EP2794609A1 - Reaction products of stannyl derivatives of naphthalene diimides with rylene compounds - Google Patents

Abstract

NDI-tin compounds are reacted with rylene compounds to form NDI-rylene compounds. The rylene compounds can be perylene compounds. The NDI-rylene compounds can be used in organic electronic devices including in a field-effect transistor.

Description

REACTION PRODUCTS OF STANNYL DERIVATIVES OF

NAPHTHALENE DIIMIDES WITH RYLENE COMPOUNDS

BACKGROUND

Organic electronics is an important area for commercial development including, for example, advanced transistors, displays, lighting, photovoltaic, and sensing devices. The broad diversity of organic compounds and materials provides advantages for organic electronics. In but one example of the versatile chemistry and material science available for organic electronics, tetracarboxylic diimide derivatives of rylenes, particularly of napthalene and perylene (NDIs amd PDIs, respectively), represent one of the most extensively studied classes of functional materials in the field of organic electronics.^{1 2} The thermal, chemical, and photochemical stability as well as their high electron affinities and charge-carrier mobilities render these materials attractive for applications in organic field-effect transistors (OFETs)^3"15 and organic photovoltaic cells (OPVs).¹²'^16"20 They have also been widely used as acceptors in transient absorption studies of photoinduced electron-transfer, again due to their redox potentials, and to the stability and distinctive absorption spectra of the corresponding radical anions.^{21 "24}

The A iV -substituents of PDIs and NDIs generally only have minimal influence on the optical and electronic properties of isolated molecules, although they can be used to control solubility, aggregation, and intermolecular packing in the solid-state. In contrast, core substitution of these species typically has a much more significant effect on the redox potentials (enabling, in some cases, the electron affinities to be brought within a range in which air-stable OFET operation can be achieved^{J IJ J}) and optical spectra of these species. Moreover, core substitution can be used as a means of constructing more elaborate architectures such as conjugated polymers^{7 11}'²⁰'^{26 27} and donor or acceptor functional ized products.¹³'¹⁴'^28"32

Functionalized NDIs are most effectively obtained through the selective bromination of naphthalene-l,4:5,8-tetracarboxylic dianhydride (NDA) with dibromoisocyanuric acid (DBI) in concentrated sulfuric acid or oleum, followed by imidization with the primary amine of choice in refluxing acetic acid.⁵'^27,32 NDA can also be brominated using Br₂ in concentrated sulfuric acid or oleum.⁵'³³ The brominated NDI can then serve as an intermediate for further functionalization through either nucleophilic substitution to afford amino, thiol or alkoxy substituted derivatives,³¹'³² or through palladium-catalyzed coupling reactions to yield cyano,⁵'²⁹ phenyl,²⁸'²⁹ alkynyl²⁹ and thienyl^{11 14}'²⁸ functionalized products. However, the range of conjugated species that can be obtained by palladium-catalyzed methods is determined by the availability of appropropriate candidate coupling partners. In particular, metallated reagents such as stannanes can be difficult to obtain for electron-poor (acceptor) building blocks. Additionally, monobrominated NDI, which is useful for a full range of NDI derived compounds, generally can only be obtained by manipulating the equivalents of brominating reagents and/or by manipulating reaction conditions; however, a difficult to separate mixture of non-brominated, monobrominated, and dibrominated results, which makes large scale production difficult or impractical.

Accordingly, metallated NDI species, whether mono- or di-metallated would be valuable building blocks for new types of conjugated NDI derivatives in which acceptor groups are directly conjugated to the NDI core. SUMMARY

Embodiments described herein include compositions and compounds, as well as methods of making, methods of using, inks, and devices comprising these compositions and compounds.

One embodiment provides a composition comprising at least one naphthalene diimide (NDI) compound comprising at least one stannyl substituent bonded to the naphthalene moiety of the NDI compound.

Another embodiment provides for naphthalene diimide organotin compounds having the structure (IV);

(IV) wherein: (a) R¹ and R¹ are independently selected from a C₁ -C30 normal, branched, or cyclic alkyl, aryl, heteroaryl, alkyl-aryl, or alkyl-heteroaryl group optionally substituted with one or more halide, cyano, alkyl, or alkoxy groups, (b) R², R³, and R⁴ are independently selected from hydrogen, halide, or a C₁-C30 organic group independently selected from cyano, normal, branched, or cyclic alkyl, perfluoroalkyl, aryl, heteroaryl, alkyl-aryl, and alkyl-heteroaryl groups, optionally substituted with one or more fluoro, cyano, alkyl, alkoxy groups; and (c) R⁹ is an alkyl or aryl group.

Another embodiment provides for a method comprising: reacting at least one first naphthalene diimide (NDI) precursor compound with at least one tin reagent to form at least one first NDI compound comprising at least one stannyl substituent bonded to the naphthalene moiety of the NDI compound.

Another embodiment is a composition comprising at least one compound, wherein the compound comprises at least one NDI moiety which is covalently bonded to at least one rylene moiety.

Another embodiment is a method comprising: reacting (i) at least one naphthalene diimide (NDI) compound comprising at least one stannyl substituent bonded to the naphthalene moiety of the NDI compound, with (ii) at least one rylene compound to form at least one reaction product compound, wherein the reaction product compound comprises at least one NDI moiety which is covalently bonded to at least one rylene moiety.

Inks and devices also can be prepared from the compositions described herein.

At least one advantage for at least one embodiment is that a wide variety of new compounds and materials can be made or, alternatively, existing compounds and materials can be made more easily. In particular, for at least one embodiment, the important Stille coupling reaction can be used more expansively for the NDI system to expand the variety of organic compounds and materials which can be made. This allows one to "tune" parameters such as, for example, the ionization potential, oxidation potential, electron affinity, reduction potential, optical absorption, and fluorescence of the compound or material for a particular application so it can function well with other components.

At least one additional advantage for at least one embodiment is that compounds and materials can be made having useful or improved properties. For example, in one embodiment, good electron mobility values can be achieved. In another embodiment, useful field-effect transistors can be prepared. In one embodiment, air, water, and thermally stable compounds can be made. Compounds with good solubility can be made.

For some embodiments, electrochemical potentials can be lowered below the air stability threshold.

For some embodiments, improved solid state packing can be achieved. Also, structural motifs in which the orientation of the molecules with respect to the electrode surfaces can be varied.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 shows the mass spectrogram of compound 3a.

Figure 2 shows the ^-NMR.

Figure 3 shows the absorption curve.

Figure 4 shows the electrochemistry curve. Figure 5 shows the mass spectrogram of compound 3b. Figure 6 shows the ^-NMR.

Figure 7 shows the absorption curve.

Figure 8 shows the electrochemistry curve.

Figure 9 shows the mass spectrogram of compound 4a.

Figure 10 shows the ^!H-NMR.

Figure 1 1 shows the absorption curve;

Figure 12 shows the electrochemistry curve.

Figure 13 shows the mass spectrogram of compound 4b.

Figure 14 shows the ^-NMR.

Figure 15 shows the absorption curve.

Figure 16 shows the electrochemistry curve.

DETAILED DESCRIPTION INTRODUCTION

All references cited herein are incorporated by reference in their entirety.

U. S. provisional application 61/475,888 filed April 15, 201 1 to Polander et al. is hereby incorporated by reference in its entirety including NDI-Sn compounds and methods of making NDI-Sn compounds. This application also provides more background information about the advantages and long-felt need associated with the presently claimed inventions.

The PhD thesis by Lauren Polander, 201 1 , "Organic Charge-Transport Materials Based on Oligothiophene and Naphthalene Diimide: Towards Ambipolar and n-Channel Organic Field-Effect Transistors," provides additional information about the presently claimed inventions.

