CN105481845A - Organic electroluminescent compound and organic photoelectric device thereof - Google Patents
Organic electroluminescent compound and organic photoelectric device thereof Download PDFInfo
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Abstract
The invention provides an organic electroluminescent compound and application thereof to an organic photoelectric device, and the organic photoelectric device containing the organic electroluminescent compound.
Description
Technical field
The present invention relates to field of organic electroluminescent materials, particularly relate to electroluminescent organic material and the application of this material in organic photoelectric device.
Background technology
In recent years, a new generation that Organic Light Emitting Diode (OLED) became domestic and international exception popular because of its luminous, high-level efficiency, the wide advantage such as colour gamut, wide viewing angle shows product.The organic materials simultaneously making OLED plays vital role.
Wherein, the material of OLED luminescent layer, after being subject to electroexcitation, creates singlet excited state (S
1) exciton and triplet excited states (T
1) exciton, according to spin statistics, two kinds of exciton quantitative proportions are 1:3.According to the difference of luminous mechanism, the material that can be used for organic light-emitting diode layer is generally following several.Fluorescent material, only utilizes the singlet S of 25%
1exciton, gets back to ground state S by radiative transition
0, so the maximum external quantum efficiency applying the OLED of this material does not break through this restriction.The second is phosphor material, not only can utilize the singlet S of 25%
1exciton, can also utilize the triplet state T of 75%
1exciton, so theoretical internal quantum efficiency can reach 100%, on OLED, illumination effect is definitely better than fluorescent material, but because phosphor material mostly is rare metal title complex, so material cost is higher, and to there is it in blue phosphor materials be applied to the problems such as efficiency and life-span in OLED be not good always.In 2011, the people such as Kyushu University professor Adachi reported good hot activation delayed fluorescence (TADF) material of luminescent properties.This material S
1state and T
1less and the T of edge energy between state
1state exciton lifetime is longer, under certain temperature condition, and T
1state exciton can realize T by reverse intersystem crossing (RISC)
1→ S
1process, then by S
1state attenuation is to ground state S
0.So can compare favourably with phosphor material by the luminous efficiency of this material as the OLED of luminescent layer, and do not need yttrium, the cost of material is low.But current this material is still few, and novel high-performance TADF material is urgently developed.
Summary of the invention
An object of the present invention is to provide a kind of compound with general formula I,
In formula (I), A
1, A
2, A
3there is not or has the group of formula (II) structure all independently of one another; And A
1, A
2, A
3can not exist simultaneously;
In formula (II), Y
1be selected from oxygen base, sulfenyl, substituted or unsubstituted imino-any one;
X
1, X
2, X
3, X
4be selected from independently of one another
R
1be selected from hydrogen, deuterium, C
1~ C
30alkyl, C
6~ C
30aryl or C
2~ C
30any one in heteroaryl;
In formula (I), B
1, B
2, B
3there is not or have the structure of formula (III) all independently of one another: and B
1, B
2, B
3can not exist simultaneously;
In formula (III), Y
2be selected from singly-bound, oxygen base, sulfenyl, substituted or unsubstituted imino-, substituted or unsubstituted methylene radical, substituted or unsubstituted silicylene any one;
X
5, X
6, X
7, X
8, X
9, X
10, X
11and X
12be selected from independently of one another
described R
2be selected from hydrogen, deuterium, C
1~ C
30alkyl, C
6~ C
30aryl or C
2~ C
30any one in heteroaryl;
In formula (I), L is the connection portion that the structure of general formula (I) can be made to form conjugated system.
Two of the object of the invention is the purposes of compound in organic photoelectric device providing one of a kind of object described.
Three of the object of the invention is to provide a kind of organic photoelectric device, described organic photoelectric device comprises anode, negative electrode and at least 1 layer of organic thin film layer between anode and negative electrode, and described organic thin film layer comprises the combination of any one or at least two kinds in the described compound of one of object.
Compared with prior art, the present invention has following beneficial effect:
Compound provided by the invention has hot activation delayed fluorescence performance, and be a kind of TADF material, luminous efficiency is higher, can improve the luminous efficiency of organic photoelectric device; And compound prepared by the present invention, belong to small organic molecule, compared to phosphorescent metal complexes, cost is lower, and not containing heavy metal and halogen, environmental friendliness.
Accompanying drawing explanation
The structural representation comprising the organic electroluminescent LED of compound of the present invention that Fig. 1 provides for embodiment one;
The structural representation comprising the organic electroluminescent LED of compound of the present invention that Fig. 2 provides for embodiment two;
The structural representation comprising the organic electroluminescent LED of compound of the present invention that Fig. 3 provides for embodiment three;
The structural representation comprising the organic electroluminescent LED of compound of the present invention that Fig. 4 provides for embodiment four;
The structural representation comprising the organic electroluminescent LED of compound of the present invention that Fig. 5 provides for embodiment five.
Embodiment
Technical scheme of the present invention is further illustrated below by embodiment.
In a specific embodiment of the present invention, provide the compound of the structure with formula (I):
In formula (I), A
1, A
2, A
3there is not or has the group of formula (II) structure all independently of one another; And A
1, A
2, A
3can not exist simultaneously;
In formula (II), Y
1be selected from oxygen base, sulfenyl, substituted or unsubstituted imino-any one;
X
1, X
2, X
3, X
4be selected from independently of one another
R
1be selected from hydrogen, deuterium, C
1~ C
30alkyl, C
6~ C
30aryl or C
2~ C
30any one in heteroaryl;
In formula (I), B
1, B
2, B
3there is not or have the structure of formula (III) all independently of one another: and B
1, B
2, B
3can not exist simultaneously;
In formula (III), Y
2be selected from singly-bound, oxygen base, sulfenyl, substituted or unsubstituted imino-, substituted or unsubstituted methylene radical, substituted or unsubstituted silicylene any one;
X
5, X
6, X
7, X
8, X
9, X
10, X
11and X
12be selected from independently of one another
described R
2be selected from hydrogen, deuterium, C
1~ C
30alkyl, C
6~ C
30aryl or C
2~ C
30any one in heteroaryl;
In formula (I), L is the connection portion that the structure of general formula (I) can be made to form conjugated system.
Described " not existing " means do not have corresponding group, or described group is hydrogen atom.
" in formula (I), A
1, A
2, A
3there is not or have the group of formula (II) structure all independently of one another " mean in formula (I), A
1, A
2, A
3can not exist arbitrarily, and the group existed can at random independently selected from the structure that formula (II) provides, and A
1, A
2, A
3can not exist simultaneously.
" in formula (I), B
1, B
2, B
3there is not or have the structure of formula (III) all independently of one another " mean in formula (I), B
1, B
2, B
3can not exist arbitrarily, and the group existed can at random independently selected from the structure that formula (III) provides, and B
1, B
2, B
3can not exist simultaneously.
In the above-described embodiment, described C
1~ C
30alkyl is preferably the alkyl containing 1 ~ 20 carbon atom.
In the above-described embodiment, described C
1~ C
30alkyl is preferably the alkyl containing 1-10 carbon atom.
In the above-described embodiment, described C
1~ C
30alkyl is preferably the alkyl containing 1-6 carbon atom.
In the above-described embodiment, described C
6 ~c
30aromatic group is preferably the aromatic group containing 6 ~ 15 carbon atoms.
In the above-described embodiment, described C
6 ~c
30aromatic group is preferably the aromatic group containing 6 ~ 10 carbon atoms.
In the above-described embodiment, described C
2 ~c
30heteroaromatic group is preferably the heteroaromatic group containing 2 ~ 20 carbon atoms.
In the above-described embodiment, described C
2 ~c
30heteroaromatic group is preferably the heteroaromatic group containing 2 ~ 10 carbon atoms.
In the above-described embodiment, described oxygen base is
described sulfenyl is
described substituted or unsubstituted imino-is
described unsubstituted methylene radical is
described substituted or unsubstituted silicylene is
described R
3, R
4, R
5, R
6, R
7be selected from hydrogen, deuterium, C all independently of one another
1~ C
30alkyl, C
6~ C
30aryl or C
2~ C
30any one in heteroaryl;
In one embodiment, the L in the structure of wherein said general formula I is the aromatic base containing 6 ~ 30 carbon atoms or the heteroaryl containing 2-30 carbon atom.
In one embodiment, the L in the structure of wherein said formula (I) is the aromatic base containing 6 ~ 16 carbon atoms.
In one embodiment, the L in the structure of wherein said formula (I) is the aromatic base with 6 ~ 14 carbon atoms.
