CN105693745B

CN105693745B - Organic pi-conjugated compound, preparation method and application

Info

Publication number: CN105693745B
Application number: CN201410698815.1A
Authority: CN
Inventors: 马玉超; 武建昌; 伊金垛; 高威; 马昌期
Original assignee: Suzhou Institute of Nano Tech and Nano Bionics of CAS
Current assignee: Suzhou Institute of Nano Tech and Nano Bionics of CAS
Priority date: 2014-11-27
Filing date: 2014-11-27
Publication date: 2019-07-05
Anticipated expiration: 2034-11-27
Also published as: CN105693745A

Abstract

The invention discloses a kind of organic pi-conjugated compound, it includes: spiral shell-[4,4]-nonyl tetraene or 5, miscellaneous-spiral shell-[4, the 4]-nonyl tetraene unit of 5-；Molecule fragment unit, and spiral shell-[4,4]-nonyl tetraene or 5, C=C double bond in miscellaneous-spiral shell-[4, the 4]-nonyl tetraene unit of 5- are connected to form 5-membered aromatic heterocycle or polynary aromatic condensed ring structure；And the end position aromatic imide unit being connect with the molecule fragment unit.Further, which also includes the short chain conjugate unit for forming pi-conjugated connection by C -- C single bond with the molecule fragment unit.Application the invention also discloses the preparation method of the compound and its in organic semiconductor device, especially in organic optoelectronic device.Organic pi-conjugated compound has very good photon absorption efficiency in visible region, ideal phase can be formed with the one-dimensional linear conjugated polymer of almost plane to separate, to improve photoelectric conversion efficiency of the material in thin-film solar cells, and it can use and be chemically synthesized preparation, it is at low cost, it is easy to industrial application.

Description

Organic pi-conjugated compound, preparation method and application

Technical field

The present invention is more particularly directed to a kind of organic pi-conjugated compound, preparation method, the composition containing the compound contains There are the compound semiconductor film and their application, the application especially in organic electro-optic device belongs to and organic partly leads Body material and semiconductor photoelectric device field.

Background technique

In organic thin film solar cell device based on organic semiconducting materials, at least contain one in organic photoactive layer Kind organic semiconducting materials, the material can absorb photon energy and form excited state molecule, i.e. exciton.Exciton is organic with another kind Generation electronic transfer process is between semiconductor molecule to form electronics and hole pair, that is, the positive and negative charge carrier separated.It is described Electronic transfer process can be electronics from exciton transfer to another molecule organic semiconductor, be also possible to electronics from another organic Semiconductor material is shifted into exciton.Wherein, the material for providing an electronics is known as electron donor, is also generally referred to as p-type half Conductor material；And the material for receiving an electronics is known as electron acceptor, is also generally referred to as type n semiconductor material.

On the one hand the efficiency of organic solar batteries device depends on organic semiconducting materials to the absorbability of photon.Half Conductor material is stronger to the absorbability of photon, and the photon collection efficiency of organic photoactive film is higher, so as to reduce light Activity is capable of the thickness of film, reduces the usage amount of material, can also reduce carrier transport and Carrier recombination occurs in the process Probability, to improve the photoelectric conversion efficiency of device.

On the other hand, the electron transfer efficiency between electron donor and electron acceptor is also to influence solar cell device efficiency A key factor.Intermolecular electron transfer efficiency is then determined by the HOMO/LUMO orbital energy level of material.For to give When body material is as multiphoton absorption material, the intermolecular lumo energy and electron acceptor that electric charge transfer occurs and then requires electron donor It is poor to there is at least 0.3eV between the lumo energy of material, to ensure electronic transfer process efficiency.And using electron acceptor material as light When sub- absorbing material, the intermolecular HOMO energy level and electron acceptor material that electric charge transfer occurs and then requires electron donor material It is poor to there is at least 0.3eV between HOMO energy level, to ensure electronic transfer process efficiency (referring to Fig. 1).

In another aspect, the efficiency of transmission in p-type and type n semiconductor material also determines positive and negative charge carrier respectively The photoelectric conversion efficiency of device.Positive and negative charge carrier transport efficiency is higher, and the loss in charge transfer process is smaller, so as to Enough effectively improve the photoelectric conversion performance of device.The charge transport properties of material then depend on material molecule structure and material point Packing of molecules situation of the son in filminess.Arrangement of the molecule under solid film state be more regular, intermolecular π-π phase interaction With stronger, the defect of material internal is fewer, so as to reduce the recombination probability of separation charge, improves the transmission effect of charge Rate, and then improve the photoelectric conversion efficiency of device.

In the past few years, using conjugated polymer as electron donor, using fullerene derivate as electron acceptor Polymer: fullerene system achieves huge success in organic solar batteries.Such as: with poly- (3- hexyl thiophene): PC₆₁BM Device photoelectric transfer efficiency as photoactive layer can achieve 3%-5% (referring to Dang, M.T.；Hirsch,L.；Wantz, G.；"P3HT:PCBM,Best Seller in Polymer Photovoltaic Research"Adv.Mater.2011,23 (31),3597-3602).And utilize narrow band gap conjugatd polymers p-type semiconductor material and the derivative PC of n-type fullerene₇₁BM Combination can more be such that organic photovoltaic cell device efficiency is increased to close to 10% (referring to Ye, L.；Zhang,S.；Zhao,W.；Yao, H.；Hou,J.；"Highly Efficient 2D-Conjugated Benzodithiophene-Based Photovoltaic Polymer with Linear Alkylthio Side Chain"Chem.Mater.2014,26(12),3603-3605).It arrives So far, fullerene derivate is the most commonly used organic solar batteries photoactive layer electron acceptor material.But this fowler Ene derivative has the following problems in actual application: 1. precursor as fullerene derivate, C₆₀And C₇₀It generallys use Physical method preparation can not achieve chemical method preparation, keep its preparation cost higher.Further functionalization on this basis is repaired Decorations, further improve the preparation cost of fullerene derivate；2. fullerene C₆₀Derivative is imitated in the photonic absorption of visible region Rate is low (referring to Wienk, M.M.；Kroon,J.M.；Verhees,W.J.H.；Knol,J.；Hummelen,J.C.；van Hal, P.A.；Janssen,R.A.J.；"Efficient Methano[70]fullerene/MDMO-PPV Bulk Heterojunction Photovoltaic Cells " Angew.Chem.Int.Ed.2003,42 (29), 3371-3375), compared with Weak photon absorption efficiency causes the film in same thickness lower to the acquisition capacity of sunlight, and then affects the light of device Photoelectric transformation efficiency receives certain limitation in practical applications.Fullerene C₇₀Derivative, such as: PC₇₁Although BM can be improved The spectral absorption performance of material, but due to C₇₀Purifies and separates it is more difficult, C₇₀The preparation cost of derivative is higher, more unfavorable In commercially producing application.

Aromatic imide analog derivative, such as: acid imide (PDI), naphthalimide (NDI) etc. have big pi-conjugated plane Molecular structure and strong electron acceptor energy.This kind of plane molecule is easy to crystallize in film forming banking process, strong point π-π interacts to form ideal charge transmission channel between son, thus aromatic imide is a kind of good n-type semiconductor material Material.At the same time, aromatic imide usually has good photon absorption efficiency in visible region, thus is a kind of ideal Organic thin film solar cell acceptor material.But organic light work is prepared being blended with organic pi-conjugated polymer or oligomer When property mixed film, since existing organic pi-conjugated polymer or oligomer are also almost plane one-dimensional linear molecule, two Ideal mutually separation state, the relatively low (ginseng of the photoelectric conversion efficiency of corresponding thin-film solar cells often can not be formed between person See: Kamm, V.；Battagliarin,G.；Howard,I.A.；Pisula,W.；Mavrinskiy,A.；Li,C.；Müllen, K.；Laquai,F.；"Polythiophene:PeryleneDiimide Solar Cells–the Impact of Alkyl- Substitution on the Photovoltaic Performance"Adv.Energy Mater.2011,1(2),297- 302), the application in organic thin film solar cell field receives certain limitation.

Summary of the invention

In view of deficiency in the prior art, one of the objects of the present invention is to provide a kind of organic pi-conjugated compound, With good photon absorption efficiency, and there is space nonplanar structure, helps to be conjugated with the one-dimensional linear of almost plane poly- It closes object and forms ideal phase separation, to improve photoelectric conversion efficiency.

Another object of the present invention is to provide a kind of methods for preparing organic pi-conjugated compound, with cost It is low, the features such as being easy to industrial application.

Another object of the present invention is to provide the application of aforementioned organic pi-conjugated compound.

For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:

A kind of organic pi-conjugated compound includes:

Spiral shell-[4,4]-nonyl tetraene or 5, miscellaneous-spiral shell-[4, the 4]-nonyl tetraene unit of 5-,

Molecule fragment unit, and spiral shell-[4,4]-nonyl tetraene or 5, the C=C in miscellaneous-spiral shell-[4, the 4]-nonyl tetraene unit of 5- Double bond is connected to form 5-membered aromatic heterocycle or polynary aromatic condensed ring structure,

And the end position aromatic imide unit being connect with the molecule fragment unit.

Further, organic pi-conjugated compound also includes:

Short chain conjugate unit forms pi-conjugated connection by C -- C single bond with the molecule fragment unit；

Wherein, the short chain conjugate unit is mainly total with π-by 1-12 aromatic rings or aromatic heterocycle or aromatic condensed ring unit The connected mode of yoke connects to be formed.

Further, end position aromatic imide unit is selected from the knot as described in general structure (IIa) or (IIb) Structure unit, and end position aromatic imide unit is connect in a manner of covalent bond adjacent via carbon atom optional on aromatic rings Molecule fragment unit or short chain conjugate unit on,

Wherein, π-Ar₃Selected from phenyl ring, thiphene ring or the polycyclic aromatic unit formed by 2-10 aromatic rings parallel connection, R₁Choosing From alkyl, miscellaneous alkyl, substituted or unsubstituted aryl or the heteroaryl of the linear chain or branched chain that carbon atom quantity is 1-20；

Preferably, the π-Ar₃Selected from as described in general formula (IIIa), (IIIb), (IIIc), (IIId) and (IIIe) Structural unit:

Wherein, 0,1 or 2 a；

It is further preferred that end position aromatic imide unit is selected from any one of following aromatic imide:

Wherein, R₁It is alkyl, miscellaneous alkyl selected from the linear chain or branched chain for being 1-20 for carbon atom quantity, substituted or unsubstituted Aryl or heteroaryl.