The substituents R (with subnumerals such as Rl or Ri) shown for the formulas described herein can be, independently, substituents which can be synthesized and provide some minimal and useful product stability as known in the art. Protecting groups can be used as known in the art. The substituents can be adapted to be reactive or non-reactive. The R groups can be, for example, independently H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted arylalkyl, or optionally substituted alkylaryl. They can be optionally substituted with groups such as halogen (such as, for example, F, CI, Br, or I), pseudohalogen (such as, for example, cyano), alkyl, or alkoxy. Heteroatoms can be substituted in such as, for example, O, N, S, and Se.

"A", "an", and "the" refers to "at least one" or "one or more" unless specified otherwise.

"Optionally substituted" groups refer to, for example, functional groups that may be substituted or unsubstituted by additional functional groups. For example, when a group is unsubstituted by an additional group it can be referred to as the group name, for example alkyl or aryl. When a group is substituted with additional functional groups it may more generically be referred to as substituted alkyl or substituted aryl.

"Alkyl" refers to, for example, straight chain, branched, or cyclic alkyl groups having from 1 to 30 carbon atoms, or 1 to 20 carbon atoms, or from 1 to 15 carbon atoms, or from 1 to 10, or from 1 to 5, or from 1 to 3 carbon atoms. This term is exemplified by groups such as for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, t-butyl, n-pentyl, ethylhexyl, dodecyl, isopentyl, and the like.

"Aryl" refers to, for example, an aromatic carbocyclic group of from 6 to 14 carbon atoms having a single ring (e.g., phenyl) or multiple condensed rings (e.g., naphthyl or anthryl) which condensed rings may or may not be aromatic provided that the point of attachment is at an aromatic carbon atom. Preferred aryls include phenyl, naphthyl, and the like.

"Heteroalkyl" refers to, for example, an alkyl group wherein one or more carbon atom is substituted with a heteroatom. The heteroatom can be, for example, O, S, N, P, etc.

"Heteroaryl" refers to, for example, an aryl group wherein one or more carbon atom is substituted with a heteroatom. The heteroatom can be, for example, O, S, N, P, etc. One example of heteroaryl is carbazole. PART IA. NDI-Sn COMPOSITIONS

One embodiment provides, for example, a composition comprising at least one naphthalene diimide (NDI) compound comprising at least one stannyl substituent bonded to the naphthalene moiety of the NDI compound.

"Naphthalene diimide" or "naphthalene tetracarboxylic diimide" (NDI) compounds, derivatives, and materials are known in the art. See, for example, US Patent Publications 201 1/0269967; 201 1/0269966; 201 1/0269265; 201 1/0266529; 201 1/0266523; 201 1/0183462; 201 1/0180784; 201 1/0120558; 201 1/0079773; 2010/0326527; and 2008/0021220. Other examples can be found in, for example, Hu et al., Chem. Mater., 201 1 , 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, 1 1 , 2703-2705; and Durban et al., Macromolecules, 2010, 43, 6348-6352; Guo et al, Organic Letters, 2008, 10, 23, 5333-5336 ("naphthalene bisimides"); Roger et al., J. Org. Chem., 2007, 72, 8070-8075; Thalaker et al., J. Org. Chem. , 2006, 71, 8098-8105; Oh et al., Adv. Funct. Mater., 2010, 20, 2148-2156; Suraru et al., Synthesis, 2009, 1 1 , 1841-1845; Polander et al, Chem. Mater. , 201 1 , 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 , 2009, 131 , 8-9. In the present application, "NDI" and "NBI" are deemed equivalent. The core NDI structure can be called l,4:5,8-napthalenetetracarboxylic acid diimide.

One representation of an NDI structure is as follows, showing the core naphthalene group and the two imide groups:

Herein, at least one of the substituents Rl , R2, R3, and/or R4 can be functionalized to be a tin (or stannyl) group wherein the tin atom is directly covalently bonded to the naphthalene core. R1 -R4 can be independently a hydrogen. The identity of the two groups, R5 and R₆ bonded to the imide, independently of each other are not particularly limited to the extent that the compounds can be synthesized. In one embodiment, the R5 and R6 groups are the same groups. One example of the R5 and R6 group alkyl, including n-alkyl or branched alkyl, including for example, hexyl. Other examples include aryl, arylalkyl, and alkylaryl.

NDI compounds can be prepared from precursor compounds including, for example, naphthalene anhydride (NDA).

The naphthalene moiety in the NDI can be substituted on one or both of the carbocyclic aromatic rings comprising the naphthalene moiety. Four substitution sites are possible at the 2, 3, 6, and 7 positions of the NDI so there can be one, two, three, or four substituents. In addition, the one or both nitrogens of the imide groups in NDI can be also substituted. Substitution can promote solubility.

The naphthalene moiety in the NDI can be substituted on one or both of the carbocyclic aromatic rings comprising the naphthalene moiety with at least one stannyl substituent. The stannyl substituent can be represented by -SnR' 3. For example, the compound can have one stannyl substituent, or it can have two stannyl substituents.

In one embodiment, the NDI compound comprises at least one NDI moiety, whereas in another embodiment, the NDI compound comprises at least two NDI moieties, or at least three NDI moieties. Hence, for example, oligomers of NDI can be derivatized with one or more stannyl moieties.

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

In one embodiment, the NDI compound is represented by:

wherein X is H or a stannyl substituent; wherein each R is independently a C1-C30 normal, branched, or cyclic alkyl, aryl, heteroaryl, alkyl-aryl, or alkyl-heteroaryl group optionally substituted with one or more halide, cyano, alkyl, or alkoxy groups; and wherein each of the R' moieties is independently an alkyl or aryl moiety. In another embodiment, each R is independently an optionally substituted C1 -C30 alkyl moiety and each of the R' moieties is independently a C1-C20 alkyl moiety.

In another embodiment, the compound is represented by:

(Π) wherein each R is independently a C 1-C30 normal, branched, or cyclic alkyl, aryl, heteroaryl, alkyl-aryl, or alkyl-heteroaryl group optionally substituted with one or more halide, cyano, alkyl, or alkoxy groups; and wherein each of the R' moieties is independently an alkyl or aryl moiety. In another embodiment, each R is independently an optionally substituted C1 -C30 alkyl and each of the R' moieties is independently a C1 -C20 alkyl moiety.

In another embodiment, the compound is represented by:

(III) wherein each R is independently a C1-C30 normal, branched, or cyclic alkyl, aryl, heteroaryl, alkyl-aryl, or alkyl-heteroaryl group optionally substituted with one or more halide, cyano, alkyl, or alkoxy groups; and wherein each of the R' moieties is independently an alkyl or aryl moiety. In another embodiment, each R is independently an optionally substituted C1 -C30 alkyl and each of the R' moieties is independently a C1-C20 alkyl moiety.

Furthermore, as described in US provisional application 61/475,888 filed April 15, 201 1 , the Applicants have unexpectedly discovered a ready and practical method for making naphthalene diimide organotin compounds (NDI-tin compounds) having the structure;

(IV) wherein

(a) R¹ and R¹ are independently selected from a C1 -C30 normal, branched, or cyclic alkyl, aryl, heteroaryl, alkyl-aryl, or alkyl-heteroaryl group optionally substituted with one or more halide, cyano, alkyl, or alkoxy groups,

(b) R², R³, and R⁴ are independently selected from hydrogen, halide, or a C1-C30 organic group independently selected from cyano, normal, branched, or cyclic alkyl, perfluoroalkyl, aryl, heteroaryl, alkyl-aryl, and alkyl-heteroaryl groups, optionally substituted with one or more fluoro, cyano, alkyl, alkoxy groups; and

(c) R⁹ is an alkyl or aryl group.

