CN105461717B - Thermal activation delayed fluorescence material based on 1,10 ferrosins and preparation method thereof, application - Google Patents
Thermal activation delayed fluorescence material based on 1,10 ferrosins and preparation method thereof, application Download PDFInfo
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- CN105461717B CN105461717B CN201610013702.2A CN201610013702A CN105461717B CN 105461717 B CN105461717 B CN 105461717B CN 201610013702 A CN201610013702 A CN 201610013702A CN 105461717 B CN105461717 B CN 105461717B
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- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H10K50/00—Organic light-emitting devices
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Abstract
The invention discloses based on 1,10 ferrosin, to inhale electrical unit, the amino unit of aryl substitution is the thermal activation delayed fluorescence material of electron-donating unit.The present invention also provides the preparation method of above-mentioned fluorescent material, comprises the following steps：(1) the bromo target product of the amino unit containing aryl substitution is prepared；(2) the bromo target product obtained by, by n-BuLi, reacted with isopropoxy pinacol borate, obtain the target product of boracic acid esters；(3) target product of boracic acid esters resulting in step (2) and the ferrosin of 3 bromine 1,10 are in the presence of palladium catalyst, thermal activation delayed fluorescence material of the generation based on 1,10 ferrosins.Materials synthesis purification of the present invention is simple, has preferable dissolubility, while has good film morphology and higher carrier mobility, has important application value and application prospect in organic electroluminescence device.
Description
Technical field
The present invention relates to luminescent material, more particularly to thermal activation delayed fluorescence material and its system based on 1,10- ferrosins
Preparation Method, application.
Background technology
Organic electroluminescent LED (OLEDs) due to it is frivolous, from main light emission (not needing backlight), flexible bendable
The advantages such as song turn into the focus of research, are described as next display.In order to realize large-area applications that OLED is shown, it is necessary to use
More efficient luminescent material, energy consumption is reduced further to improve device light emitting efficiency.Phosphor material can obtain higher device
Part efficiency, but materials synthesis cost is higher；Fluorescent material cost is relatively low, and the fluorescence with thermal activation delayed fluorescence (TADF)
Material can break through the theoretical efficiency limitation of conventional fluorescent material, obtain the device for quite even surmounting phosphor material with phosphor material
Part efficiency, therefore it is significant to develop efficient TA DF materials.
In the TADF materials of RGB three primary colours, green glow TADF Materials are very fast, optimize maximum quantum by device architecture
Efficiency has reached 30%；Feux rouges and blue light TADF Materials are relatively lagged behind, and its maximum quantum efficiency is respectively reached and exceeded
12%th, 22%.It has been reported that blue light TADF materials in, be mostly a day blue light material, dark blue luminescent material is less, and these
Dark blue smooth TADF materials, there is also problems, therefore, synthesize Gao Qian in material mobility, device efficiency and stability etc.
Shifting rate, dark blue photo-thermal activation delayed fluorescence (TADF) material that efficient, stability is good are significant.
The content of the invention
In order to overcome the disadvantages mentioned above of prior art and deficiency, an object of the present invention is that providing one kind is based on 1,
The thermal activation delayed fluorescence material of 10- ferrosins.The thermal activation delayed fluorescence material mobility of the present invention is high, stability is good, closes
It is fairly simple into purifying, while there is preferable dissolubility and good film morphology.
The second object of the present invention is the preparation for providing the above-mentioned thermal activation delayed fluorescence material based on 1,10- ferrosins
Method.
The third object of the present invention is to provide answering for the above-mentioned thermal activation delayed fluorescence material based on 1,10- ferrosins
With.
The purpose of the present invention is achieved through the following technical solutions：
Thermal activation delayed fluorescence material based on 1,10- ferrosins, there is following structure：
The R is the amino unit of aryl substitution.
Preferably, the R is with one kind in lower unit：
Wherein R1、R4-R6Any one in the alkyl chain or oxyalkyl chain for being 1~12 for H, carbon number；
R2、R3Alkyl chain either any one in oxyalkyl chain or following structure for being 1~12 for H, carbon number：
Wherein R7、R8Any one in the alkyl chain or oxyalkyl chain for being 1-12 for H, carbon number.
Preferably, the thermal activation delayed fluorescence material is Phen-CzPh, has following chemical constitution：
Preferably, the thermal activation delayed fluorescence material is Phen-Cz-t-BuPh, has following chemical constitution：
The preparation method of the described thermal activation delayed fluorescence material based on 1,10- ferrosins, comprises the following steps：
(1) the bromo target product of the amino unit containing aryl substitution is prepared；
(2) bromo target product resulting in step (1), by n-BuLi, at -70~-80 DEG C, with isopropyl oxygen
Base pinacol borate reacts, and obtains the target product of boracic acid esters；
(3) target product of boracic acid esters resulting in step (2) and the bromo- 1,10- ferrosins of 3- are in palladium catalyst
Under effect, thermal activation delayed fluorescence material of the generation based on 1,10- ferrosins.
