CN111548359B

CN111548359B - N-type neutral double-radical conductive compound and preparation method and application thereof

Info

Publication number: CN111548359B
Application number: CN201910109434.8A
Authority: CN
Inventors: 朱晓张; 袁达飞
Original assignee: Institute of Chemistry CAS
Current assignee: Institute of Chemistry CAS
Priority date: 2019-02-10
Filing date: 2019-02-10
Publication date: 2021-08-17
Anticipated expiration: 2039-02-10
Also published as: CN111548359A

Abstract

The invention belongs to the technical field of organic conductors, and in particular relates to a class of N-type neutral double-radical conducting compounds and a preparation method and application thereof. The compound of formula (I) prepared by the present invention has a rigid large π-conjugated plane and strong bi-radical properties, and has excellent electrical conductivity. Moreover, the compound of formula (I) prepared by the present invention has the characteristics of being easy to functionalize, and can effectively control the degree of self-doping by means of the aromaticity of the heterocyclic ring. In addition, the preparation method of the compound of formula (I) of the present invention is simple, the product yield is high, and is suitable for industrialized large-scale production. The structure of the compound of formula (I) is shown below:

Description

N-type neutral diradical conductive compound and preparation method and application thereof

Technical Field

The invention belongs to the technical field of organic conductors, and particularly relates to an N-type neutral diradical conductive compound and a preparation method and application thereof.

Background

The electric conduction is one of the important characteristics of organic conjugated materials, and has wide prospects in the fields of organic spin devices, superconductors, thermoelectric devices and the like (R.C. Haddon. Nature.1975,256,394.X. Chi, M.E. Itkis, B.O. Patrick, T.M. Barclay, R.W. Reed, R.T.Oakley, A.W. Cordes, R.C. Haddon, J.Am.chem.Soc.1999,121, 10395.). In recent years, neutral single-component organic conductors have received particular attention due to their simplicity of preparation and controllable properties (y.kobayashi, t.terauchi, s.sumi, y.matsushita, nat.mater.2017,16,109.y.joo, v.agarkar, s.h.sung, b.m.savoie, b.w.boudouris, science.2018,359,1391.a.mailman, a.a.leitch, w.yong, e.steven, s.m.winter, r.c.claridge, a.assouud, j.s.tse, s.desireniers, r.a.secco, r.t.oakley, j.am.chem.7, 2010). In addition, conductors based on neutral single-component organic compounds have important application prospects in the aspects of information reading and writing, biosensing, superconduction and the like (Itkis, M.E.; Chi, X.; Cordes, A.W.; Haddon, R.C. science.2002,296,1443.Pal, S.K.; Itkis, M.E.; Tham, F.S.; Reed, R.W.; Oakley, R.T.; Haddon, R.C. science.2005,309,281.Joo, Y.; Huang, L.; Eegurala, N.; London, A.E.; Ku A.; Wong, B.M.; Boudouris, B.W.; Azoy, J.D.macromolecules.2018,51,3886.). Relative to a large number of charge transfer complex-based organic conductors, a single-component organic conductor material is limited by the energy levels of the narrow energy band width and the wide conduction-valence band gap, and is less in variety, mainly TTF (Ueda, k.; Kamata, y.; Iwamatsu, m.; Sugimoto, t.; Fujita, h.j.mater.chem.1999,9,2979.Tanaka, h.; Okano, y.; Kobayashi, h.; Suzuki, w.; Kobayashi, a.science.2001,291,285.kobayashi, y.; yoshiaoka, m.; Saigo, k.; hashizme, d.; Ogura, t.am.chem.soc.2009, 1319995.isono., t.; Kamo, h.; uika, tayhaj h.; tayashi, d.; heka, t.t.m.m.s.; pikah.; pika, pikah.; pikah.20111, pika, h.; itkis, m.e.; kirschbaum, k.; pinkerton, a.a.; oakley, r.t.; cores, a.w.pal, s.k.; itkis, m.e.; tham, f.s.; reed, r.w.; oakley, r.t.; haddon, r.c. science.2005,309,281.c.j.am.chem.soc.2001,123,4041.bag, p.; itkis, m.e.; stekovic, d.; pal, s.k.; tham, f.s.; haddon, r.c.j.am.chem.soc.2015,137,10000.) derivatives. In general, most neutral single-component organic conductors are single-radical conductors and no N-type conductors have been reported, and quinoid diradicals are hardly considered as conductors.

