CN105777620B - A kind of Fluorenone pyridine green fluorescent material - Google Patents
A kind of Fluorenone pyridine green fluorescent material Download PDFInfo
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- CN105777620B CN105777620B CN201610285864.1A CN201610285864A CN105777620B CN 105777620 B CN105777620 B CN 105777620B CN 201610285864 A CN201610285864 A CN 201610285864A CN 105777620 B CN105777620 B CN 105777620B
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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Abstract
The invention discloses a kind of Fluorenone pyridine green fluorescent material, feature is that the fluorescent material is a kind of fluorenone derivatives of the pyridine groups containing conjugation, molecular formula C23H14N2O, the fluorescent material are that 2,7 diiodo-, 9 Fluorenone, 4 pyridine boronic acids are synthesized by coupling reaction and are made, and synthesis step is simple, and yield can reach 70%~90%；Prepared Fluorenone pyridine substantially increases the photoelectric activity i.e. luminous efficiency of material by introducing pyridyl group, has potential application prospect in fields such as organic luminescent devices as organic molecule fluorescent material.
Description
Technical field
The invention belongs to technical field of material chemistry, and in particular to arrive a kind of Fluorenone pyridine green fluorescent material.
Background technology
Fluorescence is usually happened in the molecule with rigid plane and pi-electron conjugated system, intramolecular conjugated degree it is big
Small is the major influence factors of material fluorescence property, therefore improves pi-electron conjugated degree in molecule, can effectively improve molecular fluorescence
Luminous efficiency.There is rigid plane biphenyl structural, intramolecular to contain larger conjugated system, Fluorenone class material tool for fluorenes and Fluorenone class
There is higher thermal stability, the fluorescence quantum efficiency of solid film is higher, and band-gap energy is wider, is a kind of important phosphor
Material, more crucial is that compound of fluorene class is easy to carry out structural modification.But because the influence of this body structure of fluorenes and Fluorenone, easy shape
At excimer and longwave transmissions are generated, the coloration of overall emission light and the stability of color can be influenced in the devices.For
The synthesis luminescent properties of this kind of material are improved, all kinds of researchers have carried out extensive work.
Common fluorenes class luminescent material is based on polyfluorene (PFO) class, the good rigid plane of polyfluorene molecule and higher total
Yoke degree has obtained the favor of many experts and scholars.The method of generally use is modified on 9 carbon of fluorenes, to improve
The dissolving of polyfluorene in organic solvent makes material embody more good performance after processing forms a film, while being adjusted by steric hindrance
The aggregated structure of material keeps the stable crystal form of polyfluorene within the scope of certain temperature, improves the luminous efficiency of material.But it is small
The structure of molecular ligh-emitting materials is easily adjusted, and can be introduced various groups to change the conjugated degree of molecule, be improved performance.For
Electroluminescent small molecule has chemical modification strong, is easy to purify.By changing the chemical constitution of micromolecular compound, we
The emission wavelength of material can be changed.The present invention provides a kind of luminous organic material based on Fluorenone, by introducing pyridine groups,
The luminous efficiency for improving material, improves the performance of material.
Invention content
The technical problem to be solved by the present invention is to be directed to the prior art, a kind of Fluorenone pyridine green fluorescent material is provided.
Technical solution is used by the present invention solves above-mentioned technical problem：A kind of Fluorenone pyridine green fluorescent material, i.e.,
2,7- bis- (4- pyridyl groups) -9-Fluorenones (abbreviation Fluorenone pyridine), molecular formula C23H14N2O, structural formula are：
Preferably, which has the electronic energy level structure of specific conjugation delocalization, and maximum emission peak is in 506nm
(excitation wavelength 339nm).