Such novel NDI-organotin compounds are highly useful in well known palladium catalyzed coupling reactions for making novel NDI-hAr oligomers, wherein hAr is, for example, an electron withdrawing heteroaryl group. There are a few examples in the art (see for example WO 2009/144205 and WO 2009/144302) to make PDI oligomers coupled to electron rich hAr groups, by coupling an electron withdrawing PDI bromide with an electron rich and nucleophilic organotin hAr precursor compound. But such coupling reactions typically fail if an electron withdrawing hAr group is employed. No starting NDI organotin compounds have (to Applicants' knowledge) been previously reported, so as to enable an "inverse" coupling method for the synthesis of NDI-hAr-NDI compounds with electron withdrawn hAr substituents.

Applicants' unexpected discovery (further described herein) of a method for synthesizing the novel NDI-organotin precursor compounds enables use of "inverted" coupling reactions for the synthesis of NDI-hAr-NDI oligomers having electron withdrawn hAr heteroaryl bridging groups, a class of NDI oligomer compounds with lower lying LUMOs (low lying LUMOs have been correlated in the art with improved air and water stability).

In many embodiments, the R¹, R¹ , R², R³, and R⁴ groups of the NDI organotin compounds can be any of the same groups as disclosed for the NDI-hAr-NDI oligomers as described in US provisional application 61/475,888. In some embodiments, R¹ and R¹ are independently a C1-C30 normal or branched alkyl or fluoroalkyl group. In some embodiments, R², R³, and R⁴ are independently selected from hydrogen, fluoro and cyano. In many embodiments, R⁹ is a C1 -C12 alkyl group.

PART IB. METHODS OF MAKING NDI-Sn COMPOUNDS

Also described herein are methods of making the compounds described in Part IA. For example, another embodiment provides for a method comprising: reacting at least one first naphthalene diimide (NDI) precursor compound with at least one tin reagent to form at least one first NDI compound comprising at least one stannyl substituent bonded to the naphthalene moiety of the NDI compound. Precursor compounds are described further below.

Tin reagents and organotin reagents are known in the art. For example, the tin reagent can be an alkyltin or aryltin reagent and preferably, an alkyltin reagent. The tin reagent can provide the tin moiety in the NDI compounds described in Part IA including formulas I, II, III, and IV. The tin reagent can comprise two tin atoms per molecule (a "ditin" compound) such as, for example, R^Sn-SnR^ wherein R' is independently alkyl or aryl and preferably alkyl. The R' alkyl group can be, for example, a C1-C20 alkyl group including, for example, methyl or butyl (including n-butyl). In one example, the tin reagent is a hexabutyl ditin reagent.

In one embodiment, the tin reagent is not a halogen tin reagent. For example, tin reagents are known which can be represented by X-SnR'₃, wherein X is a halogen. However, such reagents can be excluded.

For one embodiment, in the reacting step, only one NDI precursor compound is reacted with the at least one tin reagent.

However, mixtures of different NDI precursor compounds can be subjected to reaction with tin reagent, and this use of mixtures can provide important advantages. In another embodiment, in the reacting step, a mixture of two different NDI precursor compounds is reacted with the at least one tin reagent to form the at least one first NDI reaction product compound and also at least one second different NDI reaction product compound, wherein each of the first and second NDI compounds comprise at least one stannyl substituent bonded to the naphthalene moiety of the first and second NDI compounds.

In one embodiment, for example, the first NDI compound comprises one stannyl substituent and the second NDI compound comprises two stannyl substituents.

In one embodiment, the reacting step produces a mixture of the first and second different NDI reaction product compounds and the mixture is subjected to a separation procedure to separate the first and second NDI reaction product compounds.

In these reactions, as described in Part 1A, the first NDI compound can be represented by:

wherein X is H or a stannyl substituent; wherein each R is independently a C₁ -C30 normal, branched, or cyclic alkyl, aryl, heteroaryl, alkyl-aryl, or alkyl-heteroaryl group optionally substituted with one or more halide, cyano, alkyl, or alkoxy groups; and wherein each of the R' moieties is independently an alkyl or aryl moiety. In another embodiment, each R is independently an optionally substituted C₁ -C30 alkyl moiety and each of the R' moieties is independently a C₁-C₂0 alkyl moiety.

In one embodiment, the first NDI compound is represented by:

wherein each R is independently a C₁ -C30 normal, branched, or cyclic alkyl, aryl, heteroaryl, alkyl-aryl, or alkyl-heteroaryl group optionally substituted with one or more halide, cyano, alkyl, or alkoxy groups; and wherein each of the R' moieties is independently an alkyl or aryl moiety. In another embodiment, each R is independently an optionally substituted C1 -C30 alkyl and each of the R' moieties is independently a C1-C20 alkyl moiety.

In another embodiment, the first NDI compound is represented by:

wherein each R is independently a C1-C30 normal, branched, or cyclic alkyl, aryl, heteroaryl, alkyl-aryl, or alkyl-heteroaryl group optionally substituted with one or more halide, cyano, alkyl, or alkoxy groups; and wherein each of the R' moieties is independently an alkyl or aryl moiety. In another embodiment, each R is independently an optionally substituted C1-C30 alkyl and each of the R' moieties is independently a C1 -C20 alkyl moiety.

In another embodiment, the first NDI compound is represented by:

(IV), wherein

(a) R¹ and R¹ are independently selected from a C1-C30 normal, branched, or cyclic alkyl, aryl, heteroaryl, alkyl-aryl, or alkyl-heteroaryl group optionally substituted with one or more halide, cyano, alkyl, or alkoxy groups,

(b) R², R³, and R⁴ are independently selected from hydrogen, halide, or a C1 -C30 organic group independently selected from cyano, normal, branched, or cyclic alkyl, perfluoroalkyl, aryl, heteroaryl, alkyl-aryl, and alkyl-heteroaryl groups, optionally substituted with one or more fluoro, cyano, alkyl, alkoxy groups; and

(c) R⁹ is an alkyl or aryl group.

In addition, the below Scheme A illustrates a synthetic method starting from NDA precursor.

A B C

Scheme A In Scheme A, the three arrows can represent schematically three reaction steps which are needed to form the desired target: (i) halogenation of one or both of the naphthalene phenyl rings in compound A to allow introduction of the tin substituents to the naphthalene core, (ii) conversion of the two anhydride moieties in compound A (NDA) to the imide, and (iii) introduction of the tin moiety to the phenyl ring (replacing the halogen or halogens introduced in (i)). Starting from a single precursor compound A, the two tin reaction products, B and C, can be produced as a mixture and then separated, as illustrated in working example 2 below. In Scheme A, the imide R and tin R groups in B and C can be as described above in Parts 1A and IB, independently of each other. Purification steps can be carried out after step (iii).

In additional embodiments, NDI-organotin compounds can be made by a method comprising the steps of (a) providing or obtaining a monomeric naphthalene diimide compound substituted with a leaving group LG, and having the structure (V);

wherein LG is a halogen, such as Br or I, and (b) reacting the monomeric naphthalene diimide compound with a compound having the structure (R⁹)₃Sn-Sn(R⁹)₃, in the presence of a catalyst (typically soluble palladium compounds, such as the Stille coupling catalysts, i.e. Pd₂dba₃ and P(o-tol)3 ligand), and wherein R⁹ is an alkyl or aryl group, to form at least some of the naphthalene diimide organotin compounds.

