CN114560871B - Synthesis method of selective substituted functionalized dithienyl imide luminescent material - Google Patents

Synthesis method of selective substituted functionalized dithienyl imide luminescent material Download PDF

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CN114560871B
CN114560871B CN202110415896.XA CN202110415896A CN114560871B CN 114560871 B CN114560871 B CN 114560871B CN 202110415896 A CN202110415896 A CN 202110415896A CN 114560871 B CN114560871 B CN 114560871B
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齐婷
屈敦帅
秦媛媛
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Abstract

The invention provides a synthesis method of a selective substituted functionalized dithienyl imide luminescent material, wherein the structural formula of the compound is as follows:
Figure 29436DEST_PATH_IMAGE001
in the formula R 1 Is an alkyl group; r 2 Hydrogen atoms and aryl, heterocyclic aryl, donor/acceptor groups in different ratios. The method takes dithiophene imide monomers as raw materials, selectively obtains a series of brominated dithiophene imide compounds by bromination reaction of the dithiophene imide monomers and different brominating reagents (liquid bromine, N-bromosuccinimide, 1,2-dibromotetrachloroethane) under different conditions (trifluoroacetic acid, sulfuric acid and lithium bis (trimethylsilyl) amide), and obtains a series of micromolecule luminescent materials by coupling aryl, heterocyclic aryl or electron donating/withdrawing groups through Suzuki or Stille reaction. Such small molecules are applicable to organic light emitting diodes.

Description

Synthesis method of selective substituted functionalized dithienyl imide luminescent material
Technical Field
The invention belongs to the field of organic semiconductor materials, and particularly relates to a synthetic method and properties of a series of selectively substituted functionalized dithiophene imide compounds. The compound has light emitting and conducting properties, and can be used as a light emitting layer or an electron/hole transport layer of an organic light emitting diode.
Background
Organic semiconductor materials are widely used in various optoelectronic devices, such as Organic Field Effect Transistors (OFETs), organic Light Emitting Diodes (OLEDs) and Organic Solar Cells (OSCs), due to their advantages of low production cost, abundant material types, simple preparation process, good flexibility, etc.
Depending on the type of carriers, organic semiconductor materials can be classified into p-type and n-type organic semiconductor materials. Compared with p-type organic semiconductor materials, n-type organic semiconductor materials have relatively slow development, low carrier mobility and few electron acceptor types.
The aromatic imide is a very important receptor structural unit, and shows great application potential of the aromatic imide in constructing n-type organic semiconductor materials, and mainly comprises Perylene Diimide (PDI), naphthalene Diimide (NDI), naphthalene diimide (NAI), dithiophene imide (BTI), pyromellitic diimide (PMDI), phthalimide (PhI), thieno (3,4-c) pyrrole-4,6-diketone (TPD), maleimide(MAI), etc. Among them, BTI has been synthesized for the first time since 2008, and has drawn a great deal of attention, and is applied to various organic photoelectric devices, and its structure is
Figure SMS_1
。
The application of BTI-based derivatives is mainly focused on the research of their polymers in OFETs and OSCs, while the application of BTI-based small molecules as light emitting materials in OLEDs is rarely reported. By isomerizing the sulfur element position in the BTI structural unit to form the monomer iBTI, multi-site substitution functionalization can be carried out, and the blank of the application of the BTI structural unit in the aspect of OLED can be hopefully filled. The structure of iBTI is
Figure SMS_2
。
The invention realizes the controllable synthesis of the iBTI structural unit in different substitution sites, develops a series of iBTI compounds, and can be used as a potential luminescent functional material to be applied to OLED.
Disclosure of Invention
The present invention aims to provide a method for the selective substitution of iBTI.
The invention takes the iBTI as a main body to carry out structural modification, and improves the solubility of the iBTI by introducing a flexible alkyl chain; the conjugation length is increased by introducing aromatic ring and other auxochromic groups or chromophoric groups to increase the delocalization capacity of pi system electron cloud, so that the electron transmission capacity and the fluorescence quantum efficiency are improved; by introducing different numbers of substituent groups at alpha-, alpha '-, beta-and beta' -positions, the configuration of the molecule is regulated, the chemical property, the solubility, the luminous performance and the electronic property of the molecule are changed, the application performance of the molecule is improved, and a series of iBTI compounds are obtained by design and synthesis.
