TW201238995A - Polythiophene-fullerene conjugates for photovoltaic cells - Google Patents

Abstract

Compositions suitable for manufacture of high-efficiency organic photovoltaic devices, and methods of preparing the compositions, are provided. Polythiophene-fullerene conjugates, wherein a conductive polythiophene polymer, such as a regioregular polythiophene, and a fullerene derivative, are constructed with defined spacing between the electron donor polythiophene and electron acceptor fullerene. Photovoltaic devices containing films including the inventive compositions can provide improved photoefficiencies for solar electrical generation with the flexible, relatively inexpensive, organic photovoltaic materials described herein.

Description

</ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; [Prior Art] A photovoltaic cell using an organic material instead of a single crystal germanium as a light absorbing electron generating substrate is expected to provide a low cost, possibly flexible solar panel for power generation, for example, for residential, consumer electronic devices, external sites. Power and so on. Single crystal germanium and other inorganic photovoltaic materials can be very expensive and inefficient, and present processing challenges due to unfavorable physical properties. Photovoltaic devices based on organic materials can avoid some of these problems and make solar power economically viable. Polythiophene polymers are known to be effective electron donors in organic photovoltaic cells in which photoexcited electrons are received by materials having effective electron affinity. See, for example, T. Akikyama et al., "Solid-State Solar Cells Consisting of Polythiophene-Porphyrin Composite Films.", Jpn. J. Appl. Phys. (2005), 44 2799-2802; J. Nakamura et al. "The Photovoltaic Mechanism of a Polythiophene/Perylene Pigment Two-Layer Solar Cell", Bulletin of the Chemical Society of Japan (2004), 77(12) 2185-2188; R. Radbeh et al., "Nanoscale control of the network morphology of High efficiency polymer fullerene solar cells by the use of high material concentration in the liquid phase", iVanoiec/zno/og;; (2010), 21, 1-8; B. Fan et al. 162632.doc 201238995 person, "Polythiophene/fullerene Bulk heterojunction solar cell fabricated via electrochemical co-deposition", Solar Energy Materials and Solar Cells (2006), 90(20), 3 547-3556; all such references and references cited therein are incorporated herein by reference. . Polythiophenes having a single fullerene as a polymer capping group have been prepared; see J. Lee et al. "Synthesis of C60-end capped P3HT and its application for high performance of P3HT/PCBM bulk heterojunction solar cells", / · Maier. CAew. (2010), 20, 3287-3294 °

Radbeh et al. clarify that maximizing the interface area of donor and acceptor components of organic photovoltaic cells is desirable for improving power generation efficiency, and discusses the use of interpenetrating nano-networks of polythiophene components and fullerene components. . Polythiophene is a suitable conductive polymer known as one of the electron donors in organic photovoltaic cells. The polythiophene can be a positionally-regular polythiophene, such as H-T 2,5-polythiophene, which can be prepared, for example, according to U.S. Patent No. 7,572,880 to the inventor of the present application, and U.S. Patent Application Serial No. 2010/0004423 and No. 2010/031 1879. SUMMARY OF THE INVENTION The present invention relates to compositions for use in organic photovoltaic cells, such as those in which polythiophene/fullerene interpenetrating networks have previously been used; and in relation to methods of preparing such compositions; An electroactive membrane of the composition; a photovoltaic cell or device for use with the composition of the invention; and a method for preparing such photovoltaic cells. 162632.doc 201238995 In various embodiments, the present invention provides a composition for photovoltaic power generation comprising a polythiophene polymer having a thienyl repeating unit, wherein at least some of the porphins are not disposed at the end of the polymer chain The radical repeating unit is covalently or ionically bonded to each of the respective Fullerene® ® ° f-alkenyl groups via a respective linker, along the primary bond of the polymerized polymer bond, and a plurality of I The lenylene group can be attached to a single polymer molecule in a covalent manner or ionically. In essence, each of the repeating units may be bonded with a fullerene group, = a lower proportion of the (four) group repeating unit may have a fullerene. These fullerenes may be randomly distributed along the polymer chain, or may be present in In the segment of the polymer chain. In the various embodiments, the invention provides a film comprising any of the compositions of the invention. Electroactive membranes can be adapted for assembly into photovoltaic power generation cells or cell arrays for the fabrication of solar panels using organic materials. In various embodiments, the invention provides a method of making a composition of the invention comprising: having a linker precursor group &lt;poly0-cephene polymer with a Fuller suitable for reaction with the linker precursor group Dilute contact to form a covalent bond or an ionic bond. In other embodiments, the invention provides a process for the preparation of a composition of the invention comprising polymerizing a fullerene-substituted 2,5-dihalothiophene in the presence of a metal catalyst and optionally having no fullerene 2,5_diylthiophene copolymerization of the group. In various embodiments, the invention provides a method of making a film comprising applying a composition prepared by the process of the invention to a surface, optionally in the form of a solution, followed by evaporation of the solvent. In various embodiments, the invention provides a photovoltaic device comprising a composition or film of the invention, 162632.doc 201238995, a composition or film prepared by the method of the invention. [Embodiment] Definitions The term "fullerene" as used herein refers to a family of globular homomorphs of carbon and its derivatives. Thus, C60 and C61 fullerenes and derivatives may include

PCBM)

(6,6)-Phenyl-C61 Butyric Acid (PCBA) 162632.doc • 6 - 201238995

(6,6)-phenyl-C61-butyl-Z (PCB-based-z) For example, 'Z=〇H=PCBylOH Z=relating group=PCByl-LG (for example, sulphuric acid vinegar, etc.) The structure not labeled C60-fullerene above is referred to as "underivatized fullerene", and the C61-fullerene compound is as used herein as "derivatized fullerene" or "fullerene derived" Things." For example, C61_fullerene can be prepared by reacting a carbene olefin flooding reagent with an underivatized fullerene, wherein a carbene is inserted into a fullerene double bond to give a cyclopropane group, for example, in pcBA In this case, the cyclopropane group may have a substituent on the non-bridgehead carbon atom. Various carbene-producing precursor reagents or carbene precursor reagents include diazonium compounds, azide, chlorocarbene reagents (for example, de-commercial hydrogen reaction from a di-alkyl group), Fischer carbene reagents (carbon thinning) • Metal complexes) and the like. See, for example, N. Bespalova, "Cyclopropanation of Buckminsterfullerene by Olefin Metathesis Reaction", ...w. C/zem. 5m//. (1996), 45(5), 1255-1256 and references cited therein. The structure labeled C61-fullerene above is unsubstituted C61·fullerene' and PCBA and the like are substituted for C61_fuller. Similar to C60- and C61-Fuller ' 'The term "Fuller" is also used herein to cover 162632.doc 201238995 Similar to C70- and C71-Fuller 嫱r soil, ene (not biochemical and derivatized) . A compound such as PCBA or a fullerene derivative having a fine carboxylic acid group is referred to as a olefinic carboxylic acid; likewise, a fullerene (for example, PCBM) having a fluorene and a carboxylic acid SA S group is called For the "Fulleric acid vinegar", the substance of the reaction (4) is called "Fuller diluted methanol", and the derivative of the richer compound of Yuji is called fullerene carboxylic acid. The substance is called "fulleramide" and the like. The term "cationic fullerene" or "cationic fullerene derivative" as used herein refers to a fullerene having a positive charge at the working pH; the positive charge can be permanent and permanent (in the case of the fourth-order Syrian Lele) Lower), or may be pH dependent (in the case of an amine-rich fully, the example of a cationic fullerene is shown below:

See, for example, R. Bullard-Dillard et al., "τ. 0. 丄 issue Sites 〇f

Uptake of -C-labeled C6〇J (1996), Bi〇〇rg ^ 376' is incorporated herein by reference. Another example of cationic fullerene is the choline ester of PCBA or the test of PCByl-〇H: 162632.doc 201238995

Construction (B)) can be prepared by reacting choline with an activated ester of pCBA or activated methanol from PCBA via, for example, diborane reduction, followed by activation of the nucleophilic displacement (eg by Formation of triflate) followed by a reaction with the biliary assay. Other C61_Fuller dilutes may also be suitably derivatized using cationic groups known in the art and which may be prepared by methods in the art, such as groups having a quaternary recording ion. Accompanying the hydrazone or the term Λ, ^ ^ ...... Γ 咕 卞冨 卞冨 衍生物 衍生物 」 具有 具有 具有 具有 具有 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业s ene ene; for example, within the meaning of this article, the carboxylate form of PCBA is an anion-reductive acid derivative, an anion richer, another example - 'Preparation The edge of the show does not show up in the case of ^, but the solution is not hollow, the B household has a key map as shown in the back, to the rice. 々 does not moxibustion key pattern, so that or spherical 4 The olefin is a C6 enrichment of the bond of the roughly spherical knife Ding Jun back as shown below. Alternative representation of olefin

162632.doc -9- 201238995 In this illustration, the keys on the back are displayed in gray tones. It is recognized that the butyl or butanyl chains of PCBA and its ester or sterol derivatives or other derivatives can be replaced by linkage chains of different lengths. By varying the linkages, the distance between the polythiophene backbone and the fullerene unit can be systematically varied. Different electron transfer efficiencies from polythiophene to fullerene can be achieved depending on the length of the different linker chains under irradiation. Other fullerene derivatives which may be incorporated into the polythiophene-fullerene conjugates of the present invention may have other suitable modifications to the nuclear spherical/spherical fullerene structure. Any of these functional groups having a functional group which can be covalently or ionically coupled to a linker precursor group on the polythiophene polymer backbone can be used. The carbene insertion reaction product of fullerene with a carbene-generating reagent such as a diazonium compound and the like can provide a series of groups other than the phenyl, carboxyalkylcyclopropane group insertion product of pCBA. In addition, although the derivatives shown are monosubstituted by a cyclopropyl ring, in the meaning herein, the fullerene derivative may be disubstituted or substituted, provided that the substitution of the fullerene core is not damaged. Electron reception of a fullerene system required for photovoltaic power generation device operation The term "polythiophene" or "〇" thiophene polymer" as used herein refers to a heavy-duty system. A polymer of phenotype (commonly referred to as a porphinyl or a unit) that is directly coupled to other thiophene units such that the polymer contains a common electronic system. Some of these conjugated polythiophene polymers are known to be electrically conductive. An example of 2,5·polythiophene is shown; each &gt; empty is the 3 position of the milling and can be substituted. The terminal group of the bond may be hydrogen, halogen, fluorene alkyl or other monovalent group, depending on the method of synthesis. See, for example, U.S. Patent No. 162,632, doc to U.S. Patent Application Serial No. No. No. No. No. No. No. No. No. No. Nos. The degree of polymerization may be an oligomer length (eg, η is about 8 or 9) up to several thousand, corresponding to about 1 〇〇〇 (Dp is about ι〇) to at least about 200,000 (DP is about 2, GGG) and More polymer molecular weight (weight average molecular weight). The polythiophene may also be a 2,4- or 3'4-poly singer as defined by the position bonded to each thiophene ring, or may be a random mixing. The attachment point of Fullerene is located in a carbon atom that does not participate in the thiophene (4)-bonding of the polymer primary bond, for example, in the 3_ or 5_ position for 2,4_polyphene, or for 3 , the heart polyporosity is located in the 2 or 5 position. The positional rule μ is the form of the polymer in which the bonding positions of each repeating unit are uniform. Positional Rule 2,5-Polymer exemplification Examples As shown below, each __ asterisk in # indicates a continuous poly- 键 key' each having a terminal group at each end of the molecular polymer chain.