Disclosure of Invention

In order to improve the above technical problems, the present invention provides a compound represented by the following formula (I):

wherein each R is₁Identical or different, independently of one another, from: hydrogen, halogen, cyano, unsubstituted or optionally substituted by one, two or more R_aSubstituted of the following groups: c_1-40Alkyl radical, C_1-40Alkoxy radical, C_3-20Cycloalkyl radical, C_3-20Cycloalkyloxy, 3-20 membered heterocyclyl, 3-20 membered heterocyclyloxy, C_6-20Aryl radical, C_6-20Aryloxy, 5-20 membered heteroaryl, 5-20 membered heteroaryloxy, - (O- (CH)₂)_n-O)_mH、-COO-R₃、-CO-R₄；

Each R₂Identical or different, independently of one another, from: hydrogen, halogen, cyano, unsubstituted or optionally substituted by one, two or more R_bSubstituted of the following groups: c_1-40Alkyl radical, C_1-40Alkoxy radical, C_3-20Cycloalkyl radical, C_3-20Cycloalkyloxy, 3-20 membered heterocyclic ringGroup, 3-20 membered heterocyclyloxy group, C_6-20Aryl radical, C_6-20Aryloxy, 5-20 membered heteroaryl, 5-20 membered heteroaryloxy, - (O- (CH)₂)_n-O)_mH、-COO-R₃、-CO-R₄；

Wherein m and n are the same or different and are independently selected from the group consisting of integers of 1 to 8, preferably 1 to 6;

the R is₃、R₄Same or different, independently from each other selected from H, C_1-40Alkyl radical, C_3-20Cycloalkyl, 3-20 membered heterocyclyl, C_6-20Aryl, 5-20 membered heteroaryl;

each R₅、R₇、R₈Identical or different, independently of one another, from: o (oxygen), S (sulfur), Se (selenium), Te (tellurium), CR₉(ii) a The R is₉Selected from H, unsubstituted or optionally substituted by one, two or more R_cSubstituted of the following groups: c_1-40Alkyl radical, C_2-40Alkenyl radical, C_2-40Alkynyl, C_1-40Alkoxy radical, C_3-20Cycloalkyl, 3-20 membered heterocyclyl, C_6-20Aryl radical, C_6-20Aryloxy, 5-20 membered heteroaryl, 5-20 membered heteroaryloxy;

each R₆Identical or different, independently of one another, from: CH. N;

each R_a、R_b、R_cIdentical or different, independently of one another, from the group formed by-F, -Cl, -Br, -I, -OH, -SH, -CN, -O, -NO₂、-NH₂Halogen substituted C_1-40Alkyl, halo C_1-40Alkyloxy, C_1-40Alkyl radical, C_1-40Alkoxy radical, C_1-40Alkylthio radical, C_2-40Alkenyl radical, C_2-40Alkenyloxy radical, C_2-40Alkenylthio radical, C_2-40Alkynyl, C_2-40Alkynyloxy, C_2-40Alkynylthio, C_3-20Cycloalkyl radical, C_3-20Cycloalkyl oxy, C_3-20Cycloalkylthio, 3-20 membered heterocyclyl, 3-20 membered heterocyclyloxy, 3-20 membered heterocyclylthio, C_6-20Aryl radical, C_6-20Aryloxy radical, C_6-20Arylthio, 5-20 membered heteroaryl, 5-20-membered heteroaryloxy, 5-20-membered heteroarylthio.

In a preferred embodiment, the compound of formula (I) has the structure:

wherein R is₁、R₂、R₅、R₆、R₇、R₈Have the above definitions;

in a preferred embodiment, each R is₁Identical or different, independently of one another, from: hydrogen, halogen, unsubstituted or optionally substituted by one, two or more R_aSubstituted of the following groups: c_1-40Alkyl radical, C_1-40Alkoxy, - (O- (CH)₂)_n-O)_mH、C_6-20An aryl group; m and n are the same or different and are independently selected from integers of 1 to 3; preferably, R_aCan be selected from-F, -Cl, -Br, -I; preferably, said R is₁Can be selected from hydrogen, fluorine, chlorine, trifluoromethyl, phenyl, n-hexyl;

in a preferred embodiment, each R is₂Identical or different, independently of one another, from: cyano, unsubstituted or optionally substituted by one, two or more R_bSubstituted of the following groups: c_1-40Alkyl radical, C_1-40Alkoxy, - (O- (CH)₂)_n-O)_mH、-COO-R₃、-CO-R₄、C_6-20An aryl group; m and n are the same or different and are independently selected from integers of 1 to 3; the R is_b、R₃、R₄Having the definitions set out above; for example, R₂Can be selected from

Each R₅、R₇、R₈Identical or different, independently of one another, from: o, S, Se, Te, CR₉(ii) a The R is₉For example selected from H;

each R₆Identical or different, independently of one another, from: CH. And N is added.

