CN103732720B - Lu Dai perylene base semiconductor material - Google Patents

Lu Dai perylene base semiconductor material Download PDF

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CN103732720B
CN103732720B CN201280022657.7A CN201280022657A CN103732720B CN 103732720 B CN103732720 B CN 103732720B CN 201280022657 A CN201280022657 A CN 201280022657A CN 103732720 B CN103732720 B CN 103732720B
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alkyl
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base
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CN103732720A (en
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H·赖歇尔特
T·格斯纳
李晨
K·米伦
G·巴塔格利亚林
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Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
Clap Co Ltd
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BASF SE
Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
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    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
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    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom

Abstract

The invention provides formula (1) compound, wherein X is-Cl ,-Br or-I.Formula (1) compound is suitable as semiconductor material, especially in electron device, is used as semiconductor material.

Description

Lu Dai perylene base semiconductor material
Organic semiconductor material may be used for electron device as in organic photovoltaic (OPV) battery, organic field effect tube (OFET) and Organic Light Emitting Diode (OLED).
For the effective and long-time performance continued, wish that the device based on organic semiconductor material demonstrates high charge carrier mobility and high stability at ambient conditions, especially to the stability of oxidation.
In addition, wish that organic semiconductor material is compatible with liquid processing technology, because liquid processing technology is easily viewed from processibility angle, and therefore allow the electron device based on organic semiconductor material of production low cost.In addition, liquid processing technology is also compatible with plastic and therefore allow production lightweight and the electron device based on organic semiconductor material of flexibility.
Be suitable for electron device Zhong perylene double imide based organic semiconductor materials to be known in the art.
F.W ü rthnerChem.Commun.2004,1564-1579 Miao Shu perylene double imide derivative, such as
R.Schmidt, J.H.Oh, Y.-S.Sun, M.Deppisch, A.-M.Krause, K.Radacki, H.Braunschweig, M. p.Erk, Z.Bao and F.W ü rthnerJ.Am.Chem.Soc.2009,131,6215-6228 describe Lu Dai perylene double imide derivative, such as
M. j.H.Oh, M. h.W. a.-M.Krause, Z.Bao, F.W ü rthnerAngew.Chem.2010,122,752-755 describe following Lu Dai perylene double imide:
S.Nakazono, Y.Imazaki, H.Yoo, J.Yang, T.Sasamori, N.Tokitoh, T.C é dric, H.Kageyama, D.Kim, H.Shinokubo and A.OsukaChem.Eur.J.2009,15,7530-7533 describes You perylene tetracarboxylic acid imide and prepares 2,5,8,11-tetraalkyl perylene tetracarboxylic acid imide:
S.Nakanzono, S.Easwaramoorthi, D.Kim, H.Shinokubo, A.OsukaOrg.Lett.2009,11,5426-5429 describes You perylene tetracarboxylic acid imide and prepares 2,5,8,11-tetraalkyl perylene tetracarboxylic acid imide:
US7,282,275B2 describe a kind of composition, and it comprises:
-Shi [EC-] n-Ar 1(I) the first compound, wherein
Ar 1be the first aromatic kernel and be the divalence of numerous formula, trivalent or quaternary groups, comprise
Its numerous substituting groups not being substituted or being included fluorine replace,
EC is the first capping group and is the univalent perssad of numerous formula,
N is the integer of 2-4,
Z is NH or CH 2, and
-there is the aromatic group of the first aromatic kernel comprising the first compound, the second capping group comprising the first capping group of the first compound, the divalent group comprising the divalent group of the first capping group or its second compound combined,
Wherein said composition is unbodied and solution processable.
US7,355,198B2 describe OTFT (OFET), and organic receptor film is inserted source electrode and between drain electrode and organic semiconductor thin film by it.This organic semiconductor thin film is formed by pentacene.Specifically, this organic receptor film is selected from by least one and comprises N, and N '-two (di-tert-butyl-phenyl)-3,4,9,10-perylene dicarboximide is formed at the electrophilic material of interior numerous compounds.
US7,326,956B2 describes the thin film transistor comprising organic semiconductor material, this organic semiconductor material comprises based on tetramethyl pyromellitic imide perylene compound, and this compound has the carbocyclic ring replaced by one or more fluoro-containing group or heterocyclic aromatic ring system that are connected with each imide nitrogen atom.In one embodiment, the tetracarboxylic acid imide compound based on fluorine-containing N, N '-Er Fang Ji perylene is represented by having structure:
Wherein A 1and A 2independently for comprising carbocyclic ring and/or the heterocyclic aromatic ring system of the aromatic ring that at least one wherein one or more hydrogen atom is replaced by least one fluoro-containing group.Gai perylene endorses optionally replaced by 8 X group selected independently at the most, and wherein n is the integer of 0-8.X substituting group on perylene can comprise numerous substituting group, and this comprises halogen as fluorine or chlorine.
US7,671,202B2 describe the n-type semiconductor compound of following formula:
Wherein R 1-R 8h can be selected from independently of one another, electron-withdrawing substituent and comprise this substituent structure division.Electron-withdrawing substituent comprises numerous substituting group, and this comprises cyano group.R 9and R 10independently selected from the polyaromatic structure division of H, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl, polyaromatic and/or replacement.
WO2005/124453 Miao Shu perylene tetracarboxylic acid diimides charge transport material, such as, have following formula perylene tetracarboxylic acid diimides charge transport material:
Wherein Y in each case can independently selected from H, CN, acceptor, donor and polymerizable groups;
And X can organize greatly cited compound independently selected from one in each case.
WO2008/063609 describes the compound with following formula:
Wherein Q can be
Wherein A, B, I, D, E, F, G and H are independently selected from comprising CH and CR aat interior one group of substituting group, wherein R acan be selected from, comprise one group of substituting group of halogen.Such as, A, B, I, D, E, F, G and H can be CH, C-Br or C-CN independently.
WO2009/098252 describes the semiconductor compound with following formula:
Wherein R 1and R 2when occurring at every turn independently selected from numerous group, this comprises H, C 1-30alkyl and C 2-30alkenyl; And R 3, R 4, R 5and R 6be H or electron-withdrawing group independently.In certain embodiments, R 3, R 4, R 5and R 6can be H, F, Cl, Br, I or CN independently of each other.
WO2009/144205 describes the two embedding benzene of many rings naphthalene (rylene) base semiconductor compound, and it can be prepared by following formula: compound:
Wherein LG is leavings group, comprises Cl, Br or I,
π-1 can be
Wherein A, B, I, D, E, F, G and H are independently selected from comprising CH and CR aat interior one group of substituting group, wherein R athe one group of substituting group comprising halogen can be selected from.
Still can not prepare 2,5,8,11-tetra-Lu Dai perylene two (dicarboximide) up to now.
The object of the invention is to provide Xin perylene base semiconductor material.
This object is realized by the electron device of the compound of claim 1, the method for claim 5 and claim 6.