Further, the hetero atom in miscellaneous-spiral shell-[4, the 4]-nonyl tetraene unit of 5, the 5- is at least selected from silicon atom.

Further, the molecule fragment unit and spiral shell-[4,4]-nonyl tetraene or 5, miscellaneous-spiral shell-[4, the 4]-nonyl tetraene list of 5- A double bond in member forms the chemical structure having as described in general formula (Va) or (Vb):

Wherein, X₂Selected from O, S, Se, N-R₂Or-CH=CH-, it preferably is selected from S or-CH=CH-,

X₃Selected from O, S, Se, N-R₂、R₃-Si-R₃、R₃-C-R₃Or R₃- C=C-R₃,

R₂Alkyl, miscellaneous alkyl selected from the linear chain or branched chain that carbon atom quantity is 1-20,

R₃Selected from the alkyl of linear chain or branched chain that carbon atom quantity is 1-20, miscellaneous alkyl, substituted or unsubstituted aryl or Heteroaryl,

B is 0 or 1.

Further, the short chain conjugate unit is selected from is passed through by 1-4 independent substituted or unsubstituted phenyl ring units Isosorbide-5-Nitrae-position connects to be formed more and connects benzene unit, and has the structure as shown in general formula (VIa) or (VIb):

Wherein, R₄The miscellaneous base of alkyl, alkane selected from the linear chain or branched chain that carbon atom quantity is 1-20, R₅Selected from carbon atom quantity For the alkyl of the linear chain or branched chain of 1-20, miscellaneous alkyl, substituted or unsubstituted aryl or heteroaryl, c is any among 1~4 Integer, d are 1 or 2；

Alternatively, the short chain conjugate unit, which is selected from, passes through 2,5- by 1-6 independent substituted or unsubstituted thiophene units Position connection formed have as shown in general formula (VIIa) have symmetrical configuration oligo-thiophenes chain or general formula (VIIb) shown in The oligo-thiophenes chain of compound with regular structure:

Wherein, r, s are independently selected from 0,1 or 2, and r and s cannot be selected from any integer among 1~6 simultaneously for 0, q, R₆Selected from hydrogen, the alkyl that carbon atom quantity is 1-20 or the miscellaneous base of alkane or two R₆Between formed 5-8 member it is substituted or unsubstituted Cyclic structure, R₇、R₈In all cases independently selected from hydrogen, the alkyl that carbon atom quantity is 1-20 or the miscellaneous base of alkane or R₇With R₈Between form the substituted or unsubstituted cyclic structure of 5-8 member.

Further, organic pi-conjugated compound has single molecular weight distribution.

The preparation method of aforementioned any organic pi-conjugated compound, comprising: by the first compound, second compound and extremely A kind of few metallic catalyst is condensed at least one solvent, obtains organic pi-conjugated compound；

Wherein, first compound includes:

As spiral shell-[4,4]-nonyl tetraene structure or 5 of core, miscellaneous-spiral shell-[4, the 4]-nonyl tetraene unit of 5-,

And the Y being connect with the carbon atom in molecule fragment unit₁；

The second compound includes:

End position aromatic imide unit and the Y being connect with end position aromatic imide unit₂；

Alternatively, short chain conjugate unit and the end moieties and Y that are connect with the short chain conjugate unit₂；

Wherein, Y₁Selected from halogen atom, preferably bromine atom,

Y₂Selected from Sn (R₉)₃、B(OR₁₀)₂Or the cyclic annular substituted or unsubstituted boron ester of 5-7 member comprising-O-B-O-,

R₉Selected from containing carbon number be 1-4 linear or branched alkyl group,

R₁₀The linear or branched alkyl group for being 1-4 selected from hydrogen atom, containing carbon number.

Further, the condensation reaction used in this method includes metal catalytic Suzuki condensation or metal catalytic Stille Condensation reaction.

A kind of organic conjugate semiconductor material, comprising aforementioned any organic pi-conjugated compound or by aforementioned any side Organic pi-conjugated compound of method preparation.

A kind of composition, comprising aforementioned any organic pi-conjugated compound or by the organic of aforementioned any method preparation Pi-conjugated compound, and the composition is in liquid.

Aforementioned any organic pi-conjugated compound, organic pi-conjugated compound, preceding by aforementioned any method preparation Organic conjugate semiconductor material or aforementioned composition are stated in preparing the application in organic electronic device.

A kind of organic electronic device includes:

Aforementioned any organic pi-conjugated compound or the organic pi-conjugated compound prepared by aforementioned any method, are used Using as electron donor；

And conjugated polymer or oligomer, to as electron acceptor.

A kind of semiconductive thin film, comprising aforementioned any organic pi-conjugated compound, by aforementioned any method preparation Organic pi-conjugated compound, aforementioned organic conjugate semiconductor material or aforementioned composition；

Preferably, the semiconductive thin film include as electron donor organic pi-conjugated compound and as electronics by The conjugated polymer or oligomer of body.

A kind of electronic device includes aforesaid semiconductor film.

Further, the electronic device includes electrooptical device, and the electrooptical device includes solar battery, But not limited to this.

Compared with prior art, the beneficial effect comprise that the molecule of organic pi-conjugated compound has space Orthohormbic structure, and molecular end position is modified by aromatic imide unit, compared with existing organic semiconducting materials, organic π-is altogether Compound conjugate can be using preparation be chemically synthesized, and material preparation cost is lower, it is easier to industrial application, in addition, with existing Some fullerene derivatives are compared, which has very good photonic absorption effect in visible region Rate.And compared with existing plane aromatic imide electron-like acceptor material, which has space non- Planar structure, thus help to form ideal phase with the one-dimensional linear conjugated polymer of almost plane and separate, to improve Photoelectric conversion efficiency of the material in thin-film solar cells.

Detailed description of the invention

When respectively illustrating using electron donor and electron acceptor as multiphoton absorption material intermolecular electricity occurs for Fig. 1 a- Fig. 1 b The energy level combination diagram of sub- transfer process；

Fig. 2 a- Fig. 2 b is the structural schematic diagram of typical organic pi-conjugated compound in the present invention；

Fig. 3 a- Fig. 3 b is the structural schematic diagram of typical virtue acid imide unit in the present invention；

Fig. 4 is the structural schematic diagram of typical first compound in the present invention；

Fig. 5 a- Fig. 5 b is the structural schematic diagram of typical second compound in the present invention；

Fig. 6 is the abosrption spectrogram of the film of compound S1 in the present invention；

Fig. 7 is the organic solar batteries I-V curve figure of compound S1 in the present invention.

Specific embodiment

One aspect of the present invention provides a kind of organic pi-conjugated compound, includes spiral shell-[4,4]-nonyl four in molecule Alkene or 5,5- it is miscellaneous-spiral shell-[4,4]-nonyl tetraene unit and have general formula (Ia) or (Ib) described in molecular structure (please refer to Fig. 2 a- Fig. 2 b), wherein X₁For carbon atom, silicon atom or germanium atom；π-Ar₁Spiral shell-[4,4]-nonyl tetraene for molecule fragment, with core Or 5, the carbon-carbon double bond in miscellaneous-spiral shell-[4, the 4]-nonyl tetraene unit of 5- is connected to form five yuan or hexa-atomic aromatic rings or aromatic heterocycle, or Form polynary aromatic condensed ring structure；π-Ar₂For by 1-12 aromatic rings or aromatic heterocycle or aromatic condensed ring unit with pi-conjugated phase Mode even is connected the short chain conjugate unit to be formed, and π-Ar₂With π-Ar₁Pi-conjugated be connected is formed by carbon-carbon single bond；EG is end Position aromatic imide unit.

Preferably, the fragrant acid imide unit is selected from the unit for having the following structure general formula (IIa) or (IIb) structure (please referring to 3a- Fig. 3 b) is connect in a manner of covalent bond via carbon atom optional on aromatic rings in adjacent π-Ar₁Or π-Ar₂ On unit, wherein π-Ar₃Selected from phenyl ring, thiphene ring or the polycyclic aromatic unit formed by 2-10 aromatic rings parallel connection, R₁Choosing From the alkyl for the linear chain or branched chain for being 1-20 for carbon atom quantity, miscellaneous alkyl, substituted or unsubstituted aryl or heteroaryl.

It is highly preferred that π-Ar in formula (IIa) and (IIb)₃Selected from have as general formula (IIIa), (IIIb), (IIIc), (IIId) or structural unit described in (IIIe).

Wherein, 0,1 or 2 a.

Most preferably, end position provided by the present invention aromatic imide unit is selected from one of following structural unit:

And in each structural formula of this specification, symbolMeaning be with adjacent group unit to link site.

It is provided by the present invention to have in organic semiconducting materials described in general structure (Ia) or (Ib), the X₁Choosing From carbon atom, silicon atom or germanium atom.The nuclear structure difference of corresponding organic pi-conjugated compound provided by the present invention For spiral shell-[4,4]-nonyl tetraene (formula a1), 5,5- sila-spiral shell-[4,4]-nonyl tetraene (formula a2) or 5,5- germanium it is miscellaneous-spiral shell-[4,4]-nonyl Tetraene (formula a3).

Preferably, in the organic compound provided by the present invention as described in general formula (Ia) or (Ib), center spiro-atom X₁ For carbon atom or silicon atom.The compound of spiro-atom has better chemical stability centered on carbon atom or silicon atom Can, to assign material lower preparation cost, and more preferably device application performance.

In compound provided by the present invention as described in general formula (Ia) or (Ib), the π-Ar₁Molecule fragment and carbon Carbon double bond is connected to form five yuan or hexa-atomic aromatic rings or aromatic heterocycle, or forms polynary aromatic condensed ring structure.The formation 5-membered aromatic heterocycle includes: thiophene, furans, selenophen, pyrroles；The hexa-atomic aromatic rings includes: phenyl ring, conjugation described in pyridine Polynary condensed cyclic structure includes, but are not limited to having structure:

Wherein, R₂Alkyl, miscellaneous alkyl selected from the linear chain or branched chain for being 1-20 for carbon atom quantity；R₃Selected from carbon atoms Number is alkyl, miscellaneous alkyl, substituted or unsubstituted aryl or the heteroaryl of the linear chain or branched chain of 1-20.For clearer description π-Ar₁Molecule fragment and core spiral shell-[4,4]-nonyl tetraene or 5, the relationship of miscellaneous-spiral shell-[4, the 4]-nonyl tetraene unit of 5-, above-mentioned schema Middle broken line representation goes out core spiral shell-[4,4]-nonyl tetraene or miscellaneous-spiral shell-[the 4,4]-nonyl tetraene unit of 5,5-.

