CN114560999A

CN114560999A - N-type high molecular compound based on boron-nitrogen coordination bond and preparation method and application thereof

Info

Publication number: CN114560999A
Application number: CN202210403733.4A
Authority: CN
Inventors: 刘俊; 曹旭; 田洪坤; 王利祥
Original assignee: Changchun Institute of Applied Chemistry of CAS
Current assignee: Changchun Institute of Applied Chemistry of CAS
Priority date: 2022-04-18
Filing date: 2022-04-18
Publication date: 2022-05-31
Anticipated expiration: 2042-04-18
Also published as: CN114560999B

Abstract

An n-type high molecular compound based on boron-nitrogen coordination bonds, a preparation method and application thereof, belonging to the technical field of high molecular functional materials and organic electronics. Solves the technical problem of low mobility of organic conjugated high molecular compounds in the prior art. The conjugated main chain of the macromolecular compound contains two fragments which are respectively an electron-deficient diboron-nitrogen coordination bond bridging bipyridyl unit and an Ar unit, and the structural formula is shown as a formula (I). The high molecular compound has the characteristics of good planarity, small single bond connection proportion, strong skeleton rigidity and intermolecular interaction and the like, and can greatly improve the electron mobility of the material; the Ar structure is a fused unit, the chemical structure of the Ar structure is easy to modify, the energy level structure is adjustable and controllable, the steric hindrance is small, and the planarity is good; can be used as the charge transport layer material of the organic field effect transistor.

Description

N-type high molecular compound based on boron-nitrogen coordination bond and preparation method and application thereof

Technical Field

The invention belongs to the technical field of high molecular functional materials and organic electronics, and particularly relates to an n-type high molecular compound based on boron-nitrogen coordination bonds, and a preparation method and application thereof.

Background

The conjugated polymer semiconductor material can be used as a novel charge transport material due to the advantages of flexibility, low cost and the like, and particularly, an organic field effect transistor constructed by using a polymer semiconductor as a charge transport layer has attracted wide attention due to the potential application prospect in flexible devices and wearable electronics. The polymer semiconductor material can be classified into a p-type material (hole transport), an n-type material (electron transport), and a bipolar material (which can transport both electrons and holes) according to the transport type of carriers. For the current research, p-type materials are widely researched and developed quickly, and the mobility of some materials is far higher than that of amorphous silicon. In contrast, n-type materials and bipolar materials have been developed more slowly, have low mobility, and have poor air stability. In view of the application of bipolar materials and n-type materials in organic logic complementary circuits, the development of high mobility bipolar materials and n-type materials is the focus of current research.

In addition, the organic conjugated polymer can be applied to a conductive material by physical or chemical doping of the material. The conductive polymer is a polymer material having a pi-conjugated main chain structure and capable of realizing intrinsic conductivity by doping, such as polyaniline and polypyrrole. The conductive polymer not only can realize the conductive characteristic similar to metal, but also has the plastic characteristic of the conventional polymer material, such as flexibility, light weight, solution processing at low cost and the like. Through the control of the doping degree, the conductivity of the conductive macromolecule can be continuously adjusted in a large scale, so that the conductive macromolecule has the properties of a semiconductor or a conductor. However, the core of the research on these materials is the carrier transport problem of the organic conjugated polymer, so how to effectively improve the carrier mobility, especially the electron mobility, of the organic conjugated polymer becomes an important problem for the application of these materials.

Disclosure of Invention

In view of the above, in order to solve the technical problems in the prior art and further improve the carrier mobility of the organic conjugated polymer compound, the invention provides an n-type polymer compound based on boron-nitrogen coordination bonds, and a preparation method and an application thereof.

The technical scheme adopted by the invention for solving the technical problems is as follows.

The invention provides an n-type high molecular compound based on boron-nitrogen coordination bonds, which has a structure shown in a formula (I):

in the formula (I), n is an integer of 2-1000; m is an integer of 0-10, and the two m are the same or different; x is an integer of 1-20, y is an integer of 1-20, and x and y are the same or different; -Ar-is

a is O, S or Se, b is CH or N, and c is F, Cl or CN.

Preferably, the-Ar-is one of the following structures:

the invention also provides a preparation method of the n-type high molecular compound based on the boron-nitrogen coordination bond, which comprises the following steps:

under the protection of inert atmosphere, dissolving a bisbromine monomer, a bistrimethyltin monomer and tetrakis (triphenylphosphine) palladium of a bisboron nitrogen coordination bond bridged bipyridine in an organic solvent, carrying out Stille polymerization reaction under the conditions of light shielding and heating reflux, and after the Stille polymerization reaction is finished, purifying the obtained polymer to obtain an n-type high molecular compound based on the boron nitrogen coordination bond;

the structural formula of the double bromine monomer of the diboron-nitrogen coordination bond bridged bipyridyl is shown in the specification;

the structural formula of the bis (trimethyl tin) monomer is as follows:

preferably, the organic solvent is toluene, and the concentrations of the bisbromine monomer and the bistrimethyltin monomer of the diboron-nitrogen coordination bond bridged bipyridyl in the organic solvent are respectively 0.005-0.1 mM.

Preferably, the material amount ratio of the bisbromine monomer, the bistrimethyltin monomer and the tetrakis (triphenylphosphine) palladium of the diboron nitrogen coordination bond bridging bipyridyl is 1:1: 0.04.

Preferably, the reaction temperature of the Stille polymerization reaction is 110-120 ℃, and the reaction time is 1-96 h.

The invention also provides the application of the n-type macromolecular compound based on boron-nitrogen coordination bonds as a charge transport layer material of an organic field effect transistor,

the electron mobility of the charge transport layer material in the organic field effect transistor is 0.1cm² V^-1s^-1The above.

Preferably, the organic field effect transistor is structured as a top-gate bottom contact or a bottom-gate top contact;

the top-gate bottom contact structure comprises a substrate, a source-drain electrode, a charge transmission layer, a dielectric layer and a gate electrode; the material of the substrate is Si/SiO₂Substrate, SiO₂The thickness is 300 nm; the source and drain electrodes are made of gold and have the thickness of 10-40 nm; the thickness of the charge transport layer is 1-100 nm; the dielectric layer is made of PMMA and has the thickness of 500 nm; the gate electrode is made of gold and has a thickness of 50-90 nm;

the bottom-gate top contact structure comprises a substrate, a source electrode, a drain electrode and a charge transmission layer; the material of the substrate is Si/SiO₂Substrate, SiO₂The thickness is 300 nm; the source and drain electrodes are made of gold and have the thickness of 10-40 nm; the thickness of the charge transport layer is 1 to 100 nm.

