CN103172632B - The stannyl derivative of benzene-naphthalene diimide and the product of the embedding benzene of naphthalene - Google Patents

Abstract

NDI tin compound benzene compound embedding with naphthalene reacts the formation embedding benzene compound of NDI naphthalene.The embedding benzene compound of naphthalene can be compound.The embedding benzene compound of NDI naphthalene can use in organic electronic device (including field-effect transistor).

Description

The stannyl derivative of benzene-naphthalene diimide and the product of the embedding benzene of naphthalene

Technical field

The present invention relates to compositions and compound and manufacture their method, use their method, comprise these groups Compound and the ink of compound and device.It is sub-that said composition comprises at least one naphthalene two acyl containing at least one stannyl substituent group Amine (NDI) compound, described substituent group is bonded to the naphthalene part of NDI compound.

Background technology

Organic based device is the key areas of business development, and it includes, such as, advanced crystal pipe, display, light fill Put, Photovaltaic device and sensing device.The extensive multiformity of organic compound and material provides for organic based device Advantage.The many-sided chemistry that may be adapted to organic based device is the embedding benzene of naphthalene (rylene) with an example in material science Tetracarboxylic acid diimide derivant, especially, naphthalene and (NDIs and PDIs respectively) represent sense in organic electronics field Property investigation of materials almost widest classification (referring to list of references 1,2).Heat, chemistry and photochemical stability and their high electricity Sub-affinity and carrier mobility make these materials for organic field effect tube (OFETs) (referring to list of references 3-15) and attractive in organic photovoltaic cell (OPVs) (referring to list of references 12,16-20).Due also to they Redox potential and the special absorption spectrum of described stability and described corresponding group anion (referring to list of references 21-24), the receptor during they are also widely used as the transient absorption research of Photo-induced electron transfer.

Generally, the N of PDIs and NDIs, N '-substituent group only has atomic impact to light and the Electronic Performance of molecule, But they can be used to control the intermolecular accumulation in the case of dissolubility, aggregation and solid-state.On the contrary, the core of these materials The heart replaces (core substitution) generally (in some situation, can realize required air stable to institute's redox potential Electron affinity (referring to list of references 5,13,25) in OFET opereating specification) and the spectrum of these materials have more significantly Impact.Additionally, core replaces (core substitution) is used as constructing the mode of more precisely structure, such as Conjugated polymer (referring to list of references 7,11,20,26 and 27) and donor or receptor functional group product (referring to list of references 13, 14,28-32).

Functional NDIs is most effectively attained mode, by naphthalene-Isosorbide-5-Nitrae: 5,8-tetracarboxylic dianhydrides (NDA) are different with two bromos Cyanic acid (dibromoisocyanuric acid) (DBI) selective bromination effect in concentrated sulphuric acid oleum or oleum, so Imidization (referring to list of references 5,27,32) is carried out afterwards with primary amine primary amine in the acetic acid of backflow.NDA can also use Br₂(referring to list of references 5,33) it is brominated in concentrated sulphuric acid or oleum.Described bromination NDI can be subsequently used as further via The intermediate of nucleophilic displacement of fluorine functionalization, to provide the substituted derivant of amino, mercaptan or alkoxyl (referring to list of references 31,32) Or via palladium-catalysis coupling reaction with obtain cyano group (referring to list of references 5,29), phenyl (referring to list of references 28, 29), alkynyl (referring to list of references 29) and thienyl (referring to list of references 11,14,28) functionalized products.But it is possible to it is logical The scope crossing the conjugated material that palladium-catalysis process obtains is determined by suitable candidate coupling pairing.Especially, metallization Reagent (such as stannane) is difficult to obtain and constitutes part for electron-deficient-(receptor).It addition, the NDI of single bromination, it can be used for a whole set of The compound that NDI is derivative, is generally only capable of and obtains by utilizing the equivalent of bromide reagent and/or utilize transformationreation condition ?；However, it is very difficult to the most non-brominated, single bromination and dibromizated mixture, its make large-scale production become difficulty or Unrealistic.

Therefore, single-or two-metallized metallization NDI material, the weight of novel conjugation NDI derivant will be could be for Part to be constituted, wherein acceptor groups is directly conjugated to NDI core.

Summary of the invention

Embodiment disclosed in the present application includes compositions and compound and manufactures their method, uses their side Method, comprise these compositionss and the ink of compound and device.

One embodiment of the invention provides compositions, and it comprises at least one containing at least one stannyl substituent group Benzene-naphthalene diimide (NDI) compound, described substituent group is bonded to the naphthalene part of NDI compound.

Another embodiment of the present invention provides the benzene-naphthalene diimide organo-tin compound with structure (IV)；

Wherein:

(a)R¹And R¹' independently selected from C₁-C₃₀(normal), side chain or the cyclic alkyl of normal chain, aryl, heteroaryl, alkane Base-aryl or alkyl-heteroaryl group, it is optionally by one or more halogenide (halide), cyano group, alkyl or alkoxyl Replace, (b) R²、R³And R⁴Independently selected from hydrogen, halogenide or C₁-C₃₀Organic group, this organic group independently selected from cyano group, Normal chain, side chain or cyclic alkyl, perfluoroalkyl, aryl, heteroaryl, alkyl-aryl-group and alkyl-heteroaryl group, it is optional Replaced by one or more fluorine, cyano group, alkyl, alkoxyl；(c)R⁹It it is alkyl or aryl.

Another embodiment of the present invention provides a kind of method, and it comprises: by front at least one first benzene-naphthalene diimide (NDI) Body compound reacts with at least one tin reagent, forms at least one NDI comprising at least one stannyl substituent group Compound, described substituent group is bonded to the naphthalene part of NDI compound.

Another embodiment of the present invention is compositions, and it comprises at least one compound, wherein said compound comprise to Few a kind of NDI part being covalently bonded at least one naphthalene embedding benzene part.

Another embodiment of the present invention is method, and it comprises: (i) comprises at least one stannyl substituent group at least A kind of benzene-naphthalene diimide (NDI) compound, this substituent group is bonded to the naphthalene part of NDI compound, embedding with (ii) at least one naphthalene Benzene compound reacts, and forms at least one product, and wherein said product compound comprises at least one covalency keyed jointing NDI part at least one naphthalene embedding benzene part.

Ink and device also are able to be prepared by herein described compositions.

At least one advantage of at least one embodiment is can to manufacture to obtain various new compound and material, or, Existing compound and material can be manufactured more easily.Especially, at least one embodiment, can be more widely Use important Stille coupling reaction for NDI system to manufacture multiple organic compound and material.This allows art technology Personnel " adjust (tune) " parameter such as, such as, for compound or the ionization potential of material, oxidizing potential, the electricity of application-specific Sub-affinity, reduction potential, optical absorption and fluorescence allow it to preferably work with other component.

It is useful or improvement that at least one of at least one embodiment other advantages is that those can be made to have The compound of performance and material.Such as, an embodiment is capable of good electron transfer rate score.Another embodiment Useful field-effect transistor can be prepared.One embodiment can manufacture sky gas and water and heat-stable compound.Can manufacture There is the compound of dissolubility.

For some embodiments, electrochemical potentials can be significantly less than air stability threshold.

For some embodiments, it is possible to realize improving solid filler.Equally, the electrode table of molecule described in structure division Direction, face can change.

Accompanying drawing explanation

Fig. 1 shows compound 3a mass spectrum.

Fig. 2 shows¹H-NMR。

Fig. 3 shows absorption curve.

Fig. 4 shows electrochemical profiles.

Fig. 5 shows compound 3b mass spectrum.

Fig. 6 shows¹H-NMR。

Fig. 7 shows absorption curve.

Fig. 8 shows electrochemical profiles.

Fig. 9 shows compound 4a mass spectrum.

Figure 10 shows¹H-NMR。

Figure 11 shows absorption curve；

Figure 12 shows electrochemical profiles.

Figure 13 shows compound 4b mass spectrum.

Figure 14 shows described¹H-NMR。

Figure 15 shows absorption curve.

