TW201233679A - Thiocyanato or isothiocyanato substituted naphthalene diimide and rylene diimide compounds and their use as n-type semiconductors - Google Patents

Abstract

A compound of formula I: wherein: R1 and R2, at each occurrence, independently are selected from H, a C1-30 alkyl group, a C2-30 alkenyl group, a C2-30 alkynyl group, a C1-30 haloalkyl group, and a 3-22 membered cyclic moiety, each optionally substituted with 1-4 groups independently selected from halogen, -CN, -NO2, -C(O)H, -C(O)OH, -CONH2, -OH, -NH2, -CO(C1-14 alkyl), -C(O)OC1-14 alkyl, -CONH(C1-14 alkyl), -CON(C1-14 alkyl)2, -S-C1-14 alkyl, -O-(CH2CH2O)n(C1-14 alkyl), -NH(C1-14 alkyl), -N(C1-14 alkyl)2, a C1-14 alkyl group, a C2-14 alkenyl group, a C2-14 alkynyl group, a C1-14 haloalkyl group, a C1-14 alkoxy group, a C6-14 aryl group, a C3-14 cycloalkyl group, a 3-14 membered cycloheteroalkyl group, and a 5-14 membered heteroaryl group; R3 independently are selected from halogen-, CN, -NO2, -C(O)O(C1-14 alkyl), -C(O)O(C6-14 aryl), -CHO, C1-14 alkylsulfon, C6-14 arylsulfon, a sulfonic acid C1-14 alkylester or C6-14 arylester group, -CONH2, -CONH(C1-14 alkyl), -CONH(C6-14' aryl), -CON(C1-14 alky)2, -CON(C1-14 alkyl) (C6-14 aryl), -CON(C6-14 aryl)2, -C(O)H, a C1-14 alkoxy group, a C1-14 alkylthio group, a C6-14 aryloxy group, a C6-14 arylthio group, a C1-14 alkyl group, a 3-14 membered cycloheteroalkyl group, a C6-20 aryl group and a 5-20 membered heteroaryl group; and n is 0, 1, 2, or 3; x is 0, 1, 2, 3 or 4; y is 1, 2, 3 or 4 if z is 0, and 0, 1, 2, 3 or 4 if z is > 0; z is 1, 2, 3 or 4 if y is 0, and 0, 1, 2, 3 or 4 if y is > 0.

Description

201233679 VI. Description of the Invention: [Prior Art] Recent developments in organic light-emitting diodes (OLEDs), photovoltaics (OPVs), and field effect transistors (OFETs) have opened up many opportunities for the field of organic electronics. One challenge in this area is the development of thin film devices with environmentally stable high mobility electron transport (η-type) organic semiconductors. The properties and stability of organic η-type materials lag significantly behind their ρ-type counterparts. Some of the challenges in developing organic η-type materials technologies include their vulnerability to environmental conditions (eg, air) and solution treatability. For example, it is desirable that such materials be soluble in common solvents so that they can be formulated into inks for use in inexpensive printing processes. The most common air-stable η-type organic semiconductors include perfluorinated copper phthalocyanine (CuF^Pc), fluorononyl oligothiophene (eg, DFCO-4TCO), naphthalene dioxime substituted with N,N'-fluorocarbon. An imine (eg, NDI-F, NDI-XF), a cyano substituted indole diimide (eg, PDI-FCN2), and a cyano substituted naphthalene diimine (eg, NDI-8CN2). See, step/eg, Bao et al. (1998), ··· C/ze/w· 120: 207-208; de Oteyza et al. (2005), Jp/?/· Ze",, 87: 183504; Schon Etc. (2000),

Jdv Maier· 12: 1539-1542 ; Ye et al. (2005), 4;?/?/. corpse; 2;^· Lett., 86: 253505 i Yoon^ A (2006), J. Am. Chem. Soc , 128: 12851-12869; Tong et al. (2006), XC; 2ew·fan, 110: 17406-17413; Yuan et al. (2004), 77n>? 450: 316-319; Yoon et al. (2005), * /. dm. «Soc, 127: 1348- 1349; Katz et al. (2000), J. dm. C/zew. heart c, 122·7787-7792; Katz et al. (2000), Nature (London), 404: 478-481; 161139.doc • 6 - 201233679

Katz et al. (2001), C/zew. C/2ew·, 3: 167-172; Jung et al. (2006), but/?/. Zeii·, 88: 183102; Yoo et al. (2006), 5:5 V/ecriron Device Ze"., 27·· 737-739 ; Jones et al. (2004),

Chm., /«i.5i Wu叩/·, 43: 6363·6366; and J〇nes et al. (2007),··· Jw. CTz cryptic 15259-15278. The quinone imine is particularly attractive. This is due to its robust nature, flexible molecular orbital energetics and excellent charge transport properties. However, the mobility of the compound including the PDI_FCN2 &amp; NDI-F is poor. On the other hand, soluble two compounds generally have weak charge transport properties. Therefore, if it is possible to apply to inexpensive large-area organic electronic devices that can be manufactured by high-throughput reel-to-reel manufacturing methods, the technology requires new organic n-type semi-conductive compounds, especially such as the following. Desirable properties. Gas stability, high charge transport efficiency and good solubility in common solvents. SUMMARY OF THE INVENTION According to the above-mentioned item (4) of the present invention, a compound capable of supplying an organic semiconductor and related materials, compositions, composites and/or devices can be overcome, and the like can be overcome, including those outlined above. Prior art \ and disadvantages. The present invention provides a material having a semiconductive activity of a thiocyanate group: the naphthyl imine and a di-birth imine compound and a derivative thereof have exhibited unexpected properties and results. </ RTI> </ RTI> </ RTI> </ RTI> See 'when compared to related representative compounds, the chemistry device of the present invention (eg, thin film transistor) may have a higher carrier current 161139.doc 201233679 sub-mobility and / or Good current modulation characteristics. In addition, it has been discovered that the compounds of the present invention may have certain processing advantages such as better solubility for solution processing and/or good stability under ambient conditions (e.g., 'air stability') compared to related representative compounds. . In addition, ruthenium or the like can be embedded in other components for use in various semiconductor-based devices. This problem is solved by a compound of formula I:

