CN107056804A - A kind of luminous organic material and its organic luminescent device of dithieno cyclopentadiene derivant structure - Google Patents

A kind of luminous organic material and its organic luminescent device of dithieno cyclopentadiene derivant structure Download PDF

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CN107056804A
CN107056804A CN201710463151.4A CN201710463151A CN107056804A CN 107056804 A CN107056804 A CN 107056804A CN 201710463151 A CN201710463151 A CN 201710463151A CN 107056804 A CN107056804 A CN 107056804A
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董秀芹
蔡辉
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Changchun Haipurunsi Technology Co Ltd
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Abstract

The invention discloses a kind of luminous organic material and its organic luminescent device of dithieno cyclopentadiene derivant structure, belong to organic photoelectrical material technical field.The present invention derivative with the tetroxide of 4 H cyclopentadiene 1,4-Dithiapentalene 1,1,7,7 be agent structure, by the ligand groups for connecting opposed polarity so that the present invention obtained by derivative have stronger electrophilicity, charge transport ability and luminescent properties.The organic luminescent device prepared using the dithieno cyclopentadiene derivant of the present invention, luminous efficiency is high, it is photochromic it is uniform, have good membrane stability and heat endurance, can effectively solve the unbalanced problem of unipolarity transmission material carrier in organic luminescent device.

Description

The luminous organic material of a kind of dithieno cyclopentadiene derivant structure and its organic Luminescent device
Technical field
The present invention relates to organic photoelectrical material technical field, more particularly to a kind of dithieno cyclopentadiene derivant structure Luminous organic material and its organic luminescent device.
Background technology
Organic Light Emitting Diode (OLED) is being used as full color FPD of future generation and semiconductor illumination technique just in recent years Receive more and more attention, compared with liquid crystal display (LCD) technology, the imaging mechanism of the two is entirely different, and LCD employs the back of the body Light source, and OLED is self-luminous, without backlight, what can be done than LCD is more frivolous, saves backlight module cost.By more Contrast it can be found that OLED have it is thinner it is lighter, actively luminous, low-power consumption, response quickly, without visual angle limitation, high-resolution, highlighted Degree, temperature in use scope is wide, shock resistance strong, low cost, the features such as soft display can be achieved, it is increasing be applied to it is aobvious Show and lighting field.Up to now, OLED be widely used to mobile phone screen, notebook computer, vehicle electronics, instrument and meter, The small-medium size display field such as e-book, PDA, POS.In addition, large scale OLED display, TV also more and more go out In present daily life.As can be seen here, OLED will have before more wide application as Display Technique of future generation Scape.
The luminescence mechanism of organic electroluminescence device：Electronics and hole are injected separately into from yin, yang two-stage, the electronics being injected into Transmitted with hole by organic function layer, exciton is compounded to form in luminescent layer, exciton radiation transistion returns to ground state, so that luminous. Organic electroluminescence device can obtain the light of different demands by adjusting the species and doping of emitting layer material.In order to most The color fidelity of the raising display of big degree, that is, it is so-called full-color, mainly there are three kinds of modes：One is using white luminous Layer plus colour filter, this is to obtain the simplest method of total colouring.Two be to use three kinds of luminous organic materials of red, green, blue, therefore Luminescent layer is three layers.Three be to use blue organic luminous material, then obtains full-color with color-converting material.The second way due to Independently lighted using redgreenblue, it is easy to which the chromatic characteristic of accurate control display device, color is also more bright-coloured true to nature.
