CN108774245B - Preparation method and application of precise oxaacene functional molecular material - Google Patents

Preparation method and application of precise oxaacene functional molecular material Download PDF

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CN108774245B
CN108774245B CN201810477323.8A CN201810477323A CN108774245B CN 108774245 B CN108774245 B CN 108774245B CN 201810477323 A CN201810477323 A CN 201810477323A CN 108774245 B CN108774245 B CN 108774245B
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oxaacene
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曾泽兵
邦雅文
洪有华
刘承斌
陈娴
王燕培
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Hunan University
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Abstract

The invention discloses an organic semiconductor material of an oxaacene functional molecule, which is a series of oxaacene functional molecules. The compound has unique linear pi electron delocalization characteristics, is beneficial to the transmission of current carriers, obtains higher stability, and is a unique organic semiconductor material. In addition, the invention also introduces a one-pot method for preparing the oxaacene functional molecular material. The method has the characteristics of simple synthesis, easy operation, high yield and the like. The organic semiconductor material provided by the invention has potential and wide application prospects in the fields of organic optoelectronics, organic field effect transistors, organic luminescence, organic photodetectors, organic solar cells, pressure sensors, organic storage equipment, flexible flat panel display, electronic paper and the like.

Description

Preparation method and application of precise oxaacene functional molecular material
Technical Field
The invention relates to the field of functional materials, in particular to an organic semiconductor material of Organic Field Effect Transistors (OFETs).
Background
Polyacene aromatics (polyacenes) are a class of linear and aromatic ring hydrocarbons. It has unique linear delocalized pi-system and is one kind of unique organic semiconductor material. Polyacene compounds can realize highly ordered molecular packing and, therefore, can be applied to large-scale functional devices. The synthesis and application of high-performance polyacene materials have been remarkably advanced, and polyacene compounds are one of the most widely studied organic pi-functional materials and can be applied to a plurality of fields such as organic dyes, Organic Field Effect Transistors (OFETs), organic photovoltaic devices (OPVs), Organic Light Emitting Diodes (OLEDs) and organic memories. In particular, in the field of application of Organic Field Effect Transistors (OFETs), polyacene-based materials have been developed as main materials of the OFETs.
In recent years, as the development of organic conductive polymers, inorganic field effect transistors have approached the natural limit of miniaturization and are relatively expensive, and there are many problems in the preparation of large surface area devices, therefore, it is naturally thought that organic materials are used as active materials of Field Effect Transistors (FETs), in which the insulating layer, semiconductor and gate electrodes of inorganic field effect transistors have been tried to be replaced with organic materials, and thus a new type of organic thin film field effect transistors (OFETs) have been developed, Organic Field Effect Transistors (OFETs) are transistor devices having an organic semiconductor material as an active layer, compared to conventional inorganic semiconductor devices, since they are widely studied as being applicable to the production of large-area flexible devices, organic light emitting, organic photodetectors, organic solar cells, pressure sensors, organic memory devices, flexible flat panel displays, electronic paper, etc. organic thin film transistors have the main advantages that ① is easily available, the fabrication process of organic field effect transistors is much simpler, and thus the cost of the devices can be effectively reduced, ② field effect transistors prepared from organic materials, and good flexibility of organic field effect transistors (field effect transistors) are further modified by using organic molecules) and various types of organic materials (③) are appropriately modified.
The most critical step in the fabrication of organic thin film transistors is the formation of an organic semiconductor layer. The device characteristics and performance depend to some extent on the molecular structure of the organic semiconductor. The oxapolyacene compound has unique linear pi electron delocalization characteristic and ordered molecular structure, and can enable pi bonds of organic conjugated molecules to be overlapped to the greatest extent in the direction of a source electrode and a drain electrode, so that the transmission of carriers is improved. Meanwhile, the oxaacene is also beneficial to reducing the HOMO energy level of molecules and solving the problem of stability of the organic semiconductor. The oxygen-oxygen mode has great influence on functional materials, so that the research on a preparation technology of the organic functional molecules doped with the precise oxygen plays a key role in improving the performance of the organic thin film field effect transistor device.
Disclosure of Invention
In order to search for a new preparation technology of an ordered molecular organic thin film field effect transistor, the invention provides an oxaacene functional molecule (also called as an oxaacene cyclic compound) and aims to provide an organic semiconductor material with excellent performance.
The second purpose of the invention is to provide a preparation method of the oxaacene functional molecule.
The third purpose of the invention is to provide the application of the oxaacene functional molecule.
