaction is dropped into reaction solution in the ice after finishing, and uses the 900ml chloroform extraction again, and the clean extraction liquid twice of water 200ml, uses anhydrous sodium sulfate drying again, and obtains the white solid shown in the 5.5g formula (39) with evaporator dry in filtering the back.
Figure A20048000384600403
[synthesizing of blue light-emitting compound]
In eggplant shape flask, put into the intermediate product 5.0g shown in the aforementioned formula (39), dioxan 120ml and Phosphorus Oxychloride 150ml, about 1 hour of 115 ℃ of thermal backflows.After cooling, resultant of reaction is lost in the ice, used chloroform extraction again, dry extract then, and use evaporator dry, obtain the purpose compound shown in the 4.6g formula (35) (fusing point is 175～181 ℃) again with vacuum-drying.
This purpose compound be accredited as NMR shown in Figure 29 figure and IR figure shown in Figure 30.
[characteristics of luminescence]
(1) with acetone ito substrate (50 * 50mm, three holds vacuum industry limited-liability company systems) ultrasound is cleaned 10 minutes after, clean 10 minutes with the propyl alcohol ultrasound, use again nitrogen predrying it.Then, with photosurface treater (SEN special light sources limited-liability company system, wavelength are 254nm) ito substrate irradiation ultraviolet ray in 5 minutes is cleaned it again.
The ito substrate of cleaning is in vacuum deposition apparatus (Dare's vacuum skill is ground the UDS-M2-46 type of limited-liability company) and be set in 4 * 10 -6Under the vacuum below the torr, the layer 30nm of the blue light-emitting compound of lamination α-NPD layer 50nm and present embodiment gained (formula (35)) and the luminescent layer that forms, the aluminium alloy system electrode (Al: Li=99: 1 weight ratio, high-purity chemical institute system) of last evaporation 150nm thickness is to produce the blue-light-emitting assembly of lamination structure.
About this blue-light-emitting assembly, slowly improve voltage with the BM-7Fast of Topcon system and measure its briliancy and colourity.Consequently voltage is 2711.00Cd/m in 14V and the electric current briliancy during at 18.47mA 2, colourity X be 0.2071 and colourity Y be 0.3370.
(2) on the ito substrate that ultrasound is cleaned and uviolizing is cleaned, with the PEDT (commercially available product of Bayer corporate system, poly-Ethylenedioxy Thiophene (polyethlenedioxythiophene)/sulfonated polystyrene (sulfonationpolystyrene)), at 1000rpm with 300 seconds formation films.The film that forms was 200 ℃ of dryings 10 minutes, and afterwards, the blue light-emitting compound 30mg shown in weighing polyvinyl carbazole 70mg and the formula (35) in the 5ml chloroform the solution of uniform dissolution in chloroform, formed film at 1500rpm in 3 seconds.With vacuum deposition apparatus (Dare's vacuum skill is ground the UDS-M2-46 type of limited-liability company) on this film that forms with 1 * 10 -6The aluminium alloy of the about 1500 dust thickness of torr evaporation (Al: Li=99: 1 weight ratio, high-purity chemical institute system) electrode is to produce the EL luminescence component.
About this EL luminescence component, slowly improve voltage with the Fast BM-7 of Topcon system and measure its briliancy and colourity.Consequently the glorious degrees of voltage when 21V is 105.6Cd/m 2, colourity X be 0.2328 and colourity Y be 0.3059.
(3) after measured, maximum emission wavelength is 435nm to the fluorescence spectrum of the blue light-emitting compound shown in the formula (35) (F-45000 type spectrofluorophotometer, excitation wavelength 365nm, solvent dioxan, concentration 0.25 weight %).Fluorescence spectrum figure as shown in figure 31.
＜embodiment 12 〉
Synthesizing of blue light-emitting compound shown in the formula (40).
Figure A20048000384600421
[synthesizing of hydrazide compound]
Obtain the hydrazide compound shown in the formula (19) identical with embodiment 1.