Preferably, step (1) the bromo target product for preparing the amino unit containing aryl substitution, it is specially：
(11) when aryl substitution amino unit be following several structures in it is a kind of when：
By to bromo-iodobenzene and corresponding nitrogenous heterocyclic Ullmann reactions or Buchwald-Hartwig coupling reactions
Obtain the bromo target product of the amino unit containing aryl substitution；
(12) wherein aryl substitution amino unit be following several structures in it is a kind of when：
React with corresponding carbazole or diphenylamino group to obtain the first intermediate using the iodo carbazole with blocking group,
Then the bromo target for reacting to obtain the amino unit substituted containing aryl with the first intermediate of deprotection and to bromo-iodobenzene is produced
Thing；
(13) when the amino unit of wherein aryl substitution is following structure：
In being obtained to the Ullmann reactions of tert-butyl group bromobenzene and carbazole or Buchwald-Hartwig coupling reactions
Mesosome, the bromo target product of amino unit substituted containing aryl is then obtained by NBS bromo-reactions；Or it can pass through
3- bromines carbazole and the bromo target product for reacting to obtain the amino unit containing aryl substitution to tert-butyl group bromobenzene.
Preferably, the thermal activation delayed fluorescence material is Phen-CzPh, has following chemical constitution：
Its preparation method comprises the following steps：
(a1) 9- (4- bromophenyls) carbazole is prepared：Under nitrogen protection, cuprous iodide is added to 1,10- ferrosins, click
Azoles, in the DMF solution of bromo-iodobenzene and Anhydrous potassium carbonate, then reaction is heated to 110~120 DEG C and is stirred overnight；Question response
After being cooled to room temperature, distilled water and dichloromethane are added into reactant mixture, after liquid separation, with dichloromethane aqueous layer extracted；Have
Machine layer is separated after distilled water cleans, anhydrous magnesium sulfate is dry, filters, is evaporated under reduced pressure removing solvent with silicagel column, is eluted
Agent is petroleum ether, obtains white solid；
Wherein, carbazole, the mol ratio to bromo-iodobenzene, Anhydrous potassium carbonate, cuprous iodide, 1,10- ferrosins are 1：(1~
1.3)：(2~4)：(0.05~0.1)：(0.05-0.1)；
(a2) 9- (4- (4,4,5,5- tetramethyl -1,3,2- dioxaborolane -2- bases) phenyl) carbazole is prepared：In nitrogen
Under gas shielded, 9- (4- bromophenyls) carbazole is dissolved into anhydrous tetrahydro furan, -70~-80 DEG C is cooled to, is delayed by syringe
It is slow that n-butyllithium solution is added dropwise and keeps at such a temperature 15~20 minutes, then add isopropoxy pinacol borate；Instead
System is answered slowly to recover to room temperature and in N2It is stirred overnight under atmosphere；1~2mL ethanol terminating reactions are added after the completion of question response,
And after being evaporated under reduced pressure removing solvent, dichloromethane and distilled water extraction are added, organic layer anhydrous magnesium sulfate is dry, filters, subtracts
Pressure uses silica gel post separation after solvent is distilled off, and eluant, eluent is petroleum ether and dichloromethane, obtains white solid；
Wherein, 9- (4- bromophenyls) carbazole, n-BuLi, the molar ratio of isopropoxy pinacol borate are 1：
(1.1~1.3)：(1.3~1.5)；
(a3) prepare compound Phen-PhCz：Under nitrogen protection, palladium, tricyclohexyl phosphine are added to 3- bromo- 1,
10- ferrosins, 9- (4- (4,4,5,5- tetramethyl -1,3,2- dioxaborolane -2- bases) phenyl) carbazole, potassium carbonate are water-soluble
Liquid, ethanol, toluene mixed solution in, reaction be heated to 90~110 DEG C and be stirred overnight；After being cooled to room temperature, to reaction
Add distilled water and separation of methylbenzene layer in mixture, then with dichloromethane aqueous layer extracted；Organic layer anhydrous magnesium sulfate drying, mistake
Filter, separated after being evaporated under reduced pressure removing solvent with silicagel column, eluant, eluent is dichloromethane and ethyl acetate, and it is solid to obtain white