This method for making isolatable quantities of the naphthalene diimide organotin compounds is unexpected. Without wishing to be bound by theory, it was expected that under such "Stille Coupling" conditions, the naphthalene diimide organotin compounds would be formed as a reaction intermediate, but would cross couple "in-situ" in a "Stille Coupling" with another mole of the leaving group substituted NDI, to generate an NDI-NDI dimer with directly coupled NDI groups. Unexpectedly, (especially in view of differing results with related perylenediimide compounds) the anticipated "dimerization" coupling reaction of bromide substituted NDI compounds did not proceed at a significant rate, but as a result the NDI organotin compounds can be isolated in good yield and used as synthetic intermediates to make other NDI-based materials. The nucleophilic NDI organotin compounds isolated from these unexpected reactions can however be readily coupled (in the presence of various appropriate palladium coupling catalysts well known to those of ordinary skill in the art) with other (less sterically hindered) bromide-substituted heteroaryl compounds, even if the brominated heteroaryl compounds are highly electron withdrawing, and enable the practical synthesis of NDI-hAr-NDI oligomers with electron withdrawn hAr bridging groups.

For introducing the tin substituents, the reacting step can be carried out under reaction conditions known in the art and illustrated by the working examples herein. For example, purification, temperature, pressure, atmosphere, solvent, reaction time, catalyst, and other reaction parameters can be controlled for a particular synthesis. Examples are provided below in the working examples. Reaction temperature can be, for example, 50°C to 150°C and reflux conditions can be used. Reaction time can be, for example, 3 h to 72 h. One or more organic solvents can be used such as an aromatic solvent like toluene. The catalyst materials can be introduced in one or more than one steps. Reaction yields can be, for example, at least 10%, at least 25%, or at least 50%.

Part II

One important embodiment is reaction of the NDI-tin compound with a rylene compound to result in a reaction product having the NDI moiety covalently bonded to a rylene moiety. Dimers, trimers, oligomers, and polymers can be made. Rylene compounds and moieties are known in the art. See, for example, Zhan et al., Adv. Mater., 201 1 , 23, 268-284 ("Rylene and Related Diimides for Organic Electronics"). A leading example of a rylene is the perylene group. NDI and perylene compound are known. See, for example, Organic Field-Effect Transistors, (Eds. : Bao, Locklin), CRC Press, 2007 including pages 194-197.

One example of a representation for rylene is below:

(Ry) wherein n can be, for example, 0, 1 , 2, 3, 4, or 5. In particular, when n is 0, the compound and moiety is known as a perylene or PDI. If n is 1 , then it can be called TDI; if n is 2, it can be called QDI; if n is 3, it can be called 5DI; if n is 4, it can be called HDI.

The Ry compound can be adapted to be a reactive compound to react with the NDI-Sn compounds, for example.

The R groups, R1 -R14, in formula (Ry) can be adapted as known in the art and can be selected independently of each other. They can be hydrogen or an organic group including a relatively non-reactive group or a reactive group. For example, R5 and R10 can be substituent groups which increase the solubility of the compound such as optionally substituted CI to C50 hydrocarbyl substituents such as optionally substituted alky or aryl, whether linear or branched. In addition, each R can be independently a C 1 -C30 normal, branched, or cyclic alkyl, aryl, heteroaryl, alkyl-aryl, or alkyl-heteroaryl group optionally substituted with one or more halide, cyano, alkyl, or alkoxy groups.

Substituents Rl-4, R6-R9, and R1 1 -R14 can be, independently, hydrogen or a reactive group such as a halogen such as chlorine or a pseudohalogen. The reactive group can provide a nucleophilic or electrophilic site, but for reaction with NDI-Sn compounds, it can be an electrophilic site.

Embodiments for (Ry) when covalently bonded to an NDI compound include the R groups are independently H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted arylalkyl, or optionally substituted alkylaryl.

Reaction can be carried out at one or both sides of the rylene moiety.

In one embodiment, n is zero and R3 and R6 are each adapted to be reactive so that, for example, they can be a halogen like chlorine or a pseudohalogen. In another embodiment, n is zero and R3 and R6, as well as R2 and R7, are each adapted to be reactive so that, for example, they can be halogen like chlorine.

The following structure represents perylene, an example of a rylene structure:

The PDI formula is an example of the Ry formula wherein n is zero. It can be a reactive compound for reacting with NDI-Sn compounds.

Here, one, two, three, or four of the R2, R3, R6, and R7 substituents can be a reactive site by being, for example, a halogen such as chlorine or a pseudohalogen. If R3 and R6 are reactive, then one side of the perylene can react. If R2 and R7 are reactive, then both sides of the perylene can react.

In the PDI embodiments where the PDI moiety is covalently bonded to NDI moieties, the R groups can be, independently, H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted arylalkyl, or optionally substituted alkylaryl.

In addition, a rylene moiety such as, for example, a perylene moiety can be covalently bonded to an NDI structure as shown in the following representations based on the above PDI and NDI formulas:

As shown, one or two bonds can be used to covalently bond the NDI moiety to the perylene moiety.

In the NDI-PDI-I and NDI-PDI-II compounds, the R groups can be, for example, independently H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted arylalkyl, or optionally substituted alkylaryl.

NDI-PDI-NDI

In the NDI-PDI-NDI embodiments, the R groups can be, for example, independently H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted arylalkyl, or optionally substituted alkylaryl.

PDI-NDI-PDI

In the PDI-NDI-PDI embodiments, the R groups can be, for example, independently H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted arylalkyl, or optionally substituted alkylaryl. The optionally substituted R groups for the Ry, PDI, NDI-PDI-I, NDI-PDI-II, NDI-PDI-NDI, and PDI-NDI-PDI moieties independently can have, for example 1 to 30 carbons, or 1 to 20 carbons.

Hence, one embodiment provides a composition comprising at least one compound, wherein the compound comprises at least one NDI moiety which is covalently bonded to at least one rylene moiety. The rylene moiety can be, for example, a perylene moiety.

The ratio of the number of NDI and the number of rylene moieties can be varied. For example, one embodiment provides that the compound has one NDI moiety covalently bonded to one rylene moiety. In another embodiment, the compound comprises at least two NDI moieties, each one covalently bonded to the rylene moiety. In another embodiment, the compound comprises two NDI moieties which and one rylene moiety, wherein each of the two NDI moieties is covalently bonded to the rylene moiety. In another embodiment, the compound comprises at least two rylene moieties, each one covalently bonded to the NDI moiety. In another embodiment, the compound comprises two rylene moieties and one NDI moiety, and each of the two rylene moieties is covalently bonded to the NDI moiety. In another embodiment, the compound comprises at least two NDI moieties and at least two rylene moieties. In another embodiment, the compound comprises two NDI moieties and two rylene moieties. In one embodiment, the compound is represented by [rylene-NDI]_n, wherein n is 1 , 2, 3, 4, 5, or 6, or the composition comprises a mixture of said compounds. In each of these embodiments, the rylene moiety can be a perylene moiety.

Other embodiments relate to methods of making NDI-rylene compounds. For example, one embodiment provides a method comprising: reacting (i) at least one naphthalene diimide (NDI) compound comprising at least one stannyl substituent bonded to the naphthalene moiety of the NDI compound, with (ii) at least one rylene compound to form at least one reaction product compound, wherein the reaction product compound comprises at least one NDI moiety which is covalently bonded to at least one rylene moiety.

In one embodiment, the NDI compound has one stannyl substituent. In another embodiment, the NDI compound has two stannyl substituents.

In one embodiment, the stannyl substituent is -SnR'₃ wherein the R' groups, independently, are alkyl or aryl.

In one embodiment, the NDI compound is represented by:

wherein X is H or a stannyl substituent; wherein each R is independently a C 1 -C30 normal, branched, or cyclic alkyl, aryl, heteroaryl, alkyl-aryl, or alkyl-heteroaryl group optionally substituted with one or more halide, cyano, alkyl, or alkoxy groups; and wherein each of the R' moieties is independently an alkyl or aryl moiety. In one embodiment, each R is independently an optionally substituted C 1 -C30 alkyl moiety and each of the R' moieties is independently a C 1 -C20 alkyl moiety.

