CN105693745A

CN105693745A - Organic pi-conjugated compound and its preparation method and use

Info

Publication number: CN105693745A
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: 2016-06-22
Anticipated expiration: 2034-11-27
Also published as: CN105693745B

Abstract

The invention discloses an organic pi-conjugated compound. The organic pi-conjugated compound comprises a spiro-[4, 4]-nonatetraene or 5, 5-hetero-spiro-[4, 4]-nonatetraene unit, a molecular fragment unit which is connected to C=C double bonds of the spiro-[4, 4]-nonatetraene or 5, 5-hetero-spiro-[4, 4]-nonatetraene unit to form a five-membered aromatic heterocycle or polybasic aromatic condensed ring structure, and a terminal aromatic imide unit connected to the molecular fragment unit. Further, the organic pi-conjugated compound also comprises a short-chain conjugated unit which is connected to the molecular fragment unit through a C-C single bond in a pi-conjugated connection way. The invention also discloses a preparation method of the organic pi-conjugated compound and a use of the organic pi-conjugated compound in an organic semiconductor device and especially in an organic optoelectronic device. The organic pi-conjugated compound has very good photon absorption efficiency in a visible light zone, forms ideal phase separation from a plane-approximate one-dimensional linear conjugated polymer, improves photoelectric conversion efficiency of the material in a thin-film solar cell, can be prepared through a chemical method, has a low cost and can be industrialized easily.

Description

Organic pi-conjugated compound, its preparation method and application

Technical field

The present invention be more particularly directed to a kind of organic pi-conjugated compound, its preparation method, containing the compositions of this compound, containing this compound semiconductor film and their application, the particularly application in organic electro-optic device, belongs to organic semiconducting materials and semiconductor photoelectric device field。

Background technology

Based on, in the organic thin film solar cell device of organic semiconducting materials, at least containing a kind of organic semiconducting materials in organic photoactive layer, this material can absorb photon energy and form excited state molecule, i.e. exciton。Electronic transfer process is there is thus forming electronics and hole pair, the positive and negative charge carrier namely separated between exciton and another kind of molecule organic semiconductor。Described electronic transfer process can be that electronics is from exciton transfer to another molecule organic semiconductor, it is also possible to is that electronics shifts from another organic semiconducting materials to exciton。Wherein, the material providing an electronics is called electron donor, is also generally referred to as p-type semi-conducting material；And the material accepting an electronics is called electron acceptor, it is also generally referred to as type n semiconductor material。

The efficiency of organic solar batteries device depends on the organic semiconducting materials absorbability to photon on the one hand。Semi-conducting material is more strong to the absorbability of photon, the photon collection efficiency of organic photoactive thin film is more high, can the thickness of thin film such that it is able to reduce photolytic activity, that reduces material makes consumption, the probability that Carrier recombination occurs in carrier transport process can also be reduced, thus improving the photoelectric transformation efficiency of device。

On the other hand, the electron transfer efficiency between electron donor and electron acceptor is also the key factor affecting solar cell device efficiency。Intermolecular electron transfer efficiency is then determined by the HOMO/LUMO orbital energy level of material。For during using donor material as multiphoton absorption material, it is poor that the transfer of intermolecular generation electric charge then requires there is at least 0.3eV between the lumo energy of electron donor and the lumo energy of electron acceptor material, to guarantee electronic transfer process efficiency。And during using electron acceptor material as multiphoton absorption material, it is poor that the transfer of intermolecular generation electric charge then requires that the HOMO energy level of electron donor material and the HOMO energy inter-stage of electron acceptor material exist at least 0.3eV, to guarantee electronic transfer process efficiency (referring to Fig. 1)。

Another further aspect, the positive and negative charge carrier efficiency of transmission in p-type and type n semiconductor material respectively also determines the photoelectric transformation efficiency of device。Positive and negative charge carrier transport efficiency is more high, and the loss in charge transfer process is more little such that it is able to be effectively improved the opto-electronic conversion performance of device。The charge transport properties of material then depends on material molecule structure and the material molecule packing of molecules situation when filminess。The molecule more rule of the arrangement under solid film state, intermolecular π-π interact more strong, and the defect of material internal is more few such that it is able to reduce the recombination probability separating electric charge, improve the efficiency of transmission of electric charge, and then improve the photoelectric transformation efficiency of device。

In the past few years, using conjugated polymer as electron donor, using fullerene derivate as the polymer of electron acceptor: fullerene system achieves huge success at organic solar batteries。Such as: with poly-(3-hexyl thiophene): PC₆₁BM can reach 3%-5% (referring to Dang, M.T. as the device photoelectric conversion efficiency of photoactive layer；Hirsch, L.；Wantz, G.；" P3HT:PCBM, BestSellerinPolymerPhotovoltaicResearch " Adv.Mater.2011,23 (31), 3597-3602)。And utilize the derivative PC of narrow band gap conjugatd polymers p-type semi-conducting material and n-type fullerene₇₁BM combination more can make organic photovoltaic cell device efficiency bring up to close to 10% (referring to Ye, L.；Zhang, S.；Zhao, W.；Yao, H.；Hou, J.；" HighlyEfficient2D-ConjugatedBenzodithiophene-BasedPhotov oltaicPolymerwithLinearAlkylthioSideChain " Chem.Mater.2014,26 (12), 3603-3605)。Up to the present, fullerene derivate is the most commonly used organic solar batteries photoactive layer electron acceptor material。But this fullerene derivate there is problems in that in actual application 1. as the precursor of fullerene derivate, C₆₀And C₇₀Physical method is generally adopted to prepare, it is impossible to realize chemical method and prepare so that it is preparation cost is higher。Further functional modification on this basis, further increases the preparation cost of fullerene derivate；2. fullerene C₆₀The derivant photon absorption efficiency in visible region is low (referring to Wienk, M.M.；Kroon, J.M.；Verhees, W.J.H.；Knol, J.；Hummelen, J.C.；VanHal, P.A.；Janssen, R.A.J.；" EfficientMethano [70] fullerene/MDMO-PPVBulkHeterojunctionPhotovoltaicCells " Angew.Chem.Int.Ed.2003,42 (29), 3371-3375), more weak photon absorption efficiency causes that the thin film in same thickness is lower to the acquisition capacity of sunlight, and then have impact on the photoelectric transformation efficiency of device, receive certain restriction in actual applications。Fullerene C₇₀Derivant, as: PC₇₁Although BM can improve the spectral absorption performance of material, but due to C₇₀Purifies and separates more difficult, C₇₀The preparation cost of derivant is higher, is less useful for commercially producing application。

Aromatic imide analog derivative, for instance: acid imide (PDI), naphthalimide (NDI) etc., there is the molecular structure of big pi-conjugated plane and strong electron acceptor energy。This kind of plane molecule is prone to crystallization in film forming banking process, and strong intermolecular π-π interacts and forms desirable electric charge transmission channel, thus aromatic imide is the type n semiconductor material that a class is good。Meanwhile, aromatic imide generally has a good photon absorption efficiency in visible region, thus is the ideal organic thin film solar cell acceptor material of a class。But blended with organic pi-conjugated polymer or oligomer prepare organic photoactive mixed film time, owing to existing organic pi-conjugated polymer or oligomer are also almost plane one-dimensional linear molecules, therebetween tend not to enough formation be desirably separated state, the photoelectric transformation efficiency of corresponding thin-film solar cells is on the low side (referring to: Kamm, V.；Battagliarin, G.；Howard, I.A.；Pisula, W.；Mavrinskiy, A.；Li, C.；M ü llen, K.；Laquai, F.；" Polythiophene:PeryleneDiimideSolarCells theImpactofAlkyl-SubstitutiononthePhotovoltaicPerformanc e " Adv.EnergyMater.2011,1 (2), 297-302), its application in organic thin film solar cell field receives certain restriction。

Summary of the invention

In view of deficiency of the prior art, an object of the present invention is in that to provide a kind of organic pi-conjugated compound, it has good photon absorption efficiency, and there is space nonplanar structure, contribute to the one-dimensional linear conjugated polymer with almost plane to form desirable phase and separate, thus improving photoelectric transformation efficiency。