OLED Display Techniques are still emerging technology compared with LCD, and OLED volume production still faces many problems.It is wherein more significant The problem of be：The problem of efficiency and short comparative lifetime of blue pixel.Compared with red, green pixel, low of blue pixel efficiency grind more Study carefully display, blue pixel is only 4%, in addition two kinds up to 20%.Blue pixel is it is also possible to the life-span of reduction screen.And blue pixel effect Electron injection rate is low in the low mainly luminescent layer of rate causes, it is well known that hole transmission performance is better than in organic photoelectrical material Electronics, electron mobility is slower than hole mobility, causes in luminescent layer, and the injection rate of electronics is less than hole injection efficiency, exciton Recombination rate is low, and this phenomenon is more obvious in blue organic luminous material.Most blue light materials are respectively provided with broad-band gap, low electronics The characteristic of affinity, causes electron injection less, so that device efficiency can not be effectively improved, therefore design has height Electron affinity and the functional material such as the blue organic luminous material and electric transmission of electron transport ability, injection, and then The performance for strengthening device is very crucial.
The content of the invention
It is an object of the invention to provide a kind of luminous organic material of dithieno cyclopentadiene derivant structure and its have Machine luminescent device.The dithieno cyclopentadiene derivant of the present invention, with stronger electrophilicity, charge transport ability and luminous Performance, is the organic of function admirable with higher luminous efficiency and photochromic stability using the organic luminescent device of its preparation Luminescent material.
The invention provides a kind of luminous organic material of dithieno cyclopentadiene derivant structure, its molecular structural formula For：
Wherein, R1-R2Selected from hydrogen atom, substituted or unsubstituted C1-C40Alkyl, substituted or unsubstituted C1-C40Alcoxyl Base, R1-R2Structure can be identical, also can be different；Ar1-Ar4Selected from hydrogen atom, substituted or unsubstituted C1-C40Alkyl, substitution Or unsubstituted C6-C60Aryl, substituted or unsubstituted C10-C60Condensed ring radical, substituted or unsubstituted C8-C60Condensed hetero ring base, take Generation or unsubstituted C3-C60Heterocyclic radical in one kind, Ar1-Ar4Structure can be identical, also can be different.
It is preferred that, R1-R2Selected from hydrogen atom, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C1-C20's Alkoxy, R1-R2Structure can be identical, also can be different；Ar1-Ar4Selected from hydrogen atom, substituted or unsubstituted C1-C20Alkyl, Substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C10-C30Condensed ring radical, substituted or unsubstituted C8-C30Condensed hetero ring Base, substituted or unsubstituted C3-C30Heterocyclic radical in one kind, Ar1-Ar4Structure can be identical, also can be different.
Further preferably, R1-R2Selected from hydrogen atom, substituted or unsubstituted C1-C10Alkyl, substituted or unsubstituted C1-C10's Alkoxy, R1-R2Structure can be identical, also can be different；Ar1-Ar4Selected from hydrogen atom, substituted or unsubstituted C1-C12Alkyl, Substituted or unsubstituted C6-C24Aryl, substituted or unsubstituted C10-C20Condensed ring radical, substituted or unsubstituted C8-C20Condensed hetero ring Base, substituted or unsubstituted C3-C14Heterocyclic radical in one kind, Ar1-Ar4Structure can be identical, also can be different.
Further preferably, dithieno cyclopentadiene derivant provided by the present invention appointing in chemical constitution as follows Meaning is a kind of：
Present invention also offers a kind of organic luminescent device, including first electrode, second electrode and it is placed in two electrode Between one or more organic compound layers, it is at least one layer of comprising at least one of the present invention in the organic compound layer Dithieno cyclopentadiene derivant structure luminous organic material.
It is preferred that, the organic compound layer includes hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, sky At least one layer in cave barrier layer, electron transfer layer, electron injecting layer.
It is preferred that, organic luminescent device of the present invention can be applied to illumination, Display panel, organic photovoltaic cell, electricity The fields such as sub- paper, Organophotoreceptor or OTFT.
Beneficial effects of the present invention：
The invention provides a kind of luminous organic material and its organic light emission of dithieno cyclopentadiene derivant structure Device, the material with the tetroxide of 4-H- cyclopentadiene 1,4-Dithiapentalene 1,1,7,7- be agent structure, by connecting opposed polarity Ligand groups, the pi-conjugated property of material can be adjusted, band gap width, electrophilicity, charge transport ability and photochromic etc. so that this The dithieno cyclopentadiene derivant of invention has a relatively low band gap width, higher luminous efficiency, electronic transmission performance, film Stability and heat endurance.It is low that the organic luminescent device prepared using the present invention can effectively solve blue light material electron injection rate Problem, overcomes the unbalanced problem of conventional unipolar luminescent material carrier, so that with higher luminous efficiency, outstanding electricity Chemical property and thermal stability.