Figure 16 shows electrochemical profiles.

Detailed description of the invention

Introduction

Their entirety is hereby incorporated herein by by all documents mentioned in this application.

Polander is equal to have submitted U.S. Provisional Application 61/475 on April 15th, 2011, and 888, therefore its full text quilt It is hereby incorporated herein by, including NDI-Sn compound and the method for manufacture NDI-Sn compound.Described application also provides for The advantage of the technical scheme that current claim limits and the relevant background information of abundance demand.

The Lauren Polander PhD paper of 2011 is " based on thio phenyl oligomer (Oligothiophene) and naphthalene The Organic charge transport material of imidodicarbonic diamide: about two poles and N-shaped organic field effect tube " provide about current right want Seek the additional information of the present invention of restriction.

Substituent R in formula described herein (has subscript such as R1 or R₁) it is substituent group independently, it can be by Synthesize and some atomic and useful product stabilities as known in the art are provided.Protection well known in the art can be used Base.The substituent group being suitable for is the most reactive or non-reacted.Group R can be, such as, independently, and H, optionally substituted alkane Base, optionally substituted miscellaneous alkyl, optionally substituted aryl, optionally substituted heteroaryl optionally substituted aralkyl or optionally substituted Alkylaryl.They can be optionally to be replaced by group, this group such as halogen such as, such as, F, Cl, Br or I), false sorts halogen (pseudohalogen) (e.g., cyano group), alkyl or alkoxyl.Hetero atom can be by such as, and such as, O, N, S and Se replace.

Unless otherwise indicated, certain (" A ", " an ") and " being somebody's turn to do " " described " (" the ") represents that " at least one is (at least one years old Individual) " or " one or more (one or more) ".

" optionally substituted " group represents, for example, it may be possible to carry out substituted or unsubstituted functional group by other functional group. Such as, when group is not carry out substituted by other group, and it can be referred to as described group name, such as alkyl or aryl. When group is replaced by other functional group, more generally it may be referred to as replacing alkyl or substituted aryl.

" alkyl " represents, such as, has 1 to 30 carbon atom or 1-20 carbon atom or 1 to 15 carbon atom or 1 to 10 Individual carbon atom or 1-5 carbon atom or the straight chain of 1-3 carbon atom, side chain or cyclic alkyl.The representative example of alkyl includes, But it is not limited to, such as, methyl, ethyl, n-propyl, isopropyl, normal-butyl, the tert-butyl group, n-pentyl, ethylhexyl, dodecane Base, isopentyl etc..

" aryl " represents, such as, has group or the polycondensation of the aromatic carbocyclic of 6-14 carbon atom of monocycle (such as phenyl) Ring (such as naphthyl or anthryl), its condensed ring may or may not be aromatics, condition be described point of contact be in aromatic carbon atom On.Aryl preferably includes, but is not limited to phenyl, naphthyl etc..

" miscellaneous alkyl " represents, such as, the one or more carbon atoms in alkyl are exchanged for heteroatoms.Hetero atom can be As, such as, O, N, S and P etc..

" heteroaryl " represents, such as, the one or more carbon atoms in aryl are exchanged for heteroatoms.Hetero atom can be As, such as, O, N, S and P etc..One example of heteroaryl is carbazole (carbazole).

Part IA:NDI-Sn compositions

One embodiment of the invention provides such as compositions, and it comprises at least one benzene-naphthalene diimide (NDI) compound, It comprises at least one stannyl substituent group, and this substituent group is bonded to NDI compound naphthalene part.

" benzene-naphthalene diimide " or " naphthalenetetracarbacidic acidic diimide " (NDI) compound, derivant and material are in the art Known.See, e.g. United States Patent (USP) 2011/0269967；2011/0269966；2011/0269265；2011/0266529； 2011/0266523；2011/0183462；2011/0180784；2011/0120558；2011/0079773；2010/ 0326527；and 2008/0021220.Other example can at Hu et al., Chem.Mater., 2011,23,1204- 1215(“core-expanded naphthalene diimides”)；Wei et.al., Macromol.Chem.Phys., 2009,210,769-775 (" naphthalene bisimides " or NBI)；Jones et al., Chem.Mater., 2007,19,11,2703-2705；And Durban et al., Macromolecules, 2010,43,6348-6352；Guo Et al., Organic Letters, 2008,10,23,5333-5336 (" naphthalene bisimides ")；et Al., J.Org.Chem., 2007,72,8070-8075；Thalaker et al., J.0rg.Chem., 2006,71,8098- 8105；Oh et al., Adv.Funct.Mater., 2010,20,2148-2156；Suraru et al., Synthesis, 2009,11,1841-1845；Polander et al., Chem.Mater., 2011,23,3408-3410；Yan et al., Nature, February 5,2009,457,679-686；Chopin et al., J.Mater.Chem., 2007,4139- 4146；Bhosale et al., New J.Chem., 2009,33,2409-2413；And Chen et al., J.Am.Chem.Soc., described in 2009,131,8-9.In this application, " NDI " and " NBI " is considered as equivalent.Institute State core NDI structure and be referred to alternatively as Isosorbide-5-Nitrae: 5,8-naphthalenetetracarbacidic acidic diimides.

One in NDI structure is as follows, display core naphthylene group and two imide groups:

In the application, substituent R 1, R2, at least one of R3 and/or R4 can functionalised as stannum (or stannyl) base Group, wherein said tin atom is connected to described naphthalene core by direct covalent bonds.R1-R4 can independently be hydrogen.Two of which base can be synthesized Group is identical, independently of one another, and R₅And R₆Be bonded to acid imide, described compound.In one embodiment, described R₅And R₆ Group is identical group.R₅And R₆One example of alkyl group includes N-alkyl or branched alkyl, including, such as, hexyl. Other example includes aryl, aralkyl and alkylaryl.

NDI compound can be prepared by precursor compound, and described precursor compound includes, such as, and naphthalene acid anhydride (naphthalene anhydride)(NDA)。

Naphthalene part in NDI can be replaced on one or both of aromatic ring of carbocyclic ring, the aromatic ring bag of described carbocyclic ring Containing naphthalene part.Four replace site can be 2,3,6 and 7 positions at NDI so that can there are one, two, three or four Substituent group.

Additionally, one or two of the nitrogen of imide group in NDI can also be replaced.Replacement can promote dissolubility.

Naphthalene part in NDI can be replaced on one or two of carbocyclic ring aromatic ring, and wherein carbocyclic ring aromatic ring comprises tool There is the naphthalene part of at least one stannyl substituent group.Stannyl substituent group can be with-SnR '₃Represent.Such as, compound can There is a stannyl substituent group or can have two stannyl substituent groups.

In a specific embodiment, NDI compound comprises at least one NDI part, and is embodied as at another In scheme, NDI compound comprises at least two NDI part, or at least three NDI part.It is therefoie, for example, NDI oligomer can To use one or more stannyl parts to derive.

In a specific embodiment, the molecular weight of NDI-Sn compound is about 2,000g/mol or less, or Person about 1,000g/mol or less, or about 750g/mol or less.

In a specific embodiment, NDI compound is expressed as:

Wherein, X is H or stannyl substituent group；Wherein, each R is C independently₁-C₃₀Normal chain, side chain or ring-type Alkyl, aryl, heteroaryl, alkyl-aryl-group or alkyl-heteroaryl group, optionally with one or more halogenide, cyanogen Base, alkyl or alkoxyl replace；Wherein, each R ' part is alkyl or aryl moiety independently.Specifically real at another Executing in scheme, each R is optionally substituted C independently₁-C₃₀Moieties, and each R ' part is C independently₁-C₂₀Alkyl portion Point.

In another embodiment, described compound is expressed as:

Wherein, each R is C independently₁-C₃₀Normal chain, side chain or ring-type alkyl, aryl, heteroaryl, alkyl-aryl-group, Or alkyl-heteroaryl group, optionally replaces with one or more halogenide, cyano group, alkyl or alkoxyl；Wherein, respectively Individual R ' part is alkyl or aryl moiety independently.In another embodiment, each R is optionally substituted independently C₁-C₃₀Alkyl, and each R ' part is C independently₁-C₂₀Moieties.