(Position rule 2,5-polypyrrole) The thiol unit may be substituted, for example, the positional rule 2,5-polythiophene may be in the 3-position, 4-position or both of each repeat unit of the singular ring) The substitution unit has a thiophene pair dimer unit ^•, a head-to-head (ΗΗ), a head-to-head (ΗΗ) or a tail-to-tail (ττ) : Distribution of substituents on mono-thiophene monoterpene. For the positional rule · mouth -»-* with &amp;, when the 3_ substituent is the same as the 4-substituent, the form is simplified (phase 5 t for positional rule 3-substituted-2,5-polythiophene, per The isomeric form of the 1-2 〇 吩 吩 unit can be as follows: I62632.d〇c 201238995 xx

Head-to-head (ΗΗ) Head-to-tail (ΗΤ) tail-to-tail (ττ) where the asterisk indicates a continuous polymer chain with a terminal end. A polythiophene polymer comprising a monosubstituted porphin repeating unit or a sulfonyl substituted thiophene repeating unit substituted with two different groups of I may comprise a mixture of the three isomeric monomeric forms. The regular π polythiophene mainly includes the ruthenium form only or recently; the poly-β-enantiomer which necessarily contains the dimer also contains ruthenium or osmium dimer, or both. It is highly suitable for forming a covalent valerene as described herein. The polythiophene polymer used in the sputum and in the photovoltaic cell is a positional rule containing a monosubstituted thiophene repeating unit. ΗΤ-2,5-polythiophene

Where the asterisk (*) indicates a continuous polystimulus chain, which may have the same type of structure, wherein each chain has a respective terminal atom or group. See, for example, U.S. Patent No. 7,572,880, the disclosure of U.S. Patent No. 7, 572, 880, and U.S. Application Serial No. 2010/0004, 423, and No. 2010/031, No. 1, 162, 632, doc. A polythiophene that refers to a fullerene unit via a thiophene substituent that is covalently or ionically coupled thereto (ie, between thiophene units that are not themselves incorporated into the polymer chain). For example, in the case of the positional HT_monosubstituted-2,5-polythiophene as described above, the fullerene unit is covalently coupled to the polymer backbone via a hydrazine group, as follows Discussed. Each of the oxime groups need not have a fullerene unit, but a portion of the X group is bonded to the fullerene unit. In the case of HT-monosubstituted-2,5-polythiophene, the degree of substitution of the polythiophene backbone having a fullerene unit may be between i (in the case where each thiophene unit has fullerene) Down to between 0.01 or less (wherein one or one of the per hundred thiophene units has an average of fullerene). The term "covalent conjugate" as used herein refers to a polythiophene polymer chain and a fullerene molecular material bonded by a covalent organic bond (e.g., a single bond or a double bond). The covalent conjugate can be formed by any suitable technique for forming a bond known in the art of organic synthesis, provided that a suitable precursor having a reactive group on both the polythiophene and the fullerene is available. For example, the covalent conjugate of the present invention can be obtained by reacting a carboxylic acid group or a derivative group on a polythiophene or a fullerene with a respective alcohol group or amine group on the fullerene or polythiophene of the reaction component. Condensation is prepared to form an ester bond or a guanamine bond in the preparation of a covalent host. Alternatively, an alkylation reaction involving a nucleophile and an electrophile can be used. Alternatively, a Wittig type reaction can be carried out between the conjugated derivatives of polystimene or fullerene and the rust inner salt formed by each of the self-rich or porphin. The linker can include amines, amines, esters, anhydrides, and other linkages that can be formed from appropriate precursors under conditions known in the art of organic synthesis. When it is clarified that the thiophene repeat 162632.doc -13· 201238995 "has" or "covalently bonded to" fullerene, this means that the specific thiophene repeating unit is fuller (via the linker) Or a repeating unit that is primarily attached, but it will be appreciated that it is also bonded to other 0-secret repeating units via a thienyl-thienyl linkage of the polymer. The term "ion conjugate J" as used herein refers to a molecular entity in which a charged fullerene derivative and a polythiophene having a suitable oppositely charged group are associated via ionic interaction. For example, by an anionic group and The formation of an ionic bond between the cationic groups causes the cationic fullerene derivative to form an ionic conjugate with the anionic polythiophene polymer. For example, an anionic polythiophene (eg, a polythiophene substituted with an alkylcarboxylate substituent) can be The cationic fullerene derivative forms an ionic conjugate, such as described above. Alternatively, an anionic fullerene derivative (eg, a PCBA carboxylate ion) can be combined with a cationic polythiophene derivative (eg, substituted with an alkyl carboxylate) A choline ester of thiophene or a polythiophene substituted with a quaternary ammonium group, for example, a polythiophene substituted by an alkyl group having a leaving group such as a dentate group or a sulfonate group and a trialkylamine group The reaction forms to form an ionic conjugate. As used herein, the term "linker" or "linker group" refers to a covalently bonded bond to one or more thiophene rings of a polythiophene polymer. Machine section, although fullerene (including fullerene derivative) itself based covalently or ionically bonded manner to the organic moiety. The linker may be any suitable arrangement for covalently or ionically bonding the fullerene group to the atom of the polythiophene backbone, but may include an alkyl, an alkenyl or an alkynyl chain. Wherein, oxygen, I and sulphur are additionally included as appropriate and functional groups such as ethers, esters, guanamines, ureas, amine phthalic acid vinegars, acid anhydrides and the like can be included in the chain. 162632.doc 201238995 "Stretching base" chain means at least a bifunctional group of the formula -(CH2)n_, such as a fluorene group, an ethyl group, and the like. The "Jianxian" connection system specifically contains at least one double bond (unsaturated) alkylene linker. And the "alkenyl" linkage system incorporates at least one triple bond alkylene linker. Any of these linkers may include other functional groups and may include heteroatoms as discussed above. When referring to a linker, the "alkyl group" linker used herein includes "alkylene group", the "alkenyl" linker comprises "alkenyl group", and the "alkynyl" linker comprises "extended alkynyl group". The linker may be a straight chain, or the linker may be branched, which may include a cyclic moiety (including a cycloalkyl group, a heterocyclic group, an aryl group, and a heteroaryl group), or both. The linker can be formed during the coupling of the fullerene to the polythiophene, for example by suitably derivatizing the fullerene with a suitably derivatized polythiophene (e.g., having a W "linker precursor group" "Polyphene" reacts and forms new covalent bonds. The term "linker precursor group" as used herein refers to a substituent on the polythiophene polymer backbone which is reactive with a fullerene derivative to obtain a covalent or ionic linkage to the poly via a linker. A fullerene group of the main chain of the phenanthrene polymer. For example, a fullerene derivative containing a carboxylic acid group can be coupled with a polythiophene having an amine group (e.g., an aminoalkyl group) to form a linker comprising a guanamine bond. In this example, the aminoalkyl group on the polythiophene can be considered as a linker precursor group. Alternatively, a fullerene derivative containing a carboxylate ion may be coupled to a polythiophene having a cationic group to form a linker comprising an ammonium salt of a carboxylic acid group. Alternatively, the linker can be formed by the formation of a carbon-carbon single bond, for example by a c-alkylation reaction, for example, an enolate with 162632.doc 15 201238995 alkyl dentate, alkyl sulfonate or others Alkylation of the alkyl group of the leaving group, or by, for example, formation of an organometallic reagent, such as a Grignard reaction or an organolithium reaction, and reaction with a suitable group such as an aldehyde, ketone or ester. The linker can also be formed by the formation of a new carbon-carbon double bond, such as by a Wittig type reaction of a ruthenium salt with an aldehyde or a ketone, or by other similar reactions, such as Horner Wadsw of a phosphate ion and a carbonyl group. 〇rth Emm〇ns reaction, etc. Although each of the phenanthrene (β-thenyl) repeating units in the polyphenylene polymer may have a linker precursor group, in the fullerene-polythiophene conjugate of the present invention, not per-linkage The precursor precursor groups have all been reacted with the fullerene derivative to provide a linker-fulleric dilute substituent in a covalent manner or a reader square on the poly(tetra). In each implementation, only about 1%, or only about 1% to 5%, or only up to 10% of the thiophene repeating unit has a Fuller(IV) organism attached via a linker; most of the base repeating units may have The individual linker precursor groups or derivatives thereof that react with the Fuller's rare organism, while the small portion (tetra)-based repeat unit actually has a linker with its covalently bonded linker. In other embodiments, up to 50% or more of the thiophene mono 7L may have a fullerene group. 'The method of the inventors of the present invention can be used to polymerize the bond = dilute thiophene monomer unit to provide a fullerene substituted with fullerene, which can be coupled with fullerene and other units. The ratio of the maternal-substituted polythiophene thiophene group to 70 to prepare a partially cross-linkage between the fullerene thiophene backbone and the fullerene side group can affect the efficiency of the photovoltaic device formed by the material 162632.doc 201238995 . The length of the linker and the rigidity of the linker can be used to limit the average spacing between the olefinic group and the electron-donating polybenzazole backbone. The term "film" as used herein refers to a self-supporting or free-standing film that exhibits mechanical stability and flexibility and refers to a coating or layer on or between the support substrates. As used herein, the terms "co-property" and "covalent consumables" refer to two molecular entities joined by covalently dry bonds or ionic chemical bonds (i.e., 'not only by non-bonding association or mismatching). Examples of covalent bonds are carbon-carbon bonds. An example of an ionic bond is a salt bond. Unless the context clearly dictates otherwise, the singular forms "_(a, an)" and "the" used in the specification and the appended claims are inclusive of the The value or range varies within the specified value or within the specified value or within 5%. All percentage compositions are given in weight percent unless otherwise stated. The average average molecular weight of the polymer, unless otherwise indicated. You: Qiu or "degree of polymerization" refers to the number of repeating units in a polymer molecule. For polythiophenes, the specific molecular weight of the base soap 70 is about 100 μL. The condition is i00 DP. Corresponding to about i〇, _ Dalton polymer molecule 162632.doc 17 201238995 "DS" or "degree of substitution" refers to the average number of repeating units in the polymer chain having a substituent. For example, a polythiophene-richer conjugate of &apos; DS = 1 means that substantially every single thiophene unit has a single fullerene. The term "substantially" as used herein means completely or nearly completely; for example, a composition that is "substantially free" of a component does not have the component or contains trace amounts, wherein any relevant functional properties of the composition are not Affected by the presence of the trace ' or the compound is "substantially pure" means that there are only trace impurities that are negligible. "Chemically feasible" means a bonding arrangement or compound that does not violate the generally understood rules of organic structure; for example, a structure within the definition of the scope of the patent application, if it in some cases contains a pentavalent carbon atom that does not exist in nature , it will be understood as not being within the scope of the patent application. In all of its embodiments, the structures disclosed herein are intended to include only "chemically feasible" structures and are not intended to suggest or claim any of the chemically infeasible structures (eg, having a variable atom or group as indicated). In the structure of the group, when the substituent is specified as - or a plurality of atoms "or bonds" having the properties of the finger, the following configuration is mentioned. The substituent is chemically related to the group directly adjacent to the specified substituent. A "key" that is directly linked to each other by a bond structure. Unless explicitly stated in the stereochemical or isomeric form of the shirt, all pairs of palm, diastereomeric, and racemic forms of the structure are present. =, 2, the compounds used in the description may include any or all of the asymmetric atomicity including enrichment or resolution of optical isomers, "offset and human", the essence: the two and the individual optical isomers can be separated Or 4 is substantially free of its enantiomeric or diastereomeric constituents and such 162632.doc 201238995 are all within the scope of the invention. In general, "substituted" means one or more of them. One to many bonds to a hydrogen atom An organic group as defined herein substituted with a bond to a non-hydrogen atom, such as, but not limited to, a halogen (ie, F, Cl, Br, and I); an oxygen atom such as a hydroxyl group, an alkoxy group a base, an aryloxy group, an aralkyloxy group, a pendant oxy group (carbonyl group), a carboxyl group (including a carboxylic acid, a carboxylate, and a carboxylic acid ester); a sulfur atom such as a thiol group, an alkyl group, and the like An aryl sulfide group, a sulfhydryl group, a fluorenyl group, a sulfonyl group, and a sulfonamide group; a nitrogen atom such as an amine, a hydroxylamine, a nitrile, a nitro group, an N-oxide, an anthracene, Azides and enamines; and other heteroatoms in various other groups. Non-limiting examples of substituents J that may be bonded to substituted carbon (or other) atoms include F, CU, Br, I, OR' , 0C(0)N(R,)2, CN, NO, N〇2, 〇N02, azido, CF3, OCF3, R', 0 (sideoxy), S (thiocarbonyl), C(O ), S(O), methylene dioxy, exoethyl dioxy, N(R')2, SR', SOR', S02R', S02N(R')2, S03R', C(0 ) R,, C(0)C(0)R' ' C(0)CH2C(0)R' &gt; C(S)R' &gt; C(0)0R' ' OC(0)R' & G(o)n(r')2, oc(o)n(r')2, C(S)N(R')2, (CH2)〇.2N(R')C(0)R ', (CH2)〇-2N(R')N(R')2, N(R')N(R')C(0)R',N(R')N(R')C(0) 0R·, n(r')n(r')con(r')2, n(r')so2r,,n(r')so2n(r,)2, N(R')C(0)0R ', N(R')C(0)R;, N(R')C(S)R', N(R')C(0)N(R/)2, N(R')C(S N(R')2, N(COR')COR·, N(OR')R', C(=NH)N(R')2, C(0)N(0R')R· or C( =NOR')R·, wherein R· can be hydrogen or a carbon-based moiety, and wherein the carbon-based moiety itself can be further substituted; for example, wherein R′ can be hydrogen, alkyl, decyl, cycloalkyl , aryl, aralkyl, hetero-162632.doc -19- 201238995 cyclic, heteroaryl or heteroarylalkyl, any of which is alkyl, fluorenyl, cycloalkyl, aryl, aralkyl, hetero A cycloalkyl, heteroaryl or heteroarylalkyl group or Ri may be independently mono- or polysubstituted by J; or two R' groups bonded to a nitrogen atom or adjacent to a nitrogen atom may be bonded to one or more nitrogens The atom or atom together form a heterocyclic group. The heterocyclic group may be monosubstituted by J or independently substituted. When the substituent is a monovalent unit (e.g., 'F or Cl), it is bonded to an atom substituted with a single bond. When the substituent exceeds the monovalent (eg, hydrazine, which is divalent), it may be bonded to an atom substituted by more than one bond, ie, the divalent substituent is bonded by a double bond; for example, substituted by hydrazine C forms a carbonyl group c = 〇, which can also be written as "CO", "c(0)" or "c(=0)", where C and 0 are double bonded. When a carbon atom is substituted with a double bond oxygen (=〇) group, the oxygen substituent is referred to as a "sideoxy group". When a divalent substituent (e.g., NR) is double bonded to a carbon atom, the resulting C(-NR) group is referred to as an "imine group." When a divalent substituent (e.g., s) is double bonded to a carbon atom, the resulting c(=s) group is referred to as "thiocarbonyl." Alternatively, a divalent substituent such as deuterium, S, C(o), s(0) or s(o)2 can be attached to two different carbon atoms by two single bonds. For example, 0 (divalent substituent) can be bonded to each of two adjacent carbon atoms to provide an epoxy group, or a hydrazine can form a bridge ether group between adjacent or non-adjacent carbon atoms ( It is called "oxy"), for example, bridging a cyclohexyl group, 4_carbon to form a [2.2.1]-oxabicyclic system. Furthermore, any substituent may be bonded to a carbon or other atom by a linker (eg, (CH; 〇n4 (CR'2)n), wherein ^^, 2, 3 or greater, and each R' Independently selected. The C(〇) and S(〇)2 groups may also be bonded to one or two heteroatoms (eg, or 162632.doc -20-201238995 oxygen) rather than to a carbon atom. When the c(0) group is bonded to a carbon and a nitrogen atom, the resulting group is referred to as "guanamine" or "carboxyguanamine." When the c(o) group is bonded to two nitrogen atoms The functional group is called urea. When the c(o) is bonded to an oxygen and a nitrogen atom, the resulting group is called "urethane" (1*1^1^ or 111^113116). When the 8(〇)2 group is bonded to one carbon and one nitrogen atom, the resulting unit is called "sulfonamide". When the S(O)2 group is bonded to two nitrogen atoms, the resulting unit is called Is an "aminosulfonate". Substituted alkyl, alkenyl, alkynyl, cycloalkyl and cycloalkenyl groups and other substituted groups also include one or more bonds to a hydrogen atom through one or more a carbon atom or a bond to a hetero atom (including double Or a triple bond) substituted group such as, but not limited to, a carbonyl group (0X0), a carboxyl group, an ester, a decylamine, a quinone imine, a urethane, and an oxygen group in a glandular group; and an imine, a transimine Nitrogen in fat, knee, vein, vein and nitrile. Substituted ring groups (eg substituted cycloalkyl, aryl, heterocyclic and heteroaryl) also include bonds to hydrogen atoms to carbon atoms a ring-substituted ring and a fused ring system. Thus, substituted aryl, aryl, heterocyclyl and heteroaryl groups may also be substituted with alkyl, alkenyl and alkynyl groups as defined above. The term "ring system" as used herein. By means of a moiety comprising one, two, three or more rings which may be substituted by an acyclic group or by another ring system or both 'which may be fully saturated, partially saturated, fully unsaturated or Aromatic' and when the ring system includes more than a single ring, the rings may be fused, bridged or spiro. #工业是''''''''''''''''' Type 162632.doc -21- 201238995 Of course 'for any of the groups described herein containing one or more substituents 'It should be understood that the groups do not contain any sterically unrealistic and/or synthetically unacceptable substitution or substitution patterns. In addition, the compounds of the subject matter disclosed include all stereochemical differences resulting from the substitution of such compounds. The selected substituents in the compounds described herein are present in a regressive manner. In this context, 'recursive substituents' means that the substituents may state themselves or otherwise represent another substituent of the first substituent. Another case. Due to the regressive nature of the substituents, in theory, it can be present in a large number in any given patent application. Those of ordinary skill in the art of medicinal chemistry and organic chemistry should understand that The total number is appropriately limited by the desired properties of the given compound. Such properties include, by way of example and not limitation, physical properties (e.g., molecular weight, solubility, or log Ρ), application properties (e.g., for a given activity), and actual properties (e.g., ease of synthesis). Recursively the established aspect of the subject matter disclosed by the substituent. The general practitioners in the fields of medicinal chemistry and organic chemistry should be aware of the diversity of such substituents. The degree of recursive substituents in the scope of the patent application for the subject matter disclosed should be determined as stated above. The alkyl group includes a linear and branched alkyl group having from 1 to about 20 carbon atoms and a cycloalkyl group, and usually from 1 to 12 carbons, and in some embodiments, from 1 to 8 carbon atoms. Examples of the linear alkyl group include those having 1 to 8 carbon atoms such as decyl, ethyl, n-propyl, n-butyl, n-decyl, n-hexyl, n-heptyl and n-octyl groups. Examples of branched alkyl groups include, but are not limited to, isopropyl, isobutyl, t-butyl, t-butyl, neopentyl, isopentyl, and 162632.doc • 22-201238995 2,2-dimethyl Base propyl. The term "alkyl" as used herein, encompasses n-alkyl, isoalkyl and s-isosyl, as well as other branched forms of alkyl. Representative substituted alkyl groups may be substituted one or more times by any of the groups listed above (e.g., an amine group, a hydroxyl group, a cyano group, a carboxyl group, a nitro group, a thio group, an alkoxy group, and a dentate). A cycloalkyl-based cyclic alkyl group such as, but not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. In some embodiments, the cycloalkyl group can have from 3 to about 8 to 12 ring members, while in other embodiments, the number of ring carbon atoms is between 3 and 4, 5, 6, or 7. The cycloalkyl group further includes a polycyclic cycloalkyl group such as, but not limited to, a (tetra) group, a porphyrin group, a borneol group, an alkenyl group, an isodecyl group, and a material (such as, but not limited to, a naphthyl group and the like). . Cycloalkyl also includes rings which are substituted by straight or branched chain groups as defined above. Representative substituted cycloalkyl groups can be monosubstituted

