WO2016029843A1

WO2016029843A1 - Naphthalene diimide containing 2-(1,3-dithio/seleno-2-subunit)ethylcyanide conjugate structural unit and derivatives thereof

Info

Publication number: WO2016029843A1
Application number: PCT/CN2015/088040
Authority: WO
Inventors: 高希珂; 赵征; 胡云宾; 王中丽
Original assignee: 中国科学院上海有机化学研究所
Priority date: 2014-08-25
Filing date: 2015-08-25
Publication date: 2016-03-03
Also published as: CN104230953A; CN104230953B

Abstract

A naphthalene diimide containing a 2-(1,3-dithio/seleno-2-subunit)ethylcyanide conjugate structural unit and derivatives thereof, and particularly, a compound represented by the following formula (A), wherein the groups are as defined in the specification. The monomer can be used for preparing a series of polymers (dimers or polymers) with favorable device performance; and the polymers can be used for preparing organic photoelectric devices with favorable performance.

Description

Naphthalene diimide containing 2-(1,3-disulfide/selenium-2-ylidene) acetonitrile conjugated structural unit and its derivative

Technical field

The present invention relates to the field of organic electronic materials, and in particular, the present invention provides a class of naphthalene diimide-deficient electrons containing 2-(1,3-disulfide/selenium-2-ylidene) acetyl cyanide conjugated structural units. Type polymerized monomers, dimer compounds (oligomers) and polymers, and methods for their preparation and use.

Background technique

Organic electronic new materials are the material basis for the development of organic electronic devices. The rapid development of organic optoelectronic devices such as organic field effect transistors and polymer solar cells urgently requires organic semiconductor materials with high mobility, high stability and easy processing.

Achieving all-organic flexible electronic devices requires semiconductor materials to have good film formation and processability, and can use printed electronic technology such as enamel film, inkjet printing, roll-to-roll printing, etc., large area, low Cost and scale production of electronic devices (Arias, AC et al. Chem. Rev. 2010, 110, 3). The synthesis of oligomers and polymer materials with larger molecular weights to increase the viscosity of materials is an important way to improve the film formation and processability of materials. At present, solution-processable p-type semiconductor materials have developed rapidly and device performance has been greatly improved (Minemawari, H. et al. Nature 2011, 475, 364.; Kang, I. et al. J. Am. Chem. Soc. 2013). , 135, 14896.). The development of solution-processable n-type oligomers and high-polymer semiconductors is relatively lagging, and n-type oligomers and polymer materials with high electron mobility, air stability and good processability are particularly in short supply (Gao, X. et al. J. Mater. Chem. C, 2014, 2, 3099). However, n-type oligomers and high polymer materials with high electron mobility, air stability and good processability are critical for the realization of large-area preparation of logic gates by solution methods and the development of all-organic polymer solar cells. Role (Anthony, JE; et al. Adv. Mater. 2010, 22, 3876).

For the development of n-type oligomers and high-polymer semiconductor materials, the biggest bottleneck at present is the lack of polymerizable monomers (reaction intermediates) capable of effectively reducing the LUMO energy level of semiconductor materials (Li, HYet al. J. Am. Chem. Soc. 2013, 135, 14920.; Lei, T. et al. J. Am. Chem. Soc. 2013, 135, 12168.). Existing receptor units used to construct n-type oligomers and polymers are still concentrated in naphthalene diimides and perylene diimides (Gao, X. et al. J. Mater. Chem. C, 2014). , 2, 3099). Therefore, it is the key to develop new n-type semiconductor materials by exploring new synthetic polymer units with lower LUMO energy levels (<-4.0eV) and synthesizing larger molecular weight oligomers or polymers.

In summary, there is an urgent need in the art to develop semiconductor materials having good device performance.

Summary of the invention

It is an object of the present invention to provide a semiconductor material having good device performance.

In a first aspect of the invention, there is provided a compound of formula (A):

Wherein R is a group selected from the group consisting of H, a substituted or unsubstituted C1-C48 alkyl group, a substituted or unsubstituted C2-C48 alkenyl group, a substituted or unsubstituted C6-C24 cycloalkyl group. ;

R ₁ , R ₂ , R ₃ and R ₄ are each independently selected from the group consisting of H, halogen;

Or R ₁ and R ₂ together form a group selected from the group consisting of:

Or R ₃ and R ₄ together form a group selected from the group consisting of:

Wherein said X is selected from the group consisting of Cl, Br, and I;

And R ₁ , R ₂ , R ₃ and R _{4 are} not simultaneously a group selected from the group consisting of H or halogen;

And when the group formed by R ₁ and R ₂ and the group formed by R ₃ and R ₄ are the same, neither is

In another preferred embodiment, R is a C6-C40 alkyl group.

In another preferred embodiment, R is a C12-C40 alkyl group.

In another preferred embodiment, Y is S.

In another preferred embodiment, the compound of formula (A) has a structure selected from the group consisting of:

Wherein X, Y and R are as defined above; preferably, Y is S.

According to a second aspect of the invention, there is provided a use of a compound of formula (A) according to the first aspect of the invention for the preparation of a naphthalene diimide derivative.

In another preferred embodiment, the naphthalene diimide derivative is selected from the group consisting of π-expanded naphthalene diimide small molecule compounds, oligomers or polymers.

In another preferred embodiment, the naphthalene diimide derivative has a structure represented by the following formula:

among them,

R, R ₁ , R ₂ , R ₃ , R ₄ and Y are as defined in the first aspect of the invention;

R _{5 is} selected from the group consisting of unsubstituted, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C1-C30 heteroarylene, or 2-5 substituted or unsubstituted C6-C30 a subunit formed by coupling an arylene group and/or a substituted or unsubstituted C1-C30 heteroarylene group; preferably, R ₅ is a group selected from the group consisting of 2 or 3 selected from the group consisting of The group formed by the coupling of the group:

Wherein, an integer of n=0-1000, preferably n=0-500, more preferably n=0-300;

Wherein, any R _{6 is} independently selected from the group consisting of H, C 1 -C 20 alkyl; or when R ₆ is a substituent on the thiophene, benzene ring, naphthalene ring or pyrazine, it may also be a C1-C20 Alkoxy group;

Any Z is independently selected from the group consisting of S, Se, O, Te or a combination thereof, preferably S;

Any Z' is independently selected from the group consisting of S, Se, Te, preferably S;

In another preferred embodiment, n = 0 to 100, preferably, n = 0 to 50, and more preferably, n = 0 to 30.

In another preferred embodiment, the naphthalene diimide derivative has a structure represented by the following formula (B) or formula (C):

Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently selected from the group consisting of H, halogen;

Or R ₁ and R ₂ together form a group selected from the group consisting of:

Or R ₃ and R ₄ together form a group selected from the group consisting of:

Wherein X is selected from the group consisting of Br, I; and Y is selected from the group consisting of S, Se;

among them,

The definitions of R ₅ , n, Y are as described above.

According to a third aspect of the present invention, there is provided a naphthalene diimide polymer which is obtained by using a compound of the formula (A) as described in the first aspect of the invention as a monomer. Prepared by polymerization or copolymerization;

Preferably, the naphthalene diimide derivative has a structure represented by the following formula:

among them,

R ₁ , R ₂ , R ₃ , R ₄ are as defined in the first aspect of the invention;

R _{5 is} as defined above; preferably, R _{5 is} selected from the group consisting of: none, or from 2 to 3 groups selected from the group consisting of:

Wherein, an integer of n=0-1000, preferably n=0-500, more preferably n=0-300;

Wherein, any R _{6 is} independently selected from the group consisting of H, C1-C20 alkyl; and when R ₆ is a substituent on the thiophene, benzene ring, naphthalene ring or pyrazine, it may also be a C1-C20 alkane. Oxylate

More preferably, the naphthalene diimide polymer has a structure represented by the following formula (B):

Or R ₁ and R ₂ together form a group selected from the group consisting of:

Or R ₃ and R ₄ together form a group selected from the group consisting of:

Or the naphthalene diimide polymer has a structure represented by the following formula (C):

Or R ₁ and R ₂ together form a group selected from the group consisting of:

Or R ₃ and R ₄ together form a group selected from the group consisting of:

The definitions of R ₅ and n are as described above;

In the above formulas, R is as defined in the first aspect of the invention.

In another preferred embodiment, the chemical structure of the naphthalene diimide polymer is as shown in the following formula (2) or formula (3):

Wherein R = C6 - C30 alkyl, π-3 = H or

Wherein R = C6 - C48 alkyl, π-4 is none, or a group selected from the group consisting of: or a group of 2 to 3 groups selected from the group consisting of:

Wherein, an integer of n=0-1000, preferably n=0-500, more preferably n=0-300;

Wherein any R _{6 is} independently selected from the group consisting of H, C1-C20 alkyl;

When R ₆ is a substituent on a thiophene, a benzene ring, a naphthalene ring or a pyrazine, it may also be a C1-C20 alkoxy group;

According to a fourth aspect of the invention, there is provided a process for the preparation of a compound of formula (A) according to the first aspect of the invention, comprising the steps of:

(a) reacting a compound of formula Ia with a halogenating reagent in an inert solvent to provide a compound of formula I or a compound of formula II;

Or include the steps:

(b) reacting a compound of formula (IIIa) or a compound of formula (IIIc) with a halogenating reagent in an inert solvent to provide a compound of formula (IIIb) or (IIId);

Wherein M is CN or H, and the remaining groups are as defined in the first aspect of the invention.

In another preferred embodiment, the steps are carried out in air or under the protection of an inert gas.

In another preferred embodiment, the inert solvent is a chlorine-containing organic solvent, preferably selected from the group consisting of chloroform, carbon tetrachloride, or a combination thereof.

In another preferred embodiment, when M is H, a compound of formula I is prepared; when M is CN, a compound of formula II is prepared.

In another preferred embodiment, the compound of formula Ia is selected from the group consisting of N-alkyl (R) substituted 2-(1,3-dithio-2-ylidene) acetonitrile fused naphthalene diacyl Imine, N-alkyl (R) substituted 2-(1,3-dithio-2-ylidene)propane cyanide and 2-(1,3-dithio-2-ylidene)acetonitrile asymmetry Fused naphthalene diimide.

In another preferred embodiment, the halogenating agent is selected from the group consisting of liquid bromine, NBS, NIS, or a combination thereof.

In another preferred embodiment, the molar ratio of the compound of formula Ia to the halogenating agent is from 1:1 to 3.

In another preferred embodiment, the reaction is carried out at 0 to 50 °C.

In another preferred embodiment, the reaction time is from 30 minutes to 3 hours.

In another preferred embodiment, the compound of formula (IIIa) is prepared by the following method:

The compound of the formula (IIIc) is reacted with NaBH ₄ , Pd(dppf)Cl ₂ ·CH ₂ Cl ₂ or tetramethylethylenediamine (TMEDA) in an inert solvent to give a compound of the formula (IIIa);

Wherein each group is as defined above.