It should be pointed out that working as π-Ar₁When molecule fragment has dissymmetrical structure, π-Ar₁Molecule fragment and core spiral shell-[4, 4]-nonyl tetraene or 5,5- it is miscellaneous-spiral shell-[4,4]-nonyl tetraene carbon-carbon double bond have two different on-link mode (OLM)s.The present invention is preferred π-Ar₁On-link mode (OLM) with double bond is so that being formed by five yuan or hexa-atomic aromatic rings or aromatic heterocycle or aromatic condensed ring is logical It crosses C-C double bond and links the on-link mode (OLM) to form pi-conjugated extension.With π-Ar₁Molecule fragment forms thiphene ring with carbon-carbon double bond Example, preferred embodiment of the invention are to form the structure as shown in formula (c1), and in c3 formula between two thiophene units of the same side not Pi-conjugated extension can be formed.

According to the pi-conjugated principle for being connected to form single double bond alternating quinoid structure is formed, this field staff can be quick Establish asymmetry π-Ar provided by the present invention₁Molecule fragment and core spiral shell-[4,4]-nonyl tetraene or 5,5- it is miscellaneous-spiral shell-[4,4]- The on-link mode (OLM) of nonyl tetraene unit.

Preferably, π-Ar₁In molecule fragment and spiral shell-[4,4]-nonyl tetraene or miscellaneous-spiral shell-[the 4,4]-nonyl tetraene unit of 5,5- One double bond, which forms a double bond and formed, has the chemical structure as described in general formula (Va) or (Vb):

Wherein, X₂Selected from O, S, Se, N-R₂Or-CH=CH-；X₃Selected from O, S, Se, N-R₂、R₃-Si-R₃、R₃-C-R₃, or R₃- C=C-R₃；R₂Alkyl, miscellaneous alkyl selected from the linear chain or branched chain for being 1-20 for carbon atom quantity；R₃Selected from carbon atom quantity For the alkyl of the linear chain or branched chain of 1-20, miscellaneous alkyl, substituted or unsubstituted aryl or heteroaryl；B is 0 or 1.In order to become apparent from Description π-Ar₁Molecule fragment and core spiral shell-[4,4]-nonyl tetraene or 5, the relationship of miscellaneous-spiral shell-[4, the 4]-nonyl tetraene unit of 5-, on It states in schema and goes out core spiral shell-[4,4]-nonyl tetraene or miscellaneous-spiral shell-[the 4,4]-nonyl tetraene unit of 5,5- with broken line representation.

According to above-mentioned π-Ar₁Unit to meet with the on-link mode (OLM) of double bond so that two aromatic rings or fragrance being connected Condensed ring forms the principle of the on-link mode (OLM) of pi-conjugated extension, preferably forms with general formula (Va) or general formula (Vb) describedization Learn the π-Ar of structure₁In unit, X₂Atom and far from spiral shell-[4,4]-nonyl tetraene 5- position carbon atom or 5,5- it is miscellaneous-spiral shell-[4, 4] the heteroatomic carbon atom in the position 5- in-nonyl tetraene unit is connected.

More preferably scheme is above-mentioned X₂For sulphur atom or-CH=CH-.

Specifically, π-Ar₁Segment and core cell form following structure example:

(1)π-Ar₁Molecule fragment and carbon-carbon double bond form 5-membered aromatic heterocycle unit

Wherein, X₁For carbon atom, silicon atom or germanium atom, R₁For carbon atom quantity be 1-20 linear chain or branched chain alkyl, Miscellaneous alkyl, substituted or unsubstituted aryl or heteroaryl.

(2)π-Ar₁Molecule fragment and carbon-carbon double bond form hexa-atomic fragrant benzene ring units

(3) with X₂For sulphur atom, π-Ar₁Molecule fragment and carbon-carbon double bond are connected to form polynary condensed cyclic structure

Wherein, X₁For carbon atom, silicon atom or germanium atom, R₂For carbon atom quantity be 1-20 linear chain or branched chain alkyl, Miscellaneous alkyl；R₃For alkyl, miscellaneous alkyl, substituted or unsubstituted aryl or the heteroaryl of the linear chain or branched chain that carbon atom quantity is 1-20 Base.

It, in some embodiments, can also be miscellaneous in fragrance in order to ensure the compounds of this invention has enough dissolubilities Solubilizing group is introduced in ring or aromatic condensed ring.Well-known solubilizing group scheme may be incorporated for reality of the invention in principle It applies in scheme.Such as introduce alkyl, miscellaneous alkyl or the miscellaneous base of alkane of long-chain.

Above-mentioned only to list part-structure example, this field researcher can be according to general structure (Ia), (Ib), (Va) And (Vb), the extension for more crossing structure is carried out in conjunction with widely known compounds composing law.

In organic pi-conjugated compound provided by the present invention as described in general formula (Ib), π-Ar₂For by 1-20 aromatic rings Or aromatic heterocycle or aromatic condensed ring unit are connected by carbon-carbon single bond, form pi-conjugated be connected.The aromatic rings or aromatic heterocycle Or aromatic condensed ring unit include: substituted or unsubstituted phenyl ring, replace or for substituted thiphene ring, replace or be replace pyrroles Ring, substituted or unsubstituted furan nucleus, substitution are substituted selenophen ring.

In one of preferred embodiment, π-Ar₂Pass through 1,4- by 1-4 independent substituted or unsubstituted phenyl ring units Position connection formation connect benzene unit more, including having the structure such as general formula (VIa) and (VIb):

Wherein, R₄The miscellaneous base of alkyl, alkane selected from the linear chain or branched chain that carbon atom quantity is 1-20, R₅Selected from carbon atom quantity For the alkyl of the linear chain or branched chain of 1-20, miscellaneous alkyl, substituted or unsubstituted aryl or heteroaryl, c is the integer of 1-4, d 1 Or 2.

In another preferred embodiment, π-Ar₂Pass through 2,5- companies by 1-6 independent substituted or unsubstituted thiophene units It connects to be formed with the oligo-thiophenes chain as shown in general formula (VIIa) with symmetrical configuration or the structure as shown in general formula (VIIb) Regular oligo-thiophenes chain.

Wherein, r, s are independently selected from 0,1 or 2, and r and s cannot be selected from the integer of 1-6 simultaneously for 0, q.Wherein, R₆Choosing From hydrogen, the alkyl that carbon atom quantity is 1-20 or the miscellaneous base of alkane or two R₆Between form the substituted or unsubstituted ring-type of 5-8 member Structure, R₇、R₈In all cases independently selected from hydrogen, the alkyl that carbon atom quantity is 1-20 or the miscellaneous base of alkane or R₇With R₈It Between form the substituted or unsubstituted cyclic structure of 5-8 member.

The molecular structure of organic pi-conjugated compound provided by the present invention is single determination, thus has single molecule Measure distribution character.This makes the organic compound of this law have structure compared with the wider conjugatd polymers of molecular weight distribution Clear, material is easy to purify and the advantages such as more good repeatability energy.

Since organic pi-conjugated compound provided by the present invention has space nonplanar structure, moreover, may be used also in molecule With the alkyl containing hydrotropy or miscellaneous alkyl group, so, organic pi-conjugated compound provided by the present invention has preferable dissolution Performance.

Compound provided by the present invention with general formula (Ia) or (Ib) can be prepared by metal catalytic method of condensing.

Specifically, the synthetic method is characterized in that providing containing core spiral shell-[4,4]-nonyl tetraene structure or 5, The first compound (VIII) of miscellaneous-spiral shell-[the 4,4]-nonyl tetraene unit of 5- with the aromatic imide list with reaction active groups First (IXa) or include π-Ar₂The second compound (IXb) of conjugate unit aromatic group, and at least one metallic catalyst and It is condensed at least one solvent, obtains organic pi-conjugated compound.

First compound has structure (refering to Fig. 4) shown in formula (VIII), and the second compound has general formula (IXa) or the structure of (IXb) (refering to Fig. 5 a- Fig. 5 b) wherein, compound (VIII) and compound (IXa) carry out metal catalytic contracting Conjunction obtains having such as general formula (Ia) described organic pi-conjugated compound (refering to Fig. 2 a).

And compound (VIII) carries out metal catalytic with compound (IXb) and is condensed to yield with as general formula (Ib) is described organic Pi-conjugated compound (refering to Fig. 2 b).

Wherein, X₁, π-Ar₁, π-Ar₂And the modification meaning of substitution representated by EG is as it was noted above, Y₁Selected from halogen atom, It include: chlorine, bromine or iodine；Y₂Selected from Sn (R₉)₃、B(OR₁₀)₂Or the cyclic annular substituted or unsubstituted boron of 5-7 member comprising-O-B-O- Ester, R₉Selected from the linear or branched alkyl group for being 1-4 containing carbon number, R₁₀The linear chain or branched chain alkane for being 1-4 selected from hydrogen atom, containing carbon number Base.

More specifically, the synthetic method of the compounds of this invention include: metal catalytic Stille condensation reaction or Suzuki condensation.

When using above-mentioned Stille method of condensing prepare compound,

-- the tin reagent condensation reaction of the first compound of reaction and the second compound of reaction of halogenated modification, i.e., above-mentioned general formula (VIII) Y in₁For halogen, comprising: chlorine, bromine or iodine lead in formula (IX), Y₂For Sn (R₉)₃, R₉Selected from containing carbon number be 1-4 it is straight Chain or branched alkyl.

When using above-mentioned Suzuki method of condensing prepare compound,

-- the first compound of reaction of halogenated modification and the boric acid or borate of the second compound of reaction carry out condensation reaction, Y in i.e. above-mentioned logical formula (VIII)₁For halogen, comprising: chlorine, bromine or iodine lead in formula (IX), Y₂For B (OR₁₀)₂Or include-O-B- The cyclic annular substituted or unsubstituted boron ester of 5-7 member of O-, R₁₀The linear or branched alkyl group for being 1-4 selected from hydrogen atom, containing carbon number.