Figure SMS_3
Figure SMS_4
Figure SMS_5
Figure SMS_6
Wherein R is 1 Is an alkyl group having 1 to 18 carbon atoms; r 2 Is a hydrogen atom,
Figure SMS_7
、
Figure SMS_8
、/>
Figure SMS_9
、/>
Figure SMS_10
、/>
Figure SMS_11
、
Figure SMS_12
、/>
Figure SMS_13
And the like electron donating groups.
The preparation method of the iBTI compound comprises the following steps:
(1) The iBTI was reacted with 4 equivalents of liquid bromine at room temperature for 24 hours using trifluoroacetic acid as a solvent. And adding the reaction system into an ice-water mixture containing sodium thiosulfate until the residual liquid bromine disappears, extracting with dichloromethane and water, drying an organic phase with anhydrous magnesium sulfate, and performing column chromatography separation on the crude product to obtain the iBTI-3Br. The reaction equation is as follows:
Figure SMS_14
(2) Under the condition of room temperature, the iBTI and 1.5 or 2.5 equivalent N-bromosuccinimide are added into a reactor, and the mixed acid of trifluoroacetic acid and concentrated sulfuric acid with the volume ratio of 1:1 is used as a solvent for reaction for 18 hours. Adding the reaction system into an ice water mixture, extracting with dichloromethane and water, drying an organic phase with anhydrous magnesium sulfate, and performing column chromatography separation on the crude product to obtain iBTI-beta-Br and iBTI-alpha, beta-2 Br. The reaction equation is as follows:
Figure SMS_15
(3) Adding brominated iBTI, an organic tin compound and tetrakis (triphenylphosphine) palladium into a reaction bottle, pumping inert gas for three times, injecting a redistilled toluene solvent, and carrying out reflux reaction at 110 ℃. And after the reaction is finished, naturally cooling to room temperature, extracting with dichloromethane and water, drying an organic phase with anhydrous magnesium sulfate, and performing column chromatography separation on a crude product to obtain the dithiophene imide compound. The reaction equation is as follows:
Figure SMS_16
(4) The ibbi bromide, the boronic acid compound and tetrakis (triphenylphosphine) palladium were added to a reaction flask, and after purging the inert gas three times, a mixed solvent (toluene: water: ethanol =3 = 1) was injected, and the reaction was refluxed at 110 ℃. And after the reaction is finished, naturally cooling to room temperature, extracting with dichloromethane and water, drying an organic phase with anhydrous magnesium sulfate, and performing column chromatography separation on the crude product to obtain the dithiophene imide compound. The reaction equation is as follows:
Figure SMS_17
。
the invention develops a series of organic electroluminescent layer materials by taking iBTI as a core. The synthesis method has the advantages of easily available raw materials, simple operation, short route, wide substrate range and the like. And according to the requirement, the required organic electroluminescent layer material can be quickly and flexibly designed, and the organic electroluminescent layer material can be widely applied to the field of organic photoelectricity.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Fig. 1 is a hydrogen spectrum of an organic electroluminescent layer material iBTI- β -CzPh described in example 1.
Fig. 2 is a carbon spectrum of an organic electroluminescent layer material iBTI- β -CzPh described in example 1.
Fig. 3 is a hydrogen spectrum of an organic electroluminescent layer material iBTI- α, β -2CzPh described in example 2.
Fig. 4 is a carbon spectrum diagram of an organic electroluminescent layer material iBTI- α, β -2CzPh described in example 2.
Fig. 5 is a hydrogen spectrum of an organic electroluminescent layer material iBTI-3CzPh described in example 3.
Fig. 6 is a carbon spectrum diagram of an organic electroluminescent layer material iBTI-3CzPh described in example 3.
FIG. 7 shows a hydrogen spectrum of an organic electroluminescent layer material iBTI- α, α -2CzPh according to example 3.
Fig. 8 is a carbon spectrum of an organic electroluminescent layer material iBTI- α, α -2CzPh described in example 3.
FIG. 9 is a UV absorption spectrum of the molecules described in examples 1-3 in methylene chloride solution.
FIG. 10 shows fluorescence emission spectra of the molecules of examples 1-3 in dichloromethane.
Detailed Description
Unless explicitly defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this subject matter pertains.
