CN109503661A - Deep blue light emitting material based on condensed ring phosphine oxide group - Google Patents
Deep blue light emitting material based on condensed ring phosphine oxide group Download PDFInfo
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- CN109503661A CN109503661A CN201811628313.6A CN201811628313A CN109503661A CN 109503661 A CN109503661 A CN 109503661A CN 201811628313 A CN201811628313 A CN 201811628313A CN 109503661 A CN109503661 A CN 109503661A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
Abstract
Based on the deep blue light emitting material of condensed ring phosphine oxide group, with structure shown in formula (I):
Description
Technical field
The present invention relates to organic photoelectric new material technology fields, in particular to the dark blue light containing rigid condensed ring phosphine oxide group
Luminescent material.
Background technique
Organic electroluminescent is a kind of technology that electric energy is converted into light using luminous organic material, which can
It prepares to high-efficiency and low-cost large area flexible to show and illuminating device, shows have with healthy white-light illuminating field in full color
Very big application value.Property of the high performance electroluminescent organic device highly dependent upon associated light material, such as luminescent material
The charge injection of excitation purity, the luminous quantum efficiency of luminescent material and luminescent material and transmittability etc..Either it is applied to
Full color is shown or white-light illuminating field, and deep blue light emitting material is essential.According to the prior art, dark blue light hair
Luminescent material is mainly fluorene kind derivative, derivative of tri-arylamine group and anthracene derivative.Since chemical structure limits, these shine
Material is usually on the key performance of the excitation purity that shines, quantum efficiency and charge injection and these luminescent materials of transmittability
Be difficult to take into account, cause efficiency, service life and operating voltage of deep blue light organic electroluminescence device etc. bad, performance still need into
One step improves.
Summary of the invention
The purpose of the present invention is to provide a kind of deep blue light emitting material based on condensed ring phosphine oxide group, this kind of luminescent materials
It is all had on the key performance of the excitation purity that shines, quantum efficiency and charge injection and transmittability these luminescent materials excellent
Different performance.
In order to achieve the above object, the invention is realized by the following technical scheme:
Based on the deep blue light emitting material of condensed ring phosphine oxide group, with structure shown in formula (I):
In formula
R1Indicate Spirofluorene-based, substituted or unsubstituted fluorenyl substituted or unsubstituted, substituted or unsubstituted anthryl, substitution or
Unsubstituted xenyl, substituted or unsubstituted naphthalene, substituted or unsubstituted phenyl, substituted or unsubstituted spiral shell silicon fluorene base,
Substituted or unsubstituted dibenzofuran group, substituted or unsubstituted carbazyl, takes substituted or unsubstituted dibenzothiophene
Generation or unsubstituted triphenylamine base, substituted or unsubstituted acridinyl, substituted or unsubstituted thianthrene, substituted or unsubstituted two
Phenyl boryl, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted phenoxazine base, substituted or unsubstituted phenoxazine
Base, substituted or unsubstituted phosphine oxazolyl；
R1With selected from one of following structure:
R2Indicate Spirofluorene-based, substituted or unsubstituted fluorenyl substituted or unsubstituted, substituted or unsubstituted anthryl, substitution or
Unsubstituted xenyl, substituted or unsubstituted naphthalene, substituted or unsubstituted phenyl, substituted or unsubstituted spiral shell silicon fluorene base,
Substituted or unsubstituted dibenzofuran group, substituted or unsubstituted carbazyl, takes substituted or unsubstituted dibenzothiophene
Generation or unsubstituted triphenylamine base, substituted or unsubstituted acridinyl, substituted or unsubstituted thianthrene, substituted or unsubstituted two
Phenyl boryl, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted phenoxazine base, substituted or unsubstituted phenoxazine
Base, substituted or unsubstituted phosphine oxazolyl；R2With selected from one of following structure:
R3Indicate Spirofluorene-based, substituted or unsubstituted fluorenyl substituted or unsubstituted, substituted or unsubstituted anthryl, substitution or
Unsubstituted xenyl, substituted or unsubstituted naphthalene, substituted or unsubstituted phenyl, substituted or unsubstituted spiral shell silicon fluorene base,
Substituted or unsubstituted dibenzofuran group, substituted or unsubstituted carbazyl, takes substituted or unsubstituted dibenzothiophene
Generation or unsubstituted triphenylamine base, substituted or unsubstituted acridinyl, substituted or unsubstituted thianthrene, substituted or unsubstituted two
Phenyl boryl, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted phenoxazine base, substituted or unsubstituted phenoxazine
Base, substituted or unsubstituted phosphine oxazolyl；R3With selected from one of following structure:
The R in same molecule1、R2And R3It can be identical or entirely different.