Or substituted more than once, such as but not limited to 2,2_, 2,3_, 2,4H or 2'6-disubstituted cyclohexyl or substituted by mono-, di- or tri-substituted or cycloheptyl, It may be substituted with, for example, an amine group, a trans group, a cyano 1 group, a nitro group, a thio group, an alkoxy group, and a dentate group. The term "cycloalkenyl", alone or in combination, means a cyclic alkenyl group. Surgery. . The carbon ring, the "carbocyclic group" and the "carbocyclic ring" represent a ring structure of a ring atomic carbon such as a cycloalkyl group or an aryl group. In some embodiments, the carbocyclic ring has from 3 to 8 % members, while in other embodiments, the number of ring carbon atoms is 4 5 6 or 7. Unless expressly stated to the contrary, a carbocyclic ring may be substituted with up to N 1 substituents (wherein the size of the N-type carbocyclic ring), such as an alkyl group, a dilute group, an alkynyl group, an amine group, an aryl group, 1, 1 nitro, thio, alkoxy and i group or 162632.doc • 23- 201238995 Other groups as listed above substituted "carbocyclyl ring can be naphthenic Base ring, ring-like ring or square base. The carbocyclic group may be monocyclic or polycyclic, and if it is a polycyclic ring, the parent ring may independently be a cycloalkyl ring, a ring dilute ring or an aryl ring. (Cycloalkyl)alkyl (also denoted cycloalkylalkyl) is a substituent as defined above wherein the hydrogen or carbon bond of the alkyl group is passed to a bond of a cycloalkyl group as defined above. Alkenyl groups include straight-chain and branched and cyclic alkyl groups as defined above, except that at least one double bond is present between two carbon atoms. Thus, alkenyl groups have from 2 to about 20 carbon atoms, and usually from 2 to 12 carbons, or, in some embodiments, from 2 to 8 carbon atoms. Examples include, but are not limited to, vinyl, -ch=ch(ch3), -CH=C(CH3)2, _C(CH3)=CH2, _C(CH3)=ch(ch3), -c(ch2ch3)=ch2 , cyclohexyl, cyclopentyl, cyclohexane, butadienyl, pentadienyl and hexadienyl. The cycloaliphatic group includes a cycloalkyl group having at least one double bond between two carbons. Thus, for example, cycloalkenyl groups include, but are not limited to, cyclohexyl, cyclopentenyl, and cyclohexyl. The ring-dense group may have from 3 to about 8·12 ring members, while in other embodiments, the number of ring carbon atoms is between 3 and 5, 6 or 7. Cycloalkyl further includes polycyclic cycloalkyl groups such as, but not limited to, norbornyl, adamantyl, borneol, decenyl, isodecenyl and hexenyl, and viscosities (such as, but not limited to, decalin) The base and the like, the condition is that it includes at least one double bond in the ring). The cycloalkenyl group also includes a ring which is substituted by a straight chain or a bonded group as defined above. The (cycloalkenyl)alkyl group is an alkyl group as defined above wherein the hydrogen or carbon bond of the alkyl group is replaced by a bond to a cycloalkenyl group as defined above. 162632.doc -24- 201238995 Alkynyl includes both straight-chain and branched alkyl groups, except that there is at least one triple bond between the two carbon atoms. Thus, an alkynyl group has from 2 to about 20 carbon atoms, and typically from 2 to 12 carbons, or, in some embodiments, from 2 to 8 carbon atoms. Examples include, but are not limited to, -OCH, -CsC(CH3), -OC(CH2CH3), -CH2〇CH, -CH2C=C(CH3), and -CH2OC(CH2CH3). Unless otherwise stated, the term "heteroalkyl", by itself or in combination with another term, means a stable straight chain consisting of a specified number of carbon atoms and one or two heteroatoms selected from the group consisting of ruthenium, N and s. Or a branched alkyl group, wherein the nitrogen atom and the sulfur atom may be oxidized as appropriate and the nitrogen hetero atom may be subjected to quaternization as the case may be. The heteroatom can be placed at any position of the heteroalkyl group, including between the remainder of the heteroalkyl group and the attached moiety thereof, and the most carbon atom attached to the heteroalkyl group. Examples include: _〇_CH2_CH2_CH3, _CH2_CH2CH2-〇H '-CH2-CH2-NH-CH3 '-CH2-S-CH2-CH3 '-ch2ch2-s(=0)-ch3 and -ch2ch2-o-ch2ch2- O-ch3. Up to two heteroatoms may be consecutive 'e.g., -CH2_NH-OCH3 or -ch2-ch2-s-s-ch3. The "heterocyclic ring" ring contains a cycloalkyl ring containing at least one hetero atom. Heterocyclic base rings may also be referred to as "heterocyclic groups", as described below. Unless otherwise indicated, the term "heteroalkenyl" is itself or in conjunction with another term ''and 5' and consists of a specified number of carbon atoms and one or two heteroatoms selected from the group consisting of ruthenium, n and s. A stable linear or branched monounsaturated or bis-unsaturated hydrocarbon group, wherein the nitrogen atom and the sulfur atom may be oxidized as appropriate and the nitrogen hetero atom may be quaternized as appropriate. Up to two heteroatoms can be placed in succession. 〇CH3 ^ -CH=CH-N(CH3)-CH3 &gt; -CH2-CH=CH-CH2-SH^ 162632.doc -25· 201238995 -CH=CH-0-CH2CH2-0-CH3 〇aryl A cyclic aromatic hydrocarbon containing no heteroatoms in the ring. Thus aryl groups include, but are not limited to, phenyl, ground-based, cyclohepta-thyl, biphenyl, bicyclo-di-diphenyl, fluorenyl, phenanthryl, tri-phenyl, ke, fused, stupid, Xi-based, extended biphenyl 'fluorenyl and naphthyl. In some embodiments, the aryl group contains from about 6 to about 14 carbons in the ring portion of the groups. As defined above, the aryl group can be unsubstituted or substituted. Representative substituted aryl groups may be substituted or substituted by one or more times, such as, but not limited to, 2, 3, , or 6 or substituted phenyl or 2 to 8' substituted naphthyl, which may be carbon Or a non-carbon group (such as those listed above). The aralkyl group is an alkyl group as defined above wherein the hydrogen or carbon bond of the alkyl group is replaced by a bond of an aryl group as defined above. Representative aryl groups include a benzyl group and a phenylethyl group and a fused (cycloalkylaryl)alkyl group (e.g., 4 ethyldihydroindenyl). Fang County is a thin base as defined above, and its gas or carbon bond is replaced by a bond of an aryl group as defined above. Heterocyclyl or the term "heterocyclyl" includes both aromatic and non-aromatic ring compounds containing 3 or more ring members, wherein one or more heteroatoms such as, but not limited to, ruthenium, osmium and S ❶ And the heterocyclic group may be a heterocycloalkyl group or a heteroaryl group or, if it is a polycyclic ring, any combination thereof. In some embodiments, a heterocyclic group includes from 3 to about 20 ring members, and other such groups have from 3 to about 15 ring members. The heterocyclic group designated as a heterocyclic group may be a 5-ring having two carbon atoms and two hetero atoms, a 6-ring having two carbon atoms and four hetero atoms, and the like. Also, the Cp heterocyclic group may be a 5-ring having one hetero atom, a 6-ring having two hetero atoms, or the like. The number of carbon atoms plus the impurity 162632.doc • 26 · 201238995 The total number of children is equal to the total number of ring atoms. The heterocyclyl ring may also include one or more double bonds. Examples of heteroaryl ring heterocyclic groups. The phrase "heterocyclyl" includes fused ring materials including those containing fused aromatic and non-aromatic groups. For example, within the meaning herein, both the dioxolanyl ring and the benzo-oxolyl (tetra) (methylene:oxyphenyl ring system) are heterocyclic groups. The phrase also includes polycyclic systems containing heteroatoms such as, but not limited to, quinuclidinyl. The heterocyclic group may be unsubstituted or may be substituted as described above. Heterocyclyl groups include, but are not limited to, &quot;比比基基,钱基&quot; 基基基, 淋 基 ” 比 比 & 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比°坐基&quot;塞基基' ° than sulfhydryl, phenylthio, benzophenylthio, benzofuranyl, dibenzobenzopyranyl, 0-fluorenyl, dihydro-yl, aza T-based, :: carbazolyl, benzimidazolyl, azabenzimidazolyl, benzoxazolylbenzoxanthyl, benzon-n-diyl, _β-sitting &amp;# ϋ 比 咬 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟 嗟The sylindolinyl oxime, substituted heterocyclyl may be monosubstituted or substituted more than once, for example, but not limited to, by groups such as those listed above, 2, 3, 4, 5, or a 6-substituted or disubstituted piperidinyl or quinolyl group. A heteroaryl group containing 5 or more ring-forming aromatic ring compounds, wherein '- or a plurality of heteroatoms' are, for example but not limited to, N, 〇 and s; for example, the heteroaryl ring may have from 5 to about 8·12 a heterocyclic group is a heterocyclic group having an aromatic electronic structure. The heteroaryl group designated as a heteroaryl group may be a 5-ring having two carbon atoms and three hetero atoms, having two carbon atoms. And the four hetero atoms of the 6th ring, etc. Similarly, the &amp;heteroaryl group can be a 162632.doc -27· 201238995 5-ring having a hetero atom, 6 ring having two hetero atoms, etc. The number plus the number of heteroatoms is equal to the total of the ring atoms (4). Heteroaryl groups include, but are not limited to, the following groups: a base group, a fluorenyl group, a trisal group, an oxazolyl group, an oxazolyl group, # Oxazolyl, thiazolyl, pyridyl, phenylthio, benzophenylthio, benzoheptyl, bromo, aza-beta, thiol, benzo-salt, Azapine, benzoxyl, benzothiazolyl, benzothiadiazolyl, imidazopyridylisoxazolopyridyl, naphthyl, anthracenyl, xanthine , adenyl, fluorenyl, quinolyl, isoquinolyl, tetrahydroquinolyl, quinoxalinyl and quinazolinyl. Heteroaryl may be unsubstituted or may be as described above Substituted. Representative substituted heteroaryl groups may be substituted with one or more 0 aryl and heteroaryl groups via groups such as those listed above including, but not limited to, phenyl, biphenyl, fluorenyl, Naphthyl (1-naphthyl, 2-naphthyl), anthracene-yl-tetras-yl, anthracene-yl-trisyl. Sodium, anthracene-hydroxyimidazolyl, anthracenyl (1 - fluorenyl, 2 fluorenyl, 3 _ mercapto), phenylthio (2-thienyl, 3-thienyl), furyl (2-furyl, 3-furyl), decyl, oxadiazolyl, isoxazolyl, quinoxaline Orolinyl, fluorenyl, oxime, isoindoline, benzhydryl, acridinyl, thiazolyl, pyrrolyl (2-pyrrolyl), indolozolyl (3·β-pyrazolyl) , imidazolyl (1 • imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl), triazolyl (1,2 3 -triazole-based, 1,2,3-triazole·2- Base, 1,2,3-triazol-4-yl, 1,2,4-triazole-3-yl), oxa. Sitrate (2-oxazolyl, 4-oxazolyl, 5-oxazolyl), thiazolyl (2-thiazolyl, 4-thiazolyl, 5-thiazolyl), pyridyl (2-pyridyl, 3 -pyridyl, 4-pyridyl), pyrimidinyl (2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 6-pyrimidine 162632.doc •28·201238995 bite base), °bazinyl, snarling&quot; Qin Ji (3-Danthyl, 4-Dalaki, 5--anthra), quinoline (2-噎, 基, 3-啥琳基, 4-噎淋基, 5-啥琳基, 6-quinolyl, 7-quinolyl, 8-quinolinyl), isoquinolyl (1-isoquinolinyl, 3-isoquinolinyl, 4-isoquinolinyl, 5-isoquinoline ,6-isoquinolyl, 7-isoquinolyl, 8-isoquinolinyl), benzo[b]furanyl(2-benzo[b]furanyl,3-benzo[b]furan , 4-benzo[b]furanyl, 5-benzo[b]furanyl, 6-benzo[b]furanyl, 7-benzo[b]furanyl), 2,3-dihydro- Benzo[b]furanyl (2-(2,3-dihydro-benzo[b]furanyl), 3-(2,3-dihydro-benzo[b]furanyl), 4-(2) , 3-dihydro-benzo[b]furanyl), 5-(2,3-dihydrobenzo[b]furanyl), 6-(2,3-dihydro-benzo[b]furan Base), 7-(2,3- Argon-benzo[b]furanyl)), benzo[b]phenylthio (2-benzo[b]phenylthio, 3-benzo[b]phenylthio, 4-benzo[b] Phenylthio, 5-benzo[b]phenylthio, 6-benzo[b]phenylthio, 7-benzo[b]phenylthio), 2,3-dihydro-stuppy[b] Phenylthio (2-(2,3-dihydro-benzo[b]phenylthio), 3-(2,3-dihydro-benzo[b]phenylthio), 4-(2,3) -monohydro-benzo[b]phenylthio), 5-(2,3-dihydro-benzo[b]phenylthio),6-(2,3-dihydro-benzo[b]benzene Thio), 7-(2,3-dihydro-benzo[b]phenylthio)), fluorenyl (1 - fluorenyl, 2-indenyl, 3-indolyl, 4-»丨 丨 0 base, 5--. 引 ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” - ° 〇 〇 sit, 5 ·, sit, 6 丨〇 丨〇 sit, 7-. 引., benzopyranyl (1-benzimidazolyl, 2-benzimidazolyl , 4-benzimidazolyl, 5-benzimidazolyl, 6-benzimidazolyl, 7-benzimidazolyl, 8-benzimidyl, benzoheptyl (1 - benzene) And oxazepine, 2-benzoxazolyl), benzothiazolyl (1-benzothiazolyl, 2-benzothiazolyl, 4-benzothiazolyl, 5-phenylthiazolyl, 6-benzothiazolyl, 7-benzothiazolyl), carbazole 162632.doc -29- 201238995 base (1-咔Azyl, 2-oxazolyl, 3-oxazolyl, 4-oxazolyl), 5Η·dibenzo[b,f]azepine (5H-dibenzo[b,f]azepine-buyl , 5Η·dibenzo[匕^azhen-2-yl, 5Η-dibenzo[b,f]azetidine, 5Η-dibenzo[b,f]azep-4-yl, 5H- Dibenzo[b,f]azhen-5-yl),10,丨dihydro-5H-dibenzo[b,f]azepine (10,11-dihydro-5H-dibenzo[b] , f]azet-1·yl, 10,1 dihydro-5H-dibenzo[b,f]azhen-2-yl,10,11·dihydro-5H-dibenzo[b,f Nitrogen-3-yl, 10,11.dihydro-5H-dibenzo[b,f]azepin-4-yl, 10,11-dihydro-5H-dibenzo[b,f]nitrogen H-5-based) and the like. A heterocyclylalkyl group is an alkyl group as defined above wherein the hydrogen or carbon bond of the alkyl group as defined above is replaced by a bond to a heterocyclyl group as defined above. Representative heterocyclylalkyl groups include, but are not limited to, furan-2-ylmethyl, furan-3-ylindenyl, pyridin-3-ylmethyl, tetrahydrofuran-2-ylethyl, and 吲哚_2-ylpropane base. A heteroarylalkyl group is an alkyl group as defined above wherein the hydrogen or carbon bond of the alkyl group is replaced by a bond to a heteroaryl group as defined above. The term "alkoxy" refers to an oxygen atom attached to an alkyl group, including a cycloalkyl group, as defined above. Examples of linear alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, pentyl oxide, hexyl oxidation, and the like. Examples of branched alkoxy groups include, but are not limited to, isopropoxy butyloxy, third butoxy, isopentyl oxidized, isohexyl oxidized, and the like. Examples of cyclic alkoxy groups include, but are not limited to, cyclopropyl oxidation, cyclobutyl oxidation, cyclopentyl oxidation, cyclohexyloxygen oxime, and the like. The alkoxy group may include from i to about 12.2 carbon atoms bonded to the oxygen atom and may further include a double bond or a triple bond' and may also include a hetero atom. For example, in this document 162632.doc •30- 201238995 means within the 'slight propoxy alkoxy group. Within the meaning herein, methoxyethoxy is also an alkoxy group, such as a fluorenyldioxy group, in the case where two adjacent atoms of the structure are substituted therewith. Unless otherwise indicated, the term "halo" or "halogen" or "halide" by itself or as part of another substituent means a fluorine, chlorine, bromine or iodine atom. Preferably, fluorine, gas or bromine. The functional group includes a monohaloalkyl group, a polyhaloalkyl group in which all halogen atoms may be the same or different, and a perhalogen group in which all hydrogen atoms are replaced by a functional atom (e.g., fluorine). Examples of the south alkyl group include a trifluoromethyl group, a urethane group, an anthracene group, a monoethyl group, a 1,3-dibromo-3,3-difluoropropyl group, a perfluorobutyl group, and the like. • Tooth alkoxy group J includes a monohaloalkoxy group, a homodentate alkoxy group in which all of the functional atoms may be the same or different from the multi-fossiloxy group and all hydrogen atoms are replaced by a (tetra) atom (e.g., fluorine). Examples of the oxalyloxy group include a trifluoromethoxy group, a u-diethoxyethoxy group, a U2-diethoxyethoxy group, a bis- 3,3-dipropoxy group, a perfluorobutoxy group, and And so on. "All-gas base" (where ...) means having a minimum of X carbon atoms, wherein all hydrogen atoms are replaced by fluorine = sub. Preferably, it is a (Ci_C6) fully fluorenyl group, and a more preferred one is (4) a perfluoroalkyl group, and the best one is _CF3. 3) The term "(Cx-Cy) peroxyalkylene" (where x