π-Ar in logical formula (VIII) has been provided in existing document₁For the synthetic method of thiphene ring and phenyl ring.Such as:

Reported in document structural formula be (e4) synthetic method (Pei J., Ni J., Zhou X.H., Cao X.Y., and Lai Y.H.,Head-to-Tail Regioregular Oligothiophene-Functionalized 9,9'- Spirobifluorene Derivatives.1.Synthesis, J.Org.Chem.2002,67,4924-4936),

Document (Pozzi G., Orlandi S., Cavazzini M., Minudri D., Macor L., Otero L., and Fungo F.,Synthesis and Photovoltaic Applications of a 4,4′-Spirobi [cyclopenta-[2,1-b；3,4-b′]dithiophene]-Bridged Donor/Acceptor Dye,Org.Lett., 2013,15,4642-4645) synthetic method of 2,2 ', 6,6 '-four double ring glutaric thiophenes of bromo- spiral shell [4,4 '] is reported in,

Document (Ohshita J.J., Lee K.H., Hamamoto D., Kunugi Y., Ikadai J.N., Kwak Y.W., and Ku A., Synthesis of Novel Spiro-condensed Dithienosiloles and the Application to Organic FET, Chemistry Letters, 2004,33,892-893) reporting structural formula in is (e10) synthetic method of compound.

Reaction reagent and condition: i) lithium diisopropylamine, -78 DEG C；Si(CH₃)₃Cl, -78 DEG C of-rt；Ii) diisopropyl Lithium amide, -78 DEG C -0 DEG C；iii)CuCl₂, 78 DEG C of-rt；

IV) n-BuLi, -78 DEG C；SiCl₄, -78 DEG C of-rt；V) N- bromo-succinimide, THF, rt

The synthetic method of the compound with logical formula (VIII) according to the present invention can with reference to above three document into Row is synthetically prepared.

Organotin or organoboron reagent with general structure (IXa) can pass through metal by corresponding halides precursor Catalysis process preparation, this preparation method can refer to document.

Such as:

Reaction reagent and condition: i) 1- heptyl octylame, quinoline, 160 DEG C, 12h, 83%, ii) Br₂, I₂, acetic acid, reflux, 4.5 hours, 97%；

Iii) [PdCl2 (dppf)] .CH2Cl2, connection boric acid pinacol boron ester, dioxanes, 70 DEG C, 16 hours, 78%；

It is sub- that synthetic method for synthesizing the second compound (IXb) with general structure (Ib) can use halogen arylimidoyl 1:1 is condensed amine unit in molar ratio with having double tin or double borane reagents, and the general structure with reactivity can be obtained Molecule as described in (IXb).This synthetic method may refer to embodiment 5.Such as:

In synthetic method provided by the present invention, synthetic reaction process is carried out under the conditions of 20-180 DEG C, is preferably existed It carries out under the conditions of 20-120 DEG C, is most preferably carried out under the conditions of 25-70 DEG C.

The metallic catalyst refers to soluble Metal Palladium or nickel complex, and preferred catalyst is Pd cooperation Object, comprising: Pd (PPh₃)₄, Pd (OAc)₂, Pd (PPh₃)₂Cl₂, Pd₂dba₃, Pd₂dba₃·CHCl₃, Pd (dppf) Cl₂, more preferably Catalyst be Pd (PPh₃)₄, Pd₂dba₃·CHCl₃, Pd (dppf) Cl₂.When selection is free of the Pd catalyst Pd of ligand₂dba₃Or Pd₂dba₃·CHCl₃When, it also needs to add phosphorus ligand in catalyst system, to improve reaction efficiency, the phosphorus ligand includes: PPh₃Or HP (tBu)₃BF₄, the molar ratio of phosphorus ligand and catalyst Pd atom is 2:1.Catalytic reaction catalyst carrying capacity unit point Molar ratio be 0.05%-10%, preferably 0.5%-5%.

When selecting Suzuki catalyzing and condensing preparation method, need to be added inorganic metal aqueous slkali in reaction system.It is described Metal base include hydroxide, such as: NaOH, KOH, LiOH, Ba (OH)₂, alkoxide, such as: NaOEt, KOEt, LiOEt, KOMe, NaOMe, carbonate, such as: Na₂CO₃, NaHCO₃, K₂CO₃, KHCO₃, phosphate, such as: K₃PO₄, K₂HPO₄Or carboxylic acid Salt, such as: KOAc, NaOAc.Above-mentioned metal base is generally prepared as the aqueous solution of 1M, adds with reaction dissolvent by certain volume ratio Enter into reaction system, the ratio is 1:2-1:5, is preferably in a proportion of 1:4.

The solvent includes alkane, such as: pentane, hexane, heptane, hexamethylene, aromatic solvent, such as: toluene, diformazan Benzene or ether solvent, such as: glycol dimethyl ether, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane or polar solvent, such as: DMF, DMSO.Preferred solvent is tetrahydrofuran or DMF.

The post-processing of reaction can be used conventional mode and handle, comprising: dilution, filtering, extraction, elution, is tied precipitating again Brilliant, column chromatography or/and distillation etc..One typical post-processing scheme is as follows: after reaction, being added centainly into reaction solution Organic phase is washed with water three times in organic solvent, extraction and separation organic phase, merges organic phase, with the dry organic phase of anhydrous sodium sulfate, mistake Filter, rotary evaporation remove solvent, elute silica gel chromatographic column separation product with eluant, eluent.The organic solvent is usually with dissolvable The solvent of the compounds of this invention, such as: chloroform, methylene chloride, toluene.The eluant, eluent is molten for the mixing of chloroform and n-hexane Agent, mixed proportion are adjusted according to scheme well-known in the art.

Present invention provides by organic pi-conjugated compound prepared by above-mentioned synthetic method.

It is a further object of the present invention to provide a kind of organic pi-conjugated compound composition, organic pi-conjugated chemical combination It is described at least containing a kind of by above-mentioned organic pi-conjugated compound and a kind of solvent provided by the present invention in compositions Composition is in liquid.The organic solvent includes: alkyl halide hydro carbons, such as: chloroform, methylene chloride, 1,2- dichloroethanes, 1, 1,2- trichloroethanes, 1,1,2,2- tetrachloroethanes；Or aromatics, such as: toluene, chlorobenzene, o-dichlorohenzene, dimethylbenzene, ortho-xylene, Meta-xylene, paraxylene, trimethylbenzene, trimethylbenzene.The weight percent of organic pi-conjugated compound in the composition Concentration is 0.1%-20%, preferred concentration 0.5%-10%, most preferable concentrations 1%-5%.

It also include conjugated polymer in the composition in some embodiments of composition provided by the present invention Or conjugation small molecule compound: poly- (3- hexyl thiophene), PTB7 (poly- [[bis- [(2- ethylhexyl) oxygroup] benzo [1,2- of 4,8- B:4,5-b'] double thiophene -2,6-diyl] [the fluoro- 2- of 3- [(2- ethylhexyl) carbonyl] thieno [3,4-b] thiophene diyl]]), PCPDTBT (poly- [2,1,3- diazosulfide -4,7- diyl [bis- (2- the ethylhexyl) -4H- cyclopentano [2,1-b:3,4- of 4,4- B'] Dithiophene -2,6- diyl]]]), the OT-DCV oligo-thiophenes of modification (cyano) etc..Organic pi-conjugatedization provided by the invention Closing object and conjugated polymer or being conjugated the weight ratio of small organic molecule is 1:6-6:1, and preferred ratio is 1:4-2:1.In this way Case study on implementation in, organic pi-conjugated compound provided by the present invention is as a kind of electron acceptor, and the conjugation is poly- Closing object or conjugation small organic molecule is a kind of electron donor material.

It also include polynary condensed ring virtue in some embodiments of composition provided by the present invention, in the composition Aroma compounds as additive, such as: 1- methyl naphthalene, 2- methyl naphthalene, 1,2- dimethylnaphthalene, 9,10- dimethylanthracene etc..

Another object of the present invention is to provide the purposes of organic pi-conjugated compound provided by the present invention, one of those Typical use scheme is the organic semiconductor thin-film for being used to prepare organic electronic device.Realize purposes scheme of the invention, this hair It is bright provided by organic pi-conjugated compound be deposited over the silicon wafer containing conductive layer or electronic work ergosphere, thin polymer film or On person's glass.Well-known film deposition approach may be incorporated for preparing the organic semiconductor thin-film in principle, such as Film deposition is carried out using the method for coating or printing, the coating method includes: rotary coating, slot coated, is sprayed Coating, the printing process include: intaglio printing, silk-screen printing, flexographic printing and various ink jet printings, preferred thin Film deposition approach is rotary coating and ink jet printing.

As of the invention one preferred purposes scheme, organic semiconductor thin-film provided by the invention is used to prepare organic Electrooptical device, especially organic thin film solar cell device.For this application scheme, lead in organic semiconductor thin-film Often also additionally comprise the conjugated polymer derivant with electron performance, and organic pi-conjugated compound provided by the present invention It is the organic receptor semiconductor material as electron acceptor.

In the purposes scheme of organic semiconductor thin-film provided by the present invention, the organic semiconductor thin-film can be with There are some subsequent treatment process, comprising: the processing of chicken fire, solvent chicken fire processing (Solvent Annealing) are used for pattern The lasser cutting of change.

The present invention meets the embodiment of logical formula (I):

Embodiment: following embodiment includes the illustration of the synthesis of organic pi-conjugated compound provided by the present invention, contains The configuration method of the composition of provided organic pi-conjugated compound, partly leading containing provided organic pi-conjugated compound The organic solar batteries device of body thin film and the semiconductive thin film containing provided organic pi-conjugated compound.

Material synthesis method:

Synthesis glass apparatus used is cleaned and dried by stringent.Unless stated otherwise, institute in case study on implementation of the present invention Organic solvent is general chemistry pure reagent.Tetracarboxylic acid dianhydride (compound 1), diformazan acid dianhydride (compound 2), 4- bromine 1,8- naphthalic anhydride (compound 3), connection boric acid pinacol boron ester (compound 4), two frequency any ester (change of thiophene -2,5- hypoboric acid Close object 5), Isosorbide-5-Nitrae-two pinacol ester of benzene hypoboric acid (compound 6), bis- (the pinacol borate) (chemical combination of 9,9- dioctyl fluorenes -2,7- Object 7), 2,2', 7,7'- tetra- bromo- 9,9'- spiral shell, two fluorenes (compound 8), N, N'- dimethyl methyl acyl chlorides (compound 9), 2,3- dibromos Thiophene (compound 10), 2- ethyl-hexylamine, n-BuLi, lithium diisopropylamine, boron trifluoride ether, trim,ethylchlorosilane, Copper chloride, silicon tetrachloride, N- bromo-succinimide, Pd (dppf) Cl₂、Pd₂dba₃·CHCl₃、Pd(PPh₃)₄、HP(tBu)₃BF₄、K₂CO₃、K₃PO₄、NaHCO₃、NH₄Cl、KOAc、FeCl₃, etc. raw materials be purchased from sigma Aldrich, lark prestige Alfa Aesar, Sinopharm Chemical Reagent Co., Ltd..