As an example, the compound of formula (I) is selected from the following specific compounds:

the present invention also provides a process for the preparation of a compound of formula (I) as defined above, comprising the steps of:

A) reacting the compound of the formula (II) with malononitrile and an oxidant to obtain a compound of the formula (I);

wherein R' "is halogen (e.g., fluoro, chloro, bromo, iodo), R₁、R₂、R₅、R₆、R₇、R₈Having the above definition.

According to the present invention, there is provided,

the preparation method specifically comprises the following steps: reacting a compound of formula (II) with malononitrile; then adding an oxidant for reaction to obtain a compound shown as a formula (I);

the reaction may be carried out in a solvent selected from ethereal solvents, such as 1, 4-dioxane;

further, when the compound of formula (II) is reacted with malononitrile, a base and a catalyst may be added to the reaction; the reaction can be carried out under heating, preferably under heated reflux; the reaction time may be 2-6 hours, for example 4 hours;

the base is preferably a strong base; the strong base is for example selected from sodium hydride;

the catalyst is selected from palladium catalysts, such as palladium tetratriphenylphosphine;

further, after the reaction of the compound of formula (II) with malononitrile is completed; the reaction system is preferably cooled, for example to room temperature; then adding an oxidant into the reaction system for reaction; the reaction may add an acid, which may be selected from hydrochloric acid, e.g. hydrochloric acid solution; the reaction time may be 0.5 to 2 hours, for example 1 hour;

the oxidant may be selected from 2, 3-dichloro-5, 6 dicyanobenzoquinone;

according to the invention, the preparation method specifically comprises the following steps: dissolving strong base and malononitrile in solvent, stirring, adding compound of formula (II) and catalyst, heating and refluxing. After cooling to room temperature, hydrochloric acid and an oxidizing agent were added.

According to the invention, the compound of formula (II) can be prepared by a process comprising:

1) mixing the compound of formula (IV) with the compound of formula (V) to obtain a compound of formula (III);

2) reacting the compound shown in the formula (III) with a halogenating agent to generate a compound shown in the formula (II);

wherein R' is an organotin group such as tri-n-butylstannyl, trimethylstannyl; r ", R'" are identical or different and are independently from each other selected from fluorine, chlorine, bromine, iodine; r₁、R₂、R₅、R₆、R₇、R₈Having the above definition.

According to the present invention, in step 1),

the reaction may be carried out with the addition of a catalyst selected from palladium catalysts, such as palladium tetratriphenylphosphine.

The reaction may be carried out in a solvent selected from at least one of aromatic hydrocarbon solvents and amide solvents, for example, a mixed solvent selected from toluene and N, N-Dimethylformamide (DMF), and the volume ratio of the two may be 1: 1;

the temperature of the reaction may be 50-130 ℃, for example 90 ℃.

The reaction time may be 12 to 36 hours, for example 48 hours.

According to the present invention, in step 2),

the halogenating agent comprises a fluorinating agent, a chlorinating agent, a brominating agent and an iodizing agent; for example, the brominating agent is selected from N-bromosuccinimide.

The reaction may be carried out in a solvent selected from at least one of halogenated hydrocarbon solvents and amide solvents, for example, a mixed solvent of chloroform and N, N-dimethylformamide, and the volume ratio of the two solvents may be 3: 1.

The reaction may be carried out at room temperature.

The reaction time may be 1 to 3 hours, for example 2 hours.

According to the invention, the preparation method of the compound of formula (II) may be specifically: dissolving the compound of formula (IV) and the compound of formula (V) in a solvent, adding palladium tetratriphenylphosphine, and stirring at 90 ℃ in the dark for two days. The resulting compound of formula (III) was dissolved in a solvent, NBS was added in the dark, and stirred at room temperature for two hours.

The invention also provides application of the compound shown in the formula (I) as a thermoelectric material in wearable power supply equipment or miniature refrigeration equipment.

The invention has the beneficial effects that:

1. the compound of the formula (I) prepared by the invention has the characteristics of large rigidity pi-conjugated plane and strong diradical, and has excellent conductivity. The compounds of formula (I) of the present invention are planar molecules with a fixed structure and no isomers. The compound has high conductivity and has the characteristic property of electron type dominant carrier conduction. The characteristic property of high conductivity is related to the characteristic strong diradical property through theoretical calculation and energy spectrum analysis.