Perylene base semiconductor compound of the present invention has following formula:
Wherein
R 1and R 2be selected from H independently of each other, optionally by 1-30 substituent R athe C replaced 1-30alkyl, optionally by 1-30 substituent R athe C replaced 2-30alkenyl, optionally by 1-30 substituent R athe C replaced 2-30alkynyl, optionally by 1-10 substituent R bthe C replaced 3-10cycloalkyl, optionally by 1-10 substituent R bthe C replaced 5-10cycloalkenyl group, optionally by 1-8 substituent R bthe 3-14 person's ring replaced is mixed alkyl, optionally by 1-8 substituent R cthe C replaced 6-14aryl and optionally by 1-8 substituent R cthe 5-14 person's heteroaryl replaced,
Wherein
R athe mutual independent selected from halo when occurring at every turn ,-CN ,-NO 2,-N 3,-OH, optionally by 1-6 substituent R ithe C replaced 1-30alkoxyl group ,-O-[CH 2cH 2o] n-C 1-10alkyl (n=1-10) ,-O-[CH 2cH 2o] m-OH (m=1-10) ,-O-COR 3, optionally by 1-30 substituent R i-the S-C replaced 1-30alkyl, optionally by 1-30 substituent R i-the SO replaced 2-C 1-30alkyl ,-NH 2,-NHR 3,-NR 3r 4,-[NR 3r 4r 5] +,-NH-COR 3,-COOH ,-COOR 3,-CONH 2,-CONHR 3,-CONR 3r 4,-CO-H ,-COR 3, optionally by 1-10 substituent R iithe C replaced 3-10cycloalkyl, optionally by 1-10 substituent R iithe C replaced 5-10cycloalkenyl group, optionally by 1-10 substituent R iithe 3-14 person's ring replaced is mixed alkyl, optionally by 1-8 substituent R iiithe C replaced 6-14aryl and optionally by 1-8 substituent R iiithe 5-14 person's heteroaryl replaced;
R bthe mutual independent selected from halo when occurring at every turn ,-CN ,-NO 2,-OH, optionally by 1-30 substituent R ithe C replaced 1-30alkoxyl group ,-O-[CH 2cH 2o] n-C 1-10alkyl (n=1-10) ,-O-[CH 2cH 2o] m-OH (m=1-10) ,-O-COR 3, optionally by 1-30 substituent R i-the S-C replaced 1-30alkyl ,-NH 2,-NHR 3,-NR 3r 4,-[NR 3r 4r 5] +,-NH-COR 3,-COOH ,-COOR 3,-CONH 2,-CONHR 3,-CONR 3r 4,-CO-H ,-COR 3, optionally by 1-30 substituent R ithe C replaced 1-30alkyl, optionally by 1-30 substituent R ithe C replaced 2-30alkenyl, optionally by 1-30 substituent R ithe C replaced 2-30alkynyl, optionally by 1-10 substituent R iithe C replaced 3-10cycloalkyl, optionally by 1-10 substituent R iithe C replaced 5-10cycloalkenyl group, optionally by 1-10 substituent R iithe 3-14 person's ring replaced is mixed alkyl, optionally by 1-8 substituent R iiithe C replaced 6-14aryl and optionally by 1-8 substituent R iiithe 5-14 person's heteroaryl replaced;
R cthe mutual independent selected from halo when occurring at every turn ,-CN ,-NO 2,-N 3,-OH, optionally by 1-30 substituent R ithe C replaced 1-30alkoxyl group ,-O-[CH 2cH 2o] n-C 1-10alkyl (n=1-10) ,-O-[CH 2cH 2o] m-OH (m=1-10) ,-O-COR 3, optionally by 1-30 substituent R i-the S-C replaced 1-30alkyl, optionally by 1-30 substituent R i-the SO replaced 2-C 1-30alkyl ,-NH 2,-NHR 3,-NR 3r 4,-[NR 3r 4r 5] +,-NH-COR 3,-COOH ,-COOR 3,-CONH 2,-CONHR 3,-CONR 3r 4,-CO-H ,-COR 3, optionally by 1-30 substituent R ithe C replaced 1-30alkyl, optionally by 1-30 substituent R ithe C replaced 2-30alkenyl, optionally by 1-30 substituent R ithe C replaced 2-30alkynyl, optionally by 1-10 substituent R iithe C replaced 3-10cycloalkyl, optionally by 1-10 substituent R iithe C replaced 5-10cycloalkenyl group, optionally by 1-10 substituent R iithe 3-14 person's ring replaced is mixed alkyl, optionally by 1-8 substituent R iiithe C replaced 6-14aryl and optionally by 1-8 substituent R iiithe 5-14 person's heteroaryl replaced;
Wherein
R 3, R 4and R 5when occurring at every turn mutually independently selected from optionally by 1-30 substituent R ithe C replaced 1-30alkyl, optionally by 1-30 substituent R ithe C replaced 2-30alkenyl, optionally by 1-30 substituent R ithe C replaced 2-30alkynyl, optionally by 1-10 substituent R iithe C replaced 3-10cycloalkyl, optionally by 1-10 substituent R iithe C replaced 5-10cycloalkenyl group, optionally by 1-10 substituent R iithe 3-14 person's ring replaced is mixed alkyl, optionally by 1-8 substituent R iiithe C replaced 6-14aryl and optionally by 1-8 substituent R iiithe 5-14 person's heteroaryl replaced,
R ithe mutual independent selected from halo when occurring at every turn ,-CN ,-NO 2,-N 3,-OH, C 1-30alkoxyl group ,-O-[CH 2cH 2o] n-C 1-10alkyl (n=1-10) ,-O-[CH 2cH 2o] m-OH (m=1-10) ,-O-COR 3,-S-C 1-30alkyl ,-SO 2-C 1-30alkyl ,-NH 2,-NHR 6,-NR 6r 7,-[NR 6r 7r 8] +,-NH-COR 6,-COOH ,-COOR 6,-CONH 2,-CONHR 6,-CONR 6r 7,-CO-H ,-COR 6, C 3-10cycloalkyl, C 5-10cycloalkenyl group, 3-14 person's ring is mixed alkyl, C 6-14aryl and 5-14 person's heteroaryl,
R iithe mutual independent selected from halo when occurring at every turn ,-CN ,-NO 2,-OH, C 1-30alkoxyl group ,-O-[CH 2cH 2o] n-C 1-10alkyl (n=1-10) ,-O-[CH 2cH 2o] m-OH (m=1-10) ,-O-COR 6,-S-C 1-30alkyl ,-NH 2,-NHR 6,-NR 6r 7,-[NR 6r 7r 8] +,-NH-COR 6,-COOH ,-COOR 6,-CONH 2,-CONHR 6,-CONR 6r 7,-CO-H ,-COR 6, C 1-30alkyl, C 2-30alkenyl, C 2-30alkynyl, C 3-10cycloalkyl, C 5-10cycloalkenyl group, 3-14 person's ring is mixed alkyl, C 6-14aryl and 5-14 person's heteroaryl,
R iiithe mutual independent selected from halo when occurring at every turn ,-CN ,-NO 2,-N 3,-OH, C 1-30alkoxyl group ,-O-[CH 2cH 2o] n-C 1-10alkyl (n=1-10) ,-O-[CH 2cH 2o] m-OH (m=1-10) ,-O-COR 6,-S-C 1-30alkyl ,-SO 2-C 1-30alkyl ,-NH 2,-NHR 6,-NR 6r 7,-[NR 6r 7r 8] +,-NH-COR 6,-COOH ,-COOR 6,-CONH 2,-CONHR 6,-CONR 6r 7,-CO-H ,-COR 6, C 1-30alkyl, C 2-30alkenyl, C 2-30alkynyl, C 3-10cycloalkyl, C 5-10cycloalkenyl group, 3-14 person's ring is mixed alkyl, C 6-14aryl and 5-14 person's heteroaryl,
Wherein
R 6, R 7and R 8when occurring at every turn mutually independently selected from C 1-30alkyl, C 2-30alkenyl, C 2-30alkynyl, C 3-10cycloalkyl, C 5-10cycloalkenyl group, 3-14 person's ring is mixed alkyl, C 6-14aryl and 5-14 person's heteroaryl,
And X is-Cl ,-Br or-I.
