CN114539291B - Intrinsic quinone type near infrared receptor small molecule, and preparation method and application thereof - Google Patents
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Abstract
The invention relates to an intrinsic quinone type near infrared receptor small molecule, which has the following structure:
wherein n is a positive integer selected from 1-3; q is a quinoid unit, D is an electron donor, and A is an electron acceptor. The structure of the intrinsic quinone near-infrared receptor small molecule provided by the invention can effectively improve the quinoid content of the conjugated framework and promote the delocalization of electron cloud on the conjugated framework, thereby expanding the photoresponse range to near-infrared band; the method is applied to the field of organic photodetectors, and has high responsivity and high detection rate at 1100nm, larger cut-off bandwidth and wide linear dynamic range. The preparation method provided by the invention has the advantages of simple process, high yield, flexible structure adjustment, low manufacturing cost, suitability for industrial production and the like.
Description
Technical Field
The invention relates to the field of organic photoelectricity, in particular to an intrinsic quinoid near infrared receptor small molecule, a preparation method and application thereof.
Background
Organic Photodetectors (OPDs) are organic photoelectric devices having a photoelectric conversion function, which can convert incident light into an electrical signal for output. Compared with the traditional inorganic semiconductor photoelectric detector, the OPDs have the advantages of low cost, low power consumption, capability of realizing solution processing, flexible device preparation and the like. Meanwhile, the active layer material with various molecular structures is benefited, and the detection range can be covered from an ultraviolet light wave band to an infrared light wave band. Light with the wavelength range of 780-2500nm is called near infrared light, and the near infrared light is taken as an important component of electromagnetic spectrum, and can be widely applied to navigation, aerospace, weapon detection, night vision and other aspects in military; the method can be widely applied to communication, atmosphere monitoring, pollution detection, weather and other aspects in civil use. However, the current widely-used silicon photodetectors have a detection range of only 1100nm, so in order to achieve effective detection of near infrared light exceeding 1100nm and become a potential substitute for silicon photodetectors, the absorption spectrum of the active layer material in OPDs needs to exceed 1100nm.
The active layer of bulk heterojunction OPDs is typically composed of a blend of electron-rich p-type material and electron-deficient n-type material. Since n-type fullerene receptors and derivatives thereof have excellent electron transport properties in three dimensions, researchers have been widely used as n-type materials in combination with various near infrared p-type materials in near infrared organic photodetectors. However, fullerenes and derivatives thereof have the disadvantage that the structure is difficult to adjust and the energy level is difficult to adjust, and it is difficult to achieve good energy level matching with a wide variety of near infrared donor materials, thereby resulting in poor exciton dissociation and charge collection efficiency. Finally, OPDs devices based on near infrared p-type donor materials and n-type fullerene receptors tend to have poor External Quantum Efficiency (EQE), responsivity (R) and detection rate (D x) (adv.funct. Mater.2014,24,7605-7612;Adv.Mater.2020,2003818;Adv.Optical Mater.2018,1800038;J.Mater.Chem.C 2018,6,11645-11650). For example, zhiyuanWang et al in 2018 reported a near infrared P-type donor material P2 with an ultra-narrow optical bandgap (adv. Optical mate. 2018, 1800038). With P2 and fullerene acceptor PC 71 The detection range of the organic photodetector with BM as an active layer material exceeds 1400nm, but after the device is applied with-2V bias to promote exciton dissociation, the EQE response value at the wavelength of 1100nm is only 5%, and the corresponding responsivity is only 0.04A/W.
Therefore, it is needed to find a technical solution to solve the technical problems in the art.
Disclosure of Invention
In recent years, n-type non-fullerene receptor small molecules represented by ITIC and Y6 are rapidly developed, and near infrared absorption and continuously adjustable energy levels can be realized through reasonable molecular structure design. For organic semiconductors, the introduction of intrinsic quinoid units by structural design is an effective strategy to achieve near infrared absorption. Under the driving action of the aromatic stabilization energy, the intrinsic quinoid structure can obviously improve the quinoid content in the conjugated framework, thereby reducing the optical band gap. Meanwhile, all the constituent units of the modularized non-fullerene receptor small molecule are connected through single bonds, so that the method has the advantages of low synthesis complexity and low cost, but no modularized non-fullerene receptor small molecule with the absorption spectrum exceeding 1200nm is reported at present.
Therefore, the invention utilizes the advantages of reduced band gap and low complexity of the modularized structure by the intrinsic quinoid structure, takes the intrinsic quinoid Q unit as the core unit, firstly invents the intrinsic quinoid near-infrared receptor small molecule, one of which is near-infrared modularized non-fullerene receptor small molecule BDP4Cl with an A-D-Q-D-A structure, the absorption spectrum of which exceeds 1400nm, the EQE value of the photoelectric detector based on the photoelectric detector at 1100nm is up to 16.40% under the condition of not applying any bias, and the corresponding responsivity and detection rate are 0.15A/W and 7.7X10 respectively 11 Jones. And the BDP4 Cl-based detector has a large cut-off bandwidth (65 kHz) and a wide linear dynamic range (70 dB) for 1050nm incident light, so that the high-performance near-infrared organic photoelectric detector is realized.