Wherein: R1 and R2 are each independently selected from the group consisting of H, c _3 〇 alkyl, (^-alkenyl, 〇 2·3 decynyl, haloalkyl, and 3 to 22 member cyclic moieties, Each is optionally substituted with 1 to 4 groups independently selected from the group consisting of: halogen, -CN, -N〇2, -C(0)H, -C(0)0H, -CONH2, -OH, - NH2, -CO(C丨·丨.alkyl), -C(〇)〇C 丨·14 alkyl, -CONH(C Μ alkyl), -CONCC!.&quot;alkyl)2, -S -CM4 alkyl, -ο-(CI^CHsOWChw alkyl), -nHCCnm alkyl), -NCC,.&quot;alkyl)2, C丨-丨4 alkyl, C2·丨4 alkenyl, C2_丨4 alkynyl, C丨-丨4 haloalkyl, 161139.doc * 8 · 201233679 CU4 alkoxy, C6-U aryl, C3-14 cycloalkyl, 3 to 14 membered heterocycloalkyl and 5 to 14-membered heteroaryl; R3 is independently selected from _--, CN, -N02, -(:(0)0((:!&quot;alkyl), -C(0)0(C6-14 aryl) , _CH〇, ci-i4 alkyl sulfone group, C6_14 aryl base, acid Ci-14 alkyl acrylate or C6-14 aryl vine, -CONH2, - (: ΟΝΗ ((^-14) ), _CONH(C6-u aryl), -CONCChw base) 2, -COlSKCbM alkyl (Ce-i4 aryl), -CON ( C6.14 aryl) 2, -C(0)H, C _14 alkoxy, CM4 alkylthio, c6.14 aryloxy, 〇6-14 arylthio, CM4 alkyl, 3 to 14 members Heterocycloalkyl, c6.20 aryl and 5 to 20 membered heteroaryl; and η system 0, 1, 2 or 3; if η &gt; 0, X is 〇, 1, 2, 3 or 4; Line 0, then 1, 2, 3 or 4, and if ζ > 〇, then 〇, J, 2, 3 or 4; if y is 〇, then Z is 1, 2, 3 or 4, and If y &gt; 0, then 2 is 0, 2, 3 or 4 〇 The invention also provides methods of making such compounds and semiconductor materials, as well as various compositions, composites and devices incorporating the compounds and semiconductor materials disclosed herein. The above and other features and advantages of the present invention can be more fully understood from the following description, embodiments, and the disclosure of the scope of the present invention. [Embodiment] In the entire embodiment, when the person will be And the delta matter is illustrated as having, including or including a particular component or when the process is illustrated as having, including or comprising a particular process I61139.doc 201233679. The composition of the invention may also be substantially And the composition of the components or The process composition and process of the present invention may also consist essentially of or consist of the process steps described. In the present application, when a component or component is described as being included in and/or selected from the list of ingredients and components, it is understood that the component or component may be in the component or component. Either one or more of the two or more can be selected as described in the group of wounds or group injuries. In addition, it is to be understood that the components and/or features of the compositions, devices, or methods described herein may be combined in various ways without departing from the spirit and scope of the invention, whether directly or indirectly. The terms "including (inclUde, includes, includmg)" and "having (have, has or having)" are generally understood to have a broad meaning and are not limiting, unless explicitly stated otherwise. The singular forms used herein include the plural (and vice versa) unless specifically stated otherwise. The term "picture base" or "dental" as used herein refers to gas, gas, and moisture. As used herein, "alkoxy" refers to an alkyl group. Examples of the alkoxy group include i_ not limited to a methoxy group, an ethoxy group, a propoxy group (e.g., n-propoxy group and isopropoxy group), a third butoxy group, and the like. The alkyl group in the _0_alkyl group can be substituted as described herein. As used herein, "sulphur-based" means _s_alkyl. Examples of the sulfur-burning group include, but are not limited to, anthracenylthio group, ethylthio group, propylthio group (e.g., n-propylthio group and isopropylthio group), a third butylthio group, and the like. The alkyl group in the _s_alkyl group can be substituted as described herein. 161139.doc •10· 201233679 As used herein, "keto" refers to double bond oxygen (ie, =0). R1 and R2 may be an alkyl group. As used herein, "alkyl" refers to a straight or branched chain saturated hydrocarbon group. Examples of the alkyl group include a methyl group (Me), an ethyl group (Et), a propyl group (e.g., 'n-propyl group and isopropyl group), and a butyl group (e.g., n-butyl group, isobutyl group, second butyl group, the first group). Tributyl), pentyl (eg, n-pentyl, isopentyl, neopentyl) and the like. The alkyl group may have from 1 to 3 carbon atoms, for example, from 1 to 20 carbon atoms (i.e., a lower alkyl group usually has up to 4 carbon atoms. Examples include mercapto, ethyl, propyl (eg, n-propyl and isopropyl) and butyl (eg, n-butyl, isobutyl, t-butyl, t-butyl). In some embodiments The alkyl group may be substituted as disclosed herein. R1, R2 may be haloalkyl. "Haloalkyl" as used herein means an alkyl group having one or more halogen substituents. The haloalkyl group may have 3 碳 carbon atoms, such as '1 to 10 carbon atoms (ie, Cl_1Q_alkyl). Examples of haloalkyl groups include CF3, C2F5, CHF2, CH2F, CCI3, CHCI2, CHAl, C2C15, and the like. An alkyl group, that is, an alkyl group in which all hydrogen atoms are replaced by a halogen atom (for example, CF3 and CZF5) is a definition of "haloalkyl group". For example, a haloalkyl group may have the formula _CaE2a+i_bXb, wherein X is Each time it occurs, it is F, C, Br or I, a is an integer in the range of 1 to 20 and b is an integer in the range of 1 to 41, and the condition is not large. 2a+1 〇R, R may be a C2_3 fluorene group. As used herein, "alkenyl" refers to a straight or branched alkyl group having one or more carbon-carbon double bonds. In various embodiments, The base may have 2 to 30 carbon atoms, for example, 2 to 1 carbon atoms, I61I39.doc -11 - 201233679 (ie, alkenyl). Examples of alkenyl groups include, but are not limited to, vinyl, propenyl, Butenyl, pentenyl, hexenyl, butadienyl, pentadienyl, hexadienyl, and the like. The one or more carbon-carbon double bonds may be internal linkages (eg, in 2-butene) Or a terminal bond (for example in 1-butene). In some embodiments, an alkenyl group may be substituted as disclosed herein. R, R may be C2. alkynyl. As used herein, "alkynyl" refers to having a linear or branched alkyl group of one or more carbon-carbon triple bonds. Examples of alkynyl groups include ethynyl, propynyl, butynyl 'pentynyl, and the like. The one or more stone anti-carbon three The bond can be an internal bond (for example in 2-butyne) or a terminal bond (for example in 丨-butyne). In various embodiments, the alkynyl group can have from 2 to 3 carbon atoms, for example 2 Up to 10 carbon sources (i.e., alkynyl). In some embodiments, an alkynyl group can be substituted as disclosed herein. It can be a 3 to 22 membered cyclic moiety. As used herein, a cyclic moiety can include one or more (e.g., , 1 to 6) carbocyclic or heterocyclic ring. The cyclic moiety may be a cycloalkyl group, a heterocycloalkyl group, an aryl group or a heteroaryl group (ie, may include only a saturated bond' or may include - or more Residues and bonds, and aromaticity:), each of which includes, for example, 3 to 22 ring atoms and may be substituted as described herein. The ring portion is a "single ring portion" - some examples Medium, 1 "single ring portion" $ includes 3 to 14 members of aromatic or non-aromatic carbocyclic rings or: rings. The monocyclic moiety can include, for example, a stupid or a 5 or 6 membered heteroaryl, each of which can be substituted as described herein, as appropriate. In some embodiments of the annular portion, the anthracene ring portion may include two or more I:;:: a spiro atom, or - or a plurality of bridging atoms that are slightly coupled to each other or to each other, the polycyclic portion may include 8 Up to 22 members of aromatic or non-aromatic, carbocyclic: heterocyclic 161139.doc • 12·201233679 rings, such as c8.22 aryl or 8 to 22 membered heteroaryl, each of which may be substituted as described herein, as appropriate. R, r2 may be a cycloalkyl group having 3 to 22 carbon atoms. As used herein, "cycloalkyl" refers to a non-aromatic carbocyclic group, including cyclized alkyl, alkenyl and alkynyl groups. The cycloalkyl group may have 3 to 22 carbon atoms, for example, 3 to 碳 carbon atoms (i.e., a cycloalkyl group). A cycloalkyl group can be a monocyclic (e.g., cyclohexyl) or polycyclic (e.g., containing a fused, bridged, and/or spiro ring system) wherein the stone anti-atoms can be internal or external to the ring system. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclohexenyl, cyclohexadienyl, cycloheptatrienyl, A thiol group, a decyl group (n〇rplnj^), a decyl group (n〇rcaryl), a gold alkyl group, and a snail [4.5] fluorenyl group, and homologs, isomers thereof, and the like. In some embodiments, a cycloalkyl group can be substituted as disclosed herein. As used herein, "heteroatom" means an atom of any element other than carbon or hydrogen and includes, for example, nitrogen, oxygen, helium, sulfur, phosphorus, and selenium. R, R2 may be a heterocycloalkyl group having 3 to 22 ring atoms. As used herein, "heterocycloalkyl" refers to a non-containing one selected from the group consisting of hydrazine, S, se, N, p, and Si (eg, ' 〇, s, and N) and optionally one or more double or triple bonds. Aromatic cycloalkyl. The heterocycloalkyl group may have 3 to 22 ring atoms, 'e.g. 3 to 4 ring atoms (i.e., 3 to 14 membered heterocycloalkyl). One or more N, P, s or Se atoms (eg, N or S) in the heterocyclic ring may be oxidized (eg, 'morpholine N-oxide, thiomorpholine s-oxide, thiomorpholine S, S-dioxide). In some embodiments, the nitrogen or phosphorus atom of the heterocycloalkyl group can have a substituent 'e.g., an argon atom, a hospital base, or other substitutions as described herein 161139.doc -13 - 201233679. Heterocyclyl can also contain one or more pendant oxy groups, such as pendant hexahydro hexahydro. Pyridyl, pendant oxazolidinyl, di-oxy-(1H,3H)-pyrimidinyl, pendant oxy-2(1H)-pyridyl and the like. Examples of heterocycloalkyl groups include, in particular, morphinyl, thiophene, thiopyranyl, beta sulphate, beta mercapto, chewing sputum, °, bite base, pi嘻 基 吼 吼 吼 吼 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四The group may be substituted as disclosed herein. R, R may be an aryl group having 6 to 22 ring atoms. As used herein, "aryl" refers to a fused of two or more aromatic hydrocarbon rings (ie, shared An aromatic hydrocarbon monocyclic ring system or a polycyclic ring system in which one or more aromatic monocyclic hydrocarbon rings are fused to one or more cycloalkyl and/or heterocycloalkyl rings. The aryl group may have from 6 to 22 ring atoms in its ring system, for example, from 6 to 14 ring atoms (i.e., C6 &quot; aryl), which may include a plurality of minor rings. In some embodiments, the polycyclic aryl group can have from 8 to 22 carbon atoms. The aryl, the appropriate ring position can be covalently linked to the specified chemical structure. Examples of aryl groups having only an aromatic carbocyclic ring include, but are not limited to, phenyl, 1 -caiyl (a 1⁄4), 2-caiyl (bicyclic), anthracenyl (tricyclic), phenanthryl (tricyclic), and Similar group. Examples of polycyclic ring systems in which at least one aromatic carbocyclic ring is fused with one or more of our and/or heterocyclic alkyl rings include, in particular, benzofluorene sulfhydryl groups of cyclopentene, which are 5'6- a bicyclic cycloalkyl/aromatic ring-burning benzo derivative (ie, a tetrachatronic group, which is a 2 base/fragrance ring system), a stupid derivative of odorin (ie, benzoxene) Zolinyl, which is a 6-hexadecane derivative (i.e., I-based/reagent-purified) and a homo-p-pyridyl group, which is a 6,6-bicycloheterocycloalkyl group. Fang 161139.doc 201233679 Aromatic ring system). Other examples of aryl groups include, but are not limited to, benzodialkylene, stupid dioxolane, dimethyl, dihydro. The aryl group and the like: In some embodiments, the aryl group can be substituted as disclosed herein. In one embodiment, the '4 group may have one or more pixel substituents and may be referred to as a = group. A wholly-functional aryl group, that is, an aryl group in which all hydrogen atoms are replaced by a functional atom (for example, _C6F5) is included in the definition of "dental aryl". In some embodiments, the aryl group is —Aryl substituted and may be referred to as each of the aryl groups. The aryl group may be substituted as disclosed herein. It may be a heteroaryl group having 5 to 22 ring atoms. As used herein, a diterpene refers to a polycyclic ring containing at least one aromatic monocyclic ring system selected from 0, N, s, sim == aromatic or at least one aromatic ring present in the ring system and containing at least one ring heteroatom. system. More = square group includes two or more heteroaryl rings which are kneaded together and one or more aromatic carbocyclic rings, non-aromatic carbocyclic rings; The heteroaryl group as a whole may have from 5 to 22/heteroaryl groups, which may result in a stable structure - s designation of chemical structure attachment. , words, heteroaryl such as 0 bond. However, one or more of the heteroaryl groups may be oxidized (for example, an aryl: oxide, an oxidized oxide, an anthracene, etc. = an example of a group includes, for example, 5 or 6 membered monocyclic rings as shown below W two-ring ring 161139.doc 15 201233679 Q (&gt; Q a ^ t) ο ο ό ooo