C 1-10alkyl and C 1-30alkyl can be branching or nonbranched.C 1-10the example of alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, neo-pentyl, isopentyl, n-(1-ethyl) propyl group, n-hexyl, n-heptyl, n-octyl, n-(2-ethyl) hexyl, n-nonyl and positive decyl.C 3-8the example of alkyl is n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, neo-pentyl, isopentyl, n-(1-ethyl) propyl group, n-hexyl, n-heptyl, n-octyl and n-(2-ethyl) hexyl.C 1-30the example of alkyl is C 1-10alkyl and n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, n-heptadecane base, Octadecane base, NSC 77136 base and NSC 62789 base (C 20), n-docosane base (C 22), n-tetracosane base (C 24), n-hexacosane base (C 26), positive octacosyl (C 28) and positive triacontyl (C 30).At the C of the C place branching be connected with the N of formula I 3-25examples of alkyl is sec.-propyl, sec-butyl, n-(1-methyl) propyl group, n-(1-ethyl) propyl group, n-(1-methyl) butyl, n-(1-ethyl) butyl, n-(1-propyl group) butyl, n-(1-methyl) amyl group, n-(1-ethyl) amyl group, n-(1-propyl group) amyl group, n-(1-butyl) amyl group, n-(1-butyl) hexyl, n-(1-amyl group) hexyl, n-(1-hexyl) heptyl, n-(1-heptyl) octyl group, n-(1-octyl group) nonyl, n-(1-nonyl) decyl, n-(1-decyl) undecyl, n-(1-undecyl) dodecyl and n-(1-dodecyl) tridecyl.
C 2-30alkenyl can be branching or nonbranched.C 2-30the example of alkenyl is vinyl, propenyl, cis-2-butene base, trans-2-butene base, 3-butenyl, cis-pentenyl, trans-pentenyl, cis-3-pentenyl, trans-3-pentenyl, 4-pentenyl, 2-methyl-3-butenyl, hexenyl, heptenyl, octenyl, nonene base and decene base, sub-oil base (C 18), flax base (C 18), oil base (C 18), Eicosatetraenoic base (C 20) and two dodecenyl succinic (C 22).
C 2-30alkynyl can be branching or nonbranched.C 2-30the example of alkynyl is ethynyl, 2-propynyl, 2-butyne base, 3-butynyl, pentynyl, hexin base, heptyne base, octyne base, n-heptylacetylene base and decynyl, hendecyne base, dodecyne base, 14 carbyne bases, 15 carbyne bases, hexadecine base, 17 carbyne bases, octadecyne base, 19 carbyne bases and 20 carbyne base (C 20).
C 3-10the example of cycloalkyl is preferably monocycle C 3-10cycloalkyl as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl and ring octyl group, but also comprises many rings C 3-10cycloalkyl is as decahydro naphthyl, norcamphyl and adamantyl.
C 5-10the example of cycloalkenyl group is preferably monocycle C 5-10cycloalkenyl group as cyclopentenyl, cyclohexenyl, cyclohexadienyl and cycloheptatriene base, but also comprises many rings C 5-10cycloalkenyl group.
The mix example of alkyl of 3-14 person's ring is that monocycle 3-8 person ring is mixed alkyl and many rings, and such as dicyclo 7-12 person ring is mixed alkyl.
The mix example of alkyl of monocycle 3-8 person ring to be mixed alkyl containing a heteroatomic monocycle 5 Yuans rings, as pyrrolidyl, 1-pyrrolinyl, 2-pyrrolinyl, 3-pyrrolinyl, tetrahydrofuran base, 2,3-dihydrofuran base, tetrahydro-thienyl and 2,3-dihydro-thiophene base, containing two heteroatomic monocycles, 5 Yuans rings mix alkyl as imidazolidyl, imidazolinyl, pyrazolidyl, pyrazolinyl, oxazolidinyl, azoles quinoline base, different oxazolidinyl, different azoles quinoline base, thiazolidyl, thiazolinyl, isothiazole alkyl and isothiazoline base, mix alkyl as 1 containing three heteroatomic monocycles, 5 Yuans rings, 2, 3-triazolyl, 1, 2, 4-triazolyl and 1, 4, 2-dithiazole base, mix alkyl as piperidyl containing a heteroatomic monocycle 6 Yuans rings, piperidino-(1-position only), THP trtrahydropyranyl, pyranyl, thiophene alkyl (thianyl) and thiapyran base, mix alkyl as piperazinyl containing two heteroatomic monocycles, 6 Yuans rings, morpholinyl and morpholino and thiazinyl, mix alkyl as azepine cyclic group in heptan (azepanyl) containing a heteroatomic monocycle 7 Yuans rings, azepine base, oxa-cyclic group in heptan (oxepanyl), thiophene cyclic group in heptan (thiepanyl), thia cyclic group in heptan (thiapanyl), thia base (thiepinyl) and mix alkyl as 1,2-diaza containing two heteroatomic monocycles, 7 Yuans rings base and 1,3-sulphur azepine base (thiazepinyl).
The mix example of alkyl of dicyclo 7-12 person ring is decahydro naphthyl.
C 6-14aryl can be monocycle or many rings.C 6-14the example of aryl is monocycle C 6aryl as phenyl, dicyclo C 9-10aryl is as 1-naphthyl, 2-naphthyl, indenyl, 2,3-indanyls and tetralyl, and three ring C 12-14aryl is as anthryl, phenanthryl, fluorenyl and s-indenes thiazolinyl (indacenyl).
5-14 person's heteroaryl can be monocycle 5-8 person heteroaryl, or many rings 7-14 person heteroaryl, such as dicyclo 7-12 person heteroaryl or three ring 9-14 person heteroaryls.
The example of monocycle 5-8 person heteroaryl is containing a heteroatomic monocycle 5 Yuans heteroaryls as pyrryl, furyl and thienyl, containing two heteroatomic 5 Yuans heteroaryls as imidazolyl, pyrazolyl, azoles base, different azoles base, thiazolyl, isothiazolyl, containing three heteroatomic monocycles, 5 Yuans heteroaryls as 1,2,3-triazoles base, 1,2,4-triazolyl and di azoly, containing four heteroatomic monocycles, 5 Yuans heteroaryls as tetrazyl, containing a heteroatomic monocycle 6 Yuans heteroaryls as pyridyl, containing two heteroatomic monocycles, 6 Yuans heteroaryls as pyrazinyl, pyrimidyl and pyridazinyl, containing three heteroatomic monocycles, 6 Yuans heteroaryls as 1,2,3-triazinyl, 1,2,4-triazinyl and 1,3,5-triazinyl, containing heteroatomic 7 Yuans heteroaryls as azepine base and containing two heteroatomic 7 Yuans heteroaryls as 1,2-diaza base.
