WO2013096924A1 - Oligomers and polymers and polymers and methods derived from stannyl derivatives of naphthalene diimides - Google Patents

Abstract

New rylene and naphthalene diimide oligomers and polymers prepared from precursor tin compounds. In particular, dimer and trimer structures are prepared and used in organic electronic devices including field-effect transistors. Electron transport and air-stability can be achieved.

Description

Oligomers and polymers and polymers and methods derived from stannyl derivatives of naphthalene diimides

RELATED APPLICATIONS

This application claims priority to US provisional application serial no. 61/579,608 filed December 22, 2011 and European application serial no.

12189299.6 filed October 19, 2012, the complete disclosures of which are each hereby incorporated by reference in their entirety.

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. 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) and organic photovoltaic cells (OPVs).

The N,N'-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) and optical spectra of these species. Moreover, core substitution can be used as a means of constructing more elaborate architectures such as conjugated oligomers or polymers and donor or acceptor functionalized products.

A need exists to develop better small molecule semiconductor which provide properties such as, for example, high mobility, electron transport, solution processability, and air stability. 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 an oligomer or polymer represented by:

wherein n is zero or an integer from 1 to 20 and the R groups, independently, are 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 R' groups are, independently 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.

In another embodiment, the oligomer or polymer is represented by:

wherein R, R' and n are previously defined. In another embodiment, the R' groups are hydrogen, cyano, chloride, fluoride, acyl or perfluoroalkyl. In another embodiment, n is zero or an integer 1-6. In another embodiment, n is zero or an integer 1. Other embodiments include a composition comprising at least one oligomer or polymer represented herein.

In another embodiment, the oligomer or polymer is such that at least one R' group is cyano. In particular, the oligomer can be such that at least one R' group is cyano.

In another embodiment, the oligomer or polymer is a polymer having a number average molecular weight of at least 5,000 Da, or at least 10,000 Da. Known, standard methods can be used to measure molecular weight including GPC.

Another embodiment provides a method comprising: reacting at least one first naphthalene diimide (NDl) compound comprising at least one stannyl substituent bonded to the naphthalene core in a coupling reaction with at least one second naphthalene diimide (NDl) compound comprising at least one halogenated substituent bonded to the naphthalene core to form at least one oligomer, polymer, or a combination thereof.

In one embodiment, the method is conducted as a one-pot homo-coupling, wherein the stannyl NDl compounds are formed in situ from the halogenated NDl compounds.

In another embodiment, the reacting step comprises at least two steps, wherein in a first step the first NDl compounds are formed by reaction of an NDl precursor compound and a tin reagent, and in the second step the first stannyl NDl compounds react in a cross-coupling reaction with the second halogenated NDl compounds to form at least one oligomer, polymer, or a combination thereof.

In another embodiment, the first NDl compound is represented by the structure:

wherein:

X is H, R' or a stannyl substituent;

R is 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;

R is 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, LG is a leaving group and R⁵ is 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 R is an alkyl or aryl group.

Another embodiment is that the resulting oligomer or polymer is represented by a compound or composition as described herein.

Another embodiment provides for an ink composition comprising at least one solvent and at least one compound or composition as described herein and the compound or composition made by a methods described herein.

Other embodiments include a device comprising at least one compound or composition as described herein, or the compound or composition made by a method described herein, wherein the device is optionally an OLED, OPV, OFET, or sensing device.

Other embodiments are for the use of an oligomer or polymer compound or composition as described herein, or the compound or composition made by a methods described herein, wherein the use is optionally as a semiconducting oligomer or polymer in an OLED, OPV, OFET, or sensing device.

Inks and devices also can be prepared from the compositions described herein. The devices can be, for example, organic electronic devices including, for example, OFET devices.

Applicants have unexpectedly discovered a simple and efficient method for making naphthalene diimide organotin compounds and NDI oligomers and polymers. Applicants new method for making them, can be readily homo- or cross-coupled with functionalized NDI compounds to provide oligomers or polymers that, for example, can be employed as novel and unexpectedly superior-performing and ambient-stable electron transport semiconductors. 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 and solution processing can be made.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1. UV-vis spectra in dichloromethane (top) and cyclic

voltammograms in dichloromethane / ⁿBu₄NPF6 (bottom) for compounds 7 and 8.

Figure 2. Normalized UV-vis spectra in dichloromethane for compounds 7,

8, and 9.

Figure 3. Normalized UV-vis spectra of a film spin-coated on glass for compounds 7, 8, and 9.

Figure 4. Output (left) and transfer (right) characteristics of a particular n- channel top-gate OFET with compound 7 as semiconductor and CYTOP/AI₂O₃ gate dielectric layer with Au source / drain electrodes (W/L= 2550 μητ/180 μιη).

Figure 5. Output (left) and transfer (right) characteristics of a particular n- channel top-gate OFET with compound 8 as semiconductor and CYTOP/AI₂O₃ gate dielectric layer with Au source / drain electrodes (W/L= 2550 μητ/180 μιη).

Figure 6a discloses normalized absorption of Poly (NDIC₁₂) in a film and in solution; Figure 6b shows a cyclic voltammogram of Poly (NDIC₁₂); Figure 6c shows thermal properties of Poly (NDIC₁₂) by thermogravimetric analysis (TGA) under nitrogen; Figures 6d and 6e show the transfer and output characteristics of a particular top-gate bottom-contact OFET of a device comprising Poly

(NDIC₁₂) respectively, with Au source/drain electrodes (W/L= 2550 μηι/180 μιη).

Figure 7a discloses normalized absorption of Poly (NDIC₈Cio) in a film and in solution; Figure 7b shows a cyclic voltammogram of Poly (NDIC₈Cio); Figure 7c shows thermal properties of QS-l -17c by thermogravimetric analysis (TGA) under nitrogen; Figures 7d and 7e show the transfer and output characteristics of a particular top-gate bottom-contact OFET of a device comprising Poly (NDIC₈Cio) respectively, with Au source/drain electrodes

DETAILED DESCRIPTION

INTRODUCTION

All references cited herein are incorporated by reference in their entirety. U.S. provisional applications 61/475,888 filed April 15, 201 1 to Polander et al; 61/579,608 filed December 22, 201 1 to Polander et al; 61/591 ,767 filed January 27, 2012 to Polander et al. are hereby incorporated by reference in their entirety including NDI-Sn compounds and methods of making NDI-Sn compounds.

The PhD thesis by Lauren Polander, 2011, "Organic Charge-Transport Materials Based on Oligothiophene and Napthalene Diimide: Towards

Ambipolar and n-Channel Organic Field-Effect Transistors," provides additional information about the presently claimed inventions.