In another preferred embodiment, the molar ratio of the compound of formula (IIIc) to NaBH ₄ , Pd(dppf)Cl ₂ ·CH ₂ Cl ₂ , tetramethylethylenediamine (TMEDA) is 1:2 in the reaction. ~34: 0.05-0.2: 2~4.

In another preferred embodiment, the inert solvent is an organic solvent, preferably selected from the group consisting of tetrahydrofuran, toluene, chlorobenzene, or a combination thereof.

In another preferred embodiment, the reaction temperature of the reaction is from 0 ° C to 30 ° C.

In another preferred embodiment, the reaction is carried out under the protection of an inert gas.

In another preferred embodiment, the compound of formula (IIIc) is prepared by the following method:

The compound of the formula (IIIe) is reacted with a hydrate of 2-cyanoethene-1,1-dithiolate or 2-cyanoethene-1,1-diselenoate in an inert solvent to give the formula (IIIc) Compound;

Wherein each group is as defined above.

In another preferred embodiment, the 2-cyanoethene-1,1-dithiolate is

Wherein E is an alkali metal ion, preferably a sodium ion or a potassium ion.

In another preferred embodiment, the molar ratio of (IIIe) to 2-cyanoethylene-1,1-dithiolate is 1:1 to 2 in the reaction.

In another preferred embodiment, the inert solvent is an organic solvent. Preferably, the organic solvent is selected from the group consisting of tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N. - dimethyl acetamide, or a combination thereof.

In another preferred embodiment, the reaction temperature is -10 ° C to 50 ° C.

In another preferred embodiment, the reaction time is from 0.5 to 2 hours.

According to a fifth aspect of the invention, there is provided a process for the preparation of a naphthalenediimide polymer according to the third aspect of the invention, the method comprising the steps of:

The polymerization reaction is carried out by using a monomer represented by the formula (A) in an inert solvent to obtain a naphthalene diimide polymer according to the third aspect of the present invention; wherein the substituent of the compound of the formula (A) is as defined herein. Said in the first aspect of the invention;

Preferably, when the naphthalene diimide polymer is a compound of formula (B), the method comprises the steps of:

(i) self-coupling reaction with a compound of formula (A) in an inert solvent to give a compound of formula (B);

Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently selected from the group consisting of H, halogen; and Y is selected from the group consisting of S and Se;

Or R ₁ and R ₂ together form a group selected from the group consisting of:

Or R ₃ and R ₄ together form a group selected from the group consisting of:

Wherein said X is selected from the group consisting of Br, I;

The Y is selected from the group consisting of S, Se;

And in the compound of the formula (A), at least one of R ₁ and R ₂ or R ₃ and R ₄ together form a group selected from the group consisting of:

or

When the naphthalene diimide polymer is a compound of formula (C), the method comprises the steps of:

(ii) Polymerization of a compound of the formula (I) with a formula R _x -R ₅ -R _x (e.g., Stille, Suzuki, etc.) to give a compound of the formula (C).

Wherein said X is selected from the group consisting of Br, I;

The Y is selected from the group consisting of S, Se;

The definitions of R ₅ and n are as described above;

Rx is independently selected from the group consisting of trialkyltin, wherein the alkyl group is a C1-C4 alkyl group, or Rx is

In the above formulas, R is as defined above.

In another preferred embodiment, in the step (i), the reaction is carried out at 80 to 150 °C.

In another preferred embodiment, in the step (i), the reaction is carried out under the catalysis of palladium acetate.

In another preferred embodiment, in the step (i), the reaction is carried out in the presence of a base, and preferably, the base is diisopropylethylamine.

In another preferred embodiment, in the step (i), the inert solvent is an organic solvent, and the organic solvent is selected from the group consisting of toluene, tetrahydrofuran, and N,N-dimethylformamide. Or a combination thereof.

In another preferred embodiment, in the step (i), the molar ratio of the compound of the formula (A) to palladium acetate and diisopropylethylamine is from 1:0.5 to 2:1 to 3.

In another preferred embodiment, in the step (ii), the reaction is carried out at 60 ° C to 150 ° C.

In another preferred embodiment, the Rx-R ₅ -Rx is selected from the group consisting of monothiophene, thiophene [3,2-B] thiophene, and ditrimethyl 2,2'-bithiophene (or A bis-tin reagent or a bis-boric acid reagent or a diborate reagent of a conjugated structural unit such as a butyl)tin reagent or a double bond of a ditributyltin reagent.

In another preferred embodiment, the inert solvent is an organic solvent; preferably, the organic solvent is selected from the group consisting of toluene, xylene, chlorobenzene, dichlorobenzene, tetrahydrofuran, dioxane, and Methoxyethane, N,N-dimethylformamide, N,N-dimethylacetamide, or a combination thereof.

In another preferred embodiment, in the step (ii), the reaction is carried out in the presence of a palladium catalyst; preferably, the palladium catalyst is selected from the group consisting of Pd ₂ (dba) ₃ and Pd (PPh). ₃ ) ₄ , PdCl ₂ (PPh ₃ ) ₂ , Pd(AcO) ₂ .

In another preferred embodiment, in the step (ii), the reaction is carried out in the presence of a ligand; preferably, the ligand is P(o-tol) ₃ , P(t-Bu) ₃ or other organophosphorus ligands.

In another preferred embodiment, in the step (ii), the molar ratio of the compound of the formula (I) to the palladium catalyst, the ligand, and the tin reagent is 1:0.03 to 0.1:0.03 to 0.1:0.98 to 1.02. .

According to a sixth aspect of the invention, there is provided a use of a compound of the formula A according to the first aspect of the invention or a naphthalene diimide polymer according to the second aspect of the invention, for use in the preparation of the group consisting of Products: organic field effect transistors, organic solar cell active materials, semiconductor active layers, carrier transport materials for optoelectronic devices, organic dyes/pigments, near-infrared absorbing materials.

According to a seventh aspect of the invention, there is provided a part comprising a compound of the formula A according to the first aspect of the invention or a naphthalene diimide polymer according to the third aspect of the invention; Or the article is prepared using a compound of formula A as described in the first aspect of the invention or a naphthalene diimide polymer as described in the third aspect of the invention.

In another preferred embodiment, the article is selected from the group consisting of an organic field effect transistor, an organic solar cell active material, a semiconductor active layer, a carrier transport material for an optoelectronic device, an organic dye/pigment, and a near-infrared absorbing material. .

In another preferred embodiment, the article is an organic thin film field effect transistor.

In another preferred embodiment, the organic thin film field effect transistor has a semiconductor layer prepared using a naphthalene diimide polymer as described above.

In another preferred embodiment, the organic thin film field effect transistor has an electron mobility of 0.3 - 0.5 cm ² V ^-1 s ^-1 .

In another preferred embodiment, the organic thin film field effect transistor has a switching ratio of 10 ⁵ to 10 ⁶ .

It is to be understood that within the scope of the present invention, the various technical features of the present invention and the various technical features specifically described hereinafter (as in the embodiments) may be combined with each other to constitute a new or preferred technical solution. Due to space limitations, we will not repeat them here.

DRAWINGS

Figure 1 is an ultraviolet absorption spectrum of Compound 6-9 in dichloromethane.

Figure 2 is a UV absorption spectrum of compound 10-13 in chlorobenzene.

Figure 3 is a UV absorption spectrum of Compound 14 in dichloromethane.

Figure 4 is a cyclic voltammetry curve of compound 6-9 in dichloromethane.

Figure 5 is a cyclic voltammetry curve of a compound 10-13 film.

Figure 6 is a cyclic voltammetry curve of compound 14 in dichloromethane.

Figure 7 is an output and transfer curve of an OTFT device of Compound 6-9; wherein Figures a), b) correspond to the compound of Example 6, Figure c), d) corresponds to the compound of Example 7, Figure e), f) Corresponds to the compound of Example 8.

Figure 8 is an output and transfer curve of an OTFT device of Compound 10.

Figure 9 is an output and transfer curve of the OTFT device of Compound 11.

Figure 10 is an output and transfer curve of an OTFT device of Compound 12.

Figure 11 is an output and transfer curve of the OTFT device of Compound 13.

Figure 12 is a transfer curve of the OTFT device of Compound 14.

Figure 13 is a schematic view showing the structure of an OTFT device using Compound 6-14 as an organic layer.

Symbol Description:

In Fig. 1, Fig. 2 and Fig. 3, "Wavelength (nm)" is "absorption wavelength (nanometer)", "Absorbance (a.u.)" is "phase For the absorption intensity".

In Fig. 4, Fig. 5 and Fig. 6, "Potential (V)" is "voltage (volt)", and "Current (μA)" is "current (microampere)".

In Figure 7-12, “V _DS (V)” is “source drain voltage (volts)”, “I _DS (μA)” is “source leakage current (microampere)”, and “V _GS (V)” is “gate”. Extreme voltage (volts).

detailed description

After long-term and intensive research, the present inventors prepared a kind of monomer as described in formula (A), which can be homopolymerized or copolymerized to prepare a series of organic electronic device materials with good device properties. . Based on the above findings, the inventors completed the present invention.

In order to increase the molecular weight of the material to increase the viscosity and improve its film formability and processability, the inventors reported nine types of naphthalene containing 2-(1,3-dithio-2-ylidene) acetyl cyanide conjugate units which have not been reported. Diimide-based electron-deficient polymerizable monomers, dimer compounds (oligomers), and polymers (the following formulas are described in the following description, and the number is used):

Class I is an N-alkyl (R) substituted 2-(1,3-dithio-2-ylidene) haloacetonitrile fused naphthalene diimide derivative;

Class II is N-alkyl (R) substituted 2-(1,3-dithio-2-ylidene)propane cyanide and 2-(1,3-dithio-2-ylidene)halide a cyanide asymmetrically fused naphthalene diimide compound;

Class III is a N-alkyl (R) substituted 2-(1,3-dithio-2-ylidene) acetonitrile unilaterally condensed naphthalene diimide derivative;

Class IV is N-alkyl (R) substituted 2-(1,3-dithio-2-ylidene)propane cyanide and 2-(1,3-disulfur-2-ylidene) acetyl cyanide a dimer of a symmetrically fused naphthalene diimide derivative;

Class V is a dimer of a N-alkyl (R) substituted 2-(1,3-dithio-2-ylidene)acetate unilaterally condensed naphthalene diimide derivative;

a compound of the class VI, which is a copolymer of an N-alkyl (R)-substituted 2-(1,3-dithio-2-ylidene) acetonitrile-fused naphthalene diimide derivative and a monothiophene;

Class VII compound is an N-alkyl (R) substituted 2-(1,3-dithio-2-ylidene) acetonitrile fused naphthalene diimide derivative with thiophene [3,2-B a copolymer of thiophene;

a compound of the VIII type, which is an N-alkyl (R)-substituted 2-(1,3-dithio-2-ylidene) acetonitrile-fused naphthalene diimide derivative and 2,2'-binar a copolymer of thiophene;

The compound of the IX class is a copolymer of an N-alkyl (R)-substituted 2-(1,3-disulfo-2-ylidene) acetonitrile-fused naphthalene diimide derivative and a double bond;

The compound of the X-type is a homopolymer formed by self-polymerization of an N-alkyl (R)-substituted 2-(1,3-disulfo-2-ylidene) acetonitrile-fused naphthalene diimide derivative;

In the formula, R is a C6-C48 alkyl group, and X is a bromine or iodine atom.