Compared with existing dark blue smooth luminescent material structure and its property, the present invention has following two most bright
Aobvious innovative point and progressive:
The first, the deep blue light emitting material of the invention synthesized is using condensed ring phosphine oxide group as core, and there are three effects.1, can
The rigidity of light emitting molecule core is significantly increased, nonradiative transition caused by the vibration of molecule core can be inhibited to rotate is conducive to mention
The luminous efficiency of high material；Although 2, the material molecule core is condensed cyclic structure, because it is with oxygen atom for link atom, energy
It is enough effectively molecular conjugation length to be prevented to extend, high molecular excited level is mentioned, and then make mulecular luminescence blue shift, improves dark blue light
Excitation purity；3, the phosphine oxide group with strong electrophilic characteristic helps to enhance injection and transmittability of the luminescent material to electronics,
Advantageously reduce the operating voltage of organic electroluminescence device.
The second, due to the molecular structure to material carried out it is well-designed, so material is in luminous excitation purity, quantum efficiency
And excellent performance is all had on charge injection and the key performance of these luminescent materials of transmittability.
So the obtained molecular skeleton of the present invention is novel from the point of view of molecular structure；From the point of view of material property, the present invention
Synthesized material emission is had excellent performance.
Detailed description of the invention
Fig. 1 is the route map that deep blue light emitting material POCz is synthesized by the present invention.
Fig. 2 is the luminous spectrogram of the deep blue light emitting material POCz synthesized by the present invention.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with embodiment to of the invention each
Specific embodiment is explained in detail.However, it will be understood by those skilled in the art that in each embodiment party of the present invention
In formula, many technical details are proposed in order to make reader more fully understand the present invention.But even if without these technical details
And various changes and modifications based on the following respective embodiments, each claim skill claimed of the present invention also may be implemented
Art scheme.
Embodiment one
The deep blue light emitting material POCz, chemical formula C of the present embodiment72H42N3O4P, structural formula areReferring to attached drawing 1, synthetic method is as follows.
Step 1: the synthesis of Cz1
Carbazole boric acid (1.76g, 6.1mmol) and bromo-derivative (2.0g, 7.3mmol) is dissolved in containing Pd (PPh3)4
In the toluene (30mL) of (0.36g, 0.31mmol), the solution of potassium carbonate (20mL) of 2mol/L is then added.In nitrogen atmosphere
Above-mentioned reaction mixture is heated to 70 DEG C of stirring 6h.After reaction mixture is cooled to room temperature, it is extracted with dichloromethane.Gained organic layer
Dry with anhydrous sodium sulfate, concentration isolates and purifies on a silica gel column, finally obtains 2.3g Cz1, yield 85%, nuclear-magnetism table
Levy data are as follows:1H NMR(400MHz,CDCl3, δ): 8.22 (d, J=7.9Hz, 2H), 7.81 (dt, J=8.6,2.2Hz, 2H),
7.65 (dt, J=8.6,2.3Hz, 2H), 7.55-7.44 (m, 4H), 7.36 (t, J=7.2Hz, 2H), 7.09 (dt, J=9.6,
2.1Hz, 1H), 6.95 (dq, J=10.5,2.2Hz, 1H), 5.60-5.53 (m, 1H), 4.19 (qt, J=7.0,2.0Hz, 1H),
4.08-3.95 (m, 1H), 3.79-3.68 (m, 1H), 2.11 (q, J=2.2Hz, 1H), 1.97 (tt, J=6.1,2.8Hz, 2H),
1.88–1.62(m,3H)。
Step 2: the synthesis of Cz2
Under nitrogen atmosphere, Cz1 (2.0g, 4.57mmol) is dissolved in dry tetrahydrofuran solution (30mL), is cooled to -78
It after DEG C, is slowly dropped into n-butyllithium solution (1.8mL, 4.5mmol), after -78 DEG C of reaction 1.5h, then is added dropwise into reaction mixture
PCl3(0.13mL, 1.5mmol) is to slowly warm up to room temperature after -78 DEG C of reaction 1h, continues to be stirred to react 12h.Then Xiang Fanying again
The hydrogen peroxide (1.0mL) of 30% concentration is added in mixture, 1h is stirred at room temperature.Dilute hydrochloric acid is finally added into reaction mixture
(0.5mL, 40.5mmol), is stirred at room temperature 12h.After reaction, it is extracted with dichloromethane.Gained organic layer anhydrous sodium sulfate
Dry, concentration isolates and purifies on a silica gel column, finally obtains 0.5g Cz2, yield 11%.