The compound of the formula (I) has a rigid planar molecular structure and a narrow conduction band-valence band gap, so that the activation energy required for converting closed-shell quinoid into open-shell aromatic diradical is small, the coexistence of an electron-deficient quinoid structure and an electron-rich aromatic structure is realized, autodoping is carried out, and the generation of carriers is induced. So the conduction of the biradical molecules is very strong. The compound of the formula (I) covers different diradical intensities, the diradical intensity of the compound can be regulated and controlled through different aromaticity of thiophene and selenophene, and the characteristic value of the strongest diradical is 0.52 (calculated by quantum chemistry, namely (U) CAM-B3LYP/6-31G (d, p)). The conductivity of the film in the horizontal direction is up to 0.29S cm through a four-probe method^-1. The quinoid tetrathiophene conjugated molecule has high air stability and high conductivity and is suitable for application of N-type organic thermoelectric materials and electron transport layers. Wherein the power factor of the thermoelectric performance is as high as 1.4 mu W m^-1K^-2。

2. The compound of formula (I) prepared by the invention has the characteristic of easy functionalization, and can realize effective regulation and control of autodoping degree by virtue of the aromaticity of heterocyclic rings.

3. The preparation method of the compound shown in the formula (I) is simple, has high product yield, and is suitable for industrial large-scale production.

Definition and description of terms

Unless otherwise indicated, the definitions of groups and terms described in the specification and claims of the present application, including definitions thereof as examples, exemplary definitions, preferred definitions, definitions described in tables, definitions of specific compounds in the examples, and the like, may be arbitrarily combined and coupled with each other. The definitions of the groups and the structures of the compounds in such combinations and after the combination are within the scope of the present specification.

The term "halogen" is to be understood as fluorine, chlorine, bromine, iodine.

The term "C_1-40Alkyl is understood to preferably mean a straight-chain or branched, saturated monovalent hydrocarbon radical having from 1 to 40 carbon atoms, preferably C_1-10An alkyl group. "C_1-10Alkyl "is understood to preferably mean a straight-chain or branched, saturated monovalent hydrocarbon radical having 1,2, 3,4, 5,6, 7, 8, 9 or 10 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-ethylpropyl, 1, 2-dimethylpropyl, neopentyl, 1-dimethylpropyl, 4-methylpentyl, 3-methylpentylPentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3-dimethylbutyl, 2-dimethylbutyl, 1-dimethylbutyl, 2, 3-dimethylbutyl, 1, 3-dimethylbutyl or 1, 2-dimethylbutyl, and the like, or isomers thereof. In particular, the radicals have 1,2, 3,4, 5,6 carbon atoms ("C)_1-6Alkyl groups) such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, more particularly groups having 1,2 or 3 carbon atoms ("C)_1-3Alkyl groups) such as methyl, ethyl, n-propyl or isopropyl.

The term "C_2-40Alkenyl "is understood to preferably mean a straight-chain or branched monovalent hydrocarbon radical comprising one or more double bonds and having from 2 to 40 carbon atoms, preferably" C_2-10Alkenyl ". "C_2-10Alkenyl "is understood to preferably mean a straight-chain or branched, monovalent hydrocarbon radical which contains one or more double bonds and has 2,3, 4,5, 6, 7, 8, 9 or 10 carbon atoms, in particular 2 or 3 carbon atoms (" C_2-3Alkenyl "), it being understood that in the case where the alkenyl group comprises more than one double bond, the double bonds may be separated from each other or conjugated. The alkenyl group is, for example, vinyl, allyl, (E) -2-methylvinyl, (Z) -2-methylvinyl, (E) -but-2-enyl, (Z) -but-2-enyl, (E) -but-1-enyl, (Z) -but-1-enyl, pent-4-enyl, (E) -pent-3-enyl, (Z) -pent-3-enyl, (E) -pent-2-enyl, (Z) -pent-2-enyl, (E) -pent-1-enyl, (Z) -pent-1-enyl, hex-5-enyl, (E) -hex-4-enyl, (Z) -hex-4-enyl, m-n-2-enyl, m-n-1-enyl, m-n-E-4-enyl, m-n-2-enyl, m-n-enyl, m-E-4-enyl, m-2-enyl, m-pent-1-enyl, m-2-methyl-enyl, m-2-methylvinyl, m-2-methyl-2-methylvinyl, m-but-2-enyl, (E) -hex-3-enyl, (Z) -hex-3-enyl, (E) -hex-2-enyl, (Z) -hex-2-enyl, (E) -hex-1-enyl, (Z) -hex-1-enyl, isopropenyl, 2-methylprop-2-enyl, 1-methylprop-2-enyl, 2-methylprop-1-enyl, (E) -1-methylprop-1-enyl, (Z) -1-methylprop-1-enyl, 3-methylbut-3-enyl, 2-methylbut-3-enyl, 1-methylbut-3-enyl, 3-methylbut-2-enyl, (E) -2-methylbut-2-enyl, (Z) -2-methylbut-2-enyl, (E) -1-methylbut-2-enyl, (Z) -1-methylbut-2-enyl, (E) -3-methylbut-1-enyl, (Z) -3-methylbut-1-enyl, (E) -2-methylbut-1-enyl, (Z) -2-methylbut-1-enyl, (E) -1-methylbut-1-alkenyl, (Z) -1-methylbut-1-enyl, 1-dimethylprop-2-enyl, 1-ethylprop-1-enyl, 1-propylvinyl, 1-isopropylvinyl.