In another embodiment, the NDI compound is represented by:

wherein each R is independently a C1-C30 normal, branched, or cyclic alkyl, aryl, heteroaryl, alkyl-aryl, or alkyl-heteroaryl group optionally substituted with one or more halide, cyano, alkyl, or alkoxy groups; and wherein each of the R' moieties is independently an alkyl or aryl moiety. In one embodiment, each R is independently an optionally substituted C 1 -C30 alkyl moiety and each of the R' moieties is independently a C 1 -C20 alkyl moiety.

In another embodiment, the NDI compound is represented by:

wherein each R is independently a C1-C30 normal, branched, or cyclic alkyl, aryl, heteroaryl, alkyl-aryl, or alkyl-heteroaryl group optionally substituted with one or more halide, cyano, alkyl, or alkoxy groups; and wherein each of the R' moieties is independently an alkyl or aryl moiety. In one embodiment, each R is independently an optionally substituted C 1 -C30 alkyl moiety and each of the R' moieties is independently a C 1 -C20 alkyl moiety.

In each of these embodiments, the rylene compound can be, for example, a perylene compound.

Part III

APPLICATIONS

The compositions, compounds, and materials described herein can be used in a variety of organic electronic applications including, for examples, field-effect transistors, OLEDs, displays, lighting, photovoltaic cells, sensors, RFID, light-emitting transistors, and the like. Vacuum deposition and solution processing can be carried out. Combinations of vacuum and solution processing can be carried out. Inks can be formulated with use of solvents and additives. Inkjet printing can be used.

Organic field-effect transistors are described in, for example, Organic Field-Effect Transistors, (Eds. : Bao, Locklin), CRC Press, 2007 including sections 2. 1 , 2.2, 2.3, 3. 1 , and 5.3.

Mobility and on-off ratios can be measured.

The electron mobility value can be, for example, at least 0. 1 , or at least 0.2, or at least 0.3 cmW .

N-channel organic transistors can be made.

WORKING EXAMPLES

Additional embodiments are provided in the following non-limiting working examples.

PART I. EXAMPLE A- l : PREPARATION OF COMPOUNDS 3, 4 Scheme 1. Preparation of stannyl NDI derivatives.

1 : X = H 3: X = H (Yield 90 %)

2: X = Br 4: X = SnBu₃ (Yield 48%)

N,/v^r'-di(«-hexyl)-2-tri-(«-butyl)stannylnaphthalene- l ,4,5,8-bis(dicarb oximide), 3, and

A ,A^'-di(«-hexyl)-2,6-bis(tri(«-butyl)stannyl)naphthalene- l ,4,5,8-bis(dicarb oximide), 4, were obtained in good to moderate yields, respectively, according to Scheme 1. A mixture of of the appropriate mono- or dibromo derivative, 1 or 2, and hexabutylditin (1 eq per bromo substituent) was heated in toluene in the presence of Pd₂dba3 (0.05 eq per bromo) and P(o-tol)3 (0.2 eq per bromo). Purification of the reaction products by silica gel chromatography and recrystallization from methanol afforded the mono- and distannyl derivatives as long yellow needles; these compounds were characterized by NMR spectroscopy, mass spectrometry, elemental analysis, and, in the case of 4, X-ray crystal structure.

In comparison, under identical conditions, the monobrominated perylene diimide (PDI) derivative undergoes homocoupling to yield the bi-PDI product and the stannyl PDI intermediate could not be isolated.

The ability to isolate and thoroughly purify the distannyl derivative is important for applications in conjugated-polymer syntheses, where the ability to obtain high-molecular-weight material is critically dependent on precise control of monomer stoichiometry.

EXAMPLE A-2 : ALTERNATIVE PREPARATION METHOD; SYNTHESIS OF 5 AND 6 Scheme 2. Preparation of stannyl NDI derivatives from commercially available NDA.

The different chromatographic behavior of 3 and 4 (3: ¾ = 0.3 on silica, eluting with 1 : 1 dichloromethane / hexanes; 4: = 0.3 on silica, eluting with 1 : 10 dichloromethane / hexanes) suggested the possibility of carrying out this reaction using a mixture of mono- and dibromo species obtained from bromination and imidization of NDA, only purifying at the final stage. This transformation can indeed be carried out without separation of the mono- and difunctionalized intermediates to give isolated yields of mono- and distannyl derivatives of ca. 20% and 5%, respectively (when using 1 eq. DBI as the brominating agent). The relative yields can be somewhat tuned with respect to the brominating agent and yields of ca. 10% were obtained for both mono- and distannyl derivatives using 2. 1 eq. of DBI.

As shown in Scheme 2, in addition to 3 and 4, their N,N^"'-bis(«-dodecyl) analogues 5 and 6 have also been obtained in similar isolated yield. The dodecyl group can improve solubility compared to, for example, a hexyl group.

The facile separation of the highly soluble mono- and distannyl NDI products via column chromatography is an attractive alternative to the more difficult purification of that of the mono- and dibromo-NDI intermediates, such as 1 and 2, which are both less soluble in common organic solvents and less well-differentiated in Rf (0.4 and 0.3 for 1 and 2 on silica, eluting with dichloromethane). As such, a two-step isolation and purification of the brominated species followed by stannylation results in overall yields of ca. 9% and 2% for the mono- and distannyl NDI, respectively. SUPPLEMENTAL DESCRIPTION FOR EXAMPLES A-l AND A-2

1. Materials and General Methods

Materials. Starting materials were reagent grade and were used without further purification unless otherwise indicated. Solvents were dried by passing through columns of activated alumina (toluene, CH2CI2), by distillation from Na/benzophenone (THF), or were obtained as anhydrous grade from Acros Organics.

N,N'-Di(«-hexyl)naphthalene-l ,4,5,8-bis(dicarboximide), 9, was synthesized according to the literature: ( 1 ) Rademacher, A. ; Markle, 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. ML; Iverson, B. L. J. Am. Chem. Soc. 2006, 128, 7995.

Hexabutyltin was obtained from Sigma-Aldrich. Characterization. Chromatographic separations were performed using standard flash column chromatography methods using silica gel purchased from Sorbent Technologies (60 A, 32-63 μπι). ^!H and ^uC{^lH} NMR spectra were obtained on a Bruker AMX 400 MHz Spectrometer with chemical shifts referenced using the ^!H resonance of residual CHCI3 or the ¹³C resonance of CDCI3 unless otherwise indicated. Electrochemical measurements were carried out under nitrogen in dry deoxygenated 0.1 M tetra-«-butylammonium hexafluorophosphate in dichloromethane using a conventional three-electrode cell with a glassy carbon working electrode, platinum wire counter electrode, and a Ag wire coated with AgCl as pseudo-reference electrode. Potentials were referenced to ferrocenium/ferrocene by using decamethylferrocene (-0.55 V vs. ferrocenium / ferrocene) as an internal reference. Cyclic voltammograms were recorded at a scan rate of 50 mVs^~ . UV-vis-NIR spectra were recorded in 1 cm cells using a Varian Cary 5E spectrometer. Mass spectra were recorded on a Applied Biosystems 4700 Proteomics Analyzer by the Georgia Tech Mass Spectrometry Facility. Elemental analyses were performed by Atlantic Microlabs.