The present invention is further illustrated by the following examples, but is not limited to these examples.
Example 1: taking the synthesis of iBTI-beta-CzPh (R2 = CzPh) as an example, the structure is
Figure SMS_18
。
Step 1: synthesis of brominated iBTI (iBTI-. Beta. -Br and iBTI-. Alpha.,. Beta.' -2 Br) compounds.
Substitution reactions were performed with NBS or liquid bromine at room temperature. The reaction equation is
Figure SMS_19
。
Compound iBTI (582mg, 2.0mmol) and NBS (534mg, 3.0mmol) were placed in a reactor, and 4ml of TFA and 4ml of H were successively dropped 2 SO 4 . After stirring at room temperature for 20 hours, the reaction was slowly added to 50ml of an ice-water mixture. The crude product was isolated by column chromatography (PE: DCM = 4:1) using dichloromethane and water extracted three times, respectively, and the organic phase was dried over anhydrous magnesium sulfate to give iBTI-. Beta. -Br in 50.13% yield. 1 H NMR (400 MHz, CDCl 3 ) δ 8.53 (d,J= 5.5 Hz, 1H), 7.76 (s, 1H), 7.74 (d,J= 5.5 Hz, 1H), 4.13 (d,J= 7.3 Hz, 2H), 2.18 (dq,J= 13.9, 7.1 Hz, 1H), 0.94 (d,J= 6.8 Hz, 6H)。 13 C NMR (101 MHz, CDCl 3 ) δ=161.57, 161.17, 138.93, 138.65, 134.20, 133.32, 132.68, 132.27, 127.55, 109.51, 52.25, 27.45, 20.41。
Step 2: the compound iBTI- β -CzPh was synthesized.
The method comprises the following steps: a boric acid compound is used as a raw material, and the iBTI-beta-CZPh is synthesized by adopting a Suzuki coupling reaction. The reaction equation is
Figure SMS_20
。
Mixing iBTI-beta-Br (32.7mg, 0.1mmol), czPh-B (OH) 2 （28.7mg，0.1mmol）、Na 2 CO 3 (46.9mg, 0.45mmol) and Ph (PPh) 3 ) 4 (10 mg, 0.01mmol) was placed in a 10mL two-necked flask. Vacuumizing for more than 10min, and then pumping air for three times. The mixed solvent (toluene: water: ethanol = 3). The temperature is raised to 110 ℃, and the reaction is carried out for two hours. After the reaction system is cooled to room temperature, dichloromethane and pure water are used for extraction, anhydrous magnesium sulfate is used for drying an organic phase, and the crude product is subjected to column chromatography separation (PE: DCM = 4:1) to obtain white solid iBTI-beta-CzPh with the yield of 57%. 1 H NMR (400 MHz, CDCl 3 ) δ 8.17 (d,J= 7.7 Hz, 2H), 7.70 – 7.64 (m, 3H),7.57 (d,J= 8.2 Hz, 2H), 7.53 – 7.42 (m, 5H), 7.33 (td,J= 7.4, 6.9, 1.2 Hz, 2H), 6.76 (dd,J= 5.4, 0.8 Hz, 1H), 4.20 (d,J= 7.3 Hz, 2H), 2.25 (dt,J= 13.7, 6.8 Hz, 1H), 0.99 (d,J= 6.8 Hz, 6H)。 13 C NMR (101 MHz, CDCl 3 ) δ = 162.06, 142.41, 140.60, 139.93, 138.24, 138.02, 135.76, 134.05, 133.48, 132.98, 130.98, 128.27, 127.28, 126.19, 123.71, 120.61,120.43, 109.74, 52.20, 27.53, 20.48。
The method 2 comprises the following steps: tin compounds are used as raw materials, and Stille coupling reaction is adopted to synthesize the iBTI-beta-CzPh. The reaction equation is as follows:
Figure SMS_21
。
mixing iBTI-beta-Br (185mg, 0.5 mmol), czPh-SnBu 3 (292.8mg, 0.55mmol) and Pd (PPh) 3 ) 4 (57.8 mg, 0.05mmol) was charged into a 100ml two-necked round-bottomed flask, evacuated for 10min, purged with nitrogen three times, and injected with 30ml of toluene at room temperature. The mixture was warmed to 110 ℃ and stirred for three days, heating was stopped under nitrogen atmosphere, after it was cooled to room temperature, it was extracted with DCM in a fume hood, and the organic phase was dried over anhydrous magnesium sulfate. The crude product was subjected to column chromatography (PE: DCM = 2:1) to yield a white solid iBTI- β -CzPh with a yield of 63.65% (169.3 mg).