The invention also provides application of the n-type macromolecular compound based on the boron-nitrogen coordination bond in an organic conductor material and an organic thermoelectric material after doping.

Compared with the prior art, the invention has the beneficial effects that:

1. the n-type high molecular compound based on boron-nitrogen coordination bonds has the characteristics of good planarity, rigid skeleton and strong intermolecular interaction, and the conjugated main chain of the n-type high molecular compound only contains two repeating units which are respectively a BNBP unit and a derivative unit of benzodithiophene, so that the proportion of single bond connection among the units can be reduced to the greatest extent, and the energy disorder caused by chain twist is reduced. The steric hindrance between units can be reduced by introducing N heteroatom into the benzodithiophene unit, and the chain conformation is optimized, so that the molecular accumulation is improved, and the transmission performance is improved. In addition, electron-deficient substituents can be introduced into No. 1 and No. 4 of the benzene ring, so that the energy level structure of the polymer can be regulated and controlled in a wide range, and therefore the polymer has adjustable LUMO/HOMO energy level, and the carrier transmission characteristic can be further regulated and controlled. The BNBP unit is an electron-deficient unit, so the LUMO energy level of the polymer is relatively low, and the polymer is suitable for being used as an n-type or bipolar transmission material of an organic field effect transistor; through doping, the macromolecule can be applied to organic conductor materials and organic thermoelectric materials.

2. According to the n-type polymer compound based on boron-nitrogen coordination bonds, the-Ar-unit and the substituent thereof are changed, so that the pre-aggregation behavior and the solid state accumulation property of a polymer in a solution can be regulated and controlled, the crystallization property of the material is optimized, the transmission property of the material is improved, and higher electron mobility is facilitated.

3. The n-type high molecular compound based on boron-nitrogen coordination bonds is used as a charge transport material of an organic field effect transistor, and the experimental detection shows that the electron mobility is 0.1cm² V^-1s^-1The above.

Drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is an ultraviolet-visible absorption spectrum of Polymer P-BNBP-BBtz (C28) of example 1;

FIG. 2 is an electrochemical test curve of the polymer P-BNBP-BBtz (C28) of example 1;

FIG. 3 is an out-of-plane grazing incidence X-ray diffraction test curve for Polymer P-BNBP-BBtz (C28) of example 1;

FIG. 4 is an electrochemical test curve of the macromolecule P-BNBP-BBtz (C28) of example 13;

FIG. 5 is a block diagram of an organic field effect transistor device of a top gate bottom contact configuration (TGBC);

fig. 6 is a block diagram of an organic field effect transistor device having a bottom gate top contact configuration (BGTC);

FIG. 7 is an n-type transfer characteristic curve of the polymer organic field effect transistor device of example 21;

fig. 8 is an n-type output characteristic curve of the polymer organic field effect transistor device of example 21.

FIG. 9 is an n-type transfer characteristic curve of the polymer organic field effect transistor device of example 22;

FIG. 10 is an n-type output characteristic curve of the polymer organic field effect transistor device in example 22;

FIG. 11 is an n-type transfer characteristic curve of the polymer organic field effect transistor device according to example 23;

FIG. 12 is an n-type output characteristic curve of the polymer organic field effect transistor device of example 23;

FIG. 13 is an n-type transfer characteristic curve of the polymer organic field effect transistor device according to example 24;

FIG. 14 is an n-type output characteristic curve of the polymeric organic field effect transistor device of example 24;

FIG. 15 is an n-type transfer characteristic curve of the polymer organic field effect transistor device in example 25;

FIG. 16 is an n-type output characteristic curve of the polymer organic field effect transistor device according to example 25;

FIG. 17 is a graph showing n-type transfer characteristics of the polymer organic field effect transistor device in example 26;

FIG. 18 is an n-type output characteristic curve of the polymer organic field effect transistor device in example 26;

FIG. 19 is an n-type transfer characteristic curve of the polymer organic field effect transistor device in example 27;

FIG. 20 is an n-type output characteristic curve of the polymeric organic field effect transistor device of example 27;

FIG. 21 is a graph showing n-type transfer characteristics of the polymer organic field effect transistor device in example 28;

FIG. 22 is an n-type output characteristic curve of the polymer organic field effect transistor device in example 28;

FIG. 23 is a graph showing n-type transfer characteristics of the polymer organic field effect transistor device in example 29;

FIG. 24 is an n-type output characteristic curve of the polymer organic field effect transistor device in accordance with example 29;

fig. 25 is an n-type transfer characteristic curve of the polymer organic field effect transistor device of example 30;

fig. 26 is an n-type output characteristic curve of the polymer organic field effect transistor device according to example 30.

Detailed Description

For the purpose of further illustrating the invention, preferred embodiments of the invention are described below in conjunction with the detailed description, but it is to be understood that these descriptions are only intended to further illustrate the features and advantages of the invention, and not to limit the claims of the invention.

The repeating unit of the n-type macromolecular compound based on the boron-nitrogen coordination bond has two structural units, namely a diboron-nitrogen coordination bond bridging bipyridyl unit (BNBP) and an-Ar-unit, and the structure is shown as the formula (I):

in the formula (I), n is an integer of 2-1000, m is an integer of 0-10, alkyl side chains on nitrogen atoms on two sides are the same or different, x is an integer of 1-20, y is an integer of 1-20, and x and y are the same or different; -Ar-structure is

a is O, S or Se, b is CH or N, and c is F, Cl or CN.

In the above technical solution, preferably-Ar-is one of the following structures:

in the invention, the electronic structure of the n-type polymer compound based on the boron-nitrogen coordination bond can be effectively adjusted by changing the structure of-Ar-, so as to obtain a polymer with proper energy level and solid state accumulation. Through experimental detection, the polymer has proper LUMO energy level and relatively planar framework, strong pre-aggregation exists in a solution state, and the solid film has relatively high electron mobility (the electron mobility is 0.1 cm)² V^-1s^-1Above, can reach 0.12-0.43cm² V^-1s^-1，0.17-0.43cm² V^-1s^-1，0.2-0.43cm² V^-1s^-1，0.24-0.43cm² V^-1s^-1，0.39-0.43cm² V^-1s^-1，0.40-0.43cm² V^-1s^-1,0.41-0.43cm² V^-1s^-1) Can be used as an electron transport material in an organic field effect transistor.