Important synthetic methods which can be used as appropriate herein to prepare compounds are generally described in March 's Advanced Organic Chemistry, 6^th Ed., 2007.

As used herein, "halo" or "halogen" or even "halide" can refer to fluoro, chloro, bromo, and iodo.

As used herein, "alkyl" can refer to a straight-chain, branched, or cyclic saturated hydrocarbon group. Examples of alkyl groups include methyl (Me), ethyl (Et), propyl (e.g., n-propyl and iso-propyl), butyl (e.g., n-butyl, iso-butyl, sec-butyl, tert-butyl), pentyl groups (e.g., n-pentyl, iso- pentyl, neopentyl), and the like. In various embodiments, an alkyl group can have 1 to 30 carbon atoms, for example, 1-20 carbon atoms (i.e., C1-C20 alkyl group). In some embodiments, an alkyl group can have 1 to 6 carbon atoms, and can be referred to as a "lower alkyl group." Examples of lower alkyl groups include methyl, ethyl, propyl (e.g., n-propyl and iso-propyl), and butyl groups (e.g., n-butyl, iso-butyl, sec-butyl, tert-butyl). In some embodiments, alkyl groups can be substituted with 1-5 R¹ groups and R¹ is as defined herein.

As used herein, "haloalkyl" can refer to an alkyl group having one or more halogen substituents. At various embodiments, a haloalkyl group can have 1 to 20 carbon atoms, for example, 1 to 10 carbon atoms (i.e., C1-C10 haloalkyl group). Examples of haloalkyl groups include CF₃, C₂F₅, CHF₂, CH₂F, CCI₃, CHCI₂, CH₂C1, C₂CI₅, and the like. Perhaloalkyl groups, i.e., alkyl groups where all of the hydrogen atoms are replaced with halogen atoms (e.g., perfluoroalkyl groups such as CF₃ and C₂F₅), are included within the definition of "haloalkyl." As used herein, "alkoxy" can refer to -O-alkyl group. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy (e.g., n-propoxy and isopropoxy), t- butoxy groups, and the like. The alkyl group in the -O-alkyl group can be substituted with 1-5 R¹ groups and R¹ is as defined herein.

As used herein, "heteroatom" can refer to an atom of any element other than carbon or hydrogen and includes, for example, nitrogen, oxygen, silicon, sulfur, phosphorus, and selenium. As used herein, "heteroaryl" can refer to an aromatic monocyclic ring system containing at least one ring heteroatom selected from oxygen (O), nitrogen (N), sulfur (S), silicon (Si), and selenium (Se), or a polycyclic ring system wherein at least one of the rings present in the ring system is aromatic and contains at least one ring heteroatom. A heteroaryl group, as a whole, can have, for example, from 5 to 16 ring atoms and contain 1 -5 ring heteroatoms (i.e., 5-16 membered heteroaryl group). In some embodiments, heteroaryl groups can be substituted with one or more terminal R¹ groups, where R¹ is as defined herein. Both substituted and unsubstituted heteroaryl groups described herein can comprise between 1-30, or 1-20 carbon atoms, including the R¹ substituents.

As used herein, "aryl" can refer to a broad variety of unsaturated cyclic groups which can provide conjugation and derealization and can be fused and can be optionally substituted, as known in the art. Aryl groups with C₆ to C₄o or C₆ to C30 in carbon number can be used, for example.

PREPARATION OF NDI-Sn PRECURSOR COMPOUNDS

NDI oligomers and polymers made via the presently embodied methods can be prepared from NDI-tin compounds. These methods can be used to access a wide range of NDI compounds along with higher rylene compounds such as PDI and related perylene compounds. However, NDI compounds are the preferred moiety of the most embodiments.

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 2011/0269967; 2011/0269966; 2011/0269265;

2011/0266529; 2011/0266523; 2011/0183462; 2011/0180784; 2011/0120558; 2011/0079773; 2010/0326527; and 2008/0021220. Other examples can be found in, for example, 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"); 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, 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, 2009, 131, 8-9. In the present application, "NDI" and "NBI" are deemed equivalent. The core NDI structure can be called 1,4:5, 8-napthalenetetracarboxylic acid diimide.

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

(NDI)

Herein, at least one of the substituents R_ls 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. The identity of the two groups, R5 and 5 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. The R₅ and 5 bonded to the imide can be a broad range of organic groups. One example of the R₅ and 5 group alkyl, including n-alkyl or branched alkyl, including for example, hexyl. Cyclic alkyl structures can be also used. The R₅ and 5 groups can be optionally subsituted with groups such as, for example, halide, cyano, alkyl, and/or alkoxy.

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' . For example, the compound can have one stannyl substituent, or it can have two stannyl substituents.

The stannylated NDI compounds useful for synthesis of the embodiments herein include, but are not limited to the following embodiments:

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.

In one embodiment, the compound has one stannyl substituent. In another embodiment, the 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 comprises at least one NDI moiety. In another embodiment, the NDI compound comprises at least two NDI moieties.

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

In one embodiment, the compound is, or the compounds are, represented by:

wherein X is H or a stannyl substituent; wherein each R is independently a Ci- C₃o 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 Ci-C₃₀ alkyl moiety and each of the R' moieties is independently a C₁-C₂₀ alkyl moiety. In one embodiment, the 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 C₁-C₃₀ alkyl moiety and each of the R' moieties is independently a C₁-C₂₀ alkyl moiety.

In one embodiment, the 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.

Another embodiment provides for naphthalene diimide organotin compounds having the stru

wherein R¹ and R¹ are independently selected from a C₁-C30 normal, branched, or cyclic alkyl, aryl, heteroaryl, alkyl-aryl, or alkyl-heteroaryl group optionally

2 3 substituted with one or more halide, cyano, alkyl, or alkoxy groups; R , R , 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 R⁵ is an alkyl or aryl group. In one embodiment, 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. In one embodiment, one or more of R², R³, and R⁴ are optionally Sn(R⁵)₃.

In one embodiment, R¹ is a C₁-C30 normal or branched alkyl or fluoroalkyl

2 3 4

group. In another embodiment, R , R , and R are independently selected from hydrogen, fluoro and cyano. In another embodiment, R⁹ is a C₁-C₁₂ alkyl group.

In another embodiment, the NDI-tin compound is represented by the structure (Γ):

(Γ)

wherein R¹ and R¹ are independently selected from a C₁-C30 normal, branched, or cyclic alkyl, aryl, heteroaryl, alkyl-aryl, or alkyl-heteroaryl group optionally

2 3 substituted with one or more halide, cyano, alkyl, or alkoxy groups; R , R , 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.