The inventors also applied the above-mentioned types of naphthalene diimide oligomers and polymers containing 2-(1,3-dithio-2-ylidene)acetonitrile conjugated units to OTFT devices.

the term

As used herein, the term "alkyl of C1-C4" refers to a straight or branched alkyl group having from 1 to 4 carbon atoms, such as methyl, ethyl, propyl, butyl, or the like.

As used herein, the term "C1-C4 alkoxy" refers to a straight or branched alkoxy group having from 1 to 4 carbon atoms, such as An oxy group, an ethoxy group, a propoxy group, a butoxy group, or the like.

The term "arylene group of C6 to C30" means a group in which an aromatic ring having 6 to 30 carbon atoms loses two hydrogen atoms, such as a phenylene group, a naphthylene group, or the like.

The term "heteroarylene of C1 to C30" means a group in which a heteroaromatic ring having 1 to 30 carbon atoms loses two hydrogen atoms, such as a pyridylene group, a thienylene group, or the like.

The term "halogen" means fluoro, chloro, bromo, iodo.

As used herein, the term "polymer" includes the polymerization of all monomers, such as dimers, oligomers, and polymers.

As used herein, the term "homopolymerization" refers to a polymerization carried out by a monomer, such as a polymerization of a oxalyl hexamethylenediamine monomer. The term "homopolymer" refers to a polymer polymerized from a monomer such as polyhexamethylenediamine (nylon 66). In particular, the polymerization herein includes addition polymerization and polycondensation.

As used herein, the term "copolymerization" refers to a polymerization carried out by two or more monomers, such as a polymerization of a phenol and a formaldehyde monomer. The term "copolymer" refers to a polymer obtained by polymerizing two or more monomers, such as a phenolic resin. In particular, the polymerization herein includes addition polymerization and polycondensation.

Unless otherwise stated, all structures containing a double bond or a triple bond herein mean all cis and trans isomers.

Unless otherwise specified, herein, the expression "Y is independently selected from S, Se" means that in each formula, any group represented by Y may be optionally S or Se. In a preferred embodiment of the invention, each Y may be the same or different in the same chemical formula.

Unless specifically stated otherwise, the term "substituted" means that one or more hydrogen atoms on the group are substituted with a substituent selected from the group consisting of halogen, C1-C20 alkyl, C1-C20 alkoxy.

Compound of formula (A) (polymerized monomer)

The present inventors have provided a compound for carrying out a polymerization reaction to prepare a compound represented by the following formula (A):

Wherein R is a substituted or unsubstituted C6-C48 alkyl group;

Or R ₁ and R ₂ together form a group selected from the group consisting of:

Or R ₃ and R ₄ together form a group selected from the group consisting of:

Wherein said X is selected from the group consisting of Br, I;

And R ₁ , R ₂ , R ₃ and R _{4 are} not simultaneously H or halogen;

In another preferred embodiment, R is a C6-C30 alkyl group.

In another preferred embodiment, R is a C12-C30 alkyl group.

In another preferred embodiment, the compound of formula (A) may be a symmetrically fused naphthalene diimide derivative or an asymmetrically fused naphthalene diimide derivative having a structure selected from the group consisting of:

Wherein X and R are as defined in the first aspect of the invention.

Preparation of the compound of formula (A)

The invention also provides a preparation method of the compound of formula (A), comprising the steps of:

Or include the steps:

(b) reacting a compound of formula (IIIa) with a halogenating reagent in an inert solvent to provide a compound of formula (IIIb);

In another preferred embodiment, the inert solvent is a chlorine-containing organic solvent, preferably selected from the group consisting of chloroform and carbon tetrachloride.

In another preferred embodiment, the compound of formula Ia is selected from the group consisting of N-alkyl (R) substituted 2-(1,3-dithio-2-arylene) Ethyl cyanide fused naphthalene diimide, N-alkyl (R) substituted 2-(1,3-dithio-2-ylidene)propane cyanide and 2-(1,3-disulfide -2-subunit) acetyl cyanide asymmetrically fused naphthalene diimide.

Each starting material can be purchased commercially or by prior art in the art. In another preferred embodiment, the compound of formula Ia (preferably (2-(1,3-dithio-2-ylidene))cyanide symmetrically fused naphthalene diimide and 2-(1,3-disulfide) -2-subunit) propylenediacetate/2-(1,3-dithio-2-ylidene) acetyl cyanide asymmetrically condensed naphthalene diimide derivative) can be synthesized by the method of CN201310322972.8, N - Hydrates of alkyl (R) substituted 2,3,6,7-tetrabromonaphthalene diimide and 2-cyanoethene-1,1-dithiolate can be referred to patent CN200910197611.9 and literature Acta. Chem. Scand. 1996, 50, 432 method synthesis.

In another preferred embodiment, the reaction is carried out at 0 to 50 °C.

In a preferred embodiment of the invention, the compound of formula (IIIa) is prepared by the following method:

Wherein each group is as defined in the first aspect of the invention.

In a preferred embodiment of the invention, the compound of formula (IIIb) is prepared by the following method:

Reaction of a compound of the formula (IIIe) with a hydrate of 2-cyanoethene-1,1-dithiolate in an inert solvent to give a compound of the formula (IIIc);

Wherein each group is as defined in the first aspect of the invention.

In another preferred embodiment, the 2-cyanoethene-1,1-dithiolate is

Wherein E is an alkali metal ion, preferably a sodium ion or a potassium ion, more preferably a sodium ion.

In another preferred embodiment, the reaction time is from 0.5 to 2 hours.

Preferably, after the product is obtained by the method, it is purified by silica gel column chromatography, and the developing solvent is dichloromethane, chloroform or dichloromethane/petroleum ether or chloroform/petroleum ether mixture.

The method described, the new compound obtained by mass spectrometry (MS-TOF), nuclear magnetic resonance spectra ⁽¹ H-NMR), an element analysis or multiple representations, correct structure.

The obtained naphthalene diimide derivatives of Groups I to III containing a 2-(1,3-dithio-2-ylidene)halogenated cyanide conjugate unit are used as large molecular weight n-type oligomers or A synthetic monomer compound of a high molecular semiconductor.

Naphthalene diimide derivative

The compound of the formula (A) can be used for the preparation of a naphthalene diimide derivative such as a naphthalene diimide unit-containing polymer or a substituted (e.g., halogenated) naphthalene diimide derivative.

A preferred naphthalene diimide derivative is a dimer of a compound of formula (A) having the structure shown by formula (B):

Or R ₁ and R ₂ together form a group selected from the group consisting of:

Or R ₃ and R ₄ together form a group selected from the group consisting of:

Wherein X is selected from the group consisting of Br, I.

Another preferred naphthalene diimide derivative is a copolymer of a compound of formula (A) with other small molecules containing π electrons, the structure of which is as follows:

Wherein R ₁ and R ₂ together form a group selected from the group consisting of:

Or R ₃ and R ₄ together form a group selected from the group consisting of:

R _{5 is} as defined above as a no or fully conjugated segment, preferably R _{5 is} selected from the group consisting of: none, or substituted or unsubstituted C6 to C30 arylene, substituted or unsubstituted a heteroarylene group of C1 to C30, or a subunit formed by coupling of 2 to 5 substituted or unsubstituted C6 to C30 arylene groups and/or a substituted or unsubstituted C1 to C30 heteroarylene group; Preferably, R ₅ is a group selected from the group consisting of: or a group of 2 to 3 groups selected from the group consisting of:

An integer of n=0-1000, preferably, n=0-500, more preferably, n=0-300; wherein each occurrence of R ₆ is independently H or a C1-C20 alkyl group; When R ₆ is a substituent on a thiophene ring, a benzene ring, a naphthalene ring or a pyrazine ring, it may be a C1-C20 alkoxy group.

Wherein R = C6 - C30 alkyl, π-3 = H or

Wherein R=C6-C48 alkyl, π-4, as described in the third aspect of the invention, is selected from the group consisting of: none, or a group selected from the group below, or 2 to 3 groups selected from the group consisting of Group formed by group coupling:

An integer of n=0-1000, preferably n=0-500, more preferably n=0-300;

Each occurrence of R ₆ is independently H or a C1-C20 alkyl group; when R ₆ is a substituent on the thiophene ring, the benzene ring, the naphthalene ring or the pyrazine ring, it may also be a C1-C20 alkoxy group. ;

In another preferred embodiment, the polymer has a structure selected from the group consisting of:

Method for preparing naphthalene diimide polymer

The present invention also provides a method for preparing a naphthalenediimide polymer as described above, characterized in that the method comprises the steps of:

The naphthalene diimide polymer is obtained by polymerization with a monomer represented by the formula (A) in an inert solvent; wherein the substituent of the compound of the formula (A) is as defined in the first aspect of the invention. State

Or R ₁ and R ₂ together form a group selected from the group consisting of:

Or R ₃ and R ₄ together form a group selected from the group consisting of:

Wherein said X is selected from the group consisting of Br, I;

or

(ii) Polymerizing a compound of the formula (I) with the formula R _x -R ₅ -R _x to give a compound of the formula (C).

Or R ₃ and R ₄ together form a group selected from the group consisting of:

Wherein said X is selected from the group consisting of Br, I;

The definitions of R ₅ and n are as described above;

Rx is independently selected from the group consisting of trialkyltin wherein the alkyl group is a C1-C4 alkyl group; or Rx is

or

In the above formulas, R is as defined in the first aspect of the invention.

In another preferred embodiment, in the step (i), the reaction is carried out at 80 to 120 °C.

In another preferred embodiment, in the step (i), the reaction is carried out in the presence of a base, preferably, the base It is diisopropylethylamine.

In another preferred embodiment, the Rx-R ₅ -Ry is selected from the group consisting of monothiophene, thiophene [3,2-B] thiophene, and ditrimethyl 2,2'-bithiophene (or Butyl) tin reagent or double bond di-tributyltin reagent, or its diboronic acid reagent or diborate reagent.

In another preferred embodiment, the inert solvent is an organic solvent; preferably, the organic solvent is selected from the group consisting of toluene, chlorobenzene, tetrahydrofuran, N,N-dimethylformamide, or a combination thereof. .