The carbon atom and the largest one of the carbon eyebrows have the smallest X-sucking sinking base, in which the fluorine atom replaces the one of the best ones. _C6) Perfluoro-extension ^ = sub-(four) C3) The best _CF2 " &quot; 者-(C]-162632.doc •31 - 201238995 The terms "aryloxy" and "arylalkoxy" refer to the aryl and alkane bonded to the oxygen atom, respectively. The aryl group is bonded to the aralkyl group of the oxygen atom. Examples include, but are not limited to, phenoxy, naphthyloxy, and benzyloxy. The term "bristing group" as used herein refers to a group containing a moiety, wherein The group is bonded to the other carbon atom via a parent group carbon atom bonded to the β-rebase carbon atom, and the other carbon atom may be an alkyl group, an aryl group, an aralkyl group, a ring-based group, or a cycloalkyl group. a heterocyclic group, a heterocyclic alkyl group, a heteroaryl group, a heteroarylalkyl group or the like. In the specific case where a carbonyl carbon atom is bonded to hydrogen, the group is a "methyl group" (this article) The term thiol is defined as follows. The fluorenyl group may include from 0 to about 12 to 20 additional carbon atoms bonded to the carbonyl group. Within the meaning of the present invention, the saccharide group may include a double bond or three. An example of a fluorenyl fluorenyl group. The fluorenyl group herein may also include a hetero atom. Within the meaning herein, an example of a fluorenyl (pyridyl-3-carbonyl) fluorenyl group. Other examples include Ethylene, phenyl fluorenyl, phenylethyl fluorenyl, butyl thiol, cinnamyl and acryl fluorenyl, and the like. When a group containing a carbon atom bonded to a carbonyl carbon atom contains a halogen 'The group is referred to as the "functional group". The example is a trifluoroethylene group. The term "amine" includes, for example, a hydrazine (group) 3 mono-amine, a secondary amine, and a tertiary amine. A group may independently be oxime or non-n (eg, alkyl, aryl, and the like). Amines include, but are not limited to, r-NH2, for example, a deuteroamine, an arylamine, an alkylarylamine; each r Independently selected RzNH, such as dialkylamine, diarylamine, aralkylamine, heterocyclylamine, and the like; and each R independently selected r3N, such as a triolamine, a dialkyl group Arylamines, alkyldiarylamines, triarylamines, and the like. 162632.doc -32·201238995 Class. §§·" "Amine" also includes recorded ions. "Amine" is a type of ΝΗ2, -NHR, -NR2, -NR3 + (each of which is independently selected) and each of _NR3+ (which is not protonizable) A substituent in the protonated form. Thus, any amine-substituted compound can be considered an amine. Within the meaning herein, an "amine group" can be a primary amine group, a secondary amine group, a tertiary amine group or a quaternary amine group. "Alkylamino" includes monoalkylamino, dialkylamino and trialkylamine. "Syntax" ions include unsubstituted ammonium ions NH/, but unless otherwise stated, they also include amines. Any protonated or quaternized form. Thus, within the meaning herein, both 'trimethylammonium hydrochloride and tetradecyl ammonium oxide are sulphur and amine. The term "guanamine" (or "nonylamine") includes a c-guanamine group and an N-guanamine group, respectively, a '-C(〇)NR2 and a -NRC(0)R group. Thus, the guanamine group includes, but is not limited to, a primary carboxyguanamine group (_c(〇)NH2) and a formamidine group (-NHC(O)H). "Carboxylamido" is a group of the formula c(〇)NR2 wherein R can be an anthracene, an alkyl group, an aryl group or the like. The term "azido" refers to an Ns group. "Azide" may be an organic azide or may be a hydrazide (a salt of NO ion. The term "nitro" refers to a Ν〇2 group bonded to an organic moiety. The term "nitroso" refers to The NO group bonded to the organic moiety. The term nitrate refers to the 〇n〇2 group bonded to the organic moiety or the salt of the nitrate (NOf) ion. The term "urethane" ("amine formazan" The base (carbam〇yl or carbamyl)) includes an N-urethane group and a 〇-amino phthalate group, respectively, ie, -NRC(〇)〇r and 〇〇c(〇)NR2 group. 162632.doc •33· 201238995 The term “indoleamine” (or “mineral amine group”) includes s-amine amide group and N-sulfonamide group, ie, -S02NR2 and -NRS〇, respectively. a 2R group. Thus, a sulfonamide group includes, but is not limited to, an amine sulfonyl group (_S02NH2). It should be understood that the organic sulfur structure represented by the formula -S(0)(NR)- refers to a sulfonimide, wherein Both the oxygen atom and the nitrogen atom are bonded to a sulfur atom, which is also bonded to two carbon atoms. The term "脒" or "脒基J includes a group of the formula -c(nr)nr2. Usually, 脒Base -C(NH)NH2. The term "胍" or "胍基" includes a group of the formula -NRC(NR)NR2. Usually, the fluorenyl group -nhc(nh)nh2. In addition, when the features or aspects of the invention are described in terms of the Markush group, familiarity The skilled artisan will recognize that the invention may thus also be described in terms of any individual member or subgroup of members of the Markush group. For example, if χ is described as being selected from the group consisting of bromine, gas, and iodine, then Explain in detail the claims of bismuth bromine and the claims of X-ray bromine and gas. In addition, when describing the characteristics or aspects of the invention according to the river, those skilled in the art will recognize that it is also in accordance with the Markush group. The invention is described in any combination of individual members or subgroups of members. Thus, for example, if the group is described as being selected from the group consisting of desert, gas and moth, Y is described as being selected from the group consisting of methyl and ethyl. And the group of propyl groups' elaborates on the X-type bromine and γ-methyl groups. If the value of the variable must be an integer (for example, the number of carbon atoms in the alkyl group or the number of substituents on the ring) is described as the range (for example, 〇 to 4), this means that the value can be any integer between 〇 and 4 Including 〇 and 4) ie, 2、 2, 3 or 4. In various embodiments, for example, a compound used in the method of the invention or a 162632.doc -34·201238995, and the σ substance may be Any of the combinations and/or sub-combinations of the listed embodiments. In various embodiments, compounds are provided as in any of the examples or in the exemplary compounds. Or an embodiment imposes a limiting condition 'where the classes or embodiments may not include any one or more of the other embodiments or materials disclosed above. DETAILED DESCRIPTION In various embodiments, the invention relates to the inclusion of polythiophene polymers The composition of the polysorbent polymer is substituted along the polymer primary bond via one or more interspersed joints having a fullerene. In each of the four (4) t, the compositions of the present invention can be prepared by coupling a polythiophene polymer wherein all or at least some of the thienyl repeating units within the polymer chain have a linker precursor group 'the front linker of the linker' m can be reacted with a suitable fullerene (4) and underivatized fullerene to give a fullerene-polythiophene conjugate covalently or ionically coupled. In various embodiments, the present invention provides a composition for photovoltaic power generation comprising a polyporphyrin polymer having a (iv)-based repeating unit, wherein at least a (tetra) phenyl repeating unit that is not attached to the polymerization end is via No; the body is covalently bonded or ionically bonded to each of the fullerene groups. ^ In the composition of the invention, the fullerene group is bonded to at least some of the internal 2 base repeating units of the bond, and is not disposed at any substantial extent in the polymer gold = polydecene chain may be more than bonded - Fuller lean unit. In the bulk sample of the present invention, some individual polymer molecules may not have a rich soil band' but most of the individual polymer molecules have at least one Fuller-based I62632.doc •35·201238995 group and may have more One. Polythiophene is a polymer group which is well known to incorporate a thiophene ring (thienyl) as a repeating unit in a polymer. The thienyl groups are directly attached to each other such that the polymer contains a total of unsaturation groups. The polythiophene may be random, that is, a position in which each porphinyl unit is attached to an adjacent thiophene unit is random, or may be positionally regular 'i.e., wherein each thiophene unit bond in the polymer molecule The position of the junction to its neighboring cells is substantially identical. In various embodiments, the compositions of the present invention comprise a positionally-regular polythiophene polymer. For example, the polythiophene polymer can be a 2,5-polythiophene wherein the bond to the repeating unit of the porphinyl group is attached to a carbon atom adjacent to the thiophene group sulfur atom. In the polythiophene polymer, for each of the thienyl repeating units, in addition to the sulfur atom which is fully substituted, four carbon atoms are present for bonding. Thus, in positional polythiophenes (e.g., 2,5-polythiophene), two other positions (3-position and 4-position) are available for substitution. Substitutions that do not participate in the formation of the polymer backbone in one or both of these locations provide groups pendant from the polymer backbone. For example, the polythiophene polymer can comprise a monosubstituted thiophene repeating unit, such as a 3-substituted thiophene unit. In various embodiments, the compositions of the present invention comprise a positional HT-substituted by a monosubstituted thiophene repeating unit. 2,5-polythiophene, wherein the composition has the formula (1)