Body；
Wherein, bromo- 1, the 10- ferrosins of 3-, 9- (4- (4,4,5,5- tetramethyls -1,3,2- dioxaborolane -2- bases)
Phenyl) carbazole, palladium, tricyclohexyl phosphine molar ratio be 1：(1.1~1.3)：(0.06~0.09)：(0.12~
0.18)
Preferably, the thermal activation delayed fluorescence material is Phen-Cz-t-BuPh, has following chemical constitution：
Its preparation method comprises the following steps：
(b1) 9- (4- tert-butyl-phenyls) carbazole is prepared：Under nitrogen protection, tri-butyl phosphine is added to palladium, click
Azoles, in the toluene solution of bromine tert-butyl benzene and Anhydrous potassium carbonate, then reaction is heated to 90~100 DEG C and is stirred overnight；Treat
After reaction is cooled to room temperature, distilled water and separation of methylbenzene layer are added into reactant mixture, then with dichloromethane aqueous layer extracted；Have
Machine layer is separated after removing solvent with anhydrous magnesium sulfate drying, filtering, vacuum distillation with silicagel column, and eluant, eluent is petroleum ether,
Obtain white solid；
Wherein, carbazole, the mol ratio to bromine tert-butyl benzene, Anhydrous potassium carbonate, palladium, tri-butyl phosphine are 1：(1~
1.3)：(2~4)：(0.01~0.02)：(0.02-0.04)；
(b2) 3- bromo- 9- (4- tert-butyl-phenyls) carbazole is prepared：Under the conditions of ice bath and lucifuge, to 9- (4- bromophenyls) click
NBS is added portionwise in the chloroform soln of azoles, after reacting at room temperature 2~3 hours, distilled water is added into reaction and uses dichloromethane
Alkane extracts；Organic layer anhydrous magnesium sulfate drying, filtering, silica gel post separation is used after being evaporated under reduced pressure removing solvent, eluant, eluent is stone
Oily ether, obtains white solid；
Wherein, 9- (4- bromophenyls) carbazole, NBS molar ratio are 1：1~1：0.95
(b3) 9- (4- tert-butyl-phenyls) -3- (4,4,5,5- tetramethyl -1,3,2- dioxaborolane -2- bases) is prepared
Carbazole：Under nitrogen protection, the bromo- 9- of 3- (4- bromophenyls) carbazole is dissolved into anhydrous tetrahydro furan, is cooled to -70~-80
DEG C, n-butyllithium solution is slowly added dropwise by syringe and kept for 15~20 minutes at such a temperature, then adds isopropoxy
Pinacol borate；Slowly recover to room temperature and in N2It is stirred overnight under atmosphere；It is whole that 1~2mL ethanol is added after the completion of question response
Only react, and after being evaporated under reduced pressure and removing solvent, add dichloromethane and distilled water extraction, organic layer with anhydrous magnesium sulfate it is dry,
Filtering, silica gel post separation is used after being evaporated under reduced pressure removing solvent, eluant, eluent is petroleum ether and dichloromethane, obtains white solid；
Wherein, the bromo- 9- of 3- (4- bromophenyls) carbazole, n-BuLi, the molar ratio of isopropoxy pinacol borate
For 1：(1.1~1.3)：(1.3~1.5)；
(b4) prepare compound Phen-Cz-t-BuPh：Under nitrogen protection, palladium, tricyclohexyl phosphine are added to 3-
Bromo- 1,10- phenanthrolines, 9- (4- (tert-butyl group) phenyl) -3- (4,4,5,5- tetramethyl -1,3,2- dioxaborolanes -2-
Base) carbazole, wet chemical, ethanol, toluene mixed solution in, reaction be heated to 90~110 DEG C and be stirred overnight；Treat cold
But to after room temperature, adding distilled water and separation of methylbenzene layer, then with dichloromethane aqueous layer extracted；Organic layer is done with anhydrous magnesium sulfate
Dry, filtering, separated after being evaporated under reduced pressure removing solvent with silicagel column, eluant, eluent is dichloromethane and ethyl acetate, is obtained white
Color solid；
Wherein, bromo- 1, the 10- phenanthrolines of 3-, 9- (4- (tert-butyl group) phenyl) -3- (4,4,5,5- tetramethyls -1,3,2- dioxies
Boron heterocycle pentane -2- bases) carbazole, palladium, tricyclohexyl phosphine molar ratio be 1：(1.1~1.3)：(0.06~
0.09)：(0.12~0.18).
The application of the described thermal activation delayed fluorescence material based on 1,10- ferrosins, for preparing electroluminescent cell
Part.