Another object of the present invention is to provide a kind of method preparing described organic pi-conjugated compound, it is low that it has cost, it is easy to the features such as commercial application。

A further object of the present invention is in that to provide the application of aforementioned organic pi-conjugated compound。

For realizing aforementioned invention purpose, the technical solution used in the present invention includes:

A kind of organic pi-conjugated compound, comprises:

Spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene or 5,5-assorted-spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene unit,

Molecule fragment unit, its with spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene or 5,5-assorted-spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene unit in C=C double bond be connected to form 5-membered aromatic heterocycle or polynary aromatic condensed ring structure,

And, the end position aromatic imide unit being connected with described molecule fragment unit。

Further, described organic pi-conjugated compound also comprises:

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

Wherein, described short chain conjugate unit mainly by 1-12 aromatic rings or aromatic heterocycle or aromatic condensed ring unit by pi-conjugated connected in the way of connect and formed。

Further, described end position aromatic imide unit is selected from the construction unit having as described in general structure (IIa) or (IIb), and described end position aromatic imide unit via carbon atom optional on aromatic rings to be connected in the way of covalent bond on adjacent molecule fragment unit or short chain conjugate unit

Wherein, π-Ar₃Selected from phenyl ring, thiphene ring or the polycyclic aromatic unit that formed by 2-10 aromatic rings parallel connection, R₁Selected from the alkyl of the straight or branched that carbon atom quantity is 1-20, assorted alkyl, substituted or unsubstituted aryl or heteroaryl；

Preferably, described π-Ar₃Construction unit selected from having as described in formula (IIIa), (IIIb), (IIIc), (IIId) and (IIIe):

Wherein, a is 0,1 or 2；

It is further preferred that described end position aromatic imide unit is selected from any one in aromatic imide:

Wherein, R₁It is selected from as the alkyl of straight or branched that carbon atom quantity is 1-20, assorted alkyl, substituted or unsubstituted aryl or heteroaryl。

Further, described 5,5-assorted-spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene unit in hetero atom at least selected from silicon atom。

Further, a double bond in described molecule fragment unit and spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene or 5,5-assorted-spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene unit forms the chemical constitution having as described in formula (Va) or (Vb):

Wherein, X₂Selected from O, S, Se, N-R₂Or-CH=CH-, it is preferable that from S or-CH=CH-,

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

R₂Selected from the alkyl of the straight or branched that carbon atom quantity is 1-20, assorted alkyl,

R₃Selected from the alkyl of the straight or branched that carbon atom quantity is 1-20, assorted alkyl, substituted or unsubstituted aryl or heteroaryl,

B is 0 or 1。

Further, described short chain conjugate unit selects free 1-4 independent substituted or unsubstituted benzene ring units to connect benzene unit by what Isosorbide-5-Nitrae-position connection was formed more, and has the structure as shown in formula (VIa) or (VIb):

Wherein, R₄Selected from the alkyl of the straight or branched that carbon atom quantity is 1-20, the assorted base of alkane, R₅Selected from the alkyl of the straight or branched that carbon atom quantity is 1-20, assorted alkyl, substituted or unsubstituted aryl or heteroaryl, c is any integer among 1～4, and d is 1 or 2；

Or, described short chain conjugate unit selects free 1-6 independent substituted or unsubstituted thiophene unit to be connected the oligo-thiophenes chain with the oligo-thiophenes chain with symmetrical configuration as shown in formula (VIIa) or the compound with regular structure shown in formula (VIIb) formed by 2,5-positions:

Wherein, r, s are independently selected from 0,1 or 2, and r and s can not be 0, the q any integer among 1～6 simultaneously, R₆Selected from the alkyl that hydrogen, carbon atom quantity are 1-20 or the assorted base of alkane or two R₆Between formed 5-8 unit substituted or unsubstituted circulus, R₇、R₈In all cases independently selected from alkyl or the assorted base of alkane that hydrogen, carbon atom quantity are 1-20, or R₇With R₈Between formed 5-8 unit substituted or unsubstituted circulus。

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

The preparation method of any one organic pi-conjugated compound aforementioned, including: the first compound, the second compound and at least one metallic catalyst are carried out condensation at least one solvent, it is thus achieved that described organic pi-conjugated compound；

Wherein, described first compound comprises:

As spiral shell-[4, the 4]-ninth of the ten Heavenly Stems tetraene structure of core or 5,5-assorted-spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene unit,

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

Described second compound comprises:

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

Or, short chain conjugate unit and the end moieties being connected with described short chain conjugate unit and Y₂；

Wherein, Y₁Selected from halogen atom, it is preferred to bromine atoms,

Y₂Selected from Sn (R₉)₃、B(OR₁₀)₂Or comprise the substituted or unsubstituted boron ester of 5-7 unit ring-type of-O-B-O-,

R₉It is selected from containing the straight or branched alkyl that carbon number is 1-4,

R₁₀Selected from hydrogen atom, containing the straight or branched alkyl that carbon number is 1-4。

Further, the condensation reaction adopted in the method includes metal catalytic Suzuki condensation or metal catalytic Stille condensation reaction。

A kind of organic conjugate semi-conducting material, comprises any one organic pi-conjugated compound aforementioned or the organic pi-conjugated compound prepared by any one method aforementioned。

A kind of compositions, comprises any one organic pi-conjugated compound aforementioned or the organic pi-conjugated compound prepared by any one method aforementioned, and described compositions is liquid。

Any one organic pi-conjugated compound aforementioned, any one method aforementioned organic pi-conjugated compound prepared, aforementioned organic conjugate semi-conducting material or foregoing are in the application preparing in organic electronic device。

A kind of organic electronic device, comprises:

Any one organic pi-conjugated compound aforementioned or the organic pi-conjugated compound prepared by any one method aforementioned, in order to as electron donor；

And, conjugated polymer or oligomer, in order to as electron acceptor。

A kind of semiconductive thin film, comprises any one organic pi-conjugated compound aforementioned, any one method aforementioned organic pi-conjugated compound prepared, aforementioned organic conjugate semi-conducting material or foregoing；

Preferably, described semiconductive thin film comprises the organic pi-conjugated compound as electron donor and as the conjugated polymer of electron acceptor or oligomer。

A kind of electronic device, comprises aforesaid semiconductor thin film。

Further, described electronic device includes electrooptical device, and described electrooptical device includes solaode, but is not limited to this。

Compared with prior art, the beneficial effect comprise that the molecule of this organic pi-conjugated compound has orthogonal space structure, and molecular end position modified by aromatic imide unit, compared with existing organic semiconducting materials, this organic pi-conjugated compound can adopt and be chemically synthesized preparation, material preparation cost is lower, it is easier to commercial application, in addition, compared with existing fullerene derivant, this organic pi-conjugated compound has very good photon absorption efficiency in visible region。And compared with existing plane aromatic imide electron-like acceptor material, this organic pi-conjugated compound has space nonplanar structure, thus help in the one-dimensional linear conjugated polymer with almost plane to form desirable phase and separate, thus improving material photoelectric transformation efficiency in thin-film solar cells。

Accompanying drawing explanation

The energy level combination schematic diagram of intermolecular electronic transfer process is there is in Fig. 1 a-Fig. 1 b when respectively illustrating using electron donor and electron acceptor as multiphoton absorption material；

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

Fig. 3 a-Fig. 3 b is the structural representation of typical case's virtue acid imide unit in the present invention；

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

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

Fig. 6 is the abosrption spectrogram of the thin 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。

Detailed description of the invention

One aspect of the present invention provides a kind of organic pi-conjugated compound, its molecule comprises spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene or 5,5-is assorted-spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene unit and there is the molecular structure (referring to Fig. 2 a-Fig. 2 b) described in formula (Ia) or (Ib), wherein, X₁For carbon atom, silicon atom or germanium atom；π-Ar₁For molecule fragment, its with the spiral shell of core-[4,4]-ninth of the ten Heavenly Stems tetraene or 5,5-assorted-spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene unit in carbon-carbon double bond be 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 by pi-conjugated connected in the way of connect the short chain conjugate unit formed and π-Ar₂With π-Ar₁Pi-conjugated being connected is formed by carbon-carbon single bond；EG is end position aromatic imide unit。