The n-type polymer compound based on the boron-nitrogen coordination bond is prepared by a Stille-type reaction, and as a preferable scheme, the preparation method can be as follows:

under the protection of inert atmosphere (generally adopting argon), dissolving a bisbromine monomer, a bistrimethyltin monomer, tetrakis (triphenylphosphine) palladium and cuprous iodide (cocatalyst) of BNBP in a toluene solution according to the mass ratio of 1:1:0.04:0.1, wherein the dissolving sequence is not particularly limited, generally adding the tetrakis (triphenylphosphine) palladium, the concentrations of the bisbromine monomer and the bistrimethyltin monomer of BNBP can be respectively 0.005-0.1 mM, refluxing for 1-96 h at 110-120 ℃ under the condition of light shielding, performing Stille polymerization reaction, and after the reaction is finished, purifying the obtained polymer to obtain an n-type high molecular compound based on boron-nitrogen coordination bonds;

the reaction formula is as follows:

the method for purifying the n-type high molecular compound based on the boron-nitrogen coordination bond prepared by the method can be as follows: and cooling the reaction product system to room temperature, and then dripping the reaction product system into a pure methanol solvent to obtain a precipitated solid. And then using a Soxhlet extractor to sequentially wash the precipitated solid with acetone, n-hexane and chloroform solvents to remove the catalyst and oligomers, then using chlorobenzene to carry out hot dissolution, filtering while the solution is hot, carrying out rotary evaporation to remove most of the organic solvent, and finally settling the viscous solution in methanol to obtain the n-type macromolecular compound based on boron-nitrogen coordination bonds.

The n-type high molecular compound based on boron-nitrogen coordination bonds can be used as a charge transport layer material of an organic field effect transistor, and the application method of the charge transport layer material in the organic field effect transistor is not particularly limited, and the charge transport layer material can be used according to the using method of the conventional charge transport layer material in the field. The structure of the organic field effect transistor is not particularly limited, and the structures in the prior art are all applicable, and high electron mobility can be realized by only adopting the charge transport layer material. In the prior art, the structure of the organic field effect transistor may be a Top Gate Bottom Contact (TGBC) or a Bottom Gate Top Contact (BGTC). As shown in fig. 5, the TGBC structured device includes, from bottom to top, a substrate, a source/drain electrode, a charge transport layer, a dielectric layer, and a gate electrode. As shown in fig. 6, the device with the BGTC structure sequentially includes a substrate, a gate electrode, a charge transport layer, and source and drain electrodes from bottom to top. The material of the substrate can be Si/SiO₂Substrate, SiO₂The thickness is 300 nm; the source and drain electrodes can be made of gold and have a thickness of 10-40 nm, and are usually made of goldObtaining the product by a vapor deposition method; the charge transport layer is made of an n-type high molecular compound based on boron-nitrogen coordination bonds, is 1-100 nm thick and is usually obtained by spin coating; the dielectric layer is made of PMMA with the thickness of 500nm and is usually obtained by spin coating; the gate electrode is made of gold, has a thickness of 50-90 nm, and is usually obtained by deposition.

The invention also provides application of the n-type high molecular compound based on boron-nitrogen coordination bonds in organic conductor materials and organic thermoelectric materials after doping.

The present invention is further illustrated by the following examples.

Example 1

P-BNBP-BBtz (C28) macromolecule, the structural formula is shown as follows (in the structural formula, the end capping group is omitted):

the preparation method comprises the following steps: adding a bisbromomonomer (64.5mg, 0.05mmol) of BNBP, a benzodithiazole bistin salt (27.3mg, 0.05mmol), cuprous iodide (1.0mg, 0.005mmol) and tetrakis (triphenylphosphine) palladium (2.4mg, 0.002mmol) into a well-baked polymerization bottle, vacuumizing, introducing argon to pump and exchange gas for multiple times, adding a distilled toluene solvent (1mL) in a dark state, refluxing at 120 ℃ for 48h, settling a reaction system in methanol while the reaction system is hot, separating out a macromolecule, washing off micromolecules and a catalyst by using acetone and n-hexane in sequence through a Soxhlet extractor, and finally extracting the macromolecule by using chloroform. The yield was 64mg, 96%.

Elemental analysis of the prepared polymer resulted in the following: calculated value C, 70.79; h, 9.63; b, 1.72; f, 6.05; n, 6.69; and S, 5.11. The experimental value is C, 69.97; h, 9.62; n, 6.61; and S, 5.02.

The prepared polymer was subjected to gel permeation chromatography (GPC, trichlorobenzene, polystyrene as a standard, 150 ℃ C.) to give M_n＝61186，PDI＝1.94。

The polymer P-BNBP-BBTz (C28) prepared in example 1 was subjected to uv-vis absorption spectrum analysis, electrochemical test and out-of-plane grazing incidence X-ray diffraction test, and the test results are shown in fig. 1, fig. 2 and fig. 3, respectively. As can be seen from FIG. 1, the film of the polymer P-BNBP-BBtz (C28) has a sharp UV-VIS absorption spectrum, which indicates that the skeleton is relatively rigid; as can be seen from FIG. 2, the LUMO/HOMO energy level of the polymer P-BNBP-BBTz (C28) is-3.80/-6.04 eV, which indicates that the polymer of the present invention can be used as an electron transport material; from FIG. 3, it can be seen that the polymer P-BNBP-BBTz (C28) adopts a solid state mixed orientation, and the pi-pi stacking distance is only 0.36nm, which shows that the polymer of the present invention can realize high electron mobility.

Example 2

P-BNBP-BBtz (C32) macromolecule, the structural formula is shown as follows (in the structural formula, the end capping group is omitted):

the preparation method comprises the following steps: adding a bisbromine monomer (66.9mg, 0.05mmol) of BNBP, a benzodithiazole bistin salt (27.3mg, 0.05mmol), cuprous iodide (1.0mg, 0.005mmol) and tetrakis (triphenylphosphine) palladium (2.4mg, 0.002mmol) into a well-baked polymerization bottle, vacuumizing, introducing argon to pump and exchange gas for multiple times, adding a distilled toluene solvent (1mL) in a dark state, refluxing at 120 ℃ for 48h, settling a reaction system in methanol while the reaction system is hot, separating out a macromolecule, washing off micromolecules and a catalyst by using acetone and n-hexane in sequence through a Soxhlet extractor, and finally extracting the macromolecule by using chloroform. The yield was 63mg, 94%.