In another embodiment, described compound is expressed as:

Wherein, each R is C independently₁-C₃₀Normal chain, side chain or ring-type alkyl, aryl, heteroaryl, alkyl-aryl-group, Or alkyl-heteroaryl group, optionally replaces with one or more halogenide, cyano group, alkyl or alkoxyl；Wherein, respectively Individual R ' part is alkyl or aryl moiety independently.In another embodiment, each R is optionally substituted independently C₁-C₃₀Alkyl, and each R ' part is C independently₁-C₂₀Moieties.

Additionally, as described by US provisional application 61/475,888 (submission on April 15th, 2011), applicant is unexpected Be found that the Practical Approach preparing benzene-naphthalene diimide organo-tin compound (NDI-tin compound), wherein benzene-naphthalene diimide has Machine tin compound has a following structure:

Wherein

(a)R¹And R¹' independently selected from: C₁-C₃₀Normal chain, side chain or ring-type alkyl, aryl, heteroaryl, alkyl-virtue Base or alkyl-heteroaryl group, optionally replace with one or more halogenide, cyano group, alkyl or alkoxyl；

(b)R², R³And R⁴Independently selected from hydrogen, halogenide or C₁-C₃₀Organic group, wherein C₁-C₃₀Organic group is independent Ground is selected from cyano group, normal chain, side chain and ring-type alkyl, perfluoroalkyl, aryl, heteroaryl, alkyl-aryl-group and alkyl-heteroaryl Group, optionally replaces with one or more fluorine, cyano group, alkyl and alkoxyl；

(c)R⁹It is alkyl or aromatic yl group.

So new NDI-organo-tin compound is highly useful to well-known palladium catalysed cross coupling reaction, and described reaction is used for Preparing new NDI-hAr oligomer, wherein hAr is such as, is, electron withdrawing heteroaryl group.Some are had to prepare PDI in the art low The example (referring to WO2009/144205 and WO 2009/144302) of polymers so that PDI oligomer coupling is rich in the hAr of electronics Group, it is realized with rich in electronics nucleophilic organotin hAr precursor compound by coupling electrophilic PDI bromide.But, If using electrophilic hAr group, the most such coupling reaction is the most unsuccessful.There is no the report of NDI organo-tin compound in the past Accuse (with the cognition of applicant), can there is the NDI-hAr-NDIization of electronics hAr substituent group for synthesis by " inverse " coupling method Compound.

The unexpected discovery of applicant (as the application further disclosed in) for synthesizing new NDI-organotin precursor The method of compound, it can use the synthesis of " inverse " coupling reaction to have the NDI-hAr-of electrophilic hAr heteroaryl bridge linkage group NDI oligomer, there is a class NDI oligomer (the low LUMOs lowest empty molecule rail of relatively low lowest unoccupied molecular orbital (LUMO) LUMOs Road is considered relevant to the stability improving air and water in the art).

In many specific embodiments, the R of NDI organo-tin compound¹、R¹′、R²、R³And R⁴Can be any as at US The disclosed group for NDI-hAr-NDI oligomer in provisional application 61/475,888.In some specific embodiments, R¹ And R¹' it is C independently₁-C₃₀Normal chain or branched alkyl or fluoroalkyl group.In some specific embodiments, R²、R³ And R⁴Independently selected from hydrogen, fluorine and cyano group.In many specific embodiments, R⁹It is C₁-C₁₂Alkyl.PART IB. prepares NDI- The method of tin compound

The method that preparation compound Part IA. described in is here also disclosed.Such as, another specific embodiment party Case provides a kind of method, and it comprises: at least one the first benzene-naphthalene diimide (NDI) precursor compound is anti-with at least one tin reagent Should, forming at least one NDI compound, this NDI compound comprises at least one first being bonded to NDI compound naphthalene part Stannum alkyl substituent.Precursor compound is as described below.

Tin reagent and organotin reagent are known in the art.Such as, tin reagent can be tin alkyl or aryl Tin reagent, preferably alkyl tin reagent.Tin reagent can be provided in the stannum part described in Part IA in NDI compound, and it includes Formulas I, II, III and IV.Tin reagent per molecule can comprise two tin atoms (" two stannum " compound), such as, such as, R '₃Sn- SnR′₃, wherein R ' is alkyl or aryl, preferably alkyl independently.R ' alkyl it may be that such as, C₁-C₂₀Alkyl, it includes, Such as, methyl or butyl (including normal-butyl).In an example, tin reagent is six dibutyltin dilaurates (hexabutylditin) Reagent.

In a specific embodiment, tin reagent is not halogen tin reagent.Such as, tin reagent is known, can be with table It is shown as X-SnR '₃, wherein X is halogen.But, such reagent can be excluded.

In a specific embodiments reactions steps, only a kind of NDI precursor compound reacts with at least one tin reagent.

But, the mixture of different NDI precursor compounds can stand the reaction with tin reagent, and uses mixture permissible Dramatic benefit is provided.In another specific embodiments reactions steps, the mixture of two kinds of different NDI precursor compounds with At least one tin reagent reacts, and forms at least one NDI product compound, and at least one different second NDI product compound, wherein each the first and second NDI compound comprises at least one and is bonded to the first and second NDI The stannyl substituent group of compound naphthalene part.

In a specific embodiment, such as, a NDI compound comprises a stannyl substituent group and second NDI compound comprises two stannyl substituent groups.

In a specific embodiment, reactions steps generates the first and second different NDI product compounds Mixture, described mixture stands separating step to separate the first and second NDI product compounds.

In these react, as disclosed in Part 1A, a NDI can be expressed as:

Wherein, X is H or stannyl substituent group；Wherein, each R is C independently₁-C₃₀Normal chain, side chain or ring-type Alkyl, aryl, heteroaryl, alkyl-aryl-group or alkyl-heteroaryl group, optionally with one or more halogenide, cyanogen Base, alkyl or alkoxyl replace；Wherein, each R ' part is alkyl or aryl moiety independently.Specifically real at another Executing in scheme, each R is optionally substituted C independently₁-C₃₀Moieties, and each R ' part is C independently₁-C₂₀Alkyl portion Point.

In a specific embodiment, a NDI compound is expressed as:

Wherein, each R is C independently₁-C₃₀Normal chain, side chain or ring-type alkyl, aryl, heteroaryl, alkyl-aryl-group, Or alkyl-heteroaryl group, optionally replaces with one or more halogenide, cyano group, alkyl or alkoxyl；Wherein, respectively Individual R ' part is alkyl or aryl moiety independently.In another embodiment, each R is optionally substituted independently C₁-C₃₀Alkyl, and each R ' part is C independently₁-C₂₀Moieties.

In another embodiment, a NDI compound is expressed as:

Wherein, each R is C independently₁-C₃₀Normal chain, side chain or ring-type alkyl, aryl, heteroaryl, alkyl-aryl-group, Or alkyl-heteroaryl group, optionally replaces with one or more halogenide, cyano group, alkyl or alkoxyl；Wherein, respectively Individual R ' part is alkyl or aryl moiety independently.In another embodiment, each R is optionally substituted independently C₁-C₃₀Alkyl, and each R ' part is C independently₁-C₂₀Moieties.

In another embodiment, a NDI compound is expressed as:

Wherein

(a)R¹And R¹' independently selected from: C₁-C₃₀Normal chain, side chain or ring-type alkyl, aryl, heteroaryl, alkyl-virtue Base or alkyl-heteroaryl group, optionally replace with one or more halogenide, cyano group, alkyl or alkoxyl；

(b)R², R³And R⁴Independently selected from hydrogen, halogenide or C₁-C₃₀Organic group, wherein C₁-C₃₀Organic group is independent Ground is selected from cyano group, normal chain, side chain or ring-type alkyl, perfluoroalkyl, aryl, heteroaryl, alkyl-aryl-group and alkyl-heteroaryl Base group, optionally replaces with one or more fluorine, cyano group, alkyl and alkoxyl；

(c)R⁹It is alkyl or aromatic yl group.