An oxaacene functional molecule comprising a polyaromatic structure formed by sequentially merging N structural fragments of formula 1 via a 2, 3-linkage and a 6, 7-linkage; the 6-position or the 7-position of the first structural fragment in the poly-aromatic structure is a substituent Ra, and the ortho-position of the substituent Ra is Rb; the 2, 3 sites of the last structural fragment in the poly-aromatic structure are merged with a benzene ring, the benzene ring is provided with a substituent Rc, and the ortho position of the substituent Rc is a substituent Rd;
Figure BDA0001664383570000021
ra and Rc are independently hydroxyl or alkoxy, preferably C1～C6Alkoxy group of (a);
rb and Rd are independently hydrogen and benzyl or benzyl of at least one substituent of halogen, C1-4 alkyl and C1-4 alkoxy; a hydroxyl group or an alkoxy group;
R1is C1～C24Alkyl of (C)3～C24Cycloalkyl of, C6～C18Aryl or C of6～C18A heterocyclic aryl group;
R2、R3is alone H, C1～C24Alkyl of (C)3～C24Cycloalkyl of, C1～C24Alkoxy group of (C)1～C24Alkylamino group of (C)6～C18Aryl or C of6～C18The heterocyclic aryl group of (a);
the alkyl, the cycloalkyl, the alkoxy, the alkylamino, the aryl and the heterocyclic aryl are allowed to contain halogen, -CN and other substituents;
and N is an integer greater than or equal to 4.
The invention provides an oxaacene functional molecule with a brand new structure, and researches show that the compound has unique linear pi electron delocalization characteristics, is beneficial to the transmission of current carriers, obtains higher field effect mobility and is a unique organic semiconductor material.
In the present invention, position 6/7 of the first structural unit is not involved in the fusion, and Ra and Rb are linked thereto. The 2, 3 position of the first structural unit and the 6/7 position of the further structural unit are fused, wherein the 2 position shares a carbon atom with the 6 or 7 position of the further structural unit and the 3 position shares a carbon atom with a carbon of the further structural unit not sharing a carbon atom with the 2 position; the combination of a plurality of structural units is repeated as follows until 2, 3 of the last structural unit shares a carbon bond with the benzene ring (i.e., is combined with the benzene ring).
Preferably, the Rc on the phenyl ring fused to the last structural fragment is located meta or para to the fused atom.
Preferably, Ra and Rc are independently hydroxyl or alkoxy.
More preferably, Ra and Rc are independently an alkoxy group. Researches show that Ra and Rc are alkoxy groups, so that the performance of the material can be improved, and the stability of the material can be improved. Preferably, Ra and Rc are independently C1-C6 alkoxy; for example, methoxy, ethoxy, isopropoxy, and the like.
Preferably, Rb, Rd are independently hydrogen, benzyl; or benzyl of at least one substituent selected from halogen, C1-4 alkyl, and C1-4 alkoxy; a hydroxyl group or an alkoxy group;
more preferably, Rb and Rd are independently hydrogen or benzyl.
Preferably, the Rc on the phenyl ring to which the oxaacene functional molecule, and the last structural fragment are fused is located meta or para to the fused atoms.
Preferably, R is1Independently C6-C18 aryl or C6-C18 halogenated aryl; more preferably, R is1Is independently 2, 6-dichlorophenyl
Figure BDA0001664383570000031
Preferably, R2, R3 are H or C1-C10 alkyl;
preferably, R2、R3Is H.
Preferably, N is an even number.
Preferably, said polyaromatic structure is formed by M of said structures of formula 2 by sequentially combining 2, 3-position bonds with 6, 7-position bonds: the oxaacene functional molecule has a structure of formula 2:
Figure BDA0001664383570000041
wherein M is 0.5N.
Preferably, the Rc on the phenyl ring fused to the last structural fragment is located meta or para to the fused atom.
The oxaacene functional molecule has structural formulas of formula 3 and formula 4:
Figure BDA0001664383570000042
wherein R4 is-OH or-OMe.
The oxaacene functional molecule of the present invention is preferably a compound having the structure of formula 3. The research finds that the poly-benzoxy heterocyclic compound with 9 rings has a stacking effect, high mobility and high on-off ratio, and shows good performance in the aspect of organic field effect transistors.
The oxaacene functional molecule organic semiconductor material of the present invention preferably has a structure represented by formula 3-A, formula 3-B, or formula 4-A, formula 4-B:
Figure BDA0001664383570000051
wherein R4 is-OH or-OMe.
The invention also discloses a preparation method of the oxaacene functional molecule, which comprises the following steps of polymerizing an aldehyde compound shown as a formula 5 and a p-diphenol compound shown as a formula 6: obtaining products with Ra and Rc as hydroxyl;
Figure BDA0001664383570000061
putting the compound of formula 5 and formula 6 into an acid solution; then adding concentrated sulfuric acid; continuing the reaction, quenching the reaction after the reaction is finished, removing the solvent, and purifying to obtain the product;
the polymerization reaction is carried out under a protective atmosphere;
preferably, the acidic condition is a glacial acetic acid solution.
Preferably, the molar weight ratio of the formula 5 to the formula 6 is 1-3: 1.
Preferably, the reaction temperature is 100-. The preferred reaction time at this temperature is 18 to 26 hours. The inventor discovers through extensive research and research that the selectivity of a 9-benzene product (formula 3, wherein Ra and Rc are hydroxyl products) can be unexpectedly improved, the separation difficulty of the product is reduced, and the yield of the product is improved by reacting for the time under the temperature condition.
The invention also discloses a preferable preparation method, which comprises the step of reacting the compound shown in the formula 5-A with the compound shown in the formula 6-A under an acidic condition to obtain the organic semiconductor material shown in the formula 3-A and the formula 3-B (R4 is hydroxyl).
Figure BDA0001664383570000062
Preferably, the compound of formula 5-A and the compound of formula 6-A are put into a solution under acidic conditions in advance; then adding concentrated sulfuric acid; and (4) continuing the reaction, quenching the reaction by using a small amount of water after the reaction is finished, precipitating a solid, filtering, washing with water for multiple times, drying, and purifying to obtain the compounds of the formulas 3-A and 3-B (R4 is hydroxyl).