In the above-described embodiment, minimum singlet state S
1state and minimum triplet state T
1energy extreme difference Δ E between state
st=E
s1-E
t1≤ 0.30eV, such as 0.29eV, 0.28eV, 0.27eV, 0.26eV, 0.25eV, 0.24eV, 0.23eV, 0.22eV, 0.21eV, 0.20eV, 0.19eV, 0.18eV, 0.16eV, 0.14eV, 0.13eV, 0.12eV, 0.11eV, 0.10eV, 0.09eV, 0.08eV, 0.07eV, 0.06eV, 0.05eV, 0.04eV, 0.03eV, 0.02eV, 0.01eV etc.As Δ E
stduring > 0.30eV, the fluorescence decay DeGrain of described compound.
Preferably, described compound Δ E
st≤ 0.25eV.
Preferably, described compound Δ E
st≤ 0.20eV.
Preferably, described compound Δ E
st≤ 0.15eV.
Preferably, described compound Δ E
st≤ 0.10eV.
Preferably, described compound Δ E
st≤ 0.05eV.
Preferably, described compound Δ E
st≤ 0.02eV.
Preferably, described compound Δ E
st≤ 0.01eV.
In one embodiment, in formula (I), L is aromatic group, described A
1, A
2, A
3, B
1, B
2, B
3be connected to the optional position on the aromatic nucleus of L independently of one another.
In one embodiment, described L is selected from the aromatic group containing 6 ~ 30 carbon atoms or the assorted aromatic group containing 2 ~ 30 carbon atoms.
In one embodiment, the aromatic nucleus of described aromatic group is selected from any one in substituted or unsubstituted benzene, substituted or unsubstituted pyridine, substituted or unsubstituted biphenyl, substituted or unsubstituted azepine biphenyl, substituted or unsubstituted fused ring compound or substituted or unsubstituted fused aza-heterocyclic compound;
The substituting group of the biphenyl of the benzene of described replacement, the pyridine of replacement, replacement, the azepine biphenyl of replacement, the fused ring compound of replacement and the fused aza-heterocyclic compound of replacement is selected from hydrogen, deuterium, C all independently of one another
1~ C
30alkyl, C
6~ C
30aryl or C
2~ C
30heteroaryl.
In one embodiment, the aromatic nucleus of described aromatic group is selected from any one in benzene, biphenyl, naphthalene nucleus, anthracene nucleus, phenanthrene ring or pyrene ring.
In the above-described embodiment, described A
1, A
2, A
3, B
1, B
2, B
3at least one atom of the position of substitution interval on L.
In the above-described embodiment, described A is selected from
in any one.
In the above-described embodiment, it is characterized in that, described B is
in any one.
In one preferred embodiment, described compound is selected from any one in following compound 1 ~ 174:
In the above-described embodiment, described compound has hot activation delayed fluorescence performance.
Two of the object of the invention provides the described purposes of compound in organic photoelectric device of one of a kind of object.
Three of object of the present invention provides a kind of organic photoelectric device, described organic photoelectric device comprises anode, negative electrode and at least 1 layer of organic thin film layer between anode and negative electrode, and described organic thin film layer comprises the combination of any one or at least two kinds in the described compound of one of object.
In a preferred embodiment, described organic thin film layer comprises luminescent layer, described luminescent layer comprises the combination of any one or at least two kinds in the described compound of one of object, and described compound is used as any one in dopant material, co-doped material or material of main part.
In a preferred embodiment, described organic thin film layer also comprises the combination of any one or at least two kinds in hole transmission layer, hole injection layer, electronic barrier layer, hole blocking layer, electron transfer layer, electron injecting layer.
Definition
Unless specified otherwise herein, technology used in the present invention is identical with usual the understood implication of those skilled in the art with the implication of scientific terminology.For the term having definition in the present invention, be as the criterion with defined implication.
" alkyl " refers to the alkyl of completely saturated (not having double bond or three key), that it can be straight chain or side chain.Alkyl can contain 1 to 30 carbon atom, a 1-20 carbon atom, a 1-10 carbon atom or 1-6 carbon atom.Such as, the numerical range of " 1 to 30 " refers to all integers in this scope, and it comprises 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29 or 30.Such as, alkyl can be selected from methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group and hexyl etc.Alkyl can be replacement or unsubstituted.
" aromatic base " refers to the carbocyclic ring (being all carbon) of the π-electron system of the complete delocalization had throughout all rings, and it comprises mono-cyclic aromatic base or multiring aromatic.Described multiring aromatic contains the system of the aromatic nucleus of two or more such as phenyl ring, and this two or more aromatic nucleus can connect each other by singly-bound or condense each other by shared chemical bond.Carbonatoms alterable in aromatic base.Such as, aryl can comprise 6-30 carbon atom.Such as, the numerical range of " 6 to 30 " refers to all integers in this scope, and it comprises 6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29 or 30.The example of aromatic base includes but not limited to benzene, biphenyl, naphthalene, anthracene, phenanthrene or pyrene.Aromatic base can be replacement or unsubstituted.
" heteroaryl " refers to and comprises one or more heteroatomic monocycle or Ppolynuclear aromatic member ring systems, and heteroatoms is wherein the element except carbon, includes but not limited to nitrogen, oxygen and sulphur.Carbonatoms alterable in heteroaryl ring.Such as, heteroaryl can comprise 1-20 carbon atom in its ring, the numerical range of such as " 1 to 20 " refers to all integers in this scope, and it comprises 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20.And for example, heteroaryl can comprise 1-30 ring skeletal atom in its ring, the numerical range of such as " 1 to 30 " refers to all integers in this scope, and it comprises 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29 or 30.In addition, term " heteroaryl " comprises fused ring system, and wherein two rings (such as at least one aryl rings and at least one heteroaryl ring or at least two heteroaryl rings) share at least one chemical bond.The example of heteroaryl ring includes but not limited to furans, furazan, thiophene, thionaphthene, phthalazines, pyrroles, oxazole, benzoxazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, thiazole, 1,2,3-thiadiazoles, 1,2,4-thiadiazoles, benzothiazole, imidazoles, benzoglyoxaline, indoles, indazole, pyrazoles, benzopyrazoles, isoxazole, benzoisoxazole, isothiazole, triazole, benzotriazole, thiadiazoles, tetrazolium, pyridine, pyridazine, pyrimidine, pyrazine, purine, pteridine, quinoline, isoquinoline 99.9, quinazoline, quinoxaline, cinnolines and triazine.Heteroaryl can be replacement or unsubstituted.
Organic photoelectric device
Organic photoelectric device of the present invention comprises organic electroluminescent LED, organic solar batteries, organic photo-sensors, organic memory device etc.Below organic electroluminescent LED is described.
Organic electroluminescent LED comprises anode, negative electrode, one or more layers organic layer between anode and negative electrode.At least one deck in described organic layer is luminescent layer, and described luminescent layer comprises compound of the present invention.Organic electroluminescent LED also comprises hole transmission layer (HTL), hole injection layer (HIL), electronic barrier layer (EBL), hole blocking layer (HBL), electron transfer layer (ETL), electron injecting layer (EIL) or its combination, and the one deck that has at least in these layers comprises organic compound of the present invention.Described compound is present in described luminescent layer as dopant material or co-doped material or material of main part.
Containing the material of two or more molecular structure in luminescent layer.
When in luminescent layer only containing bi-material time, the massfraction of the first material, between 0% to 50%, does not comprise 0%, and Main Function be presented as be subject to electroexcitation after luminous, the first material is referred to as " dopant material "; The massfraction of the second material is corresponding between 100% to 50%, do not comprise 100%, and Main Function is presented as from the next hole of anode direction and produces exciton after the electron recombination that cathode direction is next, and by exciton transfer to dopant material, the second material is referred to as " material of main part ".
When containing two or more materials in luminescent layer, the material having two or more separately massfraction all between 0% to 50%, but do not comprise 0%, and the summation of their massfraction is between 0% to 50%, but do not comprise 0%, and wherein the first material Main Function is presented as and is subject to after electroexcitation luminous, is referred to as " dopant material ", other a kind of and more than one material Main Functions are presented as and exciton energy are passed to dopant material, are referred to as " co-doped material ".Except two or more material one or more materials remaining in luminescent layer aforementioned, their massfraction or massfraction summation are between 100% to 50%, but do not comprise 100%, and Main Function is presented as from the next hole of anode direction and produces exciton after the electron recombination that cathode direction is next, and by exciton transfer to dopant material and co-doped material, then they are referred to as " material of main part ".
The per-cent of described dopant material, material of main part and co-doped material, content and effect just a kind of exemplary statement, do not form limitation of the invention, those skilled in the art can carry out new explanation according to new technology to it.
Fig. 1 to Fig. 5 is the structural representation of the organic electroluminescent LED comprising compound of the present invention, wherein:
100, substrate;
110, anode;
120, negative electrode;
130, luminescent layer;
140, hole transmission layer;
150, electron transfer layer;
160, hole injection layer;
170, electron injecting layer;
180, electronic barrier layer;
190, hole blocking layer.