Additionally, below scheme A illustrates the synthetic method started from NDA precursor.

Option A

In option A, three arrows can show schematically that three reactions steps of needs are to form required target:

I one or two of () halogenated compound A naphthalene benzyl ring are to allow introducing stannum substituent group to naphthalene core, (ii) converts and changing In compound A (NDA), two anhydride components are acid imide, (iii) introduce stannum part to benzyl ring (replace the one introduced in (i) or Multiple halogen).From the beginning of single precursor compound A, the two stannum product B and C can be prepared into as a mixture Arrive, be then peeled off, as below embodiment 2 illustrates.In option A, acid imide R and stannum R group in B and C are permissible As described in Parts 1A and 1B independently of one another.Purification step can be carried out after step (iii).

In other specific embodiments, NDI-organo-tin compound can be prepared by a kind of method, its bag Include step (a) provide or obtain the monomer benzene-naphthalene diimide compound replaced by leaving group LG, there is structure (V)；

Wherein, LG is halogen, such as Br or I, (b) monomer benzene-naphthalene diimide compound with there is structure (R⁹)₃Sn-Sn (R⁹)₃Compound exist catalyst (the most soluble palladium compound, such as Stille coupling catalyst, i.e. Pd₂dba₃With P (o-tol)₃Part) in the case of react (wherein, R⁹It is alkyl or aromatic yl group), form benzene-naphthalene diimide At least some in organo-tin compound.

This is unexpected for preparing the method for a large amount of separable benzene-naphthalene diimide organo-tin compound.Not In the case of wishing to be bound by theory, it is contemplated that at such " Stille coupling " condition, benzene-naphthalene diimide organotin chemical combination Thing will be formed with reaction intermediate form, but be such that in " Stille coupling " and another mole of substituted NDI of leaving group " on the spot " coupling, produces the NDI-NDI dimer of the NDI group with direct coupling.Unexpectedly, (especially, in view of phase Close imide compound Different Results), it is contemplated that bromide substituted NDI compound " dimerization " coupling reaction not with Effectively ratio is carried out, but, as result, NDI organo-tin compound can separate with excellent yield, and is used as synthetic intermediate To prepare other materials based on NDI.The nucleophilic NDI organotin separated from unexpected reaction can easily with other (there is multiple suitable palladium well known to those skilled in the art in (less steric hindrance) bromide-substituted heteroaryl compound coupling In the case of coupling catalyst), even if the heteroaryl compound of bromination is the most electrophilic, it is possible to synthesis has electrophilic The NDI-hAr-NDI oligomer of hAr bridge linkage group.

In order to introduce stannum substituent group, carry out under the reaction condition that reactions steps can be known in the art, such as the application Anticipate shown in embodiment.Such as, purification, temperature, pressure, environment, solvent, response time, catalyst and other response parameters can To be adapted to specifically synthesize.Embodiment is provided in the following.Reaction temperature is permissible, such as, and 50 DEG C to 150 DEG C, Counterflow condition can be used.Response time it may be that such as, 3h to 72h.One or more organic solvents, such as fragrance can be used Race's solvent, such as toluene.Catalyst material can be introduced in one or more steps, and is not only to draw in one step Enter.Reaction yield can e.g. at least 10%, at least 25% or at least 50%.

Part II

A kind of important specific embodiments is that NDI-tin compound benzene compound embedding with naphthalene reacts and obtain having covalent bonding Product to the NDI part of naphthalene embedding benzene part.Dimer, trimer, oligomer and polymer can be prepared.In the art The known embedding benzene compound of naphthalene and part, such as, Zhan etc., Adv.Mater., 2011,23,268-284 (" Rylene and Related Diimides for Organic Electronics”).One example of the embedding benzene of naphthalene is group.Known NDI and Compound.Referring for example to Organic Field-Effect Transistors, (Eds.:Bao, Locklin), CRC Press, 2007 including pages 194-197.

A kind of naphthalene embedding benzene embodiment is as follows:

Wherein n is it may be that such as, and 0,1,2,3,4 or 5.Especially, when n is 0, it is known that compound and part, e.g., Or PDI.If n is 1, TDI can be referred to as；If n is 2, QDI can be referred to as；If n is 3, can be referred to as 5DI；If n is 4, HDI can be referred to as.

Such as, Ry compound may adapt to as the compound of reaction with NDI-tin compound chemically reactive.

In formula (Ry), R group, R1-R14 can use and it known in the art, and can select independently of one another.They can To be hydrogen or organic group, wherein organic group includes the most non-reacted group or reactive group.Such as, R5 and R10 can be substituted radical, the dissolubility of its described compound of increase, the most optionally substituted C1 to C50 hydrocarbyl substituent, Such as optionally substituted alkyl or aryl, the most linear or side chain.Wherein, each R can be C independently₁-C₃₀Just Chain, side chain or ring-type alkyl, aryl, heteroaryl, alkyl-aryl-group or alkyl-heteroaryl group, optionally with one Or multiple halogenide, cyano group, alkyl or alkoxyl replace.

Substituent R 1-4, R6-R9 and R11-R14 can be independently hydrogen or reactive group, such as halogen such as chlorine or Person's pseudohalogen (pseudohalogen).Described reactive group can provide nucleophilic or electrophilic site, but is not used in When reacting with NDI-Sn compound, can there is electrophilic site in it.

For the specific embodiments of (Ry), when covalently bonded to NDI compound, it is H independently including group R, appoints The substituted alkyl of selection of land, optionally substituted miscellaneous alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally Substituted aryl alkyl or optionally substituted alkylaryl.

Reaction can be carried out in the one or both sides of naphthalene embedding benzene part.

In a specific embodiment, n is 0, R3 and R6 each be reactive, such as, so that they can be Halogen such as chlorine or pseudohalogen.In another embodiment, n is 0, R3 and R6 and R2 and R7 each be reactive, Such as, so that they can be halogen such as chlorine.

Following representation, an example of naphthalene embedding benzene structure is as follows:

Formula PDI is an example of formula Ry, and wherein n is zero.It can be the reaction for reacting with NDI-Sn compound Property compound.

In the application, one, two, three or four in R2, R3, R6 and R7 substituent group can be avtive spots, example As, halogen such as chlorine or pseudohalogen.If R3 and R6 is reactive, then side can be reacted.If R2 and R7 is anti- Answering property, then both sides can be reacted.

In PDI specific embodiments, when PDI some covalent is bonded to NDI part, group R is H, optionally independently The substituted alkyl in ground, optionally substituted miscellaneous alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally take The aryl alkyl in generation or optionally substituted alkylaryl.

Additionally, naphthalene embedding benzene part, such as, part can be covalently bonded to NDI structure, as follows based on above formula PDI Shown in NDI:

As shown, one or two key can be used for covalently being bonded NDI part to part.

In NDI-PDI-I and NDI-PDI-II compound, group R can independently, such as, H, optionally substituted Alkyl, optionally substituted miscellaneous alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted aryl Alkyl or optionally substituted alkylaryl.

NDI-PDI-NDI

In the specific embodiments of NDI-PDI-NDI, group R is H, optionally substituted alkyl, optionally independently Substituted miscellaneous alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted aryl alkyl or optionally The substituted alkylaryl in ground.

PDI-NDI-PDI

In the specific embodiments of PDI-NDI-PDI, group R independently, such as, H, optionally substituted alkyl, Optionally substituted miscellaneous alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted aryl alkyl or The optionally substituted alkylaryl of person.

Optionally substituted R base in Ry, NDI-PDI-I, NDI-PDI-II, NDI-PDI-NDI and PDI-NDI-PDI part Group can have independently, such as, and 1 to 30 carbon or 1 to 20 carbon.

Therefore, a kind of specific embodiments provides a kind of compositions, and it comprises at least one compound, wherein said chemical combination Thing includes that at least one is covalently bonded to the NDI part of at least one naphthalene embedding benzene part.Described naphthalene embedding benzene part is it may be that example As, part.