&gt; CO Co 〇&gt; 〇〇

Wherein T is 〇, s, NH, N-alkyl, N. aryl, N-(arylalkyl) (for example, N-benzyl), SiH2, SiH-(alkyl), Si(alkyl) 2. SiH-(arylalkyl), Si-(arylalkyl)2 or Si(alkyl)(arylalkyl). Examples of the heteroaryl group include pyrrolyl group, furyl group, thienyl group, pyridyl group, pyrimidinyl group, pyridazinyl group, "pyridyl group, trisalyl group, tetrapyridyl group, β-salt group, taste-beta group, and different Squatting base, ° sedation, sighing, and difference. Oxazolyl, oxazolyl, oxadiazolyl, fluorenyl, isodecyl, benzofuranyl, benzothienyl, quinolyl, 2-nonylquinolinyl, isoquinolinyl, quin Porphyrin group, quinazolinyl group, benzotriazolyl group, benzimidazolyl group, benzothiazolyl group, benzisothiazolyl group, stupid and heterogeneous. Sit, stupid and oxadiazolyl, benzoxazolyl, porphyrinyl, 1 Η _. Salivation, 2Η-carbazolyl, pyridazinyl, isobenzofuranyl, naphthyridinyl, pyridazinyl, acridinyl, fluorenyl, oxazolopyridyl, thiazolopyridyl, imidazopyridyl , furopyridinyl, thienopyridyl, pyridopyrimidinyl, . Bisylindene η is a pyridyl group, D is a pyridyl oxazinyl group, a thienothiazolyl group, a thiophene is conjugated to a succinyl group, and the like. Other examples of heteroaryl groups include, but are not limited to, 4,5,6,7-tetrahydrotetradecyl, tetrahydrocarbyl, benzopyrene 161139.doc -16·201233679 phenyridylpyridyl, benzofurandpyridyl And so on. In some embodiments, a heteroaryl group can be substituted as described herein. The compound of the invention can include a "divalent group" as defined herein as a linking group capable of forming a covalent bond with two other moieties. For example, a compound of the invention may include a divalent C alkyl group, for example, a methylene group. Substituents of the compounds are disclosed in groups or sub-ranges throughout the specification. This embodiment is intended to specifically encompass each individual subcombination of the members of the group and scope. For example, the term 'Cl_6 alkyl' is intended to specifically disclose Ci, C2, C3, C4, C5, c6, CVC6, CVC5, (VC4, C, -C3 'C1-C2 'C2-C6 'C2-C5 ' C2-C4 'C2-C3 'C3-C6 ' c3-C5, C3-C4, C4-C6, C4-C5 and C5-C6 alkyl. For another example, an integer in the range of 0 to 40 is intended to be specific Reveal 〇, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39 and 40, and integers in the range of 1 to 20 are intended to specifically disclose 1, 2, respectively. 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20. Additional examples include the phrase "1 to 5 as appropriate" Substituent substitution" is intended to specifically disclose zero, one, two, three, four, five, zero to five, zero to four, zero to three, one to two , one to one, one to five, one to four, one to three, one to two, two to five, two to four, two to three, 3 to 5, 3 to 4 and 4 to 5 Chemical group of a substituent. The compounds described herein may contain asymmetric atoms (also known as the center of the palm of their hand) 161139.doc •17· 201233679 and some compounds may contain two or more asymmetric atoms or centers' Thus it can produce optical isomers (enantiomers) and diastereomers (geometric isomers). The present invention includes such optical isomers and diastereomers, including their corresponding Resolution of enantiomerically or diastereomerically pure isomers (eg '(+) or (a) stereoisomers) and racemic mixtures thereof, and such enantiomers and diastereoisomers Other mixtures of the bodies. In some embodiments, 'optical isomers may be obtained in the form of enantiomers or in pure form by standard procedures known to those skilled in the art, including, for example, For palm separation, diastereomeric salt or ester formation, kinetic resolution, enzymatic resolution, and asymmetric synthesis. The invention also encompasses the use of compounds containing alkenyl moieties (eg, olefins and imines). And trans isomers. It should also be understood that the invention encompasses All possible regioisomers in pure form and mixtures thereof, which can be obtained by standard separation procedures known to those skilled in the art, for example, column chromatography, thin layer chromatography, simulated movement Bed chromatography and high performance liquid chromatography. For example, the flower compound of the present invention includes any organism in its pure form or its _ ^ ° mouthpiece, wherein the organisms may pass through one or two, , ,ro .3, 4, 5, 6, 7 or 8 of the "ml in its pure form or a mixture thereof", and, S Xu and other naphthalene derivatives can pass 1, 2 Replaced by three $ substituents. Specific scorpions 3 or 4 s, these hydrazine derivatives may include a part of the compound: 匕牯 has the following 161139.doc •18· 201233679