In another preferred embodiment, in the step (ii), the reaction is carried out in the presence of a palladium catalyst; preferably, the palladium catalyst is selected from the group consisting of Pd ₂ (dba) ₃ or Pd ( PPh ₃ ) ₄ or PdCl ₂ (PPh ₃ ) ₂ or Pd(AcO) ₂ .

In another preferred embodiment, in the step (ii), the reaction is carried out in the presence of a ligand; preferably, the ligand is an organophosphorus ligand such as P(o-tol) ₃ or P(t-Bu) ₃ .

In another preferred embodiment, in the step (ii), the molar ratio of the compound of the formula (I) to the palladium catalyst, the ligand, and the tin reagent is 1:3% to 10%: 3% to 10%. : 0.98 to 1.02.

In the method, the product of the step (i) is purified by silica gel column chromatography, and the developing solvent is dichloromethane, chloroform or dichloromethane/petroleum ether or chloroform/petroleum ether mixture; the step (ii) The target compound was purified by Soxhlet extraction in the order of methanol, acetone, petroleum ether/n-hexane, dichloromethane/chloroform and chlorobenzene.

In the method, the new compound obtained in the step (i) is characterized by one or more of mass spectrometry (MS-TOF), nuclear magnetic resonance spectrum ( ¹ H-NMR), and elemental analysis, and the structure is correct; the step (ii) is obtained. The polymer was characterized by one or more of high temperature gel liquid chromatography (GPC), nuclear magnetic resonance spectroscopy ( ¹ H-NMR), and elemental analysis, and the structure was correct.

The naphthalene diimide dimer (formula (B)) and the polymer (formula (C)) can be used as a semiconductor active layer, and are applied to an organic thin film field effect transistor, an organic solar cell active material, an organic dye, or the like.

Among them, a particularly preferred type of article is an organic thin film field effect transistor. Preferably, the organic thin film field effect transistor has a semiconductor layer prepared using a naphthalene diimide polymer as in the present invention.

The advantages of the invention are:

1. The synthetic method disclosed in the invention is simple and effective; the raw material is easy to synthesize and prepare, and the synthesis cost is low; the obtained target compound has high purity.

2. The naphthalene diimide derivative of the 2-(1,3-dithio-2-ylidene)haloacetyl cyanide unit prepared by the invention has a lower LUMO energy level: -4.0 to -4.5 The eV, large π conjugated system and flexible solubilized alkyl chain can be used to prepare n-type oligomers and polymers having low LUMO energy levels.

3. The naphthalene diimide dimer compound containing the 2-(1,3-dithio-2-ylidene)acetonitrile conjugated unit prepared by the invention can be processed by a solution method using a non-chlorine organic solvent to achieve low Green preparation of cost organic electronic devices (such as OTFT, etc.).

4. The naphthalene diimide polymer containing 2-(1,3-dithio-2-ylidene) acetonitrile conjugated unit prepared by the invention has low LUMO energy level and wide absorption spectrum. As an n-type field effect material, an acceptor material for a polymer solar cell and a near-infrared dye.

The invention is further illustrated below in conjunction with specific embodiments. It is to be understood that the examples are not intended to limit the scope of the invention. The experimental methods in the following examples which do not specify the specific conditions are usually in accordance with conventional conditions or according to the conditions recommended by the manufacturer. Percentages and parts are by weight unless otherwise stated.

As shown in the above chemical structural formula, the present invention gives a partial exemplified compound of a naphthalene diimide derivative containing a 2-(1,3-dithio-2-ylidene) acetyl cyanide unit of Groups I to X. 1 to 14 and its synthetic scheme. An example of a class I N-alkyl(R)-substituted 2-(1,3-dithio-2-ylidene)halo-ethyl cyanide symmetrically fused naphthalene diimide derivative, which is substituted The base R is 2-mercapto-dodecyl; the second type is 2-(1,3-dithio-2-ylidene)propane cyanide and 2-(1,3-dithio-2-ylidene) Two examples of halogenated acetyl cyanide asymmetrically fused naphthalene diimide compounds, compounds 2 and 3, wherein the substituent R is 3-hexyl-undecyl or 2-decyl-dodecyl, respectively; Two examples of the class II 2-(1,3-dithio-2-ylidene) bromoacetonitrile unilaterally fused naphthalene diimide derivatives, compounds 4 and 5, the substituents R are respectively n-octyl And 2-mercapto-dodecyl; Group IV 2-(1,3-dithio-2-ylidene)propanedicarboxylate and 2-(1,3-dithio-2-ylidene)B Two examples of cyanide asymmetrically fused naphthalene diimide dimer compounds, compounds 6 and 7, wherein the substituents R are 3-hexyl-undecyl and 2-decyl-dodecyl, respectively; Two examples of V-type 2-(1,3-dithio-2-ylidene)acetonitrile unilaterally condensed naphthalene diimide dimer compounds Compounds 8 and 9 have a substituent R of n-octyl And 2-mercapto-dodecyl; the compound of class VI is N-alkyl (R An example compound of a substituted 2-(1,3-dithio-2-ylidene)acetonitrile-fused naphthalene diimide derivative with a monothiophene compound, wherein R is 2-indenyl- Dodecyl branched alkyl; Group VII compound, N-alkyl (R) substituted 2-(1,3-dithio-2-ylidene) acetonitrile fused naphthalene diimide An example compound of a derivative of a derivative with thiophene [3,2-B] thiophene, wherein R is a branched alkyl group of 2-mercapto-dodecyl group; a compound of the VIII type, which is an N-alkyl group An example compound 12 of a copolymer of (R) a substituted 2-(1,3-dithio-2-ylidene) acetonitrile fused naphthalene diimide derivative and 2,2'-bithiophene, Wherein R is a branched alkyl group of 2-mercapto-dodecyl group; a compound of class IX is an N-alkyl (R) substituted 2-(1,3-dithio-2-ylidene) acetyl cyanide An example compound of a copolymer of a fused naphthalene diimide derivative and a double bond, wherein R is a branched alkyl group of 2-mercapto-dodecyl group; a compound of class X, which is an N-alkyl group An example of a homopolymer formed by self-polymerization of (R) a substituted 2-(1,3-dithio-2-ylidene) acetonitrile-fused naphthalene diimide derivative, wherein R is 2 Mercapto-dodecyl A branched alkyl group.

The photophysical properties of compound 6-14 were studied by ultraviolet absorption spectroscopy (UV). The electrochemical properties of compound 6-14 were studied by cyclic voltammetry (CV). The organic compounds of compound 6-14 were prepared by solution processing. Thin film field effect transistor device.

Preparation Examples: Compound 1-13 (Class I: 1; Class II: 2 and 3; Class III: 4 and 5; Class IV: 6 and 7; Class V: 8 and 9; Class VI) :10; Class VII: 11; Class VIII: 12; Class IX: 13; Class X: 14) Preparation

Example 1: N-(2-Mercapto-dodecyl)-[2,3-d:6,7-d']-bis[2-(1,3-dithio-2-ylidene) Synthesis of -2-bromoacetyl cyanide-naphthalene-1,4,5,8-tetracarboxylic acid diimide (1)

1 mL of Br ₂ (179 mg, 1.12 mmol) in chloroform solution was added dropwise to N-(2-mercapto-dodecyl)-[2,3-d:6,7-d']-double [ 2-(1,3-Dithio-2-ylidene)-cyanide]-naphthalene-1,4,5,8-tetracarboxylic acid diimide (568 mg, 0.487 mmol) in 8 mL of chloroform solution, reaction for 2 h The reaction was stopped, the solvent was evaporated under reduced pressure, and the residue was purified eluting with EtOAc (EtOAc) ^{_{1 H NMR (300MHz, CDCl 3}} ) δ (ppm): 0.84-0.87 (t, 12H), 1.22 (br, 80H), 2.02 (br, 2H), 4.17 (br, 4H); 13 C NMR (100MHz, CDCl ₃ ): δ: 14.10, 22.68, 26.34, 29.36, 29.63, 29.66, 29.67, 29.70, 29.71, 30.10, 31.44, 36.49, 31.53, 31.91, 36.40, 36.44, 36.49, 46.29, 71.24, 114.13, 116.10, 116.49, 124.52,124.75,124.98,145.25,145.37,147.39,147.51,161.57,161.92,161.94,162.03,162.06;MS(MALDI-TOF)m/z:1323.3M ⁺ ;Anal.Calcd.For C ₃₅ H ₄₉ N ₃ O ₃ S ₂ : C, 61.71; H, 7.46; N, 4.23. Found: C, 61.63; H, 7.54; N, 4.11.

Example 2: N-(2-octyl-dodecyl)-[2,3-d]-[2-(1,3-dithio-2-ylidene)propanedicyano]-[6, 7-d'][2-(1,3-Dithio-2-ylidene)-2-bromoacetyl]-naphthalene-1,4,5,8-tetracarboxylic acid diimide (2) Synthesis

The compound N-(2-octyl-dodecyl)-[2,3-d]-[2-(1,3-dithio-2-ylidene)propanedicyano]-[6,7- d'][2-(1,3-Dithio-2-ylidene)acetonitrile]-naphthalene-1,4,5,8-tetracarboxylic acid diimide (30 mg, 0.028 mmol) dissolved in 3 mL of chloroform To the above solution, 0.16 mL of a solution containing bromine (0.031 mmol) in chloroform (V% = 0.01) was slowly added dropwise, and the reaction mixture was stirred under reflux for 1 hour, then cooled to room temperature, and the solvent was evaporated in vacuo. The petroleum ether (1/1) is a rinsing agent, and the crude product is separated and purified by a silica gel column to obtain 28 mg of the compound (2), yield 88%. ¹ H-NMR (300MHz, CDCl ₃ ) δ (ppm): 0.86 - 0.88 (m, 6H, -CH ₃ ), 1.25 - 1.41 (m, 32H, -CH ₂ -), 2.04 (m, 1H, CH) , 4.22 - 4.25 (m, 2H, -CH ₂ -N). ¹³ C-NMR (100MHz, CDCl ₃ ): δ 14.12, 22.67, 26.30, 29.64, 36.52, 46.35, 70.19, 111.69, 114.01, 116.18, 116.62 , 117.67, 124.91, 125.12, 143.89, 144.02, 148.82, 161.40 (C=O), 161.95 (C=O), 182.41 (=CS ₂ ).MS(MALDI-TOF)m/z 1158.1(M ⁺ ).Anal .Calcd. For C ₆₁ H ₈₂ BrN ₅ O ₄ S ₄ : C, 63.30; H, 7.14; N, 6.05; Found: C, 63.27; H, 7.00; N, 6.07.