The preparation method of above-mentioned Fluorenone pyridine green fluorescent material, includes the following steps：
1) by 2,7-, bis- iodo- 9-Fluorenones, 4- pyridine boronic acids, sodium carbonate, acid chloride, in molar ratio 1:2~3:10:0.05
Ratio is mixed in reaction unit, then by N, N '-dimethyl formamide and water by volume 10:It is anti-that 1 ratio is mixed in this
It answers in device；
2) by the reaction unit in 90~150 DEG C react 12~for 24 hours；
3) it after reaction, is extracted with dichloromethane, liquid separation, merges organic phase, then by the organic phase saturated salt solution
Washing three times, is dried with anhydrous sodium sulfate later, is filtered；
4) organic solvent in filtrate is removed up to solid powder, then using ethyl acetate as leaching by Rotary Evaporators
Lotion uses column chromatographic isolation and purification, finally removes ethyl acetate, and obtained solid powder is that the Fluorenone pyridine is green
Color fluorescent material.
Preferably, the substance for participating in reaction is that chemistry is pure.
Fluorenone and its derivative are the luminous organic materials of a kind of function admirable, and Fluorenone molecule has the structure being rigidly conjugated
Primitive, the carbonyl on 9 have stronger polarity, to make to generate dipole effect between group；By coupling reaction in fluorenes
The 2 of ketone, 7 upper introducings have the pyridine groups for being conjugated big pi bond, and compound is made to be provided with the electron energy level of specific conjugation delocalization
Structure obtains a kind of Fluorenone pyrrole with green fluorescence performance so that the compound has unique fluorescent emission performance
Acridine compound, the carbonyl and 2 of the compound 9,7 pyridyl groups keep the electron delocalization of compound stronger, to raising
The luminous efficiency for closing object, is a kind of potential luminous organic material.
Description of the drawings
Fig. 1 is the fluorescence spectra of the Fluorenone pyridine fluorescent material of the present invention.
Specific implementation mode
Below in conjunction with attached drawing embodiment, present invention is further described in detail.
Embodiment 1：
Take bis- iodo- 9-Fluorenone 3.0mmol, 4- pyridine boronic acid 6mmol of 2,7-, sodium carbonate 30mmol, acid chloride 0.15mmol
It is placed in the reaction unit of 150mL, and DMF 50mL and water 5mL is added；The reaction unit is reacted into 12h at 150 DEG C；Reaction
It finishes, the liquid separation after reaction solution cooling with dichloromethane aqueous phase extracted, and merges organic phase, then organic phase saturation is eaten
Salt water washing 3 times, is dried with anhydrous sodium sulfate later, filtering；The organic solvent in filtrate is removed with Rotary Evaporators, obtains solid
Then powder uses column chromatographic isolation and purification using ethyl acetate as eluent, be finally spin-dried for ethyl acetate to get to described
Fluorenone pyridine green fluorescent material.
Embodiment 2：
Take bis- iodo- 9-Fluorenone 3.0mmol, 4- pyridine boronic acid 9mmol of 2,7-, sodium carbonate 30mmol, acid chloride 0.15mmol
It is placed in the reaction unit of 150mL, and DMF 50mL and water 5mL is added；The reaction unit is reacted for 24 hours at 90 DEG C；Reaction
It finishes, the liquid separation after reaction solution cooling with dichloromethane aqueous phase extracted, and merges organic phase, then organic phase saturation is eaten
Salt water washing 3 times, is dried with anhydrous sodium sulfate later, filtering；The organic solvent in filtrate is removed with Rotary Evaporators, obtains solid
Then powder uses column chromatographic isolation and purification using ethyl acetate as eluent, be finally spin-dried for ethyl acetate to get to described
Fluorenone pyridine green fluorescent material.
Embodiment 3：
Take bis- iodo- 9-Fluorenone 3.0mmol, 4- pyridine boronic acid 7mmol of 2,7-, sodium carbonate 30mmol, acid chloride 0.15mmol
It is placed in the reaction unit of 150mL, and DMF 50mL and water 5mL is added；The reaction unit is reacted into 18h at 120 DEG C；Reaction
It finishes, the liquid separation after reaction solution cooling with dichloromethane aqueous phase extracted, and merges organic phase, then organic phase saturation is eaten
Salt water washing 3 times, is dried with anhydrous sodium sulfate later, filtering；The organic solvent in filtrate is removed with Rotary Evaporators, obtains solid
Then powder uses column chromatographic isolation and purification using ethyl acetate as eluent, be finally spin-dried for ethyl acetate to get to described
Fluorenone pyridine green fluorescent material.