Wherein γ may be H, thiocyano or isocyanato in each occurrence. In various embodiments, the two Y groups are deuterium and the other two Y groups are independently nitrothio or isocyanato. Thus, in the examples where the two gamma groups are Η and the other two are independently I thio or isocyanato, the compounds of the invention may have stereoisomers of the formula:

In certain embodiments, the compounds of the invention may include a compound having the formula ii or ii:

161139.doc •19- 201233679 or a mixture thereof's towel, a terrestrial thiol or isocyanato group. As used herein, "P-type semiconducting material" &lt; "p_ type semiconductor" means a semiconducting material in which a hole is a main carrier. In some embodiments, when a p-type semiconductive material is deposited on a substrate, it can provide a hole mobility in excess of about 10'5 cm2/Vs. In the case of field effect devices, the type semiconductor can also exhibit a current on/off ratio greater than about 10. As used herein, "n-type semiconducting material" or "n-type semiconductor" refers to a semiconducting material in which electrons are the main carriers. In some embodiments, when a η-type semiconductive material is deposited on a substrate, it can provide an electron mobility of more than about cm /Vs. In the case of a field effect device, the cardioid semiconductor can also exhibit a current conduction/shutdown ratio of greater than about 10. As used herein, "field effect mobility" refers to a measure of the rate at which a charge carrier moves through a material under the influence of an electric field. For example, if it is a semi-conducting material, the charge carrier is a hole (or a positive charge). Unit) and if it is a &amp; type semiconducting material' then the charge carriers are electrons. As used herein, when a compound's carrier mobility or reduction potential is maintained at about its initial measurement after exposure to environmental conditions (eg, air, ambient temperature, and humidity) for a period of time, the compound may be considered "environmental". " or "steady under environmental conditions". For example, if the compound is exposed to environmental conditions (ie, air, humidity, and temperature) for 3 days, 5 days, 1 day, the carrier mobility or reduction potential of the compound does not change from its initial value. More than 20% or no more than 1%%, the compound can be described as η ambient temperature. As used herein, "solution treatable" means a compound, material or composition that can be used in various solution phase processes, including spin coating, printing (eg, inkjet printing, silk). Screen printing, mobile printing, gravure printing, flexographic printing, lithography, microcontact printing and lithography), spray, electrospray coating, dripping, zone casting, dip coating and knife coating. The scope of the temperature is disclosed throughout the application. This embodiment is intended to specifically include a narrower temperature range within the ranges and a maximum temperature and minimum temperature including the temperature range. Throughout the specification, the structure may be represented by a chemical name or may not be represented by a chemical name. In the event of any doubt as to the nomenclature, the structure shall prevail. In one aspect the invention provides a compound having the formula Ia, Ib*Ic:

〇 / N \〇

Ic

Combination of Ie or If la ib wherein: R1 and R2 are as defined above. In yet another aspect, the invention provides a formula Id: 161139.doc • 21· 201233679

Wherein R1 and R2 are as defined above. R1 and R2 are independently selected from H, Ci. 3 alkyl, € 23 alkenyl, C: 2·3*) alkynyl, C^o haloalkyl and 3 to 22 ring in each occurrence. In part, each of them is optionally substituted with one to four groups independently selected from the group consisting of: halogen, -CN, -N〇2, -C(0)H, -C(0)〇H, -CONH2. -OH, ·ΝΗ2, -CO(Cm4 alkyl), -C(0)0CN14 alkyl, -CONH(C 丨.M alkyl), -CON(C丨.丨4 alkyl)2, -S- Cm4 alkyl, ·〇_((:Η2(:Η2Ο)η(0:Μ4 alkyl), -ΝΗ%·&quot;alkyl), -ΝΑ.&quot;alkyl)2, (:丨.14 alkane , C2•丨4, K2.u alkynyl, C丨·丨4 haloalkyl, 〇:丨·丨4 alkoxy, C6•丨4 aryl, C3.14 cycloalkyl, 3 to 14 membered heterocycloalkyl and 5 to 14 membered heteroaryl, and n is as described herein; 3 to 22 membered cyclic moiety may be selected from C6.22 aryl, 5 to 22 membered heteroaryl 'C3.22 The cycloalkyl and 3 to 22 membered heterocycloalkyl groups are each optionally substituted as described herein. In the preferred embodiment 'R1 and R2 are independently selected from Ci 12, C in each occurrence. ] 2 haloalkyl and 5 to 14 membered monocyclic moieties, each of which is optionally 1 Substituted to 4 groups independently selected from the group consisting of halogen, _CN, _N〇2, _C(0)H, -C(0)OH, -CONH2, -〇H, -NH2, -COCCum alkyl), Alkyl, -CONHCCbM alkyl), ^(^((:丨 烷 烷 161139.doc -22- 201233679 基) 2, -SC卜14 炫, -〇-(CH2CH20)n(C丨.丨4 Base), -ΝΗβΜ* alkyl), -N(C丨4), 烧.14 alkyl, C2_M^, C2-14 alkynyl, Ci.i4, halogen, C, 4 Hyun*oxy, C6-14 aryl, C3-14 cycloalkyl, 3 to 14 membered heterocycloalkyl and 5 to 14 membered heteroaryl, and η, 1, 2 or 3. In a particular embodiment 'R1 and R2 are each independently selected from the group consisting of an alkyl group, a C^i2 halogen group, a (7:2 aryl group) and a phenyl group, wherein the phenyl group is optionally one to four independently Substituted from a group selected from halogen, Cw alkyl and (^-6 haloalkyl. For example, R1 and R2 are selected from -CH3, -C2H5, -C3H7, -C4H9, -C5Hn, -C6H13 at each occurrence. , -C8H17 (specifically 2-ethylhexyl), -C 2H25, -C13H27, optionally substituted by 1 to 5 halo or Cw alkyl, (: 7-12 stylalkyl) (in which phenyl Conditions by 1-5 halo (particularly F atoms), or Cl_6 alkyl group) and a C 1 -6 _ group. Specific examples of alkyl groups are -CF3, -C2F5, -C3F7 and -CH2C3F7. Examples of specific arylalkyl groups are benzyl, phenylethyl and phenylpropyl. In each of the examples, 'R3 is an electron withdrawing group independently selected from the group consisting of halogen, -CN, -NOS'-CF3'-〇CF3, -CCMCuo alkyl), -CHO, c丨-c丨4 alkyl Sulfone, c6丨4 aryl sulfone, sulfonyl-Ci i4 alkyl or -C6·!4 aryl ester, _C〇NH(Ci i.alkyl), _c〇N (Ci 1 decane • Base) 2 ° For example, R3 can be halogen, -CN, -N〇2, -cf3 or -OCF3. In certain embodiments 'R3 is F, CI, Br, I or -CN. In another aspect the invention provides a method of making a compound as disclosed herein. In various embodiments, the method can include a compound of Formula 11a and lib, respectively, 161139.doc -23- 201233679 r

Ma lib is reacted with thiocyanate, wherein R and R are as defined above, and each occurrence of hydrazine is H or a leaving group 'suitable leaving group F, Cl, Br, I, -〇8 〇2_ζ: 6Ιΐ4_0Ή3, oso2-ch3. In various embodiments, X can be deuterium or halogen at each occurrence. For example, X may be H, F, Cl, Br, or Bu at each occurrence. In certain embodiments, X may be deuterium or Bre at each occurrence, in some embodiments, thiocyanate LisCN, NaS(:N, KS(:N, NHACN, NRACN, piscn, wherein each R is independently 18), CuSCN or AgSCN. Preferably, thiocyanate is NaScN* KSCN. In some implementations In one embodiment, the reaction can be carried out at room temperature (for example, between about 2 ° C and about 3 Torr). In some embodiments, the reaction can be carried out at a temperature other than room temperature. For example, the temperature can be lower or higher than room temperature. In certain embodiments, the reaction can be carried out at elevated temperatures (i.e., temperatures above 161139.doc • 24-201233679). The high temperature may be between 50 〇c and ^^·^. In a specific embodiment, the high temperature may be between 5 〇. 〇 and i 8 〇〇 C, for example, between 7 (^ and 15 〇 1) Between (for example, 70. (or 150. 〇. The formation of a thiocyanato compound or an isothiocyanate compound depending on the nature of the solvent. The solvent in which the thiocyano compound is mainly or almost formed only) Including DMSO, DMSO and aromatic solvents (such as toluene, diphenylbenzene, trimethylbenzene, tetrahydronaphthalene, gas, dioxane, chloronaphthalene or nitrobenzene), or DMSO and ether (such as ι,4- a mixture of dioxane or tetrahydrofuran. The solvent in which the isocyanato compound is mainly or almost formed includes methyl ethyl ketone and isobutyl methyl ketone. The reaction is carried out in the presence of a phase transfer catalyst such as a quaternary salt. Contribute to the formation of isocyanato compound. In either case, when a mixture of cyanothio-, isocyanato- and mixed cyanothio-isocyanato- compounds can be formed by standard methods ( For example, chromatography) to isolate a neat compound. In each of the examples, the compounds of formula Ila and lib can be obtained by separately making compounds of formula Ilia and Ilib, respectively.