Furthermore, the invention designs and synthesizes a series of A-D-Q-D-A near infrared small molecule acceptor materials with the intrinsic quinoid unit as a central core, and the near infrared organic photoelectric detector prepared based on the materials also realizes high-performance detection of near infrared light exceeding 1100nm, which proves that the technical scheme of the invention has wide universality and feasibility.
In the comparative examples of the examples section in the description of the present invention, it can be seen that the detection range of the non-fullerene acceptor small molecule DC4Cl of the A-D-D-A structure containing no intrinsic quinoid Q unit is within 1100nm in comparison. Further, non-fullerene acceptor small molecules DPPO4Cl and IIDCN with similar structures A-D-A-D-A, but with core structures incapable of forming intrinsic quinone Q units, can achieve EQE response spectra exceeding 1100nm, but with 0V bias, the EQE response at 1100nm is only about 1%. And, despite the introduction of the strongly electron withdrawing unit BTT as a nuclear structure, it is also possible to realize an EQE response spectrum exceeding 1100nm, and the EQE response at 1100nm is only 2% at 0V bias.
In the above comparative examples, the core structure was not able to effectively form an intrinsic quinoid structure. This illustrates that the introduction of an intrinsic quinoid Q unit is an effective method for inventing high performance near infrared modular non-fullerene receptor small molecules.
It is an object of the present invention to disclose an intrinsic quinoid near infrared receptor small molecule.
An intrinsic quinoid near infrared receptor small molecule having the structure:
wherein, the liquid crystal display device comprises a liquid crystal display device,
n is a positive integer selected from 1-3;
q is a quinone-type unit,
d is an electron donor, A is an electron acceptor;
the quinoid unit is selected from the following structures:
wherein X is selected from any one of fluorine, chlorine, bromine, iodine, cyano and trifluoromethyl;
y is selected from any one of oxygen, sulfur and selenium;
R 17 -R 20 the group is selected from any one of hydrogen, fluorine atom, chlorine atom, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 ester group and C6-C30 aryl-C4-C30 heteroaryl;
wherein all hydrogen atoms on the C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 ester, C6-C30 aryl or C4-C30 heteroaryl groups are unsubstituted,
alternatively, one or more hydrogen atoms on the C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 ester, C6-C30 aryl or C4-C30 heteroaryl group are substituted with other elements.
Further, the electron donor is selected from the following structures:
wherein X is selected from any one of fluorine, chlorine, bromine, iodine and cyano;
y is selected from any one of oxygen, sulfur and selenium;
z is selected from any one of carbon, silicon and germanium;
R 11 -R 16 the group is selected from any one of hydrogen, fluorine atom, chlorine atom, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 ester group, C6-C30 aryl and C4-C30 heteroaryl;
wherein all hydrogen atoms on the C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 ester, C6-C30 aryl, C4-C30 heteroaryl groups are unsubstituted,
alternatively, one or more hydrogen atoms on the C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 ester, C6-C30 aryl, C4-C30 heteroaryl groups are substituted with other elements.
Further, the electron acceptor is selected from the following structures:
wherein X is selected from any one of fluorine, chlorine, bromine, iodine and cyano;
y is selected from any one of oxygen, sulfur and selenium;
z is selected from any one of carbon, silicon and germanium;
R 11 -R 16 radicals (C)Any one selected from hydrogen, fluorine atom, chlorine atom, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 ester group, C6-C30 aryl and C4-C30 heteroaryl;
wherein all hydrogen atoms on the C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 ester, C6-C30 aryl, C4-C30 heteroaryl groups are unsubstituted,
alternatively, one or more hydrogen atoms on the C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 ester, C6-C30 aryl, C4-C30 heteroaryl groups are substituted with other elements.
Further, n is 1.
Another object of the present invention is to disclose a method for preparing the above-mentioned intrinsic quinoid near infrared receptor small molecule, comprising the steps of:
s1, reacting a monomer of a quinoid unit with a monomer of an electron donor under a catalyst to obtain an intermediate;
s2, formylating the intermediate to obtain a formylated intermediate;
s3, reacting the formylated intermediate with an electron acceptor monomer, and then purifying.
Further, the molar ratio of monomer of the quinoid unit to monomer of the electron donor is 1:2 to 1:3.
Further, the catalyst is selected from palladium-based catalysts.
Another object of the invention is to disclose the use of the above-mentioned intrinsic quinone type near infrared receptor small molecules in organic photodetectors.
Further, the intrinsic quinoid near-infrared receptor small molecule comprises an organic compound layer in the organic photodetector, wherein the organic compound layer comprises a photosensitive layer, and the photosensitive layer contains the intrinsic quinoid near-infrared receptor small molecule.
Further, the organic compound layer further comprises at least one of a hole transport layer and an electron transport layer.
The beneficial effects of the invention are as follows:
1. the structure of the intrinsic quinone near-infrared receptor small molecule provided by the invention can effectively improve the quinoid content of the conjugated framework and promote the delocalization of electron cloud on the conjugated framework, thereby expanding the photoresponse range to near-infrared band; the method is applied to the field of organic photodetectors, and has high responsivity and high detection rate at 1100nm, larger cut-off bandwidth and wide linear dynamic range.
2. The preparation method provided by the invention has the advantages of simple process, high yield, flexible structure adjustment, low manufacturing cost, suitability for industrial production and the like.