Wherein 2,2 ', 6,6 '-the four bromo- double ring glutaric thiophenes of spiral shell [4,4 '] (compound 11) (Pozzi G., Orlandi S.,Cavazzini M.,Minudri D.,Macor L.,Otero L.,and Fungo F.,Synthesis and Photovoltaic Applications of a 4,4′-Spirobi[cyclopenta-[2,1-b；3,4-b′] Dithiophene]-Bridged Donor/Acceptor Dye, Org.Lett., 2013,15,4642-4645),

The double ring glutaric thiophenes (compound 12) of four bromo silicon spiral shells (Ohshita J.J., Lee K.H., Hamamoto D., Kunugi Y., Ikadai J.N., Kwak Y.W., and Ku A., Synthesis of Novel Spiro-condensed Dithienosiloles and the Application to Organic FET, Chemistry Letters, 2004,33, 892-893)、(3,3'-dibromo-2,2'-bithieno[3,2-b]thiene-5,5'diyl)bis (trimethylsilane) (compound 13) (Zhong H.L., Li Z., Deledalle F., Fregoso E.C., Shahid M.,Fei Z.P.,Nielsen C.B.,Gross N.Y.,Rossbauer S.,Anthopoulos T.D.,Durrant J.R.,and Heeney M.,Fused Dithienogermolodithiophene Low Band Gap Polymers for High-Performance Organic Solar Cells without Processing Additives, J.Am.Chem.Soc.2013,135,2040-2043)、

Four acyl Asia diamines (compound 21) of 1- bromo- N, N- bis- (diethylhexyls) (Jim é nez á .J., Sekita M., Caballero E.,Marcos M.L.,Rodríguez-Morgade M.S.,Guldi D.M.,and Torres T., Assembling a Phthalocyanine and Perylenediimide Donor–Acceptor Hybrid through A Platinum (II) Diacetylide Linker, Chem.Eur.J.2013,19,14506-14514) according to the side of document Method synthesis.

The synthesis of 1 compound S1 of embodiment.

The synthesis of precursor compound 14: bromo- 1, the 8- naphthalimide (5.00g, 18.0mmol) of 4-, 2- ethyl-hexylamine are taken (15.8g, 122mmol), 20mL acetic acid be added 100mL round-bottomed flask, by reaction mixture at 108 DEG C 30 points of heating stirring Clock.Solid fades away, and reaction mixture gradually becomes grey.Reaction mixture is mixed with 400mL water, is stirred 10 minutes, Filtering collects precipitating, precipitating is washed with water, and is dried in vacuo.With silica gel column chromatography purify sample, with n-hexane/methylene chloride= 2/1 does eluent, obtains 6.33g pale solid, yield 91%.1H NMR (400MHz, CDCl3): δ=8.63 (1H), 8.55(1H),8.42(1H),8.04(1H),7.84(1H),4.16-4.05(2H),1.96-1.88(1H),1.35-1.29 (8H),0.94-0.85ppm(6H).

Reaction reagent and condition: i) 108 DEG C, acetic acid

The synthesis of precursor compound 15: taking compound 14 (0.862g, 2.22mmol), and connection boric acid pinacol boron ester (is changed Close object 4) (1.13g, 4.45mmol), 10mL dry ethylene glycol dimethyl ether, anhydrous acetic acid potassium (657mg, 6.70mmol), (C17H14P) 2Fe.PdCl2 (30mg, 41 μm of ol, 1.8%) is added in 50mL flask, reaction flask is replaced as nitrogen atmosphere, 70 Heating stirring 12 hours at DEG C, brick-red reaction mixture gradually become brown.Reaction mixture is cooled to room temperature, is added 200mL methylene chloride filters mixture, collects filtrate, and rotary evaporation removes solvent.With silica gel chromatographic column purification of crude product, use N-hexane/methylene chloride=10/1-1/2 does leacheate, obtains 0.788g pale solid, yield 82%.1H NMR (400MHz, CDCl3): δ=9.10 (1H), 8.61-8.56 (2H), 8.30 (1H), 7.77 (1H), 4.18-4.07 (2H), 1.98-1.92(1H),1.45(12H),1.30-1.26(8H),0.95-0.85ppm(6H).

Reaction reagent and condition: i) (C17H14P) 2Fe.PdCl₂, DME, 70 DEG C, anhydrous acetic acid potassium

The synthesis of compound S1: take four bromo spiral shell [4,4] double ring glutaric thiophenes (compound 11) (71.0mg, 0.108mmol), compound 15 (208mg, 0.478mmol), Pd₂(dba)3.CHCl₃(22mg, 21.2 μm of ol, 5.00%), HP (tBu)₃BF₄25mL single port bottle is added in (13mg, 44 μm of ol, 10%) under nitrogen atmosphere, and single port bottle is sealed with rubber stopper.Upwards State the K for being added in single port bottle and removing oxygen₃PO4 aqueous solution (2M, 1.00mL, 2.00mmol) removed the THF (10mL) of oxygen, Stirring at normal temperature.Reaction system is initially purple brown red liquid, and then yellowish red color is gradually deepened.After 12 hours, reaction system becomes For yellow-red liquid, and bit brownish.100mL methylene chloride is added into reaction solution, washes three times (each 100mL), with nothing Aqueous sodium persulfate dries organic phase, filtering, and rotary evaporation removes solvent and it is orange red to obtain 155mg with gel chromatographic columns separation product Solid, yield 91%.¹H NMR (400MHz, CDCl₃): δ=8.67-8.63 (8H), 8.59 (4H), 7.87 (4H), 7.73 (4H),7.11(4H),4.18-4.08(8H),1.99-1.89(2H),1.41-1.30(32H),0.95-0.85ppm(24H) .MALDI-TOF MS:Calcd for C₉₇H₉₂N₄O₈S₄:1569.6,Found:1569.1(m/z).

Reaction reagent and condition: i) Pd₂(dba)3.CHCl₃, HP (tBu)₃BF₄, DME, rt, K₃PO4

The synthesis of 2. compound S2 of embodiment

The synthesis of precursor compound 16: bromo- 1, the 8- naphthalimide (5.00g, 18.0mmol) of 4-, 2,6- diisopropyls are taken Aniline (21.6g, 122mmol), 30mL acetic acid be added 100mL round-bottomed flask, by reaction mixture at 108 DEG C heating stirring three Ten minutes.Solid fades away, and reaction mixture gradually becomes grey.Reaction mixture is mixed with 600mL n-hexane, is stirred 20 minutes, precipitating was collected in filtering, and precipitating is washed with 100mL n-hexane, is dried in vacuo.Sample is purified with silica gel column chromatography, with just Eluent is done in hexanes/ch=1/1, obtains 6.14g pale solid, yield 78%.¹H NMR (400MHz, CDCl₃):δ =8.66 (1H), 8.53 (1H), 8.40 (1H), 8.01 (1H), 7.82 (1H), 7.22 (1H), 7.11 (2H), 2.61-2.57 (2H),1.20-1.25ppm(12H).

Reaction reagent and condition: i) 108 DEG C, acetic acid

The synthesis of precursor compound 17: taking compound 16 (0.938g, 2.14mmol), and connection boric acid pinacol boron ester (is changed Close object 4) (1.09g, 4.28mmol), 15mL dry ethylene glycol dimethyl ether, anhydrous acetic acid potassium (633mg, 6.46mmol), (C17H14P) 2Fe.PdCl2 (29mg, 40 μm of ol, 1.8%) is added in 50mL flask, reaction flask is replaced as nitrogen atmosphere, 70 Heating stirring 12 hours at DEG C, brick-red reaction mixture gradually become brown.Reaction mixture is cooled to room temperature, is added 300mL methylene chloride filters mixture, collects filtrate, and rotary evaporation removes solvent.With silica gel chromatographic column purification of crude product, use N-hexane/methylene chloride=10/1-1/2 does leacheate, obtains 0.830g pale solid, yield 80%.¹H NMR (400MHz, CDCl₃): δ=9.11 (1H), 8.63-8.58 (2H), 8.31 (1H), 7.77 (1H), 7.28 (1H), 7.14 (2H), 1.45(12H),2.63-2.59(2H),1.22-1.28ppm(12H).

Reaction reagent and condition: i) (C₁₇H₁₄P)₂Fe.PdC_l2, DME, 70 DEG C, acetic acid

Take four bromo spiral shell [4,4] double ring glutaric thiophenes (compound 11) (50.0mg, 0.0760mmol), compound 17 (162mg,0.335mmol),Pd₂(dba)3.CHCl₃(15.0mg,14.8μmol),HP(tBu)₃BF₄(9.00mg,31.0μ Mol 25mL single port bottle) is added under nitrogen atmosphere, single port bottle is sealed with rubber stopper.It is added into above-mentioned single port bottle and removed oxygen K₃PO4 aqueous solution (2M, 1.00mL, 2.00mmol) removed the THF (10mL) of oxygen, stirring at normal temperature.Reaction system is initially Purple brown red liquid, then yellowish red color is gradually deepened.After 12 hours, reaction system becomes yellow-red liquid, and bit brownish. 100mL methylene chloride is added into reaction solution, washing three times (each 100mL), with the dry organic phase of anhydrous sodium sulfate, is filtered, Rotary evaporation removes solvent and obtains 121mg Orange red solid, yield 90% with gel chromatographic columns separation product.¹H NMR (400MHz, CDCl₃): δ=8.69-8.64 (8H), 8.60 (4H), 7.88 (4H), 7.75 (4H), 7.40 (4H), 7.32 (8H), 7.14(4H),2.85(8H),1.26-1.22ppm(48H).MALDI-TOF MS:Calcd for C₁₁₃H₉₂N₄O₈S₄:1761.6, Found:1762.2(m/z).

Reaction reagent and condition: i) Pd₂(dba)3.CHCl₃, HP (tBu)₃BF₄, DME, rt, K₃PO₄

The synthesis of 3. compound S3 of embodiment.