161139.doc •25- 201233679 is prepared by reacting a primary amine, I^-NH2 or R2-NH2, in an aprotic solvent, wherein X, R and R2 are as defined herein. This is preferably used for the preparation of the compound nb. However, in the case of preparing the compound Ila, it is more preferred to use a gasification agent and a brominating reagent, respectively, to gasify or bromine the naphthalene diimine compound of the formula Va. f w〇 〇5x Ο 〇, 〇 R2 Va and brominated naphthalene tetraphthalic acid dianhydride IVa and then RLNH2 and/or r2_NH2 oxime imidized compound Ilia, which resulted in higher yield of compound IIa. The invention also relates to a process for producing a naphthylquinone imine compound of the formula Ila substituted by bromine

X X

Ila wherein X is independently Η, Cl or Br, and the condition is at least one X system Cl or Br, 161139.doc •26· 201233679 R, R is as defined in claim 1 'The process comprises separately using a gasification reagent and Steps for gasification or bromination of naphthalene diimine of formula Va by desertification reagent 1

Va Ο, N, 0 Preferred gasification reagents and brominating reagents are N, N, _ di-isoisocyanuric acid and N, N'-dibromoisocyanuric acid, respectively. Gasification is preferably carried out using concentrated sulfuric acid as the reaction medium (e.g., 95_98 wt sulfuric acid). FeCi3 and FeBr3 may be separately added as a catalyst. The naphthalene diimine compound of the formula Ila is preferably obtained by reacting naphthalenetetracarboxylic dianhydride with a first-grade amine R--NH2, R2-NH2 or a mixture thereof, wherein R1, r2 are as defined herein. In various embodiments, the aprotic solvent can include an ether. In some embodiments the 'aprotic solvent can include (Cw alkyl) hydrazine (CH2CH2 fluorene) m (Ci 6 alkyl), wherein m can be Bu 2, 3, 4, 5 or 6. In a particular embodiment, the aprotic solvent can be a solvent or a solvent mixture including triethylene glycol dimethyl. For example, the aprotic solvent can be triethylene glycol dimethyl ether. In various embodiments, the reaction can be carried out at room temperature. In the examples, the reaction can be carried out at a temperature different from room temperature. For example, the temperature can be lower or higher than room temperature. In certain embodiments, ^ ^ ° is a case of A, the reaction can be carried out at a high temperature (ie, 'temperature above room temperature. For example, 'high temperature can be between I6Il39.doc -27- 201233679 50 ° C and 300 Between ° C. In particular embodiments, the elevated temperature may be between 50 ° C and 200 ° C 'for example, between 7 〇 cc and 18 〇 〇 (eg, 165 ° C ). The compounds of Ilia and Illb can be prepared by brominating the compounds of the formulae IVa and IVb, respectively, by using known brominating reagents such as molybdenum, N, N'-dioxaisocyanuric acid or ... bromide succinimide.

Bromination of compound IVb is illustrated in 〇ε 195 47 209 and F. Wurthner, Chem. Commun. 2004, 1564-1579. The bromination of indole diamine is illustrated in J. Org. Chem. 2007, 72, 5973-5979. The compounds of the present invention can be prepared according to the procedures outlined in Scheme 1A below, starting from the use of commercially available starting materials, compounds known in the references, or intermediates which can be readily prepared. Standard synthesis methods and procedures known to the skilled person are used to achieve this. Standard synthetic methods and procedures for the preparation of organic molecules, as well as functional group transformation and manipulation, are readily available from related scientific literature or from industry standard textbooks. It should be understood that, unless otherwise stated, typical or preferred process conditions (ie, reaction temperature, time, molar ratio of reactants, solvent, pressure, etc.) may also be used. 161139.doc • 28· 201233679 His process conditions. Optimum reaction conditions may vary depending on the particular reactant or solvent employed&apos; but such conditions can be determined by those skilled in the art by routine optimization procedures. Those skilled in the art of organic synthesis will recognize that the nature and sequence of the synthetic procedures may be varied for the purpose of optimizing the formation of the compounds described herein. The methods described herein can be monitored according to any suitable method known in the art. For example. , i formation can be by means of spectroscopy (such as nuclear magnetic resonance spectroscopy (NMR 'such as 'H or π.), infrared spectroscopy (four), spectrophotometer (such as W visible light), mass spectrometry (MS) or by chromatography ( For example, high pressure liquid chromatography (HPLC), gas chromatography (GC), gel permeation chromatography (Gpc) or thin layer chromatography (TLC) are used for monitoring. The reactions or processes described herein can be carried out in a suitable solvent which can be readily selected by those skilled in the art of organic synthesis. Suitable solvents are generally those which are substantially nonreactive with the reactants, intermediates and/or products at the temperature at which the reaction is carried out (i.e., the temperature between the solidification temperature of the solvent and the boiling temperature of the (four) agent). The t reaction can be carried out in a mixture of solvents and solvents. Depending on the particular reaction step, a suitable solution for the specific reaction step can be selected. 161139.doc -29- 201233679 Reaction Figure 1

As shown in the reaction scheme 1, 茈-3,4:9, l〇-tetracarboxylic dianhydride (PDA) can be desertified at the 1,7-position to provide PDA-Βι*2 b 'b in The primary amine reaction can provide bis(monomethyleneimine)c. Substitution of the thiocyanyl group in c to form a bis(dimethylimine imine) d substituted with a thiocyano group. Although not shown in the reaction scheme 1, the bromination of a can also produce regioisomers of b, for example, hydrazine, 6-dibromo-indole-3, 4:9, l-tetracarboxylic dianhydride' A regioisomer of d is produced, for example, 1,6-dicyanothiobis(dimethylimine). Instead of PDA, by amination, 161139.doc -30-201233679 to bis(diimine) can be brominated in a similar manner to give compound c. In a similar manner, naphthalocyanide bis(diimine) can be prepared from naphthalene-3,4:7,8-tetradecanoic acid dianhydride according to reaction scheme 2: Reaction Figure 2

NaSCN

〇8N人Ο d However, it is preferred to prepare a naphthalene thiocyanate bis(dimethylimine) compound according to the reaction scheme: 161139.doc -31 - 201233679 Reaction Scheme 3