Drawings
FIG. 1 is a schematic diagram of the chemical structure of PBT 7-Th.
FIG. 2 is a schematic diagram of the structure of an organic photodetector with a near infrared receptor small molecule blended with PTB7-Th as an active layer.
FIG. 3 is an EQE curve of an organic photodetector with a near infrared receptor small molecule blended with PTB7-Th as the active layer.
FIG. 4 is a plot of responsivity of an organic photodetector with a near infrared receptor small molecule blended with PTB7-Th as the active layer.
Fig. 5 is a graph of dark current of an organic photodetector with a near infrared receptor small molecule blended with PTB7-Th as an active layer.
FIG. 6 is a graph showing the detection rate of an organic photodetector using a near infrared receptor small molecule blended with PTB7-Th as an active layer.
FIG. 7 shows the cut-off bandwidths of organic photodetectors using the near infrared receptor small molecules obtained in examples 1 to 3 and comparative example 4 blended with PTB7-Th as an active layer.
FIG. 8 shows the linear dynamic range of organic photodetectors using the near infrared receptor small molecules obtained in examples 1 to 3 and comparative example 4 blended with PTB7-Th as the active layer.
Detailed Description
The invention is described in further detail below with reference to the drawings and examples, but the embodiments and the protection of the invention are not limited thereto. It should be noted that the following processes, if not specifically described in detail, can be realized or understood by those skilled in the art with reference to the prior art.
Practice of the present invention may employ conventional techniques of organic chemistry within the skill of the relevant art. In the following examples, efforts are made to ensure accuracy with respect to numbers used (including amounts, temperature, reaction time, etc.), but some experimental errors and deviations should be accounted for. The temperatures used in the examples below are in degrees Celsius and the pressure is at or near atmospheric. The solvents used were analytically or chromatographically pure, and all reactions were carried out under an inert gas atmosphere. All reagents were obtained commercially unless otherwise indicated.
Example 1
An intrinsic quinoid near infrared receptor small molecule BDP4Cl with the structural formula shown as follows:
the synthetic route is as follows:
(1) Synthesis of Compound 3
Compound 1 (150 mg,0.29 mmol), compound 2 (608 mg,0.88 mmol) and palladium tetraphenylphosphine (16 mg,0.0087 mmol) were dissolved in a mixed solvent of 4ml toluene and 0.4ml DMF under nitrogen atmosphere. Reflux-reacting at 110 deg.c for 24 hr, cooling to room temperature, extracting with dichloromethane, washing the organic phase with saturated saline solution, drying with anhydrous magnesium sulfate, and separating and purifying with column chromatographic separation to obtain green painted product in 70% yield.
(2) Synthesis of Compound 4
Super-dry phosphorus oxychloride (140 mg,0.91 mmol) and super-dry DMF (209 mg,2.86 mmol) were stirred at 0deg.C for 30min under nitrogen atmosphere. To the reaction flask was added dropwise compound 3 (249 mg,0.22 mmol) dissolved in 6ml of ultra-dry 1, 2-dichloroethane. The temperature is raised to 90 ℃ to react for 12 hours. Adding saturated sodium bicarbonate water solution, stirring for 2 hr, cooling to room temperature, extracting with dichloromethane, washing organic phase with saturated saline water, drying with anhydrous magnesium sulfate, and separating and purifying by column chromatography to obtain blue paint product with 75% yield.
(3) Synthesis of BDP4Cl
Compound 4 (250 mg,0.206 mmol) and compound 5 (217 mg, 0.706 mmol) were dissolved in 13ml of chloroform under nitrogen atmosphere, and 1.3ml of ultra-dry pyridine was added to react at 65℃for 1h. The reaction solution was concentrated and settled in 200ml of anhydrous methanol, and the crude product solid was obtained by suction filtration. And separating and purifying by adopting a column chromatography separation method to obtain a black solid product with metallic luster, wherein the yield is 90%.
Example 2
An intrinsic quinoid near infrared receptor small molecule BDPT4NF, the structural formula of which is shown as follows:
the synthetic route is as follows:
(1) Synthesis of Compound 7
Compound 6 (200 mg,0.53 mmol), compound 2 (1.10 g,1.59 mmol) and palladium tetraphenylphosphine (61 mg,0.03 mmol) were dissolved in a mixed solvent of 5ml toluene and 0.5ml DMF under nitrogen atmosphere. Reflux-reacting at 110 deg.c for 24 hr, cooling to room temperature, extracting with dichloromethane, washing the organic phase with saturated saline solution, drying with anhydrous magnesium sulfate, and separating and purifying with column chromatographic separation to obtain green painted product in 72% yield.
(2) Synthesis of Compound 8
Super-dry phosphorus oxychloride (233 mg,1.52 mmol) and super-dry DMF (361 mg,4.94 mmol) were stirred at 0deg.C for 30min under nitrogen atmosphere. To the reaction flask was added dropwise compound 7 (389 mg,0.38 mmol) dissolved in 10ml of ultra-dry 1, 2-dichloroethane. The temperature is raised to 90 ℃ to react for 12 hours. Adding saturated sodium bicarbonate water solution, stirring for 2 hr, cooling to room temperature, extracting with dichloromethane, washing organic phase with saturated saline water, drying with anhydrous magnesium sulfate, and separating and purifying by column chromatography to obtain blue paint product with yield of 80%.