Elemental analysis of the prepared polymer resulted in the following: calculated value C, 72.18; h, 10.24; b, 1.55; f, 5.44; n, 6.01; and S, 4.59. The experimental value is C, 72.21; h, 10.35; n, 6.09; and S, 4.49.

The resulting polymer was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene standard, 150 ℃ C.) to obtain Mn 14392 and PDI 2.37.

Example 3

P-BNBP-BBtz (C24) macromolecule, the structural formula is shown as follows (in the structural formula, the end capping group is omitted):

the preparation method comprises the following steps: adding a dibromide monomer (55.6mg, 0.05mmol) of BNBP, a benzodithiazole bistin salt (27.3mg, 0.05mmol), cuprous iodide (1.0mg, 0.005mmol) and tetrakis (triphenylphosphine) palladium (2.4mg, 0.002mmol) into a polymerization bottle which is baked cleanly, vacuumizing, introducing argon to pump and exchange gas for a plurality of times, adding a distilled toluene solvent (1mL) under a light-proof state, refluxing at 120 ℃ for 48h, settling a reaction system in methanol while hot, separating out macromolecules, sequentially washing off micromolecules and a catalyst by acetone and n-hexane by using a Soxhlet extractor, and finally extracting the macromolecules by using chloroform. The yield was 52mg, 90%.

Elemental analysis of the prepared polymer resulted in the following: calculated value C, 69.21; h, 9.33; b, 1.89; f, 6.63; n, 7.34; and S, 5.60. Experimental value C, 69.18; h, 9.35; n, 7.35; and S, 5.56.

The resulting polymer was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene standard, 150 ℃ C.) to obtain Mn 28106 and PDI 1.88.

Example 4

P-BNBP-2fBDT (C28) macromolecule, the structural formula is shown as follows (in the structural formula, the blocking group is omitted):

the preparation method comprises the following steps: adding a bisbromine monomer (64.5mg, 0.05mmol) of BNBP, difluorobenzodithiophene bistin salt (27.6mg, 0.05mmol), cuprous iodide (1.0mg, 0.005mmol) and tetrakis (triphenylphosphine) palladium (2.4mg, 0.002mmol) into a well-baked polymerization bottle, vacuumizing, introducing argon for pumping and exchanging gas for multiple times, adding a distilled toluene solvent (1mL) in a light-shielding state, refluxing at 120 ℃ for 48 hours, settling a reaction system in methanol while the reaction system is hot, separating out a macromolecule, washing off micromolecules and a catalyst by using acetone and n-hexane in sequence of a precipitate, and finally extracting the macromolecule by using chloroform. The yield was 60mg, 89%.

Elemental analysis of the prepared polymer resulted in the following: calculated value C, 70.99; h, 9.62; b, 1.64; f, 8.64; n, 4.25; and S, 4.86. The experimental value is C, 70.95; h, 9.65; n, 4.27; and S, 4.85.

The prepared polymer was subjected to gel permeation chromatography (GPC, trichlorobenzene, polystyrene standard, 150 ℃ C.): mn 48856 and PDI 1.72.

Example 5

P-BNBP-2fBDT (C32) macromolecule, the structural formula is shown as follows (in the structural formula, the blocking group is omitted):

the preparation method comprises the following steps: adding a bisbromine monomer (66.9mg, 0.05mmol) of BNBP, difluorobenzodithiophene bistin salt (27.6mg, 0.05mmol), cuprous iodide (1.0mg, 0.005mmol) and tetrakis (triphenylphosphine) palladium (2.4mg, 0.002mmol) into a well-baked polymerization bottle, vacuumizing, introducing argon for pumping and exchanging gas for multiple times, adding a distilled toluene solvent (1mL) in a light-shielding state, refluxing at 120 ℃ for 48 hours, settling a reaction system in methanol while the reaction system is hot, separating out a macromolecule, washing off micromolecules and a catalyst by using acetone and n-hexane in sequence of a precipitate, and finally extracting the macromolecule by using chloroform. The yield was 68mg, 95%.

Elemental analysis of the prepared polymer resulted in the following: calculated C, 72.14; h, 10.00; b, 1.51; f, 7.96; n, 3.91; and S, 4.48. Experimental value C, 72.19; h, 9.96; n, 3.93; and S, 4.50.

The prepared polymer was subjected to gel permeation chromatography (GPC, trichlorobenzene, polystyrene standard, 150 ℃ C.): mn is 67852 and PDI is 1.73.

Example 6

P-BNBP-2fBDT (C24) macromolecule, the structural formula is shown as follows (in the structural formula, the blocking group is omitted):

the preparation method comprises the following steps: adding a bisbromine monomer (55.6mg, 0.05mmol) of BNBP, difluorobenzodithiophene bistin salt (27.6mg, 0.05mmol), cuprous iodide (1.0mg, 0.005mmol) and tetrakis (triphenylphosphine) palladium (2.4mg, 0.002mmol) into a well-baked polymerization bottle, vacuumizing, introducing argon for pumping and exchanging gas for multiple times, adding a distilled toluene solvent (1mL) in a light-shielding state, refluxing at 120 ℃ for 48 hours, settling a reaction system in methanol while the reaction system is hot, separating out a macromolecule, washing off micromolecules and a catalyst by using acetone and n-hexane in sequence of a precipitate, and finally extracting the macromolecule by using chloroform. The yield was 51mg, 86%.

Elemental analysis of the prepared polymer resulted in the following: calculated C, 69.25; h, 9.06; b, 1.83; f, 9.67; n, 4.75; s, 5.44. The experimental value is C, 69.30; h, 9.11; n, 4.76; s, 5.41.

The prepared polymer was subjected to gel permeation chromatography (GPC, trichlorobenzene, polystyrene standard, 150 ℃ C.): mn 48526 and PDI 1.89.