The example of dicyclo 7-12 person heteroaryl is containing a heteroatomic dicyclo 9 Yuans heteroaryls as indyl, pseudoindolyl, indolizine base, indolinyl, benzofuryl, isobenzofuran-base, benzothienyl and isobenzo-thienyl, containing two heteroatomic dicyclos, 9 Yuans heteroaryls as indazolyl, benzimidazolyl-, benzimidazoline base, benzo azoles base, benzisoxa azoles base, benzothiazolyl, benzisothiazole base, furopyridyl and thienopyridine base, containing three heteroatomic dicyclos, 9 Yuans heteroaryls as benzotriazole base, benzo di azoly, azoles pyridyl, different azoles pyridyl, thiazolopyridinyl, isothiazole pyridyl and imidazopyridyl, containing four heteroatomic dicyclos, 9 Yuans heteroaryls as purine radicals, containing a heteroatomic dicyclo 10 Yuans heteroaryls as quinolyl, isoquinolyl, benzopyranyl and chromanyl, containing two heteroatomic dicyclos, 10 Yuans heteroaryls as quinoxalinyl, quinazolyl, cinnolinyl, 2, 3-phthalazinyl, 1, 5-phthalazinyl and 1, 8-phthalazinyl, containing three heteroatomic dicyclos, 10 Yuans heteroaryls as pyrido-pyrazine base, Pyridopyrimidine base and pyrido pyridazinyl, and containing four heteroatomic dicyclos, 10 Yuans heteroaryls as pteridyl.
The example of three ring 9-14 person heteroaryls is dibenzofuran base, acridyl, fen piperazine base, 7H-cyclopenta [1,2-b:3,4-b '] dithienyl and 4H-cyclopenta [2,1-b:3,4-b '] dithienyl.
The example of halogen is-F ,-Cl ,-Br and-I.
C 1-30the example of alkoxyl group be methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.-butoxy, n-pentyloxy, neopentyl oxygen, isopentyloxy, hexyloxy, positive heptan oxygen base, n-octyloxy, positive ninth of the ten Heavenly Stems oxygen base, n-decyloxy, n-undecane oxygen base, n-dodecane oxygen base, n-tridecane oxygen base, n-tetradecane oxygen base, Pentadecane oxygen base, n-hexadecane oxygen base, n-heptadecane oxygen base, Octadecane oxygen base and NSC 77136 oxygen base.
C 2-5the example of alkylidene group is ethylidene, propylidene, butylidene and pentylidene.
Preferably,
R 1and R 2be selected from H independently of each other, optionally by 1-30 substituent R athe C replaced 1-30alkyl, optionally by 1-30 substituent R athe C replaced 2-30alkenyl, optionally by 1-10 substituent R bthe C replaced 3-10cycloalkyl and optionally by 1-8 substituent R cthe C replaced 6-14aryl,
Wherein
R athe mutual independent selected from halo when occurring at every turn ,-CN ,-NO 2,-N 3,-OH, optionally by 1-6 substituent R ithe C replaced 1-30alkoxyl group ,-O-[CH 2cH 2o] n-C 1-10alkyl (n=1-10) ,-O-[CH 2cH 2o] m-OH (m=1-10) ,-O-COR 3, optionally by 1-30 substituent R i-the S-C replaced 1-30alkyl, optionally by 1-30 substituent R i-the SO replaced 2-C 1-30alkyl ,-NH 2,-NHR 3,-NR 3r 4,-[NR 3r 4r 5] +,-NH-COR 3,-COOH ,-COOR 3,-CONH 2,-CONHR 3,-CONR 3r 4,-CO-H ,-COR 3, optionally by 1-10 substituent R iithe C replaced 3-10cycloalkyl and optionally by 1-8 substituent R iiithe C replaced 6-14aryl;
R bthe mutual independent selected from halo when occurring at every turn ,-CN ,-NO 2,-OH, optionally by 1-30 substituent R ithe C replaced 1-30alkoxyl group ,-O-[CH 2cH 2o] n-C 1-10alkyl (n=1-10) ,-O-[CH 2cH 2o] m-OH (m=1-10) ,-O-COR 3, optionally by 1-30 substituent R i-the S-C replaced 1-30alkyl ,-NH 2,-NHR 3,-NR 3r 4,-[NR 3r 4r 5] +,-NH-COR 3,-COOH ,-COOR 3,-CONH 2,-CONHR 3,-CONR 3r 4,-CO-H ,-COR 3, optionally by 1-30 substituent R ithe C replaced 1-30alkyl, optionally by 1-30 substituent R ithe C replaced 2-30alkenyl, optionally by 1-10 substituent R iithe C replaced 3-10cycloalkyl and optionally by 1-8 substituent R iiithe C replaced 6-14aryl;
R cthe mutual independent selected from halo when occurring at every turn ,-CN ,-NO 2,-N 3,-OH, optionally by 1-30 substituent R ithe C replaced 1-30alkoxyl group ,-O-[CH 2cH 2o] n-C 1-10alkyl (n=1-10) ,-O-[CH 2cH 2o] m-OH (m=1-10) ,-O-COR 3, optionally by 1-30 substituent R i-the S-C replaced 1-30alkyl, optionally by 1-30 substituent R i-the SO replaced 2-C 1-30alkyl ,-NH 2,-NHR 3,-NR 3r 4,-[NR 3r 4r 5] +,-NH-COR 3,-COOH ,-COOR 3,-CONH 2,-CONHR 3,-CONR 3r 4,-CO-H ,-COR 3, optionally by 1-30 substituent R ithe C replaced 1-30alkyl, optionally by 1-30 substituent R ithe C replaced 2-30alkenyl, optionally by 1-10 substituent R iithe C replaced 3-10cycloalkyl and optionally by 1-8 substituent R iiithe C replaced 6-14aryl;
Wherein
R 3, R 4and R 5when occurring at every turn mutually independently selected from optionally by 1-30 substituent R ithe C replaced 1-30alkyl, optionally by 1-30 substituent R ithe C replaced 2-30alkenyl, optionally by 1-10 substituent R iithe C replaced 3-10cycloalkyl and optionally by 1-8 substituent R iiithe C replaced 6-14aryl,
R ithe mutual independent selected from halo when occurring at every turn ,-CN ,-NO 2,-N 3,-OH, C 1-30alkoxyl group ,-O-[CH 2cH 2o] n-C 1-10alkyl (n=1-10) ,-O-[CH 2cH 2o] m-OH (m=1-10) ,-O-COR 3,-S-C 1-30alkyl ,-SO 2-C 1-30alkyl ,-NH 2,-NHR 6,-NR 6r 7,-[NR 6r 7r 8] +,-NH-COR 6,-COOH ,-COOR 6,-CONH 2,-CONHR 6,-CONR 6r 7,-CO-H ,-COR 6, C 3-10cycloalkyl and C 6-14aryl,
R iithe mutual independent selected from halo when occurring at every turn ,-CN ,-NO 2,-OH, C 1-30alkoxyl group ,-O-[CH 2cH 2o] n-C 1-10alkyl (n=1-10) ,-O-[CH 2cH 2o] m-OH (m=1-10) ,-O-COR 6,-S-C 1-30alkyl ,-NH 2,-NHR 6,-NR 6r 7,-[NR 6r 7r 8] +,-NH-COR 6,-COOH ,-COOR 6,-CONH 2,-CONHR 6,-CONR 6r 7,-CO-H ,-COR 6, C 1-30alkyl, C 2-30alkenyl, C 3-10cycloalkyl and C 6-14aryl,
R iiithe mutual independent selected from halo when occurring at every turn ,-CN ,-NO 2,-N 3,-OH, C 1-30alkoxyl group ,-O-[CH 2cH 2o] n-C 1-10alkyl (n=1-10) ,-O-[CH 2cH 2o] m-OH (m=1-10) ,-O-COR 6,-S-C 1-30alkyl ,-SO 2-C 1-30alkyl ,-NH 2,-NHR 6,-NR 6r 7,-[NR 6r 7r 8] +,-NH-COR 6,-COOH ,-COOR 6,-CONH 2,-CONHR 6,-CONR 6r 7,-CO-H ,-COR 6, C 1-30alkyl, C 2-30alkenyl, C 3-10cycloalkyl and C 6-14aryl,
Wherein
R 6, R 7and R 8when occurring at every turn mutually independently selected from C 1-30alkyl, C 2-30alkenyl, C 3-10cycloalkyl and C 6-14aryl,
And X is-Cl ,-Br or I.