Preferably, described fragrant acid imide unit is selected from the unit (referring to 3a-Fig. 3 b) being structured with formula (IIa) or (IIb) structure, and it is connected on adjacent π-Ar via carbon atom optional on aromatic rings in the way of covalent bond₁Or π-Ar₂On unit, wherein, π-Ar₃Selected from phenyl ring, thiphene ring or the polycyclic aromatic unit that formed by 2-10 aromatic rings parallel connection, R₁It is selected from as the alkyl of straight or branched that carbon atom quantity is 1-20, assorted alkyl, substituted or unsubstituted aryl or heteroaryl。

It is highly preferred that π-Ar in formula (IIa) and (IIb)₃Selected from the construction unit having as described in formula (IIIa), (IIIb), (IIIc), (IIId) or (IIIe)。

Wherein, a is 0,1 or 2。

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

And in each structural formula of this specification, symbolImplication be link site with adjacent group unit。

In the organic semiconducting materials having described in general structure (Ia) or (Ib) provided by the present invention, described X₁Selected from carbon atom, silicon atom or germanium atom。The core texture respectively spiral shell-[4 of corresponding organic pi-conjugated compound provided by the present invention, 4]-tetraene in ninth of the ten Heavenly Stems (formula a1), 5,5-sila-spiral shell-tetraene in [4,4]-ninth of the ten Heavenly Stems (formula a2) or 5,5-germa-spiral shell-tetraene in [4,4]-ninth of the ten Heavenly Stems (formula a3)。

Preferably, in the organic compound as described in formula (Ia) or (Ib) provided by the present invention, center spiro-atom X₁For carbon atom or silicon atom。As the compound of center spiro-atom, there is better chemical stability using carbon atom or silicon atom, thus giving material less preparation cost, and more excellent device application performance。

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

Wherein, R₂It is selected from as the alkyl of straight or branched that carbon atom quantity is 1-20, assorted alkyl；R₃Selected from the alkyl of the straight or branched that carbon atom quantity is 1-20, assorted alkyl, substituted or unsubstituted aryl or heteroaryl。For clearer description π-Ar₁The relation of molecule fragment and core spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene or 5,5-assorted-spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene unit, above-mentioned graphic middle broken line representation goes out core spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene or 5,5-assorted-spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene unit。

It is pointed out that as π-Ar₁When molecule fragment has dissymmetrical structure, π-Ar₁Molecule fragment and core spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene or 5,5-assorted-carbon-carbon double bond of spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene has on-link mode (OLM) two kinds different。Currently preferred π-Ar₁It is so that formed five yuan or hexa-atomic aromatic rings or aromatic heterocycle or aromatic condensed ring link, by C-C double bond, the on-link mode (OLM) forming pi-conjugated extension with the on-link mode (OLM) of double bond。With π-Ar₁It is example that molecule fragment and carbon-carbon double bond form thiphene ring, and the preferred version of the present invention is to form the structure as shown in formula (c1), and can not form pi-conjugated extension between two thiophene units of the same side in c3 formula。

Replacing the principle of quinoid structure according to forming the pi-conjugated list double bond that is connected to form, this area staff can quickly set up asymmetric π-Ar provided by the present invention₁Molecule fragment and core spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene or 5,5-assorted-on-link mode (OLM) of spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene unit。

Preferably, π-Ar₁Molecule fragment and spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene or 5,5-assorted-spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene unit in a double bond form a double bond and form the chemical constitution having as described by 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；R₂It is selected from as the alkyl of straight or branched that carbon atom quantity is 1-20, assorted alkyl；R₃Selected from the alkyl of the straight or branched that carbon atom quantity is 1-20, assorted alkyl, substituted or unsubstituted aryl or heteroaryl；B is 0 or 1。For clearer description π-Ar₁The relation of molecule fragment and core spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene or 5,5-assorted-spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene unit, above-mentioned graphic middle broken line representation goes out core spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene or 5,5-assorted-spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene unit。

According to above-mentioned π-Ar₁Unit to meet the principle of the on-link mode (OLM) forming pi-conjugated extension so that two aromatic rings being connected or aromatic condensed ring with the on-link mode (OLM) of double bond, it is preferred that forms the π-Ar with the chemical constitution described by formula (Va) or formula (Vb)₁In unit, X₂Atom with away from the 5-position carbon atom in spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene or 5,5-assorted-spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene unit in the heteroatomic carbon atom in 5-position be connected。

The scheme being more highly preferred to is above-mentioned X₂For sulphur atom or-CH=CH-。

Specifically, π-Ar₁Fragment and core cell form following structure example:

(1)π-Ar₁Molecule fragment forms 5-membered aromatic heterocycle unit with carbon-carbon double bond

Wherein, X₁For carbon atom, silicon atom or germanium atom, R₁For the alkyl of straight or branched that carbon atom quantity is 1-20, assorted alkyl, substituted or unsubstituted aryl or heteroaryl。

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

(3) with X₂It is example for 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 the alkyl of straight or branched that carbon atom quantity is 1-20, assorted alkyl；R₃For the alkyl of straight or branched that carbon atom quantity is 1-20, assorted alkyl, substituted or unsubstituted aryl or heteroaryl。

In order to ensure the compounds of this invention, there is enough dissolubilities, in some embodiments, it is also possible in aromatic heterocycle or aromatic condensed ring, introduce solubilizing group。Well-known solubilizing group scheme may be incorporated in embodiment of the present invention in principle。Such as introduce the alkyl of long-chain, assorted alkyl or the assorted base of alkane。

Above-mentioned only list part-structure example, this area research worker according to general structure (Ia), (Ib), (Va) and (Vb), can carry out more crossing the extension of structure in conjunction with widely known compounds composing law。

In organic pi-conjugated compound as described in formula (Ib) provided by the present invention, π-Ar₂For being connected by carbon-carbon single bond by 1-20 aromatic rings or aromatic heterocycle or aromatic condensed ring unit, form pi-conjugated being connected。Described aromatic rings or aromatic heterocycle or aromatic condensed ring unit include: substituted or unsubstituted phenyl ring, replacement or for replace thiphene ring, replacement or for replace pyrrole ring, substituted or unsubstituted furan nucleus, replacement or for replace selenophen ring。

In one of them preferred version, π-Ar₂Connected benzene unit by 1-4 independent substituted or unsubstituted benzene ring units by what Isosorbide-5-Nitrae-position connection was formed, the structure including having such as formula (VIa) and (VIb) more:

Wherein, R₄Selected from the alkyl of the straight or branched that carbon atom quantity is 1-20, the assorted base of alkane, R₅Selected from the alkyl of the straight or branched that carbon atom quantity is 1-20, assorted alkyl, substituted or unsubstituted aryl or heteroaryl, c is the integer of 1-4, and d is 1 or 2。

In another preferred version, π-Ar₂The oligo-thiophenes chain with the oligo-thiophenes chain with symmetrical configuration as shown in formula (VIIa) or the compound with regular structure as shown in formula (VIIb) is formed by the connection of 2,5-position by 1-6 independent substituted or unsubstituted thiophene unit。

Wherein, r, s are independently selected from 0,1 or 2, and r and s can not be 0, the q integer being selected from 1-6 simultaneously。Wherein, R₆Selected from the alkyl that hydrogen, carbon atom quantity are 1-20 or the assorted base of alkane or two R₆Between formed 5-8 unit substituted or unsubstituted circulus, R₇、R₈In all cases independently selected from the alkyl that hydrogen, carbon atom quantity are 1-20 or the assorted base of alkane or R₇With R₈Between formed 5-8 unit substituted or unsubstituted circulus。