The number ratio of NDI benzene embedding with naphthalene part can change.Such as, a specific embodiments provides to have and is bonded to The compound of one NDI part of one naphthalene embedding benzene part.In another embodiment, described compound comprises at least two Individual NDI part, each is covalently bonded to naphthalene embedding benzene part.In another embodiment, described compound comprises two Individual NDI part and a naphthalene embedding benzene part, each in two of which NDI part is covalently bonded to naphthalene embedding benzene part.Separately In one specific embodiments, described compound comprises at least two naphthalene embedding benzene part, and each is covalently bonded to NDI part.? In another specific embodiments, described compound comprises at least two naphthalene embedding benzene part and a NDI part, and two embedding benzene of naphthalene Each in part is covalently bonded to NDI part.In another embodiment, described compound comprises at least two NDI part and at least two naphthalene embedding benzene part.In another embodiment, described compound comprise two NDI part and Two naphthalene embedding benzene parts.In a specific embodiment, compound is expressed as [rylene-NDI] n, wherein n be 1,2,3,4, 5 or 6, or described compositions comprises the mixture of above-claimed cpd.Each in these specific embodiments is specifically real Executing scheme, described naphthalene embedding benzene part can be part.

The method that other specific embodiments relates to preparing the embedding benzene compound of NDI-naphthalene.Such as, a specific embodiment party Case provides a kind of method, and the method includes: (i) at least one benzene-naphthalene diimide (NDI) compound, and it comprises at least one bonding To the stannyl substituent group of the naphthalene part of NDI compound, react with the embedding benzene compound of (ii) at least one naphthalene, form at least one Planting product compound, wherein said product compound comprises at least one NDI part, and it is covalently bonded at least One naphthalene embedding benzene part.

In a specific embodiment, described NDI compound has a stannyl substituent group.Specifically real at another Executing in scheme, described NDI compound has two stannyl substituent groups.

In a specific embodiment, described stannyl substituent group is-SnR '₃, wherein R ' group is alkane independently Base or aryl.

In a specific embodiment, NDI compound is expressed as:

Wherein, X is H or stannyl substituent group；Wherein, each R is C independently₁-C₃₀Normal chain, side chain or ring-type Alkyl, aryl, heteroaryl, alkyl-aryl-group or alkyl-heteroaryl group, optionally with one or more halogenide, cyanogen Base, alkyl or alkoxyl replace；Wherein, each R ' part is alkyl or aryl moiety independently.It is embodied as at one In scheme, each R is optionally substituted C independently₁-C₃₀Moieties, and each R ' part is C independently₁-C₂₀Alkyl portion Point.

In another embodiment, described NDI compound is expressed as:

Wherein, each R is C independently₁-C₃₀Normal chain, side chain or ring-type alkyl, aryl, heteroaryl, alkyl-aryl-group, Or alkyl-heteroaryl group, optionally replaces with one or more halogenide, cyano group, alkyl or alkoxyl；Wherein, respectively Individual R ' part is alkyl or aryl moiety independently.In a specific embodiment, each R is optionally substituted independently C₁-C₃₀Moieties, and each R ' part is C independently₁-C₂₀Moieties.

In another embodiment, described NDI compound is expressed as:

Wherein, each R is C independently₁-C₃₀Normal chain, side chain or ring-type alkyl, aryl, heteroaryl, alkyl-aryl-group, Or alkyl-heteroaryl group, optionally replaces with one or more halogenide, cyano group, alkyl or alkoxyl；Wherein, respectively Individual R ' part is alkyl or aryl moiety independently.In a specific embodiment, each R is optionally substituted independently C₁-C₃₀Alkyl, and each R ' part is C1-C20 moieties independently.

In each specific embodiments of these specific embodiments, the embedding benzene compound of described naphthalene it may be that such as, Compound.

Part III

Application

Described compositions disclosed herein, compound and material can be used for the application of multiple organic electronic, including, example As, field-effect transistor, OLEDs, display, light, barrier-layer cell, sensor, RFID, lighting transistor etc..Can be real Execute vacuum moulding machine and solution processing.Vacuum and the combination of solution processing can be implemented.Solvent and additive preparation ink can be used. Ink jet type can be used to print.

Such as, be disclosed in organic field effect transistor (Organic Field-Effect Transistors) (Eds.:Bao, Locklin), CRC Press, 2007 including sections 2.1,2.2,2.3,3.1, and 5.3.) in organic Field-effect transistor.

Mobility and occupation efficiency (on-off ratios) can be measured.

Described electron transfer rate score it may be that such as, at least 0.1 or at least 0.2 or at least 0.3cm²V^-1S^-1。

N-shaped track (N-channel) organic transistor can be prepared.

Embodiment

Other specific embodiments is below provided without limitation.

PART I.

Embodiment A-1 prepares compound 3,4

Scheme 1. prepares stannyl NDI derivant.

N, N '-two (n-hexyl)-2-three-(normal-butyl) stannyl naphthalene-Isosorbide-5-Nitrae, 5,8-double (dicarboximides), 3, and N, N '-two (n-hexyl)-2, double (three (normal-butyl) stannyl) naphthalene-Isosorbide-5-Nitrae of 6-, 5,8-double (dicarboximides), 4, according to scheme 1 Obtain with the yield of appropriateness.The most single-or the mixture of two bromo derivatives, 1 or 2, and six dibutyltin dilaurates (hexabutylditin) (1 equivalent every bromo substituent group) in toluene at Pd₂dba₃(the 0.05 every bromo of equivalent) and P (o- tol)₃It is heated in the case of the existence of (the 0.2 every bromo of equivalent).Product by silica gel chromatography and from methanol recrystallization It is purified, it is provided that such as list-and the methyl-tin alkyl derivative of long yellow needles；These compounds pass through nuclear magnetic resoance spectrum , mass spectrometry, elementary analysis and, in the case of compound 4, X-ray structure characterizes.

In the case of the same terms, comparatively, single bromination imidodicarbonic diamide (PDI) derivant stands from coupling (homocoupling), double PDI product is produced, it is impossible to separate stannyl PDI intermediate.

Separate and the ability of sufficiently cleaned up methyl-tin alkyl derivative be important for the application that conjugated polymer synthesizes, The ability obtaining high molecular weight material is decisively determined by the accurate control that monomer chemistries calculates.

Embodiment A-2 replaces preparation method；The synthesis of 5 and 6

Scheme 2. is prepared stannyl NDI derivant by the NDA being purchased.

Compound 3 and 4 has different chromatographic performances, and (3:Rf=0.3, on silicon oxide, uses 1: 1 dichloromethane/hexane Eluting；4:Rf=0.3, on silicon oxide, uses 1: 10 dichloromethane/hexane eluting), it is recommended to use single-and dibromo material is mixed Compound carries out this reaction, this is single-and dibromo material from the bromination of NDA and sub-acylation, only at final stage purification.Even These transformations can be implemented without separating the intermediate of described single-and di-functionalization, to obtain single-and methyl-tin alkyl The separation yield of derivant is respectively about 20% and 5% (e.g., when using bromating agent described in 1eq.DBI).

Yield advantage can be adjusted according to bromating agent, for using the single-and di-stannyl of DBI of 2.1eq. to spread out Biology can obtain the yield of about 10%.

As shown in scheme 2, in addition to 3 and 4, also obtain their N, N '-bis-(n-dodecanes with similar separation yield Base) analog 5 and 6.Compared with such as hexyl groups, described dodecyl group can improve dissolubility.

For list-and two bromo-NDI intermediate (such as 1 and 2), it is readily separated high soluble solution by column chromatography List-and methyl-tin alkyl NDI product be attractive alternative, 1 and 2 be all have in ordinary organic solvents less Dissolubility and less well differentiated Rf (on silicon oxide, for 1 and 2,0.4 and 0.3, use dichloromethane eluent).? On silicon dioxide, for 1 and 2,4 and 0.3, use dichloromethane eluent).Similarly, two steps separate and purification brominated species, so After, for single-and di-stannyl NDI, stannylated to cause overall recovery be to be of about 9% and 2% respectively.