It is further preferred that
R 1and R 2be optionally by 1-30 substituent R independently of each other athe C replaced 1-30alkyl,
Wherein
R athe mutual independent selected from halo when occurring at every turn ,-CN ,-NO 2,-N 3,-OH, optionally by 1-6 substituent R ithe C replaced 1-30alkoxyl group ,-O-[CH 2cH 2o] n-C 1-10alkyl (n=1-10) ,-O-[CH 2cH 2o] m-OH (m=1-10) ,-O-COR 3, optionally by 1-30 substituent R i-the S-C replaced 1-30alkyl, optionally by 1-30 substituent R i-the SO replaced 2-C 1-30alkyl ,-NH 2,-NHR 3,-NR 3r 4,-[NR 3r 4r 5] +,-NH-COR 3,-COOH ,-COOR 3,-CONH 2,-CONHR 3,-CONR 3r 4,-CO-H ,-COR 3, optionally by 1-10 substituent R iithe C replaced 3-10cycloalkyl and optionally by 1-8 substituent R iiithe C replaced 6-14aryl;
Wherein
R 3, R 4and R 5when occurring at every turn mutually independently selected from optionally by 1-30 substituent R ithe C replaced 1-30alkyl, optionally by 1-30 substituent R ithe C replaced 2-30alkenyl, optionally by 1-10 substituent R iithe C replaced 3-10cycloalkyl and optionally by 1-8 substituent R iiithe C replaced 6-14aryl,
R ithe mutual independent selected from halo when occurring at every turn ,-CN ,-NO 2,-N 3,-OH, C 1-30alkoxyl group ,-O-[CH 2cH 2o] n-C 1-10alkyl (n=1-10) ,-O-[CH 2cH 2o] m-OH (m=1-10) ,-O-COR 3,-S-C 1-30alkyl ,-NH 2,-NHR 6,-SO 2-C 1-30alkyl ,-NR 6r 7,-[NR 6r 7r 8] +,-NH-COR 6,-COOH ,-COOR 6,-CONH 2,-CONHR 6,-CONR 6r 7,-CO-H ,-COR 6, C 3-10cycloalkyl and C 6-14aryl,
R iithe mutual independent selected from halo when occurring at every turn ,-CN ,-NO 2,-OH, C 1-30alkoxyl group ,-O-[CH 2cH 2o] n-C 1-10alkyl (n=1-10) ,-O-[CH 2cH 2o] m-OH (m=1-10) ,-O-COR 6,-S-C 1-30alkyl ,-NH 2,-NHR 6,-NR 6r 7,-[NR 6r 7r 8] +,-NH-COR 6,-COOH ,-COOR 6,-CONH 2,-CONHR 6,-CONR 6r 7,-CO-H ,-COR 6, C 1-30alkyl, C 2-30alkenyl, C 3-10cycloalkyl and C 6-14aryl,
R iiithe mutual independent selected from halo when occurring at every turn ,-CN ,-NO 2,-N 3,-OH, C 1-30alkoxyl group ,-O-[CH 2cH 2o] n-C 1-10alkyl (n=1-10) ,-O-[CH 2cH 2o] m-OH (m=1-10) ,-O-COR 6,-S-C 1-30alkyl ,-SO 2-C 1-30alkyl ,-NH 2,-NHR 6,-NR 6r 7,-[NR 6r 7r 8] +,-NH-COR 6,-COOH ,-COOR 6,-CONH 2,-CONHR 6,-CONR 6r 7,-CO-H ,-COR 6, C 1-30alkyl, C 2-30alkenyl, C 3-10cycloalkyl and C 6-14aryl,
Wherein
R 6, R 7and R 8when occurring at every turn mutually independently selected from C 1-30alkyl, C 2-30alkenyl, C 3-10cycloalkyl and C 6-14aryl,
And X is-Cl ,-Br or-I.
Most preferably R 1and R 2be the C in the C place branching be connected with the N of formula 1 independently of each other 3-25alkyl, and X is-Cl ,-Br or-I.
Particularly preferably following formula: compound:
The method preparing following formula: compound is also a part of the present invention:
Wherein R 1and R 2as defined above,
The method comprises the steps:
I () with boron-containing compound process formula (2) compound of formula (3), forms the boron-containing compound of formula (4) under the catalyzer containing transition metal exists:
Wherein R 1and R 2as defined above, and L is linking group, and
(ii) process the boron-containing compound of formula (4) with Cl source, Br source or I source, form formula (1) compound.
L is preferably C 2-5alkylidene group, it can optionally by 1-6 C 1-10alkyl replaces.More preferably L is ethylidene or propylidene and by 2-4 methyl substituted.
Can should be as [Ir (cod) OMe] containing iridium catalyst containing the catalyzer of transition metal 2, or preferred ruthenium-containing catalyst is as RuH 2(CO) (PPh 3) 3.
If should containing the catalyzer of transition metal for containing iridium catalyst, then the first step can be carried out under alkali is as the existence of di-t-butyl dipyridyl.If should containing catalyzer of transition metal for containing iridium catalyst, then the first step usually at suitable organic solvent as tetrahydrofuran (THF) or Isosorbide-5-Nitrae-two carry out in alkane.If should containing the catalyzer of transition metal for containing iridium catalyst, then the first step usually at elevated temperatures, as carried out at the temperature of 60-110 DEG C.In principle, if should containing the catalyzer of transition metal for containing iridium catalyst, then the first step can be similar to C.W.Liskey; X.Liao; J.F.Hartwig at J.Am.Chem.Soc.2010, in 132,11389-11391 and I.A.I.Mkhalid, J.H.Barnard, T.B.Marder, J.M.Murphy and J.F.Hartwig at Chem.Rev.2010, method described in 110,890-931 is carried out.
If be ruthenium-containing catalyst containing the catalyzer of transition metal, then the first step usually suitable organic solvent as toluene, Pinacolone and or carry out in its mixture.If be ruthenium-containing catalyst containing the catalyzer of transition metal, then the first step usually at elevated temperatures, as carried out at 120-160 DEG C.
The source in Cl source can be Cu (II) Cl 2.The source in Br source can be Cu (II) Br 2.The source in I source can be the NaI combined with chloramine-T.
Second step usually at suitable solvent as water, methyl alcohol, THF and two carry out in alkane or its mixture.Second step is usual at elevated temperatures, as carried out at the temperature of 40-140 DEG C.As use Cu (II) Cl 2with Cu (II) Br 2time, second step preferably at elevated temperatures, as carried out at the temperature of 80-140 DEG C.When NaI and chloramine-T are combinationally used, second step preferably at elevated temperatures, as carried out at the temperature of 40-80 DEG C.
Formula (4) compound and formula (1) compound can pass through methods known in the art, such as column chromatography for separation.
Formula (2) compound can be obtained by methods known in the art, such as, as F.W ü rthner, obtains described in the trifle being entitled as " synthesis " of Chem.Commun., 2004,1564-1579.
Contained (1) compound is also a part of the present invention as the electron device of semiconductor material.Preferably this electron device is organic field effect tube (OFET).
Organic field effect tube comprises dielectric layer usually, semiconductor layer and substrate.In addition, organic field effect tube comprises gate electrode and source/drain electrode usually.