The preferred preparation method of the invention has the synthesis route shown in the formula 3-A and the formula 3-B (R4 is hydroxyl)
Figure BDA0001664383570000071
Dissolving 2, 6-dichlorobenzaldehyde derivative and hydroquinone in a molar ratio of 1-3:1 in glacial acetic acid, adding concentrated sulfuric acid in the absence of oxygen, stirring at 100-140 ℃ for 18-26 hours, quenching the reaction, separating out solid, performing suction filtration, washing for multiple times, drying, and separating and purifying. To obtain the compounds of formula 3-A and formula 3-B (R4 is hydroxyl).
The phenolic hydroxyl group is converted into the alkoxy group in order to increase the stability of the oxaacene functional molecule according to the instability of the phenolic hydroxyl group with a large pi conjugated molecule. Preferably, the method of the present invention comprises the step of performing alkylation reaction of phenolic hydroxyl on the product of the polymerization reaction; obtain the oxaacene functional molecule product with Ra and Rc as alkoxy.
Preferably, the polymerization reaction product is reacted with an alkylating agent under alkaline conditions, and the solvent is removed to obtain the phenolic hydroxyl alkylation reaction product.
The alkylating reagent is Re-I. Re is C1～C24Alkyl group of (1).
The alkylation reaction is preferably carried out under a protective atmosphere;
preferably, the alkaline condition is potassium carbonate solution;
preferably, the molar ratio of the polymerization product to the alkylating agent is 1:1 to 3.
After alkylation reaction, diluting with water and ethyl acetate, washing, drying, spin-drying and purifying to obtain the product of phenol hydroxyl alkylation.
The preferred preparation method and synthesis circuit of the invention are shown in equation 2
Figure BDA0001664383570000081
The invention provides the accurate oxaacene organic functional semiconductor material, and the organic material can be used in numerous fields of organic optoelectronics, organic field effect transistors, organic luminescence, organic photodetectors, organic solar cells, pressure sensors, organic storage devices, flexible flat panel displays, electronic paper and the like.
Advantageous effects
The oxaacene functional molecule provided by the invention has unique linear pi electron delocalization characteristics, is beneficial to the transmission of current carriers, obtains higher stable effect, and is a unique organic semiconductor material. In addition, the invention provides a wet synthesis method from bottom to top, wherein a plurality of oxygen atoms are accurately doped by a one-step method, and effective delocalization of pi electrons is formed. The route has the characteristics of simple synthesis steps, easy operation, high yield and the like. Can be applied to the research in the field of organic optoelectronics and devices.
Drawings
FIG. 1 is a mass spectrum of compound 3-OH-2;
FIG. 2 is a mass spectrum of compound 3-OMe-1;
FIG. 3 is a hydrogen spectrum of compound 3-OMe-1;
FIG. 4 is a single crystal structure of Compound 3-OMe-1;
FIG. 5 is a mass spectrum of compound 3-OMe-2;
FIG. 6 is a schematic diagram of a field effect transistor structure in which compound 3-OMe-1 is a semiconductor embodiment
FIG. 7 is a graph showing the output characteristics of a thin film transistor of Compound 3-OMe-1
In each mass spectrum, the ordinate is abundance (%).
The present invention will be further described with reference to the following examples. It should be understood that the following examples are illustrative only and are not intended to limit the scope of the present invention.
Example 1
Synthesis of Compound 3(R4 is hydroxy)
Figure BDA0001664383570000091
Hydroquinone (1g, 9.09mmol) and 2, 6-dichlorobenzaldehyde (1.75g, 10mmol) were charged into a 100ml two-necked round bottom flask, and 50ml of glacial acetic acid was added thereto, followed by magnetic stirring to dissolve them sufficiently. Concentrated sulfuric acid (2ml) was added under oxygen-free conditions and sealed. The reaction was stirred under heating (130 ℃ C.) for 24 hours and monitored. After the reaction, the heating was stopped, 60ml of water was added to precipitate a solid, which was filtered off with suction and washed with water several times. The dried solid is purified (by recrystallization or chromatography) to give a compound of formula 3-OH-1, formula 3-OH-2 (R4 is hydroxy).
MALDI-TOF-MS of a compound of formula 3-OH-2: the calculated value was 1419.85 and the test value was 1419.85.
Example 2
Synthesis of Compound 3(R4 is methoxy)
Figure BDA0001664383570000092
Adding the compound 3(100mg 0.80mmol) and anhydrous potassium carbonate into a dry 50ml double-mouth bottle, injecting 20ml anhydrous DMF under the protection of inert gas, stirring to dissolve, dropwise adding methyl iodide (28.4mg, 0.20mmol), reacting at room temperature in a dark condition, sealing, and monitoring the reaction. After completion of the reaction, the reaction mixture was washed with saturated brine. After drying, spin-drying and purification of the crude product by chromatography, the methoxy compound is obtained.
MALDI-TOF-MS of a compound of formula 3-OMe-1: the calculated value was 1289.92 and the test value was 1288.93.
MALDI-TOF-MS of a compound of formula 3-OMe-2: the calculated value was 1447.88 and the test value was 1448.89.
Example 3
Preparation of thin film field effect transistor of the following materials
Figure BDA0001664383570000101
A layer of OTS is modified on Si/SiO2 by adopting a vapor phase method, the material solution is used for spin coating to form a film, the annealing temperatures are respectively room temperature, 80 ℃ and 140 ℃, the annealing time is 40 minutes, and gold is used as a top electrode. The device performance was tested in air using a Keithley 4200 semiconductor parameter instrument. The field effect mobility of the product can reach up to 0.217cm at the annealing temperature of 140 DEG C2·V-1·S-1The on-off ratio reaches 1.86 multiplied by 107。