For embodiment A-1 and the supplemental instruction of A-2

1. raw material and conventional method

Unless otherwise indicated, initiation material is SILVER REAGENT, is directly employed without purification further.

By activated alumina column (toluene, CH₂Cl₂), be dried solvent by Na/ benzophenone (THF) distillation, or such as From anhydrous level Acros Organics.N, N '-two (n-hexyl) naphthalene-Isosorbide-5-Nitrae, 5,8-double (dicarboximides), 9, according to following Document synthesis obtains:

(1) Rademacher, A.；S.；Langhals, H.Chem.Ber.1982,115,2927. (2) G.Hamilton, D.；Prodi, L.；Feeder, N.；K.M.Sanders, J.J.Chem.Soc., Perkin Trans.1 1999,1057. (3) Reczek, J.J.；Villazor, K.R.；Lynch, V.；Swager, T.M.；Iverson, B.L.J.Am.Chem.Soc.2006,128,7995.

Six butyl tin obtain from Sigma-Aldrich.

Characterize

Standard flash column chromatography is utilized to use purchased from Sorbent Technologies (6032-63 μm) silica gel enter Row chromatographic isolation.

Unless otherwise indicated,¹H and¹³C{1H}NMR spectrum obtains on Bruker AMX 400MHz spectrometer, wherein makes Use CHCl₃Residue¹H resonance or CDCl₃'s¹³The chemical shift of C resonance is as reference.

Routine is used with the dry deoxidation 0.1M four-normal-butyl ammonium hexafluorophosphate in dichloromethane in the case of nitrogen Three-electrode battery and glassy carbon working electrode, platinum wire counter electrode and scribble AgCl such as false reference electrode (pseudo-reference Electrode) Ag tinsel carries out electrochemical measurement.Potential reference ferrocene/ ferrocene is by using ferrocene Decane (-0.55Vvs. ferrocene/ ferrocene) as internal reference.Sweep speed 50mVs^-1In the case of record circulation volt Peace.Use Varian Cary 5E spectrometer with 1cm battery record UV-vis-NIR spectrum.At Applied Biosystems By Georgia Tech mass spectroscopy device record mass spectrum on 4700 Proteomics Analyzer.By Atlantic Microlabs carries out elementary analysis.

The manufacture of thin film transistor (TFT)

The embodiment preparing OFET presented below.Have back contact (bottom contact) and top-gated (top gate) The OFETs of structure is in the upper manufacture of glass substrate (Eagle 2000 Corning).By thermal evaporation through shadow mask (shadow Mask) Au (50nm) is followed by source/drain electrodes.By continuing 10 seconds with 500rpm and continuing 20 with 2000rpm in substrate Second spin coating by 1,1 ', 2, solution prepared by 2 '-sym-tetrachloroethane (15mg/mL) forms organic semiconductor layer.CYTOP(45nm)/ Al₂O₃(50nm) bilayer is used as top gate medium (top gate dielectric).CYTOP solution (CTL-809M) is purchased from Asahi Glass, its concentration is 9wt.%.In order to deposit 45-nm thickness fluorinated polymer layer, use solvent (CT-solv.180) Dilution original solution: solvent ratios is 1: 3.5.Then 60 seconds are continued by spin coating precipitate C YTOP layer with 3000rpm.With 110 DEG C Use exposure trimethyl aluminium alternately and H2O layer precipitate A LD by atom) precipitate A l on CYTOP layer₂O₃(50nm) thin film, Wherein sedimentation rate is of about 0.1nm each cycle.Whole spin coating and annealing process is carried out in the drying baker that N2-fills.Finally, By thermal evaporation (thermal evaporation) through shadow mask precipitate A l (150nm) gate electrode.Use Agilent E5272A Source/supervision equipment (source/monitor unit) measures whole current-voltage (I-V) feature in N2-fills glove box (O2, H₂O ＜ 0.1ppm).

A-1 and A-2 synthetic example:

N, N '-two (n-hexyl)-2-bromonaphthalene-Isosorbide-5-Nitrae, 5,8-double (dicarboximides), 1, and N, N '-two (n-hexyl)-2, 6-dibromine naphthalene-Isosorbide-5-Nitrae, 5,8-double (dicarboximides), 2

Naphthalene Isosorbide-5-Nitrae, 5, the 8-tetracarboxylic dianhydrides (10.0g, 59.5mmol) solution in concentrated sulphuric acid (600mL) is heated to 85 ℃.After 30 minutes, add potassium dibromo isocyanates 19.3g, 59.5mmol several times), described mixture is 85 DEG C of stirrings 20h.Described mixture is introduced in frozen water (1.5L), and stirs 2 hours, is simultaneously heated to room temperature.By filtering, by methanol Wash and be dried under vacuum, collect and obtain yellow mercury oxide (16.6g).This yellow solid be transferred into have glacial acetic acid (600mL) and In the flask of n-hexylamine (19.4g, 0.191mol).Reactant mixture refluxes 20 minutes, and cooling whole night and pours methanol (1.5L) into In.Described crude product column chromatography (silicon dioxide, 3: 2 dichloromethane/hexane) purification.During post is filled, a part is not filled Point yellow solid dissolved is separated it is considered to be 2 (3.91g, 6.60mmol, 18%).First band of post provides other 2, Such as yellow solid (0.650g, 1.10mmol 21% overall recovery).Second band obtains 1, white solid (1.35g, 2.63mmol, 7%).

The data of 1:¹H NMR (400MHz, CDCl₃) δ 8.88 (s, 1H), 8.77 (d, J=7.6Hz, 1H), 8.72 (d, J= 7.6Hz, 1H), 4.16 (t, J=6.9Hz, 2H), 4.14 (t, J=6.6Hz, 2H), 1.71 (quint., J=7.1Hz, 2H), 1.69 (quint., J=7.6Hz, 2H), 1.45-1.24 (m, 12H), 0.87 (t, J=7.0Hz, 6H).¹³C{¹H}NMR (100MHz, CDCl₃) δ 162.40,161.79,161.67,160.99,138.3,131.62,130.67,128.62,128.54, 126.79,125.99,125.92,125.64,123.85,41.47,41.09,31.46,31.44,27.93,27.88,26.76, 26.67,22.54,22.50,14.02 (an aliphatic response is not observed, it may be possible to due to overlap) .HRMS (EI) m/z calcd for C₂₆H₂₉BrN₂O₄(M⁺), 512.1311；Found, 512.1280.Anal.Calcd.for C₂₆H₂₉BrN₂O₄: C, 60.82；H, 5.69；N, 5.46.Found:C, 59.91；H, 5.60；N, 5.36.

The data of 2:¹H NMR (400MHz, CDCl₃): δ 8.98 (s, 2H), 4.17 (t, J=7.8Hz, 4H), 1.72 (quint., J=7.8Hz, 4H), 1.49-1.20 (m, 12H), 0.88 (t, J=7.1Hz, 6H).¹³C{¹H}NMR (100MHz, CDCl₃) δ 160.73,139.06,128.96,128.32,127.72,125.34,124.08,41.61,31.45,27.84, 26.73,22.54,14.02.HRMS (EI) m/z calcd for C₂₆H₂₈Br₂N₂O₄(M⁺), 590.0416；Found, 590.0394.Anal.Calcd.for C₂₆H₂₈Br₂N₂O₄: C, 52.72；H, 4.76；N, 4.73.Found:C, 52.71；H, 4.69；N, 4.70.

N, N '-two (n-hexyl)-2-three (normal-butyl) stannyl naphthalene-Isosorbide-5-Nitrae, 5,8-double (dicarboximides), 3, obtain from 1 Arrive.