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.

Formation of the NDI-organotin starting materials can be made, for example, 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 R¹, R¹ are independently selected from a C₁-C30 normal, branched, or cyclic alkyl, aryl, heteroaryl, alkyl-aryl, or alkyl -heteroaryl group optionally

2 3 substituted with one or more halide, cyano, alkyl, or alkoxy groups; R , R , 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 LG is a halogen, such as Br or I; and (b) reacting the monomeric naphthalene diimide compound with a compound having the structure (R⁵)₃Sn-Sn(R⁵)3, in the presence of a catalyst (typically soluble palladium compounds, such as the Stille coupling catalysts, e.g. Pd₂(dba)3 and P(o-tol)3 ligand), and wherein R⁵ is an alkyl or aryl group, to form at least some of the naphthalene diimide organotin compounds. In another embodiment, R of the monomeric naphthalene diimide compound of Step (a) is also LG.

In 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'₃Sn-SnR'3 wherein R' is independently alkyl or aryl and preferably alkyl. The R' alkyl group can be, for example, a Ci-C₂₀ alkyl group including, for example, methyl or butyl (including n-butyl). In one example, the tin reagent is a hexabutylditin 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.

PREPARATION OF NDI-HALOGEN PRECURSOR COMPOUNDS A first NDI-Sn compound can be coupled with at least one second naphthalene diimide (NDI) compound comprising at least one halogenated substituent bonded to the naphthalene core to form at least one oligomer, polymer, or a combination thereof. The at least one halogenated substituent bonded to the naphthalene core may be functionalized by methods known in the art. For example, functionalized NDIs are most effectively obtained through the selective bromination of naphthalene- 1,4: 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. See, e.g., Jones, B. A.; et al, Chem. Mater. 2007, 19, 2703; Guo, X.; et al, Org. Lett. 2008, 10, 5333; Roger, C; Wurthner, F., J. Org. Chem. 2007, 72, 8070. NDA can also be brominated using Br₂ in concentrated sulfuric acid or oleum. See, e.g., Jones, B. A.; et al, Chem. Mater. 2007, 19, 2703; Gao, X.; et al., 0rg. Lett. 2007, 9, 3917. In one embodiment, the at least one second naphthalene diimide (NDI) compound comprising at least one halogenated substituent bonded to the naphthalene core is represented by the structure (V):

(V)

wherein R¹, R¹ are independently selected from a C₁-C30 normal, branched, or cyclic alkyl, aryl, heteroaryl, alkyl-aryl, or alkyl-heteroaryl group optionally

2 3 substituted with one or more halide, cyano, alkyl, or alkoxy groups; R , R , 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 LG is a halogen, such as Br or I.

In another embodiment, the at least one second naphthalene diimide (NDI) compound comprising at least one halogenated substituent bonded to the naphthalene core is represented by a precursor of the NDI-Sn compounds represented by formulas (I)-(IV).

METHODS OF MAKING NDI OLIGOMERS AND POLYMERS

NDI oligomers and polymers of the present embodiments can be prepared via homo- or cross-coupling of the NDI-tin compounds described herein. In one embodiment, each repeat unit in the oligomer or polymer can be an NDI unit. In other embodiments, other types of non-NDI moieties can be used as well in combination with the NDI moiety. Polymers can be homopolymers or copolymers. As used herein, an oligomer can include a dimer, a trimer, a tetramer, and the like. The number of repeat units in the oligomer and polymer are not particularly limited if they can be synthesized. Solubility may in some cases limit synthesis. However, substituent groups can be introduced in some cases to provide solubility.

The NDI moiety can be bonded to other moieties, both other NDI moieties, other rylene moieities, and non-NDI moieties, which provide for conjugation and derealization of electrons. While NDI compounds are a preferred embodiment herein, higher rylene compounds such as PDI and related perylene compounds can be also functionalized with tin substituents and reacted to form additional compounds, such as the oligomers and polymers of the present embodiments.

Both compositions and methods are provided for NDI oligomers and polymers. The method steps described herein under "METHODS OF MAKING NDI-Sn PRECURSOR COMPOUNDS" can be used to prepare compounds useful for the synthesis of NDI oligomers and polymers.

For example, one embodiment provides a method comprising: reacting at least one first naphthalene diimide (NDI) compound comprising at least one stannyl substituent bonded to the naphthalene moiety of the NDI compound in a coupling reaction to form at least one oligomer, polymer, or a combination thereof.

As evidenced further in the Working Examples, a second halogenated compound, preferably bromo, can be present to couple with the at least one first naphthalene diimide (NDI) compound comprising at least one stannyl substituent. For example, an embodiment provides a method comprising:

reacting at least one first naphthalene diimide (NDI) compound comprising at least one stannyl substituent bonded to the naphthalene core in a coupling reaction with at least one second naphthalene diimide (NDI) compound comprising at least one halogenated substituent bonded to the naphthalene core to form at least one oligomer, polymer, or a combination thereof. In one embodiment the at least one halogenated substituent of the at least one second naphthalene diimide (NDI) compound is bromo. In one embodiment, the method is conducted as a one-pot homo-coupling, wherein the stannyl NDI compounds are formed in situ from the halogenated NDI compounds

Coupling reactions, such as, cross-coupling and homo-coupling reactions are known in the art, and the coupling reaction can be a homo-coupling reaction or a cross-coupling reaction.

Stille coupling reactions are known in the art. For example, an aryl compound comprising the tin substituent (NDI-Sn) can react with an aryl or heteroaryl compound comprising the halogen or pseudohalogen substituent, resulting in carbon-carbon bond formation. Conjugated and extended conjugated structures can be formed.

In one embodiment, the reacting step comprises at least two steps, wherein in a first step the first NDI compound is formed by reaction of an NDI precursor compound and a tin reagent, and in the second step the first NDI compound reacts in a coupling reaction to form at least one oligomer, polymer, or a combination thereof.

In one embodiment, the first NDI compound is reacted with at least one halogenated compound to form the at least one oligomer, polymer, or

combination thereof.

In one embodiment, the first NDI compound comprises one stannyl substituent, and in another embodiment, the first NDI compound comprises two stannyl substituents.

In another embodiment, the first NDI compound comprises a compound represented by at least one of formulas I to IV, or a NDI compound is

represented by the structure:

wherein

X is H, R' or a stannyl substituent;

R is 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;

R is 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, LG is a leaving group and R⁵ is 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

R is an alkyl or aryl group.