162632.doc • 36 - 201238995 wherein each independently selected ruthenium comprises a linker precursor group comprising a reactive group; X' is covalently bonded to the at least one monosubstituted thiophene repeating unit a linker, wherein X, may comprise a covalent bond, an ionic bond, or both; "FLR" is covalently or ionically bonded to a fullerene of a positionally regular polythiophene via hydrazine; η' are each independently from about 3 to about 1 Å; and the parent asterisk * indicates a continuous bond having a terminal atom, each chain optionally having an additional Fuller connected to the positional regular polythiophene by a linker X. Alkene. As described above, Formula (I) depicts a 2,5-head-p-tail position regular 3_monosubstituted polythiophene containing from about 1 to about 2, one repeat unit (ie, a molecular weight of about 1,000 to about 20 Å, 〇〇〇); for example, the polymer may include from about 5 to about 2,000 repeating units (ie, having a molecular weight of from about 5 Torr to about 200,000), or may include From about 100 to about 2 repeat units (i.e., having a molecular weight of from about 10,000 to about 20,000). The bulk sample of the commercially available horn of the present invention may contain a distribution of individual polymer molecular weights (having a weight average molecular weight) and a polydispersity index. See, for example, U.S. Patent No. 7,572,880 to the present inventor, and U.S. Patent Application Serial No. 2010/0004423 and No. 2010/031 No. 1879. Each thienyl repeating unit comprises a linker precursor group X for reacting with a suitable fullerene such that at least some of the thienyl repeating units obtain a fullerene-linker conjugate, wherein the fullerene is linked The body is bonded to the polythiophene backbone in a covalent manner or ionically. More specifically, as described above, $ olefin can be C61-fuller, and the fused ring in the pot is bonded to C60-Fuqin //t ^ The nucleation can be prepared, for example, by intercalation with a carbene of C60-fullerene, or by reacting with C70·fullerene to produce a C71-fullere derivative. Because of the fact that in each of the examples, the composition of the present invention may comprise a T-type (four) phenanthrene-rich (four) co-plant

The alkyl or aryl group is optionally taken as R, hydrazine, alkyl, or aryl, either generation; η and η are each independently from about 3 to about ι 〇, 00 〇; and X is linked by A linker obtained by forming a covalent bond or an ionic bond between the precursor precursor group X and a suitable fullerene reactant. As described above, PCBA is a commercially available fullerene derivative which can be prepared by the reaction of &amp; diazo valeric acid or ester with C60-fulleric. The acid side groups or ester side groups of C61-fullerene PCBA in different organic reactions can be used for other conversions to be compatible with the C60-fullerene core. For example, a 'sale-selling pheno-fullerian mixture can have the following formula 162632.doc •38· 201238995

An ester bond) or a nitrogen atom (forming a guanamine bond) or a carboxylate group (forming an anhydride bond),

Wherein γ also includes as components a sub-structure (eg, an alkyl chain and the like) that has been incorporated into the linker precursor group X during the coupling reaction. In this example, the fragment -CH2(CH2)mCH2C(=0)Y_ constitutes the linker X' of the former formula. Alternatively, the composition of the invention may have the formula

The carboxyl group of pcBA has been reduced to methanol by the action of, for example, diborane, and then it can be coupled with a suitable X group to obtain an ether, and a methanol oxygen or a burnt bond is incorporated into the oxime. The nuclear reagent is activated and replaced to form linker Y. 162632.doc •39- 201238995 Another option is that the composition of the present invention can have a right-handed

Wherein the linker group is condensed with a Wittig type via a carboxaldehyde group on one of the fullerene or polythiophene linker precursor groups and a scaly inner salt (or phosphonate) on the other reactant Its equivalent reaction (for example, reaction) is formed. Alternatively, the composition of the invention may have the formula

Wherein the coupling of the fullerene to the polythiophene is carried out by reacting a group of organometallic reagents (for example, an organolithium reagent, a Grignard reagent or a Refrmatsky reagent) with a fullerene carboxaldehyde (for example, self-capable from the above fullerene f In particular, in various embodiments, the present invention provides the above structure wherein 162632.doc •40·201238995 m is 0 to about 12; η and η' are each independent The ground is about 3 to about 1 〇, 〇〇〇; and the X-type linker precursor group; lanthanide (CH2)r, (CH2)rCHOH(CH2)r, (CH2) NRl(CH2), (CH2) rO(CH2)r, (CH2)rS(0)q(CH2)r or (CHASCCOqNRkCHA, wherein each independently selected r is 约 to about 6, q is 〇, i or 2, and Ri is Η or alkane In various embodiments, the composition may be any of the above structures, wherein X comprises optionally substituted (C1-C12) alkylene chain, the (C1-C12) alkylene chain Further optionally, an unsaturated group, a cyclic group, and a hetero atom selected from the group consisting of ruthenium, NR, and s have a reactive group or a derivative thereof. For example, a 'reactive group' In the examples, the linker precursor group X may comprise a (C1-C12) extension having a terminal substituted with CO 2 R 1 or COR 1 , OH, a halogen group or NHR 1 . An alkyl chain, wherein R is a hydrazine or an alkyl group. In each embodiment, the 'linker X' may, when formed, comprise an ester, a guanamine, an anhydride, an alkylation product or an alkylation product. More specifically, X The excipient chain may be optionally disposed of an ester, a guanamine, an acid needle, a double bond or a methanol group. In various embodiments, the composition of the invention may have the formula 162632.doc • 41 - 201238995

Wherein m = 2 and Y is NR(CH2)r, 0(CH2)r, 〇C(=〇)(CH2)r or (CH2)r, and *, n and n' are as described above. Compounds of this type can be prepared as described above by combining the appropriate Fullerene Retinoic Acid S-derivatives with alcohols, amines, oxic acid and metallated alkyl groups to give the brewed, amine, anhydride and hydrazine. Alternatively, the composition of the invention may have the formula

Wherein m = 2 and the lanthanide (Ccan or CH2C(tetra))(CH2)m recognizes the fullerene furfural as described above. This type of compound can be prepared by condensing a derivative with an organometallic group X as described herein. Having the following formula, alternatively - in other embodiments, the composition can be 162632.doc -42 - 201238995

Or have the following formula

Wherein R 2 is an alkyl group and the other variables are as described above. This type of compound can be formed by forming an anion adjacent to the carboxylate (or ketoester) on the linker precursor group and for anionic nucleophilic reactants. The alkylation is suitably carried out by substituting a fullerene having a leaving group. In other embodiments, the linker that bonds the fullerene to the polythiophene backbone can comprise, for example, at least one ionic bond between the cationic group and the anionic group (eg, in the group X' of the formula below) Ie 'salt key' 162632.doc .43- 201238995

A linker formed from a linker precursor group x and a suitable group on the fullerene derivative. For example, the linker can comprise a bond between a cationic quaternary ammonium ion and an anionic carboxylate ion or a reductive acid ion. In various embodiments, the cation comprises a cationic fullerene derivative, such as a compound of the formula

The choline or its homologues and the esters and ethers of pCBA or pCByl_〇H are as described above.