Embodiment：
Technical scheme below in conjunction with the embodiment of the present invention is clearly and completely described, it is clear that described implementation Example only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, art technology The every other embodiment that personnel are obtained under the premise of creative work is not made, belongs to protection scope of the present invention.
The invention provides a kind of luminous organic material of dithieno cyclopentadiene derivant structure, its molecular structural formula It is as follows：
Wherein, R1-R2Selected from hydrogen atom, substituted or unsubstituted C1-C40Alkyl, substituted or unsubstituted C1-C40Alcoxyl Base, R1-R2Structure can be identical, also can be different；Ar1-Ar4Selected from hydrogen atom, substituted or unsubstituted C1-C40Alkyl, substitution Or unsubstituted C6-C60Aryl, substituted or unsubstituted C10-C60Condensed ring radical, substituted or unsubstituted C8-C60Condensed hetero ring base, take Generation or unsubstituted C3-C60Heterocyclic radical in one kind, Ar1-Ar4Structure can be identical, also can be different.
According to the present invention, the substituted alkyl, substitution alkoxy, substitution aryl, substitution condensed ring radical, substitution In condensed hetero ring base, the heterocyclic radical of substitution, the substituent may be selected from deuterium, C1-C10Alkyl, halogen, cyano group or nitro, be preferably Deuterium, C1-C5Alkyl, fluorine or cyano group, more preferably cyano group.In the condensed hetero ring base or heterocyclic radical, the hetero atom is preferably N, O Or S.
It is preferred that the R1-R2Selected from hydrogen atom, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C1-C20 Alkoxy, R1-R2Structure can be identical, also can be different；Ar1-Ar4Selected from hydrogen atom, substituted or unsubstituted C1-C20Alkane Base, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C10-C30Condensed ring radical, substituted or unsubstituted C8-C30It is thick miscellaneous Ring group, substituted or unsubstituted C3-C30Heterocyclic radical in one kind, Ar1-Ar4Structure can be identical, also can be different.
Further preferably described R1-R2Selected from hydrogen atom, substituted or unsubstituted C1-C10Alkyl, substituted or unsubstituted C1- C10Alkoxy, R1-R2Structure can be identical, also can be different；Ar1-Ar4Selected from hydrogen atom, substituted or unsubstituted C1-C12's Alkyl, substituted or unsubstituted C6-C24Aryl, substituted or unsubstituted C10-C20Condensed ring radical, substituted or unsubstituted C8-C20It is thick Heterocyclic radical, substituted or unsubstituted C3-C14Heterocyclic radical in one kind, Ar1-Ar4Structure can be identical, also can be different.
As an example, it is not particularly limited, organic hair of dithieno cyclopentadiene derivant structure of the present invention Any one of luminescent material in chemical constitution as follows：
It is enumerated above some tools of the luminous organic material of dithieno cyclopentadiene derivant structure of the present invention Body structure, but dithieno cyclopentadiene derivant structure of the present invention luminous organic material be not limited to it is listed These chemical constitutions, every based on structure shown in chemical formula of the present invention, R1、R2、Ar1、Ar2、Ar3、Ar4To be as defined above Group be included in this patent protection domain.
The preparation method of the luminous organic material of dithieno cyclopentadiene derivant structure of the present invention, can pass through Compound shown in chemical formula A is obtained into compound shown in chemical formula B through reduction reaction, compound B again by bromination reaction, Suzuki coupling reactions obtain the compound shown in chemical formula C, and compound C prepares Dithiophene of the present invention through peroxidization The luminous organic material of pentalene derivant structure.