Example 3: N-(3-hexyl-undecyl)-[2,3-d]-[2-(1,3-dithio-2-ylidene)-2-propanedicyano]-[ 6,7-d'][2-(1,3-Dithio-2-ylidene)-2-bromoacetyl]-naphthalene-1,4,5,8-tetracarboxylic acid diimide ( 3) Synthesis

Using N-(3-hexyl-undecyl)-[2,3-d]-[2-(1,3-dithio-2-ylidene)-2-propanedicyano]-[6,7 -d'][2-(1,3-Dithio-2-ylidene)-2-acetonitrile]-naphthalene-1,4,5,8-tetracarboxylic acid diimide instead of N-(2- Octyl-dodecyl)-[2,3-d]-[2-(1,3-dithio-2-ylidene)-2-propanedicyano]-[6,7-d'][ 2-(1,3-Dithio-2-ylidene)-2-ethanoyl]-naphthalene-1,4,5,8-tetracarboxylic acid diimide, the synthesis method is the same as the procedure in Example 2, preparation A purple solid (3) was obtained with a yield of 82%. MS (MALDI-TOF) m/z 1074.2 (M+H) ⁺ . ¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 0.85 - 0.88 (m, 6H, -CH ₃ ), 1.30 - 1.48 ( m, 25H, -CH ₂ -and CH), 1.70 (br, 2H, -CH ₂ -), 4.25 - 4.27 (m, 2H, -CH ₂ -N). ¹³ C-NMR (100 MHz, CDCl ₃ ): δ 9.37, 17.93, 21.77, 24.60, 25.27, 27.12, 35.92, 65.51, 67.23, 106.94, 109.31, 111.47, 111.91, 112.99, 120.11, 120.32, 138.95, 139.08, 141.95, 144.06, 156.58 (C=O), 156.80 (C=O), 156.83 (C=O), 156.90 (C=O), 177.59 (=CS ₂ ). Anal. Calcd. For C ₅₅ H ₇₀ BrN ₅ O ₄ S ₄ : C, 61.55; H, 6.57 ; N, 6.52; Found: C, 61.52; H, 6.47; N, 6.51.

Example 4: N-octyl-[2,3-d]-[2-(1,3-dithio-2-ylidene)-2-bromoacetonitrile]-naphthalene-1,4,5, Synthesis of 8-tetracarboxylic acid diimide (4)

(a) N-octyl-substituted 2,3,6,7-tetrabromonaphthalenetetracarboxylic acid diimide (50 mg, 0.062 mmol) dissolved in 5 mL of tetrahydrofuran under nitrogen protection, 2-cyanoethylene The sodium 1,1-dithiolate hydrate (17 mg, 0.074 mmol) was dissolved in 2 mL of DMF and added dropwise to the reaction mixture, which was reacted at room temperature for 1 hour. The reaction liquid was poured into a saturated ammonium chloride solution to precipitate a solid, which was filtered, and the solid was subjected to column chromatography on petroleum ether/dichloromethane as a solvent silica gel column to obtain product N-octyl-[2,3-d] -[2-(1,3-Dithio-2-ylidene)acetonitrile]-6,7-dibromo-naphthalene-1,4,5,8-tetracarboxylic acid diimide 17 mg, yield 36%. MS (MALDI-TOF) m/z 761.8 (M+H) ⁺ . ¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 0.87 (br, 3H, -CH ₃ ), 1.27 - 1.38 (m, 10H) , -CH ₂ -), 1.74 (br, 2H, -CH ₂ -), 4.20 (br, 2H, -CH ₂ -N), 5.68 (s, 1H, =CH–CN). ¹³ C-NMR (100MHz , CDCl ₃ ): δ14.07, 22.60, 27.07, 27.78, 29.18, 31.75, 42.42, 42.48, 85.32, 115.55, 116.04, 116.19, 124.36, 124.52, 126.24, 135.12, 135.23, 148.03, 148.29, 159.51, 161.41, 161.53 , 164.31. Anal. Calcd. For C ₃₃ H ₃₅ Br ₂ N ₃ O ₄ S ₂ : C, 52.04; H, 4.63; N, 5.52; Found: C, 52.41; H, 4.72; N, 5.47.

(b) N-octyl-[2,3-d]-[2-(1,3-dithio-2-ylidene)acetonitrile]-6,7-dibromo-naphthalene under nitrogen protection -1,4,5,8-tetracarboxylic acid diimide (250 mg, 0.33 mmol) was dissolved in 20 mL of tetrahydrofuran, and then Pd(dppf)Cl ₂ ·CH ₂ Cl ₂ (26 mg, 0.032 mmol), N, N,N,N-tetramethylethylenediamine (TMEDA, 0.18 mL, 1.18 mmol) and sodium borohydride (NaBH ₄ , 425 mg, 11.2 mmol), the reaction was stirred at room temperature, and the reaction was completed by TLC. The reaction was quenched, extracted with dichloromethane, and the organic phase was dried over anhydrous sodium sulfate. The solvent was evaporated to remove the solvent, and petroleum ether/dichloromethane (1/1) was used as a solvent. N-octyl-[2,3-d]-[2-(1,3-dithio-2-ylidene)acetonitrile]-naphthalene-1,4,5,8-tetracarboxylic acid diimide 165 mg, yield 83%. Mp: 192 - 193 ° C. MS (MALDI-TOF) m / z 603.9 (M + H) ⁺ . ¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 0.84 - 0.86 (m, 6H, -CH ₃ ), 1.26–1.40 (m, 20H, –CH ₂ –), 1.71 (br, 2H, –CH ₂ –), 4.14–4.18 (m, 4H, –CH ₂ –N), 5.65 (s, 1H, =CH-CN), 8.66 (s, 2H, Ar-H). ¹³ C-NMR (100MHz, CDCl ₃ ): δ 14.07, 22.60, 27.04, 27.94, 29.16, 29.22, 41.43, 41.47, 52.83, 58.87, 85.13,115.57,116.93,117.04,125.03,130.41,130.47,146.94,147.20,161.70,162.53,162.67,162.94,164.58.FT-IR(KBr,cm ^-1 )ν2955.6,2924.6(s),2854.4,2204.2 (C≡N), 1702.7, 1643.4, 1547.7, 1505.0, 1462.8, 1422.8, 1379.0, 1343.1, 1313.8, 1256.7, 1215.4, 1118.7, 939.8, 875.7, 783.4, 743.8. Anal. Calcd. For C ₃₃ H ₃₇ N ₃ O ₄ S ₂ : C, 65.64; H, 6.18; N, 6.96; Found: C, 65.48; H, 6.23; N, 6.98.

(c) N-octyl-[2,3-d]-[2-(1,3-dithio-2-ylidene)acetonitrile]-naphthalene-1,4,5,8-tetracarboxylic acid The diimide (120 mg, 0.199 mmol) was dissolved in 10 mL of chloroform, and a solution of chloroform (1.2 mL, 0.234 mmol) was added and the mixture was stirred at room temperature for 2 days. The solvent was removed under reduced pressure, and the crude product was separated and purified using silica gel column eluting with petroleum ether/dichloromethane (1/1) to give compound N-octyl-[2,3-d]-[2-(1) , 3-dithio-2-ylidene-2-bromoacetonitrile]-naphthalene-1,4,5,8-tetracarboxylic acid diimide 120 mg, yield 88%. Mp: 310 - 312 ° C. MS (MALDI-TOF) m/z 655.1 (M + H) ⁺ . ¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 0.90 (br, 12H, -CH ₃ ), 1.30 (br, 20H, -CH ₂ -), 1.78 (br, 2H, -CH ₂ -), 4.27 (br, 4H, -CH ₂ -N), 5.86 (s, 1H, =CH–CN).FT -IR(KBr, cm ^-1 )ν3035.7,2923.9(s),2854.1,2204.8(C≡N),1707.6,1650.9,1540.3,1453.2,1430.7,1384.6,1352.0,1299.2,1218.6,1142.0,965.4,788.7 , 763.7,722.3,669.7,582.7.Anal.Calcd.For C ₃₅ H ₃₅ N ₅ O ₄ S ₂ :C,64.30;H,5.40;N,10.71;Found:C,64.20;H,5.50;N,10.52 .

Example 5: N-(2-octyl-dodecyl)-[2-(1,3-dithio-2-ylidene)-2-bromoacetylene]-naphthalene-1,4,5 Synthesis of 8-tetracarboxylic acid diimide (5)

The starting material is replaced by N-(2-octyl-dodecyl)tetrabromonaphthalenetetracarboxylic acid diimide instead of N-octyl substituted 2,3,6,7-tetrabromonaphthalenetetracarboxylic acid. The diimide was synthesized in the same manner as in the steps (a), (b) and (c) of Example 4 to give a red product (5) in a yield of 85%. MS (MALDI-TOF) m/z 1019.5 (M+H) ⁺ . ¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 0.81 - 0.86 (m, 6H, -CH ₃ ), 1.21 (br, 32H) , -CH ₂ -), 1.97 - 1.98 (m, 1H, CH), 4.11 - 4.14 (m, 2H, -CH ₂ -N), 8.72 (s, 2H, Ar-H). ¹³ C-NMR (100MHz , CDCl ₃ ): δ 8.90, 17.47, 21.15, 24.43, 31.29, 40.33, 65.84, 109.13, 112.14, 112.50, 119.99, 125.62, 125.72, 140.34, 142.46, 156.82, 157.71, 157.85. Anal.Calcd.For C ₅₇ H ₈₄ Br N ₃ O ₄ S ₂ : C, 67.16; H, 8.31; N, 4.12; Found: C, 67.35; H, 8.32; N, 4.02.

Example 6: N-(2-octyl-dodecyl)-[2,3-d]-[2-(1,3-dithio-2-ylidene)propanedicyano]-[6, 7-d'][2-(1,3-Dithio-2-ylidene)acetonitrile]-naphthalene-1,4,5,8-tetracarboxylic acid diimide dimer compound (6) synthesis

The compound N-(2-octyl-dodecyl)-[2,3-d]-[2-(1,3-dithio-2-ylidene)propanedicyano]-[ 6,7-d'][2-(1,3-Dithio-2-ylidene)-2-bromoacetyl]-naphthalene-1,4,5,8-tetracarboxylic acid diimide ( 200 mg, 0.173 mmol) was dissolved in 15 mL of freshly distilled DMF, and then palladium acetate (39 mg, 0.173 mmol) and diisopropylethylamine (33 μL, 0.194 mmol) were added, and the mixture was heated to 120 ° C, stirred for 16 hours, and cooled. After the reaction mixture is poured into a saturated ammonium chloride solution, the solid is precipitated, filtered, washed with water, dried in vacuo, and dichloromethane/ petroleum ether (2/1) is used as a rinse. Separation and purification gave 95 mg of Compound 6 as a blue-green solid, yield 51%. Mp: 356 - 357 ° C. MS (MALDI-TOF) m / z 2154.2 (M + H) ⁺ . ¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 0.80 - 0.85 (m, 6H, -CH ₃ ), 1.17 - 1.25 (m, 32H, -CH ₂ -), 1.99 (m, 1H, CH), 4.16 - 4.26 (m, 2H, -CH ₂ -N). ¹³ C-NMR (100 MHz, CDCl ₃ ) : δ13.67,13.70,22.19,22.23,28.80,29.21,36.00,36.13,45.98,69.77,90.73,111.25,113.05,116.22,117.26,117.34,124.56,124.69,143.61,146.85,161.55 (C=O), 161.62(C=O),167.50(C=O),182.01(=CS ₂ ).FT-IR(KBr,cm ^-1 )ν2923.7(s),2852.3,2213.0(C≡N),1686.2,1687.8 , 1640.6 (vs), 1576.4, 1558.6, 1540.0, 1532.0, 1489.6, 1457.2, 1338.7, 1295.5, 1219.2, 1068.9, 784.8, 727.7, 675.6, 625.3. Anal. Calcd. For C ₁₂₂ H ₁₆₄ N ₁₀ O ₈ S ₈ : C, 67.99; H, 7.67; N, 6.50; Found: C, 67.93; H, 7.70; N, 6.20.