Its nuclear-magnetism characterize data are as follows:1H NMR(400MHz,DMSO-d6, δ) and 11.65 (s, 1H), 8.28 (d, J=7.6Hz,
2H), 8.03 (d, J=8.0Hz, 2H), 7.86-7.72 (m, 2H), 7.48 (d, J=5.2Hz, 5H), 7.33 (t, J=5.6Hz,
2H),7.17(s,1H).19F NMR(376MHz,CDCl3, δ) and -98.43 (d, J=6.8Hz)31P NMR(162MHz,CDCl3,
δ)21.98。
Step 3: the synthesis of deep blue light emitting material POCz
Under nitrogen atmosphere, Cz2 (0.16g, 0.14mmol) and potassium tert-butoxide (0.05g, 0.58mmol) is dissolved in N- methyl
In pyrrolidones (30mL), it is heated to 170 DEG C of stirring 1.5h.Reaction mixture is cooled to after room temperature down in deionized water
(100mL), gained organic layer is dry with anhydrous sodium sulfate, and concentration isolates and purifies on a silica gel column, finally obtains 0.13g
POCz, yield 93%.
Its nuclear-magnetism characterize data are as follows:1H NMR(400MHz,DMSO-d6, δ) and 8.18 (dq, J=7.8,0.9,0.0Hz, 6H),
7.88-7.82 (m, 6H), 7.76-7.69 (m, 6H), 7.59 (d, J=4.4Hz, 6H), 7.53-7.42 (m, 12H), 7.33
(ddd, J=8.0,6.9,1.2Hz, 6H)31P NMR(162MHz,CDCl3,δ)–48.54。
Its mass spectral characteristi data are as follows: [M+NH3]+,1060.3182。
According to above-mentioned data, that illustrate the present embodiment synthesis is deep blue light emitting material POCz.
Test to material POCz luminescent properties: deep blue light emitting material POCz is dissolved in toluene, concentration is configured as
It is 1.0 × 10-4It is as shown in Figure 2 to measure luminescent spectrum under the ultraviolet excitation of 330nm for the solution of mol/L.The CIE of the spectrum
1931 chromaticity coordinates are (0.16,0.04), show it with very high dark blue photochromic purity.Using integrating sphere to the hair of the solution
Light efficiency is measured, and luminous quantum efficiency reaches 0.72.The luminous quantum efficiency is with close dark blue photochromic purity
The column of highest are occupy in luminescent material.
Embodiment two
The deep blue light emitting material POPT, chemical formula C of the present embodiment synthesis54H30N3O4PS3, structural formula is
Its nuclear-magnetism characterize data are as follows:1H NMR(400MHz,CDCl3, δ) and 7.38-7.32 (m, 6H), 7.24 (d, J=
5.7Hz, 12H), 7.13 (ddd, J=8.5,6.1,3.0Hz, 6H), 6.64 (d, J=4.3Hz, 6H)31P NMR(162MHz,
CDCl3,δ)–48.54。
Embodiment three
The deep blue light emitting material POPO, chemical formula C of the present embodiment synthesis54H30N3O7P, structural formula are
Its nuclear-magnetism characterize data are as follows:1H NMR(400MHz,CDCl3, δ) and 6.80-6.70 (m, 4H), 6.64 (d, J=
13.7Hz,18H),6.54(s,4H),6.31–6.00(m,4H).31P NMR(162MHz,CDCl3,δ)–23.56。
A specific embodiment of the invention is described in conjunction with attached drawing above, but these explanations cannot be understood to limit
The scope of the present invention, protection scope of the present invention are limited by appended claims, any in the claims in the present invention base
Change on plinth is all protection scope of the present invention.