Precursor compound 18 according to document method synthesis (R.T.Cheriya, J.Joy, S.K.Rajagopal, K.Nagarajan and M.Hariharan,DNA-Enforced Conformational Restriction of an Atropisomer)

Reaction reagent and condition: i) 2,6- diisopropyl aniline/imidazoles/zinc acetate/H2O/190 DEG C；ii)Br₂, chlorobenzene/ 50℃

The synthesis of precursor compound 19: taking compound 18 (1.60g, 2.85mmol), joins boric acid pinacol boron ester (chemical combination Object 4) (1.45g, 5.70mmol), 22mL dry ethylene glycol dimethyl ether, anhydrous acetic acid potassium (839mg, 8.55mmol), (C₁₇H₁₄P)₂Fe.PdCl₂(37mg, 51 μm of ol, 1.8%) are added in 50mL flask, and reaction flask is replaced as nitrogen atmosphere, heats and stirs at 70 DEG C It mixes 12 hours, brick-red reaction mixture gradually becomes brown.Reaction mixture is cooled to room temperature, 360mL dichloromethane is added Alkane filters mixture, collects filtrate, and rotary evaporation removes solvent.With silica gel chromatographic column purification of crude product, with n-hexane/dichloro Methane=10/1-1/3 does leacheate, obtains 1.32g red solid, yield 76%.¹H NMR (400MHz, CDCl₃): δ= 8.65-8.61(2H),8.44-8.40(2H),8.34(1H),8.25(1H),8.18(1H),7.86(1H),7.69(1H),7.47 (1H),7.31(2H),2.73-2.14(2H),1.47(12H),1.13ppm(12H).

Reaction reagent and condition: i) (C₁₇H₁₄P)₂Fe.PdCl₂, DME, 70 DEG C, potassium acetate

The synthesis of compound S3: take four bromo spiral shell [4,4] double ring glutaric thiophenes (compound 11) (75.0mg, 0.114mmol), compound 19 (333mg, 0.549mmol), Pd₂(dba)3.CHCl₃(22mg,21.2μmol),HP(tBu)₃BF₄25mL single port bottle is added in (13mg, 44 μm of ol) under nitrogen atmosphere, and single port bottle is sealed with rubber stopper.Into above-mentioned single port bottle The K for removing oxygen is added₃PO4 aqueous solution (2M, 1.00mL, 2.00mmol) removed the THF (10mL) of oxygen, stirring at normal temperature.Instead Answering system is initially purple yellowish-brown red liquid, then gradually becomes atropurpureus.After twenty four hours, it is added into reaction solution 150mL methylene chloride, three times (each 100mL), with the dry organic phase of anhydrous sodium sulfate, filtering, rotary evaporation removes molten for washing Agent obtains 211mg atropurpureus solid, yield 82% with gel chromatographic columns separation product.¹H NMR (400MHz, CDCl₃): δ= 8.65-8.54(8H),8.44-8.32(20H),8.19(4H),7.63(4H),7.43(4H),7.36(8H),7.14(4H), 2.86(8H),1.29-1.23ppm(48H).MALDI-TOF MS:Calcd for C₁₅₃H₁₀₈N₄O₈S₄:2257.7,Found: 2257.4(m/z).

Reaction reagent and condition: i) Pd₂(dba)3.CHCl₃, HP (tBu)₃BF₄, DME, rt, potassium phosphate

The synthesis of 4 compound S4 of embodiment.

(N- (1-Heptyloctyl) -9- (4,4,5,5-tetramethyl-1,3,2- of precursor compound 20 dioxaborolan-2-yl)

Perylene-3,4-dicarboxmonoimide) according to document (Nolde F., Pisula W., M ü ller S., Kohl C.,and Müllen K.,Synthesis and Self-Organization of Core-Extended Perylene Tetracarboxdiimides with Branched Alkyl Substituents, Chem.Mater.2006,18,3715-3725 method synthesis).

The synthesis of compound S4: take four bromo spiral shell [4,4] double ring glutaric thiophenes (compound 11) (65.0mg, 0.099mmol), compound 20 (286mg, 0.436mmol), Pd₂(dba)3.CHCl₃(18.0mg,17.0μmol),HP(tBu)₃BF₄25mL single port bottle is added in (12.0mg, 42.3 μm of ol) under nitrogen atmosphere, and single port bottle is sealed with rubber stopper.To above-mentioned single port The K for removing oxygen is added in bottle₃PO4 aqueous solution (2M, 0.790mL, 1.58mmol) removed the THF (16mL) of oxygen, and room temperature stirs It mixes.Reaction system is initially purple yellowish-brown red liquid, then gradually becomes atropurpureus.After twenty four hours, add into reaction solution Enter 100mL methylene chloride, three times (each 100mL), with the dry organic phase of anhydrous sodium sulfate, filtering, rotary evaporation is removed for washing Solvent obtains 173mg atropurpureus solid, yield 71% with gel chromatographic columns separation product.¹H NMR (400MHz, THF-d₈):δ =8.86 (4H), 8.54-8.45 (24H), 8.13 (4H), 7.57 (4H), 6.86 (4H), 5.26-5.15 (4H), 2.41-2.28 (8H),1.82-1.74(8H),1.35-1.23(80H),0.86-0.80ppm(24H).MALDI-TOF MS:Calcd for C₁₆₅H₁₆₄N₄O₈S₄:2458.2,Found:2458.8(m/z).

The synthesis of 5 compound S5 of embodiment.

The synthesis of precursor compound 22: taking compound 21 (100mg, 0.144mmol), compound 5 (96.9mg, 0.288mmol), Pd (dppf) Cl₂50mL single port bottle is added in (10.0mg, 0.0140mmol) under nitrogen atmosphere, and single port bottle is used Rubber stopper sealing.The NaOAc aqueous solution (2M, 0.5mL, 1.00mmol) for removing oxygen is added into above-mentioned single port bottle, removes peroxide The THF (15mL) of gas, stirring at normal temperature.Reaction system gradually becomes atropurpureus.After one hour, 150mL bis- is added into reaction solution Chloromethanes, three times (each 100mL), with the dry organic phase of anhydrous sodium sulfate, filtering, rotary evaporation removes solvent, in for washing Property aluminum oxide column chromatography separation, using methylene chloride as eluent, obtain 77mg atropurpureus solid, yield 65%.¹H NMR (400MHz, CDCl₃): δ=8.87-8.77 (2H), 8.69-8.56 (5H), 7.66 (1H), 7.31 (1H), 4.49-4.42 (4H),2.01-1.92(2H),1.45-1.33(16H),1.26(12H),0.95-0.85ppm(12H).

Reaction reagent and condition: i) Pd (dppf) Cl₂、THF、rt、NaOAc

The synthesis of compound S5: take four bromo spiral shell [4,4] double ring glutaric thiophenes (compound 11) (53.0mg, 0.081mmol), compound 22 (319mg, 0.388mmol), Pd₂(dba)3.CHCl₃(17.0mg,16.4μmol),HP(tBu)₃BF₄25mL single port bottle is added in (11.0mg, 37.0 μm of ol) under nitrogen atmosphere, and single port bottle is sealed with rubber stopper.To above-mentioned single port The K for removing oxygen is added in bottle₃PO4 aqueous solution (2M, 1.00mL, 2.00mmol) removed the THF (10mL) of oxygen, and room temperature stirs It mixes.Reaction system is initially purple yellowish-brown red liquid, then gradually becomes atropurpureus.After twenty four hours, add into reaction solution Enter 130mL methylene chloride, three times (each 100mL), with the dry organic phase of anhydrous sodium sulfate, filtering, rotary evaporation is removed for washing Solvent obtains 192mg atropurpureus solid, yield 75% with gel chromatographic columns separation product.¹H NMR (400MHz, CDCl₃):δ =8.85-8.74 (8H), 8.67-8.53 (20H), 7.67 (4H), 7.30 (4H), 4.46-4.39 (16H), 2.01-1.93 (8H),1.42-1.31(64H),0.97-0.83ppm(48H).MALDI-TOF MS:Calcd for C₁₉₃H₁₇₆N₈O₁₆S₈: 3119.1,Found:3118.6(m/z).

Reaction reagent and condition: i) Pd₂(dba)₃.CHCl₃, HP (tBu)₃BF₄, DME, rt, potassium phosphate

The synthesis of 6 compound s 6 of embodiment.

The synthesis of precursor compound 23: taking compound 21 (100mg, 0.144mmol), compound 6 (95.0mg, 0.288mmol), Pd (dppf) Cl₂50mL single port bottle is added in (10.0mg, 0.0140mmol) under nitrogen atmosphere, and single port bottle is used Rubber stopper sealing.The NaOAc aqueous solution (2M, 0.5mL, 1.00mmol) for removing oxygen is added into above-mentioned single port bottle, removes peroxide The THF (15mL) of gas, stirring at normal temperature.Reaction system gradually becomes aubergine.After one hour, 100mL bis- is added into reaction solution Chloromethanes, three times (each 100mL), with the dry organic phase of anhydrous sodium sulfate, filtering, rotary evaporation removes solvent, in for washing Property aluminum oxide column chromatography separation, using methylene chloride as eluent, obtain 72mg aubergine solid chemical compound X, yield 62%.¹H NMR (400MHz, CDCl₃): δ=8.94-8.80 (2H), 8.70-8.55 (5H), 7.81 (2H), 7.31 (2H), 4.48-4.40 (4H),2.01-1.92(2H),1.43-1.30(16H),1.25(12H),0.96-0.87ppm(12H).

Reaction reagent and condition: i) Pd (dppf) Cl₂、THF、rt、NaOAc

The synthesis of compound s 6: take four bromo spiral shell [4,4] double ring glutaric thiophenes (compound 11) (64.0mg, 0.098mmol), compound 23 (382mg, 0.468mmol), Pd₂(dba)3.CHCl₃(20mg,19.0μmol),HP(tBu)₃BF₄25mL single port bottle is added in (13mg, 44 μm of ol) under nitrogen atmosphere, and single port bottle is sealed with rubber stopper.Into above-mentioned single port bottle The K for removing oxygen is added₃PO4 aqueous solution (2M, 1.00mL, 2.00mmol) removed the THF (10mL) of oxygen, stirring at normal temperature.Instead Answering system is initially purple yellowish-brown red liquid, then gradually becomes atropurpureus.After twenty four hours, it is added into reaction solution 130mL methylene chloride, three times (each 100mL), with the dry organic phase of anhydrous sodium sulfate, filtering, rotary evaporation removes molten for washing Agent obtains 215mg atropurpureus solid, yield 71% with gel chromatographic columns separation product.¹H NMR (400MHz, CDCl₃): δ= 8.93-8.81(8H),8.72-8.56(20H),7.77(8H),7.33(8H),4.45-4.37(16H),2.02-1.92(8H), 1.46-1.31(64H),0.97-0.86ppm(48H).MALDI-TOF MS:Calcd for C₂₀₁H₁₈₄N₈O₁₆S₄:3095.3, Found:3095.5(m/z).