The molecular structure of organic pi-conjugated compound provided by the present invention is single to determine, thus has unimodal molecular weight distribution character。This make the organic compound of this law have compared with the conjugatd polymers that molecular weight distribution is wider structure clearly, material be prone to the advantage such as purification and better repeatable performance。

Owing to organic pi-conjugated compound provided by the present invention has space nonplanar structure, and, molecule can also contain the alkyl of hydrotropy or assorted groups, so, organic pi-conjugated compound provided by the present invention has good solubility property。

Can being prepared by metal catalytic method of condensing of the compound with formula (Ia) or (Ib) provided by the present invention。

Specifically, described synthetic method is characterised by providing containing core spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene structure or 5,5-is assorted-first compound (VIII) of spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene unit with there is the aromatic imide unit (IXa) of reaction active groups or comprise π-Ar₂Second compound (IXb) of conjugate unit aromatic group, and at least one metallic catalyst and at least one solvent carry out condensation, it is thus achieved that described organic pi-conjugated compound。

Described first compound has structure (consulting Fig. 4) shown in formula (VIII), described second compound has the structure (consulting Fig. 5 a-Fig. 5 b) of formula (IXa) or (IXb) wherein, and compound (VIII) and compound (IXa) carry out metal catalytic condensation and obtain having organic pi-conjugated compound (consulting Fig. 2 a) as described in formula (Ia)。

And compound (VIII) and compound (IXb) carry out metal catalytic condensation and obtain having organic pi-conjugated compound (consulting Fig. 2 b) as described in formula (Ib)。

Wherein, X₁, π-Ar₁, π-Ar₂And implication is modified in replacement representated by EG as it was noted above, Y₁Selected from halogen atom, including: chlorine, bromine or iodine；Y₂Selected from Sn (R₉)₃、B(OR₁₀)₂Or comprise the substituted or unsubstituted boron ester of 5-7 unit ring-type of-O-B-O-, R₉Selected from containing the straight or branched alkyl that carbon number is 1-4, R₁₀Selected from hydrogen atom, containing the straight or branched alkyl that carbon number is 1-4。

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

When utilizing above-mentioned Stille method of condensing to prepare compound,

--the first compound of reaction of halo modification and the tin reagent condensation reaction of the second compound of reaction, i.e. Y in above-mentioned formula (VIII)₁For halogen, including: chlorine, bromine or iodine, in formula (IX), Y₂For Sn (R₉)₃, R₉Selected from containing the straight or branched alkyl that carbon number is 1-4。

When utilizing above-mentioned Suzuki method of condensing to prepare compound,

--the first compound of reaction and boric acid or the borate of the second compound of reaction that halo is modified carry out condensation reaction, i.e. Y in above-mentioned formula (VIII)₁For halogen, including: chlorine, bromine or iodine, in formula (IX), Y₂For B (OR₁₀)₂Or comprise the substituted or unsubstituted boron ester of 5-7 unit ring-type of-O-B-O-, R₁₀Selected from hydrogen atom, containing the straight or branched alkyl that carbon number is 1-4。

Existing document has been provided for π-Ar in formula (VIII)₁Synthetic method for thiphene ring and phenyl ring。Such as:

Document reports the synthetic method (PeiJ. that structural formula is (e4), NiJ., ZhouX.H., CaoX.Y., andLaiY.H., Head-to-TailRegioregularOligothiophene-Functionalized9,9'-SpirobifluoreneDerivatives.1.Synthesis, J.Org.Chem.2002,67,4924-4936)

Document (PozziG., OrlandiS., CavazziniM., MinudriD., MacorL., OteroL., andFungoF., SynthesisandPhotovoltaicApplicationsofa4,4 '-Spirobi [cyclopenta-[2,1-b；3,4-b '] dithiophene]-BridgedDonor/AcceptorDye, Org.Lett., 2013,15,4642-4645) in report 2, the synthetic method of 2 ', 6,6 '-four bromo-spiral shell [4,4 '] dicyclo penta 2 thiophene,

Document (OhshitaJ.J., LeeK.H., HamamotoD., KunugiY., IkadaiJ.N., KwakY.W., andKuA., SynthesisofNovelSpiro-condensedDithienosilolesandtheAppl icationtoOrganicFET, ChemistryLetters, 2004,33,892-893) synthetic method of the compound that structural formula is (e10) is reported in。

Reaction reagent and condition: i) lithium diisopropylamine ,-78 DEG C；Si (CH₃)₃Cl ,-78 DEG C of-rt；Ii) lithium diisopropylamine ,-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 formula (VIII) involved in the present invention is referred to above three document and carries out synthetically prepared。

Organotin or the organoboron reagent with general structure (IXa) can be prepared by metal catalyzed process by corresponding halides precursor, and this preparation method is referred to document。

Such as:

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

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

For synthesis, there is the synthetic method of the second compound (IXb) of general structure (Ib) halo virtue acid imide unit to be utilized and there is double; two stannum or double; two borane reagent 1:1 in molar ratio carries out condensation, the molecule as described in (IXb) of the general structure with reactivity can be obtained。This synthetic method may refer to embodiment 5。Such as:

In synthetic method provided by the present invention, synthetic reaction process carries out under 20-180 DEG C of condition, it is preferable that carry out under 20-120 DEG C of condition, it is most preferred that carry out under 25-70 DEG C of condition。

Described metallic catalyst refers to Metal Palladium or the nickel complex of solubility, it is preferred that catalyst is Pd coordination compound, including: Pd (PPh₃)₄, Pd (OAc)₂, Pd (PPh₃)₂Cl₂, Pd₂dba₃, Pd₂dba₃·CHCl₃, Pd (dppf) Cl₂, preferred catalyst is Pd (PPh₃)₄, Pd₂dba₃·CHCl₃, Pd (dppf) Cl₂。When selecting the Pd catalyst Pd without part₂dba₃Or Pd₂dba₃·CHCl₃Time, catalyst system and catalyzing also needs to add phosphorus part, to improve reaction efficiency, described phosphorus part includes: PPh₃Or HP (tBu)₃BF₄, the molar ratio of phosphorus part and catalyst Pd atom is 2:1。The mol ratio of catalytic reaction catalyst carrying capacity unit point is 0.05%-10%, it is preferable that 0.5%-5%。

When selecting Suzuki catalyzing and condensing preparation method, reaction system needs add inorganic metal aqueous slkali。Described metal base includes hydroxide, for instance: NaOH, KOH, LiOH, Ba (OH)₂, alkoxide, for instance: NaOEt, KOEt, LiOEt, KOMe, NaOMe, carbonate, as: Na₂CO₃, NaHCO₃, K₂CO₃, KHCO₃, phosphate, for instance: K₃PO₄, K₂HPO₄, or carboxylate, as: KOAc, NaOAc。Above-mentioned metal base is generally prepared as the aqueous solution of 1M, joins in reaction system with reaction dissolvent by certain volume ratio, and described ratio is 1:2-1:5, it is preferable that ratio is 1:4。

Described solvent includes alkane, for instance: pentane, hexane, heptane, hexamethylene, aromatic solvent, for instance: toluene, dimethylbenzene, or ether solvent, for instance: glycol dimethyl ether, oxolane, Isosorbide-5-Nitrae-dioxane, or polar solvent, for instance: DMF, DMSO。Preferred solvent is oxolane or DMF。

The post processing of reaction can adopt the mode of routine to process, including: dilution, precipitation, filtration, extraction, drip washing, recrystallization, column chromatography or/and distillation etc.。One typical post processing scheme is as follows: after reaction terminates, certain organic solvent is added in reactant liquor, extract and separate organic facies, wash organic facies with water three times, merge organic facies, by the dry organic facies of anhydrous sodium sulfate, filter, rotary evaporation removes solvent, with eluant drip washing silica gel chromatographic column separation product。Described organic solvent is typically by the solvent of solubilized the compounds of this invention, for instance: chloroform, dichloromethane, toluene。Described eluant is the mixed solvent of chloroform and normal hexane, and mixed proportion is adjusted according to scheme well-known in the art。