[synthesizing of chlorination acid compound]
Figure A20048000384600422
In the eggplant shape flask of 1L, put into the dicarboxylic acid compound 9g shown in the following formula (41), dioxan 450ml, pyridine 3g and thionyl chloride 150ml.The silicone bath of heating and the solution in the eggplant shape flask were heated 2.5 hours in 110 ℃.After reaction finishes, use the vaporizer solvent distillation.With the charging post of the solid filling silica gel that obtains, refining and obtain the chlorination acid compound of the light red white solid of 9.15g with the chloroform photographic developer.
[synthesizing of blue light-emitting compound intermediate product]
In 1L three mouth flasks, put into aforementioned faint yellow solid (hydrazide compound) 0.33g, aforementioned light red white solid (chlorination acid compound) 0.36g, pyridine 0.1g and tetrahydrofuran (THF) 200ml.With the silicone that is heated to 70 ℃ bathe with three mouth flasks in solution reaction 15 hours.After reaction finishes, the solids component in the fractionation solution, and wash.Solids component drying after cleaning promptly obtains the blue light-emitting compound intermediate product of 0.6g.
[synthesizing of blue light-emitting compound]
In the eggplant shape flask of 300ml, put into aforementioned blue light-emitting compound intermediate product 0.6g, phosphoryl chloride 25ml and dioxan 50ml.With the silicone that is heated to 110 ℃ bathe with eggplant shape flask in solution reaction 13 hours.Reaction is lost in the frozen water after finishing, and imposes Nutsche again and handles.Then,, use the filtered liquid of vacuum pump thickening filtration gained afterwards through washing, cleaning with methyl alcohol again, dry again to obtain the 0.1g white crystals.
Aforementioned crystalline NMR figure spectrogram is Figure 32, and its IR figure spectrogram is shown in Figure 33.By this, the crystallization of present embodiment gained is the blue light-emitting compound with the structure shown in the aforementioned formula (40) by evaluation.
In addition, after measured, maximum emission wavelength is 417.6nm to the fluorescence spectrum of the blue light-emitting compound of present embodiment gained (F-45000 type spectrofluorophotometer, excitation wavelength 365nm, solvent DMAC, concentration 0.25 weight %).Fluorescence spectrum figure as shown in figure 34.
Moreover after measured, maximum emission wavelength is 417nm to the fluorescence spectrum of the blue light-emitting compound of present embodiment gained (F-45000 type spectrofluorophotometer, excitation wavelength 365nm, solvent toluene, concentration 0.25 weight %).Fluorescence spectrum figure as shown in figure 35.
[luminous persistence]
At this, the solution that the blue light-emitting compound of 5mg embodiment 1 gained and DMAC 2g dissolving is obtained is through uviolizing, and, estimate with " luminous good ", " luminous dies down ", " can not be luminous " three stages relevant luminous persistence by the luminous light of solution.The result is that DMAC solution can be luminous good for blue light in 400 days.
And in this, the blue light-emitting compound of relevant present embodiment 12 is compared with the blue light-emitting compound of relevant embodiment 1, be about 6 times degree for solvency power as can be known as the solvent of DMAC.In addition, the known luminescence persistence is proportional for the solvency power of the solvent of compound.Therefore, the luminous persistence of having an appointment 5～6 years about the blue light-emitting compound of present embodiment 12.
Range of application on the industry
The present invention provides about guaranteeing high glorious degrees and realizing long-time luminous blue light-emitting compound, its manufacture method and the luminescence component that utilizes this.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, though the present invention discloses as above with preferred embodiment, yet be not in order to limit the present invention, any those skilled in the art, in not breaking away from the technical solution of the present invention scope, when the method that can utilize above-mentioned announcement and technology contents are made a little change or be modified to the equivalent embodiment of equivalent variations, but every content that does not break away from technical solution of the present invention, according to technical spirit of the present invention to any simple modification that above embodiment did, equivalent variations and modification all still belong in the scope of technical solution of the present invention.