The term "C_2-40Alkynyl "is understood to mean a straight-chain or branched monovalent hydrocarbon radical comprising one or more triple bonds and having from 2 to 40 carbon atoms, preferably" C₂-C₁₀Alkynyl ". The term "C₂-C₁₀Alkynyl "is understood as preferably meaning a straight-chain or branched, monovalent hydrocarbon radical which contains one or more triple bonds and has 2,3, 4,5, 6, 7, 8, 9 or 10 carbon atoms. The alkynyl group is, for example, ethynyl, prop-1-ynyl, prop-2-ynyl, but-1-ynyl, but-2-ynyl, but-3-ynyl, pent-1-ynyl, pent-2-ynyl, pent-3-ynyl, pent-4-ynyl, hex-1-ynyl, hex-2-ynyl, hex-3-ynyl, hex-4-ynyl, hex-5-ynyl, 1-methylprop-2-ynyl, 2-methylbut-3-ynyl, 1-methylbut-2-ynyl, 3-methylbut-1-ynyl, 1-ethylprop-2-ynyl, prop-2-ynyl, but-3-methylbut-1-ynyl, and so-1-ethylprop-2-ynyl, 3-methylpent-4-ynyl, 2-methylpent-4-ynyl, 1-methylpent-4-ynyl, 2-methylpent-3-ynyl, 1-methylpent-3-ynyl, 4-methylpent-2-ynyl, 1-methylpent-2-ynyl, 4-methylpent-1-ynyl, 3-methylpent-1-ynyl, 2-ethylbut-3-ynyl, 1-ethylbut-2-ynyl, 1-propylprop-2-ynyl, 1-isopropylprop-2-ynyl, 2-dimethylbut-3-ynyl, 2-methylpent-4-ynyl, 1-methylpent-4-ynyl, 2-methylpent-1-ynyl, 3-methylpent-1-ynyl, 2-ynyl, 2-dimethylbut-3-ynyl, 2-methylpent-2-ynyl, 4-methylpent-alkynyl, 4-ynyl, 2-methylpent-3-ynyl, 3-methylpent-ynyl, 3-1-methylpent-1-ynyl, 3-1-methylpent-ynyl, 3-ynyl, 2-methylpent-1-ynyl, 3-1-methylpent-1-ynyl, methyl-1-methylpent-1-ynyl, 2-1-methylpent-1-ynyl, 2-1-methylpent-1-ynyl, 2-1-methylpent-1-methylpent-1-ynyl, 2-1-ynyl, 2-1-2-1-2-ynyl, 2-alkynyl, 2-butynyl, 2-butynyl, 2, 1, 1-dimethylbut-3-ynyl, 1-dimethylbut-2-ynyl or 3, 3-dimethylbut-1-ynyl. In particular, the alkynyl group is ethynyl, prop-1-ynyl or prop-2-ynyl.

The term "C_3-20Cycloalkyl is understood to mean a saturated monovalent monocyclic or bicyclic hydrocarbon ring having 3 to 20 carbon atoms, preferably "C_3-10Cycloalkyl groups ". The term "C_3-10Cycloalkyl "is understood to mean a saturated monovalent monocyclic or bicyclic hydrocarbon ring having 3,4, 5,6, 7, 8, 9 or 10 carbon atoms. Said C is_3-10Cycloalkyl groups may be monocyclic hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl, or bicyclic hydrocarbon groups such as decalin rings.