Wherein each R1 is independently selected from the group consisting of hydrogen, alkyl and aryl, or two R groups together with the nitrogen atom to which they are bonded form a 3 to 8 membered heterocyclic group, 162632.doc 201238995,: It The star is substituted, and optionally further comprises one to three other heteroatoms selected from the group consisting of 〇, &amp; S(〇)q, where q is 〇. This type of compound can be prepared as detailed in the references described above. The combination of an ion chelantene derivative and an anionic polythiophene (e.g., a olefin having a slow acid or a reductive group on a linker's JJ group) provides the ionic linkage of the present invention. Leyne poly (four) total light object. In various embodiments, the invention provides a method of making a composition of the invention comprising contacting a polyporphyrin polymer having a linker precursor group with a rich (tetra) group suitable for reaction with a linker precursor group to form Polyporphin-linker-fullerene material. For example, in various embodiments, the linker precursor group comprises a moiety that produces a carbene (eg, a heavy gas group, a dilute, or the like), and the Fullerene is underivatized to form a fullerene The pheno-linked linker is then inserted into the C60-Fuller bond. In other embodiments, the reactive group on the linker precursor group of the polythiophene can be reacted with a suitable functional group of the fullerene derivative. For example, the linker precursor group can comprise a nucleophilic group and the fullerene comprises a derivatized fullerene of an electrophilic group. Alternatively, the linker precursor base may comprise an electrophilic group and the fullerene may be a derivatized fullerene comprising a nucleophilic group. In embodiments where the fullerene comprises an electrophilic reactive group, the derivatized fullerene can be a fullerene carboxylic acid, a fullerene carboxylate or a fullerene carboxaldehyde. For example, PCBA, which is a known compound and is commercially available, can be used in the form of a free acid or ester, or can be reduced to a carboxaldehyde form, for example by complete reduction to dimethanol by diborane and subsequent (for example) DCC/DMS〇, ncs/dms, 162632.doc •45- 201238995

Cr03/pyridine, Dess-Martin periodinane or the like to re-oxidize β. In other embodiments, the derivatized fullerene may be a fullerene alkyl dentate or an alkyl sulfonate. These compounds can be prepared by subjecting the fullerene sterols described above to transformation using standard reagents such as p〇Cl3 (for s for the function) and sulfonium oxime (for sulfonate formation). When the fullerene comprises an electrophilic component of the coupling reaction, the polythiophene linker precursor group can comprise a nucleophilic group that can be coupled to form a covalent linker group, such as a hydroxyl group, an amine group, a thiol, a carboxy group. Acid group, organolithium group, Grignard reagent or Reformatsky reagent 0 Alternatively, the polythiophene may comprise an electrophilic component such as a carboxylic acid, a carboxylic acid ester or a carboxaldehyde. Such groups can be obtained by catalytic coupling of a suitably substituted 2,5 dibromothiophene (e.g., having a protected carboxylic acid ester or a carboxaldehyde group on a 3-alkyl substituent). See, for example, U.S. Patent No. 7,572,880 to the inventor of the present application, and U.S. Patent Application Serial No. 2, No. 4, No. 4, 423, and No. 2010/031, No. 1,879. Alternatively, the linker precursor group of the polythiophene may comprise an alkyl group or an alkyl sulfonate. This type of derivatized polymer can be prepared by polymerizing a suitably substituted 2,5-monobromothiophene as described above, or by converting a substituent present in the form of a polymer as described above, for example Reduction of carboxaldehyde to methanol by, for example, sodium cyanoborohydride, followed by activation to give a dentate or sulfonate β. Although the poly(ephthene) has an electrophilic group, the fullerene derivative may have a nucleophilic group. , for example, a hydroxyl group, an amine group, a thiol, a carboxylic acid group, an organolithium group,

Grignard reagent or Reformatsky reagent. Or 'in various embodiments of the method of preparing the composition of the invention, the 162632.doc • 46-201238995 precursor precursor group and the derivatized fullerene may comprise a (iv) group or a ketone group, and The other may comprise scale internal salt, α_phosphonium based carbon anion, organic clock, Grignard reagent or Reformasky reagent. Then, respectively, via Wittig reaction, HWE reaction or addition of organometallic reagent to several groups. More specifically, the derivatized fullerene may be 1&gt; 〇3 八 or 1&gt; 〇: 81^, and the linker precursor group of the polythiophene may comprise a methanol group, an amine group or a tickic acid group - Thus, 77 forms an ester, a guanamine or an acid anhydride, for example, when the polythiophene is substituted with a 2,5-HT-positional polythiophene substituted by a hydroxyline-based amine group or a tickrate group. In other embodiments, the ionic bond is formed upon formation of a linker group. For example, one of the polythiophene linker precursor group and fullerene may comprise a cationic group and the other may comprise an anion a group, as exemplified above, 5, which can be a cation (example) The fourth-order sulphide derivative) and the polythiophene may have an anionic linker precursor group (eg, a carboxylate). In various embodiments, one of the polythiophene and the fullerene derivative may be water soluble. The component can be dissolved in water and then contacted with another component in a solution which is also optionally present in water or a water-soluble organic solvent. For example, water-soluble polybenzazole can be used, for example, …the company·,

Lincoln, N_ gets the height position of the regular poly[3_(Unloading-5_pentanoate) 嚷 _ 2'5-diyl]. The form of the continuous acid vinegar can be prepared by converting the drum acid into taurine (β-aminoethyl acid) amine, thus providing an ion-co-form formation method whose tL contains (four) (four) cluster or Wei A linker precursor group of a vinegar group. 162632.doc -47- 201238995 Formula cation fullerene

Wherein, the parent-R is independently selected from the group consisting of gas, , sinking and square groups, and the two R丨 groups are bonded to each other. The nitrogen atom - forming a 3 to 8 membered heterocyclic group, which is optionally substituted, and optionally comprises from 1 to 3 other heteroatoms selected from the group consisting of ruthenium, NR1 and S(〇)q, wherein q System, .... See (5) For example, R· Bullard-Dillard operator, “τ·〇·丨4 Tissue Sites of Uptake of labeled C60j (1995^ Bi〇〇rg. Chem., 24, 376) As described above, the method of the present invention can be The method comprises reacting at least 1%, or at least 5%, or at least 1 G% of the repeating unit of the polythiophene with the fullerene to obtain a fullerene-thienyl repeating unit covalently coupled. 162632.doc -48· 201238995 In various embodiments, the fullerene-containing polythiophene of the present invention can be substituted by a fullerene-substituted dihalothiophene in the presence of a metal catalyst, such as 2,5.H substituted by fullerene. The thiophene) is polymerized and optionally prepared by copolymerization of a bis-quinone (for example, 2,5-didentate porphin) which does not have a fullerene group. In various embodiments, the polymerization of 2,5-dihalothiophenes per monomer unit with or without a fullerene group can be as disclosed in the published PCT patent application no. 2009/056497, the disclosure of which is incorporated herein by reference. The implementation of such references in the literature is hereby incorporated by reference. For example, the dihalogenated plug 7 can be -chloroseptin or dioxin. The method of preparing a positionally-regular polythiophene polymer having a fullerene group as disclosed herein may employ an activated metal which directly inserts a metal atom into a cryptyl-fraternal or dentate-hetero-fragrance carbon bond. Preferably, the activated metal is Rieke (Zn*). If, for example, a nickel (ruthenium) catalyst or a platinum catalyst is used to achieve polymerization, a positional regular conductive copolymer can be obtained, and the fullerene-substituted polythiophene conductive polymer can be a poly(3-substituted-thiophene). Polymer or poly(3,4-disubstituted-thiophene) homopolymers 'Some or all of the 3 - substituents or 4 - substituents comprise a fullerene group. Preferably, the positional regular conducting polymer having a fullerene group is Η T poly(3-substituted-thiophene) or Η T poly(3,4-disubstituted 嗟 。). The present invention provides a method of preparing a positionally-regular conductive polymer comprising adding a nickel (II) catalyst to a monomer-metal complex solution to provide a site-regular conductive polymer, wherein at least some of the monomer units are typically via a linker The bond has a sulphur group. The method for combining the monomer-metal complex solution with a nickel (ruthenium) catalyst solution may involve a "normal addition" method 162632.doc -49 - 201238995 anti-addition" in various embodiments, A manganese (tantalum) catalyst can also be used. In various embodiments, the "anti-addition" method provides a positionally regular conductive polymer that is more regular in position than those obtained by the "normal addition" method. This increase in positional regularity is extremely advantageous because it is extremely difficult to increase the ratio of the positional regular polymer to the positional random polymer. In addition, higher position rules result in higher conductivity of the positionally-regulated conductive polymer. This is particularly advantageous for positional polythiophenes having fullerenes of the present invention which are suitable for use in photovoltaic devices (e.g., solar cells). The porphinyl monomer-metal complex can be prepared by a process comprising a 2,5-didentate substituted monomer (which can be in the 3 position or at the 3 position and 4- a fullerene substituent on both sides) in contact with an activating metal, a Grignard reagent or an organozinc reagent (eg RZnX), wherein the R is an alkyl group, a dialkyl reagent (R?Zn) or a trialkyl zincate A reagent, wherein a μ metal ion); for example, wherein R is a (C 2 -Cl 2 ) alkyl group, a lanthanide magnesium, manganese, a sodium, a potassium or a potassium, and an X system F, α, Br or I. Preferably, the dialkyl group is substituted with a single system of 2,5-digas- or 2,5-dibromo-thiophene and the activated metal system activates aluminum, manganese, copper, rhodium, magnesium, calcium, titanium, iron, Cobalt, nickel, indium or a combination thereof. More preferably, the metal system Rieke zinc (Zn*) is activated. In various embodiments, the thienyl monomer having a fullerene group may have the formula

FLR R1 X' z~^S~z S (II) where z is an independently selected dentate group, such as chlorine or bromine or iodine, but usually 162632.doc -50- 201238995 two Z groups are the same dentate Ri is hydrogen, alkyl or the like; and FLR is a fullerene group which is coupled via the linker X' to the 3-position of the thiophene monomer of formula (II). Or &quot;the thiophene monomer unit can be a 3,4, disubstituted thiophenyl group of the formula (ιπ)