Claims
(according to the modification of the 19th of treaty)
1, a kind of blue light-emitting compound is characterized in that:
This blue light-emitting compound has the structural formula shown in the following formula (3),
R in the formula 1Be carbon number at 1～15 alkyl, carbon number at cycloalkyl or the aryl in the following formula (1-1)～(1-4), wherein two R of 6～15 1Can be identical or different, R 4Be aryl or the phenyl shown in hydrogen atom or the following formula (3-1), four R wherein 4Can be identical or different,
Figure A20048000384600752
X in the formula 1Be carbon number at 1～10 alkyl, the alkyl or the hydrogen atom of carbon number 1～10 contain fluorine atoms, n is 1～15 integer,
Figure A20048000384600753
X in the formula 1As hereinbefore, Y be carbon number at 1～10 alkyl, the alkyl or the hydrogen atom of carbon number 1～10 contain fluorine atoms, m is 1～3 integer, q is 1～4 integer, and X 1With Y can be identical or different,
Figure A20048000384600761
X 1, Y, m and q as hereinbefore, and X 1With Y can be identical or different,
Figure A20048000384600762
X 1, Y, n and q as hereinbefore, and X 1With Y can be identical or different,
R in the formula (3-1) 5Be hydrogen atom or carbon number at 1～5 alkyl.
2, a kind of manufacture method of blue light-emitting compound is characterized in that it may further comprise the steps:
Fluorene compound shown in the halogenation following formula (10) obtains the aromatic series halogen compounds shown in the following formula (11);
Make the reaction of this aromatic series halogen compounds and triphenyl phosphine, to obtain an organo phosphorous compounds; And
Make the reaction of this organo phosphorous compounds and carbonyl compound, with the blue light-emitting compound shown in the formula (3) that obtains claim 1,
Figure A20048000384600771
R in the formula 1With the R in the claim 1 1It is identical,
Figure A20048000384600772
R in the formula 1With the R in the claim 1 1Identical, and Hal is meant halogen atom.
3, a kind of luminescence component is characterized in that:
This luminescence component comprises a luminescent layer, and this luminescent layer contains the blue light-emitting compound shown in the aforementioned formula (3).

Claims (6)

1, a kind of blue light-emitting compound is characterized in that:
This blue light-emitting compound has the structural formula shown in the following formula (1),
Figure A2004800038460002C1
R in the formula (1) 1Be carbon number at 1～15 alkyl, carbon number at cycloalkyl or the aryl in the following formula (1-1)～(1-4), wherein two R of 6～15 1Can be identical or different, R 2Be aryl or the furyl in the following formula (1-1)～(1-4), R 3Be base or the hydrogen atom shown in the following formula (2),
Figure A2004800038460002C2
X in the formula 1Be carbon number at 1～10 alkyl, the alkyl or the hydrogen atom of carbon number 1～10 contain fluorine atoms, n is 1～15 integer,
X in the formula 1As hereinbefore, Y be carbon number at 1～10 alkyl, the alkyl or the hydrogen atom of carbon number 1～10 contain fluorine atoms, m is 1～3 integer, q is 1～4 integer, and X 1With Y can be identical or different,
X 1, Y, m and q as hereinbefore, and X 1With Y can be identical or different,
Figure A2004800038460003C2
X 1, Y, n and q as hereinbefore, and X 1With Y can be identical or different,
Formula ( 2) in R 2As hereinbefore, and when formula ( 1) R 3When being basic shown in the formula (2), R 2Can combine or R with oxadiazoles base on one side 2Can combine with the oxadiazoles base of the other side, and can be mutually identical or different.