The compounds of formula I are useful in the preparation of semiconductor materials (e.g., compositions and composites), which in turn can be used to make a variety of articles, structures and devices, "semiconductor materials incorporating compounds or compounds of the invention" Presenting η-type semiconducting activity. The compounds disclosed herein are soluble in common solvents, and the present invention provides processing advantages in the fabrication of isoelectric devices such as thin film semiconductors, field effect devices, organic light emitting diodes (OLEDs), Organic Photovoltaic, Photodetector, Capacitor and Sensor. As used herein, when at least 1 mg of the compound is soluble, 161139.doc •32-201233679 when used in [mU], the compound can be considered to be soluble in the organic solvent. Including petroleum ether; B fell. - Common g W, square aromatic hydrocarbon toluene, diphenylbenzene and trimethylbenzene; ketones; such as Ben, 趟 'such as four gas gnaw, Ershiyuan, bis (2-methoxyl) , hydrazine, diiso (tetra) and tert-butylmethyl sulphate; alcohols, such as methanol: hydrazine: butanol and isopropanol 'aliphatic, such as hexane; acetate _, such as acetic acid vinegar, acetic acid Formic acid methylation, A T loss, isopropyl butyl acetate; guanamine, such as dimethylformamide and diτ · Φ · brewing amine; sulfoxide 'such as dimethyl sulfoxide; toothed fat Groups and aromatic hydrocarbons, &lt;column two: burning, gas imitation, dioxene, gas, benzene, gas and stupid; and = agent, such as cyclopentanone, cyclohexyl and 2_ Examples of the methyl phase solvent include water and an ionic liquid. Thus, the present invention further provides that one or more of the solvent is dissolved or dispersed in a liquid medium (for example, an organic solvent, an inorganic solvent, or a combination thereof (for example, an organic solvent). a composition of a compound disclosed herein in a mixture, a mixture of inorganic solvents, or a mixture of organic and inorganic solvents). In some embodiments, the composition may further comprise - or a plurality of independently selected from the following Additives: detergents, dispersants, binders, solubilizers, curing agents, starters, humectants, defoamers, wetting agents, oxime conditioners. For example, 'surfactants and/or other polymerizations (Example: and: styrene, polyethylene, poly-α-methyl styrene, Isobutylene, polypropylene, polymethyl methacrylate, and the like can be included as dispersing agents, binders, solubilizers, and/or antifoaming agents. In some embodiments, the compositions can include one or more of the texts. For the disclosed compounds, for example, two or more different compounds of the invention may be dissolved in an organic solvent to prepare a composition for deposition. In certain embodiments, the composition is 161139.doc • 33-201233679. Two or more stereoisomers may be included. In addition, it is to be understood that the devices described herein may also comprise one or more compounds of the invention, for example, two or more stereoisomers as described herein. Various deposition techniques, including various solution processing techniques, have been used to prepare organic electronic devices. For example, most printed electronic device technologies have focused on inkjet printing 'mainly because of this technology to better control feature position and multilayer alignment. . Inkjet printing is a non-contact process that provides the advantages of not requiring a preformed master (as compared to contact printing techniques) and jetting ink into the &lt;亍 digital control to provide drop-on-demand )print. Microdispersion is another non-contact printing method. However, contact printing technology has the key advantage that is well suited for very fast roll-to-roll processing. Exemplary contact printing techniques include, but are not limited to, screen printing, gravure printing, lithography, flexographic printing, lithography, pad printing, and microcontact printing. As used herein, "printing" includes non-contact processes such as ink jet printing, microdispensing, and the like; and contact processes such as screen printing, gravure printing, lithography, flexographic printing, lithography, and shifting. Printing, microcontact printing and the like. Other solution processing techniques include, for example, spin coating, drip, zone casting, dip coating, knife coating or spray coating. Additionally, the deposition step can be carried out by vacuum vapor deposition. Accordingly, the present invention further provides methods of making semiconductor materials. The methods can include preparing a composition comprising one or more of the compounds disclosed herein dissolved or dispersed in a liquid medium such as a solvent or solvent mixture, and 161139.doc-34·201233679 depositing the S-hai composition on the substrate. Semiconductor materials (eg, 'thin film semiconductors') comprising one or more of the compounds disclosed herein are provided. In various embodiments, the liquid medium can be an organic solvent, an inorganic solvent such as water, or a combination thereof. In some embodiments, the composition may further comprise one or more additives independently selected from the group consisting of viscosity modifiers, detergents, dispersants, binders, solubilizers, curing agents, starters, humectants, Defoamer, wetting agent, pH adjuster, biocide and bacteriostatic agent. For example, surfactants and/or polymers (eg, polystyrene, polyethylene, poly-α-mercaptostyrene, polyisoprene, polypropylene, decyl acrylate, and the like) can be used as Dispersants, binders, solubilizers and/or defoamers are included. In some embodiments, the deposition step can be performed by printing, including inkjet printing and various contact printing techniques (eg, screen printing, gravure, lithography, pad printing, lithography, flexography, and Microcontact Printing In other embodiments, the deposition step can be performed by spin coating, dripping, zone casting, dip coating, coating or spraying. Including electronic devices, optical devices, and optoelectronic devices (eg, field effect electricity) Crystals (eg, thin film transistors), photovoltaics, organic light emitting diodes (OLEDs), complementary metal oxide semiconductors (CM〇s), complementary inverters, D-type flip-flops, rectifiers, and ring oscillators) Various articles of manufacture and methods of making the same without the compounds and semiconductor materials disclosed herein are within the scope of the present invention. Accordingly, the present invention provides articles of manufacture, such as the semiconductor materials of the present invention, including substrate groups, as described herein. Various devices for the composite of the parts and/or dielectric components. The substrate component may be selected from the group consisting of the following materials: doped Shixia, I61139.doc • 35-2012336 79 Indium tin oxide (ITO), ITO coated glass, coated iranium or other plastic, aluminum or other metal coated with polymer or other substrate alone or above, modified by polycondensation Porphin or other polymers and the like. The dielectric component can be prepared from inorganic dielectric materials such as various oxides (eg, Si〇2, Al2〇3, Hf〇2), such as various polymeric materials (eg, , organic dielectric materials such as polycarbonate, polyester, polystyrene, polyvinyl halide, polyacrylate, self-assembled superlattice/self-assembled nano dielectric (SAS/SAND) materials (for example, described in γοοη, M_H . et al., 102 (13): 4678-4682 (2005), the entire disclosure of which is hereby incorporated by reference, and the disclosure of the &lt;RTI ID=0.0&gt; The entire disclosure of this patent is incorporated herein by reference in its entirety. In some embodiments, the dielectric component can include such a case as described in U.S. Patent Application Serial Nos. 1 1/315,076, No. 60/816,952, and No. 60/861,308. The entire disclosures of each are incorporated herein by reference. The composite may also include one or more electrical contacts. Materials suitable for source, drain and gate electrodes include metals (eg, All, Al, Ni, Cu), transparent conductive oxides (eg, ιτο, ιζΟ, ZITO, GZO, GIO, GITO) and conductive polymers (for example, poly(3,4·ethylidenethiophene) poly(styrenesulfonate) (PEd〇T:PSS), polyaniline (PANI), polypyrrole (PPy). One or more of the composites described herein can be incorporated into a variety of organic electronic, optical, and optoelectronic devices, such as organic thin film transistors (OTFTs) (specifically, organic field effect transistors (〇FETs)), as well as sensors, capacitors. , unipolar circuits, complementary circuits (eg, inverting circuits) and 161139.doc -36· 201233679 and the like. Accordingly, one aspect of the present invention pertains to a method of fabricating an organic field effect transistor that can be incorporated into a semiconductor material of the present invention. The semiconductor material of the present invention can be used to fabricate a variety of organic field effect transistors, including a top gate top contact capacitor structure, a top gate bottom contact capacitor structure, a bottom gate top contact capacitor structure, and a bottom gate bottom contact capacitor. structure. Figure 1 illustrates four common types of 0FET structures: top contact bottom gate structure (top left), bottom contact bottom gate structure (top right), bottom contact top gate structure (bottom left), and top contact Top gate structure (bottom right). As shown in FIG. 1, the FET can include a dielectric layer (eg, shown as 8, 8', 8', and 8, &quot;), a semiconductor layer (eg, shown as 6, &amp; 6, 6, and 6) Gate contacts (for example, shown as Η, Mi, Μ, and 1〇,,,), US boards (for example, shown as ^, a, Η, and a&quot;) and source and bungee Points (for example, displayed as 2, 2, 2 &quot;, 2, &quot;, 4, 4', 4&quot; and 4, &quot;). In certain embodiments, an OTFT device can be fabricated from a doped germanium substrate using a compound of the invention' in the top contact geometry. 〗 as a dielectric. In a particular embodiment, the active semiconducting layer incorporating at least one compound of the present invention can be deposited by vacuum vapor deposition at room temperature or at elevated temperatures. In other embodiments, the active semiconducting layer incorporating at least one compound of the invention can be applied by a solution based process (e.g., spin coating or ink jet printing). For the top contact device, the metal contacts can be patterned using a shadow mask on the film. In certain embodiments, the compound of the present invention can be used to form an OTFT device on a plastic drop. The polymer 161139.doc-37-201233679 is used as a dielectric in the top gate bottom contact geometry. In a particular embodiment, the active semiconducting layer incorporating at least one compound of the invention can be deposited at room temperature or at elevated temperatures. In other embodiments, the active semiconducting layer incorporating at least one compound of the invention can be applied by spin coating or printing as described herein. The gate and source/drain contacts can be made of Αι, other metals or conductive polymers and deposited by vapor deposition and/or printing. Other articles of manufacture in which the compounds of the invention may be used are photovoltaic or solar cells. The compounds of the present invention can exhibit broad light absorption and/or very high positive/metastatic reduction potential&apos; to make them desirable for such applications. Thus, the compounds described herein can be used as n-type semiconductors in photovoltaic design, including adjacent p-type semiconducting materials that form P-n junctions. The compounds may be in the form of a thin film semiconductor which may be a composite of thin film semiconductors deposited on a substrate. The use of the compounds of the invention in such devices is within the knowledge of those skilled in the art. Accordingly, another aspect of the present invention is directed to a method of making an organic light-emitting transistor, an organic light-emitting diode (OLED) or an organic photovoltaic device incorporating one or more semiconductor materials of the present invention. The following examples are provided to further illustrate the invention and to facilitate the understanding of the invention and are not intended to limit the invention in any way. Unless otherwise stated, all reagents were gambling from commercial sources and were not purified step by step. Some of the reagents were synthesized according to known procedures. The water-free tetrahydrogenate (THF) is derived from sodium/benzophenone. The reaction was carried out in nitrogen unless otherwise stated. Record υν-ν- using a uv_vis spectrometer. The NMR spectra (!H, 400 MHz and 500 MHz; 13C, 125 MHz) were recorded on a Varian Unity p]us 5 light meter and a 161J39.doc •38·201233679 spectrometer. Electrospray mass spectrometry was performed using a Thermo Finnegan LCQ Advantage mass spectrometer. EXAMPLE 1 Example Preparation of 2,6-dibromo-N,N'-bis(1Η,1Η·perfluorobutyl)-naphthalene[1,8:4,5]-bis(dimethylanimine)