Compared with prior art, the present invention has advantages below and beneficial effect：
(1) it is electrically single to be used as the suction with thermal activation delayed fluorescence (TADF) material by the present invention first for 1,10- ferrosins
Member, then access electron-donating unit and synthesized the luminescent material with thermal activation delayed fluorescence (TADF) effect, with applied to organic
The luminescent layer of electroluminescent device.
(2) present invention realizes the preparation of dark blue light-emitting material, is expected to by selecting suitable electron-donating unit R
To high color purity and efficient device.
(3) the thermal activation delayed fluorescence material based on 1,10- ferrosins prepared by the present invention has preferable dissolubility,
Phen-PhCz, which can be dissolved in, common are solvent such as dichloromethane, chloroform etc., and Phen-Cz-t-BuPh can be dissolved in dichloro
Methane, chloroform, tetrahydrofuran, ethanol, isopropanol etc., vacuum evaporation and solution processing (Phen-Cz-t- can be carried out
BuPh can carry out alcoholic solution processing) mode film forming, there is good film morphology, the potential higher and carrier that more balances
Mobility etc., be advantageous to obtain the device of efficient stable.
(4) the thermal activation delayed fluorescence material based on 1,10- ferrosins prepared by the present invention can not only be used as luminous material
Material, at the same can be as the main body of phosphorescence and fluorescent material for organic electroluminescence device luminescent layer.
(5) purification of the thermal activation delayed fluorescence materials synthesis based on 1,10- ferrosins that prepared by the present invention is fairly simple, can
To realize a large amount of preparations, there is important application value and application prospect in organic electroluminescence device.
Brief description of the drawings
Fig. 1 is thermal activation delayed fluorescence (TADF) material based on 1,10- ferrosins prepared by embodiments of the invention 1
Phen-PhCz hydrogen nuclear magnetic resonance spectrogram.
Fig. 2 is thermal activation delayed fluorescence (TADF) material based on 1,10- ferrosins prepared by embodiments of the invention 1
Phen-PhCz absorption and PL spectrum.
Fig. 3 is thermal activation delayed fluorescence (TADF) material based on 1,10- ferrosins prepared by embodiments of the invention 1
Phen-PhCz solvatochromism curve.
Fig. 4 is thermal activation delayed fluorescence (TADF) material based on 1,10- ferrosins prepared by embodiments of the invention 1
Phen-PhCz electrochemical profiles.
Fig. 5 be embodiments of the invention 1 electro-chemical test in ferrocene electrochemical profiles.
Fig. 6 is thermal activation delayed fluorescence (TADF) material based on 1,10- ferrosins prepared by embodiments of the invention 1
Phen-PhCz TG curves.
Fig. 7 is thermal activation delayed fluorescence (TADF) material based on 1,10- ferrosins prepared by embodiments of the invention 1
Phen-PhCz DSC curve.
Fig. 8 is thermal activation delayed fluorescence (TADF) material based on 1,10- ferrosins prepared by embodiments of the invention 1
Attenuation curves of the Phen-PhCz after nitrogen deoxygenation in toluene solution.
Fig. 9 is the instrument respective function in the attenuation curve test of embodiments of the invention 1.
Figure 10 is thermal activation delayed fluorescence (TADF) material based on 1,10- ferrosins prepared by embodiments of the invention 2
Phen-Cz-t-BuPh hydrogen nuclear magnetic resonance spectrogram.
Figure 11 is thermal activation delayed fluorescence (TADF) material based on 1,10- ferrosins prepared by embodiments of the invention 2
Phen-Cz-t-BuPh absorption and PL spectrum.
Figure 12 is thermal activation delayed fluorescence (TADF) material based on 1,10- ferrosins prepared by embodiments of the invention 2
Phen-Cz-t-BuPh solvatochromism curve.
Figure 13 is thermal activation delayed fluorescence (TADF) material based on 1,10- ferrosins prepared by embodiments of the invention 2
Phen-Cz-t-BuPh electrochemical profiles.
Figure 14 be embodiments of the invention 2 electro-chemical test in ferrocene electrochemical profiles.
Figure 15 is thermal activation delayed fluorescence (TADF) material based on 1,10- ferrosins prepared by embodiments of the invention 2
Attenuation curve in toluene solutions of the Phen-Cz-t-BuPh after nitrogen deoxygenation.