According to Fig. 1 to Fig. 5, organic electroluminescent LED structure comprises anode layer 110 and cathode layer 120 on plaque layer 100.Luminescent layer 130 is at least comprised between anode layer 110 and cathode layer 120.
Embodiment one provides a kind of organic electroluminescent LED comprising compound of the present invention, and as shown in Figure 1, organic electroluminescent LED only comprises luminescent layer 130 to its structural representation between anode layer 110 and cathode layer 120.Electronics and hole stimulated luminescence layer after luminescent layer compound is luminous.
Embodiment two provides a kind of organic electroluminescent LED comprising compound of the present invention, as shown in Figure 2, organic electroluminescent LED comprises hole transmission layer (HTL) 140 and luminescent layer 130 to its structural representation between anode layer 110 and cathode layer 120.Hole transmission layer mainly plays hole-transfer to the effect of luminescent layer.
Embodiment three provides a kind of organic electroluminescent LED comprising compound of the present invention, as shown in Figure 3, organic electroluminescent LED comprises hole transmission layer (HTL) 140, luminescent layer 130 and electron transfer layer (ETL) 150 to its structural representation between anode layer 110 and cathode layer 120.Electron transfer layer mainly plays electron transmission to the effect of luminescent layer.
Embodiment four provides a kind of organic electroluminescent LED comprising compound of the present invention, as shown in Figure 4, organic electroluminescent LED comprises hole injection layer (HIL) 160, hole transmission layer (HTL) 140, luminescent layer 130, electron transfer layer (ETL) 150 and electron injecting layer (EIL) 170 to its structural representation between anode layer 110 and cathode layer 120.Hole injection layer mainly improves ability hole being delivered to organic layer from anode, and electron injecting layer mainly improves ability electronics being delivered to organic layer from negative electrode, to reduce the driving voltage of diode.
Embodiment five provides a kind of organic electroluminescent LED comprising compound of the present invention, as shown in Figure 5, organic electroluminescent LED comprises hole injection layer (HIL) 160, hole transmission layer (HTL) 140, electronic barrier layer (EBL) 180, luminescent layer 130, hole blocking layer (HBL) 190 and electron transfer layer (ETL) 150 to its structural representation between anode layer 110 and cathode layer 120.
Below layers of material is illustrated, but is not limited to described material ranges.
Anode layer 110 can use the electrode materials with large work function.Can comprise as the material of anode: the such as metal of copper, gold and silver, iron, chromium, nickel, manganese, palladium, platinum or its mixture; The alloy of the metals such as such as copper, gold and silver, iron, chromium, nickel, manganese, palladium or platinum; The such as metal oxide of Indium sesquioxide, zinc oxide, tin indium oxide (ITO), indium zinc oxide (IZO) or its mixture; Comprise the electric conductive polymer of polyaniline, polypyrrole, poly-(3 methyl thiophene) or its mixture.Preferably, in the embodiment comprising organic compound of the present invention, use tin indium oxide (ITO) as the material of anode layer.
Cathode layer 120 can use the electrode materials with low work function.Can comprise as the material of negative electrode: the such as metal of aluminium, magnesium, silver, indium, tin, titanium, calcium, sodium, potassium, lithium, ytterbium, lead or its mixture; Comprise the multiple layer metal material of LiF/Al, Liq (oxine)/Al or its mixture.Preferably, in the embodiment comprising organic compound of the present invention, use magnesium silver alloys or LiF/Al double layer material as the material of cathode layer.
Hole injection layer (HIL) 160 hole being conducive to increasing anode and organic layer interface can be used to inject and can be good with ito anode surface bonding performance material.Can comprise as the material of hole injection layer: as the poly-porphyrin compound of CuPc (CuPc), as 4,4 '; 4 " the starlike triphenylamine derivative containing naphthylene diamine of-three-N-naphthyl-N-anilino-triphenylamine (TNATA), as poly-(3,4-ethylenedioxy thiophene): the macromolecular material that this kind of HOMO energy level of poly styrene sulfonate (PEDOT:PSS) mates with ITO work function, as 2,3,6,7,10,11-, six cyano group-Isosorbide-5-Nitrae, 5,8,9,12-six azepine benzophenanthrene (HATCN) draw electro nitrogen-containing heterocycle compound etc.
Hole transmission layer (HTL) 140 and electronic barrier layer (EBL) 180 can use the material with high glass transition temperature and hole mobility.Can comprise as the material of hole transmission layer and electronic barrier layer: as the benzidine derivative of phenylbenzene naphthyl diamines (NPD), as 2,2 ', 7,7 '-four (hexichol amido)-9, the decussate texture diamines biphenyl derivatives of 9 '-spiral shell two fluorenes (spiro-TAD), as 4,4 ', 4 " the starlike triphenylamine derivative etc. of-three (N-carbazyl) triphenylamine (TCTA).
Hole blocking layer (HBL) 190 and electron transfer layer (ETL) 150 can use has low HOMO energy level and the high material of electronic mobility.Can comprise as the material of hole blocking layer and electron transfer layer: as the quinoline metal complex of two (8-hydroxy-2-methylquinoline)-biphenol aluminium (BAlq), three (oxine) aluminium (Alq) and oxine lithium, as 4,7-phenylbenzene-1, the phenanthroline derivative of 10-phenanthroline (Bphen), as 1,3,5, the imdazole derivatives of-three (N-Phenyl-benzoimidazol-2-base) benzene (TPBI), as 2,4,6-tri-carbazyl-1, the pyrrolotriazine derivatives etc. of 3,5-triazine.
The making method of organic electroluminescent LED is as follows: on transparent or opaque smooth substrate, form anode, anode forms organic layer, organic layer forms negative electrode.Form organic layer and can adopt film as known in evaporation, sputtering, spin coating, dipping, ion plating etc.
Hereinafter, the present invention will be explained in detail to understand all respects of the present invention and advantage thereof better by following embodiment.But, should be appreciated that following embodiment is nonrestrictive and only for illustration of certain embodiments of the present invention.
Embodiment
the analog calculation of compound
The minimum singlet S of organic materials
1with lowest triplet state T
1energy level difference can be completed by Guassian09 software (GuassianInc.).Energy level difference Δ E
stconcrete analogy method with reference to J.Chem.TheoryComput., 2013, DOI:10.1021/ct400415r, molecular structure optimization and excite all available TD-DFT method " B3LYP " and base group " 6-31g (d) " to complete.
Embodiment 1
According to above-mentioned modeling scheme, compound 29 is simulated;
Embodiment 2
According to above-mentioned modeling scheme, compound 30 is simulated;
Embodiment 3
According to above-mentioned modeling scheme, compound 55 is simulated;
Embodiment 4
According to above-mentioned modeling scheme, compound 40 is simulated;
Embodiment 5
According to above-mentioned modeling scheme, compound 174 is simulated;
Embodiment 6
According to above-mentioned modeling scheme, compound 1 is simulated;
Embodiment 7
According to above-mentioned modeling scheme, compound 65 is simulated;
Embodiment 8
According to above-mentioned modeling scheme, compound 70 is simulated;
Embodiment 9
According to above-mentioned modeling scheme, compound 33 is simulated;
Embodiment 10
According to above-mentioned modeling scheme, compound 80 is simulated;
Embodiment 11
According to above-mentioned modeling scheme, compound 168 is simulated;
Embodiment 12
According to above-mentioned modeling scheme, compound 151 is simulated;
Embodiment 13
According to above-mentioned modeling scheme, compound 84 is simulated;
Embodiment 14
According to above-mentioned modeling scheme, compound 91 is simulated;
Embodiment 15
According to above-mentioned modeling scheme, compound 103 is simulated.
Analog calculation result is as shown in table 1.
The analog calculation result of table 1 embodiment 1 ~ 15
According to table 1 result, the singlet of embodiment 1 to 15 and triplet difference Δ E
stall less, this shows that the compound in table 1 can realize efficient reverse intersystem crossing, has TADF performance.
the preparation of compound
Embodiment 16: the synthesis of compound 29
The first step: synthetic compound 29-a
By bromo-for 3-4-nitrobenzene methyl (20g, 76.9mmol) phenoxazine (14.1g, 76.9mmol), palladium (0.8g, 3.8mmol), tertiary butyl phosphine (1.1g, 5.8mmol) and cesium carbonate (37.5g, 115.4mmol) are dissolved in toluene, under nitrogen atmosphere, heating reflux reaction 8 hours.Solvent in vacuo is evaporated, adds pentane in surplus materials and stir, filter, purified by silica gel chromatographic column, obtain solid chemical compound 29-a (15.6g, yield 56%).