Claims (3)

1. An oxaacene functional molecule, comprising a compound having the structure of formula 3-B:
Figure 4559DEST_PATH_IMAGE001
formula 3-B
Wherein R is4is-OMe.
2. A process for preparing oxaacene functional molecule as claimed in claim 1, wherein 2, 6-dichlorobenzaldehyde and hydroquinone are dissolved in glacial acetic acid at a molar ratio of 1-3:1, concentrated sulfuric acid is added in the reaction under oxygen-free condition, stirring is carried out at 100-4Is the polymerization product of hydroxyl groups; then separating and purifying the obtained R4The hydroxyl polymer is obtained by reacting a polymerization product of hydroxyl with an alkylating reagent under an alkaline condition and removing a solvent;
the alkylating reagent is Re-I; re is methyl;
the alkylation reaction is carried out under a protective atmosphere;
the alkaline condition is potassium carbonate solution;
the molar weight ratio of the polymerization product to the alkylating agent is 1: 1-3.
3. Use of the oxaacene functional molecule of claim 1 or the oxaacene functional molecule prepared by the preparation method of claim 2 as an organic semiconductor material in organic optoelectronics, organic field effect transistors, organic light emitting, organic photodetectors, organic solar cells, pressure sensors, organic memory devices, flexible flat panel displays or electronic paper.
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