Figure 16 is the instrument respective function in the attenuation curve test of embodiments of the invention 2.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1
The structural formula such as following formula institute of thermal activation delayed fluorescence (TADF) material based on 1,10- ferrosins of the present embodiment
Show：
Its synthesis step is as follows：
Step 1: the preparation of 9- (4- bromophenyls) carbazole：
Under nitrogen protection, by cuprous iodide (455mg, 2.39mmol) be added to 1,10- ferrosins (430mg,
2.39mmol), carbazole (4g, 23.92mmol), to bromo-iodobenzene (8.12g, 28.71mmol) and Anhydrous potassium carbonate (9.92g,
In DMF (60mL) solution 71.76mmol), then reaction is heated to 110~120 DEG C and is stirred overnight.Question response is cooled to room
Wen Hou, distilled water and dichloromethane are added into reactant mixture, after liquid separation, with dichloromethane aqueous layer extracted three times.Organic layer
Through distilled water cleaning three times, anhydrous magnesium sulfate is dry, filtering, be evaporated under reduced pressure remove solvent after separated with silicagel column, elute
Agent is petroleum ether, obtains white solid, and yield is 74% (5.7g).
1H NMR(300MHz,CDCl3):δ 8.15 (d, J=7.7,2H), 7.74 (d, J=8.5,2H), 7.43 (m, 6H),
7.32(m,2H)
Step 2：Prepare 9- (4- (4,4,5,5- tetramethyl -1,3,2- dioxaborolane -2- bases) phenyl) carbazole
Under nitrogen protection, 9- (4- bromophenyls) carbazoles (3g, 9.32mmol) are dissolved into anhydrous tetrahydro furan (120mL)
In, -78 DEG C or so are cooled to, n-butyllithium solution (1.6mL, 2.5M, 4.84mmol) is slowly added dropwise by syringe, and at this
At a temperature of kept for 15~20 minutes, then add isopropoxy pinacol borate (2.6mL, 13.04mmol)；Reaction system is delayed
Slowly recover to room temperature and in N2It is stirred overnight under atmosphere.1~2mL ethanol terminating reactions are added after the completion of question response, and depressurize steaming
After solvent is removed in distillation, dichloromethane and distilled water extraction are added, organic layer anhydrous magnesium sulfate is dry, filters, is evaporated under reduced pressure and removes
Silica gel post separation is used after removing solvent, eluant, eluent is petroleum ether and dichloromethane, obtains white solid, and yield is 80% (2.75g).
1H NMR(300MHz,CDCl3,ppm):δ 8.14 (2H, d, J=7.7), 8.04 (2H, s), 7.60 (2H, d, J=
8.2),7.44(4H,m),7.34–7.26(2H,m),1.40(12H,s)
Step 3: prepare compound Phen-PhCz
Under nitrogen protection, palladium (13mg, 0.059mmol), tricyclohexyl phosphine (33mg, 0.118mmol) are added
To the bromo- 1,10- ferrosins (511mg, 1.97mmol) of 3-, 9- (4- (4,4,5,5- tetramethyl -1,3,2- dioxaborolanes -
2- yls) phenyl) carbazole (800mg, 2.17mmol), wet chemical (2mL, 2M), ethanol (20mL), toluene (20mL) it is mixed
Close in solution, reaction is heated to 90~110 DEG C and is stirred overnight.After being cooled to room temperature, distillation is added into reactant mixture
Water and separation of methylbenzene layer, then with dichloromethane aqueous layer extracted three times.Organic layer anhydrous magnesium sulfate drying, filtering, it is evaporated under reduced pressure
Separated after removing solvent with silicagel column, eluant, eluent is dichloromethane and ethyl acetate, obtains white solid, yield is
91% (755mg).
1H NMR(400MHz,CDCl3,ppm):δ 9.56 (1H, s), 9.26 (1H, d, J=4.3), 8.52 (1H, s), 8.31
(1H, d, J=8.1), 8.18 (2H, d, J=7.7), 8.03 (2H, d, J=8.1), 7.90 (2H, q, J=8.8), 7.78 (2H,
D, J=8.0), 7.69 (1H, dd, J=8.0,4.4), 7.52 (2H, d, J=8.2), 7.45 (2H, t, J=7.6), 7.33 (2H,
T, J=7.4)
Fig. 1 is thermal activation delayed fluorescence (TADF) the material Phen-PhCz manufactured in the present embodiment based on 1,10- ferrosins
Hydrogen nuclear magnetic resonance spectrogram.
Fig. 2 is thermal activation delayed fluorescence (TADF) the material Phen-PhCz manufactured in the present embodiment based on 1,10- ferrosins
Absorption and PL spectrum.The solid-state emission peak of material is 436nm, shows as deep blue emission
Fig. 3 is thermal activation delayed fluorescence (TADF) the material Phen-PhCz manufactured in the present embodiment based on 1,10- ferrosins
Solvatochromism curve.With the increase of solvent polarity, material solution emission peak red shift, show the presence of CT states.