Second step: synthetic compound 29-b
Above-mentioned intermediate 29-a (15.6g, 43.1mmol) is dissolved in methyl alcohol, under protection argon gas, slowly adds 3gPd/C, after the gas with hydrogen exchange reaction vessel, keep atmosphere of hydrogen to react 20 hours.Filter, after solvent evaporated, obtain intermediate 29-b (13.3g, yield 93%).
3rd step: synthetic compound 29-c
By Sodium Nitrite (7.5g, 108.7mmol) be dissolved in 10mL water, under condition of ice bath, this solution is slowly added drop-wise to intermediate 29-b (12.0g by (0 DEG C), 36.1mmol) with in the mixture of 48% Hydrogen bromide (about 91.0mmol) of 11mL, stir 1 hour.Under condition of ice bath, in above-mentioned mixed solution, add the hydrobromic acid solution 10mL of cuprous bromide (5.4g, 37.9mmol), react 1 hour under ice bath, be then heated to 60 DEG C of reactions 2 hours.With ethyl acetate 50mL extraction after cooling, organic layers with water is washed for several times, with anhydrous magnesium sulfate drying, obtains intermediate 29-c (10.3g, yield 72%) after filtering evaporating solvent.
4th step: synthetic compound 29-d
29-c (10.3g, 26.0mmol) is dissolved in 30mL methyl alcohol, in this solution, adds LiOH (3.1g, 130.0mmol), stirring at room temperature 2 hours.Methyl alcohol is evaporated, by 50mL ethyl acetate and the extraction of 20mL water, organic phase washed several times with water, with anhydrous magnesium sulfate drying, filters evaporating solvent and obtain intermediate 29-d (8.4g, yield 85%).
5th step: synthetic compound 29-e
Intermediate 29-d (8.4g, 22.1mmol) is dissolved in 100mL sulfur oxychloride, drips several DMF as catalyzer, reflux 20 hours.Vacuum-evaporation is dissolved in the methylene dichloride of 300mL after falling remaining sulfur oxychloride.Add 2-bromaniline (7.6g, 44.2mmol) under ice cooling, 4, slowly drip 15mL triethylamine, at room temperature stir after dripping and spend the night.Reaction suspension is filtered, with methylene dichloride cleaning twice.Obtain intermediate 29-e (10.6g, yield 73%).
6th step: synthetic compound 29-f
Will by above-claimed cpd 29-e (8.7g under argon gas stream protection; 16.1mmol), cuprous iodide (0.3g; 1.7mmol), cesium carbonate (10.5g; 32.2mmol); with 1; 10-phenanthroline (0.7g, 3.3mmol) is dissolved in 200mL dioxane, and constant temperature 120 DEG C of reactions are spent the night.Dilute with the water of 300mL ethyl acetate and 500mL after being cooled to room temperature.Filtering suspension liquid also obtains intermediate 29-f (5.7g, yield 78%) with water, ethanol purge.
7th step: synthetic compound 29-g
Under nitrogen flowing, will catalyst P d (dppf) Cl
2(0.2g, 0.3mmol), Potassium ethanoate (0.3g, 3.0mmol), boric acid pinacol ester (2.3g is joined, 8.9mmol) be mixed in reaction flask, by intermediate 29-f (2.5g, dioxane solution 5.5mmol) being dissolved in 150mL joins in above-mentioned reaction flask, back flow reaction 10 hours.With adding toluene extraction after cooling, washed several times with water, uses anhydrous magnesium sulfate drying.Filter, purified by silica gel chromatographic column after solvent evaporated, obtain intermediate 29-g (1.4g, yield 49%).8th step: synthetic compound 29
By intermediate 29-g (1.4g, 2.7mmol), intermediate 29-f (1.2g, 2.7mmol), Pd (dppf) Cl under argon gas stream
2(0.04g, 0.05mmol), 10mL2MNa
2cO
3aqueous solution in 100mL toluene, reflux 10 hours.Dichloromethane extraction is used after cooling.Organic phases washed with water for several times, with anhydrous magnesium sulfate drying, is filtered, is purified after evaporation by silica gel chromatographic column, obtain solid chemical compound 29 (0.7g, yield 33%).
Obtained ESI-MS (m/z): 751.2 [M+H] by liquid chromatography mass spectrometric combination analysis
+.
Embodiment 17: the synthesis of compound 30
The first step: synthetic compound 30-a
By 2,2 '-two bromo-4,4 '-dicarboxylate biphenyl (20g, 50.0mmol), 2-mercaptoaniline (12.5g, 100.0mmol) and 100.0g polyphosphoric acid (PPA), at 140 DEG C of heated and stirred 5h, naturally cool to room temperature.Slowly add the deionized water of 100.0ml, be fully hydrolyzed, after filtration, fully dissolved by filter residue methylene dichloride, filter, get filtrate and pump solvent under vacuo, purifying with silica gel chromatographic column obtains intermediate 30-a (12.7g, yield 44%).
Second step: synthetic compound 30
By above-mentioned intermediate 30-a (12.7g, 22.0mmol), phenoxazine (8.1g, 44.0mmol), palladium (0.5g, 2.2mmol), tertiary butyl phosphine (0.7g, 3.3mmol) with cesium carbonate (21.5g, 66.0mmol) be dissolved in toluene, under nitrogen atmosphere, heating reflux reaction 10 hours.Solvent in vacuo is evaporated, adds pentane in surplus materials and stir, filter, purified by silica gel chromatographic column, obtain solid chemical compound 30 (4.8g, yield 28%).
Obtained ESI-MS (m/z): 783.1 [M+H] by liquid chromatography mass spectrometric combination analysis
+.
Embodiment 18: the synthesis of compound 55
The first step: synthetic compound 55-a
By 2,2 '-dicarboxyl-4,4 '-'-dibromobiphenyl (20g, 50.0mmol), 2-hydroxyanilines (10.9g, 100.0mmol) and 100.0g polyphosphoric acid (PPA) at 140 DEG C of heated and stirred 5h, naturally cool to room temperature.Slowly add the deionized water of 100.0ml, be fully hydrolyzed, after filtration, fully dissolved by filter residue methylene dichloride, filter, get filtrate and pump solvent under vacuo, purifying with silica gel chromatographic column obtains intermediate 55-a (6.8g, yield 25%).
Second step: synthetic compound 55
By above-mentioned intermediate 55-a (6.8g, 12.5mmol), phenoxazine (4.6g, 25.0mmol), palladium (0.3g, 1.3mmol), tertiary butyl phosphine (0.4g, 1.9mmol) with cesium carbonate (12.2g, 37.5mmol) be dissolved in toluene, under nitrogen atmosphere, heating reflux reaction 10 hours.Solvent in vacuo is evaporated, adds pentane in surplus materials and stir, filter, purified by silica gel chromatographic column, obtain solid chemical compound 55 (2.9g, yield 31%).
Obtained ESI-MS (m/z): 751.2 [M+H] by liquid chromatography mass spectrometric combination analysis
+.
Embodiment 19: the synthesis of compound 40
The first step: synthetic compound 40-a
By bromo-for 3-5-nitrobenzene methyl (20g, 76.9mmol), phenoxazine (14.1g, 76.9mmol), palladium (0.8g, 3.8mmol), tertiary butyl phosphine (1.1g, 5.8mmol) with cesium carbonate (37.5g, 115.4mmol) be dissolved in toluene, under nitrogen atmosphere, heating reflux reaction 8 hours.Solvent in vacuo is evaporated, adds pentane in surplus materials and stir, filter, purified by silica gel chromatographic column, obtain solid chemical compound 40-a (14.5g, yield 52%).
Second step: synthetic compound 40-b
Above-mentioned intermediate 40-a (14.5g, 40.0mmol) is dissolved in methyl alcohol, under protection argon gas, slowly adds 3gPd/C, after the gas with hydrogen exchange reaction vessel, keep atmosphere of hydrogen to react 20 hours.Filter, after solvent evaporated, obtain intermediate 40-b (12.0g, yield 90%).
3rd step: synthetic compound 40-c
By Sodium Nitrite (7.5g, 108.7mmol) be dissolved in the water of 10mL, under condition of ice bath, this solution is slowly added drop-wise to intermediate 40-b (12.0g by (0 DEG C), 36.1mmol) and 11mL 48% Hydrogen bromide (about 91.0mmol) mixture in, stir 1 hour.Under condition of ice bath, in above-mentioned mixed solution, add the hydrobromic acid solution 10mL of cuprous bromide (5.4g, 37.9mmol), react 1 hour under ice bath, be then heated to 60 DEG C of reactions 2 hours.With ethyl acetate 50mL extraction after cooling, organic layers with water is washed for several times, with anhydrous magnesium sulfate drying, obtains intermediate 40-c (11.3g, yield 79%) after filtering evaporating solvent.