In one embodiment, the reacting step produces at least one dimer as the primary reaction product. In one embodiment, the reacting step produces at least one trimer as the primary reaction product. The stoichiometries of the reactions can be controlled as known in the art of organic synthesis and polymer chemistry.

In one embodiment, the reacting step produces at least one oligomer as the primary reaction product, whereas in another embodiment, the reacting step produces at least one polymer as the primary reaction product. The molecular weight of the oligomer can be, for example, 2,000 g/mol or less.

In one embodiment of the method, the first NDI compound is represented by any of the Sn-NDI compounds (I) to (V).

In one embodiment of the method, the oligomer or polymer is represented

which illustrates two end groups and optional backbone repeat moiety. The value n is not particularly limited as noted above but can be, for example, zero or an integer such as 1-20. In one embodiment, n is zero; in another embodiment, n is 1. In (VI), the R groups of the imides, independently, can be, for example, 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. In (VI), the naphthalene substituents R' can be, for example, independently 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.

In one embodiment, R' groups in (VI) are H. In one embodiment, R groups in (VI) are alkyl.

In another embodiment of the method, the reaction product oligomer or polymer is represented by any of the NDI oligomers or polymers in the section titled "NDI OLIGOMERS AND POLYMERS." The methods described herein can be used to make the oligomers and polymers described herein. These oligomers and polymers can be used in inks, devices, and optionally as a conductive oligomer or polymer in an OLED, OPV, OFET, or sensing device, as described further herein.

NDI OLIGOMERS AND POLYMERS

Oligomeric and polymeric NDI compounds are described herein. In many cases, these compounds can be synthesized from the methods described herein, and can comprise the optionally-substituted stannylated NDI compounds described herein. For example, the NDI-organotin compounds can be used to form oligomer and polymer compounds of the generic structure:

which illustrates two end groups and optional backbone repeat moiety. The value n is not particularly limited as noted above but can be, for example, zero or an integer such as 1-20. In one embodiment, n is zero; in another embodiment, n is 1. In (VI), the R groups of the imides, independently, can be, for example, 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. In (VI), the naphthalene substituents R' can be, for example, independently 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.

In one embodiment, R' groups in (VI) are H. In one embodiment, R groups in (VI) are alkyl.

One embodiment provides for a oligomer or polymer of Formula (VI) wherein R and R' can correspond to any of the correspondingly positioned substituents of the stannylated NDI compounds of Formulas (I)-(V), and n can be, for example, zero or an integer 1-20.

In one embodiment, n is zero or 1-6. In another embodiment, n is zero or an integer 1 or 2. In another embodiment, n is zero or an integer 1.

Another embodiment provides that the oligomer or polymer is represented

wherein the R groups independently are 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 n is an integer of at least 1.

Another embodiment provides that the oligomer or polymer is represented by:

wherein n is an integer 1-21 and the R groups, independently, are 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.

In one embodiment, n is zero or 1-6. In another embodiment, n is 1 or 2. One embodiment provides a composition comprising at least one oligomer or polymer represented by any of the NDI oligomers or polymers embodied herein.

In the working examples, compounds 7 and 8 are a dimer and a trimer, respectively. The oligomers and polymers, including structures such as 7 and 8, can be further functionalized if desired. Compound 9 is the NDI monomer of 7 or 8.

Again, while NDI compounds are a preferred embodiment herein, higher rylene compounds such as PDI and related perylene compounds can be also functionalized with tin substituents and reacted to form additional compounds, such as oligomers and polymers, for use in, for example, organic electronic devices. Rylene compounds and moieties are known in the art. See, for example, Zhan et al, Adv. Mater., 2011, 23, 268-284. Besides NDI and PDI, other known rylene compounds include TDI, QDI, 5DI, and HDI, for example.

APPLICATIONS AND USE OF OLIGOMERS AND POLYMERS

References cited herein relate to applications of the compounds and materials. For example, 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, light emitting transistors, and the like. Vacuum deposition and solution processing can be carried out. One embodiment provides for a device comprising at least one compound or composition or of a compound or composition made by a method embodied herein. The device is optionally an OLED, OPV, OFET, or sensing device. Another embodiment provides for a use at least one compound or composition or of a compound or composition made by a method embodied herein, wherein the use is optionally as a semiconducting oligomer or polymer in an OLED, OPV, OFET, or sensing device.

Inks can be formulated with use of solvents and additives. One

embodiment provides for an ink composition comprising at least one solvent and at least one NDI oligomer or polymer compound, composition or compound or composition made by a method embodied herein.

The working examples below provide further embodiments for applications and performance parameters.

The devices may be flexibile, and are generally known in the art. OFETs are an important application including use of flexible and/or polymeric substrates. For example, N-channel organic transistors can be made. The electron mobility value can be, for example, at least 0.1, or at least 0.2, or at least 0.3 cmVS^"1.

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

WORKING EXAMPLES 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. A ,N'-Di(n-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. M.; 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 μιη). 1H and ¹³C{¹H} NMR spectra were obtained on a Bruker AMX 400 MHz Spectrometer with chemical shifts

1 13 referenced using the H resonance of residual CHCI₃ or the C resonance of CDCI₃ unless otherwise indicated. Electrochemical measurements were carried out under nitrogen in dry deoxygenated 0.1 M tetra-n-butylammonium

hexaf uorophosphate 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 ¹. 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. 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 1,1 ',2,2'- tetrachloro ethane (15 mg / mL) at 500 rpm for 10 sec and at 2000 rpm for 20 sec. A CYTOP (45 nm) / AI₂O₃ (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 110 °C using alternating exposures of trimethyl aluminum and H₂0 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).

2. Synthetic Details

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

2: X = Br 4: X = SnBu₃ (Yield 48%)

A ,N'-di(/7-hexyl)-2-tri-(/?-butyl)stannylnaphthalene-l, 4,5,8- bis(dicarboximide), 3, and N,N'-di(/?-hexyl)-2,6-bis(tri(/?- butyl)stannyl)naphthalene-l,4,5,8-bis(dicarboximide), 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 2: ALTERNATIVE PREPARATION METHOD; SYNTHESIS OF

5 AND 6

Scheme 2. Preparation of stannyl NDI derivatives from commercially available

NDA.

3: 4:

5: 6:

The different chromatographic behavior of 3 and 4 (3: R_f = 0.3 on silica, eluting with 1 : 1 dichloromethane / hexanes; 4: R_f = 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 R_f (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.