Present invention provides by the 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, at least containing a kind of by above-mentioned organic pi-conjugated compound provided by the present invention with a kind of solvent in described organic pi-conjugated compound composition, described compositions is liquid。Described organic solvent includes: alkyl halide hydro carbons, as: chloroform, dichloromethane, 1,2-dichloroethanes, vinyl trichloride, sym.-tetrachloroethane；Or aromatics, as: toluene, chlorobenzene, o-dichlorohenzene, dimethylbenzene, o-Dimethylbenzene, meta-xylene, xylol, trimethylbenzene, a trimethylbenzene。In described compositions, the weight percent concentration of organic pi-conjugated compound is 0.1%-20%, it is preferable that concentration is 0.5%-10%, it is most preferred that concentration is 1%-5%。

In some embodiments of compositions provided by the present invention, described compositions also includes conjugated polymer or conjugation micromolecular compound: poly-(3-hexyl thiophene), PTB7 (poly-[[4, double, two [(2-ethylhexyl) oxygen base] benzo [1 of 8-, 2-b:4, 5-b'] double, two thiophene-2, 6-diyl] [the fluoro-2-of 3-[(2-ethylhexyl) carbonyl] thieno [3, 4-b] thiophene two base]]), PCPDTBT (poly-[2, 1, 3-diazosulfide-4, 7-bis-base [4, double, two (2-the ethylhexyl)-4H-cyclopentano [2 of 4-, 1-b:3, 4-b'] two thiophene-2, 6-bis-base]]]), OT-DCV (oligo-thiophenes that cyano group is modified) etc.。The weight ratio of organic pi-conjugated compound provided by the invention and conjugated polymer or conjugation organic molecule is 1:6-6:1, it is preferred that ratio is 1:4-2:1。In such case study on implementation, organic pi-conjugated compound provided by the present invention is as a kind of electron acceptor, and described conjugated polymer or conjugation organic molecule are a kind of electron donor materials。

In some embodiments of compositions provided by the present invention, described compositions also includes polynary polycyclic aromatic compounds as additive, for instance: 1-methyl naphthalene, 2-methyl naphthalene, 1,2-dimethylnaphthalene, 9,10-dimethylanthracenes etc.。

Another object of the present invention is to provide the purposes of organic pi-conjugated compound provided by the present invention, and one of them typical use scheme is the organic semiconductor thin-film for preparing organic electronic device。Realizing the purposes scheme of the present invention, organic pi-conjugated compound provided by the present invention is deposited over containing on conductive layer or the silicon chip of electronic work ergosphere, thin polymer film or glass。Well-known thin film deposition scheme may be incorporated for the organic semiconductor thin-film that preparation is described in principle, the method of coating or printing is such as utilized to carry out thin film deposition, described coating process includes: rotary coating, slot coated, spraying coating, described printing process includes: intaglio printing, silk screen printing, flexographic printing and various ink jet printing, it is preferred that thin film deposition scheme is rotary coating and ink jet printing。

As a preferred purposes scheme of the present invention, organic semiconductor thin-film provided by the invention is used for preparing organic photoelectric switching device, particularly organic thin film solar cell device。For this application scheme, organic semiconductor thin-film generally also additionally comprises and has to the conjugated polymer derivant of Electronic Performance, and organic pi-conjugated compound provided by the present invention is the organic receptor semi-conducting material as electron acceptor。

In the purposes scheme of organic semiconductor thin-film provided by the present invention, described organic semiconductor thin-film can also have the process technique that some are follow-up, including: chicken fire processes, solvent chicken fire processes (SolventAnnealing) or the lasser cutting for patterning。

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

Embodiment: following example include the organic solar batteries device of the illustration of the synthesis of organic pi-conjugated compound provided by the present invention, the collocation method of the compositions containing the organic pi-conjugated compound provided to some extent, the semiconductive thin film containing the organic pi-conjugated compound provided to some extent and the semiconductive thin film containing the organic pi-conjugated compound provided to some extent。

Material synthesis method:

Glass apparatus used by synthesis is all through strict cleaning-drying。Unless stated otherwise, organic solvent used in the invention process case is general chemistry pure reagent。Tetracarboxylic acid dianhydride (compound 1), dioctyl phthalate dianhydride (compound 2), 4-bromine 1, 8-naphthalic anhydride (compound 3), connection boric acid pinacol boron ester (compound 4), thiophene-2, 5-hypoboric acid two frequency any ester (compound 5), 1, 4-benzene hypoboric acid two pinacol ester (compound 6), 9, 9-dioctyl fluorene-2, 7-double, two (pinacol borate) (compound 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-dibromo thiophene (compound 10), 2-ethyl-hexylamine, n-BuLi, lithium diisopropylamine, boron trifluoride diethyl etherate, trim,ethylchlorosilane, copper chloride, Silicon chloride., N-bromo-succinimide, Pd (dppf) Cl₂、Pd₂dba₃·CHCl₃、Pd(PPh₃)₄、HP(tBu)₃BF₄、K₂CO₃、K₃PO₄、NaHCO₃、NH₄Cl、KOAc、FeCl₃, etc. raw material purchased from sigmaAldrich, lark prestige AlfaAesar, Chemical Reagent Co., Ltd., Sinopharm Group。

Wherein 2,2 ', 6,6 '-four bromo-spiral shell [4,4 '] dicyclo penta 2 thiophene (compound 11) (PozziG., OrlandiS., CavazziniM., MinudriD., MacorL., OteroL., andFungoF., SynthesisandPhotovoltaicApplicationsofa4,4 '-Spirobi [cyclopenta-[2,1-b；3,4-b '] dithiophene]-BridgedDonor/AcceptorDye, Org.Lett., 2013,15,4642-4645),

Four bromo silicon spiral shell dicyclo penta 2 thiophene (compound 12) (OhshitaJ.J., LeeK.H., HamamotoD., KunugiY., IkadaiJ.N., KwakY.W., andKuA., SynthesisofNovelSpiro-condensedDithienosilolesandtheAppl icationtoOrganicFET, ChemistryLetters, 2004, 33, 892-893), (3, 3'-dibromo-2, 2'-bithieno [3, 2-b] thiene-5, 5'diyl) bis (trimethylsilane) (compound 13) (ZhongH.L., LiZ., DeledalleF., FregosoE.C., ShahidM., FeiZ.P., NielsenC.B., GrossN.Y., RossbauerS., AnthopoulosT.D., DurrantJ.R., andHeeneyM., FusedDithienogermolodithiopheneLowBandGapPolymersforHigh-PerformanceOrganicSolarCellswithoutProcessingAdditives, J.Am.Chem.Soc.2013, 135, 2040-2043),

The bromo-N of 1-, double; two (diethylhexyl) four acyl Asia diamidogen (compound 21) (the Jim é nez á .J. of N-, SekitaM., CaballeroE., MarcosM.L., Rodr í guez-MorgadeM.S., GuldiD.M., andTorresT., AssemblingaPhthalocyanineandPerylenediimideDonor AcceptorHybridthroughaPlatinum (II) DiacetylideLinker, Chem.Eur.J.2013,19,14506-14514) synthesize according to the method for document。

The synthesis of embodiment 1 compound S1。

The synthesis of precursor compound 14: take bromo-1, the 8-naphthalimide (5.00g, 18.0mmol) of 4-, 2-ethyl-hexylamine (15.8g, 122mmol), 20mL acetic acid adds 100mL round-bottomed flask, by reactant mixture heated and stirred 30 minutes at 108 DEG C。Solid fades away, and reactant mixture gradually becomes Lycoperdon polymorphum Vitt。Reactant mixture is mixed with 400mL water, stirs 10 minutes, filter, collect precipitation, precipitation is washed with water, vacuum drying。Purify sample with silica gel column chromatography, do eluent with normal hexane/dichloromethane=2/1, obtain 6.33g pale solid, productivity 91%。1HNMR (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: take compound 14 (0.862g, 2.22mmol), connection boric acid pinacol boron ester (compound 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%) add in 50mL flask, reaction bulb is replaced as blanket of nitrogen, heated and stirred 12 hours at 70 DEG C, bolarious reactant mixture gradually becomes brown。Reactant mixture being cooled to room temperature, adds 200mL dichloromethane, filtering mixt, collect filtrate, rotary evaporation removes solvent。With silica gel chromatographic column purification of crude product, do leacheate with normal hexane/dichloromethane=10/1-1/2, obtain 0.788g pale solid, productivity 82%。1HNMR (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] dicyclos penta 2 thiophene (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)₃BF₄(13mg, 44 μm of ol, 10%) adds 25mL single port bottle under nitrogen atmosphere, is sealed by single port bottle rubber stopper。The K removing oxygen is added in above-mentioned single port bottle₃PO4 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 deepened gradually。After 12 hours, reaction system becomes yellow-red liquid bit brownish。Adding 100mL dichloromethane in reactant liquor, wash three times (each 100mL), by the dry organic facies of anhydrous sodium sulfate, filter, rotary evaporation removes solvent, with gel chromatographic columns separation product, obtains 155mg Orange red solid, productivity 91%。¹HNMR (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-TOFMS:CalcdforC₉₇H₉₂N₄O₈S₄:1569.6,Found:1569.1(m/z).