4th step: synthetic compound 40-d
Intermediate 40-c (11.3g, 28.5mmol) is dissolved in 30mL methyl alcohol, in this solution, adds LiOH (3.4g, 142.5mmol), stirring at room temperature 2 hours.Methyl alcohol is evaporated, by 50mL ethyl acetate and the extraction of 20mL water, organic phase washed several times with water, with anhydrous magnesium sulfate drying, filters evaporating solvent and obtain intermediate 40-d (9.7g, yield 89%).
5th step: synthetic compound 40-e
Intermediate 40-d (9.7g, 25.4mmol) is dissolved in 100mL sulfur oxychloride, drips several DMF as catalyzer, reflux 20 hours.Vacuum-evaporation is dissolved in the methylene dichloride of 300mL after falling remaining sulfur oxychloride.Add 2-bromaniline (8.7g, 50.8mmol) under ice cooling, 4, slowly drip 15mL triethylamine, at room temperature stir after dripping and spend the night.Reaction suspension is filtered, with methylene dichloride cleaning twice.Obtain intermediate 40-e (10.6g, yield 78%).
6th step: synthetic compound 40-f
Will by above-claimed cpd 40-e (10.6g under argon gas stream protection; 19.8mmol), cuprous iodide (0.4g; 2.1mmol), cesium carbonate (12.9g; 39.6mmol) and 1; 10-phenanthroline (0.8g; 4.0mmol) be dissolved in 200mL dioxane, constant temperature 120 DEG C of reactions are spent the night.Dilute with the water of 300mL ethyl acetate and 500mL after being cooled to room temperature.Filtering suspension liquid also obtains intermediate 40-f (7.5g, yield 83%) with water, ethanol purge.
7th step: synthetic compound 40-g
Under nitrogen flowing, will catalyst P d (dppf) Cl
2(0.2g, 0.3mmol), Potassium ethanoate (0.3g, 3.0mmol), connection boric acid pinacol ester (2.3g, 8.9mmol) be mixed in reaction flask, intermediate 40-f (3.7g, 8.1mmol) be dissolved in the dioxane solution of 150mL, join in above-mentioned reaction flask, back flow reaction 10 hours.With adding toluene extraction after cooling, washed several times with water, uses anhydrous magnesium sulfate drying.Filter, purified by silica gel chromatographic column after solvent evaporated, obtain intermediate 40-g (2.2g, yield 53%).8th step: synthetic compound 40
By intermediate 40-g (2.2g, 4.3mmol), intermediate 40-f (2.0g, 4.3mmol), Pd (dppf) Cl under argon gas stream
2(0.06g, 0.09mmol), 20mL2MNa
2cO
3aqueous solution in 100mL toluene, reflux 10 hours.Dichloromethane extraction is used after cooling.Organic phases washed with water for several times, with anhydrous magnesium sulfate drying, is filtered, is purified after evaporation by silica gel chromatographic column, obtain solid chemical compound 40 (1.2g, yield 36%).
Obtained ESI-MS (m/z): 751.1 [M+H] by liquid chromatography mass spectrometric combination analysis
+.
Embodiment 20: the synthesis of compound 1
The first step: synthetic compound 1-a
5-bromo m-phthalic acid (20g, 81.6mmol) is dissolved in 100mL sulfur oxychloride, drips several DMF as catalyzer, reflux 20 hours.Vacuum-evaporation is dissolved in the methylene dichloride of 300mL after falling remaining sulfur oxychloride.After ice bath cooling, add 2-bromaniline (28.1g, 163.2mmol), slowly drip 30mL triethylamine, at room temperature stir after dropping and spend the night.Reaction suspension is filtered, with methylene dichloride cleaning twice.Obtain intermediate 1-a (38.4g, yield 85%).
Second step: synthetic compound 1-b
Will by above-claimed cpd 1-a (38.4g under argon gas stream protection; 69.4mmol), cuprous iodide (1.3g; 6.9mmol), cesium carbonate (45.2g; 138.7mmol) and 1; 10-phenanthroline (2.5g; 13.9mmol) be dissolved in 300mL dioxane, constant temperature 120 DEG C of reactions are spent the night.Dilute with the water of 500mL ethyl acetate and 700mL after being cooled to room temperature.Filtering suspension liquid also obtains white solid 1-b (19.8g, yield 73%) with water, ethanol purge.
3rd step: synthetic compound 1
By above-mentioned intermediate 1-b (19.8g, 50.6mmol), phenoxazine (9.3g, 50.6mmol), palladium (0.6g, 2.7mmol), tertiary butyl phosphine (0.8g, 3.8mmol) with cesium carbonate (24.7g, 75.9mmol) be dissolved in toluene, under nitrogen atmosphere, heating reflux reaction 8 hours.Solvent in vacuo is evaporated, adds pentane in surplus materials and stir, filter, purified by silica gel chromatographic column, obtain solid chemical compound 1 (8.1g, yield 31%).
Obtained ESI-MS (m/z): 494.1 [M+H] by liquid chromatography mass spectrometric combination analysis
+.
Embodiment 21: the synthesis of compound 70
The first step: synthetic compound 70-a
By luxuriant and rich with fragrance for 2,9-dibromo-4,7-dioctyl phthalate (20g, 47.2mmol), 2-hydroxyanilines (10.4g, 94.4mmol) and 100.0g polyphosphoric acid (PPA) at 140 DEG C of heated and stirred 5h, naturally cool to room temperature.Slowly add the deionized water of 100.0ml, be fully hydrolyzed, filter, obtain greyish-green filter residue.Filter residue methylene dichloride is fully dissolved, filters, obtain the filtrate of orange red clarification.Pump solvent under vacuo, purifying with silica gel chromatographic column obtains intermediate 70-a (19.4g, yield 72%).
Second step: synthetic compound 70
By above-mentioned intermediate 70-a (19.4g, 34.0mmol), phenoxazine (12.5g, 68.0mmol), palladium (0.4g, 1.8mmol), tertiary butyl phosphine (0.5g, 2.5mmol) with cesium carbonate (16.6g, 51.0mmol) be dissolved in toluene, under nitrogen atmosphere, heating reflux reaction 8 hours.Solvent in vacuo is evaporated, adds pentane in surplus materials and stir, filter, purified by silica gel chromatographic column, obtain solid chemical compound 70 (9.9g, yield 39%).
Obtained ESI-MS (m/z): 775.1 [M+H] by liquid chromatography mass spectrometric combination analysis
+.
Embodiment 22: the synthesis of compound 33
The first step: synthetic compound 33-a
By 2,2 '-two bromo-4,4 '-dicarboxylate biphenyl (20g, 50.0mmol), 2-amido-4-pyridone (11.0g, 100.0mmol) and 100.0g polyphosphoric acid (PPA) at 140 DEG C of heated and stirred 5h, naturally cool to room temperature.Slowly add the deionized water of 100.0ml, be fully hydrolyzed, after filtration, fully dissolved by filter residue methylene dichloride, filter, get filtrate and pump solvent under vacuo, purifying with silica gel chromatographic column obtains intermediate 33-a (18.9g, yield 69%).
Second step: synthetic compound 33
By above-mentioned intermediate 33-a (18.9g, 34.5mmol) phenoxazine (12.6g, 69.0mmol), palladium (0.4g, 1.8mmol), tertiary butyl phosphine (0.5g, 2.5mmol) and cesium carbonate (16.9g, 51.9mmol) are dissolved in toluene, under nitrogen atmosphere, heating reflux reaction 8 hours.Solvent in vacuo is evaporated, adds pentane in surplus materials and stir, filter, purified by silica gel chromatographic column, obtain solid chemical compound 33 (8.8g, yield 34%).
Obtained ESI-MS (m/z): 753.1 [M+H] by liquid chromatography mass spectrometric combination analysis
+.
Embodiment 23: the synthesis of compound 80
The first step: synthetic compound 80-a
By 3,5-bis-bromo-3 ', 5 '-dicarboxylate biphenyl (20g, 50.0mmol), 2-hydroxyanilines (10.9g, 100.0mmol) and 100.0g polyphosphoric acid (PPA), at 140 DEG C of heated and stirred 5h, naturally cool to room temperature.Slowly add the deionized water of 100.0ml, be fully hydrolyzed, after filtration, fully dissolved by filter residue methylene dichloride, filter, get filtrate and pump solvent under vacuo, purifying with silica gel chromatographic column obtains intermediate 80-a (10.4g, yield 38%).
Second step: synthetic compound 80
By above-mentioned intermediate 80-a (10.4g, 19.0mmol), phenoxazine (7.0g, 38.0mmol), palladium (0.4g, 1.9mmol), tertiary butyl phosphine (0.6g, 2.9mmol) with cesium carbonate (18.6g, 57.0mmol) be dissolved in toluene, under nitrogen atmosphere, heating reflux reaction 10 hours.Solvent in vacuo is evaporated, adds pentane in surplus materials and stir, filter, purified by silica gel chromatographic column, obtain solid chemical compound 80 (3.3g, yield 23%).