2, a kind of blue light-emitting compound is characterized in that:
This blue light-emitting compound has the structural formula shown in the following formula (3),
Figure A2004800038460003C4
R in the formula 1With the R in the claim 1 1Identical, R 4Be the aryl shown in hydrogen atom or the following formula (3-1)～(3-2), four R wherein 4Can be identical or different,
Figure A2004800038460004C1
R in the formula (3-1) 5Be hydrogen atom or carbon number at 1～5 alkyl,
Figure A2004800038460004C2
R in the formula (3-2) 6Be hydrogen atom or carbon number at 1～5 alkyl, and n is identical with n in the claim 1.
3, a kind of manufacture method of blue light-emitting compound is characterized in that it may further comprise the steps:
The chlorination acid compound that dicarboxylic acid compound shown in the following formula (4) and halogen agent reaction is obtained reacts with hydrazide compound and obtains the blue light-emitting compound intermediate product shown in the following formula (5); And
This blue light-emitting compound intermediate product is carried out dehydration reaction, obtaining the blue light-emitting compound shown in the following formula (6),
Figure A2004800038460004C3
R in the formula 1With the R in the claim 1 1It is identical,
Figure A2004800038460004C4
R in the formula 1, R 2With the R in the claim 1 1, R 2It is identical,
Figure A2004800038460005C1
R 1And R 2As hereinbefore.
4, a kind of manufacture method of blue light-emitting compound is characterized in that it may further comprise the steps:
The chlorination acid compound that carboxylic acid cpd shown in the following formula (7) and halogen agent reaction is obtained reacts with hydrazide compound and obtains the intermediate product shown in the following formula (8); And
This intermediate product is carried out dehydration reaction, obtaining the blue light-emitting compound shown in the following formula (9),
R in the formula 1With the R in the claim 1 1It is identical,
R in the formula 1, R 2With the R in the claim 1 1, R 2It is identical,
R 1And R 2As hereinbefore.
5, a kind of manufacture method of blue light-emitting compound is characterized in that it may further comprise the steps:
Fluorene compound shown in the halogenation following formula (10) obtains the aromatic series halogen compounds shown in the following formula (11);
Make the reaction of this aromatic series halogen compounds and triphenyl phosphine, to obtain an organo phosphorous compounds; And
Make the reaction of this organo phosphorous compounds and carbonyl compound, with the blue light-emitting compound shown in the formula (3) that obtains claim 2,
R in the formula 1With the R in the claim 1 1It is identical,
Figure A2004800038460006C2
R in the formula 1With the R in the claim 1 1Identical, and Hal is meant halogen atom.
6, a kind of luminescence component is characterized in that:
This luminescence component comprises a luminescent layer, and this luminescent layer contains the blue light-emitting compound shown in aforementioned formula (1) or the formula (3).
CN 200480003846 2003-03-17 2004-03-15 Blue light-emitting compound, method for producing same and light-emitting device utilizing same Pending CN1747944A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101851216A (en) * 2009-03-31 2010-10-06 株式会社半导体能源研究所 The electronics and the means of illumination of oxadiazole derivative, use oxadiazole derivative
CN109096220A (en) * 2018-09-12 2018-12-28 信阳师范学院 2- carbonyl -5- aryl -1,3,4-- oxadiazoles steric hindrance type luminescent material and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101851216A (en) * 2009-03-31 2010-10-06 株式会社半导体能源研究所 The electronics and the means of illumination of oxadiazole derivative, use oxadiazole derivative
CN105884709A (en) * 2009-03-31 2016-08-24 株式会社半导体能源研究所 Oxadiazole Derivative, Light Emitting Element Employing The Same, and Light Emitting Apparatus
CN109096220A (en) * 2018-09-12 2018-12-28 信阳师范学院 2- carbonyl -5- aryl -1,3,4-- oxadiazoles steric hindrance type luminescent material and preparation method thereof
CN109096220B (en) * 2018-09-12 2020-08-28 信阳师范学院 2-carbonyl-5-aryl-1, 3, 4-oxadiazole steric hindrance type luminescent material and preparation method thereof

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