The term "3-20 membered heterocyclyl" means a saturated monovalent monocyclic or bicyclic hydrocarbon ring comprising 1-5 heteroatoms independently selected from N, O or S, preferably "3-10 membered heterocyclyl". The term "3-10 membered heterocyclyl" means a saturated monovalent monocyclic or bicyclic hydrocarbon ring comprising 1-5, preferably 1-3 heteroatoms selected from N, O or S. The heterocyclic group may be attached to the rest of the molecule through any of the carbon atoms or nitrogen atom (if present). In particular, the heterocyclic group may include, but is not limited to: 4-membered rings such as azetidinyl, oxetanyl; 5-membered rings such as tetrahydrofuranyl, dioxolyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, pyrrolinyl; or a 6-membered ring such as tetrahydropyranyl, piperidinyl, morpholinyl, dithianyl, thiomorpholinyl, piperazinyl, or trithianyl; or a 7-membered ring such as diazepanyl. Optionally, the heterocyclic group may be benzo-fused. The heterocyclyl group may be bicyclic, for example but not limited to a 5,5 membered ring, such as a hexahydrocyclopenta [ c ] pyrrol-2 (1H) -yl ring, or a 5,6 membered bicyclic ring, such as a hexahydropyrrolo [1,2-a ] pyrazin-2 (1H) -yl ring. The nitrogen atom containing ring may be partially unsaturated, i.e., it may contain one or more double bonds, such as, but not limited to, 2, 5-dihydro-1H-pyrrolyl, 4H- [1,3,4] thiadiazinyl, 4, 5-dihydrooxazolyl, or 4H- [1,4] thiazinyl, or it may be benzo-fused, such as, but not limited to, dihydroisoquinolinyl. According to the invention, the heterocyclic radical is non-aromatic.

The term "C_6-20Aryl "is understood to preferably mean a mono-, bi-or tricyclic hydrocarbon ring having a monovalent or partially aromatic character with 6 to 20 carbon atoms, preferably" C_6-14Aryl ". The term "C_6-14Aryl "is to be understood as preferably meaning a mono-, bi-or tricyclic hydrocarbon ring having a monovalent or partially aromatic character with 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms (" C_6-14Aryl group "), in particular a ring having 6 carbon atoms (" C₆Aryl "), such as phenyl; or biphenyl, or is a ring having 9 carbon atoms ("C₉Aryl), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C₁₀Aryl "), e.g. tetrahydronaphthylDihydronaphthyl or naphthyl, or is a ring having 13 carbon atoms ("C)₁₃Aryl radicals), such as the fluorenyl radical, or a ring having 14 carbon atoms ("C)₁₄Aryl), such as anthracenyl.

The term "5-20 membered heteroaryl" is understood to include such monovalent monocyclic, bicyclic or tricyclic aromatic ring systems: having 5 to 20 ring atoms and comprising 1 to 5 heteroatoms independently selected from N, O or S, such as "5-14 membered heteroaryl". The term "5-14 membered heteroaryl" is understood to include such monovalent monocyclic, bicyclic or tricyclic aromatic ring systems: which has 5,6, 7, 8, 9, 10, 11, 12, 13 or 14 ring atoms, in particular 5 or 6 or 9 or 10 carbon atoms, and which contains 1 to 5, preferably 1 to 3 heteroatoms selected independently of one another from N, O or S and, in addition, can be benzo-fused in each case. In particular, heteroaryl is selected from thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl and the like and their benzo derivatives, such as benzofuryl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, benzotriazolyl, indazolyl, indolyl, isoindolyl and the like; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the like, and benzo derivatives thereof, such as quinolyl, quinazolinyl, isoquinolyl, and the like; or azocinyl, indolizinyl, purinyl and the like and benzo derivatives thereof; or cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, and the like.

Unless otherwise indicated, heterocyclyl, heteroaryl or heteroarylene include all possible isomeric forms thereof, e.g., positional isomers thereof. Thus, for some illustrative, non-limiting examples, pyridyl or pyridinylene includes pyridin-2-yl, pyridinylene-2-yl, pyridin-3-yl, pyridinylene-3-yl, pyridin-4-yl, and pyridinylene-4-yl; thienyl or thienylene includes thien-2-yl, thien-3-yl and thien-3-yl.

Drawings

FIG. 1 is the UV-visible absorption spectra of compound 2DQQT-Se prepared in example 1 of the present invention and compound 2DQQT-S prepared in example 2.

FIG. 2 is a cyclic voltammogram of compound 2DQQT-Se prepared in example 1 of the present invention and compound 2DQQT-S prepared in example 2.

FIG. 3 is a current-voltage curve of compound 2DQQT-Se prepared in example 1 of the present invention and compound 2DQQT-S prepared in example 2.

Detailed Description

The compounds of the general formula and the preparation and use thereof according to the present invention will be described in further detail with reference to the following examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.

Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.