To 2.00 g (3.17 mmol) of N,N'-bis(1H,1H-perfluorobutyl)-naphthalene [1,8:4,5]-bis(diimine) at room temperature [discussed in η. E. Katz et al., Materials Re-search Society Symposium Proceedings (2002), 665 (Electronics, Optical and Opto-electronic

Polymers and Oligomers), 271-280] 1.17 g (3·96 mmol) of 97% strength N,N'-dibromoisocyanuric acid was added to a solution of 240 ml of 95% to 97% strength sulfuric acid. The reaction flask was protected from light by means of aluminum foil. The solution was stirred at room temperature for 28 hours. Subsequently, the solution was poured onto 丨5 kg of ice and neutralized with NaOH. The aqueous phase was extracted twice with 750 ml of di-methane. The combined organic extracts were dried with MgSO4, filtered and evaporated. The residue 161139.doc •39· 201233679 was suspended in n-heptane and filtered. The obtained cake was dried to give a 2 g g yellow solid. Recrystallization from 80 ml of isobutanol gave 2 〇 6 g (theoretical amount of 83 / 〇) of the R color solid' which showed only one spot in the thin layer chromatography. 'H-NMR (400 MHz, D8-THF): 5 = 9.00 (s5 2H), 5.08 (t, 4H) Example lb Ν,Ν·-bis(1H,1H-perfluorobutyl)_2,6-di Preparation of thiocyano-naphthalene (dimethylimine)

0.50 g (0.63 mmol) of N,N'-bis(1H,1H-perfluorobutyl)-2,6-dibromo-naphthalene [1,8:4,5] double at 95 ° C in 2 hours (Diimine imine) Add 0128 g (159 mmol) of sodium thiocyanate to a solution of 50 ml of dimethyl hydrazine while stirring constantly. At 95. (The solution was further stirred for 1 hour and cooled to room temperature. Then 150 ml of water was added to the reaction solution, thereby forming a precipitate. The precipitate was filtered, washed with water and dried. The crude product was suspended in 200 ml of a methyl ring. After heating, it was heated under reflux for 1 hour and filtered while hot. The filter cake was washed with petroleum ether and dried, whereby 0.207 g of a tan solid was obtained, which was purified by chromatography on silica gel. 'H-NMR (400 M,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Preparation of isothiocyanyl·6·cyanothio-naphthalene [1,8:4,5]-bis(diimine)

0.50 g (0.64 mmol) of 2,6-bis(1Η,1Η-perfluorobutyl)-naphthalene [1,8:4,5] bis(diimine) at 95 °C in 3 hours 0. 〇〇56 g (0.013 mmol) Aliquat® 134 (phase transfer catalyst) A solution of 0.13 g (1.6 mmol) of sodium thiocyanate in isobutyl methyl ketone was added to a solution of 50 ml of isobutylmethyl hydrazine. The solution was stirred at 95 ° C for an additional 2 hours and cooled to room temperature. After adding 3 g of tannin, the solution was concentrated to dryness. The crude product was purified by chromatography on silica gel using di-methane as eluent. From this, 0.075 g (15% of theory) of a tan solid was obtained. • H-NMR (400 MHz, CD2C12): 8 = 9.28 (s, 1H), 8.70 (s, 1H), 5.06 (t, 2H), 5.00 (t, 2H) ppm 〇 Example 3 N, NL bis (benzene Preparation of ethyl)-1,7(6)-dicyanothioguanidine[3,4:9,10]-bis(dimethylanimine) 161139.doc 201233679

0.50 g (〇·65 mmol) of 2,6-dibromo-N,N,-bis(phenethyl)_flower_[3,4:9,10] bis(diimine) US 2007/0259475) A solution of 12 ml of dimethyl sulfoxide and 12 ml of benzene was heated to 95 °C. Then, a solution of 0.13 g (1.6 mmol) of sodium thiocyanate in 15 ml of dimethoprim was slowly added over 1 hour. The reaction solution was maintained at this temperature for 5 hours. After the reaction solution was cooled to room temperature, chlorobenzene was removed by evaporation. 5 〇 ml of water was added, thereby forming a precipitate. The precipitate was filtered and washed with water and methanol and then dried. The deep red crude product was purified twice by chromatography on silica gel using toluene/ethyl acetate (20:1). This gave a dark red solid of g·11 g (Μ% of theory). !H-NMR (400 MHz, CD2C12): 6=9.09 (s, 2Η), 8.80 (d, 2H), 8.47 (d, 2H), 7.10-7.42 (m, 10H), 4.45 (t, 4H), 3.08 (t, 4H) ppm ° Example 4 Example 4a Ν,Ν·-bis(1-methylpentyl)4,7(6)-dibromo-indole [3,4:9,1〇]_double ( Preparation of dimethyl quinone imine) 161139.doc -42- 201233679

Br

8.03 g (14.6 mm 〇〇17(6) dibromo[3,4:9'10] tetradecanoic dianhydride (1,7- and 1,6-dibromo isomer) in a Roth reactor The mixture) [described in DE B547209] and 3·12 g (3〇8 _〇1)(8)(+)2 The suspension of the aminohexane in 120 ml of anhydrous hydrazine-dioxane was heated to 16 Torr. And maintaining at this temperature for 1 hour while continuously stirring. After cooling the reaction solution to room temperature, 450 ml of sterol was added. The mixture was stirred for 5 hours. The precipitate was filtered, washed with methanol and then dried" by using two gas. The dark red crude product was purified by chromatography on silica gel eluting with methane, whereby 5 24 g (50% of theory) of dark red solid was obtained. !H-NMR (400 MHz, CDC13): 5 = 9.48 (d, 2H), 8.90 (s, 2H), 8.69 (d, 2H), 5.28 (m, 2H), 2.24 (m, 2H), 1.92 (m, 2H), i.6〇 (m, 6H) , 1.35 (m, 6H), 1.25 (m, 2H), 0.87 (t, 6H) ppm. Example 4b N,N'-bis(1-methylpentyl)-1,7(6)-dicyandiamide Preparation of bis-[3,4:9,10]-bis(dimethylimine)