Example 7

P-BNBP-2CNBDT (C28) macromolecule, the structural formula is shown as follows (in the structural formula, the blocking group is omitted):

the preparation method comprises the following steps: adding a bisbromine monomer (64.5mg, 0.05mmol) of BNBP, dicyanobenzodithiophene bistin salt (28.3mg, 0.05mmol), cuprous iodide (1.0mg, 0.005mmol) and tetrakis (triphenylphosphine) palladium (2.4mg, 0.002mmol) into a well-baked polymerization bottle, vacuumizing, introducing argon for pumping and exchanging gas for a plurality of times, adding a distilled toluene solvent (1mL) in a light-proof state, refluxing at 120 ℃ for 48 hours, settling a reaction system in methanol while hot, separating out a macromolecule, washing off micromolecules and a catalyst by using an Soxhlet extractor sequentially with acetone and n-hexane, and finally extracting the macromolecule by using chloroform. The yield was 59mg, 91%.

Elemental analysis of the prepared polymer resulted in the following: calculated C, 71.76; h, 9.42; b, 1.66; f, 5.82; n, 6.44; and S, 4.91. The experimental value is C, 71.70; h, 9.45; n, 6.41; and S, 4.93. The prepared polymer was subjected to gel permeation chromatography (GPC, trichlorobenzene, polystyrene standard, 150 ℃ C.): mn is 32557, PDI is 1.76.

Example 8

P-BNBP-2CNBDT (C32) macromolecule, the structural formula is shown as follows (in the structural formula, the blocking group is omitted):

the preparation method comprises the following steps: adding a bisbromine monomer (66.9mg, 0.05mmol) of BNBP, dicyanobenzodithiophene bistin salt (28.3mg, 0.05mmol), cuprous iodide (1.0mg, 0.005mmol) and tetrakis (triphenylphosphine) palladium (2.4mg, 0.002mmol) into a well-baked polymerization bottle, vacuumizing, introducing argon for pumping and exchanging gas for a plurality of times, adding a distilled toluene solvent (1mL) in a light-proof state, refluxing at 120 ℃ for 48 hours, settling a reaction system in methanol while hot, separating out a macromolecule, washing off micromolecules and a catalyst by using an Soxhlet extractor sequentially with acetone and n-hexane, and finally extracting the macromolecule by using chloroform. The yield was 63mg, 89%.

Elemental analysis of the prepared polymer resulted in the following: calculated value C, 72.85; h, 9.81; b, 1.52; f, 5.36; n, 5.93; s, 4.52. Experimental value C, 72.83; h, 9.82; n, 5.91; and S, 4.50. The prepared polymer was subjected to gel permeation chromatography (GPC, trichlorobenzene, polystyrene standard, 150 ℃ C.): mn is 44366, PDI is 1.52.

Example 9

P-BNBP-2CNBDT (C24) macromolecule, the structural formula is shown as follows (in the structural formula, the blocking group is omitted):

the preparation method comprises the following steps: adding a bisbromine monomer (55.6mg, 0.05mmol) of BNBP, dicyanobenzodithiophene bistin salt (28.3mg, 0.05mmol), cuprous iodide (1.0mg, 0.005mmol) and tetrakis (triphenylphosphine) palladium (2.4mg, 0.002mmol) into a well-baked polymerization bottle, vacuumizing, introducing argon for pumping and exchanging gas for a plurality of times, adding a distilled toluene solvent (1mL) in a light-proof state, refluxing at 120 ℃ for 48 hours, settling a reaction system in methanol while hot, separating out a macromolecule, washing off micromolecules and a catalyst by using an Soxhlet extractor sequentially with acetone and n-hexane, and finally extracting the macromolecule by using chloroform. The yield was 54mg, 91%. .

Elemental analysis of the prepared polymer resulted in the following: calculated value C, 70.45; h, 8.95; b, 1.81; f, 6.37; n, 7.04; s, 5.37. Experimental value C, 70.44; h, 8.89; n, 7.06; s, 5.41.

The obtained polymer was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene standard, 150 ℃ C.) to obtain Mn 28997 and PDI 1.63.

Example 10

P-BNBP-2fBBtz (C28) macromolecule, the structural formula is shown as follows (in the structural formula, the blocking group is omitted):

the preparation method comprises the following steps: adding a bisbromine monomer (64.5mg, 0.05mmol) of BNBP, difluorobenzodithiazole bistin salt (27.7mg, 0.05mmol), cuprous iodide (1.0mg, 0.005mmol) and tetrakis (triphenylphosphine) palladium (2.4mg, 0.002mmol) into a completely baked polymerization bottle, vacuumizing, introducing argon to evacuate the system for multiple times, adding a distilled toluene solvent (1mL) in a lightproof state, refluxing at 120 ℃ for 48 hours, settling the reaction system in methanol while hot, separating out macromolecules, washing off micromolecules and a catalyst by using acetone and n-hexane in sequence by using a Soxhlet extractor, and finally extracting the macromolecules by using chloroform. The yield was 63mg, 97%.

Elemental analysis of the prepared polymer resulted in the following: calculated C, 68.71; h, 9.35; b, 1.67; f, 8.81; n, 6.50; and S, 4.96. The experimental value is C, 68.71; h, 9.40; n, 6.48; s, 4.97.

The prepared polymer was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene standard, 150 ℃ C.) to obtain Mn 48777 and PDI 1.49.

Example 11

P-BNBP-2fBBtz (C32) macromolecule, the structural formula is shown as follows (in the structural formula, the blocking group is omitted):

the preparation method comprises the following steps: adding a bisbromine monomer (66.9mg, 0.05mmol) of BNBP, difluorobenzodithiazole bistin salt (27.7mg, 0.05mmol), cuprous iodide (1.0mg, 0.005mmol) and tetrakis (triphenylphosphine) palladium (2.4mg, 0.002mmol) into a completely baked polymerization bottle, vacuumizing, introducing argon to evacuate the system for multiple times, adding a distilled toluene solvent (1mL) in a lightproof state, refluxing at 120 ℃ for 48 hours, settling the reaction system in methanol while hot, separating out macromolecules, washing off micromolecules and a catalyst by using acetone and n-hexane in sequence by using a Soxhlet extractor, and finally extracting the macromolecules by using chloroform. The yield was 64mg, 92%.

Elemental analysis of the prepared polymer resulted in the following: calculated value C, 70.06; h, 9.75; b, 1.54; f, 8.11; n, 5.98; s, 4.56. Experimental value C, 70.10; h, 9.71; n, 5.99; s, 4.51.

The obtained polymer was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene standard, 150 ℃ C.) to obtain Mn 58891 and PDI 2.01.