(3) Synthesis of BDPT4NF
Compound 8 (327 mg,0.30 mmol) and compound 9 (252 mg,0.90 mmol) were dissolved in 13ml of chloroform under nitrogen atmosphere, and 1.3ml of ultra-dry pyridine was added to react at 65℃for 1h. The reaction solution was concentrated and settled in 200ml of anhydrous methanol, and the crude product solid was obtained by suction filtration. And separating and purifying by adopting a column chromatography separation method to obtain a black solid product with metallic luster, wherein the yield is 90%.
Example 3
An intrinsic quinoid near infrared receptor small molecule BPDO4Cl, the structural formula of which is shown as follows:
the synthetic route is as follows:
(1) Synthesis of Compound 12
Compound 10 (300 mg,0.45 mmol), compound 11 (954 mg,1.35 mmol) and tetrakis triphenylphosphine palladium (55 mg,0.03 mmol) were dissolved in a mixed solvent of 6ml toluene and 0.6ml DMF under nitrogen. Reflux-reacting at 110 deg.c for 24 hr, cooling to room temperature, extracting with dichloromethane, washing the organic phase with saturated saline solution, drying with anhydrous magnesium sulfate, and separating and purifying with column chromatographic separation to obtain green painted product in 65% yield.
(2) Synthesis of Compound 13
Super-dry phosphorus oxychloride (178 mg,1.16 mmol) and super-dry DMF (275 mg,3.77 mmol) were stirred at 0deg.C for 30min under nitrogen. To the reaction flask was added dropwise compound 12 (3836 mg,0.29 mmol) dissolved in 8ml of ultra-dry 1, 2-dichloroethane. The temperature is raised to 90 ℃ to react for 12 hours. Saturated sodium bicarbonate aqueous solution is added, stirring is continued for 2 hours, cooling is carried out to room temperature, dichloromethane extraction is carried out, an organic phase is washed by saturated saline water, drying is carried out by anhydrous magnesium sulfate, and a blue paint-like product is obtained after separation and purification by a column chromatography separation method, and the yield is 78%.
(3) Synthesis of BPDO4Cl
Compound 13 (319 mg,0.23 mmol) and compound 5 (201 mg,0.92 mmol) were dissolved in 13ml of chloroform under nitrogen atmosphere, and 1.3ml of ultra-dry pyridine was added to react at 65℃for 1h. The reaction solution was concentrated and settled in 200ml of anhydrous methanol, and the crude product solid was obtained by suction filtration. And separating and purifying by adopting a column chromatography separation method to obtain a black solid product with metallic luster, wherein the yield is 90%.
Example 4
An intrinsic quinoid near infrared receptor small molecule BDPO4Cl with the structural formula shown as follows:
the synthetic route is as follows:
(1) Synthesis of Compound 14
Compound 1 (230 mg,0.45 mmol), compound 11 (954 mg,1.35 mmol) and tetrakis triphenylphosphine palladium (55 mg,0.03 mmol) were dissolved in a mixed solvent of 6ml toluene and 0.6ml DMF under nitrogen. Reflux-reacting at 110 deg.c for 24 hr, cooling to room temperature, extracting with dichloromethane, washing the organic phase with saturated saline solution, drying with anhydrous magnesium sulfate, and separating and purifying with column chromatographic separation to obtain green painted product in 60% yield.
(2) Synthesis of Compound 15
Super-dry phosphorus oxychloride (178 mg,1.16 mmol) and super-dry DMF (275 mg,3.77 mmol) were stirred at 0deg.C for 30min under nitrogen. To the reaction flask was added dropwise compound 14 (356 mg,0.30 mmol) dissolved in 8ml of ultra-dry 1, 2-dichloroethane. The temperature is raised to 90 ℃ to react for 12 hours. Adding saturated sodium bicarbonate water solution, stirring for 2 hr, cooling to room temperature, extracting with dichloromethane, washing organic phase with saturated saline water, drying with anhydrous magnesium sulfate, and separating and purifying by column chromatography to obtain blue paint product with 82% yield.
(3) Synthesis of BDPO4Cl
Compound 15 (248 mg,0.20 mmol) and compound 5 (210 mg,0.80 mmol) were dissolved in 13ml of chloroform under nitrogen atmosphere, and 1.3ml of ultra-dry pyridine was added to react at 65℃for 1h. The reaction solution was concentrated and settled in 200ml of anhydrous methanol, and the crude product solid was obtained by suction filtration. And separating and purifying by adopting a column chromatography separation method to obtain a black solid product with metallic luster, wherein the yield is 91%.
Example 5
An intrinsic quinoid near infrared receptor small molecule BDTDO4Cl with the structural formula shown as follows:
the synthetic route is as follows:
(1) Synthesis of Compound 16
Compound 6 (170 mg,0.45 mmol), compound 11 (954 mg,1.35 mmol) and tetrakis triphenylphosphine palladium (55 mg,0.03 mmol) were dissolved in a mixed solvent of 6ml toluene and 0.6ml DMF under nitrogen. Reflux-reacting at 110 deg.c for 24 hr, cooling to room temperature, extracting with dichloromethane, washing the organic phase with saturated saline solution, drying with anhydrous magnesium sulfate, and separating and purifying with column chromatographic separation to obtain green painted product in 55% yield.