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

The synthesis of embodiment 2. compound S2.

The synthesis of precursor compound 16: take bromo-1, the 8-naphthalimide (5.00g, 18.0mmol) of 4-, 2,6-DIPA (21.6g, 122mmol), 30mL acetic acid adds 100mL round-bottomed flask, by reactant mixture heated and stirred 30 minutes at 108 DEG C。Solid fades away, and reactant mixture gradually becomes Lycoperdon polymorphum Vitt。Reactant mixture is mixed with 600mL normal hexane, stirs 20 minutes, filter, collect precipitation, precipitation 100mL normal hexane is washed, vacuum drying。Purify sample with silica gel column chromatography, do eluent with normal hexane/dichloromethane=1/1, obtain 6.14g pale solid, productivity 78%。¹HNMR (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: take compound 16 (0.938g, 2.14mmol), connection boric acid pinacol boron ester (compound 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%) add in 50mL flask, reaction bulb is replaced as blanket of nitrogen, heated and stirred 12 hours at 70 DEG C, bolarious reactant mixture gradually becomes brown。Reactant mixture being cooled to room temperature, adds 300mL dichloromethane, filtering mixt, collect filtrate, rotary evaporation removes solvent。With silica gel chromatographic column purification of crude product, do leacheate with normal hexane/dichloromethane=10/1-1/2, obtain 0.830g pale solid, productivity 80%。¹HNMR (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] dicyclos penta 2 thiophene (compound 11) (50.0mg, 0.0760mmol), compound 17 (162mg, 0.335mmol), Pd₂(dba)3.CHCl₃(15.0mg,14.8μmol),HP(tBu)₃BF₄(9.00mg, 31.0 μm of ol) add 25mL single port bottle under nitrogen atmosphere, are sealed by single port bottle rubber stopper。The K removing oxygen is added in above-mentioned single port bottle₃PO4 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 deepened gradually。After 12 hours, reaction system becomes yellow-red liquid bit brownish。Adding 100mL dichloromethane in reactant liquor, wash three times (each 100mL), by the dry organic facies of anhydrous sodium sulfate, filter, rotary evaporation removes solvent, with gel chromatographic columns separation product, obtains 121mg Orange red solid, productivity 90%。¹HNMR (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-TOFMS:CalcdforC₁₁₃H₉₂N₄O₈S₄:1761.6,Found:1762.2(m/z).

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

The synthesis of embodiment 3. compound S3。

Precursor compound 18 synthesizes (R.T.Cheriya, J.Joy, S.K.Rajagopal, K.NagarajanandM.Hariharan, DNA-EnforcedConformationalRestrictionofanAtropisomer) according to the method for document

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

The synthesis of precursor compound 19: take compound 18 (1.60g, 2.85mmol), connection boric acid pinacol boron ester (compound 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%) adds in 50mL flask, and reaction bulb is replaced as blanket of nitrogen, and heated and stirred 12 hours at 70 DEG C, bolarious reactant mixture gradually becomes brown。Reactant mixture being cooled to room temperature, adds 360mL dichloromethane, filtering mixt, collect filtrate, rotary evaporation removes solvent。With silica gel chromatographic column purification of crude product, do leacheate with normal hexane/dichloromethane=10/1-1/3, obtain 1.32g red solid, productivity 76%。¹HNMR (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] dicyclos penta 2 thiophene (compound 11) (75.0mg, 0.114mmol), compound 19 (333mg, 0.549mmol), Pd₂(dba)3.CHCl₃(22mg,21.2μmol),HP(tBu)₃BF₄(13mg, 44 μm of ol) add 25mL single port bottle under nitrogen atmosphere, are sealed by single port bottle rubber stopper。The K removing oxygen is added in above-mentioned single port bottle₃PO4 aqueous solution (2M, 1.00mL, 2.00mmol), removed the THF (10mL) of oxygen, stirring at normal temperature。Reaction system is initially purple yellowish-brown red liquid, then gradually becomes atropurpureus。After twenty four hours, in reactant liquor, add 150mL dichloromethane, wash three times (each 100mL), by the dry organic facies of anhydrous sodium sulfate, filtering, rotary evaporation removes solvent, with gel chromatographic columns separation product, obtain 211mg atropurpureus solid, productivity 82%。¹HNMR (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-TOFMS:CalcdforC₁₅₃H₁₀₈N₄O₈S₄:2257.7,Found:2257.4(m/z).

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

The synthesis of embodiment 4 compound S4。

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

Perylene-3,4-dicarboxmonoimide) according to document (NoldeF., PisulaW., M ü llerS., KohlC., andM ü llenK., SynthesisandSelf-OrganizationofCore-ExtendedPeryleneTetr acarboxdiimideswithBranchedAlkylSubstituents, Chem.Mater.2006,18,3715-3725) method synthesis。

The synthesis of compound S4: take four bromo spiral shell [4,4] dicyclos penta 2 thiophene (compound 11) (65.0mg, 0.099mmol), compound 20 (286mg, 0.436mmol), Pd₂(dba)3.CHCl₃(18.0mg,17.0μmol),HP(tBu)₃BF₄(12.0mg, 42.3 μm of ol) add 25mL single port bottle under nitrogen atmosphere, are sealed by single port bottle rubber stopper。The K removing oxygen is added in above-mentioned single port bottle₃PO4 aqueous solution (2M, 0.790mL, 1.58mmol), removed the THF (16mL) of oxygen, stirring at normal temperature。Reaction system is initially purple yellowish-brown red liquid, then gradually becomes atropurpureus。After twenty four hours, in reactant liquor, add 100mL dichloromethane, wash three times (each 100mL), by the dry organic facies of anhydrous sodium sulfate, filtering, rotary evaporation removes solvent, with gel chromatographic columns separation product, obtain 173mg atropurpureus solid, productivity 71%。¹HNMR (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-TOFMS:CalcdforC₁₆₅H₁₆₄N₄O₈S₄:2458.2,Found:2458.8(m/z).