Fig. 4 is thermal activation delayed fluorescence (TADF) the material Phen-PhCz manufactured in the present embodiment based on 1,10- ferrosins
Electrochemical profiles.The initial oxidation current potential of material is 1.2V
Fig. 5 be the present embodiment electro-chemical test in ferrocene electrochemical profiles.
Fig. 6 is thermal activation delayed fluorescence (TADF) the material Phen-PhCz manufactured in the present embodiment based on 1,10- ferrosins
TG curves.Material decomposition temperature is more than 360 DEG C, has preferable heat endurance
Fig. 7 is thermal activation delayed fluorescence (TADF) the material Phen-PhCz manufactured in the present embodiment based on 1,10- ferrosins
DSC curve.The glass transition temperature of material is between 110~120 DEG C, and at 265 DEG C, material shows stronger crystallization and melted
Melt peak
Fig. 8 is thermal activation delayed fluorescence (TADF) the material Phen-PhCz manufactured in the present embodiment based on 1,10- ferrosins
The attenuation curve in the toluene solution of nitrogen saturation.With reference to the Instrument response function in Fig. 9 during corresponding test, show that material postpones
The presence of fluorescence.
Fig. 9 is the Instrument response function in the attenuation curve test of the present embodiment.
Experimental phenomena：
Thermal activation delayed fluorescence (TADF) material Phen-PhCz's manufactured in the present embodiment based on 1,10- ferrosins is thin
Film shows obvious Enhancement of Fluorescence after deoxygenation.
Embodiment 2
The structural formula of thermal activation delayed fluorescence (TADF) material based on 1,10- phenanthrolines is shown below：
The synthesis step of thermal activation delayed fluorescence (TADF) material of the present embodiment based on 1,10- phenanthrolines is as follows：
Step 1: the preparation of 9- (4- tert-butyl-phenyls) carbazole：
Under nitrogen protection, tri-butyl phosphine (0.5mL, 1M in tolene, 0.478mmol) is added to palladium
(54mg, 0.239mmol), carbazole (4g, 23.92mmol), to bromine tert-butyl benzene (5.1g, 23.91mmol) and Anhydrous potassium carbonate
In toluene (20mL) solution of (10g, 71.76mmol), then reaction is heated to 90 DEG C and is stirred overnight.Question response is cooled to room
Wen Hou, distilled water and separation of methylbenzene layer are added into reactant mixture, then with dichloromethane aqueous layer extracted three times.Merge organic layer
Separated after removing solvent with anhydrous magnesium sulfate drying, filtering, vacuum distillation with silicagel column, eluant, eluent is petroleum ether, is obtained
White solid, yield are 76% (5.65g).
1H NMR(300MHz,CDCl3,ppm):δ 8.18 (d, J=7.7Hz, 2H), 7.64 (d, J=8.2Hz, 2H), 7.52
(d, J=8.1Hz, 2H), 7.44 (q, J=8.3Hz, 4H), 7.32 (t, J=7.5Hz, 2H), 1.45 (s, 9H).
Step 2: prepare 3- bromo- 9- (4- tert-butyl-phenyls) carbazole：
Under the conditions of lucifuge, to chloroform (100mL) solution of 0 DEG C of 9- (4- bromophenyls) carbazoles (3g, 10mmol)
In be added portionwise after NBS (1.78,10mmol) reacts at room temperature two hours, add and distilled water and extracted with dichloromethane into reaction
Three times.Organic layer anhydrous magnesium sulfate drying, filtering, silica gel post separation is used after being evaporated under reduced pressure removing solvent, eluant, eluent is oil
Ether, obtains white solid, and yield is 95% (3.6g).