Fluorenone pyridine green fluorescent material obtained is pulverulent solids in above-described embodiment, through nucleus magnetic hydrogen spectrum, infrared, purple
Outside, it is C that mass spectrum, elemental analysis etc., which measure its molecular formula,23H14N2O。
Fluorescence property test, fluorescence spectra will be carried out after obtained Fluorenone pyridine green fluorescent material natural air drying
As shown in Figure 1.
Claims (2)
1. a kind of bis- (4- pyridyl groups) -9-Fluorenones of 2,7- are used as the purposes of green fluorescent material.
2. 2,7- bis- (4- pyridyl groups) -9-Fluorenone according to claim 1 is used as the purposes of green fluorescent material, feature
It is, which has the electronic energy level structure of specific conjugation delocalization, maximum emission peak 506nm.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6255449B1 (en) * | 1995-07-28 | 2001-07-03 | The Dow Chemical Company | Fluorene-containing polymers and compounds useful in the preparation thereof |
| US20020132134A1 (en) * | 2001-01-26 | 2002-09-19 | Xerox Corporation | Electroluminescent (EL) devices |
| EP1284258A2 (en) * | 2001-08-17 | 2003-02-19 | MERCK PATENT GmbH | Mono-, oligo- and polyalkylidenefluorenes and their use as charge transport materials |
| CN101928276A (en) * | 2010-07-15 | 2010-12-29 | 太原理工大学 | Method for synthesizing organic red light material |
| CN102838442A (en) * | 2012-08-09 | 2012-12-26 | 烟台万润精细化工股份有限公司 | 9-alkenylfluorene derivatives and application thereof |
| CN105503766A (en) * | 2015-12-18 | 2016-04-20 | 昆山国显光电有限公司 | Thermal activation delayed fluorescent material and organic electroluminescent device |
-
2016
- 2016-04-29 CN CN201610285864.1A patent/CN105777620B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6255449B1 (en) * | 1995-07-28 | 2001-07-03 | The Dow Chemical Company | Fluorene-containing polymers and compounds useful in the preparation thereof |
| US20020132134A1 (en) * | 2001-01-26 | 2002-09-19 | Xerox Corporation | Electroluminescent (EL) devices |
| EP1284258A2 (en) * | 2001-08-17 | 2003-02-19 | MERCK PATENT GmbH | Mono-, oligo- and polyalkylidenefluorenes and their use as charge transport materials |
| CN101928276A (en) * | 2010-07-15 | 2010-12-29 | 太原理工大学 | Method for synthesizing organic red light material |
| CN102838442A (en) * | 2012-08-09 | 2012-12-26 | 烟台万润精细化工股份有限公司 | 9-alkenylfluorene derivatives and application thereof |
| CN105503766A (en) * | 2015-12-18 | 2016-04-20 | 昆山国显光电有限公司 | Thermal activation delayed fluorescent material and organic electroluminescent device |
Non-Patent Citations (3)
| Title |
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| Syntheses, Electrochemical Behaviors, Spectral Properties and DFT Calculations of Two 1,3-Dithiole Derivatives.;NIU Zhigang et al.;《Chem. Res. Chin. Univ.》;20140711;第30卷(第3期);第425-430页，尤其第426页Scheme 1 * |
| 杨伟等.吡啶 芴类电荧光聚合物的光谱特性.《高分子学报》.2005,(第2期),第177-180页. * |
| 芴类有机发光材料的合成及性能表征;刘志鹏;《宁波大学硕士学位论文》;20130413 * |
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Effective date of registration: 20211111 Address after: 256600 No. 1, Gaosi Road, high tech Industrial Development Zone, Binzhou City, Shandong Province Patentee after: Binzhou Kechuang Incubator Co., Ltd Address before: 313000 room 1020, first floor, Nanxun science and technology entrepreneurship Park, No. 666, Chaoyang Road, Nanxun Town, Nanxun District, Huzhou City, Zhejiang Province Patentee before: Huzhou Youyan Intellectual Property Service Co., Ltd |