Obtained ESI-MS (m/z): 751.1 [M+H] by liquid chromatography mass spectrometric combination analysis
+.
Embodiment 24: the synthesis of compound 84
The first step: synthetic compound 84
By intermediate 1-b (5.0g, 12.8mmol), 9,9-dimethyl acridinium (5.4g, 25.6mmol), palladium (0.3g, 1.3mmol), tertiary butyl phosphine (0.4g, 1.9mmol) and cesium carbonate (12.5g, 38.4mmol) are dissolved in toluene, under nitrogen atmosphere, heating reflux reaction 8 hours.Solvent in vacuo is evaporated, adds pentane in surplus materials and stir, filter, purified by silica gel chromatographic column, obtain solid chemical compound 84 (1.9g, yield 28%).
Obtained ESI-MS (m/z): 520.1 [M+H] by liquid chromatography mass spectrometric combination analysis
+.
Embodiment 25: the synthesis of compound 91
The first step: synthetic compound 91-a
By 3,3 '-dicarboxyl-5,5 '-'-dibromobiphenyl (20g, 50.0mmol), 2-hydroxyanilines (10.9g, 100.0mmol) and 100.0g polyphosphoric acid (PPA) at 140 DEG C of heated and stirred 5h, naturally cool to room temperature.Slowly add the deionized water of 100.0ml, be fully hydrolyzed, after filtration, fully dissolved by filter residue methylene dichloride, filter, get filtrate and pump solvent under vacuo, purifying with silica gel chromatographic column obtains intermediate 91-a (10.1g, yield 37%).
Second step: synthetic compound 91
By above-mentioned intermediate 91-a (10.1g, 18.5mmol), 9,9-dimethyl acridinium (7.7g, 37.0mmol), palladium (0.4g, 1.9mmol), tertiary butyl phosphine (0.6g, 2.8mmol) and cesium carbonate (18.1g, 55.5mmol) are dissolved in toluene, under nitrogen atmosphere, heating reflux reaction 10 hours.Solvent in vacuo is evaporated, adds pentane in surplus materials and stir, filter, purified by silica gel chromatographic column, obtain solid chemical compound 91 (4.2g, yield 28%).
Obtained ESI-MS (m/z): 803.2 [M+H] by liquid chromatography mass spectrometric combination analysis
+.
Embodiment 26: the synthesis of compound 103
The first step: synthetic compound 103-a
By luxuriant and rich with fragrance for 4,9-dibromo-2,7-dioctyl phthalate (20g, 47.2mmol), 2-hydroxyanilines (10.3g, 94.4mmol) and 100.0g polyphosphoric acid (PPA) at 140 DEG C of heated and stirred 5h, naturally cool to room temperature.Slowly add the deionized water of 100.0ml, be fully hydrolyzed, after filtration, fully dissolved by filter residue methylene dichloride, filter, get filtrate and pump solvent under vacuo, purifying with silica gel chromatographic column obtains intermediate 103-a (5.7g, yield 21%).
Second step: synthetic compound 103
By above-mentioned intermediate 103-a (5.7g, 9.9mmol), 9,9-dimethyl acridinium (4.1g, 19.8mmol), palladium (0.2g, 1.0mmol), tertiary butyl phosphine (0.3g, 1.5mmol) and cesium carbonate (9.7g, 29.7mmol) are dissolved in toluene, under nitrogen atmosphere, heating reflux reaction 10 hours.Solvent in vacuo is evaporated, adds pentane in surplus materials and stir, filter, purified by silica gel chromatographic column, obtain solid chemical compound 103 (2.2g, yield 27%).
Obtained ESI-MS (m/z): 827.3 [M+H] by liquid chromatography mass spectrometric combination analysis
+.
Embodiment 27: the synthesis of compound 6
The first step: synthetic intermediate 6-a
5-bromo m-phthalic acid (10g, 40.8mmol) is dissolved in 50mL sulfur oxychloride, drips several DMF as catalyzer, heated overnight at reflux under argon gas condition.Vacuum-evaporation is dissolved in the methylene dichloride of 150mL after falling remaining sulfur oxychloride.After ice bath cooling, add N '-3 '-phenyl-2,3-pyridine diamines (15.1g, 81.6mmol), slowly drip 15mL triethylamine, at room temperature stir after dropping and spend the night.Reaction suspension is filtered, with methylene dichloride cleaning twice.Obtain intermediate 6-a (19.6g, yield 83%).
Second step: synthetic intermediate 6-b
Under water-bath cooling conditions, by POCl
3(20.8g, 135.6mmol) slowly joins in the dioxane solution of intermediate 6-a (19.6g, 33.9mmol).Mixture is heated to 100 DEG C and stirs and spends the night.Add ice cube after mixture cool to room temperature, and use Na
2cO
3solution is neutralized to neutrality.With dichloromethane extraction twice, use anhydrous Na
2sO
4dry.Purify with silica gel chromatographic column after organic phase is concentrated, obtain intermediate 6-b (13.6g, yield 74%).
3rd step: synthetic compound 6
By above-mentioned intermediate 6-b (13.6g, 25.1mmol), phenoxazine (5.1g, 27.6mmol), palladium (0.3g, 1.3mmol), tertiary butyl phosphine (0.4g, 1.9mmol) with cesium carbonate (12.3g, 37.7mmol) be dissolved in toluene, under argon atmosphere, heating reflux reaction 8 hours.Solvent in vacuo is evaporated, adds pentane in surplus materials and stir, filter, purified by silica gel chromatographic column, obtain solid chemical compound 6 (6.0g, yield 37%).
Obtained ESI-MS (m/z): 646.1 [M+H] by liquid chromatography mass spectrometric combination analysis
+.
Embodiment 28: the synthesis of compound 12
Except replacing 2-amido-4-pyridone with 3-aminopyridine-2-mercaptan and replacing 2,2 '-two bromo-4 with 5-bromo m-phthalic acid, beyond 4 '-dicarboxylate biphenyl, other building-up processes are with embodiment 22.Purified by silica gel chromatographic column, obtain solid chemical compound 12 (9.0g, yield 21%).
Obtained ESI-MS (m/z): 528.1 [M+H] by liquid chromatography mass spectrometric combination analysis
+.
Embodiment 29: the synthesis of compound 17
Except replacing 5-bromo m-phthalic acid with 3,5-dibromobenzoic acid and replacing beyond N '-3 '-phenyl-2,3-pyridine diamines with N '-2 '-phenyl-2,3-pyridine diamines, other building-up processes are with embodiment 27.Purified by silica gel chromatographic column, obtain solid chemical compound 17 (5.4g, yield 24%).
Obtained ESI-MS (m/z): 634.2 [M+H] by liquid chromatography mass spectrometric combination analysis
+.
Embodiment 30: the synthesis of compound 24
Except replacing 3-aminopyridine-2-mercaptan with 2-amino-3-pyridone and replacing beyond 5-bromo m-phthalic acid with 3,5-dibromobenzoic acid, other building-up processes are with embodiment 22.Purified by silica gel chromatographic column, obtain solid chemical compound 24 (7.6g, yield 19%).
Obtained ESI-MS (m/z): 559.1 [M+H] by liquid chromatography mass spectrometric combination analysis
+.
Embodiment 31: the synthesis of compound 51
Remove with 3,3 '-two bromo-5,5 '-dicarboxylate biphenyl replaces 5-bromo m-phthalic acid and replaces beyond N '-3 '-phenyl-2,3-pyridine diamines with N '-2 '-phenyl-2,3-pyridine diamines, and other building-up processes are with embodiment 27.Purified by silica gel chromatographic column, obtain solid chemical compound 51 (3.8g, yield 17%).
Obtained ESI-MS (m/z): 903.2 [M+H] by liquid chromatography mass spectrometric combination analysis
+.
Embodiment 32: the synthesis of compound 76
Except replacing luxuriant and rich with fragrance-4, the 7-dioctyl phthalate of 2,9-dibromo with luxuriant and rich with fragrance-2, the 9-dioctyl phthalate of 4,7-dibromo and replacing beyond 2-hydroxyanilines with 2-amino-3-pyridone, other building-up processes are with embodiment 21.Purified by silica gel chromatographic column, obtain solid chemical compound 76 (8.8g, yield 24%).
Obtained ESI-MS (m/z): 777.2 [M+H] by liquid chromatography mass spectrometric combination analysis
+.
Embodiment 33: the synthesis of compound 128
The first step: synthetic intermediate 128-e
Except replacing beyond 2-hydroxyanilines with N-phenyl benzene-1,2-diamines, other building-up processes are with the building-up process of the intermediate 29-e of embodiment 16.Solid intermediate 128-e (9.7g, yield 23%) is obtained after purification.