Example 2: to synthesize iBTI-alpha, beta' -2CZPh (R) 2 = CzPh) as an example, the structure is as
Figure SMS_22
。
In step 1 of this example, the equivalent of NBS was increased to 2.5, and the other steps of this step were the same as in example 1. The yield of iBTI-alpha, beta' -2Br was 58.10%. 1 H NMR (400 MHz, CDCl 3 ) δ 8.53 (s, 1H), 7.76 (s,1H), 4.10 (d,J= 7.4 Hz, 2H), 2.17 (dt,J= 13.8, 6.9 Hz, 1H), 0.93 (d,J= 6.7 Hz, 7H)。 13 C NMR (101 MHz, CDCl 3 ) δ = 160.75, 160.47, 140.01, 139.22, 134.51, 133.34, 133.26, 130.20, 122.56, 109.47, 52.26, 27.38, 20.37。
In step 2 of this exampleThe equivalent of the tin compound or boric acid compound was increased to 2.1, and the other steps of this step were the same as in example 1. The other steps were the same as in example 1 to prepare an iBTI- α, β' -CzPh as a yellow solid with a yield of 37% for method 1 and 61.03% for method 2. 1 H NMR (400 MHz, CDCl 3 ) δ 8.12 (m,J= 7.8, 2.3, 1.1 Hz, 4H), 7.80 – 7.73 (m, 3H), 7.67 (d,J= 8.3 Hz, 2H), 7.57 (d,J= 8.5 Hz, 2H), 7.52 – 7.45 (m, 4H), 7.40 – 7.27 (m, 8H), 7.21 (t,J= 7.5 Hz, 2H), 6.98 (s, 1H), 4.24 (d,J= 7.3 Hz, 2H), 2.30 (dt,J= 13.8, 6.9 Hz, 1H), 1.03 (d,J= 6.7 Hz, 6H)。 13 C NMR (101 MHz, CDCl 3 ) δ = 161.88, 161.56, 149.44, 142.39, 140.60, 140.38, 139.90, 138.78, 138.22, 137.04, 136.03, 134.97, 133.40,132.66, 131.30, 131.27, 127.52, 127.47, 127.25, 126.31, 126.22, 124.10, 123.71, 120.67, 120.57, 120.47, 109.86, 109.43, 52.22, 27.58, 20.53。
Example 3: taking the synthesis of iBTI-3CzPh and iBTI- α, α' -CzPh (R2 = CzPh) as examples, the structures are respectively:
Figure SMS_23
。
in step 1 of this example, 2.5 equivalents of NBS were replaced with 4 equivalents of liquid bromine, and the mixed acid was replaced with an equal volume of trifluoroacetic acid, and the other steps of this step were the same as in example 1. The yield of iBTI-3Br was 58.10%. 1 H NMR (400 MHz, CDCl 3 ) δ 8.52 (s, 1H), 4.08 (d,J= 7.4 Hz, 2H), 2.21 – 2.11 (m, 1H), 0.92 (d,J= 6.8 Hz, 6H)。 13 C NMR (101 MHz, CDCl 3 ) δ = 160.23, 140.32, 139.24, 132.84, 131.92, 129.98, 125.23, 122.65, 113.80, 52.28, 27.35, 20.33。
In step 2 of this example, the equivalent of tin compound was increased to 3.1, and the other steps of this step were the same as in example 1. The other steps were the same as in example 1, but were prepared by method 2, yielding yellow solids, iBTI-3CzPh and iBTI- α, α' -CzPh. The yield of iBTI-3CzPh was 62.28%. 1 H NMR (400 MHz, CDCl 3 ) δ 8.16 – 8.09 (m, 6H), 7.80 (d,J= 8.3 Hz, 2H), 7.68 – 7.64 (m, 2H), 7.62 – 7.54 (m, 6H), 7.48 (dd,J= 8.2, 4.6 Hz, 4H), 7.46 – 7.40 (m, 4H), 7.40 – 7.36 (m, 2H), 7.35 – 7.28 (m, 8H), 7.20 (t,J= 7.5 Hz, 2H), 6.90 (s, 1H), 4.28 (d,J= 7.4 Hz, 2H), 2.37 – 2.29 (m, 1H), 1.05 (d,J= 6.8 Hz, 6H)。 13 C NMR (101 MHz, CDCl 3 ) δ = 161.89, 161.61, 140.41, 140.34, 138.28, 137.80, 135.19, 132.61, 131.26, 130.97, 127.79, 127.46, 83 54zxft 5483, 126.39, 126.26, 126.21, 123.89, 123.77, 123.74, 123.69, 120.68, 120.51, 120.46, 109.87, 109.77, 109.31, 52.26, 27.62, 20.54. The yield of iBTI-alpha, alpha' -CzPh was 10%. 1 H NMR (400 MHz, CDCl 3 ) δ 8.16 (d,J= 7.7 Hz, 2H), 8.01 – 7.94 (m, 2H), 7.84 (s,1H), 7.74 – 7.68 (m, 2H), 7.53 – 7.39 (m, 4H), 7.36 – 7.28 (m, 2H), 4.24 (d,J= 7.3 Hz, 1H), 2.32 – 2.23 (m, 0H), 1.02 (d,J= 6.7 Hz, 3H)。 13 C NMR (101 MHz, CDCl 3 ) δ = 151.79, 140.53, 139.08,135.30, 131.49, 127.91, 127.67, 126.25, 123.75, 122.76, 120.58, 120.51, 109.80, 77.43, 77.12, 76.80, 51.97, 27.47, 20.52。