Fabrication of Thin-Film Transistors. The following provides an example for how to prepare an OFET. OFETs with bottom contact and top gate structure were fabricated on glass substrates (Eagle 2000 Corning). Au (50 nm) bottom contact source / drain electrodes were deposited by thermal evaporation through a shadow mask. The organic semiconductor layer was formed on the substrates by spin coating a solution prepared from l , l ',2,2'-tetrachloroethane ( 15 mg / mL) at 500 rpm for 10 sec and at 2000 rpm for 20 sec. A CYTOP (45 nm) / A1₂0₃ (50 nm) bi-layer was used as top gate dielectric. The CYTOP solution (CTL-809M) was purchased from Asahi Glass with a concentration of 9 wt.%. To deposit the 45-nm-thick fluoropolymer layer, the original solution was diluted with solvent (CT-solv.180) to have solution: solvent ratios of 1 :3.5. The CYTOP layers were then deposited by spin coating at 3000 rpm for 60 sec. AI2O3 (50 nm) films were deposited on CYTOP layers by atomic layer deposition (ALD) at 1 10 °C using alternating exposures of trimethyl aluminum and H2O vapor at a deposition rate of approximately 0.1 nm per cycle. All spin coating and annealing processes were carried out in a N₂-filled dry box. Finally, Al ( 150 nm) gate electrodes were deposited by thermal evaporation through a shadow mask. All current-voltage (I-V) characteristics were measured with an Agilent E5272A source/monitor unit in a N₂-filled glove box (0₂, H₂0 < 0. 1 ppm).

Synthesis Supporting Examples A- l and A-2 :

1 : X = H 2: X = Br

A^7^'-Di(«-hexyl)-2-bromonaphthalene- l ,4,5,8-bis(dicarboximide), 1 , and A^_JV'-di(«-hexyl)-2,6-dibromonaphthalene- l ,4,5,8-bis(dicarboximide), 2.

A solution of naphthalene- 1 ,4, 5, 8-tetracarboxydianhydride (10.0 g,

59.5 mmol) in concentrated sulfuric acid (600 mL) was heated to 85 °C. After 30 min, potassium dibromoisocyanurate ( 19.3 g, 59.5 mmol) was added portionwise and the mixture was allowed to stir at 85 °C for 20 h. The mixture was poured into ice water ( 1.5 L) and allowed to stir for 2 h, while allowing to warm to room temperature. The resulting yellow precipitate was collected by filtration, washed with methanol, and dried under vacuum ( 16.6 g). The yellow solid was transferred to a flask with glacial acetic acid (600 mL) and w-hexylamine ( 19.4 g, 0. 191 mol). The reaction mixture was refluxed for 20 min, allowed to cool overnight, and poured into methanol (1.5 L). The resulting precipitate was collected by filtration, washed with methanol, and dried under vacuum. The crude product was purified by column chromatography (silica, 3 :2 dichloromethane / hexanes). During column packing, a portion of a poorly soluble yellow solid was isolated and found to be 2 (3.91 g, 6.60 mmol, 18%). The first band from the column afforded additional 2 as a yellow solid (0.650 g, 1. 10 mmol, 21 % overall yield). The second band gave 1 as a white solid (1.35 g, 2.63 mmol, 7%).

Data for 1 : ^!H NMR (400 MHz, CDC1₃) δ 8.88 (s, 1 H), 8.77 (d, J = 7.6 Hz, 1 H), 8.72 (d, J = 7.6 Hz, 1 H), 4. 16 (t, J = 6.9 Hz, 2H), 4. 14 (t, J = 6.6 Hz, 2H), 1.71 (quint, J = 7. 1 Hz, 2H), 1.69 (quint , J = 7.6 Hz, 2H), 1.45-1.24 (m, 12H), 0.87 (t, J = 7.0 Hz, 6H). ¹³C{^!H} NMR (100 MHz, CDC1₃) 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 (one aliphatic resonance not observed, presumably due to overlap). HRMS (EI) m/z calcd for C₂₆H2₉BrN₂0₄ (M⁺), 512.1311; found, 512.1280. Anal. Calcd. for C₂6H₂₉BrN₂0₄: C, 60.82; H, 5.69; N, 5.46. Found: C, 59.91; H, 5.60; N, 5.36.

Data for 2: ^lH NMR (400 MHz, CDCI3): δ 8.98 (s, 2H), 4.17 (t, J = 7.8 Hz, 4H), 1.72 (quint., J = 7.8 Hz, 4H), 1.49-1.20 (m, 12H), 0.88 (t, J =

7.1 Hz, 6H).¹³C{^lU} NMR (100 MHz, CDC1₃) 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 C₂₆H₂₈Br₂N₂0₄ (M⁺), 590.0416; found, 590.0394.

Anal. Calcd. for C₂₆H₂₈Br₂N₂0₄: C, 52.72; H, 4.76; N, 4.73. Found: C, 52.71; H, 4.69; N, 4.70.

1 3 V,N'-Di(«-hexyl)-2-tri(«-butyl)stannylnaphthalene-l,4,5,8-bis(dicarbo ximide), 3, from 1.

A solution of 1 (1.45 g, 2.82 mmol), 1,1,1,2,2,2-hexabutyldistannane

(1.64 g, 2.82 mmol), and tri-o-tolylphosphine (0.172 g, 0.565 mmol) in dry toluene (30 mL) was deoxygenated with nitrogen for 5 min. Tris(dibenzylideneacetone)dipalladium (0.129 g, 0.141 mmol) was added and the reaction was heated to 90 °C for 24 h. After cooling, the reaction mixture was precipitated in methanol (100 mL), the solid was removed via filtration, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography (silica, dichloromethane) to yield a yellow solid (1.53 g, 2.11 mmol, 75%). ^lH NMR (400 MHz, CDC1₃) δ 8.94 (s, 1H), 8.70 (d, J = 7.6 Hz, 1H), 8.67 (d, J = 7.6 Hz, 1H), 4.18 (t, J = 7.6 Hz, 2H), 4.16 (t, J = 8.0 Hz, 2H), 1.75-1.64 (m, 4H), 1.55-1.45 (m, 6H), 1.40-1.23 (m, 18H), 1.19 (t, J= 8.2 Hz, 6H), 0.90-0.80 (m, 15H). ^uC{^lH} NMR (100 MHz, CDCI3) 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 CssHseNzC^Sn (M⁺), 725.3340; found, 725.3325. Anal. Calcd. for C₃8H56N₂0₄Sn: C, 63.08; H, 7.80; N, 3.87. Found: C, 62.81; H, 7.99; N, 3.93.

N,7 '-Di(«-hexyl)-2,6-bis(tri(n-butyl)stannyl)naphthalene-l,4,5,8-bis( dicarboximide), 4, from 2.

A solution of 2 (0.500 g, 0.844 mmol), 1,1,1,2,2,2-hexabutyldistannane (1.00 g, 1.73 mmol), and trio-tolylphosphine (0.051 g, 0.169 mmol) in dry toluene (10 mL) was deoxygenated with nitrogen for 5 min.

Tris(dibenzylideneacetone)dipalladium (0.039 g, 0.042 mmol) was added and the reaction was heated to 90 °C for 24 h. Additional portions of tri-o-tolylphosphine (0.051 g, 0.169 mmol) and tris(dibenzylideneacetone)dipalladium (0.039 g, 0.042 mmol) were added and the reaction was stirred at 90 °C for an additional 2 d. After cooling, the reaction mixture was filtered through a plug of silica gel eluting with chloroform / hexanes ( 1 : 1) and the solvent was removed under reduced pressure. The crude product was recrystallized from methanol to yield a yellow solid (0.407 g, 0.402 mmol, 48%). ^lU NMR (400 MHz, CDC1₃) δ 8.92 (s, 2H), 4. 18 (t, J = 7.4 Hz, 4H), 1.68 (quint, J = 7.5 Hz, 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). ^uC{^lH} NMR ( 100 MHz, CDC1₃) δ 165. 12, 163.82, 154.61 , 138.04, 131.84, 126.90, 123. 1 1 , 40.92, 31.53, 29.22, 28.08, 27.39, 26.69, 22.49, 14.02, 13.69, 1 1.54. MS (MALDI) m/z 898.3 (M-(C₄H₉)₂ ²⁺). Anal. Calcd. for C50H82N5O4S112: C, 59.31 ; H, 8.16; N, 2.77. Found: C, 59.30; H, 7.98; N, 2.83.