(2) Synthesis of Compound 17
Super-dry phosphorus oxychloride (178 mg,1.16 mmol) and super-dry DMF (275 mg,3.77 mmol) were stirred at 0deg.C for 30min under nitrogen. To the reaction flask was added dropwise compound 16 (305 mg,0.29 mmol) dissolved in 8ml of ultra-dry 1, 2-dichloroethane. The temperature is raised to 90 ℃ to react for 12 hours. Adding saturated sodium bicarbonate water solution, stirring for 2 hr, cooling to room temperature, extracting with dichloromethane, washing organic phase with saturated saline water, drying with anhydrous magnesium sulfate, and separating and purifying by column chromatography to obtain blue paint product with 75% yield.
(3) Synthesis of BDTDO4Cl
Compound 17 (255 mg,0.23 mmol) and compound 5 (242 mg,0.92 mmol) were dissolved in 13ml of chloroform under nitrogen atmosphere, and 1.3ml of ultra-dry pyridine was added to react at 65℃for 1h. The reaction solution was concentrated and settled in 200ml of anhydrous methanol, and the crude product solid was obtained by suction filtration. And separating and purifying by adopting a column chromatography separation method to obtain a black solid product with metallic luster, wherein the yield is 93%.
Example 6
An intrinsic quinoid near infrared receptor small molecule TQTP2F, the structural formula of which is shown as follows:
the synthetic route is as follows:
(1) Synthesis of Compound 20
Compound 18 (308 mg,0.45 mmol), compound 19 (783 mg,1.35 mmol) and palladium tetraphenylphosphine (55 mg,0.03 mmol) were dissolved in a mixed solvent of 6ml toluene and 0.6ml DMF under a nitrogen atmosphere. Reflux-reacting at 110 deg.c for 24 hr, cooling to room temperature, extracting with dichloromethane, washing the organic phase with saturated saline solution, drying with anhydrous magnesium sulfate, and separating and purifying with column chromatographic separation to obtain green painted product in 66% yield.
(2) Synthesis of Compound 21
Super-dry phosphorus oxychloride (178 mg,1.16 mmol) and super-dry DMF (275 mg,3.77 mmol) were stirred at 0deg.C for 30min under nitrogen. To the reaction flask was added dropwise compound 20 (284 mg,0.29 mmol) dissolved in 8ml of ultra-dry 1, 2-dichloroethane. The temperature is raised to 90 ℃ to react for 12 hours. Saturated sodium bicarbonate aqueous solution is added, stirring is continued for 2 hours, cooling is carried out to room temperature, dichloromethane extraction is carried out, an organic phase is washed by saturated saline water, drying is carried out by anhydrous magnesium sulfate, and a blue paint-like product is obtained after separation and purification by a column chromatography separation method, and the yield is 88%.
(3) Synthesis of TQTP2F
Compound 21 (255 mg,0.23 mmol) and compound 22 (211 mg,0.92 mmol) were dissolved in 13ml of chloroform under nitrogen atmosphere, and 1.3ml of ultra-dry pyridine was added to react at 65℃for 1h. The reaction solution was concentrated and settled in 200ml of anhydrous methanol, and the crude product solid was obtained by suction filtration. And separating and purifying by adopting a column chromatography separation method to obtain a black solid product with metallic luster, wherein the yield is 88%.
Example 7
An intrinsic quinoid near infrared receptor small molecule TQFCN having the structural formula shown below:
the synthetic route is as follows:
(1) Synthesis of Compound 24
Compound 18 (308 mg,0.45 mmol), compound 23 (1406 mg,1.35 mmol) and palladium tetraphenylphosphine (55 mg,0.03 mmol) were dissolved in a mixed solvent of 6ml toluene and 0.6ml DMF under nitrogen atmosphere. Reflux-reacting at 110 deg.c for 24 hr, cooling to room temperature, extracting with dichloromethane, washing the organic phase with saturated saline solution, drying with anhydrous magnesium sulfate, and separating and purifying with column chromatographic separation to obtain green painted product in 75% yield.
(2) Synthesis of Compound 25
Super-dry phosphorus oxychloride (178 mg,1.16 mmol) and super-dry DMF (275 mg,3.77 mmol) were stirred at 0deg.C for 30min under nitrogen. To the reaction flask was added dropwise compound 24 (390 mg,0.29 mmol) dissolved in 8ml of ultra-dry 1, 2-dichloroethane. The temperature is raised to 90 ℃ to react for 12 hours. Adding saturated sodium bicarbonate water solution, stirring for 2 hr, cooling to room temperature, extracting with dichloromethane, washing organic phase with saturated saline water, drying with anhydrous magnesium sulfate, and separating and purifying by column chromatography to obtain blue paint product with 75% yield.
(3) TQFCN synthesis
Compound 25 (325 mg,0.23 mmol) and compound 26 (201 mg,0.92 mmol) were dissolved in 13ml of chloroform under nitrogen atmosphere, and 1.3ml of ultra-dry pyridine was added to react at 65℃for 1h. The reaction solution was concentrated and settled in 200ml of anhydrous methanol, and the crude product solid was obtained by suction filtration. And separating and purifying by adopting a column chromatography separation method to obtain a black solid product with metallic luster, wherein the yield is 92%.