FLR FLR X', X, S (III) wherein the groups are as defined for formula (II), the conditions being two fullerene groups FLR and two linkers 可ι but not necessarily the same β in each implementation In the example, the X' alkyl chain is optionally mixed with a double bond, a triple bond, or an aryl group, or a group selected from the group consisting of ruthenium, NR1, S, S(O), and S(0)2. An atom wherein R1 is a hydrazine or an alkyl group, wherein the alkylene chain is optionally substituted with a hydroxy group or a carbonyl group. The fullerene-containing polythiophenes of the present invention can be prepared by polymerization, for example, as described in WO 2007/146074 and WO 2009/056497, the use of a metal catalyst (such as nickel or the like). The phenyl unit is lightly bonded. The di-i-thiophene can be converted to an organometallic derivative, such as an organic hydrazine, a hydrazine or a manganese derivative, which is then coupled in the presence of a catalyst. For example, σ ' can be used as a catalyst to make a positional rule polystimulus, and palladium can be used to produce a positional random polythiophene. The polymer product obtained by homopolymerization of the thienyl monomer of formula (II) will provide a polythiophene having a fullerene group on substantially every thienyl repeating unit; the thiophene monomer of formula (III) The poly will provide polybenzazole having two fullerene groups on substantially each of the thienyl repeating units. In various other embodiments, the monomeric thienyl reagent of formula (II), or the monomeric thienyl reagent of formula 162632.doc 51 201238995, formula (III), or mixtures thereof, may be sold in a similar manner to the lack of fullerene substituents. The phenomonomer is copolymerized. In this way, the average ratio of polythiophene polymers having fullerene units can be predicted based on the relative ratio of the monomeric agent having a fullerene group bonded to the monomer reagent having no fullerene group bonded thereto. Degree of substitution (DS). For example, since the fullerene-thiophene bond of the monomeric thienyl unit is stable to the polymerization conditions, the average degree of substitution can be directly calculated from the ratio of the reagent. Similar to a fullerene-polymer conjugate prepared by coupling a fullerene to a linker precursor group in a complete (eg, preformed) polythiophene polymer, by substituting fullerene The fullerene polythiophene co-light formed by the polymerization of a thienyl monomer reagent or, as appropriate, with other thiophene monomer reagents, can provide a ketene group bonded to the polyfluorene via a linker of different length and rigidity. The product of the main chain. For example, if a system is attached to a base chain, the length can vary from a total of up to a single carbon up to about 24 carbon atoms. It should be remembered that the alkyl chain may also contain optional heteroatoms inserted therein, for example, oxygen, sulfur (sulfur) Light, sub-stone, hard) or nitrogen. &amp; Large rigid linkers can be obtained by the presence of, for example, an olefinic double bond, an acetylene triple bond, an aryl group, a fused bicyclic aryl group, and the like in a linker. Unsubstituted alkyl chains have considerable flexibility 'and can be referred to as 'and groups such as acetylene triple bonds are non-foldable rigid linear groups' forcing each triple bond to have at least four carbon atoms in a direct bond configuration . Similarly, since the degree of freedom is limited, the phenyl group can increase rigidity and can be used to fix the minimum distance between the fullerene group and the polybenzazole backbone. Since it is believed that the distance between the fullerene group and the polypeptone backbone can affect the efficiency of photoinduced electron transfer between them, the inventors believe that the best 162632.doc -52· 201238995 linker can be developed without undue experimentation. . The present invention is also directed to a positionally regular conductive polymer composed of an improved positionally regular conductive polymer having excellent electrical conductivity. The positional regular conductive polymer of Wenliang is characterized by its monomer composition, its degree of positional regularity, and its physical properties, such as its molecular weight and number average molecular weight, its polydispersity, its electrical conductivity, and its direct preparation characteristics. Determine the purity and other characteristics. A modified method for the location of regular conductive polymers. The degree of substitution of the celite dilute to the polymer can be varied. Although in theory, it is not the case that every phenanthrene unit is replaced by Fuller Roast, which is believed to be hampered by the space requirement of C60_Fuller or even larger C7〇Fuller High degree of substitution. In various embodiments, each of the ordered phenanthrene molecules (eight per denier per polymer chain) has an average of more than one fullerene. Polymers having a higher molecular weight (i.e., more pheno-based repeat units) may have more fullerene conjugate groups than the polyporphin shorter bond form. In various embodiments, from about 1% to about 1% of the thienyl repeating units of the polythiophene have fullerenes. Alternatively, from about 1% to about 5% of the thienyl repeat of the polythiophene is a single cooker: fullerene. In other embodiments, the fullerene content can be as high as (example =) 5 〇 % ' or in some embodiments up to (10) the poly(fullerene) (four) sample of the present invention can be determined by using standard analytical techniques. Medium rich, lean average content, including elemental analysis, gel permeation chromatography, mass spectrometry, c NMR (in solution or solid form), and the like. In various embodiments of the invention, the present invention suitable for photovoltaic devices or the polythiophene-fuller prepared by the present method may have at least about 85%, or at least about 162632.doc -53.201238995 90%, or at least about 95%, or at least about 99. /. Purity. Purification of the polythiophene fullerene prepared by the process of the invention may be carried out after the polymerization step described above, for example by using a hexane in a Sohxlet extractor or the like (for example) followed by gas or two gas The methane is subjected to solvent extraction, as the case may be two or more times. The composition of the present invention can be formed into a film or layer suitable for photovoltaic power generation, wherein the surface area of the light-receiving device determines how much light (eg, daylight) can be trapped and thus limits the amount of electricity that can be generated by the device, which is directed to the light of the photovoltaic device. Efficiency is adjusted. In various embodiments, the invention provides a film comprising a composition of the invention. The film may also include other materials such as binders to increase physical film strength, and, for example, adjuvant materials for absorbing light from a molecularly excited state to a polythiophene-fullerene conjugate and transferring energy in a split manner. The geometry of the membrane can be adjusted to provide maximum power generation per composition of the composition of the invention, which is an economically important factor in determining the cost of solar power. Excessively thick layers of the main photovoltaic material are not economically viable. Films of the invention can be prepared by distributing the compositions of the invention (as appropriate with binders, adjuvants, and the like) on a support surface. The support surface can include conductive elements to allow collection of current generated by light exposure. The film of the present invention can be placed in a photovoltaic device having a support conductor and a conductive cover glass (e.g., 11 () indium titanium oxide glass) in order to achieve a device that can generate a voltage potential and support a large amount of current flowing therefrom. In each of the examples, the present invention provides a photovoltaic device incorporating the polythiophene-fullerene composite prepared by the present invention or by the method of the present invention. Relative to its 162632, doc •54· 201238995 He contains polythiophene organic photovoltaic devices or relative to other general photovoltaic devices. These photovoltaic devices can exhibit high light efficiency. 1 shows an example of a block diagram of a photovoltaic device 100 in accordance with an embodiment of the present invention. The photovoltaic device 100 includes a first electrode 11A and a second electrode 112 separated by a polymer 12〇. The polymer 120 includes a donor portion 124 and a receptor portion 122. In the example of FIG. 1, the donor portion ι24 is conjugated with the acceptor portion m to form a bulk heterojunction at the donor portion 124. A short diffusion distance is provided between the receptor portions 122. In one example, the donor portion 124 and the acceptor portion! The mix of 22 is random. In one example, there is a microstructure order level in the mixing of the donor portion 124 and the acceptor portion 122. Electronic device 13A is also illustrated, which is coupled to photovoltaic device 100 via circuit 丨32. In an example operation, photons incident on the photovoltaic device 1 产生 generate excitons in the polymer 120. The excitons are separated into electrons and holes at the interface between the donor portion ι24 and the acceptor portion 122. Electrons then flow through circuit 1 32 to provide current for electronic device i3 to operate. Examples of receptor moiety 122 include fullerene structures as described herein. Examples of donor moieties include polythiophene polymers as described herein. 2 shows another block diagram embodiment of a photovoltaic device 200 in accordance with an embodiment of the present invention. The photovoltaic device 200 includes a first electrode 21A and a second electrode 212. The receptor layer 222 is shown to form an interface with the first electrode 21A. The donor layer 224 is shown forming an interface with the second electrode 220 and the acceptor layer 222. Similar to FIG. 1, electronic device 23A is illustrated in FIG. 2, which is coupled to photovoltaic device 200 via circuit 232. In an example operation, photons incident on light 162632.doc -55 - 201238995 voltaic device 200 generate excitons in donor layer 224" are separated into electrons and electricity at the interface between exciton donor layer 224 and acceptor layer 222. hole. Electrons then flow through circuit 232 to provide current to cause electronic device 230 to operate. Example materials for acceptor layer 222 include fullerene structures as described herein. Exemplary materials for the donor layer 224 include polythiophene polymers as described herein. The compositions of the present invention or compositions prepared by the methods of the present invention can be components of photovoltaic devices such as solar panels. The inventors of the present invention anticipate that the composition of the present invention can be used in existing solar panels, for example, in "Ran Radbh et al., "Nanoscale control of the network morphology 〇f high efficiency polymer fullerene solar cells by the use of high material concentration in the liquid phase", ATcmoiecko/og;; (2010), 21, 1-8 and the references cited therein. The inventors herein believe that 'a highly closely controlled degree of contact between photoexcited electron-producing polyphenesis and electron-receiving fullerenes can provide enhanced light efficiency, for example, in devices described in the above documents. . The surface area of contact between the electron donor and the electron acceptor (molecular level when using the conjugate of the present invention) must be greater than that achieved by using a nanoscale control. This nanostructure contains a plurality of individual molecules. The inventors herein also anticipate that the light efficiency of the compositions of the present invention can be optimized by varying the distance between the polythiophenes and the fullerenes and the nature of the linker groups. Examples Preparation of alcohols Method 1 162632.doc -56· 201238995

Procedure: 0.5 g of polymer [4033] was placed in a 50 mL round bottom flask (rbf). Attach the oil bubbler and purge with Ar for 5 minutes. Add 10 mL of gas and cool to 0 °C. Add 2.5 mL of borane tetrahydrofuran complex. Stir for 3 hours. Add 10 mL of water. The phases were separated and back-extracted 3 times with 20 mL of gas. The solvent was removed and dried under high vacuum for 1 hour. Coupling [4033] alcohol with PCBM Method 1

v^-^C〇LPCB (incorporating 1% PCB) Procedure: 0.5 g of polymer alcohol was placed in a 500 mL round bottom flask (rbf) under Ar and purged with Ar for 5 minutes. Add 100 mL of chloroform and 0.35 mL0 to 0. 0.020 g of (6,6)-phenyl-C61 butyric acid (PCBM) was added. Reflux for 3 hours. The solvent was removed on a rotary evaporator. Dry under high vacuum for 1 hour. Coupling [4033] alcohol with PCBM Method 2 162632.doc -57- 201238995

Procedure: 0.5 g of polymer alcohol was placed in a 500 mL round bottom flask (rbf) under Ar. Purge with Ar for 5 minutes. Add 100 mL of THF and 4 mL of n-butyl (1.6 liters in hexane) and stir for 30 minutes. 0.020 g of (6,6)-phenyl-C61 butyric acid (PCBM) was added. Reflux for 3 hours. Remove the solvent on a rotary evaporator. Dry under high vacuum for 1 hour. Preparation of hernia method 1

Procedure: 0.5 g of polymer [4033] was placed in a 50 mL round bottom flask (rbf). A condenser, oil bubbler and KOH trap are attached. Purge with Ar for 5 minutes. Add 10 mL of air and 0.1 mL DMF. Add sulfoxide and gently heat until the bubbling stops. The solvent was removed by simple distillation. Vacuum the pump with a dry ice trap and a KOH trap for 1 hour to protect the vacuum pump. Preparation of brewing gas Method 2 162632.doc -58 · 201238995

Procedure: 0.5 g of polymer [4033] was placed in a 50 mL round bottom flask (rbf). A short path distillation unit connected to the oil bubbler and a KOH trap are attached. Purge with Ar for 5 minutes. Add 10 mL of sulfinium chloride and gently heat until the bubbling stops. Excess sulphur sulphur gas is removed by simple distillation under atmospheric pressure. A high vacuum was applied for 1 hour to remove any traces of sulphurous acid chloride, and a dry ice trap and a KOH trap were used to protect the vacuum pump. Coupling [4033] with PCBA Method 1

(Incorporating 1% PCB) Procedure: Place 0.5 g of polymer helium into a 50 mL round bottom flask (rbf). Attach the 3 condenser and purge with Ar for 5 minutes. Add 10 mL of chloroform and 0.18 mL of pyridine. Add 0.020 g (6,6) phenyl-C61 butyric acid (PCBA). Gently reflux for 3 hours. The solvent was removed on a rotary evaporator. 20 mL of toluene was added and removed with a rotary evaporator to help remove any residual pyridine. Dry under high vacuum for 1 hour. Coupling [4033] with PCBA 162632.doc -59- 201238995 Method 2

Ha,C^&gt;^ ” DCC solution * J 2) EffAV —/ k PC6A -- o.or When * hcci,

Procedure: 0.5 g of polymer [4033] was placed in a 500 mL round bottom flask (rbf) under Ar. Purge with Ar for 5 minutes. Add 100 mL of gas and 0.1 g of DMAP. Add 0.020 g (6,6) phenyl-C61 butyric acid (PCBA). Add 2.2 mL of DCC solution. Stir for 12 hours. The solvent was removed on a rotary evaporator. Dry under high vacuum for 1 hour. Note: DMAP is 4-(didecylamino)pyridine DCC is a dicyclohexylcarbodiimide. The solution used is stored in CH2C12, but is also stored in xylene and 1-mercapto-2-pyrrolidone (NMP). Coupling with Fullerene-C6〇Kefene Method 1