X¹ = H, Br 3: X² = H

4: X² = SnBu₃ 3 and 4 from naphthalene- 1 ,4, 5, 8 -tetracarboxydi anhydride.

A solution of naphthalene- 1 ,4, 5, 8-tetracarboxydianhydride (NDA) (5.00 g, 18.6 mmol) in concentrated sulfuric acid ( 180 mL) was heated to 55 °C. In a separate flask, potassium dibromoisocyanurate (6.06 g, 18.6 mmol) was dissolved in concentrated sulfuric acid (90 mL) while stirring at room temperature for 1 h. Once dissolved, the solution was added to the reaction flask and the mixture was allowed to stir at 85 °C for 48 h. The mixture was poured into ice water (1 L) and allowed to stir for 2 h, while warming to room temperature. The resulting yellow precipitate was collected by filtration, washed with methanol, and dried under vacuum (4.51 g). The yellow solid was transferred to a flask with glacial acetic acid (100 mL) and «-hexylamine (7.2 g, 71. 1 mmol). The reaction mixture was refluxed for 2 h, allowed to cool overnight, and poured into methanol (1 L). The resulting precipitate was collected by filtration, washed with methanol, and dried under vacuum (5.51 g). The orange solid was transferred to a dry Schlenk flask with 1 , 1 , 1 ,2,2,2-hexabutyldistannane ( 1 1.3 g, 19.5 mmol), tri-o-tolylphosphine ( 1. 13 g, 3.71 mmol) and tris(dibenzylideneacetone)dipalladium (0.850 g, 0.930 mmol). The flask was pump-filled three times with nitrogen. Anhydrous toluene (80 mL) was added and the reaction was heated to 100 °C for 18 h. After cooling, the reaction mixture was diluted with hexanes ( 100 mL) and filtered through a plug of silica gel eluting with hexanes. Dichloromethane / hexanes ( 1 : 1 ) was used to elute the first yellow band (impure 4). The second yellow band was collected using dichloromethane as an eluent and was evaporated to give 3 as a yellow solid (2.60 g, 3.59 mmol, 19% overall yield from NDA). The first fraction was further purified by column chromatography (silica gel, 10: 1 hexanes / dichloromethane) to yield 4 a yellow solid (0.780 g, 0.770 mmol, 4% from NDA). *H NMR data were consistent with those obtained for 3 and 4 synthesized from 1 and 2, respectively.

X¹ = H, Br 5: X² = H

6: X² = SnBu₃ jV,jV'-Di(«-dodecyl)-2-tri(«-butyl)stannylnaphthalene- l ,4,5,8-bis(dicar boximide), 5, and V,N'-di(«-dodecyl)-2,6-bis(tri(«-butyl)stannyl)naphthalene-l ,4,5,8-bis(dic arboximide), 6, from naphthalene- 1 ,4, 5, 8-tetracarboxydianhydride. A solution of NDA (5.00 g, 1 8.6 mmol) in concentrated sulfuric acid ( 180 mL) was heated to 55 °C. In a separate flask, potassium dibromoisocyanurate (6.06 g, 18.6 mmol) was dissolved in concentrated sulfuric acid (90 mL) while stirring at room temperature for 1 h. Once dissolved, the solution was added to the reaction flask and the mixture was allowed to stir at 85 °C for 48 h. The mixture was poured into ice water (1 L) and stirred for 2 h, while allowing to warm to room temperature. The resulting yellow precipitate was collected by filtration, washed with methanol, and dried under vacuum (8.33 g). The yellow solid was transferred to a flask with glacial acetic acid ( 190 mL) and ft-dodecylamine ( 14.2 g, 76.4 mmol). The reaction mixture was refluxed for 2 h, allowed to cool overnight, and poured into methanol (1 L). The resulting precipitate was collected by filtration, washed with methanol, and dried under vacuum. The resultant orange solid (10.0 g) was transferred to a dry schlenk flask with 1 , 1 , 1 ,2,2,2-hexabutyldistannane ( 16.0 g, 27.6 mmol), tri-o-tolylphosphine ( 1.60 g, 5.26 mmol) and tris(dibenzylideneacetone)dipalladium ( 1.20 g, 1.31 mmol). The flask was pump-filled three times with nitrogen. Anhydrous toluene (60 mL) was added and the reaction was heated to 90 °C for 24 h. After cooling, the reaction mixture was diluted with hexanes, filtered through a plug of Celite, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography (silica gel): the first band was eluted using hexanes / dichloromethane (10: 1 ) and, on evaporation, gave a yellow oil (impure 6). The second band was eluted using hexanes / dichloromethane ( 1 : 1 ) and was evaporated to give 5 as a yellow solid (3.87 g, 4.34 mmol, 23% overall yield from NDA). The first yellow fraction was further purified by column chromatography (silica gel, 10: 1 hexanes / toluene) to yield pure 6 as a yellow oil ( 1.25 g, 1.06 mmol, 6% overall yield from NDA).

Data for 5 : ^lH NMR (400 MHz, CDC1₃) δ 8.95 (s, 1 H), 8.70 (d, J =

7.6 Hz, 1 H), 8.67 (d, J = 7.7 Hz, 1 H), 4. 18 (m, 4H), 1.78- 1.64 (m, 4H), 1.58- 1.45 (m, 6H), 1.40- 1. 15 (m, 48 H), 0.90-0.82 (m, 15H). ¹³0{Ή} NMR (100 MHz, CDC1₃) 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/z 893.5 (7 %, M⁺), 835.4 (100 %, M-(C₄H₉)⁺). Anal. Calcd. for C₅₀H₈₀N₂O₄S11: C, 67.33; H, 9.04; N, 3.14. Found: C, 67.40; H, 9.03; N, 3.13.

Data for 6: ^lH NMR (300 MHz, CDCI3) δ 8.93 (s, 2H), 4.19 (t, J= 7.2 Hz, 4H), 1.71 (quint., J = 7.3 Hz, 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). C{^lH} NMR (75 MHz, CDCI3) 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 (one aliphatic resonance not observed, presumably due to overlap). MS (MALDI) m/z 1066.4 (M-(C₄H₉)₂ ²⁺). Anal. Calcd. for C₆2H₁₀6N2O4Sn2: C, 63.06; H, 9.05; N, 2.37. Found: C, 62.87; H, 9.09; N, 2.32.

PART II: WORKING EXAMPLES

Additional embodiments are provided in the following non-limiting working examples.

Example B- 1

Synthesis Protocol:

(1) 0.4 mmol mono-stannum functionalized naphthalene - 3,4:9, 10-tetracarboxylic acid diimide and 0.4 mmol dichloro - perylene-3,4:9, 10-tetra carboxylic acid diimide were added in a reaction system, in which the syntheses of dichloro-perylene-3,4:9, 10 tetra carboxylic acid diimide was disclosed in Org. Lett., 2009, 1 1 , 3804- 3807; 0.04 mmol Pd(PPh₃)₄ and 0.08 mmol Cul were further added as catalyses; then 8 ml toluene was added as solvent under an inert-gas protection, heated to 100°C for 20h;

(2) After terminating the reaction, cooled to room temperature, evaporated solvents, separated and purified to obtain naphthalene - 3,4:9, 10 - tetra carboxylic acid diimide hybridizated perylene - 3,4:9, 10 - tetra carboxylic acid diimide compounds 3b and 3a, in which compound 3a was 159 mg green powder, yield being 33 %.

C78H76N408 1 H-NMR (CDC13, 400 MHz): δ =9.77 (s, 2H), δ =9.22,

9.20 (d, 2H), 5 = 9. 1 1, 9.09 (d, 2H), 5 =9.01 (s, 2H), 5 =7.55-7.51 (m, 2H), 5 =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): 1 196.7 Anal. Calcd for: 1 196.6.