With nitrogen by 1 (1.45g, 2.82mmol), 1,1,1,2,2,2-six dibutyltin dilaurate alkane (1.64g, 2.82mmol) and three- The o-tolylphosphine (0.172g, 0.565mmol) solution deoxygenation in dry toluene (30mL) 5 minutes.Add three (two benzals third Ketone) two palladiums (0.129g, 0.141mmol), heat described reaction to 90 DEG C of 24h.After cooling, in methanol (100mL), precipitation is anti- Answer mixture, solid is filtered to remove, remove solvent under reduced pressure.Crude product with column chromatography eluting (silicon dioxide, Dichloromethane), obtain yellow solid (1.53g, 2.11mmol, 75%).

¹H NMR (400MHz, CDCl₃) δ 8.94 (s, 1H), 8.70 (d, J=7.6Hz, 1H), 8.67 (d, J=7.6Hz, 1H), 4.18 (t, J=7.6Hz, 2H), 4.16 (t, J=8.0Hz, 2H), 1.75-1.64 (m, 4H), 1.55-1.45 (m, 6H), 1.40-1.23 (m, 18H), 1.19 (t, J=8.2Hz, 6H), 0.90-0.80 (m, 15H).¹³C{¹H}NMR (100MHz, CDCl₃) δ 164.91,163.62,163.12,163.04,156.00,138.65,131.67,130.24,130.13,126.84, 126.72,126.70,125.98,123.64,53.40,41.00,40.91,31.50,29.20,28.25,28.07,28.02, 27.39,26.76,26.65,22.54,22.48,17.27,14.02,13.69,13.58,11.58.HRMS (MALDI) m/z calcd for C₃₈H₅₆N₂O₄Sn(M⁺), 725.3340；Found, 725.3325.Anal.Calcd.for C₃₈H₅₆N₂O₄Sn:C, 63.08；H, 7.80；N, 3.87.Found:C, 62.81；H, 7.99；N, 3.93

N, N '-two (n-hexyl)-2, double (three (normal-butyl) stannyl) naphthalene-Isosorbide-5-Nitrae of 6-, 5,8-double (dicarboximides), 4, obtain from 2.

With nitrogen by 2 (0.500g, 0.844mmol) 1,1,1,2,2,2-six dibutyltin dilaurate alkane (1.00g, 1.73mmol) and Three-o-the tolylphosphine (0.051g, 0.169mmol) solution deoxygenation in dry toluene (10mL) 5 minutes.Add three (dibenzyls Fork acetone) two palladiums (0.039g, 0.042mmol), heat described reaction and continue 24h to 90 DEG C.Add the other positive toluene of part three Base phosphine (0.051g, 0.169mmol) and three (two benzylideneacetones) two palladiums (0.039g, 0.042mmol), described instead 90 DEG C of stirrings 2 days should be continued.After cooling, by using the silica gel of chloroform/hexane (1: 1) eluting to filter reactant mixture, under reduced pressure Remove solvent.From recrystallizing methanol crude product, obtain yellow solid (0.407g, 0.402mmol, 48%).

¹H NMR (400MHz, CDCl₃) δ 8.92 (s, 2H), 4.18 (t, J=7.4Hz, 4H), 1.68 (quint., J= 7.5Hz, 4H), 1.53-1.46 (m, 12H), 1.45-1.36 (m, 4H), 1.35-1.25 (m, 20H), 1.23-1.09 (m, 12H), 0.90-0.80 (m, 24H).¹³C{¹H}NMR (100MHz, CDCl₃) δ 165.12,163.82,154.61,138.04,131.84, 126.90,123.11,40.92,31.53,29.22,28.08,27.39,26.69,22.49,14.02,13.69,11.54.MS (MALDI)m/z 898.3(M-(C₄H₉)₂ ²⁺).Anal.Calcd.forC₅₀H₈₂N₅O₄Sn₂: C, 59.31；H, 8.16；N, 2.77.Found:C, 59.30；H, 7.98；N, 2.83.

From naphthalene-Isosorbide-5-Nitrae, the 3 and 4 of 5,8-tetracarboxylic dianhydrides

Heating naphthalene-Isosorbide-5-Nitrae, 5, the 8-tetracarboxylic dianhydrides (NDA) (5.00g, 18.6mmol) solution in concentrated sulphuric acid (180mL) To 55 DEG C.In point mouth flask, potassium dibromo isocyanates (6.06g, 18.6mmol) is dissolved in concentrated sulphuric acid (90mL), in room temperature Lower stirring 1h.Once dissolve, solution is added in reaction flask, stir mixture 48h at 85 DEG C.Pour the mixture into frozen water (1L) stirring 2h in, recovery temperature is to room temperature.Collect the yellow mercury oxide obtained, filter, wash with methanol, and under vacuum condition It is dried (4.51g).This yellow solid is transferred in the flask with glacial acetic acid (100mL) and n-hexylamine (7.2g, 71.1mmol). Reactant mixture backflow 2h, cooling whole night and is poured in methanol (1L).Collect the yellow mercury oxide obtained, filter, wash with methanol, And it is dried (5.51g) under vacuum condition.Orange solids is proceeded in the Schlenk flask being dried, wherein has 1,1,1,2,2, 2-six dibutyltin dilaurate alkane (11.3g, 19.5mmol), three-o-tolylphosphine (1.13g, 3.71mmol) and three (two benzylideneacetones) Two palladiums (0.850g, 0.930mmol).Described flask is filled three times with nitrogen pump.Add dry toluene (80mL), heat described instead Should be to 100 DEG C of lasting 18h.After cooling, with hexane (100mL) diluted reaction mixture, by using the silica gel plug of Hex. Dichloromethane/hexane (1: 1) is used for eluting the first yellow band (impurity 4).Dichloromethane is used to collect second as eluent Yellow band, evaporates to obtain 3, yellow solid (2.60g, 3.59mmol, 19% overall recovery, NDA).With column chromatography (silica gel, 10: 1 hexanes/ch) further purification the first fraction to obtain 4, yellow solid (0780g, 0.770mmol, 4% NDA)。¹H nuclear magnetic resonance data with respectively by 1 and 2-in-1 become 3 and 4 data consistent.

N, N '-two (n-dodecyl)-2-three (normal-butyl) stannyl naphthalene-Isosorbide-5-Nitrae, 5,8-double (dicarboximides), 5 Hes N, N '-two (dodecyl)-2, double (three (normal-butyl) stannyl) naphthalene-Isosorbide-5-Nitrae of 6-, 5,8-double (dicarboximides), 6, come From naphthalene-Isosorbide-5-Nitrae, 5,8-tetracarboxylic dianhydrides

Heating NDA (5.00g, 18.6mmol) solution in concentrated sulphuric acid (180mL) is to 55 DEG C.In point mouth flask, will Potassium dibromo isocyanates (6.06g, 18.6mmol) is dissolved in concentrated sulphuric acid (90mL), is stirred at room temperature 1h.Once dissolve, by institute State solution and add in reaction flask, stir mixture 48 hours at 85 DEG C.Pour the mixture into frozen water 1L) in, stir 2h, reply Temperature is to room temperature.The yellow mercury oxide obtained described in collection, filters, washes with methanol, be dried (8.33g) under vacuum condition.This is yellow Color solid is transferred in the flask with glacial acetic acid (190mL) and n-dodecane amine (14.2g, 76.4mmol).Back flow reaction is mixed Compound 2h, cooling whole night, is poured in methanol (1L).The precipitation obtained described in collection, filtration methanol is washed, is done under vacuum condition Dry.Obtained orange solids (10.0g) is proceeded in the Schlenk flask being dried, wherein has 1,1,1,2,2,2-six butyl Two stannanes (16.0g, 27.6mmol), three-o-tolylphosphine (1.60g, 5.26mmol) and three (two benzylideneacetones) two palladiums (1.20g, 1.31mmol).Described flask is filled three times with nitrogen pump.Add dry toluene (60mL), heat described reaction to 90 DEG C continue 24h.After cooling, use hexane diluted reaction mixture, filter through Celite plug, under reduced pressure remove solvent.Use color Spectrum column purification crude product (silica gel): hexanes/ch (10: 1) is used for eluting the first yellow band, evaporation, it is thus achieved that yellow oil (impurity 6).Use hexanes/ch (1: 1) to be used for eluting the second yellow band, evaporate to obtain 5, yellow solid (3.87g, 4.4mmol, 23% overall recovery, NDA).By column chromatography (silica gel, 10: 1 hexanes/ch) further Purification the first yellow fraction to obtain pure 6, yellow oil (1.25g, 1.06mmol, 6% response rate, NDA).