Example 1: preparation of 2DQQT-Se

1) Preparation of Compound (III-1): compound (IV-1) (100mg,0.11mmol) and (V-1) (148mg,0.264mmol) were dissolved in a dry mixed solvent of toluene (2mL) and DMF (2mL), added to a pressure tube under inert conditions, and deoxygenated by aeration for 20 minutes. Tetratriphenylphosphine palladium [ Pd (PPh) was added₃)₄](6.36mg,0.0055 mmol). Wherein the compound (IV-1) and the compound (V-1) and Pd (PPh)₃)₄In a molar ratio of 1:2.4: 0.05. Stirring for two days at 90 ℃, cooling to room temperature after the reaction is finished, removing the solvent, and purifying the crude product by silica gel column chromatography to obtain 134mg of red solid compound (III-1) with the yield of 90%.

2) Preparation of Compound (II-1): compound (III-1) (134mg,0.099mmol) was added to a single-necked flask under protection from light. Chloroform (3mL) and DMF (1mL) were added to dissolve, followed by NBS (39mg,0.219mmol) in a molar ratio of compound (III-1) to NBS of 1: 2.21. Stir at room temperature for about 2 hours. Extraction with dichloromethane and washing with saturated sodium hydrogen sulfite, saturated sodium bicarbonate and saturated brine in this order, the organic phase was collected and dried over anhydrous magnesium sulfate, the solvent was removed, and the crude product was subjected to silica gel column chromatography to give 130mg of compound (II-1) as a dark red solid in a yield of 90%.

3) Preparation of 2 DQQT-Se: sodium hydride (7.9mg,0.198mmol) and malononitrile (6.5mg,0.099mmol) at 60% oil dispersion were added to a schlenk reaction tube, which had been previously dried, under inert gas conditions. After stirring for about 15 minutes using anhydrous 1, 4-dioxane (4mL) as a solvent, compound (II-1) (60mg,0.0413mmol) and tetratriphenylphosphine palladium catalyst (5.0mg,0.00413mmol) were added, and the mixture was refluxed for 4 hours. Wherein the molar ratio of the sodium hydride, the malononitrile, the compound (II-1) and the tetratriphenylphosphine palladium is 4.8:2.4:1: 0.1. After the reaction cooled to room temperature, 1M dilute hydrochloric acid (2mL) was slowly added dropwise, DDQ (18.75mg,0.083mmol) was added and stirred under air for about 1 hour. The mixture was extracted with dichloromethane, washed with saturated brine, the organic phase was collected and dried over anhydrous magnesium sulfate, and the solvent was removed. The crude product was subjected to silica gel column chromatography and then washed with chloroform and methanol to give 18mg of a brown solid, i.e., 2DQQT-Se, in 30% yield. HRMS (MALDI-TOF) molecular formula: c₇₄H₉₄N₆O₄S₄Se₂。[M+H]⁺Theoretical value 1419.464094, found: 1419.464145.

example 2: preparation of 2DQQT-S

2DQQT-S was prepared with a 50% yield according to the preparation method of example 1. HRMS (MALDI-TOF) molecular formula: c₇₄H₉₄N₆O₄S₄S₂。[M+H]⁺Theoretical value 1322.565533, found: 1322.564814.

example 3: performance testing

The compound 2DQQT-Se and the compound 2DQQT-S in the above examples were dissolved in dichloromethane (about 0.00001mol/L) and spin-coated into thin films, respectively, and tested using a uv-vis spectrophotometer at room temperature, and some results are shown in fig. 1. In which it can be seen that: solutions of both compounds exhibit strong absorption in the near infrared region. The absorption of the film is obviously red-shifted compared with the solution, and a shoulder peak is generated in the region of 1300-1500nm wavelength, so that a very narrow band gap is formed, and the surface molecules can generate quinoid and aromatic resonance and perform self-doping at room temperature, which can be further proved by combining theoretical calculation with energy spectrum and single crystal data. In addition, in the 2DQQT-Se thin film, the appearance of wide charge vibration peak absorption is corresponding to the high doping degree, which also proves that the introduction of the selenophene ring can further improve the electric conductivity.

Respectively dissolving the compounds in the above examples in dichloromethane, using tetrabutylammonium perchlorate (concentration 0.1mol/L) as electrolyte, glassy carbon electrode as working electrode, platinum electrode as counter electrode, Ag/Ag using electrochemical workstation⁺The ferrocene is taken as a reference electrode and is tested under the room temperature oxygen removal condition at a certain concentration (about 0.0004-0.001 mol/L), and partial results are shown in figure 2. In which it can be seen that: in both the oxidation and reduction potential regions, the compounds exhibit a standard reversible double peak. The deep LUMO level in the figure, both compounds on the surface are N-type conductor materials and can maintain the air stability of the conductance.