The present invention does not have particular/special requirement to the condition of above-mentioned all kinds of reactions, is such reaction well known to those skilled in the art Normal condition, wherein R1、R2、Ar1、Ar2、Ar3、Ar4Selection it is same as above, will not be repeated here.
Present invention also offers a kind of organic luminescent device, including first electrode, second electrode and it is placed in two electrode Between one or more organic compound layers, it is at least one layer of comprising at least one of the present invention in the organic compound layer Dithieno cyclopentadiene derivant structure luminous organic material.
Organic compound layer in organic luminescent device of the present invention includes hole injection layer, hole transmission layer, electronics Barrier layer, luminescent layer, hole blocking layer, electron transfer layer, at least one layer of electron injecting layer.
The luminous organic material of dithieno cyclopentadiene derivant structure of the present invention can in singular form or It is present in other material mixing forms in above-mentioned organic compound layer.
It is preferred that, the luminous organic material of dithieno cyclopentadiene derivant structure of the present invention can be as organic Fluorescent host material, fluorescence dopant material in luminescent device luminescent layer or alone as luminescent layer, more preferably as hair Photosphere fluorescence dopant material.
It is preferred that, the luminous organic material of dithieno cyclopentadiene derivant structure of the present invention has been alternatively arranged as The electron transport layer materials or electron injecting layer material of machine luminescent device, more preferably as electron transport layer materials.
Organic luminescent device of the present invention can be applied to illumination, Display panel, organic photovoltaic cell, Electronic Paper, organic The field such as photoreceptor or OTFT.
The synthesis of [embodiment 1] compound 1
* intermediate 1-1 synthesis
4-H- cyclopentadiene 1,4-Dithiapentalene (1.92g, 10.8mmol), 50mL DMSO, bromoethane are added in reactor (2.44g, 22.4mmol), KI (0.05g, 0.30mmol).Under nitrogen purging, condition of ice bath, levigate 2g KOH powder is added End, afterwards by mixture stirring reaction 24h at ambient temperature, is put into addition 50mL water in ice bath groove by reactor afterwards, has Machine is extracted twice with ether, is rinsed afterwards with water, bittern and ammonium chloride, MgSO4Dry, solvent is removed in distillation, crude product leads to Cross silica gel column chromatography purifying and obtain compound 1-1 (2.12g, 86%).
* intermediate 1-2 synthesis
Under nitrogen no light condition, 1-1 (2.34g, 10.0mmol), DMF solution 60mL, glacial acetic acid are added in reactor 60mL, chloroform 50mL, add under NBS (4.44g, 25.0mmol), room temperature condition and stir 2h, obtain crude product precipitation, filtering, first Alcohol is washed, and obtains compound 1-2 (3.57g, 91%).
* intermediate 1-3 synthesis
The THF solution 300mL of diisopropylamine (3.03g, 30.0mmoL) is added in reactor, reactor is placed in ice bath groove In, kept for 0 DEG C, rear hexane solution 16.7mL of the addition containing butyl lithium (3.07g, 48mmol) in a nitrogen atmosphere, is stirred 30min, is transferred to -78 DEG C of reactions by reaction afterwards, now adds compound 1-2 (8.67g, 22.0mmol) THF solution 45mL, is to slowly warm up to room temperature afterwards, stirs 17h, and reaction completion cools the temperature to 0 DEG C, diluted with hexane, strong brine is quenched instead Should, organic phase anhydrous Na2SO4Dry, vacuum distillation removes solvent, the purifying of crude product purified by silica gel column chromatography obtains compound 1-3 (7.8g, 90%).* intermediate 1-4 synthesis
In reaction vessel plus 1-3 (3.29g, 8.4mmol), (4- cyano-phenyls) boric acid (3.79g, 17.07mmol), four or three Phenylphosphine palladium (0.7g, 1.08mmol), potassium carbonate (5.3g, 38.3mmol), toluene 60mL, ethanol 20mL and distilled water 20mL, 3h is stirred under the conditions of 120 DEG C.Reaction is stopped reacting after terminating with distilled water, is extracted with ethyl acetate, organic layer MgSO4 Dry, vacuum distillation obtains compound 1-4 (2.57g, 70%) after removing solvent with silicon gel column purification.