Example 12

P-BNBP-2fBBtz (C32') macromolecule, the structural formula is shown as follows (in the structural formula, the blocking group is omitted):

the preparation method comprises the following steps: adding a bisbromine monomer (66.9mg, 0.05mmol) of BNBP, difluorobenzodithiazole bistin salt (27.7mg, 0.05mmol), cuprous iodide (1.0mg, 0.005mmol) and tetrakis (triphenylphosphine) palladium (2.4mg, 0.002mmol) into a well-baked polymerization bottle, vacuumizing, introducing argon for pumping and exchanging gas for multiple times, adding a distilled toluene solvent (1mL) in a light-shielding state, refluxing at 120 ℃ for 48 hours, settling a reaction system in methanol while the reaction system is hot, separating out a macromolecule, washing off micromolecules and a catalyst by using acetone and n-hexane in sequence of a precipitate by using a Soxhlet extractor, and finally extracting the macromolecule by using chloroform. The yield was 67mg, 95%.

Elemental analysis of the prepared polymer resulted in the following: calculated value C, 70.06; h, 9.75; b, 1.54; f, 8.11; n, 5.98; s, 4.56. Experimental value C, 70.11; h, 9.73; n, 5.96; s, 4.53.

The resulting polymer was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene standard, 150 ℃ C.) to obtain Mn 42877 and PDI 1.52.

Example 13

P-BNBP-2CNBBtz (C28) polymer, the structural formula is as follows (in the structural formula, the end capping group is omitted):

the preparation method comprises the following steps: adding a bisbromine monomer (64.5mg, 0.05mmol) of BNBP, difluorobenzodithiazole bistin salt (28.4mg, 0.05mmol), cuprous iodide (1.0mg, 0.005mmol) and tetrakis (triphenylphosphine) palladium (2.4mg, 0.002mmol) into a well-baked polymerization bottle, vacuumizing, introducing argon for pumping and exchanging gas for multiple times, adding a distilled toluene solvent (1mL) in a light-shielding state, refluxing at 120 ℃ for 48 hours, settling a reaction system in methanol while the reaction system is hot, separating out a macromolecule, washing off micromolecules and a catalyst by using acetone and n-hexane in sequence of a precipitate by using a Soxhlet extractor, and finally extracting the macromolecule by using chloroform. The yield was 57mg, 87%.

Elemental analysis of the prepared polymer resulted in the following: calculated value C, 69.81; h, 9.25; b, 1.65; f, 5.81; n, 8.57; and S, 4.90. The experimental value is C, 69.85; h, 9.21; n, 8.59; and S, 4.93.

The obtained polymer was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene standard, 150 ℃ C.) to obtain Mn 33517 and PDI 1.48.

The P-BNBP-2CNBBtz (C28) polymer prepared in example 13 was electrochemically tested, and the test results are shown in FIG. 4. As can be seen from FIG. 4, the LUMO/HOMO energy level of the polymer P-BNBP-2CNBBTz (C28) is-4.36/-6.04 eV, which indicates that the polymer of the present invention can be used as an electron transport material.

Example 14

P-BNBP-fBBtz (C28) polymer, the structural formula is as follows (in the structural formula, the end capping group is omitted):

the polymer P-BNBP-fBBtz (C28) was prepared as in example 1. Except that monofluorobenzothiazole bistnnum salt was used instead of the benzodithiazole bistnnum salt. The polymer yield was 59mg, 93%.

Elemental analysis of the prepared polymer resulted in the following: calculated value C, 69.68; h, 9.56; b, 1.69; f, 7.45; n, 6.59; and S, 5.03. The experimental value is C, 69.61; h, 9.57; n, 6.61; and S, 5.06.

The prepared polymer was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene standard, 150 ℃ C.) to obtain Mn 46180 and PDI 1.72.

Example 15

P-BNBP-CNBBtz (C28) macromolecule, the structural formula is shown as follows (in the structural formula, the blocking group is omitted):

the preparation of the P-BNBP-CNBBtz (C28) polymer was the same as in example 1. Except that the bisthiobenzobistin salt was replaced by a bisthiobenzobisthiozole bisthiotin salt. The polymer yield was 58mg, 90%.

Elemental analysis of the prepared polymer resulted in the following: calculated as C, 70.24; h, 9.51; b, 1.69; f, 5.93; n, 7.64; s, 5.00. The experimental value is C, 70.26; h, 9.50; n, 7.70; and S, 5.04.

The resulting polymer was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene standard, 150 ℃ C.) to obtain Mn 44369 and PDI 1.82.

Example 16

P-BNBP-CNBBSez (C28) macromolecule, the structural formula is as follows (in the structural formula, the blocking group is omitted):

the polymer of P-BNBP-CNBBSez (C28) was prepared as in example 1. Except that the bisthiobenzobisstannate was replaced by the bisthiobenzobisselenazole salt. The polymer yield was 65mg, 94%.

Elemental analysis of the prepared polymer resulted in the following: calculated value C, 65.45; h, 8.86; b, 1.57; f, 5.52; n, 7.12; se, 11.47. Experimental value C, 65.44; h, 8.88; and N, 7.10.

The prepared polymer was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene standard, 150 ℃ C.) to obtain Mn 32758 and PDI 1.69.

Example 17

P-BNBP-2CNBBSez (C28) macromolecule, the structural formula is as follows (in the structural formula, the blocking group is omitted):

the macromolecule of P-BNBP-2CNBBSez (C28) was prepared as in example 1. Except that the bisthiobenzobisstannate was replaced by the bisthiobenzobisselenazole bisstannate. The polymer yield was 66mg, 95%.

Elemental analysis of the prepared polymer resulted in the following: calculated value C, 65.14; h, 8.63; b, 1.54; f, 5.42; n, 8.00; se, 11.27. Experimental value C, 65.11; h, 8.67; and N, 7.95.

The obtained polymer was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene standard, 150 ℃ C.) to obtain Mn 27358 and PDI 1.87.

Example 18

P-BNBP-2fBBSez (C28) macromolecule, the structural formula is shown as follows (in the structural formula, the blocking group is omitted):

the polymer of P-BNBP-2fBBSez (C28) was prepared as in example 1. Except that the benzodithiazole bistin salt was replaced by difluorobenzodiselenazole bistin salt. The polymer yield was 57mg, 82%.

Elemental analysis of the prepared polymer resulted in the following: calculated C, 64.07; h, 8.72; b, 1.56; f, 8.22; n, 6.06; se, 11.38. The experimental value is C, 64.17; h, 8.67; and N, 6.11.