EXAMPLE 3 : PREPARATION OF OLIGOMERS 7 AND 8

As an example of the utility of stannyl NDI derivatives as reagent for cross-coupling with electron-poor moieties, we carried out stannyl-NDI / bromo- NDI cross-couplings to obtain NN',N",N' "-tetra(n-hexyl)-[2,2'-binaphthalene]- 1 ,4:5,8: 1 ',4' :5 ',8'-tetra(dicarboximide), 7, and Ν,Ν',Ν' ',Ν' ' ',Ν" ' ',Ν' ' ' ' '-hexa(n- hexyl)-[2,2' :6',2"-ternaphthalene]-l,4:5,8: l ',4' :5',8' : l ",4" :5",8" :- hexa(dicarboximide) 8 (Scheme 3). In addition to using the cross-coupling of 1 and 3 (Scheme 3, B), 7 was also obtained by the one-pot homo-coupling of 1 (Scheme 3, A) using 5.0 mol% of Pd(PPh₃)₄, 10 mol% of Cul, and 0.5 eq.

hexabutylditin in hot toluene over 6 d, a reaction that presumably involves the in situ generation and reaction of 3. Purification of the reaction mixture by silica- gel chromatography and recrystallization from isopropanol afforded 7 in 25% yield. The cross-coupling of 1 and 3 was performed in the presence of 5.0 mol% of Pd(PPh₃)₄ and 10 mol% of Cul in hot toluene over only 3 h and afforded 7 in 59% yield after identical purification procedures.

Scheme 3. Preparation of bi- and ter-NDI derivatives.

The preparation of 8 was performed by cross-coupling of 1 and 4 in the presence of 5.0 mol% of Pd(PPh₃)₄ and 10 mol% of Cul in hot toluene over 15 h. Purification of the reaction mixture by silica-gel chromatography and

recrystallization from isopropanol afforded 8 in 56% yield.

EXAMPLE 4: OPTICAL AND ELECTROCHEMICAL PROPERTIES The optical and electrochemical properties of compounds 7 and 8 were compared to those of the corresponding monomeric parent NDI,

hexyl)naphthalene-l,4:5,8-bis(dicarboximide), 9. The UV-vis absorption spectra of 7 and 8 are similar in shape to that of 9 and the molar absorptivity, ε _max, increases with the number of NDI units, suggesting that each NDI sub-unit behaves largely independently of the other(s), consistent with inter-NDI steric interactions leading to significant deviation of the NDI sub-units from

coplanarity. However, the nonlinear increase of ε _max with the degree of oligomerization, some broadening seen in the spectra of 7 and 8, and the appearance of a distinct shoulder on the low-energy side of the main absorption of 8 indicates that there are some interactions, possibly excitonic coupling, between the NDI sub-units (differences in bandshape are more clearly seen in normalized spectra of 7, 8 and 9, see Figure 2). Additional UV-vis data are provided in Figure 3.

Cyclic voltammetry showed four reversible reduction waves for 7 and six reversible reduction waves for 8 corresponding to the sequential reduction of each NDI to the radical anions and then to dianions (Figure 1). No oxidation could be observed in the potential window investigated. The first halfwave reduction potentials are reported in Table 1. 7 and 8 are reduced at very similar potential to one another and at only marginally more anodic potential than the monomeric NDI, 9, suggesting no signifcant derealization of the charge between the NDI units, consistent with the picture of weakly interacting NDIs indicated by the optical data. The slight anodic shift in the oligomeric species is perhaps attributable to the inductive electron-withdrawing effect of one NDI upon another, while the separation between the multiple reductions is likely to be due to electrostatic effects, given the close proximity of the multiple redox centers.

Table 1. Opticaf and Electronic¹⁵ Properties of Mono-, Bi- and Ter-NDIs.

— OF— no. of NDI -max ¾nax ^max, solid Ί/2

Cpd

units / nm / 10⁴ ivr ¹ / nm / V

9 1 380 2.76 393 -1.13

7 2 381 4.10 388 -1.03

8 3 383 6.09 389 -1.00 ^a Optical properties measured in dichloromethane. Half- wave poten-tials determined by cyclic voltammetry in a solution of 0.1 M ⁿBu₄NPF₆ in dichloromethane vs FeCp₂ ^{+ 0}.

EXAMPLE 5 : FIELD-EFFECT TRANSISTOR PERFORMANCE Top-gate, bottom-contact geometry organic field-effect transistor devices were fabricated with a CYTOP / AI2O3 bilayer gate dielectric, 7 or 8 as the active layer and Au source / drain electrodes. The materials were spin-coated from 1 ,1 ',2,2'-tetrachloroethane solutions to yield devices with n-channel electrical

2 —1 —1 characteristics with moderate electron mobility values of up to 0.34 cm V s

2 —1 —1

and 0.014 cm V s for 7 and 8, respectively (see Figures 4 and 5). Although the mobility value measured for 7 is not state of the art for solution-processed n-

2 —1 —1

channel devices (ju_e = 1.5 cm V s ), it is an order of magnitude higher than the electron mobility reported for solution-processed devices based on an unsubstituted NDI core (μ_Β = 0.01 cn^v ¹). See Table 2.

2 —1 —1

Table 2. Saturation Electron Mobility Values (cm V s ), Threshold Voltages

(V), and Current On / Off Ratios for OFETs Based on 7 and 8. cmpd 'on / 'off

7 0.27 (± 0.04) 7.5 (± 0.5) 10⁴

8 0.010 (± 0.004) 12.5 (± 1.2) 10^{3 a}Average values are calculated based on 6 to 9 devices with W = 2550 and L = 180 μιη from a single substrate.

EXAMPLE 6: N,N',N",N" '-Tetra(/7-hexyl)-[2,2'-binaphthalene]- 1,4:5, 8: ,4':5',8'-tetra(dicarboximide), 7, from homocoupling of 1