Example 7: N-(3-hexyl-undecyl)-[2,3-d]-[2-(1,3-dithio-2-ylidene)propanedicyano]-[6,7 Synthesis of -d'][2-(1,3-Dithio-2-ylidene)acetonitrile]-naphthalene-1,4,5,8-tetracarboxylic acid diimide dimer compound (7)

Using N-(3-hexyl-undecyl)-[2,3-d]-[2-(1,3-dithio-2-ylidene)propanedicyano]-[6,7-d' [2-(1,3-Dithio-2-ylidene)-2-bromoacetyl]-naphthalene-1,4,5,8-tetracarboxylic acid diimide instead of N-(2-octyl) -dodecyl)-[2,3-d]-[2-(1,3-dithio-2-ylidene)propanedicyano]-[6,7-d'][2-(1 , 3-dithio-2-ylidene-2-bromoacetonitrile]-naphthalene-1,4,5,8-tetracarboxylic acid diimide, synthesized in the same manner as in Example 6, to obtain compound 7, Yield: 38%. Mp: > 420 ° C. MS (MALDI-TOF) m / z 1986.6 (M + H) ⁺ . ¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 0.82 - 0.90 (m, 6H, -CH ₃ ) , 1.25–1.51 (m, 25H, –CH ₂ –and CH), 1.66–1.71 (m, 2H, –CH ₂ –), 4.23–4.31 (m, 2H, –CH ₂ –N). ¹³ C-NMR (100MHz, CDCl ₃ ): δ14.10, 14.13, 22.64, 22.69, 26.46, 29.54, 31.80, 40.74, 70.48, 91.23, 111.71, 113.44, 116.74, 117.76, 124.93, 125.06, 144.04, 144.09, 147.10, 147.15, 161.60 (C=O), 167.88 (C=O), 182.30 (=CS ₂ ). FT-IR (KBr, cm ^-1 ) ν 2923.2 (s), 2851.5, 2199.8 (C≡N), 1709.1, 1651.7 ( Vs), 1541.5, 1576.4, 1452.9, 1425.2, 1356.8, 1298.4, 1256.8, 1220.6, 1065.8, 995.9, 788.3, 722.4, 678.6, 665.9, 622.4, 584.6, 552.8. Anal. Calcd. For C ₁₁₀ H ₁₄₀ N ₁₀ O ₈ S ₈ : C, 66.50; H, 7.10; N, 7.05; Found: C, 66.16; H, 7.13; N, 6.93.

Example 8: N-octyl-[2,3-d]-[2-(1,3-dithio-2-ylidene)acetonitrile]-naphthalene-1,4,5,8-tetracarboxylic acid Synthesis of Diimide Dimer Compound (8)

The synthesis method is the same as that in Example 6. The imide derivative of the starting material is N-octyl-[2,3-d]-[2-(1,3-dithio-2-ylidene)-2-bromo Instead of N-(2-octyl-dodecyl)-[2,3-d]-[2-(1), acetonitrile]-naphthalene-1,4,5,8-tetracarboxylic acid diimide ,3-dithio-2-ylidene)propanedicyano]-[6,7-d'][2-(1,3-dithio-2-ylidene)-2-bromoacetonitrile]-naphthalene -1,4,5,8-tetracarboxylic acid diimide, Compound 8 was obtained in a yield: 80%. MS (MALDI-TOF) m/z 1206.1 (M+H) ⁺ . ¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 0.81 - 0.90 (m, 3H, -CH ₃ ), 1.23 - 1.31 (m) , 10H, -CH ₂ -), 1.71 - 1.80 (m, 2H, -CH ₂ -), 4.15 - 4.30 (m, 2H, -CH ₂ -N), 8.79 (ds, 2H, Ar-H). FT -IR(KBr, cm ^-1 )ν2953.0,2916.7,2849.7,2201.2,1697.0,1643.5,1594.3,1551.2,1537.3,1463.1,1435.6,1417.6,1378.2,1343.3,1320.2,1284.4,1254.4,1224.3,1181.0,1121.9 , 1081.6, 1067.8, 999.1, 939.0, 887.7, 796.5, 781.9, 761.1, 748.0, 716.2, 677.8, 628.2, 601.0, 582.6, 547.2. Anal. Calcd. For C ₆₆ H ₇₂ N ₆ O ₈ S ₄ : C, 65.75 ;H, 6.02; N, 6.97; Found: C, 65.74; H, 6.11; N, 6.83.

Example 9: N-(2-octyl-dodecyl)-[2,3-d]-[2-(1,3-dithio-2-ylidene)acetonitrile]-naphthalene-1, Synthesis of 4,5,8-tetracarboxylic acid diimide dimer compound (9)

The synthesis method was the same as in Example 6. The starting material was N-(2-octyl-dodecyl)-[2,3-d]-[2-(1,3-dithio-2-ylidene)- 2-bromoacetyl cyanide-naphthalene-1,4,5,8-tetracarboxylic acid diimide instead of N-(2-octyl-dodecyl)-[2,3-d]-[2 -(1,3-Dithio-2-ylidene)propanedicyano]-[6,7-d'][2-(1,3-dithio-2-ylidene)-2-bromoacetonitrile ]-Naphthalene-1,4,5,8-tetracarboxylic acid diimide, Compound 9 was obtained in a yield: 52%. MS (MALDI-TOF) m/z 1879.7 (M+H) ⁺ . ¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 0.80 - 0.85 (m, 6H, -CH ₃ ), 1.16 - 1.31 (m) , 32H, -CH ₂ -), 1.96 - 2.02 (m, 1H, CH), 4.09 - 4.20 (m, 2H, -CH ₂ -N), 8.75 - 8.79 (m, 1H, Ar-H). ¹³ C - NMR (100 MHz, CDCl ₃ ): δ 14.06, 14.10, 22.64, 29.27, 29.94, 36.41, 36.56, 45.59, 90.53, 113.87, 117.88, 118.09, 125.27, 131.04, 146.30, 162.16, 163.02, 168.71. FT-IR (KBr,cm ^-1 )ν2923.7,2852.6,2200.2,1698.4,1644.7,1550.6,1502.4,1463.1,1419.1,1378.6,1310.1,1219.3,1120.4,1068.2,888.1,782.8,746.3,721.2,676.3.Anal.Calcd .For C ₁₁₄ H ₁₆₈ N ₆ O ₈ S ₄ : C, 72.88; H, 9.01; N, 4.47; Found: C, 72.82; H, 8.97; N, 4.42.

Example 10: N-(2-Mercapto-dodecyl)-[2,3-d:6,7-d']-bis[2-(1,3-dithio-2-ylidene) Synthesis of Copolymer (10) of Ethyl Cyanide-Naphthalene-1,4,5,8-Tetracarboxylic Acid Diimide and Monothiophene

N-(2-mercapto-dodecyl)-[2,3-d:6,7-d']-bis[2-(1,3-dithio-2-ylidene) under nitrogen protection )-2-bromoacetyl cyanide-naphthalene-1,4,5,8-tetracarboxylic acid diimide (170 mg, 0.128 mmol), 2,5-ditrimethyltinthiophene (51 mg, 0.124 mmol) Pd ₂ (dba) ₃ (3.5 mg, 3% mmol), and P(o-tol) ₃ (3.0 mg, 8% mmol) were sequentially added to a 50 mL Schlenk tube, and 20 mL of toluene was added thereto, and the mixture was reacted at 110 ° C. When the reaction solution became a gel, the reaction was terminated by dropwise addition of dilute hydrochloric acid. After cooling to room temperature, the organic phase was added dropwise to 500 mL of methanol to precipitate a green solid. The obtained solid was sequentially extracted with methanol, acetone, n-hexane and chloroform to remove small molecular weight fragments. After chlorobenzene was collected, methanol was added dropwise, and the solid was precipitated, then filtered, and dried to give a product (yield: 35%). The polymer was poorly soluble and sufficient ¹ H NMR and ¹³ C NMR signals could not be collected. Anal.Calcd.For(C ₇₂ H ₁₀₂ N ₄ O ₄ S ₅ ) _n :C, 69.30; H, 8.24; N, 4.49. Found: C, 68.95; H, 8.22; N, 4.32. Gel Permeation Chromatography (GPC) , with trichlorobenzene as eluent at 150 ° C): M _n : 33.2 kDa, M _w : 232.8 kDa, PDI: 7.0.

Example 11: N-(2-Mercapto-dodecyl)-[2,3-d:6,7-d']-bis[2-(1,3-dithio-2-ylidene) Synthesis of Copolymer (11) of Ethyl Cyanide-Naphthalene-1,4,5,8-Tetracarboxylic Acid Diimide and Thiophene [3,2-b]-thiophene

N-(2-mercapto-dodecyl)-[2,3-d:6,7-d']-bis[2-(1,3-dithio-2-ylidene) under nitrogen protection )-2-bromoacetyl cyanide]-naphthalene-1,4,5,8-tetracarboxylic acid diimide (200 mg, 0.151 mmol), 2,5-ditrimethyltinthiophene [3,2-b And thiophene (68 mg, 0.145 mmol), Pd ₂ (dba) ₃ (4 mg, 3% mmol), P(o-tol) ₃ (4.0 mg, 8% mmol) and 20 mL of toluene were sequentially added to a 50 mL Schlenk tube. The reaction was carried out at 110 ° C for 3 h, and the reaction was terminated by dropwise addition of dilute hydrochloric acid when the reaction mixture became a gel. After cooling to room temperature, the organic phase was added dropwise to 500 mL of methanol to precipitate a dark green solid. The solid was sequentially subjected to removal of a small molecular weight fragment by methanol, acetone, n-hexane or chloroform. After chlorobenzene was collected, methanol was added dropwise, and the solid was precipitated, filtered, and dried to give a product (yield: 71%). The polymer was poorly soluble and sufficient ¹ H NMR and ¹³ C NMR signals could not be collected. Anal.Calcd.For(C ₇₂ H ₁₀₂ N ₄ O ₄ S ₆ ) _n :C,68.16;H,7.88;N,4.30.Found:C,68.41;H,7.92;N,4.17.Gel Permeation Chromatography(GPC , with trichlorobenzene as eluent at 150 ° C): M _n : 19.0 kDa, M _w : 86.9 kDa, PDI: 4.6.