The synthesis of embodiment 5 compound S5。

The synthesis of precursor compound 22: take compound 21 (100mg, 0.144mmol), compound 5 (96.9mg, 0.288mmol), Pd (dppf) Cl₂(10.0mg, 0.0140mmol) adds 50mL single port bottle under nitrogen atmosphere, is sealed by single port bottle rubber stopper。In above-mentioned single port bottle, add the NaOAc aqueous solution (2M, 0.5mL, 1.00mmol) removing oxygen, remove the THF (15mL) of oxygen, stirring at normal temperature。Reaction system gradually becomes atropurpureus。After one hour, 150mL dichloromethane is added in reactant liquor, wash three times (each 100mL), by the dry organic facies of anhydrous sodium sulfate, filtering, rotary evaporation removes solvent, separate with neutral aluminum oxide column chromatography, with dichloromethane for eluent, obtain 77mg atropurpureus solid, productivity 65%。¹HNMR (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] dicyclos penta 2 thiophene (compound 11) (53.0mg, 0.081mmol), compound 22 (319mg, 0.388mmol), Pd₂(dba)3.CHCl₃(17.0mg,16.4μmol),HP(tBu)₃BF₄(11.0mg, 37.0 μm of ol) add 25mL single port bottle under nitrogen atmosphere, are sealed by single port bottle rubber stopper。The K removing oxygen is added in above-mentioned single port bottle₃PO4 aqueous solution (2M, 1.00mL, 2.00mmol), removed the THF (10mL) of oxygen, stirring at normal temperature。Reaction system is initially purple yellowish-brown red liquid, then gradually becomes atropurpureus。After twenty four hours, in reactant liquor, add 130mL dichloromethane, wash three times (each 100mL), by the dry organic facies of anhydrous sodium sulfate, filtering, rotary evaporation removes solvent, with gel chromatographic columns separation product, obtain 192mg atropurpureus solid, productivity 75%。¹HNMR (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-TOFMS:CalcdforC₁₉₃H₁₇₆N₈O₁₆S₈:3119.1,Found:3118.6(m/z).

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

The synthesis of embodiment 6 compound s 6。

The synthesis of precursor compound 23: take compound 21 (100mg, 0.144mmol), compound 6 (95.0mg, 0.288mmol), Pd (dppf) Cl₂(10.0mg, 0.0140mmol) adds 50mL single port bottle under nitrogen atmosphere, is sealed by single port bottle rubber stopper。In above-mentioned single port bottle, add the NaOAc aqueous solution (2M, 0.5mL, 1.00mmol) removing oxygen, remove the THF (15mL) of oxygen, stirring at normal temperature。Reaction system gradually becomes aubergine。After one hour, 100mL dichloromethane is added in reactant liquor, wash three times (each 100mL), by the dry organic facies of anhydrous sodium sulfate, filtering, rotary evaporation removes solvent, separate with neutral aluminum oxide column chromatography, with dichloromethane for eluent, obtain 72mg aubergine solid chemical compound X, productivity 62%。¹HNMR (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] dicyclos penta 2 thiophene (compound 11) (64.0mg, 0.098mmol), compound 23 (382mg, 0.468mmol), Pd₂(dba)3.CHCl₃(20mg,19.0μmol),HP(tBu)₃BF₄(13mg, 44 μm of ol) add 25mL single port bottle under nitrogen atmosphere, are sealed by single port bottle rubber stopper。The K removing oxygen is added in above-mentioned single port bottle₃PO4 aqueous solution (2M, 1.00mL, 2.00mmol), removed the THF (10mL) of oxygen, stirring at normal temperature。Reaction system is initially purple yellowish-brown red liquid, then gradually becomes atropurpureus。After twenty four hours, in reactant liquor, add 130mL dichloromethane, wash three times (each 100mL), by the dry organic facies of anhydrous sodium sulfate, filtering, rotary evaporation removes solvent, with gel chromatographic columns separation product, obtain 215mg atropurpureus solid, productivity 71%。¹HNMR (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-TOFMS:CalcdforC₂₀₁H₁₈₄N₈O₁₆S₄:3095.3,Found:3095.5(m/z).

The synthesis of embodiment 7 compound S7。

The synthesis of precursor compound 24: take compound 21 (100mg, 0.144mmol), compound 7 (95.0mg, 0.288mmol), Pd (dppf) Cl₂(10.0mg, 0.0140mmol) adds 50mL single port bottle under nitrogen atmosphere, is sealed by single port bottle rubber stopper。In above-mentioned single port bottle, add the NaOAc aqueous solution (2M, 0.5mL, 1.00mmol) removing oxygen, remove the THF (15mL) of oxygen, stirring at normal temperature。Reaction system gradually becomes aubergine。After one hour, 100mL dichloromethane is added in reactant liquor, wash three times (each 100mL), by the dry organic facies of anhydrous sodium sulfate, filtering, rotary evaporation removes solvent, separate with neutral aluminum oxide column chromatography, with dichloromethane for eluent, obtain 72mg aubergine solid chemical compound X, productivity 62%。¹HNMR (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-TOFMS:CalcdforC₇₅H₉₃BN₂O₆:1128.7,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] dicyclos penta 2 thiophene (compound 11) (64.0mg, 0.098mmol), compound 24 (382mg, 0.468mmol), Pd₂(dba)3.CHCl₃(20mg,19.0μmol),HP(tBu)₃BF₄(13mg, 44 μm of ol) add 25mL single port bottle under nitrogen atmosphere, are sealed by single port bottle rubber stopper。The K removing oxygen is added in above-mentioned single port bottle₃PO4 aqueous solution (2M, 1.00mL, 2.00mmol), removed the THF (10mL) of oxygen, stirring at normal temperature。Reaction system is initially purple yellowish-brown red liquid, then gradually becomes atropurpureus。After twenty four hours, in reactant liquor, add 130mL dichloromethane, wash three times (each 100mL), by the dry organic facies of anhydrous sodium sulfate, filtering, rotary evaporation removes solvent, with gel chromatographic columns separation product, obtain 215mg atropurpureus solid, productivity 71%。¹HNMR (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-TOFMS:CalcdforC₂₉₃H₃₂₈N₈O₁₆S₄:4345.4,Found:4345.6(m/z).

The synthesis of embodiment 8 compound S8。

The synthesis of precursor compound 25: take compound 13 (2.10g, 3.62mmol) and add bis-mouthfuls of bottles of 100mL, reaction bulb is replaced as blanket of nitrogen。In reaction bulb, add 50mL anhydrous tetrahydro furan, reaction system is cooled to-78 DEG C。Dripping n-BuLi (7.24mmol, 3.02mL, 2.4M, hexane solution) with vigorous stirring in reaction system, reactant mixture becomes bright yellow solution。After half an hour, reactant mixture is warming up to 0 DEG C, is stirred for half an hour。Silicon chloride. (308mg, 1.81mmol) is dripped with vigorous stirring in reactant mixture。Continuing stirring mixture at 0 DEG C, reactant mixture becomes brown。One hour backward reaction system adds 10mL shrend go out reaction。Reactant mixture being poured into 100mL normal hexane, washes organic facies with water three times, use water 100mL every time, by the dry organic facies of anhydrous sodium sulfate, filter, collect filtrate, rotary evaporation removes solvent。With silica gel chromatographic column separation purification of samples, do eluent with normal hexane, obtain yellow solid 1.21g, productivity 77%。¹HNMR (400MHz, CDCl₃): δ=6.51 (4H), 0.32ppm (36H) .MALDI-TOFMS:CalcdforC₃₆H₄₀S₈Si₅:867.9,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: take compound 25 (500mg, 0.575mmol) and be placed in bis-mouthfuls of bottles of 100mL, add 20mL oxolane, two mouthfuls of bottles are replaced as blanket of nitrogen, with aluminium-foil paper, reaction bulb are encased, lucifuge。NBS (441mg, 2.42mmol) is dissolved in 15mL oxolane, is added dropwise to reaction bulb with vigorous stirring。Reactant mixture at room temperature stirs 24 hours。Reactant mixture is concentrated to 2mL, is added dropwise to 15mL cold methanol。Filter, obtain yellow solid 443mg, productivity 86%。¹HNMR (400MHz, CDCl₃): δ=6.49ppm (4H)。

Reaction reagent and condition: the i) THF containing NBS

The synthesis of compound S8: take 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) add 25mL single port bottle under nitrogen atmosphere, are sealed by single port bottle rubber stopper。The K removing oxygen is added in above-mentioned single port bottle₃PO4 aqueous solution (2M, 0.5mL, 1.00mmol), removed the THF (30mL) of oxygen, stirring at normal temperature。Reaction system is initially purple yellowish-brown red liquid, then gradually becomes atropurpureus。After twenty four hours, in reactant liquor, add 150mL dichloromethane, wash three times (each 100mL), by the dry organic facies of anhydrous sodium sulfate, filtering, rotary evaporation removes solvent, with gel chromatographic columns separation product, obtain 192mg atropurpureus solid, productivity 75%。¹HNMR (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-TOFMS:CalcdforC₂₀₁H₁₇₆N₈O₁₆S₁₂:3342.9,Found:3342.5(m/z).