A solution of 1 (1.00 g, 1.95 mmol), 1,1,1,2,2,2-hexabutyldistannane

(0.551 g, 0.950 mmol), and copper(I) iodide (0.018 g, 0.095 mmol) in dry toluene (20 mL) was heated to 50 °C to dissolve the reagents and deoxygenated with nitrogen for 5 min. Tetrakis(triphenylphosphine)palladium (0.055 g, 0.048 mmol) was added and the reaction was heated to 90 °C for 6 d while monitoring by TLC. After cooling, the reaction mixture was diluted with dichloromethane, filtered through a plug of Celite, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography (silica, dichloromethane) followed by precipitation in methanol to yield a yellow solid (0.202 g, 0.233 mmol, 25%). 1H NMR (400 MHz, CDC1₃) δ 8.83 (d, J= 7.6 Hz, 2H), 8.79 (d, J= 7.6 Hz, 2H), 8,43 (s, 2H), 4.17 (t, J= 7.6 Hz, 4H), 3.95-3.90 (m, 4H), 1.72 (quint., J= 7.6, 4H), 1.59-1.48 (m, 4H), 1.48-1.35 (m, 4H), 1.35- 1.27 (m, 8H), 1.27-1.13 (m, 12H), 0.87 (t, J= 6.9 Hz, 6H), 0.78 (t, J= 6.6 Hz, 6H). ¹³C{1H} NMR (100 MHz, CDC1₃) δ 162.76, 162.74, 162.51, 146.38, 132.28, 131.61, 130.86, 127.44, 126.80, 126.36, 126.15, 122.41, 41.03, 41.96, 31.46, 31.37, 27.99, 27.86, 26.70, 26.62, 22.50, 22.48, 14.01, 13.92 (two aromatic resonances not observed, presumably due to overlap). HRMS (MALDI) m/z calcd for C^H^Og (MH⁺), 867.4333; found, 867.4349. Anal. Calcd. For C₅2H₅₈N₄0₈: C, 72.03; H, 6.74; N, 6.46. Found: C, 71.77; H, 6.71; N, 6.43.

EXAMPLE 7: N,N',N",N" '-Tetra(/7-hexyl)-[2,2'-binaphthalene]- 1,4:5, 8: ,4':5',8'-tetra(dicarboximide), 7, from cross-coupling of 1 and 3

A solution of 1 (0.071 g, 0.138 mmol), 3 (0.095 g, 0.131 mmol), and copper(II) iodide (0.002 g, 0.013 mmol) in dry toluene (5 mL) was heated to 50 °C to dissolve the reagents and deoxygenated with nitrogen for 5 min.

Tetrakis(triphenylphosphine)palladium (0.008 g, 0.007 mmol) was added and the reaction was heated to 90 °C for 3 h while monitoring by TLC. After cooling, the reaction mixture was diluted with dichloromethane, filtered through a plug of Celite, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography (silica, dichloromethane) followed by recrystallization from isopropanol to yield 7 as a yellow solid (0.067 g, 0.077 mmol, 59%). The 1H NMR spectrum was consistent with that obtained for 7 synthesized by the homocoupling of 3.

EXAMPLE 8: N,N',N",N" ',N"",N"" '-Hexa(/7-hexyl)-[2,2' :6',2"- ternaphthalene]-l,4:5,8: l ',4' :5',8': l ",4":5",8"-hexa(dicarboximide), 8.

A solution of 1 (0.958 g, 1.87 mmol), 4 (0.900 g, 0.889 mmol), and copper(I) iodide (0.034 g, 0.178 mmol) in dry toluene (10 mL) was

deoxygenated with nitrogen for 5 min. Tetrakis(triphenylphosphine)palladium (0.102 g, 0.088 mmol) was added and the reaction was heated to 90 °C for 26 h while monitoring by TLC. After cooling, the reaction mixture was diluted with dichloromethane, filtered through a plug of Celite, and the solvent was removed under reduced pressure. The crude product was purified by column

chromatography (silica, dichloromethane to 3% methanol in dichloromethane) followed by recrystallization from isopropanol to yield 8 as a yellow solid (0.644 g, 0.496 mmol, 56%). 1H NMR (400 MHz, CDC1₃) δ 8.86 (d, J= 7.6 Hz, 2H), 8.81 (d, J= 7.6 Hz, 2H), 8.53 (d, J= 2.0 Hz, 2H), 8.46 (d, J= 3.7 Hz, 2H), 4.20 (t, J= 7.4 Hz, 4H), 4.45-3.88 (m, 8H), 1.85-1.69 (m, 4H), 1.67-1.55 (m, 8H), 1.48-1.40 (m, 4H), 1.38-1.30 (m, 8H), 1.30-1.15 (m, 24H), 0.87 (t, J= 7.1 Hz, 6H), 0.87-0.70 (m, 12H). ¹³C{1H} NMR (100 MHz, CDCI3) δ 162.81, 162.79, 162.77, 162.56, 162.49, 162.25, 146.34, 146.30, 132.92, 132.21, 131.68, 130.93, 127.48, 127.16, 126.86, 126.82, 126.43, 126.37, 126.28, 122.70, 122.46, 41.11, 41.02, 31.51, 31.42, 31.29, 28.05, 27.90, 28.87, 26.77, 26.73, 26.67, 26.63, 22.56, 22.52, 22.50, 14.05, 13.98, 13.95. HRMS (MALDI) m/z calcd for C₇8H₈7N₆Oi2 (MH⁺), 1299.6391; found, 1299.6382. Anal. Calcd. For

C₇₈H₈₆N₆Oi₂: C, 72.09; H, 6.67; N, 6.47. Found: C, 71.84; H, 6.56; N, 6.37.

Example 9

N,N^,,N^M,N^,M-Tetra(n-octyl)-[2,2^,-binaphthalene]-l,4:5,8:l^,,4^,:5^,,8'- tetra(dicarboximide). A solution of N,N'-di(n-octyl)-2-bromonaphthalene- 1 ,4,5,8-bis(dicarboximide) (0.569 g, 1.OOmmol) and N,N'-di(n-octyl)-2-tri(n- butyl)stannylnaphthalene-l,4,5,8-bis(dicarboximide) (0.780 g, 1.00 mmol) in dry toluene (11 mL) was heated to 50 °C to dissolve the reagents.

Tetrakis(triphenylphosphine)palladium (0.058 g, 0.05 mmol) and copper(I) iodide (0.019 g, 0.10 mmol) were added and the reaction was heated to 110 °C for 19 h while monitoring by TLC. After cooling, the reaction mixture was diluted with dichloromethane, filtered through a plug of Celite, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography (silica, dichloromethane) to yield a yellow solid (0.760 g, 78%). 1H NMR (300 MHz, CDC1₃) δ 8.88 (d, J = 7.5 Hz, 2H), 8.83 (d, J= 7.5 Hz, 2H), 8.44 (s, 2H), 4.19 (t, J= 7.5 Hz, 4H), 3.97-3.92 (m, 4H), 1.74 (quint., J= 7.4 Hz, 4H), 1.47-1.19 (m, 32H), 0.88-0.79 (m, 12H). ¹³C{1H} NMR (75 MHz, CDCI3) δ 162.75, 162.71, 162.48, 146.36, 132.28,131.60, 130.86, 127.42, 126.77,

126.33, 126.12, 122.40, 41.01, 31.77, 31.70, 29.26, 29.13, 28.08, 27.91, 27.06, 26.99, 22.61, 22.54, 14.07, 14.02 (two aromatic resonances not observed, presumably due to overlap). HRMS (MALDI) m/z calcd for C60H74N4O8 (MH+), 979.5585; found, 979.5600. Anal. Calcd. for C60H74N4O8: C, 73.59; H, 7.62; N, 5.72. Found: C, 73.35; H, 7.59; N, 5.62.