* intermediate 1-5 synthesis
Under nitrogen no light condition, 1-4 (3.49g, 8.0mmol), DMF solution 50mL, glacial acetic acid are added in reactor 50mL, chloroform 40mL, add under NBS (3.55g, 20.0mmol), room temperature condition and stir 2h, obtain crude product precipitation, filtering, first Alcohol is washed, and obtains compound 1-5 (4.23g, 89%).
* intermediate 1-6 synthesis
In reaction vessel plus intermediate 1-5 (4.99g, 8.4mmol), (4- cyano-phenyls) boric acid (2.5g, 18.4mmol), Tetra-triphenylphosphine palladium (0.7g, 1.08mmol), potassium carbonate (5.3g, 38.3mmol), toluene 60mL, ethanol 20mL and distilled water 20mL, 3h is stirred under the conditions of 120 DEG C.Distilled water stops reaction after reaction terminates, and ethyl acetate extraction, organic layer is used MgSO4Dry, solvent is removed in vacuum distillation, obtain compound 1-6 (3.49g, 65%) with silica gel column chromatography purification afterwards.
* compound 1 is synthesized
Under argon gas protection, by 20mL H2O2Slowly it is added drop-wise to 1-6 (5.36g, 8.4mmol) acetic acid (60ml) and DCM The in the mixed solvent of (25ml).Reaction system is reacted after 1h at room temperature, is heated to 90 DEG C, reacts 36h, the head product of reactant Extracted with DCM, cross column chromatography for separation and obtain compound 1 (2.66g, 45%).
The synthesis of [embodiment 2] compound 8
The synthetic method of reference compound 1 obtains compound 8 (3.56g, 52%).
The synthesis of [embodiment 3] compound 20
The synthetic method of reference compound 1 obtains compound 20 (3.26g, 57%).
The synthesis of [embodiment 4] compound 25
The synthetic method of reference compound 1 obtains compound 25 (3.61g, 54%).
The synthesis of [embodiment 5] compound 34
The synthetic method of reference compound 1 obtains compound 34 (3.07g, 49%).
The synthesis of [embodiment 6] compound 60
The synthetic method of reference compound 1 obtains compound 60 (2.57g, 48%).
The FD-MS values of the luminous organic material of dithieno cyclopentadiene derivant structure prepared by the embodiment of the present invention are such as Shown in table 1.
【Table 1】
Compound FD-MS
1 M/z=702.14 (C41H26N4O4S2=702.80)
8 M/z=814.13 (C49H34O4S4=815.05)
20 M/z=680.11 (C39H24N2O6S2=680.75)
25 M/z=796.16 (C45H36N2O4S4=797.03)
34 M/z=866.11 (C49H30N4O4S4=867.04)
60 M/z=638.15 (C31H26N8O4S2=638.72)
[comparative example 1] device prepares embodiment：
The glass substrate for being coated with transparent conductive layer is placed in cleaning agent and carries out ultrasonic washing, it is anti-with distilled water Clean 3 times again, after distilled water cleaning terminates, the ultrasonic washing in acetone, alcohol mixed solution is dried remove moisture afterwards, It is then transferred in plasma washing machine and washs, then the ito substrate after processing is put into evaporator.In the following order successively Evaporation：Hole injection layer 2-TNATA, thickness 60nm；Hole transmission layer NPB, thickness 30nm；Luminescent layer material of main part AND and mix Miscellaneous material DPAP-DPPA (7%), luminescent layer evaporation film gross thickness is 30nm；Then hole blocking layer and electron transfer layer is deposited TPBi, thickness 30nm；Negative electrode LiF, thickness 0.5nm, metal Al, thickness 50nm.
[embodiment 7] device prepares embodiment：
DPAP-DPPA in comparative example 1 is changed into the compound 1 of embodiment 1.
[embodiment 8] device prepares embodiment：
DPAP-DPPA in comparative example 1 is changed into the compound 8 of embodiment 2.