Second step: synthetic intermediate 128-f
Under water-bath cooling conditions, by POCl
3(5.4g, 35.4mmol) slowly joins in the dioxane solution of intermediate 128-e (9.7g, 17.7mmol).Mixture is heated to 100 DEG C and stirs and spends the night.Add ice cube after mixture cool to room temperature, and use Na
2cO
3solution is neutralized to neutrality.With dichloromethane extraction twice, use anhydrous magnesium sulfate drying.Purify with silica gel chromatographic column after organic phase is concentrated, obtain intermediate 128-f (7.4g, yield 79%).
3rd step: synthetic compound 128
By intermediate 29-g (7.0g, 14.0mmol), intermediate 128-f (7.4g, 14.0mmol), Pd (dppf) Cl under argon gas stream
2(0.2g, 0.3mmol), 50mL2MNa
2cO
3aqueous solution in 200mL toluene, reflux 10 hours.Dichloromethane extraction is used after cooling.Organic phases washed with water for several times, with anhydrous magnesium sulfate drying, is filtered, is purified after evaporation by silica gel chromatographic column, obtain solid chemical compound 128 (3.0g, 26% yield).
Obtained ESI-MS (m/z): 826.2 [M+H] by liquid chromatography mass spectrometric combination analysis
+.
Embodiment 34: the synthesis of compound 138
The first step: synthetic intermediate 138-a
Replace the bromo-4-nitrobenzene methyl of 3-with 2-nitro-5-methyl-bromobenzoate, other building-up processes are with synthetic example 16 intermediate 29-g process.Purified by silica gel chromatographic column, obtain solid intermediate 138-a (3.1g, yield 8%).
Second step: synthetic intermediate 138-b
Replace the bromo-4-nitrobenzene methyl of 3-with 2-nitro-5-methyl-bromobenzoate, replace phenoxazine with 9,9-dimethyl acridinium, other building-up processes are with synthetic example 16 intermediate 29-f process.Purified by silica gel chromatographic column, obtain solid intermediate 138-b (5.9g, yield 16%).
3rd step: synthetic compound 138
By intermediate 138-a (3.1g, 6.1mmol), intermediate 138-b (2.9g, 6.1mmol), Pd (dppf) Cl under argon gas stream
2(0.08g, 0.11mmol), 25mL2MNa
2cO
3aqueous solution in 150mL toluene, reflux 10 hours.Dichloromethane extraction is used after cooling.Organic phases washed with water for several times, with anhydrous magnesium sulfate drying, is filtered, is purified after evaporation by silica gel chromatographic column, obtain solid chemical compound 138 (1.3g, 27% yield).
Obtained ESI-MS (m/z): 777.1 [M+H] by liquid chromatography mass spectrometric combination analysis
+.
Embodiment 35: the synthesis of compound 162
Except replace luxuriant and rich with fragrance-4, the 7-dioctyl phthalate of 2,9-dibromo with 1,5-dinitrobenzene-3,7-dibromine naphthalene beyond, other building-up processes are with embodiment 21.Purified by silica gel chromatographic column, obtain solid chemical compound 162 (6.2g, yield 16%).
Obtained ESI-MS (m/z): 725.1 [M+H] by liquid chromatography mass spectrometric combination analysis
+.
Embodiment 36: make organic photoelectric device
To there is anode substrate distilled water that thickness is the ito thin film of 100nm, acetone, Virahol ultrasonic cleaning put into oven drying, by UV treat surface 30 minutes, then move in vacuum evaporation chamber.Be 2 × 10 in vacuum tightness
-6the each layer film of evaporation is started under Pa, the phenylbenzene naphthyl diamines (NPD) that evaporation 60nm is thick, then evaporation 10nm thick 4,4 ', 4 "-three (N-carbazyl) triphenylamine (TCTA) form hole transmission layer (HTL).On hole transmission layer, with the Ir (ppy) of 6wt%
3as green phosphorescent dopant material, the compound 29 of 94wt% is as material of main part, and this green phosphorescent dopant material and material of main part of evaporation simultaneously, forms the luminescent layer that 30nm is thick.Then two (8-hydroxy-2-methylquinoline)-biphenol aluminium (BAlq) that evaporation is thick on luminescent layer form the thick hole blocking layer of 5nm (HBL).On hole blocking layer, evaporation 4,7-phenylbenzene-1,10-phenanthroline (Bphen) is to form the electron transfer layer (ETL) of 20nm.The thick Al of LiF and 100nm that evaporation 1nm is thick successively is on the electron transport layer as electron injecting layer (EIL) and negative electrode.Thus make organic photoelectric device.
Organic photoelectric device has ITO (100nm)/NPD (60nm)/TCTA (10nm)/Ir (ppy)
3: the structure of compound 29 (6wt%:94wt%, 30nm)/BAlq (5nm)/Bphen (20nm)/LiF (1nm)/Al (100nm).
Embodiment 37: make organic photoelectric device
Except using compound 30 to replace compound 29 as except material of main part, make organic photoelectric device according to the method identical with embodiment 36.
Embodiment 38: make organic photoelectric device
Except using compound 55 to replace compound 29 as except material of main part, make organic photoelectric device according to the method identical with embodiment 36.
Embodiment 39: make organic photoelectric device
Except using compound 40 to replace compound 29 as except material of main part, make organic photoelectric device according to the method identical with embodiment 36.
Embodiment 40: make organic photoelectric device
Except using compound 1 to replace compound 29 as except material of main part, make organic photoelectric device according to the method identical with embodiment 36.
Embodiment 41: make organic photoelectric device
Except using compound 33 to replace compound 29 as except material of main part, make organic photoelectric device according to the method identical with embodiment 36.
Embodiment 42: make organic photoelectric device
Except using compound 80 to replace compound 29 as except material of main part, make organic photoelectric device according to the method identical with embodiment 36.
Embodiment 43: make organic photoelectric device
Except using compound 84 to replace compound 29 as except material of main part, make organic photoelectric device according to the method identical with embodiment 36.
Embodiment 44: make organic photoelectric device
Except using compound 91 to replace compound 29 as except material of main part, make organic photoelectric device according to the method identical with embodiment 36.
Embodiment 45: make organic photoelectric device
Except using compound 6 to replace compound 29 as except material of main part, make organic photoelectric device according to the method identical with embodiment 36.
Embodiment 46: make organic photoelectric device
Except using compound 12 to replace compound 29 as except material of main part, make organic photoelectric device according to the method identical with embodiment 36.
Embodiment 47: make organic photoelectric device
Except using compound 17 to replace compound 29 as except material of main part, make organic photoelectric device according to the method identical with embodiment 36.
Embodiment 48: make organic photoelectric device
Except using compound 24 to replace compound 29 as except material of main part, make organic photoelectric device according to the method identical with embodiment 36.
Embodiment 49: make organic photoelectric device
Except using compound 51 to replace compound 29 as except material of main part, make organic photoelectric device according to the method identical with embodiment 36.
Embodiment 50: make organic photoelectric device
Except using compound 76 to replace compound 29 as except material of main part, make organic photoelectric device according to the method identical with embodiment 36.
Embodiment 51: make organic photoelectric device
Except using compound 128 to replace compound 29 as except material of main part, make organic photoelectric device according to the method identical with embodiment 36.
Embodiment 52: make organic photoelectric device
Except using compound 138 to replace compound 29 as except material of main part, make organic photoelectric device according to the method identical with embodiment 36.
Embodiment 53: make organic photoelectric device
Except using compound 162 to replace compound 29 as except material of main part, make organic photoelectric device according to the method identical with embodiment 36.
Embodiment 54: make organic photoelectric device
Be dopant material except using with 1wt%TBRb, the compound 29 of 25wt% is co-doped material and with the thick co-deposited layer of the CBP of the 74wt% 30nm that is material of main part for except luminescent layer, other parts make organic photoelectric device according to the method identical with embodiment 36.
Organic photoelectric device has the structure of ITO (100nm)/NPD (60nm)/TCTA (10nm)/TBRb: compound 29:CBP (1wt%:25wt%:74wt%, 30nm)/BAlq (5nm)/Bphen (20nm)/LiF (1nm)/Al (100nm).
Embodiment 55: make organic photoelectric device
Except using compound 30 to replace compound 29 as except co-doped material, make organic photoelectric device according to the method identical with embodiment 54.
Embodiment 56: make organic photoelectric device
Except using compound 1 to replace compound 29 as except co-doped material, make organic photoelectric device according to the method identical with embodiment 54.
Embodiment 57: make organic photoelectric device
Except using compound 33 to replace compound 29 as except co-doped material, make organic photoelectric device according to the method identical with embodiment 54.