Example 1

N,N^,,N^M,N^,M-Tetra(n-decyl)-[2,2^,-binaphthalene]-l,4:5,8:l^,,4^,:5^,,8'- tetra(dicarboximide). A solution of N,N'-di(n-decyl)-2-bromonaphthalene- l,4,5,8-bis(dicarboximide) (0.624 g, 1.00 mmol) and N,N'-di(n-decyl)-2-tri(n- butyl)stannylnaphthalene-l,4,5,8-bis(dicarboximide) (0.836 g, 1.00 mmol) in dry toluene (11 mL) was heated to 50 °C to dissolve the reagents.

Tetrakis(triphenylphosphine)palladium (0.058 g, 0.05 mmol) and copper(I) iodide (0.019 g, 0.1 mmol) were added and the reaction was heated to 110 °C for 19 h while monitoring by TLC. After cooling, the reaction mixture was diluted with dichloromethane, filtered through a plug of Celite, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography (silica, dichloromethane) to yield a yellow solid (0.92 g, 84%). 1H NMR (300 MHz, CDC1₃) δ 8.83 (d, J= 7.6 Hz, 2H), 8.88 (d, J= 7.5 Hz, 2H), 8.83 (d, J= 7.5 Hz, 2H), 8.44 (s, 2H), 4.19 (t, J= 7.5 Hz, 4H), 3.97-3.92 (m, 4H), 1.74 (quint., J= 7.4, 4H), 1.47-1.19 (m, 48H), 0.88-0.79 (m, 12H).

1³C{1H} NMR (75 MHz, CDC1₃) δ 162.74, 162.69, 162.46, 146.36,

132.28,131.59, 130.85, 127.41, 126.77, 126.33, 126.12, 122.41, 41.03, 41.00, 40.98, 31.85, 31.82, 29.53, 29.50, 29.47, 29.31,29.27, 29.25, 29.22, 28.06, 27.93, 27.08, 27.01, 22.66, 22.62, 14.10, 14.07 (two aromatic resonances not observed, presumably due to overlap). HRMS (MALDI) m/z calcd for C68H90N4O8 (MH+), 1091.6837; found, 1091.6801. Anal. Calcd. for CegH^Og: C, 74.83; H, 8.31; N, 5.13. Found: C, 74.54; H, 8.25; N, 5.00.

Example 1

N,N^,,N^M,N^,M-Tetra(n-dodecyl)-[2,2^,-binaphthalene]-l,4:5,8:l^,,4^,:5^,,8'- tetra(dicarboximide). A solution of N,N'-di(n-dodecyl)-2-bromonaphthalene- l,4,5,8-bis(dicarboximide) (0.720 g, 1.06 mmol) and N,N'-di(n-dodecyl)-2-tri(n- butyl)stannylnaphthalene-l,4,5,8-bis(dicarboximide) (0.990 g, 1.11 mmol) in dry toluene (11 mL) was heated to 50 °C to dissolve the reagents.

Tetrakis(triphenylphosphine)palladium (0.060 g, 0.053 mmol) and copper(I) iodide (0.020 g, 0.106 mmol) were added and the reaction was heated to 90 °C for 19 h while monitoring by TLC. After cooling, the reaction mixture was diluted with dichloromethane, filtered through a plug of Celite, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography (silica, dichloromethane) to yield a yellow solid (0.522 g, 41%). 1H NMR (400 MHz, CDC1₃) δ 8.83 (d, J= 7.6 Hz, 2H), 8.79 (d, J= 7.6 Hz, 2H), 8.43 (s, 2H), 4.16 (t, J = 7.4 Hz, 4H), 4.01-3.84 (m, 4H), 1.70 (quint., J= 7.4, 4H), 1.59-1.46 (m, 4H), 1.44-1.31 (m, 8H), 1.29-1.20 (m, 40H), 1.19-1.14 (m, 24H), 0.88-0.79 (m, 12H). ¹³C{1H} NMR (100 MHz, CDCI3) δ 162.79, 162.76, 162.52, 146.40, 132.31, 131.64, 130.89, 127.47, 126.83, 126.39, 126.18, 122.46, 41.07, 41.01, 31.92, 31.90, 29.64, 29.62, 29.60, 29.54, 29.35, 29.33, 29.28, 28.09, 27.96, 27.10, 27.04, 22.68, 14.12. HRMS (MALDI) m/z calcd for C76H106N4O8 (MH+), 1203.8089; found, 1203.8033. Anal. Calcd. for

C76H106N4O8: C, 75.84; H, 8.88; N, 4.65. Found: C, 75.61; H, 8.94; N, 4.69.

Example

poly{N,N'-bisdodecyl-naphthalene-l,4,5,8-bis(dicarboximide)}. In a microwave vial equimolar amounts of N,N'-di(n-dodecyl)-2,6-bis(tri(n- butyl)stannyl)naphthalene-l,4,5,8-bis(dicarboximide) (0.4 mmol, 473 mg) and N,N'-di(n-dodecyl)-2,6-dibromonaphthalene-l,4,5,8-bis(dicarboximide) (0.4 mmol, 304 mg) were added and followed by addition of

tetrakis(triphenylphosphine)palladium(0) (23 mmol, 0.02 mg) and Cul (0.005 mmol, 1 mg). Then the vial was transferred to the glove -box, added anhydrous o- xylene (2 ml) and securely sealed. The glass vial was placed into a microwave reactor and heated for 2 h. After being cooled to room temperature, the vial was transferred to the glove-box, added 0.5 ml of bromobenzene and sealed securely again. The glass vial was placed into a microwave reactor and heated for 15 min. Then the reaction mixture was precipitated into a mixture of methanol and stirred for 1 hour at RT. The precipitate was filtered and was under extraction (Soxhlet) with methanol, acetone and chloroform. Finally, the polymer was purified by size exclusion column chromatography over Bio-Rad Bio-Beads S-Xl eluting with chloroform. The polymer was recovered as a purple solid from the chloroform fraction by rotary evaporation (270 mg, 59%). 1H NMR (300 MHz, CDC1₃) δ 8.65 (br, 2H), 3.99 (br, 4H), 1.65 (br, 4H), 1.24 (br, 36H), 0.86 (br, 6H). GPC: Mn 14.3 kDa; Mw 29.4 kDa; Mw/Mn 2.1. Anal. Calcd. for (C38H52 2O4) n: C, 75.96; H, 8.72; N, 4.66. Found: C, 76.06; H, 8.67; N, 4.50%.