Example 12: N-(2-Mercapto-dodecyl)-[2,3-d:6,7-d']-bis[2-(1,3-dithio-2-ylidene) Synthesis of copolymer of acetyl cyanide-naphthalene-1,4,5,8-tetracarboxylic acid diimide and 2,2'-biphenylene (12)

N-(2-mercapto-dodecyl)-[2,3-d:6,7-d']-bis[2-(1,3-dithio-2-ylidene) under nitrogen protection )-2-bromoacetyl cyanide-naphthalene-1,4,5,8-tetracarboxylic acid diimide (200 mg, 0.151 mmol), 2,5-bis(trimethyltin)-dithiophene (72 mg) A mixture of Pd ₂ (dba) ₃ (4 mg, 3% mmol) and P(o-tol) ₃ (4.0 mg, 8% mmol) was added to a 50 mL Schlenk tube and the nitrogen was distilled three times. 20 mL of toluene was added and reacted at 110 ° C for 3 h. The reaction solution became a gel, and the reaction was terminated by dropwise addition of dilute hydrochloric acid. After cooling to room temperature, the organic phase was added dropwise to methanol to precipitate a dark green solid. The obtained solid was sequentially subjected to removal of a small molecular weight fragment by methanol, acetone, n-hexane or chloroform. After chlorobenzene was collected, methanol was added dropwise, and the solid was precipitated, filtered, and dried to give 150 mg (yield: 75%). The polymer was poorly soluble and sufficient ¹ H NMR and ¹³ C NMR signals could not be collected. Anal.Calcd.For(C ₇₆ H ₁₀₄ N ₄ O ₄ S ₆ ) _n :C,68.63;H,7.88;N,4.21.Found:C,68.53;H,7.77;N,4.11.Gel Permeation Chromatography(GPC , with trichlorobenzene as eluent at 150 ° C): M _n : 29.3 kDa, M _w : 130.6 kDa, PDI: 4.5.

Example 13: N-(2-Mercapto-dodecyl)-[2,3-d:6,7-d']-bis[2-(1,3-dithio-2-ylidene) Synthesis of copolymer of acetyl cyanide-naphthalene-1,4,5,8-tetracarboxylic acid diimide and double bond (13)

N-(2-mercapto-dodecyl)-[2,3-d:6,7-d']-bis[2-(1,3-dithio-2-ylidene) under nitrogen protection )-2-bromoacetyl cyanide-naphthalene-1,4,5,8-tetracarboxylic acid diimide (160 mg, 0.121 mmol), di-tris(butyltin)ethylene (80 mg, 0.127 mmol), Pd ₂ ( Dba) ₃ (3.0 mg, 3% mmol), and P(o-tol) ₃ (3.0 mg, 8% mmol) were added to 50 mL of Schlenk, and 20 mL of toluene was added and reacted at 110 °C. When the reaction solution became a gel, the reaction was immediately terminated. After cooling to room temperature, the organic phase was added dropwise to methanol to precipitate a solid. The solid obtained was sequentially subjected to extraction with methanol, acetone and n-hexane to remove small molecular weight fragments. The product was collected by chloroform, and then methanol was added dropwise, and the solid was precipitated, filtered, and dried to give 97 mg of product. The polymer was poorly soluble and sufficient ¹ H NMR and ¹³ C NMR signals could not be collected. Anal.Calcd.For(C ₇₀ H ₁₀₂ N ₄ O ₄ S ₄ ) _n :C,70.54;H,8.63;N,4.70.Found:C,70.86;H,8.74;N,4.32.Gel Permeation Chromatography(GPC , with trichlorobenzene as eluent at 150 ° C): M _n : 14.5 kDa, M _w : 90.5 kDa, PDI: 6.2.

Example 14: N-(2-Mercapto-dodecyl)-[2,3-d:6,7-d']-bis[2-(1,3-dithio-2-ylidene) Synthesis of homopolymer (14) of self-polymerization of acetyl cyanide-naphthalene-1,4,5,8-tetracarboxylic acid diimide

N-(2-mercapto-dodecyl)-[2,3-d:6,7-d']-bis[2-(1,3-dithio-2-ylidene) under nitrogen protection )-2-bromoacetyl cyanide-naphthalene-1,4,5,8-tetracarboxylic acid diimide (200 mg, 0.165 mmol), 1,1,1,2,2,2-hexabutyl Tin (0.083 mL, 0.165 mmol), tris(dibenzylideneacetone)dipalladium (7.6 mg, 0.00826 mmol) and tris(o-tolyl)phosphine (10 mg, 0.033 mmol) were dissolved in 20 mL of freshly distilled toluene and heated to Stir at 120 ° C for 72 h. After cooling to room temperature, the obtained solution was slowly added dropwise to 200 mL of vigorously stirred methanol, and filtered, and the obtained solid was subjected to lock extraction with methanol, acetone, petroleum ether and chloroform, and the chloroform extract was collected, and the solvent was removed under reduced pressure. , dark green solid 142mg, yield 82%. Mn: 6125, PDI: 1.12; ¹ H-NMR (300MHz, CDCl ₃ ) δ (ppm): 0.84 - 0.86 (br, 6H, -CH ₃ ), 1.15 - 1.21 (br, 32H, -CH ₂ -), 2.03 (br, 1H, CH), 4.20 (br, 2H, -CH ₂ -N); Anal. Calcd. For C ₆₀ H ₈₂ Br ₂ N ₄ O ₄ S ₄ : C, 66.87; H, 7.86; 5.03; Found: C, 67.36; H, 7.93; N, 4.94. Gel Permeation Chromatography (GPC, with chorloform as eluent at room temperature): M _n : 6.13 kDa, M _w : 7.32 kDa, PDI: 1.12.

Test example:

Example 15 UV absorption spectrum and the naphthalene diimide derivative (Examples 6-14) of Group IV-X containing a 2-(1,3-dithio-2-ylidene)acetonitrile conjugated structural unit Electrochemical properties

The UV absorption spectrum was carried out on a U-3900 spectrometer. The sample solution was dichloromethane (molar concentration 1×10 ^-6 M), the scanning range was 800-200 nm, and the UV-visible near-infrared spectrum was carried out above the Jasco-V570 spectrum. The optical band gap is calculated by the following formula:

E _gap ^opt =1240nm/λ _onset (1)

Cyclic voltammetry was performed on a computer-controlled CHI610D electrochemical analyzer using a conventional three-electrode test system with a platinum electrode as the working electrode, a saturated calomel electrode (SCE) as the reference electrode, and a platinum wire as the counter electrode. Dissolved in freshly distilled dichloromethane (molar concentration 1×10 ^-3 M), Bu ₄ NPF ₆ (0.1M) as supporting electrolyte, scanning speed 50mV/s, saturated calomel as reference, saturated calomel The energy level is -4.44 eV with respect to the vacuum level, and the LUMO level of the material can be calculated from the formula of the following energy levels:

E _LUMO =-(E _1/2 ^red1 +4.44)eV (2)

Class I-III compounds act as polymerized monomers or synthetic intermediates, so spectral and electrochemical data are not provided here.

Figure 1 shows the ultraviolet absorption spectrum of the compound 6-9 solution. As can be seen from Fig. 1, the maximum absorption peaks of the ultraviolet absorption spectra of the compound compounds 6 and 7 of the class IV naphthalene diimide derivative are around 605 nm, and the optical band gap is calculated by the formula (1) to be about 1.7 eV. . From the cyclic voltammetry curves of the

compounds

6 and 7, and the formula (2), the LUMO energy levels were -4.27 eV and -4.26 eV, respectively. The maximum absorption peaks of the

compounds

8 and 9 were about 528 nm, and the optical band gap of these compounds was calculated by the formula (1) to be 1.9 eV. From the cyclic voltammetry curve and the formula (2), it can be calculated that the LUMO energy levels of the

compounds

8 and 9 are both -3.87 eV.

Figure 2 shows the UV absorption spectrum of the copolymer 10-13 solution. Examples of the naphthalene diimide copolymer of the VI-IX type The maximum absorption peaks of the ultraviolet absorption spectrum of the compound 10-13 are about 920 nm, 946 nm, 931 nm, and 904 nm, respectively, and the optical band gap calculated by the formula (1) is 1.25, respectively. eV, 1.15eV, 1.15eV and 1.26eV. Figure 3 shows the ultraviolet absorption spectrum of the homopolymer 14 solution. Example of the X-type naphthalene diimide homopolymer The maximum absorption peak of the ultraviolet absorption spectrum of the compound 14 is about 870 nm, and the optical band gap calculated by the formula (1) is about 1.27 eV.

Figure 4 shows the cyclic voltammetry curves of compounds 6-9, both showing two reversible redox processes with half-wave potentials E _1/2 ^red1 of -0.09, -0.12, -0.48 and -0.50 eV, respectively. The LUMO levels calculated by the formula (2) are -4.27, -4.26, -3.87 and -3.87 eV, respectively. From the cyclic voltammogram of the copolymer 10-13 film (see Fig. 5) and formula (2), the LUMO energy levels can be calculated to be about -4.25 eV, -4.27 eV, -4.29 eV, and -4.29 eV, respectively. From the cyclic voltammogram of the homopolymer 14 (see Figure 6) and the formula (2), the LUMO level can be calculated to be -4.20 eV.

Thus, the Group IV-X naphthalene diimide dimer and polymer (Examples 6-14) all have low LUMO energy levels (-3.87 to -4.29 eV), wide optical absorption, and narrow optical bands. The gap (1.9 to 1.15 eV) can be used as an n-type organic field effect transistor semiconductor material and an organic solar cell acceptor material, and can also be used for a near-infrared organic dye or the like.

Example 16 Compounds 6-8 and 10-14 as Organic Semiconductor Thin Film Field Effect Transistors

This example provides Examples 6-8 of the naphthalene diimide dimer and polymer of Group IV-X containing 2-(1,3-dithio-2-ylidene)acetonitrile conjugated units. 10-14 Application as a semiconductor active layer in an organic thin film transistor (OTFT) device.