Example 8
An intrinsic quinoid near infrared receptor small molecule IIDTCN having the structural formula shown below:
the synthetic route is as follows:
(1) Synthesis of Compound 28
Compound 27 (293 mg,0.45 mmol), compound 2 (932 mg,1.35 mmol) and palladium tetraphenylphosphine (55 mg,0.03 mmol) were dissolved in a mixed solvent of 6ml toluene and 0.6ml DMF under nitrogen atmosphere. Reflux-reacting at 110 deg.c for 24 hr, cooling to room temperature, extracting with dichloromethane, washing the organic phase with saturated saline solution, drying with anhydrous magnesium sulfate, and separating and purifying with column chromatographic separation to obtain green painted product in 70% yield.
(2) Synthesis of Compound 29
Super-dry phosphorus oxychloride (178 mg,1.16 mmol) and super-dry DMF (275 mg,3.77 mmol) were stirred at 0deg.C for 30min under nitrogen. To the reaction flask was added dropwise compound 28 (375 mg,0.29 mmol) dissolved in 8ml of ultra-dry 1, 2-dichloroethane. The temperature is raised to 90 ℃ to react for 12 hours. Saturated aqueous sodium bicarbonate solution was added and stirred for 2 hours, then cooled to room temperature, extracted with dichloromethane, the organic phase was washed with saturated brine, dried over anhydrous magnesium sulfate, and separated and purified by column chromatography to give a blue lacquer-like product in 79% yield.
(3) Synthesis of IIDTCN
Compound 29 (311 mg,0.23 mmol) and compound 26 (201 mg,0.92 mmol) were dissolved in 13ml of chloroform under nitrogen atmosphere, and 1.3ml of ultra-dry pyridine was added to react at 65℃for 1h. The reaction solution was concentrated and settled in 200ml of anhydrous methanol, and the crude product solid was obtained by suction filtration. And separating and purifying by adopting a column chromatography separation method to obtain a black solid product with metallic luster, wherein the yield is 88%.
Example 9
An intrinsic quinoid near infrared receptor small molecule IIDTN2F, having the structural formula shown below:
the synthetic route is as follows:
(1) Synthesis of Compound 30
Compound 27 (293 mg,0.45 mmol), compound 19 (783 mg,1.35 mmol) and palladium tetraphenylphosphine (55 mg,0.03 mmol) were dissolved in a mixed solvent of 6ml toluene and 0.6ml DMF under nitrogen atmosphere. Reflux-reacting at 110 deg.c for 24 hr, cooling to room temperature, extracting with dichloromethane, washing the organic phase with saturated saline solution, drying with anhydrous magnesium sulfate, and separating and purifying by column chromatography to obtain green painted product in 53% yield.
(2) Synthesis of Compound 31
Super-dry phosphorus oxychloride (178 mg,1.16 mmol) and super-dry DMF (275 mg,3.77 mmol) were stirred at 0deg.C for 30min under nitrogen. To the reaction flask was added dropwise compound 30 (327 mg,0.29 mmol) dissolved in 8ml of ultra-dry 1, 2-dichloroethane. The temperature is raised to 90 ℃ to react for 12 hours. Saturated sodium bicarbonate aqueous solution is added, stirring is continued for 2 hours, cooling is carried out to room temperature, dichloromethane extraction is carried out, an organic phase is washed by saturated saline water, drying is carried out by anhydrous magnesium sulfate, and a blue paint-like product is obtained after separation and purification by a column chromatography separation method, and the yield is 74%.
(3) Synthesis of IIDTN2F
Compound 31 (260 mg,0.23 mmol) and compound 9 (257 mg,0.92 mmol) were dissolved in 13ml of chloroform under nitrogen atmosphere, and 1.3ml of ultra-dry pyridine was added to react at 65℃for 1h. The reaction solution was concentrated and settled in 200ml of anhydrous methanol, and the crude product solid was obtained by suction filtration. And separating and purifying by adopting a column chromatography separation method to obtain a black solid product with metallic luster, wherein the yield is 93%.
Comparative example 1
A small receptor molecule DC4Cl that does not contain an intrinsic quinoid unit, having the structural formula:
the synthetic route is as follows:
(1) Synthesis of Compound 33
Compound 32 (800 mg,1.86 mmol), pdCl was reacted under nitrogen atmosphere 2 (PhCN) 2 (22 mg,0.056 mmol), potassium fluoride (216 mg,3.72 mmol) and silver nitrate (630 mg,3.72 mmol) were dissolved in 6ml of ultra-dry DMSO and stirred overnight at 60 ℃. Cooled to room temperature, extracted with dichloromethane, and the organic phase was washed with saturated saline, dried over anhydrous magnesium sulfate, and separated and purified by column chromatography to give a red solid product in 60% yield.