Organic field effect tube can have various design.
The most common the relating to of organic field effect tube is bottom-gate design.The example of bottom-gate design is shown in Figure 1.
Another design of organic field effect tube is top gate design.The example of top gate design is shown in Figure 2.
This semiconductor layer comprises semiconductor material of the present invention.Semiconductor layer can have 5-500nm, preferred 10-100nm, more preferably the thickness of 20-50nm.
Dielectric layer comprises dielectric materials.Dielectric materials can be silicon-dioxide, or organic polymer is as polystyrene (PS), poly-(methyl methacrylate) (PMMA), poly-(4-Vinyl phenol) (PVP), poly-(vinyl alcohol) (PVA), benzocyclobutene (BCB) or polyimide (PI).Dielectric layer can have 10-2000nm, preferred 50-1000nm, more preferably the thickness of 100-800nm.
Source/drain electrode can by any suitable source/drain electrode material, and such as gold (Au) or tantalum (Ta) are made.Source/drain electrode can have 1-100nm, the thickness of preferred 5-50nm.
Gate electrode can by any suitable grid material as the silicon of high doped, aluminium (Al), tungsten (W), tin indium oxide, gold (Au) and/or tantalum (Ta) be made.Gate electrode can have 1-200nm, the thickness of preferred 5-100nm.
Substrate can be any suitable substrate as glass, or plastic is as polyethersulfone, polycarbonate, polysulfones, polyethylene terephthalate (PET) and PEN (PEN).Depend on the design of organic field effect tube, the combination of gate electrode and dielectric layer also can play substrate.
Organic field effect tube can be prepared by methods known in the art.
Such as bottom-gate organic field effect tube can by following preparation:
Gate electrode can by deposition of gate material on the dielectric layer side of being made up as silicon-dioxide of suitable dielectric material, the silicon of such as high doped and being formed.The opposite side of this dielectric layer can optionally with suitable reagent, such as hexamethyldisilazane (HMDS) process.Source/drain electrode can such as by the suitable source/drain electrode material of vapour deposition, such as tantalum (Ta) and/or gold (Au) and to be deposited on this side of dielectric layer on (optionally with the side of suitable agent treated).Then can be processed by solution, such as, drip painting semiconductor material of the present invention and cover source/drain electrode as the solution in chloroform with this semiconductor layer at suitable solvent.
Formula (1) compound is also a part of the present invention as the purposes of semiconductor material.
Fig. 1 shows two designs of bottom-gate organic field effect tube.
Fig. 2 shows two designs of top grid organic field effect tube.
Fig. 3 shows the bottom-gate organic field effect tube of embodiment 6.
Fig. 4 show for embodiment 6 inclusion compound 1c as semiconductor material bottom-gate organic field effect tube at drain voltage V sDfor under 100V relative to grid voltage V sGthe leakage current I of [V] sD[A] (top transition curve) and relative to grid voltage V sGthe leakage current I of [V] sD 0.5[μ A 0.5] (bottom transition curve).
Fig. 5 show for embodiment 6 inclusion compound 1c as semiconductor material bottom-gate organic field effect tube at grid voltage V sGfor under 100V (top first curve), 90V (the second curve), 80V (the 3rd curve), 70V (the 4th curve) and 0V (bottom the 5th curve) relative to drain voltage V sDthe leakage current I of [V] sD[A] (curve of output).
Fig. 6 show for embodiment 6 inclusion compound 1b as semiconductor material the end contact organic field effect tube at drain voltage V sDfor under 100V relative to grid voltage V sGthe leakage current I of [V] sD[A] (top transition curve) and relative to grid voltage V sGthe leakage current I of [V] sD 0.5[μ A 0.5] (bottom transition curve).
Fig. 7 show for embodiment 6 inclusion compound 1b as semiconductor material bottom-gate organic field effect tube at grid voltage V sGfor under 100V (top first curve), 90V (the second curve), 80V (the 3rd curve), 0V (bottom the 4th curve) relative to drain voltage V sDthe leakage current I of [V] sD[A] (curve of output).
Fig. 8 show for embodiment 6 inclusion compound 1c as semiconductor material bottom-gate organic field effect tube for relative to grid voltage V sGthe charge carrier mobility μ of [V] sat[cm 2/ Vs].
Fig. 9 show for embodiment 6 inclusion compound 1b as semiconductor material bottom-gate organic field effect tube for relative to grid voltage V sGthe charge carrier mobility μ of [V] sat[cm 2/ Vs].
In the advantage of the semiconductor material of the present invention solvent that to be these materials process at applicable solution, there is high-dissolvability.In addition, semiconductor material display of the present invention can allow high charge carrier mobility.In addition, these semiconductor materials are stablized at ambient conditions, especially to oxidation-stabilized.
Embodiment
Embodiment 1
[4,4,5,5-tetramethyl--1,3,2-dioxa boron is mixed penta ring-2-base] perylene-3,4:9,10-tetracarboxylic acid imide (4a) in preparation N, N '-two (1-ethyl propyl)-2,5,8,11-tetra-
By N, N '-two (1-ethyl propyl) perylene-3,4:9,10-tetracarboxylic acid imide (2a) (100mg, 0.189mmol) and two Pinacolone diborate (3a) (0.383g, 1.51mmol) mixes and to be dissolved in 2mL anhydrous with in the anhydrous Pinacolone of 0.15mL.Bubbling argon is passed through this solution 30 minutes.By RuH 2(CO) (PPh 3) 3(0.082mg, 0.09mmol) adds in reaction mixture, container is heated to 140 DEG C and keeps 30 hours.Evaporating solvent after this system is cooled to room temperature by column chromatography (silicon-dioxide, CH 2cl 2/ AcOEt50/1) purification required compound.Productive rate with 60% obtains bright orange solid (117mg, 0.113mmol).
1HNMR(250MHz，CD 2Cl 2)δ8.59(s，J=7.3Hz，4H)，4.94(tt，J=9.2，6.0Hz，2H)，2.33-2.10(m，4H)，2.04-1.84(m，4H)，1.51(s，J=7.2Hz，48H)，0.92(t，J=7.4Hz，12H)。FD mass spectrum (8kV): m/z=1033.33 (100%) [M+].Absorb: 537nm (in toluene).Launch: 548nm (in toluene, exc537nm).Optical extinction coefficient: 7.30 × 10 4m -1cm -1.Fluorescence quantum yield: 0.89.Ultimate analysis: theoretical value: C:67.34%; H:7.21%; N:2.71%; Trial value: C:67.29%; H:7.40%; N:2.96%.
Embodiment 2
Preparation N, N '-two (1-ethyl propyl)-2,5,8,11-tetra-Xiu perylene-3,4:9,10-tetracarboxylic acid imide (1a)
By the N prepared as described in Example 1, N '-two (1-ethyl propyls)-2,5,8,11-tetra-[4,4,5,5-tetramethyl--1,3,2-dioxa boron is mixed penta ring-2-base] perylene-3,4:9,10-tetracarboxylic acid imide (4a) (400mg, 0.387mmol) and cupric bromide (II) (1.73g, 7.73mmol) to be suspended in the mixture of methyl alcohol (3mL) and water (3mL) and to heat 6 hours at 100 DEG C.Then dichloromethane extraction will be used in reaction mixture impouring water.By organic phase dry also evaporating solvent over magnesium sulfate.After column chromatography (silicon-dioxide, methylene dichloride), obtain compound 1a with orange solids, productive rate is 90% (295mg, 0.39mmol). 1HNMR(250MHz，CD 2Cl 2)δ8.71(s，4H)，4.95(m，2H)，2.23-2.02(m，4H)，1.97-1.78(m，4H)，0.84(t，J=7.5Hz，12H)。FD mass spectrum (8kV): m/z=844.8 (100%) [M+].