Fig. 13 is a view showing the structure of an OTFT

device using compound

6, 7, 8, 10, 11, 12, 13 or 14 as an organic semiconductor layer. The OTFT device is prepared by dissolving 5-15 mg of the

compound

6, 7, 8, 10, 11, 12, 13 or 14 in 1 mL of chlorobenzene or dichlorobenzene or xylene (heatable to help dissolve), OTS modified SiO ₂ /Si substrate (highly doped silicon substrate as gate, thermal oxide silica insulating layer thickness 300nm, capacitance 11nFcm ^-2 ) 甩 a layer of organic thickness of about 20-80nm A semiconductor thin film is deposited on the upper surface of the organic thin film by using a mask to deposit a gold or silver source drain electrode, thereby producing an upper electrode structure OTFT device having a semiconductor channel length of 30-50 μm and a channel width of 3 mm. The electrical properties of the OTFT were measured in a room temperature in air using a Keithley 4200 semiconductor tester. Among them, the example compound 6 was coated with its dichlorobenzene and xylene solution, and the OFET performance of the unannealed film and the film annealed at 120 ° C and 180 ° C was tested; the example compound 7 was used in its xylene solution. The ruthenium film was tested for the OFET performance of the unannealed film and the film annealed at 120 ° C and 180 ° C; and the example compound 8 was tested for the OFET performance of the unannealed film using the ruthenium film of the dichlorobenzene solution. Example Polymers 10-14 used a dichlorobenzene solution tantalum film, an unannealed film and OFET properties of the heat treated film at different annealing temperatures.

Figure 7 shows the output and transfer curves of the OTFT devices of the example compounds 6, 7, and 8. The example compound 6 was prepared using a dichlorophenyl hydrazine film with an electron mobility of 0.13 cm ² V ^-1 s ^-1 . The switching ratio is 10 ⁵ -10 ⁶ and the threshold voltage is 3-14V. When the device is prepared by using a non-chlorine solvent xylene ruthenium film, the electron mobility can reach 0.45 cm ² V ^-1 s ^-1 , the switching ratio is 10 ⁵ -10 ⁶ , and the threshold voltage is 1-9V. The device of Example 7 prepared using a dichlorophenyl hydrazine film has an electron mobility of 0.19 cm ² V ^-1 s ^-1 , a switching ratio of 10 ⁴ -10 ⁵ , and a threshold voltage of 6-12 V. The device prepared by using the xylene ruthenium film of the example compound 8 can reach 0.45 cm ² V ^-1 s ^-1 without annealing electron mobility. The electrical property characterization data (including mobility, switching ratio, and threshold voltage) of the OTFT devices (≥10) of

Compounds

6, 7 and 8 are listed in Table 1.

8-12 sequentially show the transfer curves of the OTFT devices of the example polymers 10-14, both of which were prepared using a dichlorobenzene solution ruthenium film. The OTFT device of the example polymer 10 exhibited a single electron transport behavior, 120 ° C. After annealing the film, the electron mobility can reach 0.38 cm ² V ^-1 s ^-1 , the switching ratio is 10 ⁵ -10 ⁶ , and the threshold voltage is 3-10 V. The OTFT device of the polymer 11 of the example exhibits bipolarity. The carrier transport behavior has a hole and electron mobility of about 10 ^-3 and 10 ^-2 cm ² V ^-1 s ^{-1 , respectively} ; the OTFT device of the embodiment polymer 12 mainly exhibits the behavior of electron transport, and its electrons The mobility is about 10 ^-2 cm ² V ^-1 s ^-1 ; the OTFT device of the polymer 13 of the example exhibits a single electron transport behavior, the film is not annealed, and the electron mobility can reach 0.22 cm ² V ^-1 s ^-1 , the switching ratio is 10 ⁵ -10 ⁷ , and the threshold voltage is -1 to 1 V; the OTFT device of the polymer 14 of the embodiment exhibits a single electron transporting behavior, and the electron mobility of the film after annealing at 120 ° C can reach 0.003 cm. ² V ^-1 s ^-1 , the switching ratio is 10 ⁵ -10 ⁸ , and the threshold voltage is 3 to 11V.

Table 1 based compound and 6,7 OTFT devices (gold source and drain electrodes) 8 electrical characterization data and annealed at different annealing temperatures not including maximum (average) electron mobility (μ _e, unit: cm ² / Vs), switching ratio (I _on /I _off ) and threshold voltage (V _T , unit: V).

Table 1 Characterization data of electrical properties of OTFT devices of

compounds

6, 7 and 8

^a dichlorobenzene solution ruthenium film; ^b xylene solution ruthenium film.

Table 2 based on the polymer OTFT devices 10-14 (gold source-drain electrode) electrically characterization data and annealed at different annealing temperatures not including maximum (average) electron mobility (μ _e, unit: cm ² / Vs ), switching ratio (I _on /I _off ) and threshold voltage (V _T , unit: V).

Table 2 Electrical property characterization data of polymer 10-14 OTFT devices

All documents mentioned in the present application are hereby incorporated by reference in their entirety in their entireties in the the the the the the the the In addition, it should be understood that various modifications and changes may be made by those skilled in the art in the form of the appended claims.

Claims

A compound of the following formula (A):

Wherein R is a group selected from the group consisting of H, a substituted or unsubstituted C1-C48 alkyl group, a substituted or unsubstituted C2-C48 alkenyl group, a substituted or unsubstituted C6-C24 cycloalkyl group. ;

R 1 , R 2 , R 3 and R 4 are each independently selected from the group consisting of H, halogen;

Or R 1 and R 2 together form a group selected from the group consisting of:

Or R 3 and R 4 together form a group selected from the group consisting of:

Wherein said X is selected from the group consisting of Cl, Br, and I;

The Y is selected from the group consisting of S, Se;

And R 1 , R 2 , R 3 and R 4 are not simultaneously a group selected from the group consisting of H or halogen;

And when the group formed by R 1 and R 2 and the group formed by R 3 and R 4 are the same, neither is
Use of a compound of formula (A) according to claim 1 for the preparation of a naphthalene diimide derivative, preferably for the preparation of a naphthalene diimide polymer.
A naphthalene diimide polymer, characterized in that the naphthalene diimide polymer is prepared by homopolymerization or copolymerization of a compound of the formula (A) according to claim 1 as a monomer;

Preferably, the naphthalene diimide derivative has a structure represented by the following formula:

among them,

R 1 , R 2 , R 3 , R 4 and Y are as defined in claim 1; preferably, Y is S;

R 5 is selected from the group consisting of: none, or substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C1-C30 heteroarylene, or 2-5 substituted or unsubstituted C6-C30 a subunit formed by coupling an arylene group and/or a substituted or unsubstituted C1 to C30 heteroarylene; preferably, R 5 is a group selected from the group consisting of 2 or 3 selected from the group consisting of Groups formed by group coupling:

An integer of n=0-1000, preferably n=0-500, more preferably n=0-300;

Wherein, any R 6 is independently selected from the group consisting of H, C1-C20 alkyl, or C1-C20 when R 6 is a substituent on the thiophene ring, the benzene ring, the naphthalene ring, or the pyrazine ring. Alkoxy group;

Any Z is independently selected from the group consisting of S, Se, O, Te, preferably S;

Any Z' is independently selected from the group consisting of S, Se, Te, preferably S;

More preferably, the naphthalene diimide polymer has a structure represented by the following formula (B):

Wherein R 1 , R 2 , R 3 and R 4 are each independently selected from the group consisting of H, halogen; Y is selected from the group consisting of S and Se;

Or R 1 and R 2 together form a group selected from the group consisting of:

Or R 3 and R 4 together form a group selected from the group consisting of:

Wherein said X is selected from the group consisting of Br, I;

The Y is selected from the group consisting of S, Se;

Or the naphthalene diimide polymer has a structure represented by the following formula (C):

among them,

Said Y is each independently selected from S, Se; R 5 is as defined in claim 3;

In the above formulas, R is as defined in claim 1;

Preferably, in formulas (B) and (C), Y is S;

Preferably, in formula (C), R 5 is selected from the group consisting of: none, or a group selected from the group consisting of: or a group of 2 to 3 groups selected from the group consisting of:

n=2-1000 integer, preferably n=2-500, more preferably, n=2-300;

Wherein, any R 6 is independently selected from the group consisting of H, C 1 -C 20 alkyl, or C 1 -C 20 when R 6 is a substituent on the thiophene ring, the benzene ring, the naphthalene ring, or the pyrazine ring. Alkoxy.
A method of preparing a compound of formula (A) according to claim 1, comprising the steps of:

(a) reacting a compound of formula Ia with a halogenating reagent in an inert solvent to provide a compound of formula I or a compound of formula II;

Or include the steps:

(b) reacting a compound of formula (IIIa or IIIc) with a halogenating reagent in an inert solvent to provide a compound of formula IIIb or IIId;

Wherein M is CN or H, and the remaining groups are as defined in claim 1.
The method of claim 4 wherein said compound of formula (IIIa) is prepared by the following method:

The compound of the formula (IIIc) is reacted with NaBH 4 , Pd(dppf)Cl 2 ·CH 2 Cl 2 or tetramethylethylenediamine (TMEDA) in an inert solvent to give a compound of the formula (IIIa);

Wherein each group is as defined in claim 1.
The method of claim 5 wherein said compound of formula (IIIc) is prepared by the following method:

The compound of the formula (IIIe) is reacted with a hydrate of 2-cyanoethene-1,1-dithiolate or 2-cyanoethene-1,1-diselenoate in an inert solvent to give the formula (IIIc) Compound;

Wherein each group is as defined in claim 1.
The method for preparing a naphthalenediimide polymer according to claim 3, wherein the method comprises the steps of:

The polymerization reaction of the monomer represented by the formula (A) is carried out in an inert solvent to obtain the naphthalenediimide polymer according to claim 3; wherein the substituent of the compound of the formula (A) is as defined in claim 1. Said in

Preferably, when the naphthalene diimide polymer is a compound of formula (B), the method comprises the steps of:

(i) self-coupling reaction with a compound of formula (A) in an inert solvent to give a compound of formula (B);

Wherein R 1 , R 2 , R 3 and R 4 are each independently selected from the group consisting of H, halogen;

Or R 1 and R 2 together form a group selected from the group consisting of:

Or R 3 and R 4 together form a group selected from the group consisting of:

Wherein said X is selected from the group consisting of Br, I;

And in the compound of the formula (A), at least one of R 1 and R 2 or R 3 and R 4 together form a group selected from the group consisting of:

or

When the naphthalene diimide polymer is a compound of formula (C), the method comprises the steps of:

(ii) polymerizing a compound of the formula (I) with the formula R x -R 5 -R x to give a compound of the formula (C);

Wherein said X is selected from the group consisting of Br, I;

R 5 , n are as defined in claim 3;

Rx is selected from the group consisting of trialkyltin,
Wherein the alkyl group is a C1-C4 alkyl group;

In the above formulas, R is as defined in claim 1.
Use of a compound of the formula A according to claim 1 or a naphthalene diimide polymer according to claim 3, for the preparation of a product selected from the group consisting of organic field effect transistors, organic solar cells Active material, carrier transport material of photovoltaic device, semiconductor active layer, organic dye/pigment, near-infrared absorbing material.
An article comprising: the compound of formula A according to claim 1 or the naphthalene diimide polymer of claim 3; or the article is used Prepared from a compound of formula A as claimed in claim 1 or a naphthalene diimide polymer as claimed in claim 3.
The article of claim 9 wherein said article is an organic thin film field effect transistor.