SCN

16ll39.doc -43- 201233679 0.50 g (0.70 mmol) of n,N,-bis(1-methylpentyl)-1,7(6)-dibromo-indole in 1.5 hours at 95 °C , 4:9,10] bis (diimine) in a solution of 25 ml of dimethyl hydrazine, 0.12 g (1.5 mmol) of sodium thiocyanate in 1 〇ml of dimethyl sulfoxide, At the same time continue to stir. The solution was further mixed at 951 for 21 hours and cooled to room temperature. Then 15 〇 ml of water was added to the solution, thereby forming a precipitate. The precipitate was filtered, washed with water and methanol and then dried. The deep red crude product was purified by chromatography on silica gel using di-methane as eluent. Thus, 0.30 g (64% of theory) of a dark red solid was obtained. According to the WNMR spectrum, the ratio of the 1,6·dicyanothio isomer was 11 Å/〇. A NMR of the 1,7-dicyanothio isomer (500 MHz, CDC13): δ=9.10 (s, 2H), 8.80 (d, 2H), 8.47 (d, 2H), 5.29 (m, 2H) , 2.23 (m, 2H), 1.94 (m, 2H), 1.61 (m, 6H), 1.35 (m, 6H), 1.25 (m, 2H), 0.88 (t, 6H) ppm. iH NMR of 1,6-dicyanothio isomer (500 MHz, CDC13): δ = 9.12 (s, 2H), 8.81 (d, 2H), 8.40 (d, 2H) ppm; only aromatics will be assigned The signal in the area. Pure ruthenium can be obtained by recrystallization from isopropanol, and the melting point of the 7 • dicyanthio isomer is from 229 eC to 230 ° C (decomposed from 225 ° C). Example 5 2,6(7)-diqi-N,N,·bis(1H,1H-perfluorobutyl)-naphthalene [1,8:4,5]-bis(di-imine) and 2 Preparation of a mixture of 6,7-tris-N,N,-bis(1H,1H-perfluorobutyl)-naphthalene [1,8:4,5]-bis(dimethylimine) 16II39. Doc • 44 * 201233679

To 0,50 g (0,79 mmol) N,N'·bis(1H,1H-perfluorobutyl)-naphthalene[1,8:4,5]-bis(dimethylimine) Η. E. Katz et al. Materials Research Society Symposium Proceedings (2002), 665 (Electronics, Optical and Optoelectronic Polymers and

Oligomers), 271-280) 1,06 g (5,4 mmol) of N,N'-di-isocyanoic acid was added to a solution of 60 ml of 95-97 wt.% sulfuric acid. After stirring at room temperature for 30 min, the solution was heated to 85 ° C and maintained at this temperature for 24 h. The reaction solution was cooled to room temperature and diluted with 1 1 of ice water, whereby a yellow solid was precipitated. The suspension was stirred for 1 h and then neutralized with dilute NaOH. The solid was separated by glass frit and washed with warm water. The dioxane 9 was added to the dry solid to filter the yellow solution and evaporated to dryness. The residue was dried and purified by chromatography using silica gel and dichloromethane/hexanes (65:35) as mobile phase. Two major fractions were taken and each was evaporated and concentrated to give a yellow solid. One fraction was 0.18 g (33% of theory), and based on the 丨h_nmr data, it contained 50% by weight of a trichloro compound and 5% by weight of two isomeric two-gas compounds. In addition, the fraction is 〇 〇7〇 g (13% of the theoretical amount), according to the data of the • 应 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 66 [Simple description of the diagram] 161139.doc -45· 201233679 Figure 1 illustrates the different configurations of field effect transistors. [Main component symbol description] 2 source contact 2' source contact 2&quot; source contact 2&quot;' source contact 4 drain contact 4' bungee contact 4&quot; bungee contact 4&quot;' Bipolar contact 6 semiconductor layer 6' semiconductor layer 6&quot; semiconductor layer 6&quot;, semiconductor layer 8 dielectric layer 8, dielectric layer 8&quot; dielectric layer 8&quot;, dielectric layer 10 gate contact 10' gate contact 10&quot; Pole contact 10'&quot; gate contact 12 substrate 12' substrate 161139.doc ·46· 201233679 12&quot;12,&quot; substrate 161139.doc -47-

Claims (1)

201233679 VII. Patent application scope: 1. A compound of formula I, Wherein: R and R are each independently selected from the group consisting of H, c丨·3〇alkyl, Gw fluorenyl, C2-30 fast radical, ci.3〇 haloalkyl, and 3 to 22 member cyclic moieties, Each of them is optionally substituted with one to four groups independently selected from the group consisting of: i, -CN, -N〇2, -C(〇)H, -C(0)OH, -CONH2, -OH , -NH2, ·(:0((:,-" "alkyl), -(:(0)0(:,-,4 alkyl, -C0NH(Ci-i4 alkyl), -CONiCi-M alkyl ) 2,-S-Ci-14 Hyun·Base, -O-CCHzCHzOWC,.&quot;Hyun base), -NH(Ci.I4 alkyl), -N(Ci.i4 炫基)2, Ci-i4 , C2-I4 fluorenyl, C2.14 alkynyl, C].14 halogen-based, Cl.丨4 alkoxy, C6-14 aryl, C3-M ring, 3- to 14-member heterocycloalkane And 5 to 14 membered heteroaryl; R3 is independently selected from the group consisting of a peptidin, -CN, -N02, -(:(0)0((^-,4 alkyl), -C(0)〇(C6. 14 aryl), -CH0, (:, ~alkyl fluorenyl, C6.14 aryl fluorenyl, sulfonic acid Cl- fluorenyl aryl or C6-14 aryl ester, 16ll39.doc 201233679 _CONH2, - CONHiCi.M alkyl), _c〇NH(C6.14 aryl), -CON(C,-14 alkyl)2, -CONd.M alkyl) (c6_14 aryl), •CON(C6.14 芳Base) 2 -C(0)H, Cuu alkoxy, Cl.u alkylthio, Ce-14 aryloxy, C 6-14 arylthio, Ci-|4 cyclyl, 3 to 14 membered heterocycloalkyl, C6-20 aryl and 5 to 20 membered heteroaryl; and η is 0, 1, 2 or 3; X is 0, 1, 2, 3 or 4; if ζ is 〇 ', y is 1, 2, 3 Or 4, and if ζ> 〇, then y is 〇, 1, 2, 3 or 4; if y is 0 ' then z is 1, 2, 3 or 4 ' and if y &gt; 0, then z is 〇, 1 2. 2, 3 or 4. 2. The compound of claim 1 wherein Ri&amp;R2 is selected from the group consisting of Ci-u alkyl, Cl_12 haloalkyl and (:72〇arylalkyl). The compound of claim 2 or wherein R 2 and R 2 are selected from the group consisting of Ci i2 alkyl, ci-i 2 hydroxyalkyl and Clk phenylalkyl, wherein the phenyl group is optionally substituted with 1 to 5 halogen atoms. 4. For the compound of claim 1, wherein ^=0. 5. For the compound of claim 1, wherein n = 1. 6. For example, the compound of the formula 1 'where x = 〇, 丫 = 〇 and z = 2. 7. The compound of claim 1, wherein x = 〇, y = ! and ζ = ι. 8. The compound of claim 1 wherein x = 〇, y = 2 and z = 0 〇 9. The compound of claim 1 has the formula la, lb or Ic: I61139.doc 201233679 ίο. 11.12. 13. 14. 15. R1 A field effect transistor device comprising the thin film semiconductor device of claim 11: The photovoltaic device 1 comprises a thin semiconductor device as claimed in claim u, an organic light emitting diode device comprising a conductor such as a request. Thin film half of item 11 A monopolar or complementary circuit device comprising a thin film 161139.doc 201233679 conductor of the spring item 11. 16. A method for producing a gas of the formula Ila or a naphthalene diimine compound of the first generation R %/ Lla has at least one of the constraints wherein X is independently Η, Cl or Br, Cl or Br, R1, R2 are as defined in claim 1, and Va contains respectively (iv) gasification reagent (tetra) reagent to gas Steps for the formation or desertification of naphthalene diimine Va R = The method of claim 16, wherein the gasification acid is acid and the desertification agent is N,N,-dibromoisocyanuric acid. Cyanuric acid 18. The method of claim 16, by using the method of the composition of the genus of the genus of the genus of the genus of the genus of the genus of the genus 161139.doc 201233679 It is obtained by reacting with a primary amine RLNHz and/or R2-NH2. 161139.doc