Compound 3b, red powder, 1 10 mg, yield of 25 %

1H-NMR(CDC13, 400MHZ): 5 = 8.95-8.80 (m, 6H), 5 = 8.41 (s, 1H) , 5 = 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), 1.75-1.1 1 (m, 52H), 0.90-0.75 (m, 6H). MS (MALDI-TOF, m/z): C78H78N408: 1 198.7, Anal. Calcd for: 1 198.6.

Figures 1 -4 show characterization of compound 3a. Figures 5-8 show characterization of the compound 3b.

Example B-2

Synthesis Protocol:

(1) 0.4 mmol mono-stannum functionalized naphthalene - 3,4:7,8 tetra carboxylic acid diimide and 0.2 mmol tetrachloro perylene - 3,4:9, 10 - tetra carboxylic acid diimide were added in a reaction system reaction system. 0.04 mmol catalyse quantitative Pd(PPh₃)₄ was added, and then 8 mL toluene was added as solvent, under inert-gas protection, heated to 100°C, and reacted for 20h.

(2) After terminating the reaction, cooled to room temperature, evaporated solvents, separated and purified to obtain naphthalene - 3,4:9, 10 - tetra carboxylic acid diimide hybridizated perylene - 3,4:9, 10 - tetra carboxylic acid diimides compound 159 mg, purple powder, yield being 46 %.

1H-NMR(CDC13,400MHZ): 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, CiosHnoNeOii-

Figures 9-12 show characterization of compound 4a.

Example B-3

Synthesis Protocol:

(1) 0.4 mmol mono-stannum functionalized naphthalene - 3,4:7,8 tetrabasic carboxylic acid diimide and 0.2 mmol tetrachloro perylene - 3,4:9, 10 - tetrabasic carboxylic acid diimide were added in a reaction system. 0.04 mmol catalyse quantitative Pd(PPh₃)₄ was added, then 8 ml toluene was added as solvent, under inert-gas protection, heated to 100°C, reacted for 20h.

(2) After terminating the reaction, cooled to room temperature, evaporated solvents, separated and purified to obtain naphthalene - 3,4:9, 10 - tetrabasic carboxylic acid diimide hybridizated perylene - 3,4:9, 10 - tetrabasic carboxylic acid diimides compound, 150 mg purple powder, yield being 40 %.

MS(MALDI-TOF, m/z): 1783. 1, Anal.Calcd for: 1783.0, Ci i4Hi38N₆0i₂ 1 H-NMR(CDC13,400MHZ): 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).

Figures 13-16 show characterization of compound 4b. References

No admission is made that any of the references cited herein are prior art.

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Claims

1. A composition comprising at least one compound, wherein the compound comprises at least one NDI moiety which is covalently bonded to at least one rylene moiety.

2. The composition of claim 1 , wherein the compound has one NDI moiety covalently bonded to one rylene moiety.

3. The composition of claim 1, wherein the compound comprises at least two NDI moieties, each one covalently bonded to the rylene moiety.

4. The composition of claim 1, wherein the compound comprises two

NDI moieties which and one rylene moiety, wherein each of the two NDI moieties is covalently bonded to the rylene moiety.

5. The composition of claim 1 , wherein the compound comprises at least two rylene moieties, each one covalently bonded to the NDI moiety.

6. The composition of claim 1 , wherein the compound comprises two rylene moieties and one NDI moiety, and each of the two rylene moieties is covalently bonded to the NDI moiety.

7. The composition of claim 1, wherein the compound comprises at least two NDI moieties and at least two rylene moieties.

8. The composition of claim 1 , wherein the compound comprises two

NDI moieties and two rylene moieties.

9. The composition of claim 1, wherein the compound is represented by

[rylene-NDI]_n, wherein n is 1 , 2, 3, 4, 5, or 6, or the composition comprises a mixture of said compounds.

10. The composition of claim 1 , wherein the rylene moiety is a perylene moiety.

1 1. The composition of claim 1 , wherein the compound is represented by:

wherein optionally the R groups are independently H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted arylalkyl, or optionally substituted alkylaryl.

12. The composition of claim 1 , wherein the compound is represented by:

wherein optionally the R groups are independently H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted arylalkyl, or optionally substituted alkylaryl.

13. The composition of claim 1 , wherein the compound is represented by:

wherein optionally the R groups are independently H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted arylalkyl, or optionally substituted alkylaryl.

14. The composition of claim 1 , wherein the compound is represented by:

wherein optionally the R groups are independently H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted arylalkyl, or optionally substituted alkylaryl.

15. The composition of claim 1 , wherein the NDI' s imide nitrogen atoms have an alkyl substituent.

16. The composition of claim 1 , wherein the perylene' s imides nitrogen atoms have an alkyl substituent.

17. The composition of claim 13, wherein the NDI's imide nitrogen atoms have an alkyl substituent.

18. The composition of claim 13, wherein the perylene's imides nitrogen atoms have an alkyl substituent.

19. The composition of claim 14, wherein the NDI's imide nitrogen atoms have an alkyl substituent.

20. The composition of claim 14, wherein the perylene's imides nitrogen atoms have an alkyl substituent.

21. A method comprising:

reacting (i) at least one naphthalene diimide (NDI) compound comprising at least one stannyl substituent bonded to the naphthalene moiety of the NDI compound, with (ii) at least one rylene compound to form at least one reaction product compound, wherein the reaction product compound comprises at least one NDI moiety which is covalently bonded to at least one rylene moiety.

22. The method of claim 21 , wherein the NDI compound has one stannyl substituent.

23. The method of claim 21 , wherein the NDI compound has two stannyl substituents.

24. The method of claim 21 , wherein the stannyl substituent is -SnR'₃ wherein the R' groups, independently, are alkyl or aryl.

25. The method of claim 21 , wherein the NDI compound is represented by:

wherein X is H or a stannyl substituent; wherein each R is independently a C 1 -C30 normal, branched, or cyclic alkyl, aryl, heteroaryl, alkyl-aryl, or alkyl-heteroaryl group optionally substituted with one or more halide, cyano, alkyl, or alkoxy groups; and wherein each of the R' moieties is independently an alkyl or aryl moiety.

26. The method of claim 21 , wherein the NDI compound is represented by:

(Π) wherein each R is independently a C 1 -C30 normal, branched, or cyclic alkyl, aryl, heteroaryl, alkyl-aryl, or alkyl-heteroaryl group optionally substituted with one or more halide, cyano, alkyl, or alkoxy groups; and wherein each of the R' moieties is independently an alkyl or aryl moiety.

27. The method of claim 21 , wherein the NDI compound is represented by:

(III) wherein each R is independently a C1 -C30 normal, branched, or cyclic alkyl, aryl, heteroaryl, alkyl-aryl, or alkyl-heteroaryl group optionally substituted with one or more halide, cyano, alkyl, or alkoxy groups; and wherein each of the R' moieties is independently an alkyl or aryl moiety.

28. The method of claim 25 , wherein each R is independently an optionally substituted C1 -C30 alkyl moiety and each of the R' moieties is independently a C1 -C20 alkyl moiety.

29. The method of claim 26, wherein each R is independently an optionally substituted C1 -C30 alkyl moiety and each of the R' moieties is independently a C 1 -C20 alkyl moiety.

30. The method of claim 27, wherein each R is independently an optionally substituted C 1 -C30 alkyl moiety and each of the R' moieties is independently a C1 -C20 alkyl moiety.

31. The method of claim 21 , wherein the rylene compound is a perylene compound.

32. A device comprising the composition of claim 1 .

33. The device of claim 32, wherein the device is a field-effect transistor.

34. An ink composition comprising the composition of claim 1 , wherein the composition further comprises at least one solvent.