Embodiment 58: make organic photoelectric device
Except using compound 103 to replace compound 29 as except co-doped material, make organic photoelectric device according to the method identical with embodiment 54.
Comparative example 1: make organic photoelectric device
Be dopant material except using with 1wt%TBRb, with 99wt%CBP be co-deposited layer that the 30nm of material of main part is thick for beyond luminescent layer, make organic photoelectric device according to the method identical with embodiment 54.
the performance evaluation of organic photoelectric device
With the test of Keithley2365A digital nanovoltmeter according to the electric current of organic photoelectric device under different voltage manufactured in embodiment 36-58 and comparative example 1, then obtain the current density under different voltage of organic photoelectric device divided by light-emitting area with electric current.The brightness of the organic photoelectric device made according to embodiment 36-58 and comparative example 1 of the test of KonicaminoltaCS-2000 spectroradio luminance meter under different voltage and radiant emittance.According to the current density of organic photoelectric device under different voltage and brightness, obtain at same current density (10mA/cm
2) under current efficiency (Cd/A) and external quantum efficiency EQE.
Experiment shows, for the compound in embodiment 36-53, its voltage tested lower than 5V, current efficiency greater than or equal to 39Cd/A and EQE higher than 15, this shows that tested compound has the effect as material of main part, and wherein the result of embodiment 36-44 illustrates in table 2.
The result of embodiment 54-58 and comparative example 1 illustrates in table 3.
The test result of table 2 embodiment 36 ~ 44
| Voltage (V) | Current efficiency (Cd/A) | EQE | |
| Embodiment 36 | 4.5 | 42.8 | 17.2 |
| Embodiment 37 | 4.6 | 43.1 | 16.9 |
| Embodiment 38 | 4.0 | 48.6 | 18.8 |
| Embodiment 39 | 4.2 | 45.1 | 17.9 |
| Embodiment 40 | 4.4 | 46.2 | 17.4 |
| Embodiment 41 | 4.3 | 47.8 | 18.4 |
| Embodiment 42 | 4.7 | 41.4 | 16.7 |
| Embodiment 43 | 4.7 | 40.9 | 15.8 |
| Embodiment 44 | 4.9 | 39.0 | 15.2 |
The test result of table 3 embodiment 54-58 and comparative example 1
| Voltage (V) | Current efficiency (Cd/A) | EQE | |
| Embodiment 54 | 6.9 | 35.4 | 9.5 |
| Embodiment 55 | 8.2 | 25.2 | 8.1 |
| Embodiment 56 | 7.6 | 32.2 | 9.3 |
| Embodiment 57 | 7.4 | 38.9 | 10.7 |
| Embodiment 58 | 8.5 | 19.2 | 7.2 |
| Comparative example 1 | 9.3 | 7.9 | 2.5 |
According to the test result for compound in embodiment 36 ~ 53, at 10mA/cm
2under identical current density, the driving voltage of these compounds is lower than 5V, and current efficiency is higher than 39Cd/A, and EQE is higher than 15.As can be seen here, in embodiment 36 ~ 53, institute's test compounds all has lower driving voltage and higher current efficiency and external quantum efficiency.This shows that compound of the present invention has the effect as material of main part.
The test result of table 3 shows, embodiment 54 ~ 58 is relative to comparative example 1, and the compound tested has lower driving voltage and higher current efficiency and external quantum efficiency.This shows that compound of the present invention has the effect as co-doped material or dopant material.
In sum, the organic photoelectric device comprising compound of the present invention all has excellent luminescent properties.
The generality of the above-mentioned technical scheme to relating in the present invention describes and the description of its embodiment be should not be understood as to the restriction formed technical solution of the present invention.Those skilled in the art are according to the present invention, can under the prerequisite without prejudice to involved inventive concept, describe or/and the public technology feature in embodiment (comprising embodiment) increases, reduces or combines above-mentioned generality, formation belongs to other technical scheme of the present invention.
Claims (21)
1. there is a compound for general formula (I) structure,
In formula (I), A
1, A
2, A
3there is not or has the group of formula (II) structure all independently of one another; And A
1, A
2, A
3can not exist simultaneously;
In formula (II), Y
1be selected from oxygen base, sulfenyl, substituted or unsubstituted imino-any one;
X
1, X
2, X
3, X
4be selected from independently of one another
R
1be selected from hydrogen, deuterium, C
1~ C
30alkyl, C
6~ C
30aryl or C
2~ C
30any one in heteroaryl;
In formula (I), B
1, B
2, B
3there is not or have the structure of formula (III) all independently of one another: and B
1, B
2, B
3can not exist simultaneously;
In formula (III), Y
2be selected from singly-bound, oxygen base, sulfenyl, substituted or unsubstituted imino-, substituted or unsubstituted methylene radical, substituted or unsubstituted silicylene any one;
X
5, X
6, X
7, X
8, X
9, X
10, X
11and X
12be selected from independently of one another
described R
2be selected from hydrogen, deuterium, C
1~ C
30alkyl, C
6~ C
30aryl or C
2~ C
30any one in heteroaryl;
In formula (I), L is the connection portion that the structure of general formula (I) can be made to form conjugated system.
2. compound as claimed in claim 1, is characterized in that, minimum singlet state S
1with minimum triplet state T
1energy extreme difference Δ E between state
st=E
s1-E
t1≤ 0.30eV.
3. compound as claimed in claim 2, is characterized in that, described compound Δ E
st≤ 0.25eV.
4. compound as claimed in claim 3, is characterized in that, described compound Δ E
st≤ 0.20eV.
5. compound as claimed in claim 4, is characterized in that, described compound Δ E
st≤ 0.15eV.
6. compound as claimed in claim 5, is characterized in that, described compound Δ E
st≤ 0.10eV.
7. compound as claimed in claim 6, is characterized in that, described compound Δ E
st≤ 0.05eV.
8. compound as claimed in claim 7, is characterized in that, described compound Δ E
st≤ 0.02eV.
9. compound as claimed in claim 1, it is characterized in that, in formula (I), L is aromatic group, described A
1, A
2, A
3, B
1, B
2, B
3be connected to the optional position on the aromatic nucleus of L independently of one another.
10. compound as claimed in claim 1, is characterized in that, described L is selected from the aromatic group containing 6 ~ 30 carbon atoms or the assorted aromatic group containing 2 ~ 30 carbon atoms.
11. compounds as claimed in claim 10, it is characterized in that, the aromatic nucleus of described aromatic group be selected from substituted or unsubstituted benzene, substituted or unsubstituted pyridine, substituted or unsubstituted biphenyl, substituted or unsubstituted azepine biphenyl, substituted or unsubstituted fused ring compound or substituted or unsubstituted fused aza-heterocyclic compound any one;
The substituting group of the biphenyl of the benzene of described replacement, the pyridine of replacement, replacement, the azepine biphenyl of replacement, the fused ring compound of replacement and the fused aza-heterocyclic compound of replacement is selected from hydrogen, deuterium, C all independently of one another
1~ C
30alkyl, C
6~ C
30aryl or C
2~ C
30heteroaryl.
12. compounds as claimed in claim 10, is characterized in that, the aromatic nucleus of described aromatic group be selected from benzene, biphenyl, naphthalene nucleus, anthracene nucleus, phenanthrene ring or pyrene ring any one.
13. compounds as claimed in claim 1, is characterized in that, described A
1, A
2, A
3, B
1, B
2, B
3at least one atom of the position of substitution interval on L.
14. compounds as claimed in claim 1, it is characterized in that, described A is selected from
in any one.
15. compounds as claimed in claim 1, it is characterized in that, described B is
in any one.
16. compounds as claimed in claim 1, is characterized in that, described compound be selected from following compound any one:
17. compounds as claimed in claim 1, it is characterized in that, described compound has hot activation delayed fluorescence performance.
The purposes of compound in organic photoelectric device that one of 18. claims 1 ~ 17 are described.
19. 1 kinds of organic photoelectric devices, it is characterized in that, described organic photoelectric device comprises anode, negative electrode and at least one deck organic thin film layer between anode and negative electrode, and described organic thin film layer comprises the combination of any one or at least two kinds in the described compound of one of claim 1 ~ 17.
20. organic photoelectric devices as claimed in claim 19, it is characterized in that, described organic thin film layer comprises luminescent layer, described luminescent layer comprises the combination of any one or at least two kinds in the described compound of one of claim 1 ~ 16, and described compound is used as any one in dopant material, co-doped material or material of main part.
21. organic photoelectric devices as claimed in claim 19, it is characterized in that, described organic thin film layer also comprises the combination of any one or at least two kinds in hole transmission layer, hole injection layer, electronic barrier layer, hole blocking layer, electron transfer layer, electron injecting layer.
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