The synthesis of embodiment 9 compound S9: take compound 8 (2,2', 7, bromo-9,9'-spiral shell two fluorenes of 7'-tetra-) (137mg, 0.217mmol), compound 15 (416mg, 0.956mmol), Pd₂(dba)3.CHCl₃(43mg, 42.2 μm of ol, 5.00%), HP (tBu)₃BF₄(26mg, 87 μm of ol, 10%) adds 25mL single port bottle under nitrogen atmosphere, is sealed by single port bottle rubber stopper。The K removing oxygen is added in above-mentioned single port bottle₃PO4 aqueous solution (2M, 1.74mL, 3.48mmol), removed the THF (40mL) of oxygen, and heating is to 70 DEG C, and reaction system is initially purple brown red liquid, and puce fades away, and presents lark。After 24 hours, reactant mixture is cooled to room temperature, 200mL dichloromethane is added in reactant liquor, wash three times (each 100mL), by the dry organic facies of anhydrous sodium sulfate, filter, rotary evaporation removes solvent, with gel chromatographic columns separation product, obtain 242mg pistac solid, productivity 72%。¹HNMR (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-TOFMS:CalcdforC₁₀₅H₁₀₀N₄O₈:1545.7,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 is stirred 2 hours with 0.5mL o-dichlorohenzene at 55 DEG C, prepares the o-dichlorobenzene solution of compound S1。

Embodiment 11: utilize the o-dichlorobenzene solution of compound S1 prepared by embodiment 10 to be obtained the thin film of compound S2 by spin coating method spin coating on ito glass。Consult Fig. 6 and show the abosrption spectrogram of this compound。This figure shows that the maximum absorption wavelength of compound film is 570nm, and its initial absorption wavelength is 380nm, and corresponding material spectrum bandwidth is 2.25eV, belongs to quasiconductor bandgap range。

Embodiment 12: take compound S1, compound S4 and each 6mg of compound S7 is blended with 6mg poly-(3-hexyl thiophene) (P3HT) respectively, respectively it is dissolved in 0.5mL chlorobenzene, stir 12 hours at 55 DEG C,, prepare the chlorobenzene solution of P3HT/ compound S1, P3HT/ compound S4, P3HT/ compound S7。

Embodiment 13: following for utilizing what the solution of preparation in embodiment 12 prepared organic solar batteries to be embodied as details。

Specific embodiments list of references (FischerM.K.R., MaC.Q., JanssenR.A.J., DebaerdemaekerT.and prepared by batteryP.,Core-functionalizeddendriticoligothiophenes—noveldonor–acceptorsystems,J.Mater.Chem.,2009,19,4784–4795)。

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

The general preparation process of organic solar batteries device in the present invention。By the clean glass scribbling ITO, it is placed in ultra violet lamp device, the one side irradiation under ultraviolet ray 30 minutes of ITO will be scribbled。

Drawing PEDOT:PSS4083 with syringe, install 0.45 μm of aqueous phase filter on the injector, fill, after being filtered by PEDOT:PSS4083, the one side scribbling ITO, with 3000 rpms of rotating speed spin coating PEDOT:PSS, spin-coating time is 60s。

The ito glass scribbling PEDOT:PSS is placed on full nitrogen, water and oxygen content less than, in 1ppm glove box, annealing 10 minutes at 124 DEG C。

The chlorobenzene solution of the P3HT/ compound S1 of preparation in embodiment 12 is spin-coated on PEDOT:PSS layer, rotating speed 1000 rpms, after being painted with, place three minutes in the glove box of full nitrogen, anneal 5 minutes at 124 DEG C, make photoactive layer。Afterwards, the ito glass being coated with PEDOT:PSS layer and photoactive layer is put into evaporation chamber, is first deposited with 1nmLiF, then is deposited with 100nmAl, namely complete device and prepare。

According to the general preparation process of organic solar batteries device in the present invention, namely prepare as the organic solar batteries of photoactive layer as the thin film of electron donor and the blended preparation of electron donor P3HT with compound S1, S4, S7。

Embodiment 14: organic solar batteries prepared in embodiment 13 is simulated at sunlight the photoelectric transformation efficiency testing device under the irradiation of lamp, 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

Should be appreciated that described above and in the embodiment shown on drawing, can not resolve is limited determines the design philosophy of the present invention。Holding identical skill in the technical field of the present invention can the technical thought of the present invention be changed with various form improvement, such improvement and change are interpreted as belonging in protection scope of the present invention。

Claims

1. an organic pi-conjugated compound, it is characterised in that comprise:

2. organic pi-conjugated compound according to claim 1, it is characterised in that also comprise:

3. organic pi-conjugated compound according to claim 1 and 2, it is characterized in that described end position aromatic imide unit is selected from the construction unit having as described in general structure (IIa) or (IIb), and described end position aromatic imide unit via carbon atom optional on aromatic rings to be connected in the way of covalent bond on adjacent molecule fragment unit or short chain conjugate unit

Wherein, a is 0,1 or 2；

4. organic pi-conjugated compound according to claim 1, it is characterised in that described 5,5-assorted-spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene unit in hetero atom at least selected from silicon atom。

5. organic pi-conjugated compound according to claim 1, it is characterized in that described molecule fragment unit and spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene or 5,5-is assorted-spiral shell-[4,4]-ninth of the ten Heavenly Stems tetraene unit in a double bond form the chemical constitution having as described in formula (Va) or (Vb):

B is 0 or 1。

6. organic pi-conjugated compound according to claim 1, it is characterised in that:

Described short chain conjugate unit selects free 1-4 independent substituted or unsubstituted benzene ring units to connect benzene unit by what Isosorbide-5-Nitrae-position connection was formed more, and has the structure as shown in formula (VIa) or (VIb):

7. the organic pi-conjugated compound according to any one of claim 1-6, it is characterised in that described compound has single molecular weight distribution。

8. the preparation method of organic pi-conjugated compound according to any one of claim 1-7, it is characterized in that including: at least one solvent, the first compound, the second compound and at least one metallic catalyst are carried out condensation, it is thus achieved that described organic pi-conjugated compound；

Wherein, described first compound comprises:

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

Described second compound comprises:

Wherein, Y₁Selected from halogen atom, it is preferred to bromine atoms,

9. the preparation method of organic pi-conjugated compound described in claim 8, it is characterised in that the condensation reaction adopted in the method includes metal catalytic Suzuki condensation or metal catalytic Stille condensation reaction。

10. an organic conjugate semi-conducting material, it is characterised in that comprise the organic pi-conjugated compound according to any one of claim 1-7 or organic pi-conjugated compound prepared by method according to any one of claim 8-9。

11. a compositions, it is characterised in that comprise the organic pi-conjugated compound according to any one of claim 1-7 or organic pi-conjugated compound prepared by method according to any one of claim 8-9, and described compositions is liquid。

12. the organic conjugate semi-conducting material described in organic pi-conjugated compound prepared by the organic pi-conjugated compound according to any one of claim 1-7, method according to any one of claim 8-9, claim 10 or the compositions described in claim 11 are in the application preparing in organic electronic device。

13. an organic electronic device, it is characterised in that comprise:

Organic pi-conjugated compound prepared by organic pi-conjugated compound according to any one of claim 1-7 or method according to any one of claim 8-9, in order to as electron donor；

And, conjugated polymer or oligomer, in order to as electron acceptor。

14. a semiconductive thin film, it is characterised in that comprise the organic pi-conjugated compound according to any one of claim 1-7, the organic conjugate semi-conducting material described in organic pi-conjugated compound prepared by method according to any one of claim 8-9, claim 10 or the compositions described in claim 11；

15. an electronic device, it is characterised in that comprise the semiconductive thin film described in claim 14。

16. electronic device according to claim 15, it is characterised in that described electronic device includes electrooptical device, and described electrooptical device includes solaode。