[embodiment 9] device prepares embodiment：
DPAP-DPPA in comparative example 1 is changed into the compound 20 of embodiment 3.
[embodiment 10] device prepares embodiment：
DPAP-DPPA in comparative example 1 is changed into the compound 25 of embodiment 4.
[embodiment 11] device prepares embodiment：
DPAP-DPPA in comparative example 1 is changed into the compound 34 of embodiment 5.
[embodiment 12] device prepares embodiment：
DPAP-DPPA in comparative example 1 is changed into the compound 60 of embodiment 6.
The characteristics of luminescence test result such as table 2 of luminescent device prepared by 7-12 of the embodiment of the present invention and comparative example 1 It is shown.
[table 2]
Result above shows that the luminous organic material of dithieno cyclopentadiene derivant structure of the invention is applied to have In machine luminescent device, especially as luminescent layer object dopant material, the luminous efficiency of its organic luminescent device is significantly increased, The luminous organic material of the dithieno cyclopentadiene derivant structure of the present invention is luminous organic material of good performance.
It should be pointed out that the present invention is particularly described with individual embodiments, but before the principle of the invention is not departed from Put, ordinary skill people can carry out the improvement on various forms or details to the present invention, these improvement also fall into this hair In bright protection domain.

Claims (7)

1. a kind of luminous organic material of dithieno cyclopentadiene derivant structure, its molecular structural formula is：
Wherein, R1-R2Selected from hydrogen atom, substituted or unsubstituted C1-C40Alkyl, substituted or unsubstituted C1-C40Alkoxy, R1-R2Structure can be identical, also can be different；Ar1-Ar4Selected from hydrogen atom, substituted or unsubstituted C1-C40Alkyl, substitution or Unsubstituted C6-C60Aryl, substituted or unsubstituted C10-C60Condensed ring radical, substituted or unsubstituted C8-C60Condensed hetero ring base, substitution Or unsubstituted C3-C60Heterocyclic radical in one kind, Ar1-Ar4Structure can be identical, also can be different.
2. a kind of luminous organic material of dithieno cyclopentadiene derivant structure according to claim 1, its feature It is, R1-R2Selected from hydrogen atom, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C1-C20Alkoxy, R1- R2Structure can be identical, also can be different；Ar1-Ar4Selected from hydrogen atom, substituted or unsubstituted C1-C20Alkyl, substitution or do not take The C in generation6-C30Aryl, substituted or unsubstituted C10-C30Condensed ring radical, substituted or unsubstituted C8-C30Condensed hetero ring base, substitution or not Substituted C3-C30Heterocyclic radical in one kind, Ar1-Ar4Structure can be identical, also can be different.
3. a kind of luminous organic material of dithieno cyclopentadiene derivant structure according to claim 1, its feature It is, R1-R2Selected from hydrogen atom, substituted or unsubstituted C1-C10Alkyl, substituted or unsubstituted C1-C10Alkoxy, R1- R2Structure can be identical, also can be different；Ar1-Ar4Selected from hydrogen atom, substituted or unsubstituted C1-C12Alkyl, substitution or do not take The C in generation6-C24Aryl, substituted or unsubstituted C10-C20Condensed ring radical, substituted or unsubstituted C8-C20Condensed hetero ring base, substitution or not Substituted C3-C14Heterocyclic radical in one kind, Ar1-Ar4Structure can be identical, also can be different.
4. a kind of luminous organic material of dithieno cyclopentadiene derivant structure according to claim 1, its feature It is, any one in chemical constitution as follows：
5. a kind of organic luminescent device, including first electrode, second electrode and it is placed in one or more between two electrode Organic compound layer, it is characterised in that at least one layer of in the organic compound layer to appoint comprising at least one such as claim 1-4 The luminous organic material of dithieno cyclopentadiene derivant structure described in meaning one.
6. organic luminescent device according to claim 5, it is characterised in that the organic compound layer injects including hole At least one layer in layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer.