Embodiment 3
[4,4,5,5-tetramethyl--1,3,2-dioxa boron is mixed penta ring-2-base] perylene-3,4:9,10-tetracarboxylic acid imide (4b) in preparation N, N '-two (1-heptyl octyl group)-2,5,8,11-tetra-
By N, N '-two (1-heptyl octyl group) perylene-3,4:9,10-tetracarboxylic acid imide (2b) (100mg, 0.12mmol) and two Pinacolone diborate (3a) (250mg, 0.99mmol) mixes and to be dissolved in 1mL anhydrous with in the anhydrous Pinacolone of 1mL.Bubbling argon is passed through this solution 30 minutes.By RuH 2(CO) (PPh 3) 3(23mg, 0.03mmol) to add in this mixture and is heated 30 hours at 140 DEG C by reaction mixture.After this system is cooled to room temperature, evaporating solvent also passes through column chromatography (CH 2cl 2) purification required compound.Obtain 4b with red solid, productive rate is 70% (113mg, 0.09mmol).
1HNMR(250MHz，CD 2Cl 2)δ8.58(s，4H)，5.06(s，2H)，2.35-2.06(m，4H)，1.98-1.72(m，4H)，1.50(s，48H)，1.24(s，40H)，0.84(t，J=6.5Hz，12H)。 13CNMR(126MHz，CD 2Cl 2)δ166.27(d，J=98.5Hz)，139.79-138.86(m)，133.80(s)，128.82(s)，127.57(d，J=69.0Hz)，127.30(s)，126.29(s)，84.90(s)，55.19(s)，32.83(s)，32.45(s)，30.03(s)，29.76(s)，27.37(s)，25.38(s)，23.22(s)，14.43(s)。FD/MS(8kV)：m/z=1312.4(100%)[M+]。UV-Vis (in toluene): λ max(ε [M -1cm -1]): 538nm (5.57 × 10 4).Fluorescence (in toluene, λ ex=538nm): 548nm.Φ F：0.83。Ultimate analysis: theoretical value: C:71.24%; H:8.74%; N:2.13%; Trial value: C:70.76%; H:8.27%; N:2.50%.
Embodiment 4
Preparation N, N '-two (1-heptyl octyl group)-2,5,8,11-tetra-Lv perylene-3,4:9,10-tetracarboxylic acid imide (1b)
By the N prepared as described in Example 3, N '-two (1-heptyl octyl group)-2,5,8,11-tetra-[4,4,5,5-tetramethyl--1,3,2-dioxa boron is mixed penta ring-2-base] perylene-3,4:9,10-tetracarboxylic acid imide (4b) (1.00g, 0.76mmol) and cupric chloride (II) (1.23g, 9.13mmol) to be suspended in the mixture of methyl alcohol (3mL) and water (3mL) and to heat 6 hours at 100 DEG C in encloses container.Then dichloromethane extraction will be used in reaction mixture impouring water.Organic phase is dry also evaporating solvent over magnesium sulfate.After column chromatography (silicon-dioxide, methylene dichloride), obtain compound 1b with orange solids, productive rate is 87% (0.628g, 0.66mmol).
1HNMR(250MHz，CD 2Cl 2)δ8.43(s，4H)，5.06(m，2H)，2.22-1.99(m，4H)，1.79(m，4H)，1.20(m，40H)，0.82-0.69(m，12H)。FD mass spectrum (8kV): m/z=947.7 (100%) [M+].
Embodiment 5
Preparation N, N '-two (1-heptyl octyl group)-2,5,8,11-tetra-Xiu perylene-3,4:9,10-tetracarboxylic acid imide (1c)
By the N prepared as described in Example 3, N '-two (1-heptyl octyl groups)-2,5,8,11-tetra-[4,4,5,5-tetramethyl--1,3,2-dioxa boron is mixed penta ring-2-base] perylene-3,4:9,10-tetracarboxylic acid imide (4b) (1.00g, 0.76mmol) and bromination ketone (II) (3.39g, 15.20mmol) are suspended in 80mL bis- heat 12 hours in 1/1/1 mixture of alkane/methanol/water and at 120 DEG C.Then reaction mixture is cooled, use dichloromethane extraction in impouring water.Organic phase is dry also evaporating solvent over magnesium sulfate.After column chromatography (silicon-dioxide, methylene dichloride: sherwood oil 1:1), obtain compound 1c with orange solids, productive rate is 92% (0.79g, 0.70mmol).
1HNMR(500MHz，CD 2Cl 2)　8.74(s，4H)，5.22-5.07(m，2H)，2.19(m，4H)，1.88(m，4H)，1.39-1.18(m，40H)，0.84(t，J=6.3Hz，12H)。 13CNMR(126MHz，CD 2Cl 2)　161.65(s)，133.11(s)，132.76(s)，132.05(s)，129.36(s)，125.15(s)，122.07(s)，56.26(s)，32.80(s)，32.37(s)，30.03(s)，29.78(s)，27.52(s)，23.20(s)，14.41(s)。FD/MS(8kV)：m/z=1124.8(100%)[M+]。UV-Vis (in methylene dichloride): λ max(ε [M -1cm -1]): 509nm (7.9 × 10 4).Fluorescence (in methylene dichloride, λ ex=509nm): 519nm.Φ F：0.21。Ultimate analysis: theoretical value: C:57.56%; H:5.90%; N:2.49%; Trial value: C:57.25%; H:6.27%; N:2.52%.
Embodiment 6
Preparation is containing the bottom-gate organic field effect tube of compound 1b or 1c as semiconductor material
The silicon-dioxide (thickness: 200nm) heat grown is as dielectric layer.Gate electrode is formed by the silicon of the doping of height of deposition on the side of this dielectric layer.The opposite side of this dielectric layer uses hexamethyldisilazane process by vapour deposition hexamethyldisilazane (HMDS).The surface contact angle of the HMPS process side of this dielectric layer is 93.2 ± 1.3 °.By vapour deposition by by golden Au (thickness: 40nm)) (Ta (thickness: 10nm) is deposited on the HMPS process side of this dielectric layer for the source/drain electrode that covers.Passage length is 20 μm and passage width is 1.4mm, obtains W/L=70.Then by using Keithley4200 machine to fill glove box (O at nitrogen 2content: 0.1ppm, H 2o content: 0.0ppm, pressure: 1120Pa, temperature: 17 DEG C) in drip and be coated with the solution of compound 1b or 1c in chloroform (concentration=10mg/mL) and cover source/drain electrode with semiconductor layer (thickness: about 100nm).
The design of the bottom-gate organic field effect tube of embodiment 6 is shown in Figure 3.
Keithley4200 machine is used to fill glove box (O at nitrogen 2content: 0.1ppm, H 2o content: 0.0ppm, pressure: 1120Pa, temperature: 17 DEG C) in measure for embodiment 6 inclusion compound 1c as semiconductor material bottom-gate organic field effect tube at drain voltage V sDfor under 100V relative to grid voltage V sGthe leakage current I of [V] sD[A] (top transition curve) and relative to grid voltage V sGthe leakage current I of [V] sD 0.5[μ A 0.5] (bottom transition curve).Result is shown in Figure 4.