The resulting polymer was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene standard, 150 ℃ C.) to obtain Mn 47878 and PDI 2.11.

Example 19

P-BNBP-2ClBBTz (C28) macromolecule, the structural formula is shown as follows (in the structural formula, the end capping group is omitted):

the preparation of the polymer P-BNBP-2ClBBTz (C28) was the same as in example 1. Except that the bisthiazole bistin salt was replaced by a bisthiazole bistin salt. The polymer yield was 58mg, 88%.

Elemental analysis of the prepared polymer resulted in the following: calculated value C, 67.01; h, 9.12; b, 1.63; cl, 5.35; f, 5.73; n, 6.34; and S, 4.83. The experimental value is C, 67.05; h, 9.06; and N, 6.30.

The obtained polymer was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene standard, 150 ℃ C.) to obtain Mn 78542 and PDI 1.85.

Example 20

P-BNBP-2ClBBSez (C28) macromolecule, the structural formula is shown as follows (in the structural formula, the blocking group is omitted):

the polymer of P-BNBP-2ClBBSez (C28) was prepared as in example 1. Except that the benzodithiazole bistin salt was replaced with the dichlorobenzodiselenazole bistin salt. The polymer yield was 63mg, 89%.

Elemental analysis of the prepared polymer resulted in the following: calculated C, 62.58; h, 8.52; b, 1.52; cl, 4.99; f, 5.35; n, 5.92; se, 11.12. The experimental value is C, 62.52; h, 8.55; and N, 6.01.

The obtained polymer was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene standard, 150 ℃ C.) to obtain Mn 54278 and PDI 1.55.

Example 21

The application of the n-type high molecular compound based on boron-nitrogen coordination bonds as a charge transport layer material of an organic field effect transistor device comprises the following steps: using the polymer P-BNBP-BBTz (C28) of example 1 as a charge transport layer, an organic field effect transistor device having a structure of Si/SiO was fabricated₂(300nm)/Au(25nm)/P-BNBP-BBTz(C28)(30nm)/PMMA(500nm)/Au(80nm)。

The organic field-effect transistor device of example 21 was examined for its performance, and fig. 7 is a transfer characteristic curve of this polymer transistor device, and fig. 8 is an output characteristic curve of this polymer transistor device. Using the n-type polymer compound of the present invention based on boron-nitrogen coordinate bonds as a charge transport material, the electron mobility of the material calculated from the transfer characteristic curve was 0.12cm² v_- ¹s^-1。

Example 22

N-type high molecular compound based on boron-nitrogen coordination bond as charge transfer of organic field effect transistor deviceApplication of material for conveying layer: using the polymer P-BNBP-BBTz (C32) of example 2 as a charge transport layer, an organic field effect transistor device having a structure of Si/SiO was fabricated₂(300nm)/Au(25nm)/P-BNBP-DTBX(100nm)/PMMA(500nm)/Au(80nm)。

The organic field effect transistor device of example 22 was tested for performance, and fig. 9 is an n-type transfer characteristic curve of the polymer transistor device, and fig. 10 is an n-type output characteristic curve of the polymer transistor device. Using the n-type polymer compound of the present invention based on a boron-nitrogen coordinate bond as a charge transport material, the electron mobility of the material calculated from the transfer characteristic curve was 0.41cm² v^-1s^-1。

Example 23

The application of the n-type high molecular compound based on boron-nitrogen coordination bonds as a charge transport layer material of an organic field effect transistor device comprises the following steps: using the polymer P-BNBP-2fBBTz (C32) of example 11 as a charge transport layer, an organic field effect transistor device having a structure of Si/SiO was fabricated₂(300nm)/Au(25nm)/P-BNBP-2fBBTz(C32)(40nm)/PMMA(500nm)/Au(80nm)。

The organic field-effect transistor device of example 23 was examined for its performance, and fig. 11 is an n-type transfer characteristic curve of this polymer transistor device, and fig. 12 is an n-type output characteristic curve of this polymer transistor device. It is explained that the electron mobility of the material calculated from the transfer characteristic curve using the n-type polymer compound based on boron-nitrogen coordinate bond of the present invention as a charge transport material is 0.20cm² V^-1s^-1。

Example 24

The application of the n-type high molecular compound based on boron-nitrogen coordination bonds as a charge transport layer material of an organic field effect transistor device comprises the following steps: using the polymer P-BNBP-2fBBTz (C32') obtained in example 12 as a charge transport layer, an organic field effect transistor device having a structure of Si/SiO₂(300nm)/Au(25nm)/P-BNBP-2fBBTz(C32’)(20nm)/PMMA(500nm)/Au(80nm)。

Performance testing of the organic field effect transistor device of example 24 was conducted, and FIG. 13 shows the typeThe n-type transfer characteristic curve of the polymer transistor device, and fig. 14 is an n-type output characteristic curve of the polymer transistor device. It is explained that the electron mobility of the material calculated from the transfer characteristic curve using the n-type polymer compound based on boron-nitrogen coordinate bond of the present invention as a charge transport material is 0.43cm² V^-1s^-1。

Example 25

The application of the n-type high molecular compound based on boron-nitrogen coordination bonds as a charge transport layer material of an organic field effect transistor device comprises the following steps: using the polymer P-BNBP-2CNBBtz (C28) of example 13 as a charge transport layer, an organic field effect transistor device having a structure of Si/SiO was fabricated₂(300nm)/Au(25nm)/P-BNBP-2CNBBTz(C28)(30nm)/PMMA(500nm)/Au(80nm)。

The organic field-effect transistor device of example 25 was examined for its performance, and fig. 15 is an n-type transfer characteristic curve of this polymer transistor device, and fig. 16 is an n-type output characteristic curve of this polymer transistor device. It is explained that the electron mobility of the material calculated from the transfer characteristic curve using the n-type polymer compound based on boron-nitrogen coordinate bond of the present invention as a charge transport material is 0.41cm² V^-1s^-1。

Example 26

The application of the n-type high molecular compound based on boron-nitrogen coordination bonds as a charge transport layer material of an organic field effect transistor device comprises the following steps: using the polymer P-BNBP-2fBBSez (C28) of example 18 as a charge transport layer, an organic field effect transistor device having a structure of Si/SiO was fabricated₂(300nm)/P-BNBP-2fBBSez(C28)(30nm)/Au(40nm)。