(2) Synthesis of DC4Cl
Compound 33 (300 mg,0.35 mmol) and compound 5 (367 mg,1.4 mmol) were dissolved in 15ml of chloroform under nitrogen atmosphere, and 1.5ml of ultra-dry pyridine was added to react at 65℃for 1h. The reaction solution was concentrated and settled in 200ml of anhydrous methanol, and the crude product solid was obtained by suction filtration. Separating and purifying by column chromatography to obtain blue-black solid product with metallic luster, with a yield of 90%.
Comparative example 2
A near infrared receptor small molecule DPPO4Cl that does not contain an intrinsic quinoid structure, having the structural formula:
the synthetic route is as follows:
(1) Synthesis of Compound 35
Super-dry phosphorus oxychloride (140 mg,0.91 mmol) and super-dry DMF (209 mg,2.86 mmol) were stirred at 0deg.C for 30min under nitrogen atmosphere. To the reaction flask was added dropwise compound 34 (262 mg,0.22 mmol) dissolved in 6ml of ultra-dry 1, 2-dichloroethane. The temperature is raised to 90 ℃ to react for 12 hours. Adding saturated sodium bicarbonate water solution, stirring for 2 hr, cooling to room temperature, extracting with dichloromethane, washing organic phase with saturated saline solution, drying with anhydrous magnesium sulfate, and separating and purifying by column chromatography to obtain product with 75% yield.
(2) Synthesis of DPPO4Cl
Compound 35 (255 mg,0.206 mmol) and compound 5 (217 mg, 0.706 mmol) were dissolved in 13ml of chloroform under nitrogen atmosphere, and 1.3ml of ultra-dry pyridine was added to react at 65℃for 1h. The reaction solution was concentrated and settled in 200ml of anhydrous methanol, and the crude product solid was obtained by suction filtration. And separating and purifying by adopting a column chromatography separation method to obtain a black solid product with metallic luster, wherein the yield is 90%.
Comparative example 3
A near infrared receptor small molecule IIDCN not comprising an intrinsic quinoid structure, having the structural formula:
the synthetic route is as follows:
(1) Synthesis of Compound 37
Compound 36 (170 mg,0.29 mmol), compound 2 (608 mg,0.88 mmol) and palladium tetraphenylphosphine (16 mg,0.0087 mmol) were dissolved in a mixed solvent of 4ml toluene and 0.4ml DMF under nitrogen atmosphere. Reflux-reacting at 110 deg.c for 24 hr, cooling to room temperature, extracting with dichloromethane, washing the organic phase with saturated saline solution, drying with anhydrous magnesium sulfate, and separating and purifying with column chromatography to obtain product in 68% yield.
(2) Synthesis of Compound 38
Super-dry phosphorus oxychloride (140 mg,0.91 mmol) and super-dry DMF (209 mg,2.86 mmol) were stirred at 0deg.C for 30min under nitrogen atmosphere. To the reaction flask was added dropwise compound 37 (270 mg,0.22 mmol) dissolved in 6ml of ultra-dry 1, 2-dichloroethane. The temperature is raised to 90 ℃ to react for 12 hours. Adding saturated sodium bicarbonate water solution, stirring for 2 hr, cooling to room temperature, extracting with dichloromethane, washing organic phase with saturated saline solution, drying with anhydrous magnesium sulfate, and separating and purifying by column chromatography to obtain product with 80% yield.
(3) Synthesis of IIDCN
Compound 38 (260 mg,0.206 mmol) and compound 22 (190 mg,0.206 mmol) were dissolved in 13ml of chloroform under nitrogen atmosphere, and 1.3ml of ultra-dry pyridine was added to react at 65℃for 1h. The reaction solution was concentrated and settled in 200ml of anhydrous methanol, and the crude product solid was obtained by suction filtration. And separating and purifying by adopting a column chromatography separation method to obtain a black solid product with metallic luster, wherein the yield is 91%.
Comparative example 4
A near infrared receptor small molecule BTTCIC-4F which does not contain an intrinsic quinoid structure has the following structural formula:
the synthetic route is as follows:
(1) Synthesis of Compound 40
Compound 39 (102 mg,0.29 mmol), compound 2 (608 mg,0.88 mmol) and palladium tetraphenylphosphine (16 mg,0.0087 mmol) were dissolved in a mixed solvent of 4ml toluene and 0.4ml DMF under nitrogen atmosphere. Reflux-reacting at 110 deg.c for 24 hr, cooling to room temperature, extracting with dichloromethane, washing the organic phase with saturated saline solution, drying with anhydrous magnesium sulfate, and separating and purifying with column chromatography to obtain the product in 73% yield.
(2) Synthesis of Compound 41
Super-dry phosphorus oxychloride (140 mg,0.91 mmol) and super-dry DMF (209 mg,2.86 mmol) were stirred at 0deg.C for 30min under nitrogen atmosphere. To the reaction flask was added dropwise compound 40 (219 mg,0.22 mmol) dissolved in 6ml of ultra-dry 1, 2-dichloroethane. The temperature is raised to 90 ℃ to react for 12 hours. Adding saturated sodium bicarbonate water solution, stirring for 2 hr, cooling to room temperature, extracting with dichloromethane, washing organic phase with saturated saline solution, drying with anhydrous magnesium sulfate, and separating and purifying by column chromatography to obtain product with 80% yield.