Procedure: 0.5 g of polymer ruthenium chloride was placed in a 50 mL round bottom flask (rbf). Add 10 mL THF and 0.35 mL triethylamine. Stir for 1 hour. Add 0.016 g 162632.doc •60· 201238995 Fullerene-C60. Stir for 3 hours. Remove the solvent from the shovel. Dry under high vacuum for 1 hour. Note: All patents and publications referred to herein may also be incorporated herein by reference to the extent of the disclosure of the disclosure of each of The entire disclosure of the disclosure is hereby incorporated by reference in its entirety herein in its entirety, unless the Any equivalents of the features or portions thereof, but it should be understood that various modifications may be made within the scope of the claimed invention. Accordingly, it should be understood that The present invention is susceptible to modifications and variations of the concepts disclosed herein, and such modifications and variations are still considered to be within the scope of the invention as defined by the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows an example of a photovoltaic device according to an embodiment of the present invention. Fig. 2 shows another example of a photovoltaic device according to an embodiment of the present invention. [Description of main components] 100 photovoltaic device 110 first Pole 112 Second electrode 120 Polymer 122 Receptor portion 124 Donor portion 162632.doc - 61 - 201238995 130 Electronic device 132 Circuit 200 Photovoltaic device 210 First electrode 220 Second electrode 222 Receptor layer 224 Donor layer 230 Electronics 232 circuit 162632.doc -62

Claims (1)

201238995 VII. Patent Application Range: 1. A composition for photovoltaic power generation comprising a polythiophene polymer having a thienyl repeating unit, at least some of which are not disposed at the end of the polymer chain, such as a thiophene repeating unit The respective fullerene groups are bonded to each other via a respective linker in a covalent manner or ionically. 2. The composition of claim 1 wherein the polythiophene polymer is a regular polymer. 3. The composition of claim 1, wherein the polythiophene polymer has a molecular weight of from about (9) Daltons to about 200,000 Daltons. 4. The composition of the present invention, wherein the polythiophene polymer is 2,5-polythiophene 0. 5. The composition of claim 1, wherein the polythiophene polymer comprises a monosubstituted porphinyl group. Repeat unit. 6. If you ask for it! a composition comprising a positional rule Ητ·2,5•polythiophene comprising a monosubstituted thiophene repeating unit, wherein the composition has the formula (1) (I) wherein each independently selected X comprises a linker oxime group comprising a reactive group; χ' is covalently bonded to at least one of the monosubstituted thiophene repeating units Linker 'where X, may contain covalent bond, ionic bond or 162632.doc 201238995 FLR" is covalently or ionically bonded to the positional polythiophene via X'; η and η' are each independently from about 3 to about 1 Å; and each asterisk * Indicates a contiguous chain of terminal atoms, each chain optionally having an additional fullerene attached to the positional polythiophene by linker X. 7. The composition of claim 6 wherein the oxime is an alkyl chain, optionally containing a double bond, a triple bond, or an aryl group, or selected from the group consisting of ruthenium, NR1, s, s ((7) and S (〇) And a hetero atom of the group consisting of H or an alkyl group, wherein the alkylene chain is optionally substituted with a hydroxyl group or a carbonyl group. 8. The composition of claim 1, which comprises a polythiophene fullerene of the formula Yoke η and η· are each independently from about 3 to about 10,000; and X′ is obtained by forming a covalent bond or an ionic bond between the linker precursor group of X and a suitable fullerene reactant. The connector. 162632.doc 201238995 9. The composition of claim 8 which comprises a polythiophene-fullerene conjugate of the formula Polythiophene-fullerene conjugate Or a polythiophene-fullerene conjugate of the formula 162632.doc 201238995 or polythiophene fullerene conjugates of the formula m is 0 to about 12; η and η' are each independently from about 3 to about 10,000; and the X-based linker precursor group; Y#(CH2)r^(CH2)rCHOH(CH2)r &gt; CH2)rNR1(CH2)r '(CH2)r〇(CH2)r ^ (CH2)rS(0)q(CH2)ril&gt; wherein each independently selected r system is about 24, q system 〇, 1 Or 2, and R1 is a hydrazine or a flammable group. The composition of any one of claims 7 to 9, wherein X comprises an optionally substituted (C1-C12) alkylene chain, the (C1-C12) alkyl chain further comprising an unsaturated group as the case may be. a cyclic group and a hetero atom selected from the group consisting of hydrazine, NR and S, wherein R is a hydrazine or an alkyl group. The alkylene group has a reactive group or a derivative thereof. 11. The composition of claim </ RTI> wherein the reactive group is an acid, an ester, a substituent, an amine or a group. 12_ The composition of claim 1 wherein X comprises a (Cl-Cl2) alkyl chain terminated at the end via cc^r1 or 162632.doc 201238995 COR1, 〇H, halo or NHR1, wherein R is H or Burning base. 13. The composition of claim 8 wherein X comprises an ester, a guanamine, an anhydride, an alkylation product or an alkylation product. 14. The composition of claim 3, wherein χι comprises an alkyl chain optionally containing an ester, a guanamine, an anhydride, a double bond or a methanol group. 15. The composition of claim 9 which has the formula Its center 2 and γ system NR(CH2)r, 〇(CH2)r, 〇c(=〇)(CH2) or (CH2)r 0 1 6. The composition of claim 9 having the formula 162632.doc 201238995 wherein m=2 and Y is (CH2)r*CH2C(=〇)(CH2)r. 17. The composition of claim 9, which has the formula Wherein R 2 is an alkyl group. 18. The composition of claim 7 wherein X' comprises at least one ionic bond. 19. The composition of claim 18, wherein X, comprises a bond between a cation and an anionic carboxylate ion or a sulfonate ion. The composition of claim 19, wherein the cation comprises a cation rich Rene 162632.doc 201238995 Derivatives. 21. The composition of claim 20, wherein the cation Wherein m and m' are each independently from about 12 to about 12. The compound of claim 20, wherein the cationic fullerene derivative is a compound of the formula Wherein each -R is independently selected from the group consisting of hydrogen, an alkyl group and an aryl group, or two R1 groups are formed together with the nitrogen atom to which they are bonded to form a 3- to 8-membered heterocyclic group which is substituted as appropriate. Further, depending on the case, i to 3 additional heteroatoms from 0 NR and 8 (0) 9 are selected, wherein ^ is 〇, J or 2. 23. The composition of claim 1, wherein each polythiophene molecule has an average of more than one fullerene. 24. The composition of claim 1 wherein the polythiophene is from about 0.1% to at least about 50°/. The thienyl repeating units have fullerenes. 25. The composition of claim 24, wherein from about 1% to about 5% of the polythiophene, the porphinyl repeating unit has a fullerene beta 26-containing film, as claimed in claim 1 Composition. 27. The membrane of claim 26, further comprising other concentrating material. 28. A method of preparing a composition as claimed in claim 1, comprising contacting a polythiophene polymer having a linker precursor group with a fullerene adapted to react with the linker precursor group to form a poly Thiophene-linker_fullerene material. 29. The method of claim 28, wherein the linker precursor group comprises a moiety that produces a carbene and the fullerene is underivatized fullerene. 30. The method of claim 28, wherein the linker precursor group comprises a nucleophilic group and the fullerene comprises a derivatized fullerene of the electrophilic group. The method of claim 28, wherein the linker precursor group comprises an electrophilic group, and the rich (d) is a derivatized Fullerian comprising a nucleophilic group. 32. The method of claim 30, wherein the fullerene-rich fullerene acid, fullerene carboxylate or fullerene carboxaldehyde is derivatized. Wherein the derivatized fullerene-based fullerene alkyl group 33. The method of claim 30, a halide or an alkyl sulfonate 34. The method group of claim 32 or 33, a thiol, a carboxylic acid group, Reformatsky reagent. Wherein the nucleophilic group is a trans-group, an amine organic group, a Grignard reagent or wherein the linker precursor group comprises a carboxyl group. 35. The method of claim 31, an acid, a carboxylic acid ester or a carboxaldehyde. 36. The method of claim 31 wherein the linker precursor group comprises an alkyl group 162632.doc 201238995 halide or alkyl sulfonate. The method of claim 35 or 36, wherein the nucleophilic group is a hydroxyl group, an amine group, a thiol group, a carboxylic acid group, an organolithium group, a Grignard reagent or a Reformatsky reagent. 3. The method of claim 28, wherein one of the linker precursor group and the derivatized fullerene comprises a carboxaldehyde group or a ketone group, and the other comprises a scale rust inner salt, alpha - a phosphonium based carbanion, an organolithium reagent, a Grignard reagent or a Reformasky reagent. 39. The method of claim 28 wherein the derivatized fullerene system pcBA or PCBM&apos; and the linker precursor group of the polythiophene comprises a methanol group, an amine group or a carboxylic acid group. 40. The method of claim 39, wherein the polythiophene is a 2,5-HT•positional polythiophene substituted with a hydroxyalkyl, aminoalkyl or alkylcarboxylate group. 41. The method of claim 28, wherein one of the polythiophene linker precursor group and the fullerene comprises a cationic group and the other comprises an anionic group. W 42. The method of claim 41, wherein at least one of the polythiophene and the fullerene is water soluble, and the water soluble polythiophene or fullerene is dissolved in water and then The other of the polythiophene or fullerene in a solution in water or a water-soluble organic solvent is contacted. 43. The method of claim 41, wherein the mesophyll "m嗔% &amp;" comprises a linker precursor group comprising a slow acid vine group or a sulfonate group. 44. The method of claim 41 Wherein the fuller is a compound of the formula 162632.doc 201238995 Wherein m and m' are each independently from about 12 to about 12. 45. The method of claim 41, wherein the fullerene is a compound of the formula Wherein each -R丨 is independently selected from the group consisting of hydrogen, alkyl and aryl; two R] groups together with the nitrogen atom to which they are bonded form a 3 to 8 membered heterocyclic group, which is optionally substituted, and Further, depending on the case, one to three additional heteroatoms selected from the group consisting of ruthenium, NR and S(0)q, wherein q is 〇, 46. A method of the composition comprising polymerizing a functional group (tetra) organometallic reagent in the presence of a metal catalyst by contacting a didentylthiophene having a fullerene group with a metal or metal derivative. 47. The method of claim 46, 48. The method of claim 46, wherein the metal catalyst comprises nickel or palladium. Wherein the thiophene organometallic reagent system is 162632.doc •10·201238995, the magnesium or manganese organometallic reagent β 49·4, the method of claim 46, further comprising one of the ones having a fullerene group The halothiophene is copolymerized with another dihalothiophene having no fullerene group. The method of any one of claims 46 to 49, wherein the bis-thiophene having a fullerene group has the formula (II) Ζ (II) or have formula (III) Each of the oximes is independently selected thiol; R1 is hydrogen, or unsubstituted or substituted alkyl or unsubstituted or substituted aryl; each FLR is independently selected fullerene And each - χ is an independently selected linker. 51. The method of claim 46, wherein the dihalothithiophene has 2,5- gas of fullerene. The phenotype or the 2,5-two deserts are sold. 52. The method of claim 50, wherein the dihalothiophene having a fullerene group has the formula (II) 'and the X' is a pendant base chain, wherein optionally a double bond, a double bond, or an aryl group Or a hetero atom selected from the group consisting of ruthenium, NR1, S, S(〇) and S(0)2, wherein R1 is a hydrazine or an alkyl group, wherein the alkylene chain is optionally substituted with a hydroxy group or a carbonyl group. 162632.doc -11 - 201238995 53. A method of preparing a film comprising applying a composition prepared by the method of claim 26 to a surface. 54. The method of claim 53, wherein the composition is first dissolved in a solvent and then applied to the surface&apos; and then the solvent is removed. 55. A photovoltaic device comprising the composition of claim 1. 56. The photovoltaic device of claim 55, wherein the plurality of cells having the composition or film respectively coupled to the conductor are adapted to generate a voltage between the conductors when the battery is exposed to the sun. 57. A photovoltaic device comprising: a first electrode and a second electrode separated by a polymer, wherein the polymer comprises: a poly(e) having a repeating unit of a thiophene group. a phenanthrene polymer; and a plurality of fullerene groups in contact with the polythiophene polymer; wherein at least some of the thiophene repeating units not disposed at the end of the polymer chain are covalently or via a respective linker Ionically bonded to each of the fullerene groups. 5. The photovoltaic device of claim 57, wherein the polythiophene polymer and the fullerene group are mixed to form a composite. 59. The photovoltaic device of claim 57 wherein the polythiophene polymer and the fullerene group are formed in alternating layers. 162632.doc