Claims (5)
1. the deep blue light emitting material based on condensed ring phosphine oxide group, which is characterized in that it is with structure shown in formula (I):
In formula
R1It indicates Spirofluorene-based, substituted or unsubstituted fluorenyl substituted or unsubstituted, substituted or unsubstituted anthryl, substitution or does not take
The xenyl in generation, substituted or unsubstituted phenyl, substituted or unsubstituted spiral shell silicon fluorene base, replaces substituted or unsubstituted naphthalene
Or unsubstituted dibenzofuran group, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted carbazyl, substitution or
Unsubstituted triphenylamine base, substituted or unsubstituted acridinyl, substituted or unsubstituted thianthrene, substituted or unsubstituted diphenyl
Boryl, substituted or unsubstituted phenoxazine base, substituted or unsubstituted phenoxazine base, takes substituted or unsubstituted phenothiazinyl
Generation or unsubstituted phosphine oxazolyl；
R2It indicates Spirofluorene-based, substituted or unsubstituted fluorenyl substituted or unsubstituted, substituted or unsubstituted anthryl, substitution or does not take
The xenyl in generation, substituted or unsubstituted phenyl, substituted or unsubstituted spiral shell silicon fluorene base, replaces substituted or unsubstituted naphthalene
Or unsubstituted dibenzofuran group, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted carbazyl, substitution or
Unsubstituted triphenylamine base, substituted or unsubstituted acridinyl, substituted or unsubstituted thianthrene, substituted or unsubstituted diphenyl
Boryl, substituted or unsubstituted phenoxazine base, substituted or unsubstituted phenoxazine base, takes substituted or unsubstituted phenothiazinyl
Generation or unsubstituted phosphine oxazolyl；
R3It indicates Spirofluorene-based, substituted or unsubstituted fluorenyl substituted or unsubstituted, substituted or unsubstituted anthryl, substitution or does not take
The xenyl in generation, substituted or unsubstituted phenyl, substituted or unsubstituted spiral shell silicon fluorene base, replaces substituted or unsubstituted naphthalene
Or unsubstituted dibenzofuran group, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted carbazyl, substitution or
Unsubstituted triphenylamine base, substituted or unsubstituted acridinyl, substituted or unsubstituted thianthrene, substituted or unsubstituted diphenyl
Boryl, substituted or unsubstituted phenoxazine base, substituted or unsubstituted phenoxazine base, takes substituted or unsubstituted phenothiazinyl
Generation or unsubstituted phosphine oxazolyl.
2. the deep blue light emitting material according to claim 1 based on condensed ring phosphine oxide group, which is characterized in that its feature exists
In the R in same molecule1、R2And R3It can be identical or entirely different.
3. the deep blue light emitting material according to claim 1 based on condensed ring phosphine oxide group, which is characterized in that its feature exists
In,
R1With selected from one of following structure:
4. the deep blue light emitting material according to claim 1 based on condensed ring phosphine oxide group, which is characterized in that its feature exists
In R2With selected from one of following structure:
5. the deep blue light emitting material according to claim 1 based on condensed ring phosphine oxide group, which is characterized in that its feature exists
In R3With selected from one of following structure:
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818738A (en) * | 2019-11-22 | 2020-02-21 | 西安交通大学 | Thermal activation delayed fluorescence material based on ether bond conformation locking triphenylphosphine oxide receptor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016219487A (en) * | 2015-05-15 | 2016-12-22 | コニカミノルタ株式会社 | Organic electroluminescent element, display device, illuminating device, organic electroluminescent element material and novel compound |
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- 2018-12-28 CN CN201811628313.6A patent/CN109503661A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016219487A (en) * | 2015-05-15 | 2016-12-22 | コニカミノルタ株式会社 | Organic electroluminescent element, display device, illuminating device, organic electroluminescent element material and novel compound |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818738A (en) * | 2019-11-22 | 2020-02-21 | 西安交通大学 | Thermal activation delayed fluorescence material based on ether bond conformation locking triphenylphosphine oxide receptor |
| CN110818738B (en) * | 2019-11-22 | 2023-05-30 | 西安交通大学 | Thermally activated delayed fluorescence material based on ether bond conformation locking triphenylphosphine oxide receptor |
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Application publication date: 20190322 |