(3) Synthesis of BTTCIC-4F
Compound 41 (216 mg,0.206 mmol) and compound 22 (190 mg,0.206 mmol) were dissolved in 13ml of chloroform under nitrogen atmosphere, and 1.3ml of ultra-dry pyridine was added to react at 65℃for 1 hour. The reaction solution was concentrated and settled in 200ml of anhydrous methanol, and the crude product solid was obtained by suction filtration. And separating and purifying by adopting a column chromatography separation method to obtain a black solid product with metallic luster, wherein the yield is 91%.
Test case
Test example 1
All near infrared receptor small molecules obtained in the above examples and comparative examples are taken as examples, and the application of the near infrared receptor small molecules in a near infrared organic photodetector is illustrated.
The specific preparation process of each near infrared organic photoelectric detector is as follows:
and spin-coating a 40nm PEDOT: PSS hole transport layer on ITO, spin-coating a polymer donor PTB7-Th of about 100nm and a near infrared receptor micromolecular blending photoactive layer obtained in each example or comparative example respectively, spin-coating an amino polyfluorene quaternary ammonium bromide (PFN-Br) of about 5nm as a cathode interface layer, and evaporating a 100nm Ag layer to prepare the device. The structural formula of PTB7-Th is shown in FIG. 1.
The organic photoelectric detector comprises a transparent conductive anode, an anode interface layer, a polymer donor/micromolecular acceptor active layer, a cathode interface layer and a cathode from bottom to top. The resulting device structure is shown in fig. 2. EQE and dark current measurements at 0V bias were performed on the above organic photodetectors and corresponding responsivity R and detection rate D were calculated, with specific performance parameters as shown in table 1. The responsivity R is the ratio of the photocurrent of the photoelectric detector to the incident light intensity, the unit is A/W, and the calculation formula of R is as follows:
where EQE is directly proportional to R, both reflecting the efficiency of photon to electron conversion. The detection rate D is defined as the inverse of the Noise Equivalent Power (NEP), which is an indicator for measuring the capability of the detector to detect the minimum incident light signal, and the unit is Jones, where the calculation formula of D is as follows:
wherein R is responsivity, q is charge, J d Is dark current.
Fig. 3 to 6 show EQEs of several of the resulting front-mounted organic photodetector devices using all of the near infrared receptor small molecules obtained in examples and comparative examples as the receptor material and PTB7-Th as the donor material, respectively.
Fig. 7 to 8 show responsivity of several of the resulting front-mounted organic photodetector devices using all of the near infrared acceptor small molecules obtained in examples and comparative examples as acceptor materials, PTB7 to Th as donor materials, respectively. The device data obtained are shown in table 1.
TABLE 1 device parameters at 1100nm for organic photodetectors with near infrared receptor small molecules PTB7-Th as active layer at 0V bias in test example 1
Table 2 shows the response parameters of the near infrared receptor small molecules of the specific examples and comparative examples applied to an organic photodetector to a 1050nm LED.
TABLE 2 response parameters of organic photodetectors with near infrared receptor small molecules PTB7-Th as active layer at 0V bias to 1050nm LEDs in test example 1
The above data demonstrate that the detection range of small molecules of non-fullerene receptors of a-D-a structure that does not contain an intrinsic quinoid Q unit is within 1100nm. While non-fullerene acceptor small molecules with similar structures A-D-A-D-A, but whose core structures cannot form intrinsic quinoid Q units, can achieve EQE response spectra exceeding 1100nm, the EQE response at 1100nm is only about 1% at 0V bias. Whereas non-fullerene receptor small molecules based on intrinsic quinoid Q units can achieve high EQE responses of over 16% at 1100nm, indicating that the introduction of intrinsic quinoid Q units is an effective method of inventing high performance near infrared modular non-fullerene receptor small molecules.
The above examples of the present invention are only for the purpose of clearly illustrating the present invention and are not to be construed as limiting the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (6)
1. An intrinsic quinoid near infrared receptor small molecule, characterized in that the intrinsic quinoid near infrared receptor small molecule is selected from the following structures:
2. the method for preparing the intrinsic quinone small molecule of claim 1, comprising the steps of:
s1, reacting a monomer of a quinoid unit with a monomer of an electron donor under a catalyst to obtain an intermediate;
s2, formylating the intermediate to obtain a formylated intermediate;
s3, reacting the formylated intermediate with an electron acceptor monomer, and then purifying;
the monomer of the quinoid unit is selected from the following structures:
the monomers of the electron donor are selected from the following structures:
the monomer of the electron acceptor is selected from the following structures:
3. the method of claim 2, wherein the molar ratio of monomer of the quinoid unit to monomer of the electron donor is 1:2-1:3.
4. The method of preparing an intrinsic quinoid near infrared receptor small molecule according to claim 2, wherein the catalyst is selected from palladium-based catalysts.
5. Use of the intrinsic quinoid near infrared receptor small molecule according to claim 1 in an organic photodetector, wherein the intrinsic quinoid near infrared receptor small molecule comprises an organic compound layer in the organic photodetector, wherein the organic compound layer comprises a photoactive layer containing the intrinsic quinoid near infrared receptor small molecule.
6. The use of the intrinsic quinoid near infrared acceptor small molecule according to claim 5 in an organic photodetector, wherein the organic compound layer further comprises at least one of a hole transport layer and an electron transport layer.
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