The organic field-effect transistor device of example 26 was examined for its performance, and fig. 17 is an n-type transfer characteristic curve of this type of polymer transistor device, and fig. 18 is an n-type output characteristic curve of this type of polymer transistor device. It is explained that the electron mobility of the material calculated from the transfer characteristic curve using the n-type polymer compound based on boron-nitrogen coordinate bond of the present invention as a charge transport material is 0.39cm² V^-1s^-1。

Example 27

The application of the n-type high molecular compound based on boron-nitrogen coordination bonds as a charge transport layer material of an organic field effect transistor device comprises the following steps: using the polymer P-BNBP-2fBDT (C28) of example 4 as a charge transport layer, an organic field effect transistor device having a structure of Si/SiO was fabricated₂(300nm)/Au(25nm)/P-BNBP-2fBDT(C28)(30nm)/PMMA(500nm)/Au(80nm)。

The organic field-effect transistor device of example 27 was examined for its performance, and fig. 19 is an n-type transfer characteristic curve of this type of polymer transistor device, and fig. 20 is an n-type output characteristic curve of this type of polymer transistor device. It is explained that the electron mobility of the material calculated from the transfer characteristic curve using the n-type polymer compound based on boron-nitrogen coordinate bond of the present invention as a charge transport material is 0.17cm² V^-1s^-1。

Example 28

The application of the n-type high molecular compound based on boron-nitrogen coordination bonds as a charge transport layer material of an organic field effect transistor device comprises the following steps: using the polymer P-BNBP-2fBDT (C32) of example 5 as a charge transport layer, an organic field effect transistor device having a structure of Si/SiO was fabricated₂(300nm)/Au(25nm)/P-BNBP-2fBDT(C32)(30nm)/PMMA(500nm)/Au(80nm)。

The organic field-effect transistor device of example 28 was examined for its performance, and fig. 21 is an n-type transfer characteristic curve of this polymer transistor device, and fig. 22 is an n-type output characteristic curve of this polymer transistor device. It is explained that the electron mobility of the material calculated from the transfer characteristic curve using the n-type polymer compound based on boron-nitrogen coordinate bond of the present invention as a charge transport material is 0.24cm² V^-1s^-1。

Example 29

The application of the n-type high molecular compound based on boron-nitrogen coordination bonds as a charge transport layer material of an organic field effect transistor device comprises the following steps: using the polymer P-BNBP-2fBDT (C24) of example 5 as a charge transport layer, an organic field effect transistor device having a structure of Si/SiO was fabricated₂(300nm)/Au(25nm)/P-BNBP-2fBDT(C24)(30nm)/PMMA(500nm)/Au(80nm)。

The organic field-effect transistor device of example 29 was examined for its performance, and fig. 23 is an n-type transfer characteristic curve of this type of polymer transistor device, and fig. 24 is an n-type output characteristic curve of this type of polymer transistor device. It is explained that the electron mobility of the material calculated from the transfer characteristic curve using the n-type polymer compound based on boron-nitrogen coordinate bond of the present invention as a charge transport material is 0.41cm² V^-1s^-1。

Example 30

The application of the n-type high molecular compound based on boron-nitrogen coordination bonds as a charge transport layer material of an organic field effect transistor device comprises the following steps: using the polymer P-BNBP-2CNBDT (C24) of example 9 as a charge transport layer, an organic field effect transistor device having a structure of Si/SiO was fabricated₂(300nm)/P-BNBP-2CNBDT(C24)(30nm)/Au(40nm)。

The organic field effect transistor device of example 30 was tested for performance, and fig. 25 is an n-type transfer characteristic curve of the polymer transistor device, and fig. 26 is an n-type output characteristic curve of the polymer transistor device. It is explained that the electron mobility of the material calculated from the transfer characteristic curve using the n-type polymer compound based on boron-nitrogen coordinate bond of the present invention as a charge transport material is 0.40cm² V^-1s^-1。

Examples 21 to 30 show that the n-type polymer compound based on boron-nitrogen coordinate bond of the present invention can regulate its charge transport type by adjusting-Ar-unit.

It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims

1. An n-type high molecular compound based on boron-nitrogen coordination bonds is characterized in that the structure is shown as formula (I):

a is O, S or Se, b is CH or N, and c is F, Cl or CN.

2. The n-type polymer compound according to claim 1, wherein-Ar-is one of the following structures:

3. the method for producing an n-type polymer compound based on a boron-nitrogen coordinate bond according to claim 1 or 2, characterized by comprising the steps of:

the structural formula of the bis (trimethyl tin) monomer is as follows:

4. the method for preparing an n-type polymer compound based on boron-nitrogen coordination bonds according to claim 3, wherein the organic solvent is toluene, and the concentrations of the bisbromine monomer and the bistrimethyltin monomer of the diboron-nitrogen coordination bond-bridged bipyridine in the organic solvent are respectively 0.005-0.1 mM.

5. The method for preparing an n-type polymer compound based on boron-nitrogen coordination bonds according to claim 3, wherein the weight ratio of the bisbromine monomer, the bistrimethyltin monomer and the tetrakis (triphenylphosphine) palladium in the bisboron-nitrogen coordination bonds to the bipyridine is 1:1: 0.04.

6. The method for preparing an n-type polymer compound based on boron-nitrogen coordination bonds according to claim 3, wherein the Stille polymerization reaction is carried out at a reaction temperature of 110-120 ℃ for 1-96 h.

7. The method for preparing an n-type polymer compound based on boron-nitrogen coordination bonds according to claim 3, wherein a cocatalyst of cuprous iodide is further added in the Stille polymerization reaction, and the mass ratio of the cuprous iodide to the bisbromine monomer of the bisboron-nitrogen coordination bond-bridged bipyridyl is 0.1: 1.

8. Use of an n-type polymer compound based on boron-nitrogen coordination bonds as claimed in claim 1 or 2 as a charge transport layer material for an organic field effect transistor, wherein: the electron mobility of the charge transport layer material in the organic field effect transistorAt 0.1cm²V^-1s^-1As described above.

9. The application of the n-type high molecular compound based on boron-nitrogen coordination bonds as a charge transport layer material of an organic field effect transistor, which is characterized in that the structure of the organic field effect transistor is a top-gate bottom contact or a bottom-gate top contact;

10. The use of an n-type polymeric compound based on boron-nitrogen coordinate bonds as claimed in claim 1 or 2, after doping, in organic conductor materials and organic thermoelectric materials.