1H NMR(300MHz,CDCl3,ppm):δ 8.21 (s, 1H), 8.05 (d, J=7.7Hz, 1H), 7.57 (d, J=
7.6Hz,2H),7.49–7.34(m,5H),7.23(m,2H),1.39(s,9H)。
Step 3: prepare 9- (4- tert-butyl-phenyls) -3- (4,4,5,5- tetramethyl -1,3,2- dioxaborolanes -2-
Base) carbazole：
Under nitrogen protection, the bromo- 9- of 3- (4- bromophenyls) carbazoles (2g, 5.29mmol) are dissolved into anhydrous tetrahydro furan
In (120mL), -78 DEG C or so are cooled to, n-butyllithium solution (2.5mL, 2.5M, 6.25mmol) is slowly added dropwise by syringe
And keep at such a temperature 15~20 minutes, then add isopropoxy pinacol borate (7.54mL, 6.877mmol)；Instead
System is answered slowly to recover to be stirred overnight to room temperature and under N2 atmosphere.1~2mL ethanol terminating reactions are added after the completion of question response,
And after being evaporated under reduced pressure removing solvent, dichloromethane and distilled water extraction are added, organic layer anhydrous magnesium sulfate is dry, filters, subtracts
Pressure uses silica gel post separation after solvent is distilled off, and eluant, eluent is petroleum ether and dichloromethane, obtains white solid, yield 75%
(1.69g)。
1H NMR(300MHz,CDCl3,ppm):δ 8.65 (s, 1H), 8.18 (d, J=7.7Hz, 1H), 7.85 (dd, J=
8.3,1.0Hz,1H),7.65–7.57(m,2H),7.51–7.44(m,2H),7.40(m,3H),7.29(m,1H),1.43(s,
9H),1.41(s,12H)。
Step 4: prepare compound Phen-CzPh：
Under nitrogen protection, palladium (13mg, 0.058mmol), tricyclohexyl phosphine (24mg, 0.116mmol) are added
To the bromo- 1,10- phenanthrolines (300mg, 1.16mmol) of 3-, 9- (4- (tert-butyl group) phenyl) -3- (4,4,5,5- tetramethyl -1,3,
2- dioxaborolane -2- bases) carbazole (33mg, 1.27mmol), wet chemical (2mL, 2M), ethanol (20mL), first
In the mixed solution of benzene (20mL), reaction is heated to 90~110 DEG C and is stirred overnight.After being cooled to room temperature, mixed to reaction
Distilled water and separation of methylbenzene layer are added in thing, then with dichloromethane aqueous layer extracted three times.Organic layer anhydrous magnesium sulfate drying, mistake
Filter, separated after being evaporated under reduced pressure removing solvent with silicagel column, eluant, eluent is dichloromethane and ethyl acetate, and it is solid to obtain white
Body, yield are 89% (614mg).
1H NMR(300MHz,CDCl3,ppm):δ 9.58 (d, J=2.3Hz, 1H), 9.22 (dd, J=4.4,1.7Hz,
1H), 8.51 (dd, J=9.1,1.8Hz, 2H), 8.26 (dd, J=8.5,1.0Hz, 2H), 7.90 (d, J=8.8Hz, 1H),
7.86–7.78(m,2H),7.69–7.60(m,3H),7.60–7.43(m,5H),7.35(m,1H),1.51–1.40(s,9H).
Figure 10 is thermal activation delayed fluorescence (TADF) the material Phen-Cz- manufactured in the present embodiment based on 1,10- ferrosins
T-BuPh hydrogen nuclear magnetic resonance spectrogram.
Figure 11 is thermal activation delayed fluorescence (TADF) the material Phen-Cz- manufactured in the present embodiment based on 1,10- ferrosins
T-BuPh absorption and PL spectrum.The solid-state emission peak of material shows as deep blue emission in 444nm
Figure 12 is thermal activation delayed fluorescence (TADF) the material Phen-Cz- manufactured in the present embodiment based on 1,10- ferrosins
T-BuPh solvatochromism curve.With the increase of solvent polarity, material solution emission peak red shift, show depositing for CT states
.
Figure 13 is thermal activation delayed fluorescence (TADF) the material Phen-Cz- manufactured in the present embodiment based on 1,10- ferrosins
T-BuPh electrochemical profiles.The initial oxidation current potential of material is 1.2V
Figure 14 be the present embodiment electro-chemical test in ferrocene electrochemical profiles.
Figure 15 is thermal activation delayed fluorescence (TADF) the material Phen-Cz- manufactured in the present embodiment based on 1,10- ferrosins
Attenuation curve in toluene solutions of the t-BuPh after nitrogen deoxygenation.With reference to the Instrument response function in Figure 15 during corresponding test,
Show the presence of material delayed fluorescence.
Figure 16 is the Instrument response function in the attenuation curve test of the present embodiment.
Experimental phenomena：
Thermal activation delayed fluorescence (TADF) material Phen-Cz-t-BuPh manufactured in the present embodiment based on 1,10- ferrosins
Film obvious Enhancement of Fluorescence is showed after deoxygenation.
In the above-mentioned thermal activation delayed fluorescence material based on 1,10- ferrosins, the amino unit of aryl substitution can also be
Wherein R1、R4-R6Any one in the alkyl chain or oxyalkyl chain for being 1~12 for H, carbon number；
R2、R3Alkyl chain either any one in oxyalkyl chain or following structure for being 1~12 for H, carbon number：
Wherein R7、R8Any one in the alkyl chain or oxyalkyl chain for being 1-12 for H, carbon number.