The synthesis of 7 compound S7 of embodiment.

The synthesis of precursor compound 24: taking compound 21 (100mg, 0.144mmol), compound 7 (95.0mg, 0.288mmol), Pd (dppf) Cl₂50mL single port bottle is added in (10.0mg, 0.0140mmol) under nitrogen atmosphere, and single port bottle is used Rubber stopper sealing.The NaOAc aqueous solution (2M, 0.5mL, 1.00mmol) for removing oxygen is added into above-mentioned single port bottle, removes peroxide The THF (15mL) of gas, stirring at normal temperature.Reaction system gradually becomes aubergine.After one hour, 100mL bis- is added into reaction solution Chloromethanes, three times (each 100mL), with the dry organic phase of anhydrous sodium sulfate, filtering, rotary evaporation removes solvent, in for washing Property aluminum oxide column chromatography separation, using methylene chloride as eluent, obtain 72mg aubergine solid chemical compound X, yield 62%.¹H NMR (400MHz, CDCl₃): δ=8.82-8.80 (1H), 8.70-8.68 (1H), 8.61-8.59 (2H), 8.09-8.07 (1H), 7.99-7.96(1H),7.88-7.86(1H),7.81-7.79(1H),7.73-7.71(1H),7.67(1H),7.57-7.55 (2H),4.25-4.03(4H),2.03-1.91(6H),1.47(12H),1.44-1.28(18H),1.11-0.89(30H), 0.78-0.69ppm(10H).MALDI-TOF MS:Calcd for C₇₅H₉₃BN₂O₆:1128.7,Found:1128.5(m/z).

Reaction reagent and condition: i) Pd (dppf) Cl₂、THF、rt、NaOAc

The synthesis of compound S7: take four bromo spiral shell [4,4] double ring glutaric thiophenes (compound 11) (64.0mg, 0.098mmol), compound 24 (382mg, 0.468mmol), Pd₂(dba)3.CHCl₃(20mg,19.0μmol),HP(tBu)₃BF₄25mL single port bottle is added in (13mg, 44 μm of ol) under nitrogen atmosphere, and single port bottle is sealed with rubber stopper.Into above-mentioned single port bottle The K for removing oxygen is added₃PO4 aqueous solution (2M, 1.00mL, 2.00mmol) removed the THF (10mL) of oxygen, stirring at normal temperature.Instead Answering system is initially purple yellowish-brown red liquid, then gradually becomes atropurpureus.After twenty four hours, it is added into reaction solution 130mL methylene chloride, three times (each 100mL), with the dry organic phase of anhydrous sodium sulfate, filtering, rotary evaporation removes molten for washing Agent obtains 215mg atropurpureus solid, yield 71% with gel chromatographic columns separation product.¹H NMR (400MHz, CDCl₃): δ= 8.71-8.68(4H),8.66-8.64(8H),8.58-8.56(8H),8.03-8.01(4H),7.94-7.92(4H),7.83- 7.81(4H),7.76-7.74(4H),7.66-7.64(4H),7.55(4H),7.45-7.41(8H),7.09(4H),4.21- 4.00(16H),1.98-1.86(24H),1.42-1.25(72H),1.05-0.83(120H),0.73-0.64ppm(40H) .MALDI-TOF MS:Calcd for C₂₉₃H₃₂₈N₈O₁₆S₄:4345.4,Found:4345.6(m/z).

The synthesis of 8 compound S8 of embodiment.

The synthesis of precursor compound 25: it takes compound 13 (2.10g, 3.62mmol) that bis- mouthfuls of bottles of 100mL are added, will react Bottle is replaced as nitrogen atmosphere.50mL anhydrous tetrahydro furan is added into reaction flask, reaction system is cooled to -78 DEG C.Acutely stirring Lower dropwise addition n-BuLi (7.24mmol, 3.02mL, 2.4M, hexane solution) into reaction system is mixed, reaction mixture becomes Bright yellow solution.After half an hour, reaction mixture is warming up to 0 DEG C, is stirred for half an hour.It is mixed with vigorous stirring to reaction Silicon tetrachloride (308mg, 1.81mmol) is added dropwise in object.Continue to stir mixture at 0 DEG C, reaction mixture becomes brown.One 10mL water quenching reaction is added in hour backward reaction system.Reaction mixture is poured into 100mL n-hexane, organic phase is washed with water Three times, water 100mL is used every time, and with the dry organic phase of anhydrous sodium sulfate, filtrate is collected in filtering, and rotary evaporation removes solvent.Use silicon Glue chromatography column separating purification sample, does eluent with n-hexane, obtains yellow solid 1.21g, yield 77%.¹H NMR (400MHz, CDCl₃): δ=6.51 (4H), 0.32ppm (36H) .MALDI-TOF MS:Calcd for C₃₆H₄₀S₈Si₅: 867.9,Found:868.2(m/z).

Reaction reagent and condition: i) n-BuLi, -78 DEG C；ii)SiCl₄, -78 DEG C of-rt

The synthesis of precursor compound 26: taking compound 25 (500mg, 0.575mmol) to be placed in bis- mouthfuls of bottles of 100mL, is added Two mouthfuls of bottles are replaced as nitrogen atmosphere, encase reaction flask with aluminium-foil paper, be protected from light by 20mL tetrahydrofuran.By NBS (441mg, It 2.42mmol) is dissolved in 15mL tetrahydrofuran, is added dropwise to reaction flask with vigorous stirring.Reaction mixture is stirred at room temperature 24 Hour.Reaction mixture is concentrated to 2mL, is added dropwise to 15mL cold methanol.Filtering, obtains yellow solid 443mg, yield 86%.¹H NMR (400MHz, CDCl₃): δ=6.49ppm (4H).

Reaction reagent and condition: i) containing the THF of NBS

The synthesis of compound S8: taking compound 26 (58.0mg, 0.0647mmol), compound 22 (234mg, 0.285mmol),Pd₂(dba)3.CHCl₃(13.0mg,13.0μmol),HP(tBu)₃BF₄(8.41mg, 28.3 μm of ol) are in nitrogen 25mL single port bottle is added under atmosphere, single port bottle is sealed with rubber stopper.The K for removing oxygen is added into above-mentioned single port bottle₃PO4 is water-soluble Liquid (2M, 0.5mL, 1.00mmol) removed the THF (30mL) of oxygen, stirring at normal temperature.Reaction system is initially purple yellowish-brown red liquid Body then gradually becomes atropurpureus.After twenty four hours, 150mL methylene chloride is added into reaction solution, washing is (each three times 100mL), it with the dry organic phase of anhydrous sodium sulfate, filters, rotary evaporation removes solvent and obtained with gel chromatographic columns separation product 192mg atropurpureus solid, yield 75%.¹H NMR (400MHz, CDCl₃): δ=8.84-8.72 (8H), 8.65-8.51 (20H), 7.66(4H),7.31(4H),4.43-4.37(16H),1.98-1.91(8H),1.40-1.30(64H),0.98-0.82ppm (48H).MALDI-TOF MS:Calcd for C₂₀₁H₁₇₆N₈O₁₆S₁₂:3342.9,Found:3342.5(m/z).

The synthesis of 9 compound S9 of embodiment: take compound 8 (bromo- two fluorenes of 9,9'- spiral shell of 2,2', 7,7'- tetra-) (137mg, 0.217mmol), compound 15 (416mg, 0.956mmol), Pd₂(dba)3.CHCl₃(43mg, 42.2 μm of ol, 5.00%), HP (tBu)₃BF₄25mL single port bottle is added in (26mg, 87 μm of ol, 10%) under nitrogen atmosphere, and single port bottle is sealed with rubber stopper.Upwards State the K for being added in single port bottle and removing oxygen₃PO4 aqueous solution (2M, 1.74mL, 3.48mmol) removed the THF (40mL) of oxygen, 70 DEG C are heated to, reaction system is initially purple brown red liquid, and puce fades away, and lark is presented.It, will after 24 hours Reaction mixture is cooled to room temperature, and 200mL methylene chloride is added into reaction solution, is washed three times (each 100mL), with anhydrous sulphur The dry organic phase of sour sodium, filtering, rotary evaporation remove solvent, and with gel chromatographic columns separation product, it is solid to obtain 242mg pistac Body, yield 72%.¹H NMR (400MHz, CDCl₃): δ=8.82-8.77 (8H), 8.73 (4H), 7.92 (4H), 7.87 (4H), 7.76(4H),7.71(4H),7.63(4H),4.25-4.12(8H),2.01-1.96(4H),1.43-1.35(32H),0.97- 0.88ppm(24H).MALDI-TOF MS:Calcd for C₁₀₅H₁₀₀N₄O₈:1545.7,Found:1545.9(m/z).

Reaction reagent and condition: i) Pd₂(dba)₃.CHCl₃, HP (tBu)₃BF₄, DME, 70 DEG C, potassium phosphate

Embodiment 10: 12mg compound S1 and 0.5mL o-dichlorohenzene are stirred 2 hours at 55 DEG C, chemical combination is prepared The o-dichlorobenzene solution of object S1.

Embodiment 11: the o-dichlorobenzene solution of the compound S1 prepared using embodiment 10 is by spin coating method in ITO glass Spin coating obtains the film of compound S2 on glass.The abosrption spectrogram of the compound is shown refering to Fig. 6.The bright compound of the chart is thin The a length of 570nm of the maximum absorption wave of film, initial absorption wavelength are 380nm, and corresponding material spectrum bandwidth is 2.25eV, are belonged to Semiconductor bandgap range.

Embodiment 12: compound S1, compound S4 and each 6mg of compound S7 (3- hexyl thiophene) poly- with 6mg respectively are taken (P3HT) it is blended, is respectively dissolved in 0.5mL chlorobenzene, is stirred 12 hours at 55 DEG C, P3HT/ compound S1, P3HT/ compound is made The chlorobenzene solution of S4, P3HT/ compound S7.