Claims (3)

1. A dithiophene imide compound is characterized by the following structural general formula:
Figure QLYQS_1
、
Figure QLYQS_2
、/>
Figure QLYQS_3
、/>
Figure QLYQS_4
wherein R is 1 Is an alkyl group having 1 to 18 carbon atoms; r is 2 Is->
Figure QLYQS_5
。
2. Use of the dithienimide compound of claim 1 in an emissive layer or an electron/hole transporting layer of an organic light emitting diode.
3. A method for selectively synthesizing a dithienimide compound as claimed in claim 1, characterized in that the method comprises the steps of:
step a:
a-1. Mixing iBTI
Figure QLYQS_6
Reacting with 4 equivalents of liquid bromine, reacting for 24 hours at room temperature by using trifluoroacetic acid as a solvent, adding a reaction system into an ice water mixture containing sodium thiosulfate until the residual liquid bromine disappears, extracting with dichloromethane and water, drying an organic phase by using anhydrous magnesium sulfate, and performing column chromatography separation on a crude product to obtain the tribromo-substituted dithiophene imide, wherein the structure of the dithiophene imide is as follows: />
Figure QLYQS_7
；
Or a-2, under the condition of room temperature, adding dithiophene imide and 1.5 or 2.5 equivalent N-bromosuccinimide into a reactor, reacting for 18 hours by taking mixed acid of trifluoroacetic acid and concentrated sulfuric acid with the volume ratio of 1:1 as a solvent, adding a reaction system into an ice water mixture, extracting by using dichloromethane and water, drying an organic phase by using anhydrous magnesium sulfate, and carrying out column chromatography separation on a crude product to obtain the beta-monobromo-substituted dithiophene imide, wherein the structure is as follows:
Figure QLYQS_8
and α, β -dibromo substituted dithiophene imides having the structure: />
Figure QLYQS_9
；
Step b:
b-1, adding the bromide obtained in the step a, an organic tin compound and tetrakis (triphenylphosphine) palladium into a reaction bottle, pumping inert gas for three times, injecting a redistilled toluene solvent, carrying out reflux reaction at 110 ℃, naturally cooling to room temperature after the reaction is finished, extracting with dichloromethane and water, drying an organic phase with anhydrous magnesium sulfate, and carrying out column chromatography separation on a crude product to obtain the dithienylimide compound as claimed in claim 1;
or b-2, adding the bromide obtained in the step a, the boric acid compound and tetrakis (triphenylphosphine) palladium into a reaction bottle, pumping inert gas for three times, injecting a mixed solvent, namely toluene, water and ethanol = 3.
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