Keithley4200 machine is used to fill glove box (O at nitrogen 2content: 0.1ppm, H 2o content: 0.0ppm, pressure: 1120Pa, temperature: 17 DEG C) in measure for embodiment 6 inclusion compound 1c as semiconductor material bottom-gate organic field effect tube at drain voltage V sGfor under 100V (top first curve), 90V (the second curve), 80V (the 3rd curve), 70V (the 4th curve) and 0V (bottom the 5th curve) relative to drain voltage V sDleakage current I sD(curve of output).Result is shown in Figure 5.
Keithley4200 machine is used to fill glove box (O at nitrogen 2content: 0.1ppm, H 2o content: 0.0ppm, pressure: 1120Pa, temperature: 17 DEG C) in measure for embodiment 6 inclusion compound 1b as semiconductor material bottom-gate organic field effect tube at drain voltage V sDfor under 100V relative to grid voltage V sGthe leakage current I of [V] sD[A] (top transition curve) and relative to grid voltage V sGthe leakage current I of [V] sD 0.5[μ A 0.5] (bottom transition curve).Result is shown in Figure 6.
Keithley4200 machine is used to fill glove box (O at nitrogen 2content: 0.1ppm, H 2o content: 0.0ppm, pressure: 1120Pa, temperature: 17 DEG C) in measure for embodiment 6 inclusion compound 1b as semiconductor material bottom-gate organic field effect tube at drain voltage V sGfor under 100V (top first curve), 90V (the second curve), 80V (the 3rd curve) and 0V (bottom the 4th curve) relative to drain voltage V sDleakage current I sD(curve of output).Result is shown in Figure 7.
Fig. 8 show for embodiment 6 inclusion compound 1c as semiconductor material bottom-gate organic field effect tube for relative to grid voltage V sGthe charge carrier mobility μ of [V] sat[cm 2/ Vs].
Fig. 9 show for embodiment 6 inclusion compound 1b as semiconductor material bottom-gate organic field effect tube for relative to grid voltage V sGthe charge carrier mobility μ of [V] sat[cm 2/ Vs].
For embodiment 6 inclusion compound 1b or 1c as semiconductor material bottom-gate organic field effect tube for charge carrier mobility μ sat[cm 2/ Vs], I open/ I closeratio and cut-in voltage V sOmean value and 90% fiducial interval (in bracket) of [V] award in table 1.Cut-in voltage V sO[V] is wherein leakage current I sD[A] starts the grid voltage V increasing (disengaging closing condition) sG[V].
Table 1
Embodiment 7
Preparation N, N '-two (1-heptyl octyl group)-2,5,8,11-tetra-Dian perylene-3,4:9,10-tetracarboxylic acid imide (1d)
By the N prepared as described in Example 3, N '-two (1-heptyl octyl groups)-2,5,8,11-tetra-[4,4,5,5-tetramethyl--1,3,2-dioxa boron is mixed penta ring-2-base] perylene-3,4:9,10-tetracarboxylic acid imide (4b) (100mg, 0.08mmol) is suspended in the mixture (50mL) of 1/1 water/THF.Chloramine-T (600mg, 4.53mmol) and sodium iodide (680mg, 4.53mmol) is added in this mixture.By this container sealing and in 55 DEG C of heating 12 hours under unglazed.After reaction mixture is cooled to room temperature, add S-WAT saturated solution (10mL).Then reaction mixture is added in water (100mL).By solid filtering, dry also by column chromatography (1/1 sherwood oil, methylene dichloride) purification.Obtain compound 1d with red solid, productive rate is 42%.
1HNMR(700MHz，CD 2Cl 2)δ9.10(s，4H)，5.22-5.11(m，2H)，2.26-2.14(m，4H)，1.95-1.87(m，4H)，1.40-1.18(m，40H)，0.84(t，J=7.0Hz，12H)。 13CNMR(176MHz，CD 2Cl 2)δ161.27(s)，139.06(s)，138.60(s)，132.38(s)，131.73(s)，126.28(s)，124.09(s)，56.56(s)，32.76(s)，32.38(s)，30.04(s)，29.80(s)，27.52(s)，32.22(s)，14.43(s)。FD/MS(8kV)：m/z=1315.4(100%)[M+]。UV-VIS (in methylene dichloride): λ max(ε [M -1cm -1]): 518nm (7.23 × 10 4).Ultimate analysis: theoretical value: C:49.33%; H:5.06%; N:2.13%; Trial value: C:49.68%; H:5.01%; N:2.24%.
Embodiment 8
Preparation N, N '-dioctyl-2,5,8,11-tetra-Xiu perylene-3,4:9,10-tetracarboxylic acid imide (1e)
By N, N '-dioctyl-2,5,8,11-tetra-[4,4,5,5-tetramethyl--1,3,2-dioxa boron is mixed penta ring-2-base] perylene-3,4:9,10-tetracarboxylic acid imide (0.68mg, 0.61mmol) and cupric bromide (II) (1.62g, 7.3mmol) are suspended in two heat 12 hours in the mixture of alkane (10mL), methyl alcohol (3ml) and water (3ml) and at 120 DEG C.Then the solid so obtained will also be filtered in reaction mixture impouring HCl (1.0M).After column chromatography (silicon-dioxide, methylene dichloride), obtain required compound with orange solids, productive rate is 30% (0.17mg, 0.18mmol).
1HNMR(250MHz，THF-d8)δ=9.02(s，4H)，4.20(m，4H)，1.42(m,24H)，0.95(t，J=6.0，6H)。FD mass spectrum (8kV): m/z=932.6 (100%) [M+].
Embodiment 9
Preparation N, N '-two (2-ethylhexyl)-2,5,8,11-tetra-Xiu perylene-3,4:9,10-tetracarboxylic acid imide (1f)
'-two (2-ethylhexyl)-2,5 by N, N, 8,11-tetra-[4,4,5,5-tetramethyl--1,3,2-dioxa boron is mixed penta ring-2-base] perylene-3,4:9,10-tetracarboxylic acid imide (0.68mg, 0.61mmol) and cupric bromide (II) (1.62g, 7.3mmol) are suspended in two heat 12 hours in the mixture of alkane (10mL), methyl alcohol (3ml) and water (3ml) and at 120 DEG C.Then by reaction mixture impouring HCl (1.0M) and the solid filtering that will so obtain.After column chromatography (silicon-dioxide, methylene dichloride), obtain required compound with orange solids, productive rate is 39% (0.22mg, 0.24mmol).
1hNMR (250MHz, methylene dichloride-d2) δ=8.56 (s, 4H), 4.06 (m, 4H), 2.16 (m, 2H), 1.17 (m, 16H), 0.82 (m, 12H).FD mass spectrum (8kV): m/z=932.8 (100%) [M+].

Claims (4)

1. a following formula: compound:
Wherein
R 1and R 2be the C in the C place branching be connected with the N of formula 1 independently of each other 3-25alkyl,
And X is-Cl ,-Br or-I.
2. prepare the method for following formula: compound for one kind:
Wherein R 1, R 2with X as claim 1 define, the method comprises the steps:
I () with boron-containing compound process formula (2) compound of formula (3), forms the boron-containing compound of formula (4) under the catalyzer containing transition metal exists:
Wherein R 1and R 2as claim 1 define, and L is linking group, and
(ii) process the boron-containing compound of formula (4) with Br source, Cl source or I source, form formula (1) compound.
3. one kind comprises the electron device of formula according to claim 1 (1) compound as semiconductor material.
4. formula according to claim 1 (1) compound is as the purposes of semiconductor material.
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