7. organic luminescent device according to claim 5, it is characterised in that can be applied to illumination, Display panel, You Jitai The fields such as positive electricity pond, Electronic Paper, Organophotoreceptor or OTFT.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109575046A (en) * 2018-11-30 2019-04-05 四川师范大学 A kind of four aryl of dithienothiophene replace and double luxuriant and rich with fragrance condensed compounds and preparation
CN109824691A (en) * 2019-03-11 2019-05-31 四川师范大学 Liquid-crystal compounds and its preparation based on cyclopentadiene 1,4-Dithiapentalene -4- ketone
CN113061141A (en) * 2019-12-31 2021-07-02 华南理工大学 Water-soluble conjugated polymer for photothermal therapy, polymerized monomer thereof, preparation method and application

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09292726A (en) * 1996-02-13 1997-11-11 Konica Corp Electrophotographic photoreceptor
CN101389634A (en) * 2006-02-22 2009-03-18 住友化学株式会社 Fluorine-containing compound and method for producing same, fluorine-containing polymer, organic thin film, and organic thin film device
CN101712674A (en) * 2009-11-13 2010-05-26 华南理工大学 Alkyl substituted-S,S-dioxo-dibenzothiophene monomer, preparation method and polymer thereof
CN104629725A (en) * 2013-11-08 2015-05-20 海洋王照明科技股份有限公司 Red light phosphorescent host material, preparation method and applications thereof
CN106566533A (en) * 2016-10-26 2017-04-19 华南理工大学 Condensed ring oxidized thiophene-based organic luminescent material, and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09292726A (en) * 1996-02-13 1997-11-11 Konica Corp Electrophotographic photoreceptor
CN101389634A (en) * 2006-02-22 2009-03-18 住友化学株式会社 Fluorine-containing compound and method for producing same, fluorine-containing polymer, organic thin film, and organic thin film device
CN101712674A (en) * 2009-11-13 2010-05-26 华南理工大学 Alkyl substituted-S,S-dioxo-dibenzothiophene monomer, preparation method and polymer thereof
CN104629725A (en) * 2013-11-08 2015-05-20 海洋王照明科技股份有限公司 Red light phosphorescent host material, preparation method and applications thereof
CN106566533A (en) * 2016-10-26 2017-04-19 华南理工大学 Condensed ring oxidized thiophene-based organic luminescent material, and preparation method and application thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHIA-HUA TSAI ET AL.: ""Synthesis of Thiophene 1,1-Dioxides and Tuning Their Optoelectronic Properties"", 《ORG. LETT.》 *
JIN-DOU HUANG ET AL.: ""First-Principles Investigation of the Electronic and Conducting Properties of Oligothienoacenes and their Derivatives"", 《CHEM. ASIAN J.》 *
NETA SHEFER ET AL.: ""Synthesis of Oxidized Thienopyrroles using HOFH3CN"", 《J.ORG.CHEM.》 *
NETA SHEFER ET AL.: ""Synthesis of Oxygenated Fused Oligothiophenes with HOFCH3CN"", 《J. ORG. CHEM.》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109575046A (en) * 2018-11-30 2019-04-05 四川师范大学 A kind of four aryl of dithienothiophene replace and double luxuriant and rich with fragrance condensed compounds and preparation
CN109824691A (en) * 2019-03-11 2019-05-31 四川师范大学 Liquid-crystal compounds and its preparation based on cyclopentadiene 1,4-Dithiapentalene -4- ketone
CN113061141A (en) * 2019-12-31 2021-07-02 华南理工大学 Water-soluble conjugated polymer for photothermal therapy, polymerized monomer thereof, preparation method and application
WO2021135482A1 (en) * 2019-12-31 2021-07-08 华南理工大学 Water-soluble conjugated polymer for photothermal therapy, polymerized monomer thereof, preparation method therefor, and application thereof
CN113061141B (en) * 2019-12-31 2022-03-29 华南理工大学 Water-soluble conjugated polymer for photothermal therapy, polymerized monomer thereof, preparation method and application

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