The data of 5:¹H NMR (400MHz, CDCl₃) δ 8.95 (s, 1H), 8.70 (d, J=7.6Hz, 1H), 8.67 (d, J= 7.7Hz, 1H), 4.18 (m, 4H), 1.78-1.64 (m, 4H), 1.58-1.45 (m, 6H), 1.40-1.15 (m, 48H), 0.90- 0.82 (m, 15H).¹³C{¹H}NMR (100MHz, CDCl₃) δ 164.90,163.60,163.09,163.02,155.98, 138.63,131.65,130.22,130.12,126.82,126.71,126.69,125.96,123.62,40.98,40.91, 31.89,31.57,28.61,28.52,29.48,29.33,29.20,29.10,28.12,28.06,27.39,27.11, 26.99,22.67,14.09,13.70,11.57 (five aliphatic resonances not observed, Presumably due to overlap) .MS (MALDI) m/z893.5 (7%, M⁺), 835.4 (100%, M-(C₄H₉)⁺) .Anal.Calcd.for C₅₀H₈₀N₂O₄Sn:C, 67.33；H, 9.04；N, 3.14.Found:C, 67.40；H, 9.03；N, 3.13.

The data of 6:¹H NMR (300MHz, CDCl₃) δ 8.93 (s, 2H), 4.19 (t, J=7.2Hz, 4H), 1.71 (quint., J=7.3Hz, 4H), 1.53-1.46 (m, 12H), 1.57-1.42 (m, 12H), 1.42-1.02 (m, 60H), 0.94- 0.76 (m, 24H).¹³C{¹H}NMR (75MHz, CD Cl₃) δ 165.11,163.82,154.60,138.04,131.84, 126.89,123.10,40.93,31.90,29.64,29.62,29.50,29.38,29.34,29.23,28.12,27.41, 27.04,22.67,14.10,13.72,11.52 (an aliphatic response is not observed, it may be possible to due to overlap) .MS (MALDI)m/z 1066.4(M-(C₄H₉)₂ ²⁺).Anal.Calcd.forC₆₂H₁₀₆N₂O₄Sn₂: C, 63.06；H, 9.05；N, 2.37.Found:C, 62.87；H, 9.09；N, 2.32.

Detailed description of the invention

Embodiment 1

Concrete synthesis step is:

(1). in reaction system add 0.4mmol mono-stannum functionalization naphthalene-3,4:9,10-tetracarboxylic acid diimide and 0.4mmol monolateral two chloro-3,4:9, and 10-tetracarboxylic acid diimide (the most monolateral two chloro-3,4:9,10-tetrabasic carboxylic acid two acyl The synthesized reference document Org.Lett of imines, 2009,11,3804-3807)；Add catalyst 0.04mmol Pd (PPh3) 4 And 0.08mmolCuI, it is subsequently adding 8ml toluene as solvent, under inert gas shielding, is heated to 100 DEG C of 20h；

(2). reaction terminates, and is cooled to room temperature, solvent evaporated, and separating-purifying obtains naphthalene-3, and 4:9,10-tetrabasic carboxylic acid two acyl is sub- Amine hydridization-3, compound 3b and 3a of 4:9,10-tetracarboxylic acid diimide class, wherein compound 3a, 159mg, productivity is 33%.Green powder, C78H76N4O8¹H-NMR(CDCl₃, 400MHz): δ=9.77 (s, 2H), δ=9.22,9.20 (d, 2H), δ=9.11,9.09 (d, 2H), δ=9.01 (s, 2H), and δ=7.55-7.51 (m, 2H), δ=7.39,7,37 (d, 4H), 4.13-4.09 (m, 4H), 2.85 (m, 4H), 1.39-1.84 (m, 4H), 1.30-1.20 (m, 52H), 0.88-0.82 (m, 6H) .MS (MALDI-TOF, m/z): 1196.7Anal.Calcd for:1196.6.

Compound 3b, red powder, 110mg, productivity is 25%¹H-NMR(CDCl₃, 400MHZ): δ=8.95-8.80 (m, 6H), δ=8.41 (s, 1H), δ=8.35 (s, 1H), 8.15 (d, 1H), 7.75,7.73 (d, 1H), 7.51-7.45 (m, 2H), 7.37-7.26 (m, 4H), 4,15-4.09 (m, 4H), 2.86-2.66 (m, 4H), 1.75-1.11 (m, 52H), 0.90-0.75 (m, 6H) .MS (MALDI-TOF, m/z): C78H78N4O8:1198.7, Anal.Calcd for:1198.6.

The sign of compound 3a is as Figure 1-4；The sign of compound 3b is as viewed in figures 5-8.

Embodiment 2

Concrete synthesis step is: concrete synthesis step is:

1). in reaction system add 0.4mmol mono-stannum functionalization naphthalene-3,4:7,8-tetracarboxylic acid diimide and 0.2mmol tetra-chloro-3,4:9,10-tetracarboxylic acid diimide；Adding the Pd (PPh3) 4 of 0.04mmol catalytic amount, then adding Enter 8ml toluene as solvent, under inert gas shielding, be heated to 100 DEG C, react 20h；

2). reaction terminates, and is cooled to room temperature, solvent evaporated, and separating-purifying obtains naphthalene-3, and 4:9,10-tetrabasic carboxylic acid two acyl is sub- Amine hydridization-3, the compound 159mg of 4:9,10-tetracarboxylic acid diimide class, productivity is 46%.Purple powder,¹H-NMR (CDCl₃, 400MHZ): δ=10.15 (s, 4H), δ=9.08 (s, 4H), δ=7.61-7.57 (m, 2H), δ=7.46-7.44 (d, 4H), δ=4.31-4.27 (m, 8H), δ=3.00-2.97 (m, 4H), δ=1.93-1.91 (m, 8H), δ=10.15 (s, 4H), δ=1.48-1.27 (m, 64H), δ=0.90-0.87 (m, 12H) .MS (MALDI-TOF, m/z): 1683.2, Anal.Calcd for:1682.8, C108H110N6O12.

The sign of compound 4a is as shown in figs9-12.

Embodiment 3

Concrete synthesis step is:

(1). in reaction system add 0.4mmol mono-stannum functionalization naphthalene-3,4:7,8-tetracarboxylic acid diimide and 0.2mmol tetra-fluoro-3,4:9,10-tetracarboxylic acid diimide；Adding the catalyst Pd (PPh3) 4 of 0.04mmol catalytic amount, It is subsequently adding 8ml toluene as solvent, under inert gas shielding, is heated to 100 DEG C, react 20h；

(2). reaction terminates, and is cooled to room temperature, solvent evaporated, and separating-purifying obtains naphthalene-3, and 4:9,10-tetrabasic carboxylic acid two acyl is sub- Amine hydridization-3, the compound 150mg of 4:9,10-tetracarboxylic acid diimide class, productivity is 40%.Purple powder, MS (MALDI- TOF, m/z): 1783.1, Anal.Calcd for:1783.0C114H138N6O12¹H-NMR(CDCl₃, 400MHZ): δ= 10.03,9.99 (d, 4H), δ=9.05 (s, 4H), δ=5.30-5.27 (m, 2H), δ=4.36-4.32 (m, 8H), δ=2.34- 2.30 (m, 4H), δ=1.98,1.97 (m, 8H), δ=1.47-1.09 (m, 80H), δ=0.8-0.96 (m, 24H).

The sign of compound 4b is as shown in figures 13-16.

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Claims (4)

1. compositions, comprises at least one compound, and wherein said compound is selected from:

；

；

；With

。

2. device, it comprises compositions according to claim 1.

3. claim 2 device, wherein said device is field-effect transistor.

4. ink composition, it comprises compositions according to claim 1, and wherein said compositions comprises at least one further Plant solvent.