Embodiment 13: the following are the specific implementation for preparing organic solar batteries using the solution prepared in embodiment 12 is thin Section.

Battery preparation specific embodiment bibliography (Fischer M.K.R., Ma C.Q., Janssen R.A.J., Debaerdemaeker T.andP.,Core-functionalized dendritic oligothiophenes— novel donor–acceptor systems,J.Mater.Chem.,2009,19,4784–4795)。

Prepared organic solar batteries device architecture is ITO/PEDOT:PSS/ the compounds of this invention in the present invention: PC₆₁BM/LiF/Al.

The general preparation process of organic solar batteries device in the present invention.By the clean glass for being coated with ITO, it is placed on purple In outer light irradiation device, the one side of ITO will be coated with ultraviolet light 30 minutes.

PEDOT:PSS 4083 is drawn with syringe, 0.45 μm of water phase filter is installed on the injector, by PEDOT:PSS The one side for being coated with ITO is filled after 4083 filterings, with 3000 rpms of revolving speeds spin coating PEDOT:PSS, spin-coating time 60s.

The ito glass for being coated with PEDOT:PSS is placed on full of nitrogen, water and oxygen content are less than in 1ppm glove box, 124 DEG C are annealed 10 minutes.

The chlorobenzene solution of the P3HT/ compound S1 prepared in embodiment 12 is spin-coated on PEDOT:PSS layer, revolving speed 1000 Rpm, it after being painted with, is placed three minutes in the glove box full of nitrogen, anneals 5 minutes at 124 DEG C, photoactive layer is made. Later, the ito glass for having applied PEDOT:PSS layers and photoactive layer is put into vapor deposition chamber, 1nm LiF is first deposited, then 100nm is deposited Al, the i.e. preparation of completion device.

According to the general preparation process of organic solar batteries device in the present invention, with compound S1, S4, S7 is as electronics The film that preparation is blended with electron donor P3HT for donor is prepared as the organic solar batteries of photoactive layer.

Embodiment 14: organic solar batteries prepared in embodiment 13 are tested under the irradiation of sun optical analog lamp The photoelectric conversion efficiency of device obtains result shown in following table:

Donor	Receptor	Solvent	Voc/V	J_sc/mA cm^-2	FF	PCE/%
							P3HT	Compound S1	Chlorobenzene	0.64	0.96	0.39	0.24
P3HT	Compound S4	Chlorobenzene	0.83	3.46	0.48	1.38
							P3HT	Compound S7	Chlorobenzene	0.88	3.28	0.44	1.27

It should be appreciated that it is described above and in the embodiment shown on drawing, the design for being limited surely of the invention can not be parsed and thought Think.Holding identical skill in technical field of the invention can be improved technical thought of the invention in the form of multiplicity Change, such improvement and change are interpreted as belonging to the scope of protection of the present invention interior.

Claims

1. a kind of organic pi-conjugated compound, it is characterised in that include:

Molecule fragment unit, and spiral shell-[4,4]-nonyl tetraene or 5, a C=C in miscellaneous-spiral shell-[4, the 4]-nonyl tetraene unit of 5- Double bond is connected and forms 5-membered aromatic heterocycle or polynary aromatic condensed ring structure with the C=C double bond,

And the end position aromatic imide unit being connect with the molecule fragment unit；

Also, organic pi-conjugated compound has structure shown in following formula (Ia) or (Ib):

Wherein, X₁Selected from carbon atom, silicon atom or germanium atom, π-Ar₁For the molecule fragment unit, EG is end position aromatics Acid imide unit, π-Ar₂For short chain conjugate unit, the short chain conjugate unit and the molecule fragment unit pass through C -- C single bond Pi-conjugated connection is formed, the short chain conjugate unit is mainly by > 1 but≤12 phenyl ring or thiphene ring or aromatic condensed ring list Member connects to be formed in pi-conjugated connected mode；

End position aromatic imide unit is selected from the structural unit having as described in general structure (IIa) or (IIb), and described End position aromatic imide unit is connect in a manner of covalent bond via carbon atom optional on aromatic rings in adjacent molecule fragment list On first or short chain conjugate unit,

Wherein, π-Ar₃Selected from phenyl ring, thiphene ring or the polycyclic aromatic unit formed by 2-10 aromatic rings parallel connection, R₁Selected from containing Carbon atom number is alkyl, miscellaneous alkyl, substituted or unsubstituted aryl or the heteroaryl of the linear chain or branched chain of 1-20.

2. organic pi-conjugated compound according to claim 1, which is characterized in that the π-Ar₃Selected from such as general formula (IIIa), structural unit described in (IIIb), (IIIc), (IIId) and (IIIe):

Wherein, 0,1 or 2 a.

3. organic pi-conjugated compound according to claim 2, which is characterized in that the end position aromatic imide unit choosing From any one of following aromatic imide:

Wherein, R₁Alkyl, miscellaneous alkyl, substituted or unsubstituted aryl selected from the linear chain or branched chain for being 1-20 for carbon atom quantity Or heteroaryl.

4. organic pi-conjugated compound according to claim 1, it is characterised in that: 5, the 5- is miscellaneous-spiral shell-[4,4]-nonyl four Hetero atom X in alkene unit₁For silicon atom.

5. organic pi-conjugated compound described in any one of -4 according to claim 1, it is characterised in that: the compound has Single molecular weight distribution.

6. a kind of organic pi-conjugated compound, it is characterised in that include:

Spiral shell-[4,4]-nonyl tetraene or miscellaneous-spiral shell-[the 4,4]-nonyl tetraene unit of 5,5-；

Molecule fragment unit, and spiral shell-[4,4]-nonyl tetraene or 5, a double bond in miscellaneous-spiral shell-[4, the 4]-nonyl tetraene unit of 5- Form the chemical structure having as described in general formula (Va) or (Vb):

Wherein, X₂Selected from O, S, Se, N-R₂Or-CH=CH-,

R₃Alkyl, miscellaneous alkane or base, substituted or unsubstituted aryl or heteroaryl selected from the linear chain or branched chain that carbon atom quantity is 1-20 Base,

B is 0 or 1；And

The end position aromatic imide unit being connect with the molecule fragment unit；

7. organic pi-conjugated compound according to claim 6, which is characterized in that wherein, X₂Selected from S or-CH=CH-.

8. organic pi-conjugated compound according to any one of claim 6-7, it is characterised in that: the compound has Single molecular weight distribution.

9. a kind of organic pi-conjugated compound, it is characterised in that include:

Molecule fragment unit, and spiral shell-[4,4]-nonyl tetraene or 5, a C=C in miscellaneous-spiral shell-[4, the 4]-nonyl tetraene unit of 5- Double bond is connected and forms 5-membered aromatic heterocycle or polynary aromatic condensed ring structure with the C=C double bond；

Wherein, X₁Selected from carbon atom, silicon atom or germanium atom, π-Ar₁For the molecule fragment unit, EG is end position aromatics Acid imide unit, π-Ar₂For short chain conjugate unit, the short chain conjugate unit and the molecule fragment unit pass through C -- C single bond Pi-conjugated connection is formed, the short chain conjugate unit, which is selected from, passes through 1 by 1~4 independent substituted or unsubstituted phenyl ring unit, What 4- connections were formed there are the structure as shown in general formula (VIa) or (VIb) to connect benzene unit more:

Wherein, R₄The miscellaneous base of alkyl, alkane selected from the linear chain or branched chain that carbon atom quantity is 1-20, R₅It is 1- selected from carbon atom quantity Alkyl, miscellaneous alkyl, substituted or unsubstituted aryl or the heteroaryl of 20 linear chain or branched chain, c are any integer among 1~4, D is 1 or 2；

10. organic pi-conjugated compound according to claim 9, it is characterised in that: the compound has single point Son amount distribution.

11. a kind of organic pi-conjugated compound, it is characterised in that include:

Wherein, X₁Selected from carbon atom, silicon atom or germanium atom, π-Ar₁For the molecule fragment unit, EG is end position aromatics Acid imide unit, π-Ar₂For short chain conjugate unit, the short chain conjugate unit and the molecule fragment unit pass through C -- C single bond Pi-conjugated connection is formed, the short chain conjugate unit, which is selected from, passes through 2 by 1~6 independent substituted or unsubstituted thiophene unit, 5- connection formed have as shown in general formula (VIIa) have symmetrical configuration oligo-thiophenes chain or general formula (VIIb) shown in Compound with regular structure oligo-thiophenes chain:

Wherein, r, s are independently selected from 0,1 or 2, and r and s cannot be selected from any integer among 1~6, R simultaneously for 0, q₆Choosing From hydrogen, the alkyl that carbon atom quantity is 1-20 or the miscellaneous base of alkane or two R₆Between form the substituted or unsubstituted ring-type of 5-8 member Structure, R₇、R₈In all cases independently selected from hydrogen, the alkyl that carbon atom quantity is 1-20 or the miscellaneous base of alkane or R₇With R₈It Between form the substituted or unsubstituted cyclic structure of 5-8 member；

12. organic pi-conjugated compound according to claim 11, it is characterised in that: the compound has single point Son amount distribution.

13. a kind of organic conjugate semiconductor material, it is characterised in that include organic π-of any of claims 1-12 Conjugated compound.

14. a kind of composition, it is characterised in that it include organic pi-conjugated compound of any of claims 1-12, and And the composition is in liquid.

15. organic conjugate described in organic pi-conjugated compound of any of claims 1-12, claim 13 half Composition described in conductor material or claim 14 is used to prepare the application in organic electronic device.

16. a kind of organic electronic device, it is characterised in that include:

Organic pi-conjugated compound of any of claims 1-12, to as electron acceptor；And

Conjugated polymer or oligomer, to as electron donor.

17. a kind of semiconductive thin film, it is characterised in that include organic pi-conjugated chemical combination of any of claims 1-12 Composition described in organic conjugate semiconductor material or claim 14 described in object, claim 13.

18. semiconductive thin film according to claim 17, it is characterised in that: the semiconductive thin film include as electronics by Organic pi-conjugated compound of body and conjugated polymer or oligomer as electron donor.

19. a kind of electronic device, it is characterised in that include semiconductive thin film described in claim 17 or 18.

20. electronic device according to claim 19, it is characterised in that: the electronic device is solar battery.