Example 13

poly {N,N '-bis(2-octyldodecyl)-naphthalene- 1 ,4,5,8- bis(dicarboximide)}. In a microwave vial equimolar amounts of N,N'-di(2- octyldodecyl)-2,6-bis(tri(n-butyl)stannyl)naphthalene-l,4,5,8-bis(dicarboximide) (0.6 mmol, 843 mg) and N,N'-di(2-octyldodecyl)-2,6-dibromonaphthalene- l,4,5,8-bis(dicarboximide) (0.6 mmol, 589 mg) were added and followed by addition of tetrakis(triphenylphosphine)palladium(0) (0.03 mmol, 34.7 mg) and Cul (0.008 mmol, 1.5 mg). Then the vial was transferred to the glove -box, added anhydrous o-xylene (3 mL) and securely sealed. The glass vial was placed into a microwave reactor and heated for 2 h. After being cooled to room temperature, the vial was transferred to the glove -box, added 0.75 ml of bromobenzene and sealed securely again. The glass vial was placed into a microwave reactor and heated for 15 min. Then the reaction mixture was precipitated into a mixture of methanol and stirred for 1 hour at RT. The precipitate was filtered and was under extraction (Soxhlet) with methanol, acetone and chloroform. Finally, the polymer was purified by size exclusion column chromatography over Bio-Rad Bio-Beads S-Xl eluting with chloroform. The polymer was recovered as a purple solid from the chloroform fraction by rotary evaporation (680 mg, 72%). 1H NMR (300

MHz, CDCls) δ 8.65 (br, 2H), 3.98 (br, 4H), 1.90 (br, 2H), 1.24 (br, 64H), 0.86 (br, 12H). GPC: Mn \ \ . \ kDa; Mw 21.0 kDa; Mw/Mn 1.9. Anal. Calcd. for

(C₅4H₈4N₂04) n: C, 78.59; H, 10.26; N, 3.39. Found: C, 78.06; H, 10.00; N,

3.32%.

Table 1 The Optical and Electrochemistry Properties of PolyNDI

E_1/2 ^0/- vs Cp₂Fe^0/+ E_1/2 ¹-^/2-vs Cp₂Fe^0/+ (V, cmpd λ_∞Ά 7 nm λ

nm (V, DCM) DCM)

Poly(NDIC₁₂) 319, 365, 320, 389 -1.00

-1.48

387

Poly(NDIC₈C₁₀) 367, 387 368, 388 -1.05 -1.32

Table 2 OFET Characteristics of PolyNDI

^Cin _c , S/D

cmpd W/L ₂ Solvent , , „ (_cm 2 ry_s) V

(nF/cm ) electrode ^μ ^'" ^{1 v} ^ TH (V) ' / on/off

Poly(NDI 2550 μπι/180

dichloro 1.6 (±0.1) 5.0

CeCio) μιη 35.2 Au 4^χ 10 benzene x lO^ (±0.6) n-mode

Example 14 - Synthesis of " Bis(CN-NDI)":

A solution of N,N'-di-/7-hexyl-2-cyano-6-bromo-naphthalene- 1,8:4,5- bis(dicarboximide) (0.21 g, 0.38 mmol), A ,N'-di-/7-hexyl-2-(tri-n-butylstannyl)- 6-cyano-naphthalene-l,8:4,5-bis(dicarboximide) (0.29 g, 0.38 mmol),

copper(I)iodide (0.007 g, 0.038 mmol,) in DMF (7.3 mL) was degassed under nitrogen for 10 min. Tetrakis(triphenylphosphine)palladium (0.023 g, 0.019 mmol) was added and the reaction mixture was heated to 120 °C under nitrogen for 30 min. After cooling to room temperature, solvent was removed under reduced pressure. The crude product was purified by column chromatography (silica gel, dichloromethane), followed by recrystallization from ethylacetate to afford bis(CN-NDI) as a yellow solid. Yield: 0.21 g (59%).

Electrochemical data (0.1 M ⁿBu₄NPF₆/CH₂Cl₂ in V vs FeCp₂ ^+/0): Ei_/2 ^+/0

(V): N/A; E_1/2 ^0/2" (V): 0.71, -0.90; E_1/2 ^2"/4" (V): -1.37, -1.54. Field-effect transistor properties (spin-coated glass OFET device): μ_ε (cm²V^"1s^"1)^a : 0.056 (0.055±0.001); V (V) : 3.2(±0.1); /₀n/of_f: lxlO⁵.

Claims

1. An oligomer or polymer represented by:

(VI), wherein n is zero or an integer from 1 to 20 and the R groups,

independently, are 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 R' groups are, independently 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.

2. The oligomer or polymer of claim 1 represented by:

wherein n is an integer from 1 to 21 and the R groups, independently, are 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

3. The oligomer or polymer of claims 1-2, wherein n is zero or 1-6.

4. The oligomer or polymer of claims 1-3, wherein n is 1 or 2.

5. A method comprising : reacting at least one first naphthalene diimide (NDI) compound comprising at least one stannyl substituent bonded to the naphthalene moiety of the NDI compound in a coupling reaction to form at least one oligomer, polymer, or a combination thereof.

6. The method of claim 5, wherein the first NDI compound is reacted with at least one halogenated compound to form the at least one oligomer, polymer, or combination thereof.

7. The method of claims 5-6, wherein the first NDI compound comprises one stannyl substituent

8. The method of claims 5-6, wherein the first NDI compound comprises two stannyl substituents.

9. The method of claim 5, wherein the reacting step produces at least one dimer as the primary reaction product.

10. The method of claim 5, wherein the reacting step produces at least one trimer as the primary reaction product.

11. The method of claim 5, wherein the first 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.

12. The method of claim 5, wherein 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.

13. An ink composition comprising at least one solvent and at least one oligomer or polymer according to claims 1-4 or at least one oligomer or polymer prepared by the methods of claims 5-12.

14. A device comprising at least one oligomer or polymer according to claims 1-4 or at least one oligomer or polymer prepared by the methods of claims

5-12.

15. The device of claim 14, wherein the device is an OLED, OPV, OFET, or sensing device.

16. The oligomer or polymer of claims 1-4, wherein at least one R' gi is cyano.

17. The oligomer or polymer of claims 1-4, wherein the oligomer or polymer is a polymer having a number average molecular weight of at least 5,000 Da.