The physical properties related to the conductivity, etc. of the compounds prepared in the examples of the present invention are shown in table 1 below.

Table 1: conductivity and other related physical properties of the compounds of the invention

^aRepresents the average value;^bthe maximum value is indicated.

As can be seen from table 1: the compounds of the present invention have a narrow band gap, a deep LUMO energy level and a strong dual free character. Having up to 0.29S cm without external doping^-1Is electrically conductedThe ratio can keep high Seebeck coefficient, thus obtaining higher thermoelectric performance.

As can be seen from fig. 3: both 2DQQT-S and 2DQQT-Se are conductors; the introduction of selenium atoms will significantly reduce the resistance.

The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1.A compound of the following formula (I):

wherein each R is₁Identical or different, independently of one another, from C_1-40Alkyl radical, C_1-40An alkoxy group;

each R₂Identical or different, independently of one another, from C_1-40Alkyl radical, C_1-40An alkoxy group;

each R₅Identical or different, independently of one another, from: o, S, Se, Te;

R₆is selected from N;

R₇selected from: CH (CH);

each R₈Identical or different, independently of one another, from: o, S, Se, Te.

2. The compound of formula (I) according to claim 1, wherein said formula (I) has the following structure:

wherein R is₁、R₂、R₅、R₈Having the definition set forth in claim 1.

3. A compound of formula (I) according to claim 1 or 2, wherein R is₁Selected from n-hexyl;

R₂is selected from

Each R₅、R₈Identical or different, independently of one another, from: o, S, Se, Te;

R₆is selected from N;

R₇is selected from CH.

4. The compound of formula (I) according to claim 1 or 2, characterized in that it is selected from the following specific compounds:

5. a process for the preparation of a compound of formula (I) according to claim 1 or 2, characterized in that it comprises the following steps:

wherein R' "is selected from halogen, R₁、R₂、R₅、R₆、R₇、R₈Having the definition as claimed in claim 1 or 2.

6. The method according to claim 5, wherein the method comprises: reacting a compound of formula (II) with malononitrile; then adding an oxidant for reaction to obtain a compound shown as a formula (I);

the reaction is carried out in a solvent selected from ether solvents.

7. The preparation method according to claim 5, wherein when the compound of formula (II) is reacted with malononitrile, the reaction is carried out by adding a base and a catalyst; the reaction is carried out under heating conditions; the reaction time is 2-6 hours;

the alkali is strong alkali;

the catalyst is selected from palladium catalysts.

8. The process for the preparation of the compound of formula (I) according to claim 5, characterized in that it comprises the following steps:

wherein R' is selected from an organotin group; r ", R'" are identical or different and are independently from each other selected from fluorine, chlorine, bromine, iodine; r₁、R₂、R₅、R₆、R₇、R₈Having the definition as claimed in claim 1 or 2;

in the step 1), the step (A) is carried out,

adding a catalyst into the reaction, wherein the catalyst is selected from palladium catalysts;

the reaction is carried out in a solvent, and the solvent is at least one selected from aromatic hydrocarbon solvents and amide solvents;

the reaction temperature is 50-130 ℃;

the reaction time is 12-36 hours;

in the step 2), the step (c) is carried out,

the halogenating agent comprises a fluorinating agent, a chlorinating agent, a brominating agent and an iodizing agent;

the reaction is carried out in a solvent, and the solvent is at least one selected from halogenated hydrocarbon solvents and amide solvents;

the reaction is carried out at room temperature;

the reaction time is 1-3 hours.

9. The process for the preparation of the compound of formula (I) according to claim 8, characterized in that R' is selected from tri-n-butyltin group or trimethyltin group;

in the step 1), the solvent is selected from a mixed solvent of toluene and N, N-dimethylformamide, and the volume ratio of the toluene to the N, N-dimethylformamide is 1: 1;

in the step 2), the brominating agent is selected from N-bromosuccinimide; the solvent is a mixed solvent of trichloromethane and N, N-dimethylformamide, and the volume ratio of the trichloromethane to the N, N-dimethylformamide is 3: 1.

10. A compound represented by the following formula (II):

wherein, R is₁、R₂、R₅、R₆、R₇、R₈Having the definition as claimed in any of claims 1 to 3, R' "is selected from halogen.

11. Use of a compound of formula (I) according to any one of claims 1 to 4 as a thermoelectric material in a wearable power supply device or a micro-refrigeration device.