Particularly, when R is
In it is a kind of when, can obtain dark blue photoemissive fluorescent material.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (3)
1. the thermal activation delayed fluorescence material based on 1,10- ferrosins, it is characterised in that the thermal activation delayed fluorescence material is
Phen-Cz-t-BuPh, there is following chemical constitution：
2. the preparation method of the thermal activation delayed fluorescence material based on 1,10- ferrosins described in claim 1, its feature exist
In the thermal activation delayed fluorescence material is Phen-Cz-t-BuPh, has following chemical constitution：
Its preparation method comprises the following steps：
(b1) 9- (4- tert-butyl-phenyls) -9H- carbazoles are prepared：Under nitrogen protection, tri-butyl phosphine is added to palladium, click
Azoles, in the toluene solution of bromine tert-butyl benzene and Anhydrous potassium carbonate, then reaction is heated to 90~100 DEG C and is stirred overnight；Treat
After reaction is cooled to room temperature, distilled water and separation of methylbenzene layer are added into reactant mixture, then with dichloromethane aqueous layer extracted；Have
Machine layer is separated after removing solvent with anhydrous magnesium sulfate drying, filtering, vacuum distillation with silicagel column, and eluant, eluent is petroleum ether,
Obtain white solid；
Wherein, carbazole, the mol ratio to bromine tert-butyl benzene, Anhydrous potassium carbonate, palladium, tri-butyl phosphine are 1：(1~1.3)：
(2~4)：(0.01~0.02)：(0.02-0.04)；
(b2) 3- bromo- 9- (4- tert-butyl-phenyls) -9H- carbazoles are prepared：Under the conditions of ice bath and lucifuge, to 9- (4- bromophenyls)-
NBS is added portionwise in the chloroform soln of 9H- carbazoles, after reacting at room temperature 2~3 hours, addition distilled water is used in combination into reaction
Dichloromethane extracts；Organic layer anhydrous magnesium sulfate drying, filtering, silica gel post separation is used after being evaporated under reduced pressure removing solvent, eluted
Agent is petroleum ether, obtains white solid；
Wherein, 9- (4- bromophenyls) -9H- carbazoles, NBS molar ratio are 1：1~1：0.95
(b3) 9- (4- tert-butyl-phenyls) -3- (4,4,5,5- tetramethyl -1,3,2- dioxaborolane -2- bases) -9H- is prepared
Carbazole：Under nitrogen protection, the bromo- 9- of 3- (4- bromophenyls) -9H- carbazoles are dissolved into anhydrous tetrahydro furan, are cooled to -70
~-80 DEG C, n-butyllithium solution is slowly added dropwise by syringe and kept for 15~20 minutes at such a temperature, then adds isopropyl
Epoxide pinacol borate；Slowly recover to room temperature and in N2It is stirred overnight under atmosphere；1~2mL second is added after the completion of question response
Alcohol terminating reaction, and after being evaporated under reduced pressure and removing solvent, dichloromethane and distilled water extraction are added, organic layer done with anhydrous magnesium sulfate
Dry, filtering, silica gel post separation is used after being evaporated under reduced pressure removing solvent, eluant, eluent is petroleum ether and dichloromethane, obtains white solid；
Wherein, the bromo- 9- of 3- (4- bromophenyls) -9H- carbazoles, n-BuLi, the molar ratio of isopropoxy pinacol borate
For 1：(1.1~1.3)：(1.3~1.5)；
(b4) prepare compound Phen-Cz-t-BuPh：Under nitrogen protection, by palladium, that tricyclohexyl phosphine is added to 3- is bromo-
1,10- phenanthrolines, 9- (4- (tert-butyl group) phenyl) -3- (4,4,5,5- tetramethyl -1,3,2- dioxaborolane -2- bases) -
9H- carbazoles, wet chemical, ethanol, toluene mixed solution in, reaction be heated to 90~110 DEG C and be stirred overnight；Treat cold
But to after room temperature, adding distilled water and separation of methylbenzene layer, then with dichloromethane aqueous layer extracted；Organic layer is done with anhydrous magnesium sulfate
Dry, filtering, separated after being evaporated under reduced pressure removing solvent with silicagel column, eluant, eluent is dichloromethane and ethyl acetate, is obtained white
Color solid；
Wherein, bromo- 1, the 10- phenanthrolines of 3-, 9- (4- (tert-butyl group) phenyl) -3- (4,4,5,5- tetramethyls -1,3,2- dioxo boras
Pentamethylene -2- bases) -9H- carbazoles, palladium, tricyclohexyl phosphine molar ratio be 1：(1.1~1.3)：(0.06~
0.09)：(0.12~0.18).
3. the application of the thermal activation delayed fluorescence material based on 1,10- ferrosins described in claim 1, it is characterised in that use
In preparing electroluminescent device.
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